JP2009003197A - Volume hologram transfer foil and volume hologram laminate - Google Patents

Abstract

A main object of the present invention is to provide a volume hologram transfer foil capable of producing a volume hologram laminate having a high anti-counterfeit function.
The present invention relates to a substrate, a volume hologram layer formed on the substrate and having a volume hologram recorded thereon, a heat seal layer formed on the volume hologram layer and containing a thermoplastic resin. An ultraviolet absorbing layer formed between the substrate and the volume hologram layer or between the volume hologram layer and the heat seal layer and having a function of absorbing ultraviolet rays, and the heat seal more than the ultraviolet absorption layer. A fluorescent image forming layer formed on the layer side and having an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays, and the wavelength of ultraviolet rays absorbed by the ultraviolet absorbing layer and the fluorescent material The above problem is solved by providing a volume hologram transfer foil characterized in that the wavelength of ultraviolet rays to be absorbed is different.
[Selection] Figure 1

Description

  The present invention relates to a volume hologram layer transfer foil used for producing a volume hologram laminate by transferring a volume hologram layer onto a transfer target, and a volume hologram laminate.

  A hologram is the one where the wavefront of object light is recorded on the photosensitive material as interference fringes by interfering two lights with the same wavelength (object light and reference light), and the same wavelength as the reference light at the time of interference fringe recording When the light is applied, a diffraction phenomenon occurs due to interference fringes, and the same wavefront as that of the original object light can be reproduced. Holograms are widely used for security applications and the like because they have advantages such as beautiful appearance and relatively difficult replication. In particular, in plastic cards represented by credit cards, cash cards, and the like, hologram-attached cards have been widely used mainly from the viewpoint of preventing duplication and imparting design properties.

  Such holograms can be classified into several types depending on the recording pattern of interference fringes, but typically can be classified into surface relief holograms and volume holograms. Here, the surface relief hologram is a hologram recorded by forming a fine uneven pattern on the surface of the hologram layer. On the other hand, the volume hologram is a hologram recorded by three-dimensionally drawing interference fringes generated by light interference as stripes having different refractive indexes in the thickness direction. Among these, since the volume hologram is a hologram image recorded by the difference in refractive index of the material, it has the advantage that it is difficult to duplicate compared to the relief hologram, so that securities and cards can be used. It is expected to be used as an anti-counterfeiting measure.

  Further, in the case of using a hologram as a design imparting or forgery prevention means, etc., as a method for imparting a hologram to securities, cards, etc., for example, a method of weaving a slit-shaped hologram or a hologram visible from the outside As described above, a method of embedding in a medium is known. Generally, a method of attaching a hologram at a predetermined position is used. Among them, as a simple method, a method of sticking a hologram at a predetermined position by transferring a hologram from a hologram transfer foil in which a hologram is formed on an arbitrary base material has been widely used.

  Here, the hologram transfer foil has a configuration in which a hologram layer in which a hologram is recorded on a base material and a heat seal layer having thermal adhesiveness are laminated in this order, and the heat seal layer The hologram layer has a function of transferring the hologram layer onto the transfer medium. Such a hologram transfer foil is disclosed in Patent Documents 1 and 2, for example.

  By the way, the hologram has been conventionally used for various purposes as an anti-counterfeiting means because it has been difficult to duplicate, but in recent years, a technique for simply duplicating a hologram has begun to spread. It has been pointed out that using a simple hologram is not sufficient as a means for preventing forgery. For this reason, the hologram transfer foil is also required to have a higher anti-counterfeit function and to transfer a hologram with excellent security.

JP 2003-316239 A Japanese Patent Laid-Open No. 2005-3809

  The present invention has been made in view of such a situation, and a main object of the present invention is to provide a volume hologram transfer foil capable of producing a volume hologram laminate excellent in forgery prevention function. is there.

  In order to solve the above-described problems, the present invention provides a base material, a volume hologram layer formed on the base material and having a volume hologram recorded thereon, and a heat formed on the volume hologram layer and containing a thermoplastic resin. Than the sealing layer, the ultraviolet absorbing layer formed between the base material and the volume hologram layer or between the volume hologram layer and the heat sealing layer, and having a function of absorbing ultraviolet rays, than the ultraviolet absorbing layer. A fluorescent image-forming layer formed on the heat-seal layer side and having an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays, and the wavelength of ultraviolet rays absorbed by the ultraviolet-absorbing layer; and Provided is a volume hologram transfer foil characterized in that the wavelength of ultraviolet rays absorbed by a fluorescent material is different.

According to the present invention, since the fluorescent image forming layer is used in addition to the volume hologram layer, the volume hologram layer is produced when a volume hologram laminate is produced using the volume hologram transfer foil of the present invention. Can be transferred together with the fluorescent image forming layer, so that a volume hologram laminate excellent in anti-counterfeiting function can be produced.
According to the present invention, since the ultraviolet absorbing layer is used, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention, at least the transferred object is deteriorated with ultraviolet light over time. Can be prevented. Moreover, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention by forming the ultraviolet absorbing layer between the base material and the volume hologram layer, not only the transfer target but also the volume The hologram layer can also be prevented from being deteriorated by ultraviolet rays over time. For this reason, according to the volume hologram transfer foil of this invention, the volume hologram transfer foil excellent in durability can be produced.
Further, according to the present invention, the wavelength of ultraviolet rays absorbed by the ultraviolet absorbing layer is different from the wavelength of ultraviolet rays in which the fluorescent material used in the fluorescent image forming layer emits ultraviolet rays. Therefore, it is possible to prevent the fluorescent image formed on the fluorescent image forming layer from being visually recognized. For this reason, according to the volume hologram laminated body of this invention, the volume hologram laminated body excellent in the designability is producible.
For this reason, according to the present invention, it is possible to provide a volume hologram transfer foil capable of producing a volume hologram laminate excellent in the forgery prevention function.

  In the present invention, it is preferable that the ultraviolet absorbing layer is formed between the base material and the volume hologram layer. As a result, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention, it is possible to prevent the volume hologram layer from being deteriorated with time, so that a volume hologram laminate excellent in volume hologram durability can be obtained. Because it can be obtained.

  In the present invention, a peelable protective layer is preferably formed between the substrate and the volume hologram layer. By forming the peelable protective layer, the adhesiveness between the substrate and the volume hologram layer can be adjusted. As a result, the volume hologram layer is transferred from the volume hologram transfer foil of the present invention. This is because the peelability of the volume hologram layer can be improved when producing the laminate. Moreover, when producing a volume hologram laminate using the volume hologram layer transfer foil of the present invention, the peelable protective layer is transferred together with the volume hologram layer, so that the transferred volume hologram layer is peelable. This is because it can be protected by the protective layer.

  Further, the present invention provides a transferred body, a heat seal layer formed on the transferred body and containing a thermoplastic resin, a volume hologram layer formed on the heat seal layer and having a volume hologram recorded thereon, An ultraviolet ray absorbing layer formed on the volume hologram layer or between the volume hologram layer and the heat seal layer and having a function of absorbing ultraviolet rays; and formed on the heat seal layer side of the ultraviolet ray absorbing layer. A fluorescent image forming layer in which an image is formed by a fluorescent material that emits fluorescence when irradiated with UV light, and the ultraviolet wavelength absorbed by the UV absorbing layer and the UV wavelength absorbed by the fluorescent material are Provided is a volume hologram laminate characterized by being different.

According to the present invention, by using the fluorescent image forming layer in addition to the volume hologram layer, it is possible to obtain a volume hologram laminate having a more excellent anti-counterfeit function.
In addition, according to the present invention, since the ultraviolet absorbing layer is used, it is possible to prevent the transferred object and the volume hologram layer from being deteriorated by ultraviolet rays over time. A hologram laminate can be obtained.
Further, according to the present invention, the wavelength of the ultraviolet ray absorbed by the ultraviolet absorbing layer is different from the wavelength of the ultraviolet ray absorbed by the fluorescent material used in the fluorescent image forming layer. It is possible to prevent the fluorescent image formed on the fluorescent image forming layer from being visually recognized. For this reason, according to this invention, the volume hologram laminated body excellent in the designability can be obtained.

  In the present invention, the ultraviolet absorbing layer is preferably formed on the volume hologram layer. This is because the volume hologram layer can be prevented from being deteriorated with time, and thus a volume hologram laminate having excellent volume hologram durability can be obtained.

  In the present invention, a peelable protective layer is preferably formed on the volume hologram layer or the ultraviolet absorbing layer. This is because the volume hologram layer can be protected by the peelable protective layer.

  The present invention has an effect of providing a volume hologram transfer foil capable of producing a volume hologram laminate having a high anti-counterfeit function.

The present invention relates to a volume hologram transfer foil and a volume hologram laminate.
Hereinafter, the volume hologram transfer foil and the volume hologram laminate of the present invention will be described in order.

A. Volume hologram transfer foil First, the volume hologram transfer foil of the present invention will be described. The volume hologram transfer foil of the present invention includes a base material, a volume hologram layer formed on the base material and having a volume hologram recorded thereon, and a heat seal layer formed on the volume hologram layer and containing a thermoplastic resin. And an ultraviolet absorbing layer formed between the substrate and the volume hologram layer or between the volume hologram layer and the heat seal layer and having a function of absorbing ultraviolet rays, and the heat more than the ultraviolet absorbing layer. A fluorescent image-forming layer formed on the seal layer side and having an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays, the wavelength of ultraviolet rays absorbed by the ultraviolet-absorbing layer, and the fluorescent material It is characterized in that the wavelength of ultraviolet rays absorbed by is different.

Such a volume hologram transfer foil of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the volume hologram transfer foil of the present invention. As illustrated in FIG. 1, a volume hologram transfer foil 10 of the present invention includes a base material 1, a volume hologram layer 2 formed on the base material 1 and having a volume hologram recorded thereon, and the volume hologram layer 2. A heat seal layer 3 containing a thermoplastic resin, an ultraviolet absorbing layer 4 formed between the substrate and the volume hologram layer, and having a function of absorbing ultraviolet rays, and the ultraviolet absorbing layer 4. Is formed on the side of the heat seal layer 3, that is, between the volume hologram layer 2 and the heat seal layer 3, and an image is formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays. Layer 5.
In such an example, the volume hologram transfer foil 10 of the present invention is different in the wavelength of ultraviolet rays absorbed by the ultraviolet absorbing layer 4 and the wavelength of ultraviolet rays absorbed by the fluorescent material contained in the fluorescent image forming layer 5. It is characterized by being.

According to the present invention, since the fluorescent image forming layer is used in addition to the volume hologram layer, the volume hologram layer is produced when a volume hologram laminate is produced using the volume hologram transfer foil of the present invention. Can be transferred together with the fluorescent image forming layer, so that a volume hologram laminate excellent in anti-counterfeiting function can be produced.
According to the present invention, since the ultraviolet absorbing layer is used, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention, at least the transferred object is deteriorated with ultraviolet light over time. Can be prevented. Moreover, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention by forming the ultraviolet absorbing layer between the base material and the volume hologram layer, not only the transfer target but also the volume The hologram layer can also be prevented from being deteriorated by ultraviolet rays over time. For this reason, according to the volume hologram transfer foil of this invention, the volume hologram transfer foil excellent in durability can be produced.
Further, according to the present invention, the wavelength of the ultraviolet ray absorbed by the ultraviolet absorbing layer is different from the wavelength of the ultraviolet ray absorbed by the fluorescent material used in the fluorescent image forming layer. It is possible to prevent the fluorescent image formed on the fluorescent image forming layer from being visually recognized. For this reason, according to the volume hologram laminated body of this invention, the volume hologram laminated body excellent in the designability is producible.
For this reason, according to the present invention, it is possible to provide a volume hologram transfer foil capable of producing a volume hologram laminate excellent in the forgery prevention function.

The volume hologram transfer foil of the present invention has at least a base material, a volume hologram layer, a heat seal layer, an ultraviolet absorption layer, and a fluorescent image forming layer, and other optional configurations as necessary. It may be used.
Hereafter, each structure used for the volume hologram transfer foil of this invention is demonstrated in order.

1. Volume hologram layer Next, the volume hologram layer used in the present invention will be described. The volume hologram layer used in the present invention is one in which a volume hologram is recorded, and is transferred to a transfer target when a volume hologram laminate is manufactured using the volume hologram layer transfer foil of the present invention. is there.
Hereinafter, such a volume hologram layer will be described in detail.

(1) Constituent material The material constituting the volume hologram layer used in the present invention is not particularly limited as long as it can record a volume hologram, and a material generally used for a volume hologram is used. It can be used arbitrarily. Examples of such a material include known volume hologram recording materials such as silver salt materials, dichromated gelatin emulsions, photopolymerizable resins, and photocrosslinkable resins. i) a first photosensitive material containing a binder resin, a photopolymerizable compound, a photopolymerization initiator and a sensitizing dye, or (ii) a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator system, and A second photosensitive material comprising a cationic photopolymerization initiator system can be suitably used.
Hereinafter, the first photosensitive material and the second photosensitive material will be described in order.

(I) First photosensitive material First, the first photosensitive material will be described. As described above, the first photosensitive material contains a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye.

(Binder resin)
Examples of the binder resin include at least one copolymerizable monomer group such as poly (meth) acrylic acid ester or a partially hydrolyzed product thereof, polyvinyl acetate or a hydrolyzed product thereof, acrylic acid, and an acrylic acid ester. As a polymerization component, or a mixture thereof, polyisoprene, polybutadiene, polychloroprene, polyvinyl acetal which is a partial acetalization product of polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, etc. Or a mixture thereof. Here, when the volume hologram layer is formed, a step of moving the monomer by heating may be performed in order to stabilize the recorded volume hologram. For this reason, it is preferable that the binder resin used in the present invention has a relatively low glass transition temperature and can easily move the monomer.

(Photopolymerizable compound)
As the photopolymerizable compound, there can be used photopolymerization having at least one ethylenically unsaturated bond in one molecule, photocrosslinkable monomer, oligomer, prepolymer and a mixture thereof as described later. . Specific examples include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amide compounds of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and the like.

  Here, specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like. Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include, for example, acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butanediol diacrylate. , Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, and the like.

  Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolethane trimethacrylate. Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, and 1,3-butanediol diitaconate. Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Furthermore, examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Furthermore, examples of the maleic ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of the halogenated unsaturated carboxylic acid include 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and the like. Can be mentioned.
Specific examples of the amide monomer of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bis. And methacrylamide.

(Photopolymerization initiator)
Examples of the photopolymerization initiator used in the present invention include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, Examples thereof include N-phenylglycine, 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers. Among them, the photopolymerization initiator used in the present invention is preferably one that is decomposed after hologram recording from the viewpoint of stabilizing the recorded volume hologram. For example, organic peroxides are preferable because they are easily decomposed by irradiation with ultraviolet rays.

(Sensitizing dye)
Sensitizing dyes used in the present invention include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamines. And dyes, thiopyrylium salt dyes, pyrylium ion dyes, diphenyliodonium ion dyes, and the like.

(Ii) Second Photosensitive Material Next, the second photosensitive material used in the present invention will be described. As described above, the second photosensitive material contains a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator system, and a cationic polymerization initiator system.

  Here, when such a second photosensitive material is used, a method for recording a volume hologram on the volume hologram layer is to irradiate light such as laser light that is photosensitized by a photo radical polymerization initiator system, and then to photo cation. A method of irradiating light having a wavelength different from that of the laser light that the polymerization initiator system is sensitive to will be used.

(Cationically polymerizable compound)
As the cationic polymerizable compound, a liquid compound at room temperature is preferably used because it is preferable that the polymerization of the radical polymerizable compound is performed in a composition having a relatively low viscosity. Examples of such cationically polymerizable compounds include diglycerol diether, pentaerythritol polydiglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, 1,6- Examples thereof include hexanediol glycidyl ether, polyethylene glycol diglycidyl ether, and phenyl glycidyl ether.

(Radically polymerizable compound)
As the radical polymerizable compound, those having at least one ethylenically unsaturated double bond in the molecule are preferable. The average refractive index of the radical polymerizable compound used in the present invention is preferably larger than the average refractive index of the cationic polymerizable compound, and more preferably 0.02 or more. This is because a volume hologram is formed by the difference in refractive index between the radical polymerizable compound and the cationic polymerizable compound. Therefore, when the average refractive index difference is not more than the above value, the refractive index modulation becomes insufficient. Examples of the radical polymerizable compound used in the present invention include acrylamide, methacrylamide, styrene, 2-bromostyrene, phenyl acrylate, 2-phenoxyethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, Examples thereof include methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, and β-acryloxyethyl hydrogen phthalate.

(Photo radical polymerization initiator system)
As the radical photopolymerization initiator system used in the present invention, any active radical can be generated by the first exposure when the volume hologram is recorded, and the active radical can polymerize the radical polymerizable compound. It is not particularly limited. Moreover, you may use combining the sensitizer which is a component which generally absorbs light, an active radical generating compound, and an acid generating compound. A sensitizer in such a radical photopolymerization initiator system often uses a colored compound such as a dye to absorb visible laser light, but in the case of a colorless transparent hologram, a cyanine dye is used. Is preferred. Since cyanine dyes are generally easily decomposed by light, the dyes in the hologram are decomposed and absorbed in the visible range by being left exposed for several hours to several days under post-exposure or indoor light or sunlight in the present invention. This is because a colorless and transparent volume hologram can be obtained.

  Specific examples of the cyanine dye include anhydro-3,3′-dicarboxymethyl-9-ethyl-2,2′thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9′-diethyl-2. , 2 'thiacarbocyanine betaine, 3,3', 9-triethyl-2,2'-thiacarbocyanine iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine Iodine salt, 3,3 ′, 9-triethyl-2,2 ′-(4,5,4 ′, 5′-dibenzo) thiacarbocyanine iodine salt, 2- [3- (3-ethyl-2-benzo Thiazolidene) -1-propenyl] -6- [2- (3-ethyl-2-benzothiazolidene) ethylideneimino] -3-ethyl-1,3,5-thiadiazolium iodine salt, 2- [[3-Allyl-4 Oxo-5- (3-n-propyl-5,6-dimethyl-2-benzothiazolidene) -ethylidene-2-thiazolinylidene] methyl] 3-ethyl-4,5-diphenylthiazolinium-iodine salt, 1 , 1 ', 3,3,3', 3'-hexamethyl-2,2'-indotricarbocyanine / iodine salt, 3,3'-diethyl-2,2'-thiatricarbocyanine / perchlorate Anhydro-1-ethyl-4-methoxy-3'-carboxymethyl-5'-chloro-2,2'-quinothiocyanine betaine, anhydro-5,5'-diphenyl-9-ethyl-3,3'- Examples thereof include disulfopropyloxacarbocyanine hydroxide and triethylamine salts, and one or more of these can be used in combination.

  Examples of the active radical generating compound include diaryliodonium salts and 2,4,6-substituted-1,3,5-triazines. The use of diaryliodonium salts is particularly preferred when high photosensitivity is required. Specific examples of the diaryl iodonium salts include diphenyl iodonium, 4,4′-dichlorodiphenyl iodonium, 4,4′-dimethoxydiphenyl iodonium, 4,4′-ditertiary butyl diphenyl iodonium, 3,3′-dinitrodiphenyl iodonium. Such as chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and the like. Specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6 -Tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( p-methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like. .

(Photocationic polymerization initiator system)
The cationic photopolymerization initiator system used in the present invention has low photosensitivity for the first exposure when a volume hologram is recorded, and is sensitive to post-exposure by irradiating light having a wavelength different from that of the first exposure. The initiator system is not particularly limited as long as it generates a Bronsted acid or a Lewis acid and polymerizes a cationically polymerizable compound. In particular, in the present invention, it is particularly preferable to use a compound that does not polymerize the cationic polymerizable compound during the first exposure. Examples of such a cationic photopolymerization initiator system include diaryliodonium salts, triarylsulfonium salts, iron allene complexes, and the like. Preferable diaryliodonium salts include iodonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like shown in the radical photopolymerization initiator system described above. Preferable triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, and the like.

(Other)
In the second photosensitive material, a binder resin, a thermal polymerization inhibitor, a silane coupling agent, a plasticizer, a colorant, and the like may be used in combination as necessary. The binder resin is used to improve the film formability and film thickness uniformity of the composition before hologram formation, and to stabilize interference fringes formed by polymerization by irradiation with light such as laser light until post-exposure. Used to make it exist. The binder resin only needs to be compatible with the cationic polymerizable compound or the radical polymerizable compound. For example, a copolymer of chlorinated polyethylene, polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates. And a copolymer of vinyl chloride and acrylonitrile, polyvinyl acetate, and the like. The binder resin may have reactivity such as a cation polymerizable group in its side chain or main chain.

(Measurement method of refractive index)
Here, the refractive index of the resin obtained by adding a photocationic polymerization initiator to the cationic polymerizable compound can be measured as follows. That is, a resin obtained by adding a photocationic polymerization initiator to the above cationic polymerizable compound to a surface release-treated PET film (for example, trade name “SP-PET” 50 μm, manufactured by Tosero Co., Ltd.) The coating is applied to a thickness of about 20 μm, thermally dried, and then cured by irradiation with ultraviolet rays. Next, the surface release treated PET film is peeled from the layer of the cationic polymerizable compound + photo cationic polymerization initiator / surface release treatment PET film to produce a single layer of the cationic polymerizable compound + photo cationic polymerization initiator. . Monobromonaphthalene as a refractive index compensation solution using a monolayer of the cationic polymerizable compound + photo cationic polymerization initiator prepared as described above, using a refractive index measuring device (manufactured by Atago Co., Ltd., multiwavelength Abbe refractometer DR-M4). Is used to measure the refractive index at a measurement wavelength of 589 nm.
In addition, also about resin obtained by adding radical photopolymerization initiator to a radically polymerizable compound, a refractive index can be measured by the method similar to the above.

(2) Others The thickness of the volume hologram layer used in the present invention is not particularly limited as long as it is within a range in which a predetermined volume hologram can be recorded, and is appropriately adjusted according to the type of the constituent material described above. can do. In particular, the thickness of the volume hologram layer used in the present invention is preferably in the range of 1 μm to 50 μm, and particularly preferably in the range of 3 μm to 25 μm.

2. Next, the heat seal layer used in the present invention will be described. The heat seal layer used in the present invention contains a thermoplastic resin, and when the volume hologram laminate is manufactured using the volume hologram transfer foil of the present invention, the volume hologram layer and the transfer target are bonded. It has a function.
Hereinafter, the heat seal layer used in the present invention will be described in detail.

  The thermoplastic resin used in the present invention is not particularly limited as long as it can adhere the volume hologram layer and the transferred object depending on the type of the transferred object to which the volume hologram layer is transferred from the volume hologram transfer foil of the present invention. It is not particularly limited. Examples of such thermoplastic resins include maleic acid-modified vinyl chloride-vinyl acetate copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate copolymer resins, polyamide resins, polyester resins, polyethylene resins, ethylene -Isobutyl acrylate copolymer resin, butyral resin, polyvinyl acetate and its copolymer resin, ionomer resin, acid-modified polyolefin resin, acrylic / methacrylic (meth) acrylic resin, acrylic ester resin, ethylene・ (Meth) acrylic acid copolymer, ethylene / (meth) acrylic ester copolymer, polymethyl methacrylate resin, cellulose resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, Nord resin, vinyl resin, maleic resin, alkyd resin, polyethylene oxide resin, urea resin, melamine resin, melamine alkyd resin, silicone resin, rubber resin, styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene Examples thereof include a block copolymer (SIS), a styrene ethylene butylene styrene block copolymer (SEBS), and a styrene ethylene propylene styrene block copolymer (SEPS). In the present invention, any of these thermoplastic resins can be suitably used.

  In addition, the thermoplastic resin used for this invention may be only 1 type, or 2 or more types may be sufficient as it.

  The heat seal layer used in the present invention may contain other additives in addition to the thermoplastic resin. Examples of the additive used in the present invention include a dispersant, a filler, a plasticizer, and an antistatic agent.

  The thickness of the heat seal layer used in the present invention is not particularly limited, and the type of volume hologram layer foil, the type of transfer target to which the volume hologram layer is transferred using the volume hologram transfer foil of the present invention, etc. However, it is usually preferably in the range of 0.3 μm to 50 μm, and more preferably in the range of 0.5 μm to 25 μm. This is because if the thickness is less than the above range, the adhesiveness to the transferred object may be insufficient. If it is thicker than the above range, the temperature for heating the heat seal layer becomes too high when transferring the volume hologram layer from the volume hologram transfer foil of the present invention, which may cause damage to the substrate and the like. Because there is.

3. Next, the substrate used in the present invention will be described. The substrate used in the present invention is not particularly limited as long as it can support the volume hologram layer and the heat seal layer. Specific examples of such a substrate include, for example, a polyethylene film, a polypropylene film, a polyvinyl fluoride film, a polyvinylidene fluoride film, a polyvinyl chloride film, a polyvinylidene chloride film, an ethylene-vinyl alcohol copolymer film, and polyvinyl. Alcohol film, polymethyl methacrylate film, polyethersulfone film, polyetheretherketone film, polyamide film, tetrafluoroethylene-perfluoroalkylvinylether copolymer film, polyester film such as polyethylene terephthalate film, resin film such as polyimide film, etc. Can be mentioned.

  The thickness of the substrate used in the present invention is appropriately selected according to the use and type of the volume hologram laminate produced by the present invention, but is usually 2 μm to 200 μm, preferably 10 μm to 50 μm. Within the range of

4). Fluorescent image forming layer Next, the fluorescent image forming layer used in the present invention will be described. The fluorescent image forming layer used in the present invention has an image formed by a fluorescent material that absorbs ultraviolet rays and emits fluorescence. In the volume hologram transfer foil of the present invention, the heat seal layer is more than the ultraviolet absorbing layer described later. It is formed on the side.
Hereinafter, such a fluorescent image forming layer will be described in detail.

  The fluorescent material used for the fluorescent image forming layer in the present invention is not particularly limited as long as it can emit fluorescence by absorbing ultraviolet rays in a desired wavelength range. Especially, as for the fluorescent material used for this invention, it is preferable that the wavelength of the ultraviolet-ray absorbed when light-emitting fluorescence is in the range of 100 nm-400 nm, and it is more preferable that it exists in the range of 200 nm-400 nm.

  At least one type of fluorescent material used in the present invention is used, but in the present invention, it is preferable to use a plurality of fluorescent materials having different wavelengths of emitted fluorescence, and in particular each color of red, green, and blue is used. It is preferable to use a fluorescent material that develops color. This is because the fluorescent image forming layer used in the present invention can be made capable of forming a full-color image with fluorescence.

Examples of the fluorescent material used in the present invention include organic fluorescent dyes and inorganic fluorescent dyes.
Examples of the organic fluorescent dye include, for example, diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, derivatives such as triazole, carbazole, pyridine, naphthalic acid, imidazolone, dyes such as fluorescein and eosin, anthracene, etc. And a compound having a benzene ring. Specifically, as visible and colorless fluorescent dyes, EB-501 (Mitsui Chemicals, Inc., emission color: blue), EG-302 (Mitsui Chemicals, emission color: yellow green), EG -307 (Mitsui Chemicals, Inc., emission color: green), ER-120 (Mitsui Chemicals, emission color: red), ER-122 (Mitsui Chemicals, emission color: red), Ubitex OB (manufactured by Ciba Specialty Chemicals Co., Ltd., emission color: blue), europium-thenoyl trifluoroacetone chelate (Sinloihi Co., Ltd., red-orange) and the like, which are called optical brighteners, can be mentioned.
As the inorganic fluorescent dye, the inorganic fluorescent dye is mainly composed of crystals such as oxides such as Ca, Ba, Mg, and Sr, sulfides, silicates, phosphates, and tungstates. , Eu, Mn, Pb, Fe, Mn, Zn, Ag, Cu, or other metal elements or rare earth elements added as a dopant can be used. Specifically, under the visible light, colorless to white G-300 series (SrAl ₂ O ₄ : Eu, Dy, manufactured by Nemoto Special Chemical, luminescent color: green) and V-300 series (CaAl ₂ O ₄ : Eu, Nd, root special) Chemical emission color: purple).

  Examples of the fluorescent material used in the present invention include thiophene fluorescent dyes, β-quinophthalone fluorescent dyes, coumarin fluorescent dyes, bisstyrylbenzene fluorescent dyes, oxazole fluorescent dyes, and europium complex fluorescent dyes. Can be mentioned. Specific examples of these fluorescent dyes include those described in JP-A No. 2004-122690.

  In addition, it is preferable that the fluorescent image forming layer used in the present invention usually contains a binder resin in addition to the fluorescent material. Examples of the binder resin used in the present invention include cellulose resins such as ethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, and cellulose acetate; vinyls such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl pyrrolidone. Examples thereof include acrylic resins, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, polyester resins, and mixtures of these resins. In the present invention, any of these resins can be suitably used.

5). Next, the ultraviolet absorbing layer used in the present invention will be described. The ultraviolet absorbing layer used in the present invention is a fluorescent material formed between the base material and the volume hologram layer or between the volume hologram layer and the heat seal layer and used for the fluorescent image forming layer. Absorbs ultraviolet light having a wavelength different from that of the ultraviolet light absorbed.

  The position where the ultraviolet absorbing layer used in the present invention is formed may be either between the base material and the volume hologram layer, or between the volume hologram layer and the heat seal layer. In particular, it is preferably formed between the substrate and the volume hologram layer. The ultraviolet absorbing layer used in the present invention has a function of preventing deterioration of the volume hologram layer or the transferred material with time due to ultraviolet light in the volume hologram laminate produced using the volume hologram transfer foil of the present invention. However, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention by forming the ultraviolet absorption layer between the substrate and the volume hologram layer, the ultraviolet absorption layer is a volume hologram layer. This is because it is arranged on the upper side, so that deterioration of the volume hologram layer and the transferred body with time due to ultraviolet rays can be prevented.

  The wavelength of ultraviolet rays absorbed by the ultraviolet absorbing layer used in the present invention is not particularly limited as long as it is in a range different from the wavelength of ultraviolet rays absorbed by the fluorescent material used in the fluorescent image forming layer. Here, in the volume hologram laminate produced using the volume hologram transfer foil of the present invention, the ultraviolet absorbing layer has a function of preventing deterioration of the transferred object or volume hologram layer with time due to ultraviolet rays. From such a viewpoint, the wavelength range absorbed by the ultraviolet absorbing layer is preferably in the range of 100 nm to 400 nm.

  As a material used for the ultraviolet absorption layer used in the present invention, an ultraviolet absorption capable of absorbing ultraviolet rays having a wavelength different from the wavelength of ultraviolet rays absorbed by the fluorescent material, depending on the type of the fluorescent material contained in the fluorescent image forming layer. If it is a material, it will not specifically limit. Examples of such UV absorbing materials include organic UV absorbers, reactive UV absorbers, and inorganic UV absorbers.

  Examples of the organic ultraviolet absorbers include salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines, phenyl triazines, oxalic anilides, malonic esters, etc. An ultraviolet absorber is mentioned.

  Examples of the reactive ultraviolet absorber include the above organic ultraviolet absorbers, for example, an addition polymerizable double bond such as a vinyl group, an acryloyl group, and a methacryloyl group, or an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate. A group into which a group or the like has been introduced is reacted and fixed to a resin binder. As a method for reaction fixation, a copolymer is obtained by radical polymerization of a resin component of a conventionally known monomer, oligomer, or reactive polymer and a reactive ultraviolet absorber having an addition polymerizable double bond as described above. be able to. When the reactive ultraviolet absorber has a hydroxyl group, an amino group, a carboxyl group, an ethoxy group, or an isocyanate group, a thermoplastic resin having reactivity with the above reactive group is used, and a catalyst is used as necessary. The reactive ultraviolet absorber can be reactively fixed to the thermoplastic resin by heat or the like.

  Examples of the inorganic ultraviolet absorber include fine particles of zinc oxide, titanium oxide, cerium oxide, and iron oxide, which can be used by being dispersed in a binder in a timely manner.

6). Arbitrary Configuration The volume hologram transfer foil of the present invention has at least the above-mentioned base material, volume hologram layer, heat seal layer, fluorescent image forming layer, and ultraviolet absorption layer. A configuration can be used. The arbitrary structure used for this invention is not specifically limited, According to the use etc. of the volume hologram laminated body manufactured using the volume hologram transfer foil of this invention, it can select suitably and can be used. Among these, as an arbitrary configuration suitably used in the present invention, a peelable protective layer formed between the substrate and the volume hologram layer can be exemplified.

  The case where a peelable protective layer is used for the volume hologram transfer foil of the present invention will be described with reference to the drawings. FIG. 2 is a schematic sectional view showing an example in which a peelable protective layer is used in the volume hologram transfer foil of the present invention. As illustrated in FIG. 2, a peelable protective layer 6 may be formed between the substrate 1 and the volume hologram layer 2 in the volume hologram transfer foil 10 ′ of the present invention.

By using the peelable protective layer for the volume hologram transfer foil of the present invention, advantageous effects are obtained in the following two points.
First, since the peelable protective layer is used, the adhesive force between the substrate and the volume hologram layer can be adjusted to an arbitrary range. Therefore, the volume hologram layer is removed from the volume hologram transfer foil of the present invention. When transferring, the peelability of the volume hologram layer from the substrate can be improved.
Second, by using the peelable protective layer, the surface of the volume hologram layer is covered with the peelable protective layer when the volume hologram layer is transferred to the transfer object using the volume hologram transfer foil of the present invention. Therefore, the transferred volume hologram layer can be protected by the peelable protective layer.

  Examples of the material used for the peelable protective layer used in the present invention include acrylic and methacrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, Examples include various surfactants, metal oxides, or a mixture of two or more.

  In addition to the above, as an optional configuration used in the present invention, for example, in order to improve the adhesiveness between the volume hologram layer and the heat seal layer, or the adhesiveness between the volume hologram layer and the peelable protective layer. Mention may be made of the primer layer used. Examples of such a primer layer include polyurethane, polyester, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, ethylene and acetic acid. Examples include those using a copolymer with vinyl or acrylic acid, an epoxy resin, or the like.

  In the present invention, as an arbitrary configuration, a barrier layer may be formed between the volume hologram layer and the heat seal layer. Depending on the combination of the photosensitive material used for the volume hologram layer and the thermoplastic resin used for the heat seal layer, the low molecular weight component may be transferred from the volume hologram layer to other layers over time. This is because the reproduction wavelength of the volume hologram recorded on the layer may shift to the blue side (short wavelength side), but such a problem can be solved by providing a barrier layer.

  The material used for the barrier layer is not particularly limited as long as it can exhibit a desired barrier property, but a transparent organic resin material is usually used. As the transparent organic resin material used in the present invention, for example, a solvent-free trifunctional or higher functional group, preferably a hexafunctional or higher functional ionizing radiation curable epoxy-modified acrylate resin that reacts with ionizing radiation such as ultraviolet rays or electron beams, Examples include urethane-modified acrylate resins and acrylic-modified polyester resins.

7). Volume hologram transfer foil The volume hologram transfer foil of the present invention has the above-mentioned base material, volume hologram layer, heat seal layer, ultraviolet absorption layer and fluorescent image forming layer. As an aspect in which these configurations are arranged, The ultraviolet absorbing layer is formed between the base material and the volume hologram layer or between the volume hologram layer and the heat seal layer, and the fluorescent image forming layer is more than the ultraviolet absorbing layer. It will not specifically limit if it is the aspect arrange | positioned at the heat seal layer side. Which aspect is used for the volume hologram transfer foil of the present invention can be appropriately determined according to the use of the volume hologram laminate produced using the volume hologram transfer foil of the present invention.
Here, the configuration of the volume hologram transfer foil of the present invention includes an aspect in which the ultraviolet absorbing layer is formed between the base material and the volume hologram layer, and the ultraviolet absorbing layer includes the volume hologram layer and the heat seal. It can be divided roughly into two modes: a mode formed between the layers.

The configuration of the volume hologram transfer foil of the present invention will be specifically described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of an embodiment in which the ultraviolet absorbing layer is formed between the substrate and the volume hologram layer in the volume hologram transfer foil of the present invention.
As illustrated in FIG. 3, the volume hologram transfer foil 10 of this aspect may be an aspect in which the ultraviolet absorbing layer 4 is formed between the substrate 1 and the volume hologram layer 2. Moreover, the volume hologram transfer foil of such a mode can be further classified into three modes depending on the position where the fluorescent image forming layer 5 is formed. That is, when the ultraviolet absorbing layer 4 is formed between the substrate 1 and the volume hologram layer 2, the fluorescent image forming layer 5 is formed of the ultraviolet absorbing layer 4 as illustrated in FIG. 3 may be formed between the volume hologram layer 2 and the heat seal layer 3 as illustrated in FIG. 3B, or as illustrated in FIG. It may be formed on the heat seal layer 3 as illustrated in (c).

  In addition, when the said ultraviolet absorption layer is formed between the said base material and the said volume hologram layer, the said peelable protective layer will be formed between the said base material and the said ultraviolet absorption layer.

On the other hand, FIG. 4 is a schematic sectional view showing an example of an aspect in which the ultraviolet absorbing layer is formed between the volume hologram layer and the heat seal layer in the volume hologram transfer foil of the present invention.
As illustrated in FIG. 4, the volume hologram transfer foil 10 ″ of this aspect may be an aspect in which the ultraviolet absorbing layer 4 is formed between the volume hologram layer 2 and the heat seal layer 3. Moreover, the volume hologram transfer foil of such a mode can be further classified into two modes depending on the position where the fluorescent image forming layer 5 is formed. That is, when the ultraviolet absorbing layer 4 is formed between the volume hologram layer 2 and the heat seal layer 3, the fluorescent image forming layer 5 is formed of an ultraviolet absorbing layer as illustrated in FIG. 4 may be formed between the heat seal layer 3 and may be formed on the heat seal layer 3 as illustrated in FIG.

8). Production Method of Volume Hologram Transfer Foil As a production method of the volume hologram transfer foil of the present invention, a method of sequentially laminating a volume hologram layer and a heat seal layer on a substrate can be used. Since such a method is generally the same as a known method for producing a volume hologram transfer foil, a detailed description thereof is omitted here.

B. Volume hologram laminate Next, the volume hologram laminate of the present invention will be described. The volume hologram laminate of the present invention is a volume to be transferred, a heat seal layer formed on the transfer body and containing a thermoplastic resin, and a volume hologram recorded on the heat seal layer. A hologram layer, an ultraviolet absorption layer formed on the volume hologram layer or between the volume hologram layer and the heat seal layer, and having a function of absorbing ultraviolet rays; and closer to the heat seal layer than the ultraviolet absorption layer A fluorescent image forming layer that is formed and has an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet light, and the ultraviolet wavelength absorbed by the ultraviolet absorbing layer and the ultraviolet light absorbed by the fluorescent material This is characterized in that the wavelength is different.

Such a volume hologram laminate of the present invention will be described with reference to the drawings. FIG. 5 is a schematic sectional view showing an example of the volume hologram laminate of the present invention. As illustrated in FIG. 5, the volume hologram laminate 20 of the present invention includes a transfer target 21, a heat seal layer 3 formed on the transfer target 21 and containing a thermoplastic resin, and the heat seal layer 3. A volume hologram layer 2 on which volume holograms are recorded, an ultraviolet absorption layer 4 formed on the volume hologram layer 2 and having a function of absorbing ultraviolet rays, and the heat seal more than the ultraviolet absorption layer 4. A fluorescent image forming layer 5 which is formed on the layer 3 side, that is, between the volume hologram layer 2 and the heat seal layer 3 and in which an image is formed by a fluorescent material which emits fluorescence when irradiated with ultraviolet rays. Is.
In such an example, the volume hologram laminate 20 of the present invention is different in the wavelength of ultraviolet rays absorbed by the ultraviolet absorbing layer 4 and the wavelength of ultraviolet rays absorbed by the fluorescent material included in the fluorescent image forming layer 5. It is characterized by being.

According to the present invention, by using the fluorescent image forming layer in addition to the volume hologram layer, it is possible to obtain a volume hologram laminate having a more excellent anti-counterfeit function.
In addition, according to the present invention, since the ultraviolet absorbing layer is used, it is possible to prevent the transferred object and the volume hologram layer from being deteriorated by ultraviolet rays over time. A hologram laminate can be obtained.
Further, according to the present invention, the wavelength of the ultraviolet ray absorbed by the ultraviolet absorbing layer is different from the wavelength of the ultraviolet ray absorbed by the fluorescent material used in the fluorescent image forming layer. It is possible to prevent the fluorescent image formed on the fluorescent image forming layer from being visually recognized. For this reason, according to this invention, the volume hologram laminated body excellent in the designability can be obtained.

The volume hologram laminate of the present invention has at least the transfer target, a heat seal layer, a volume hologram layer, an ultraviolet absorption layer, and a fluorescent image forming layer, and other arbitrary configurations are used as necessary. Is also good.
Hereafter, each structure used for the volume hologram laminated body of this invention is demonstrated in order.

  The heat seal layer, the volume hologram layer, the fluorescent image forming layer, and the ultraviolet absorbing layer used in the present invention are the same as those described in the above section “A. Volume hologram transfer foil”. Description is omitted.

1. Transfer object First, the transfer object used in the present invention will be described. The transfer medium used in the present invention is not particularly limited as long as it can be adhered to the volume hologram layer via the heat seal layer, and the use of the volume hologram laminate of the present invention is not limited. It can be arbitrarily selected according to the use. Examples of such a member to be transferred include various cards such as paper used for passports, booklets and gift certificates, ID cards, films, cloths, metals, and glass.

2. Arbitrary Configuration The volume hologram laminate of the present invention has at least the transfer target body, the volume hologram layer, and the heat seal layer, but the present invention uses any other configuration other than these as necessary. Can do. The arbitrary structure used for this invention is not specifically limited, According to the use etc. of the volume hologram laminated body of this invention, it can select suitably and can be used. Among these, as an arbitrary configuration suitably used in the present invention, a peelable protective layer formed on the volume hologram layer can be exemplified.

  The case where a peelable protective layer is used in the volume hologram laminate of the present invention will be described with reference to the drawings. FIG. 6 is a schematic cross-sectional view showing an example where a peelable protective layer is used in the volume hologram laminate of the present invention. As illustrated in FIG. 6, in the volume hologram laminate 20 ′ of the present invention, the peelable protective layer 6 may be formed on the volume hologram layer 2.

  The details of the peelable protective layer used in the present invention are the same as those described in the above section “A. Volume hologram transfer foil”, and thus the description thereof is omitted here.

  In addition to the above, a primer layer or a barrier layer described in the section “A. Volume hologram transfer foil” can be used as an arbitrary configuration used in the present invention.

3. Volume hologram laminate The volume hologram laminate of the present invention has the above-mentioned transfer target, volume hologram layer, heat seal layer, ultraviolet absorption layer, and fluorescent image forming layer. As an aspect in which these configurations are arranged. The ultraviolet absorbing layer is formed on the volume hologram layer or between the volume hologram layer and the heat seal layer, and the fluorescent image forming layer is closer to the heat seal layer than the ultraviolet absorber layer. If it is the aspect arrange | positioned, it will not specifically limit. Which aspect the volume hologram laminate of the present invention is used can be appropriately determined according to the application of the volume hologram laminate of the present invention.

  Here, the configuration of the volume hologram laminate of the present invention is such that the ultraviolet absorption layer is formed on the volume hologram layer and the ultraviolet absorption layer is formed between the volume hologram layer and the heat seal layer. It can be roughly divided into two modes.

The configuration of the volume hologram laminate of the present invention will be specifically described with reference to the drawings. FIG. 7 is a schematic cross-sectional view showing an example of an aspect in which the ultraviolet absorbing layer is formed on the volume hologram layer in the volume hologram laminate of the present invention.
As illustrated in FIG. 7, the volume hologram laminate 20 of the present invention may have an aspect in which the ultraviolet absorption layer 4 is formed on the volume hologram layer 2. Further, the volume hologram laminate 20 of such an aspect can be further classified into three aspects depending on the position where the fluorescent image forming layer 5 is formed. That is, when the ultraviolet absorbing layer 4 is formed on the volume hologram layer 2, the fluorescent image forming layer 5 is composed of the ultraviolet absorbing layer 4 and the volume hologram layer 2 as illustrated in FIG. It may be formed between, and may be formed between the volume hologram layer 2 and the heat seal layer 3 as illustrated in FIG. 7B, or as illustrated in FIG. Further, it may be formed between the heat seal layer 3 and the transfer target 21.

  In addition, when the said ultraviolet absorption layer is formed on the said volume hologram layer, when a peelable protective layer is used for the volume hologram laminated body of this invention, a peelable protective layer is formed on the said ultraviolet absorption layer. It will be.

On the other hand, FIG. 8 is a schematic cross-sectional view showing an example of an aspect in which the ultraviolet absorbing layer is formed between the volume hologram layer and the heat seal layer in the volume hologram laminate of the present invention.
As illustrated in FIG. 8, the volume hologram laminate 20 ″ of the present invention may have a mode in which the ultraviolet absorption layer 4 is formed between the volume hologram layer 2 and the heat seal layer 3. Further, the volume hologram laminate in such a mode can be further classified into two modes depending on the position where the fluorescent image forming layer 5 is formed. That is, when the ultraviolet absorbing layer 4 is formed between the volume hologram layer 2 and the heat seal layer 3, the fluorescent image forming layer 5 is an ultraviolet absorbing layer as illustrated in FIG. 4 may be formed between the heat seal layer 3 and the heat seal layer 3 as illustrated in FIG. 8B.

4). Production Method of Volume Hologram Laminate The volume hologram laminate of the present invention can be produced by a generally known method. As a specific example of the method for producing the volume hologram laminate of the present invention, for example, the volume hologram transfer foil according to the present invention is used, and the transfer object is bonded to the heat seal layer of the volume hologram transfer foil. The method which consists of an adhesion | attachment process and the base material peeling process which peels the base material of the said volume hologram transfer foil can be mentioned.

  A method for manufacturing such a volume hologram laminate will be described with reference to the drawings. FIG. 9 is a schematic view showing an example of the method for producing a volume hologram laminate of the present invention. As illustrated in FIG. 9, the volume hologram laminate of the present embodiment uses the volume hologram transfer foil 10 according to the present invention (FIG. 9A), and the heat seal layer of the volume hologram transfer foil 10. 3 to be transferred member bonding step (FIG. 9B) for bonding the transfer member 21 onto 3, and a substrate peeling step for peeling the substrate 1 of the volume hologram transfer foil 10 (FIG. 9C), It is characterized by having.

  The method for adhering the transfer object onto the heat seal layer in the transfer object adhering step is not particularly limited as long as the heat seal layer can be adhered to a predetermined position of the transfer object. Usually, a method of adhering the transfer object by heating the heat seal layer is used. The means for heating the heat seal layer in this step is not particularly limited as long as only a desired region can be heated to a predetermined temperature. Examples of the method include a method using a heating roller, a hot press, a hot stamp, and the like. Any of these heating means can be suitably used in this step.

  In addition, the method for peeling the substrate in the substrate peeling step is not particularly limited as long as the method can peel the substrate only in the region bonded to the transfer target. Usually, a method is used in which the volume hologram transfer foil is peeled off by physically separating it from the transfer target.

5). Volume hologram laminate The volume hologram laminate of the present invention has the above-mentioned transfer target, a heat seal layer, a volume hologram layer, an ultraviolet absorption layer, and a fluorescent image forming layer, and is recorded in advance on the transfer target. In addition to the various information, information such as a volume hologram and a fluorescence image based on the fluorescence image forming layer is further added.
The volume hologram laminate of the present invention will be specifically described with reference to the drawings. FIG. 10 is a schematic diagram showing a specific example of the volume hologram laminate of the present invention and the transfer target used in the present invention. As illustrated in FIG. 10 (a), as the transfer object used in the present invention, one in which all kinds of information such as face image information, character information, and graphic information are recorded in advance can be used. Then, as illustrated in FIG. 10B, the volume hologram laminate of the present invention is transferred by transferring the volume hologram layer and the fluorescence image forming layer to the transfer target illustrated in FIG. Further information is recorded.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

1. Example 1
(First laminate)
A PET film (trade name Lumirror T60 (50 μm): manufactured by Toray Industries, Inc.) is prepared as a first film, and a volume hologram recording material having the following composition is gravure as a hologram forming material so as to have a dry film thickness of 7 μm. Coating was performed with a coat, and a surface release treatment PET film (trade name: SP-PET (50 μm), manufactured by Tosero Co., Ltd.) was laminated on the coated surface to prepare a first laminate.

<Composition of volume hologram recording material>
・ Binder resin (polymethyl methacrylate resin (molecular weight 200,000))
50 parts by weight- 3,9-diethyl-3'-carboxylmethyl-2,2'-thiacarbocyanine iodine salt 0.5 parts by weight diphenyliodonium hexafluoroantimonate 6 parts by weight 2,2-bis (4- (Acryloxydiethoxy) phenyl) propane
80 parts by weight, 1,6-hexanediol diglycidyl ether 80 parts by weight, fluorine fine particles 8 parts by weight, solvent (methyl isobutyl ketone / n-butanol = 1/1 (weight ratio)
200 parts by weight

(Second laminate)
A PET film (trade name Lumirror T60 (50 μm): manufactured by Toray Industries, Inc.) is prepared as a second film, and an ultraviolet absorbing material having the following composition is used as an ultraviolet absorbing layer forming material so that the dry film thickness is 2 μm. It was prepared by coating with a gravure coat.

<Composition of UV absorbing material>
・ 100 parts by weight of polymethyl methacrylate resin (molecular weight: 1,000,000) ・ UV absorber (trade name: Hostabin PR-25 Clariant Japan Co., Ltd., UV absorption wavelength: about 240 nm to 350 nm) 10 parts by weight ・ Solvent (methyl ethyl ketone / toluene = 1/1) 100 parts by weight

(Preparation of transfer film for fluorescent image forming layer)
The following heat-resistant slip layer material is applied to the surface of a 6 μm thick polyethylene terephthalate transparent substrate by gravure printing so that the surface becomes 0.5 μm, and the following release layer material is applied to the opposite surface of the substrate. The entire surface was coated by gravure printing so that the fluorescent image forming layer had a thickness of 0 μm and a fluorescent image forming layer of 1.5 μm to obtain a transfer film for a fluorescent image forming layer.

<Composition of heat-resistant slip layer material>
Polyvinyl butyral resin (trade name “ESREC BX-1” manufactured by Sekisui Chemical Co., Ltd.) 3.6 parts by weight Polyisocyanate (trade name “Bernock D750” manufactured by Dainippon Ink and Chemicals, Inc.) 8.6 parts by weight Phosphoric acid Ester surfactant (trade name “Plisurf A208S” manufactured by Daiichi Pharmaceutical Co., Ltd.) 2.8 parts by weight • Talc (trade name “Microace P-3” manufactured by Nippon Talc Kogyo Co., Ltd.)
0.7 parts by weight ・ Methyl ethyl ketone / toluene = 1/1 64 parts by weight

<Composition of release layer forming material>
・ Acrylic resin (trade name: BR-87, manufactured by Mitsubishi Rayon) 20 parts by weight ・ Polyester resin (trade name: V-200, manufactured by Toyobo) 0.1 part by weight ・ Solvent (methyl ethyl ketone / toluene = 1/1) 100 parts by weight

<Composition of fluorescent image forming layer forming material>
・ Organic blue fluorescent agent (trade name: Ubitex OB, manufactured by Ciba Specialty Chemicals, UV absorption wavelength: about 366 nm, fluorescence emission wavelength: about 420 nm)
1 part by weight-vinyl chloride-vinyl acetate copolymer resin solution (trade name: Solvain CNL, manufactured by Nissin Chemical Industry) 100 parts by weight-solvent (methyl ethyl ketone / toluene = 1/1) 100 parts by weight

(Preparation of fluorescent image forming layer)
The ultraviolet absorption layer side of the second laminated body and the fluorescent image forming layer forming material layer side of the transfer film for the fluorescent image forming layer are overlapped, and the thermal absorption is performed on the ultraviolet absorption layer of the second laminated body by using a thermal head. Image information was printed at 5 J / mm ² .

(Volume hologram recording)
(Lamination of first laminate and second laminate with fluorescent image forming layer)
A volume hologram was photographed and recorded on the first film / layer of volume hologram recording material / surface release treatment PET film using a laser beam having a wavelength of 532 nm. After recording, this laminate was heated in an atmosphere of 100 ° C. for 10 minutes, and after heating, the surface release-treated PET film was peeled off and exposed to a layer of volume hologram recording material that was exposed to the second film / ultraviolet absorption. The layer / fluorescence imaging layer laminate is laminated so that the fluorescent imaging layer side is in contact with each other, and is passed between a pair of heated rollers at 80 ° C. so that the first film / volume hologram layer / fluorescence imaging layer / After obtaining the laminate of the ultraviolet absorbing layer / second film, the volume hologram recording material layer was fixed by irradiating the entire surface with ultraviolet rays having an irradiation dose of 2500 mJ / cm ² using a high-pressure mercury lamp. .

(Coating of heat seal layer)
The first film / volume hologram layer / fluorescent image forming layer / ultraviolet ray absorbing layer / second film laminate prepared as described above is peeled off, and a material having the following composition is formed on the volume hologram layer, A transfer foil was prepared by applying a gravure coat so that the dry film thickness was 4 μm.

<Composition of heat seal layer forming material>
・ Polyester resin (product name: Bayronal MD1985, manufactured by TOYOBO)
100 parts by weight / silica particles (particle size 4 μm, manufactured by Fuji Silysia) 4 parts by weight

2. Example 2
(Volume hologram recording)
(Lamination of the first laminate and the second laminate)
A first laminated body and a second laminated body were produced in the same manner as in Example 1. Next, a volume hologram was imaged and recorded on the first film / layer of volume hologram recording material / surface release treatment PET film using a laser beam having a wavelength of 532 nm. After recording, this laminate was heated in an atmosphere of 100 ° C. for 10 minutes, and after heating, the surface release-treated PET film was peeled off and exposed to a layer of volume hologram recording material that was exposed to the second film / ultraviolet absorption. The laminated body of the first film / volume hologram layer / ultraviolet absorption layer / second film is passed through a pair of heated rollers at 80 ° C. which are stacked so that the ultraviolet absorption layer side of the layer laminate is in contact with each other. After being obtained, the volume hologram recording material layer was fixed by irradiating the entire surface with an irradiation dose of 2500 mJ / cm ² using a high-pressure mercury lamp.

(Preparation of fluorescent image forming layer)
The first film of the laminate of the first film / volume hologram layer / ultraviolet absorption layer / second film obtained above was peeled off, and the fluorescent image forming layer was formed on the volume hologram layer in the same manner as in Example 1. Image information was printed using a transfer film to obtain a laminate of fluorescent image forming layer / volume hologram layer / ultraviolet absorption layer / second film.

(Coating of heat seal layer)
On the fluorescent image forming layer of the fluorescent image forming layer / volume hologram layer / ultraviolet absorption layer / second film laminate obtained above, a heat seal layer material was applied in the same manner as in Example 1 to produce a transfer foil. Was done.

3. Example 3
As in Example 2, recording of a volume hologram and bonding of the first laminate and the second laminate were performed. The obtained first film of first film / volume hologram layer / ultraviolet absorption layer / second film was peeled off, and a heat seal layer material was applied in the same manner as in Example 1. On the heat seal layer of the obtained heat seal layer / volume hologram layer / ultraviolet absorption layer / second film laminate, image information was printed using the transfer film for fluorescent image forming layer in the same manner as in Example 1, and transfer foil was obtained. Was made.

4). Example 4
(Third laminate of substrate / peelable protective layer / ultraviolet absorption layer)
A PET film (trade name Lumirror T60 (50 μm): manufactured by Toray Industries, Inc.) is prepared as a third film, and a material having the following composition is applied as a peelable protective layer to a gravure coat so as to have a dry film thickness of 1 μm. And coated.

<Composition of material for forming peelable protective layer>
Polyethylene methacrylate resin (molecular weight: 1,000,000) 97 parts by weight Polyethylene wax (molecular weight: 10,000, average particle size: 5 μm) 3 parts by weight Solvent (methyl ethyl ketone / toluene = 1/1 (weight ratio)) 400 parts by weight

  Next, an ultraviolet absorbing material was applied on the peelable protective layer of the substrate / peelable protective layer in the same manner as in Example 1 to obtain a substrate / peelable protective layer / ultraviolet absorbing layer laminate.

(Bonding of the first laminate and the third laminate)
A volume hologram was photographed and recorded on the first film / layer of volume hologram recording material / surface release treatment PET film using a laser beam having a wavelength of 532 nm. After recording, the laminate was heated in an atmosphere of 100 ° C. for 10 minutes, and after heating, the surface release-treated PET film was peeled and exposed to a layer of volume hologram recording material, which was exposed to a third film / peelability. The first film / volume hologram layer / ultraviolet absorption layer / peelable protective layer is passed through a pair of heated rollers at 80 ° C. which are stacked so that the ultraviolet absorption layer side of the protective layer / ultraviolet absorption layer laminate is in contact with each other. / After obtaining the laminate of the third film, the entire surface of the volume hologram recording material was fixed by irradiating the whole surface with an ultraviolet ray having an irradiation dose of 2500 mJ / cm ² using a high-pressure mercury lamp.

(Preparation of fluorescent image forming layer)
The first film of the laminate of the first film / volume hologram layer / ultraviolet absorption layer / peelable protective layer / third film obtained above was peeled off, and the same procedure as in Example 1 was performed on the volume hologram layer. Image information was printed using the transfer film for fluorescent image forming layers, and a laminate of fluorescent image forming layer / volume hologram layer / ultraviolet ray absorbing layer / peelable protective layer / third film was obtained.

(Coating of heat seal layer)
On the fluorescent image forming layer of the laminate of the fluorescent image forming layer / volume hologram layer / ultraviolet ray absorbing layer / peelable protective layer / third film obtained above, a heat seal layer material was applied in the same manner as in Example 1. A transfer foil was prepared.

5). Example 5
A first laminate was produced in the same manner as in Example 1. Next, after the surface release treatment PET film of the first laminate was peeled off, an ultraviolet absorbing material was applied onto the volume hologram layer in the same manner as in Example 1 to laminate the first film / volume hologram layer / ultraviolet absorption layer. Got the body.

(Preparation of fluorescent image forming layer)
On the ultraviolet absorbing layer of the first film / volume hologram layer / ultraviolet absorbing layer laminate obtained above, image information was printed using the transfer film for fluorescent image forming layer in the same manner as in Example 1, and the first film A laminate of / volume hologram layer / ultraviolet absorption layer / fluorescence image forming layer was obtained.

(Coating of heat seal layer)
On the fluorescent image forming layer of the laminate of the first film / volume hologram layer / ultraviolet absorption layer / fluorescent image forming layer obtained above, a heat seal layer material was applied in the same manner as in Example 1 to produce a transfer foil. Went.

6). Example 6
A first film / volume hologram layer / ultraviolet absorption layer laminate was obtained in the same manner as in Example 5.

(Coating of heat seal layer)
On the first film / volume hologram layer / ultraviolet absorption layer laminate obtained above, a heat seal layer material was applied in the same manner as in Example 1, and the first film / volume hologram layer / ultraviolet absorption layer / heat seal was applied. A layer stack was obtained.

(Preparation of fluorescent image forming layer)
On the heat seal layer of the first film / volume hologram layer / ultraviolet absorption layer / heat seal layer laminate obtained above, image information is printed and transferred using the transfer film for fluorescent image forming layer in the same manner as in Example 1. A foil was prepared.

7). Example 7
The transfer foil produced in Examples 1 to 3 was transferred to a gift certificate using a hot stamping machine manufactured by Navitas Co., Ltd. at a transfer temperature of 150 ° C. and a pressure of 0.8 Mpa, and the second film was peeled off to laminate the volume hologram. Got the body.

8). Example 8
The transfer foil produced in Example 4 was transferred to a gift certificate using a hot stamp machine manufactured by Navitas Co., Ltd. at a transfer temperature of 150 ° C. and a pressure of 0.8 Mpa, and the third film was peeled off to form a volume hologram laminate. Obtained.

9. Example 9
The transfer foil produced in Examples 5 and 6 was transferred to a gift certificate using a hot stamping machine manufactured by Navitas Co., Ltd. at a transfer temperature of 150 ° C. and a pressure of 0.8 Mpa, and the first film was peeled off to laminate the volume hologram. Got the body.

10. Example 10
The transfer foil produced in Examples 1 to 3 was transferred onto a polyvinyl chloride card on which face images and character information had been transferred by sublimation transfer in advance using a hot stamping machine manufactured by Navitas Co., Ltd., and a transfer temperature of 150 ° C. and a pressure of 0.8 Mpa. Then, the second film was peeled off to obtain a volume hologram laminate.

11. Example 11
The transfer foil produced in Example 4 was transferred at a transfer temperature of 150 ° C. and a pressure of 0.8 MPa on a polyvinyl chloride card on which face images and character information had been transferred by sublimation transfer in advance using a hot stamping machine manufactured by Navitas. The third film was peeled off to obtain a volume hologram laminate.

12 Example 12
The transfer foil produced in Examples 5 and 6 was transferred onto a polyvinyl chloride card onto which face images and character information had been transferred in advance by sublimation transfer, using a hot stamping machine manufactured by Navitas Co., Ltd., transfer temperature 150 ° C., pressure 0.8 Mpa. Then, the first film was peeled off to obtain a volume hologram laminate.

It is a schematic sectional drawing which shows an example of the volume hologram transfer foil of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram transfer foil of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram transfer foil of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram transfer foil of this invention. It is a schematic sectional drawing which shows an example of the volume hologram laminated body of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram laminated body of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram laminated body of this invention. It is a schematic sectional drawing which shows the other example of the volume hologram laminated body of this invention. It is a schematic sectional drawing which shows an example of the manufacturing method of the volume hologram laminated body of this invention. It is the schematic which shows an example of the to-be-transferred body used for this invention, and the volume hologram laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Volume hologram layer 3 ... Heat seal layer 4 ... Ultraviolet absorption layer 5 ... Fluorescence image formation layer 6 ... Peelable protective layer 10, 10 ', 10''... Volume hologram transfer foil 20, 20', 20 ''… Volume hologram laminate 21… Transferee

Claims (8)

A substrate;
A volume hologram layer formed on the substrate and having a volume hologram recorded thereon;
A heat seal layer formed on the volume hologram layer and containing a thermoplastic resin;
An ultraviolet absorbing layer formed between the base material and the volume hologram layer or between the volume hologram layer and the heat seal layer, and having a function of absorbing ultraviolet rays;
A fluorescent image forming layer that is formed on the heat seal layer side of the ultraviolet absorbing layer and has an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays;
The volume hologram transfer foil, wherein an ultraviolet wavelength absorbed by the ultraviolet absorbing layer is different from an ultraviolet wavelength absorbed by the fluorescent material.   The volume hologram transfer foil according to claim 1, wherein the ultraviolet absorbing layer is formed between the base material and the volume hologram layer.   The volume hologram transfer foil according to claim 1, wherein a peelable protective layer is formed between the substrate and the volume hologram layer.   The volume hologram transfer foil according to claim 2, wherein a peelable protective layer is formed between the substrate and the ultraviolet absorbing layer. A transferred object;
A heat seal layer formed on the transfer body and containing a thermoplastic resin;
A volume hologram layer formed on the heat seal layer and having a volume hologram recorded thereon;
An ultraviolet absorbing layer formed on the volume hologram layer or between the volume hologram layer and the heat seal layer, and having a function of absorbing ultraviolet rays;
A fluorescent image forming layer that is formed on the heat seal layer side of the ultraviolet absorbing layer and has an image formed by a fluorescent material that emits fluorescence when irradiated with ultraviolet rays;
The volume hologram laminate, wherein an ultraviolet wavelength absorbed by the ultraviolet absorbing layer is different from an ultraviolet wavelength absorbed by the fluorescent material.   The volume hologram laminate according to claim 5, wherein the ultraviolet absorbing layer is formed on the volume hologram layer.   6. The volume hologram laminate according to claim 5, wherein a peelable protective layer is formed on the volume hologram layer.   The volume hologram laminate according to claim 6, wherein a peelable protective layer is formed on the ultraviolet absorbing layer.

Images