JP2009104099A - Volume hologram laminate, volume hologram transfer sheet, volume hologram adherend, and manufacturing method of volume hologram laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a volume hologram laminate making copying of a volume hologram difficult even when contact copying with a single wavelength laser beam is tried, and to provide a manufacturing method of the volume hologram laminate for manufacturing it via a simple process. <P>SOLUTION: In this volume hologram laminate, a resin layer is partially formed on a substrate, and a volume hologram layer is formed on the substrate adjacently to the resin layer. On the resin layer, the volume hologram is formed in the volume hologram laminate, reproduction center wavelength of a part wherein the resin layer is formed is different from that of a part wherein no resin layer is formed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a volume hologram laminate excellent in forgery prevention (reuse prevention) and design, and a method for producing the same.

  The volume hologram is a means capable of recording information in the thickness direction and capable of recording / reproducing a three-dimensional image. Since the volume hologram is expressed by a light interference color, it is difficult to obtain by other image forming means. Appearance. Although the volume hologram manufacturing method itself is known, it is difficult to imitate the volume hologram because it requires precise work using an optical device in manufacturing, and the above characteristics of such a volume hologram are utilized. It is used to prevent imitation of ID cards, bank cards, etc.

  For example, as disclosed in Patent Document 1 and Patent Document 2, the present inventors made the volume hologram layer unpeelable from an identification card to which the volume hologram layer was pasted as shown in Patent Document 1 and Patent Document 2, for example. Various studies have been made to prevent counterfeiting by destroying the hologram, but volume holograms are used when contact copying is attempted with a single-wavelength laser beam using a volume hologram laminate on which volume holograms are recorded. There is a need to develop a volume hologram laminate that makes it difficult to imitate volume holograms.

JP-A 63-284586 JP 2002-358018 A

  The present invention provides a volume hologram laminate that makes it difficult to imitate a volume hologram even if contact copying is attempted with a single wavelength laser beam, and a manufacturing method that can be manufactured by a simple process.

  The volume hologram laminate of the present invention is a volume hologram laminate in which a resin layer is partially provided on a substrate, the volume hologram layer is adjacent to the resin layer, and the volume hologram layer is laminated on the substrate. The volume hologram is formed in the resin layer, and the reproduction center wavelength is different between a portion where the resin layer is provided in the volume hologram laminate and a portion where the resin layer is not provided.

  The resin layer and the base material are adjacent to each other. In addition, a primer layer is formed between the resin layer and the base material.

  The volume hologram layer is a volume hologram layer derived from a volume hologram recording material containing a radical polymerizable monomer and a cation polymerizable monomer, and the volume hologram based on the migration of the polymerizable monomer from the volume hologram recording material adjacent to the resin layer Is formed.

  The resin layer is made of a resin selected from polymethyl methacrylate resin, polyvinyl acetate resin, and polyester resin, and the reproduction center wavelength of the portion where the resin layer is provided in the volume hologram laminate is the reproduction center of the portion where the resin layer is not provided. It is characterized by being on the long wavelength side compared to the wavelength.

  The resin layer is made of a resin selected from polyvinyl butyral resin and polyvinyl acetal resin, and the reproduction center wavelength of the portion provided with the resin layer in the volume hologram laminate is compared with the reproduction center wavelength of the portion where the resin layer is not provided. It is on the short wavelength side.

  In the volume hologram laminate, the difference between the reproduction center wavelength of the portion where the resin layer is provided and the reproduction center wavelength of the portion where the resin layer is not provided is at least 10 nm or more.

In the method for producing a volume hologram laminate of the present invention, a resin layer is partially applied and formed on a base material, and then adjacent to the resin layer and a radical polymerizable monomer and a cationic polymerizable monomer on the base material. After coating and forming a volume hologram recording material layer containing
(1) A step of transferring the polymerizable monomer in the volume hologram recording material layer to the resin layer by performing an aging treatment,
(2) Hologram exposure process by laser exposure from the substrate side,
(3) Heat treatment and ultraviolet irradiation treatment are performed to move the polymerizable monomer between the resin layer and the volume hologram recording material layer and to fix the hologram in order, and the resin layer is adjacent to the resin layer. A volume hologram based on the polymerizable monomer transferred from the volume hologram recording material layer is formed, and the reproduction center wavelength is made different between a portion where the resin layer is provided and a portion where the resin layer is not provided in the laminate. Features.

  The first volume hologram transfer sheet of the present invention is characterized in that an adhesive layer is provided on the volume hologram layer in the volume hologram laminate of the present invention.

  In the second volume hologram transfer sheet of the present invention, a second substrate is detachably provided on the volume hologram layer in the volume hologram laminate of the present invention, and the substrate in the volume hologram laminate is peeled off. An adhesive layer is provided on the exposed resin layer and volume hologram layer. Alternatively, the second base material is provided on the volume hologram layer in the volume hologram laminate of the present invention so as to be peelable, and the adhesive layer is provided on the surface of the volume hologram laminate from which the base material has been peeled off. And

  The first or second volume hologram transfer sheet is a volume hologram transfer foil having the adhesive layer as a heat seal layer, or a volume hologram transfer label having the adhesive layer as an adhesive layer. Features.

  The volume hologram sticking body of the present invention is attached to the adherend from the adhesive layer side in the first volume hologram transfer sheet, and the base material is peeled off or left and left. The protective layer is a hologram layer.

  The volume hologram sticking body of the present invention is stuck to the adherend from the adhesive layer side in the second volume hologram transfer sheet, and the second substrate is peeled off or left. And a protective layer for the volume hologram layer.

  In the volume hologram laminate of the present invention and the volume hologram sticking body, the interference fringe cycle of the volume hologram layer adjacent to the partially provided resin layer in the layer direction is not adjacent to the resin layer in the layer direction. Since a volume hologram having an interference fringe period that is enlarged or reduced compared to the interference fringe period of the volume hologram layer in FIG. 6 is formed, the reproduction center is divided between the part where the resin layer is provided in the volume hologram and the part where it is not provided. The wavelength can be made different, and the design can be made unconventional.

  In addition, the volume hologram laminate of the present invention is used as an original plate, and a volume hologram recording material layer is adhered to the original, and contact copying is performed with a single wavelength laser for the purpose of copying the volume hologram in a portion where the resin layer is not provided. Even if an attempt is made, a portion having a different reproduction center wavelength provided with a resin layer becomes dark and cannot be copied well, so that a volume hologram laminate excellent in forgery prevention can be obtained.

  The volume hologram laminate production method of the present invention can produce a volume hologram laminate excellent in design and anti-counterfeit in a simple process, and when the volume hologram transfer sheet of the present invention is used, The adherend can be easily produced by transfer.

FIG. 1 is a schematic cross-sectional view of a volume hologram laminate of the present invention, in which a resin layer 2 partially provided on a base material 1 and radical polymerization adjacent to the base material 1 and the resin layer 2 are provided. A volume hologram layer 3 derived from a volume hologram recording material containing a polymerizable monomer and a cationic polymerizable monomer is laminated (FIG. 1 (a)).
Here, in FIG. 1A, the embodiment in which the base material 1 and the resin layer 2 are adjacent to each other is illustrated, but the volume hologram laminate of the present invention is not limited to such a correspondence. For example, the primer layer 8 may be formed between the base material 1 and the resin layer 2 (FIG. 1B).

  The substrate 1 is not particularly limited as long as it can support the resin layer 2 and the volume hologram layer 3. For example, a polyethylene film, a polypropylene film, a polyvinyl fluoride film, a polyvinylidene fluoride film, a polyvinyl chloride film is used. , Polyvinylidene chloride film, ethylene-vinyl alcohol copolymer film, polyvinyl alcohol film, polymethyl methacrylate film, polyether sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film Examples thereof include polyester films such as polyethylene terephthalate film and polyimide films. The thickness of the substrate is usually 2 μm to 200 μm, preferably 10 μm to 50 μm.

  Moreover, in the volume hologram sticking body mentioned later, you may make a base material function as a protective film, and you may peel and remove. In order to function as a protective film, adhesion between the base material and the resin layer or volume hologram recording material layer is required, and the surface of the base material is treated with, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, heavy chromium. A surface treatment such as acid treatment, anchor or primer treatment may be performed. Examples of the anchor agent or primer agent include urethane, acrylic, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system, and the like. However, it is preferable to use an anchor agent or a primer agent different from the resin layer described later. This is because if the same one is used, the reproduction center wavelength cannot be made different between the portion of the volume hologram where the resin layer is provided and the portion where the resin layer is not provided. In the case of peeling and removing, the substrate is preferably subjected to a release treatment, and a resin layer and a volume hologram layer are preferably provided with or without a protective layer.

  Next, the resin layer 2 is a resin layer having transparency, and is obtained by applying and forming a resin solution in a part of a substrate, for example, a pattern such as a logo. Examples of the resin forming the resin layer include acrylic resins such as polymethyl methacrylate resin, vinyl resins such as polyvinyl acetate resin, polyester resins, polyvinyl butyral resins, and polyvinyl acetal resins.

  If the resin forming the resin layer is a polymethyl methacrylate resin, a polyvinyl acetate resin, a polyester resin, or the like, the detailed reason is unknown, but the portion where the resin layer 2 is laminated in the volume hologram laminate (base material) The reproduction center wavelength in 1 / resin layer 2 / volume hologram layer 3 ′) is made to be different from the reproduction center wavelength in the portion where the resin layer is not laminated (base material / volume hologram layer 3 ″) on the longer wavelength side. The degree of difference is influenced by the weight average molecular weight of the resin, and the weight average molecular weight is 5,000 to 1,000,000, preferably 5,000 to 500,000, particularly preferably 10, The reproduction center wavelength can be differentiated on the longer wavelength side when the molecular weight is 000 to 300,000, and the molecular weight of the resin is GPC (gel permeation). The weight average molecular weight in terms of polystyrene measured by chromatography).

  The difference between the reproduction center wavelength in the portion where the resin layer is provided and the reproduction center wavelength in the portion where the resin layer is not provided is preferably at least 10 nm or more, preferably 15 nm or more. The difference is 100 nm at the maximum.

  Further, if the resin forming the resin layer is a polyvinyl butyral resin or a polyvinyl acetal resin, the detailed reason is unclear, but unlike the above, the reproduction center wavelength in the portion where the resin layer is provided is It has been found that a difference is made on the short wavelength side as compared with the reproduction center wavelength in the portion where the layer is not laminated. The degree of difference is influenced by the magnitude of the weight average molecular weight of the resin as described above, and the weight average molecular weight is 5,000 to 1,000,000, preferably 5,000 to 500,000, particularly preferably 10,000 to When it is 300,000, the reproduction center wavelength can be made different on the shorter wavelength side.

  The difference between the reproduction center wavelength in the portion where the resin layer is provided and the reproduction center wavelength in the portion where the resin layer is not provided is preferably at least 10 nm or more, preferably 15 nm or more. The difference is 100 nm at the maximum.

  Each reproduction center wavelength in the portion where the resin layer is provided and the portion where the resin layer is not provided is obtained by measuring the transmittance using a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) to obtain a spectral transmittance curve. This is calculated from the spectral transmittance curve by the following method together with the diffraction efficiency and the half width, and will be described with reference to FIG.

(Diffraction efficiency)
The peak transmittance A and the base transmittance B of the spectral transmittance are obtained and set as | B−A | / B (%).
(Half width)
The left end (C) and right end (D) of the spectral transmittance curve in transmittance (A + | B−A | / 2) obtained by adding half of the difference between base transmittance A and peak transmittance B to peak transmittance A The half value width is determined as | D−C | (nm).
(Reproduction center wavelength)
A wavelength (= C + | D−C | / 2) obtained by adding half of the half width to C obtained at the time of calculating the half width is set as a reproduction center wavelength.

  The resin layer 2 has a range that does not affect the difference in the reproduction center wavelength, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, and a flame retardant. A filler or the like may be added. Examples of antioxidants include phenols, sulfurs, phosphoruss, etc., UV absorbers such as benzophenones, benzotriazoles, salicylates / cyanoacrylates, formamidines, oxanilides, etc. Hindered amines, nickel complexes, etc., heat stabilizers such as hindered phenols, sulfurs, hydrazines, etc., and plasticizers depending on the type of resin, for example, phthalate esters, phosphate esters, fatty acids Ester, aliphatic dibasic acid ester, oxybenzoic acid ester, epoxy, polyester, etc., examples of lubricants include fatty acid ester, fatty acid, metal soap, fatty acid amide, higher alcohol, paraffin, etc. Antistatic agents include, for example, cationic, anionic, noni Examples of flame retardants such as bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, and zirconium, and fillers such as calcium carbonate and talc , Wax stone, kaolin and the like.

The resin layer 2 has a resin solution in which components such as the above resin are dissolved in methyl ethyl ketone, toluene, ethyl acetate or the like on a substrate, 0.1 μm to 10 μm, preferably 0.5 μm to 5 μm, particularly preferably 0.5 μm to It is partially coated and formed on the substrate by gravure printing, screen printing or the like so as to have a dry film thickness of 3 μm.
In addition, the resin layer 2 may be formed so as to be adjacent to the base material 1 or may be adjacent to another layer formed so as to be adjacent to the base material 1 such as a primer layer. It may be formed.

  Next, as shown in FIG. 1, a volume hologram recording material layer is directly applied and formed on the resin layer 2 formed on the substrate 1 without using an intermediate layer.

  The volume hologram recording material layer used in the present invention contains a photopolymerizable material, and from the viewpoint that a high-contrast hologram image can be recorded, in particular, a radically polymerizable monomer and a cationically polymerizable monomer are used in combination. It is preferably used together with a radical photopolymerization initiator system and a cationic photopolymerization initiator system.

  Hereinafter, the radical polymerizable compound, the photo radical polymerization initiator system, the cationic polymerizable compound, and the photo cationic polymerization initiator system used in the present invention will be described in order.

  The radical polymerizable monomer used in the present invention is a compound that is polymerized by the action of active radicals generated from a photo radical polymerization initiator system, for example, by laser irradiation or the like when forming a volume hologram layer, and at least in the molecule. Those having one ethylenically unsaturated double bond are preferred.

  Examples of the radical polymerizable monomer include methyl methacrylate, hydroxyethyl methacrylate, lauryl acrylate, N-acryloylmorpholine, 2-ethylhexyl carbitol acrylate, isobornyl acrylate, methoxypropylene glycol acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-cyclohexanediol diacrylate, 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, tri Methylolethane triacrylate, trimethylolpropane tria Relate, trimethylolpropane tri (acryloyloxypropyl) ether, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexa Acrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, acrylamide, methacrylamide, methylenebisacrylamide, styrene, 2-bromostyrene, 2-phenyl Xylethyl acrylate, phenol ethoxylate monoacrylate, 2- (p-chlorophenoxy) ethyl acrylate, p-chlorophenyl acrylate, phenyl acrylate, 2-phenylethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, Methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, β-acryloxyethyl hydrogen phthalate, phenoxy polyethylene glycol acrylate, benzyl acrylate, 2,4,6-tribromophenyl acrylate, 2,3-dibromopropyl acrylate, 2-hydroxy- 3-phenoxypropyl acrylate, 2-naphthyl acrylate, 2- (1-naphthyloxy) ethyl acrylate, o-bif Nyl acrylate, dicyclopentanyl acrylate, dibromoneopentyl glycol diacrylate, 1,3-bis [2-acryloxy-3- (2,4,6-tribromophenoxy) propoxy] benzene, N-vinylcarbazole, 2 -(9-Galvazolyl) ethyl acrylate, diphenic acid (2-methacryloxyethyl) monoester, diphenic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diester, 2,3-naphthalene dicarboxylic acid (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diestyl, 4,5-phenanthrene dicarboxylic acid (2-acryloxy) (3-acryloxypropyl-2-hydroxy) diester, bis (4-acrylic) Roxydiethoxyphenyl Methane, bis (4-acryloxyethoxy-3,5-dibromophenyl) methane, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, 9,9-bis (4-acryloxydiethoxyphenyl) fluorene, 9,9-bis (4-acryloxytriethoxyphenyl) ) Fluorene, 9,9-bis (4-acryloxydipropoxyphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-) 3-ethylphenyl) fluorene, 9,9-bis (4-acryloxyethoxy-3,5-dimethyl) fluorene Rene, diethylenedithioglycol acrylate, triphenylmethylthioacrylate, 2- (tricyclo (5,2,102.6) dibromodecylthio) ethyl acrylate, S- (1-naphthylmethyl) thioacrylate, bis (4-acryloxyethoxy) Phenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone, bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone and the above-mentioned “acrylate body” to “methacrylate body”, and “acryloxy” And a sulfur-containing acrylic compound disclosed in JP-A-61-72748, for example, 4,4′-bis (β-acryloyloxy). Ethylthio) diphenylsulfone, 4 4'-bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4'-bis (β-acryloyloxyethylthio) -3,3 ', 5,5'-tetrabromodiphenyl ketone, 2,4-bis (Β-acryloyloxyethylthio) diphenyl ketone and compounds in which the “acryloyl” group in the above is changed to a “methacryloyl” group, and those described in JP-A-2-247205 and JP-A-2-261808 An ethylenically unsaturated double bond-containing compound containing at least two S atoms in the molecule can be mentioned, and these can be used alone or in combination.

  Examples of the photo radical polymerization initiator system include U.S. Pat. Nos. 4,766,055, 4,868,092, 4,965,171, JP-A-54-151024, and 58-. 15,503, 58-29,803, 59-189,340, 60-76735, JP-A-1-28715, Japanese Patent Application 3-5569 and “Proceedings” Of the initiator system described in “CONFERENCE ON CONFERENCE ON RADIATION CURING ASIA” (P.461-477, 1988), etc. .

  Next, the cationically polymerizable monomer used in the present invention is a compound that is subjected to energy irradiation and undergoes cationic polymerization with a Bronsted acid or Lewis acid generated by the decomposition of a photocationic polymerization initiator system described later.

  Here, the volume hologram layer forms an interference fringe by polymerizing a radical polymerizable compound with, for example, laser light or light with excellent coherence, and forms a hologram image. Therefore, as the radically polymerizable compound and the cationically polymerizable compound, those having different refractive indexes in each are preferably selected and used. The magnitude relationship between the refractive indices of the radically polymerizable compound and the cationically polymerizable compound used in the present invention is not particularly limited, but the average refractive index of the radically polymerizable compound is not particularly limited in terms of material selectivity. It is preferably larger than that of the polymerizable compound, and specifically, the difference in average refractive index is preferably 0.02 or more. This is because when the difference in average refractive index between the radical polymerizable compound and the cationic polymerizable compound is lower than the above value, the refractive index modulation becomes insufficient, and it becomes difficult to form a high-definition hologram image. There is a case. In addition, the average refractive index here means the average value of the refractive index measured about the polymer after superposing | polymerizing a cationically polymerizable compound or a radically polymerizable compound. Further, the average refractive index in the present invention means a value measured by an appe refractometer.

  In addition, when a radically polymerizable compound and a cationically polymerizable compound are used as the photopolymerizable material, the volume hologram recording in this step is usually performed by radical polymerization at a portion where the light intensity of the interference fringes is high when performing interference exposure. After the polymerizable compound is polymerized, the entire surface is irradiated with energy to polymerize an uncured substance such as a cationic polymerizable compound. At this time, the laser or the like used for forming the hologram image and the energy irradiated with energy on the entire surface are usually those having different wavelengths. Therefore, the cationically polymerizable compound used in the present invention has a hologram image. It is preferably a compound that does not polymerize at the wavelength of the light source used when forming. In addition, the cationic polymerizable compound used in the present invention is preferably in a liquid state at normal temperature because the radical polymerizable compound is preferably polymerized in a composition having a relatively low viscosity.

  Examples of such cationically polymerizable compounds include Chemtech Oct. Jct. V. Described in JV Crivello, page 624 (1980), JP-A-62-149784, Journal of the Adhesion Society of Japan (Vol. 26, No. 5, pp. 179-187 (1990)), etc. The compound which has been described can be mentioned.

More specifically, diglycerol polyglycidyl ether, pentaerythritol polyglycidyl edel, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcindi Glycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, paratertiary butylphenyl glycidyl ether, adipic acid diglycidyl ester, orthophthalic acid diglycidyl ester, dibromophenyl glycidyl ether, dibromoneo Pentyl glycol diglycidyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethyl Roll perfluorohexane diglycidyl ether, 4,4′-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4- Epoxycyclohexyloxirane, 1,2,5,6-diepoxy-4,7-methanoperhydroindene, 2- (3,4-epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5 Spirocyclohexane, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane), 4 ′, 5′-epoxy-2′-methylcyclohexylmethyl-4,5-epoxy-2-methylcyclohexanecarboxylate, Ethylene glycol-bis (3,4-epoxycyclohexane Xanthate carboxylate), bis- (3,4-epoxycyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether, vinyl-2-chloroethyl ether, vinyl-n-butyl ether, triethylene glycol divinyl ether, 1, Examples include 4-cyclohexanedimethanol divinyl ether, trimethylol ethane trivinyl ether, vinyl glycidyl ether, and compounds represented by the following formulae.

  In the above formula, n represents an integer of 1 to 5. M is 3 or 4, and R represents an ethyl group or a hydroxymethyl group.

  In the present invention, any of these cationically polymerizable compounds can be suitably used, and among them, it is preferable to use a cationically polymerizable compound having a polymerizable functional group having three or more functional groups per molecule. . This is because the crosslink density in the volume hologram layer can be increased, and the foil cutting property of the volume hologram layer can be improved. In addition, the cationically polymerizable compound used in the present invention may be only one type or two or more types.

Next, the cationic photopolymerization initiator system is not particularly limited as long as it generates Bronsted acid or Lewis acid by energy irradiation and can polymerize the cationic polymerizable compound. In particular, in the present invention, it does not react to a laser for polymerizing the radical polymerizable compound or light having excellent coherence, and the photosensitive material is exposed to energy irradiated to the entire surface thereafter. preferable. This is because, when the radical polymerizable compound is polymerized, the cationic polymerizable compound can be left with almost no reaction, so that a large refractive index modulation can be obtained in the volume hologram layer.

  Here, the photocationic polymerization initiator having low photosensitivity with respect to laser light or light with excellent coherence is initiated by a photocationic polymerization initiator system when thermal analysis is performed under the following conditions. The maximum DSC value resulting from photopolymerization is 500 mW or less (including 0 mW) per 1 mg of the measurement sample.

(Measurement condition)
Measuring device: Seiko Electronics Co., Ltd. SSC5200H thermal analysis system using differential scanning calorimetry DSC220 and light source device UV-1 Measurement sample: target photocationic polymerization initiator system UVR-6110 (Union Carbide Co., Ltd.) Prepared by dissolving 3% by mass with respect to the cationically polymerizable compound (the organic solvent may be evaporated after the organic solvent is added and dissolved.) Irradiation light: use of interference filter (half-value width about 10 nm) Then, 200 mJ / cm ^{2 of} light adjusted to the same level as laser light or light with excellent coherence is irradiated.

  As such a photocationic polymerization initiator system, for example, “UV Curing: Science and Technology”, pages 23-76, edited by S. Peter Pappas, • Technology Marketing Publication and “Comments Inorg. Chem.”, B. Klingert, M. Reediker and A. Ledrik (B. Klingert, M. Riedk), “Technology Marketing Publication” and “Comments Inorg. Chem.” and A. Roloff), Vol. 7, No. 3, pages 109-138 (1988), and the like. Or it may be used two or more kinds.

  Among the above, preferable diaryl iodonium salts include iodonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9, Examples thereof include 10-dimethoxyanthracene sulfonate. Preferred triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium, and the like. Examples include sulfonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and the like.

  In the present invention, as the photo radical polymerization initiator system or the photo cationic polymerization initiator system, an initiator system having the properties as the photo radical polymerization initiator system and the properties as the photo cationic polymerization initiator system is used. It may be used. Examples of such initiator systems include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. Specifically, chlorides of iodonium such as diphenyliodonium, ditolyliodonium, bis (pt-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromides, borofluoride salts, hexafluorophosphate salts, hexafluoroantimony salts Iodonium salts such as nate salts, chlorides of sulfonium such as triphenylsulfonium, 4-t-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluoride salts, hexafluorophosphate salts, hexafluoroantimonate salts Sulfonium salts such as 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl · -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- Methyl-4,6 Etc. and bis (trichloromethyl) -1,3,5-2,4,6-substituted-1,3,5-triazine compounds such as triazines.

  The volume hologram layer used in the present invention includes, for example, a sensitizing dye, fine particles, a thermal polymerization inhibitor, a silane coupling agent, a plasticizer, a colorant, and a polymer binder in addition to the above-described photopolymerizable material. Etc. In particular, in the present invention, it is particularly preferable to use a binder resin, fine particles, and a sensitizing dye.

  This is because the volume hologram layer can be made uniform by using the binder resin, and it becomes easy to maintain the hologram image formed by the polymerization of the radical polymerizable compound. Examples of the binder resin include polymethacrylate ester or a partially hydrolyzed product thereof, polyvinyl acetate or a hydrolyzed product thereof, polyvinyl alcohol or a partially acetalized product thereof, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, and silicone rubber. , Polystyrene, polyvinyl butyral, polyvinyl chloride, polyarylate, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinyl carbazole or derivatives thereof, poly-N-vinyl pyrrolidone or derivatives thereof, styrene and maleic anhydride Examples thereof include a coalescence or a half ester thereof. Further, at least one selected from the group consisting of copolymerizable monomers such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylimide, acrylonitrile, ethylene, propylene, vinyl chloride, and vinyl acetate. Copolymers obtained by polymerizing monomers can also be used. Furthermore, in the present invention, one or a mixture of two or more of these binder resins can be used.

  In the present invention, an oligomer type curable resin can also be used as the binder resin. Examples of such resins include epoxy compounds produced by the condensation reaction of various phenolic compounds such as bisphenol A, bisphenol S, novolak, o-cresol novolak, p-alkylphenol novolak and epichlorohydrin. Can be mentioned.

  Furthermore, in the present invention, an organic-inorganic hybrid polymer utilizing a sol-gel reaction can also be used as the binder resin. Examples of such a resin include a copolymer of an organometallic compound having a polymerizable group represented by the following general formula (1) and a vinyl monomer.

Rm M (OR ') n (1)
(Where M is a metal such as Si, Ti, Zr, Zn, In, Sn, A1, and Se, R is a carbon number of 1 to 100) vinyl group or (meth) acryloyl group, R 'is a carbon number of 1 to 10 M + n is the valence of the metal M. )
Examples of organometallic compounds when the metal M is Si include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, vinyltriallyloxysilane, vinyltetraethoxysilane, vinyltetramethoxysilane, acryloxypropyl Examples include trimethoxysilane and methacryloxypropyltrimethoxysilane.

  Examples of the vinyl monomer include acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester.

  In the volume hologram laminate of the present invention, since the volume hologram is formed by recording and forming interference fringes as refractive index modulation or transmittance modulation, there is a difference in refractive index between the binder resin and the photopolymerizable material. Larger is preferred. In the present invention, an organometallic compound represented by the following general formula (2) can be added in order to increase the difference in refractive index between the binder resin and the photopolymerizable material.

M '(OR ") k (2)
(Here, M ′ represents a metal such as Ti, Zr, Zn, In, Sn, A1, Se, R ″ represents an alkyl group having 1 to 10 carbon atoms, and k represents the valence of the metal M) .

  When the compound represented by the above formula (2) is added, a network structure is formed with the binder resin by a sol-gel reaction in the presence of water and an acid catalyst, so that not only the refractive index of the binder resin is increased, It has the effect of improving toughness and heat resistance. Therefore, in order to increase the difference in refractive index with the photopolymerizable material, it is preferable to use a metal M ′ having a high refractive index.

  Further, by using the fine particles, it is possible to easily impart desired foil breakability to the volume hologram layer. Examples of the fine particles include low-density polyethylene, high-density polyethylene, polypropylene, poly (meth) acryl, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyepoxy or polyurethane as a resin skeleton, and organic fine particles containing these copolymers, silica , Mica, talc, clay, graphite, calcium carbonate, alumina, aluminum hydroxide, ferrite, china clay, kaolin, titanium dioxide, glass flakes, asbestos, wax stone powder, quartzite powder, barium sulfate, sherben, chamotte, titania, etc. Particles or the like can be used, and these fine particles may be used alone or in combination of two or more.

  Many of the above photopolymerizable materials are active with respect to ultraviolet rays. However, the use of a sensitizing dye makes the photopolymerizable material also active with respect to visible light, and it is possible to record a volume hologram using visible laser light. The sensitizing dye is selected in consideration of the wavelength of the laser beam used when recording interference fringes, and is not particularly limited. Examples of sensitizing dyes used in the present invention include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, coumarin dyes, ketocoumarin dyes, thioxanthene dyes, xanthine dyes, oxonol dyes Dyes, cyanine dyes, rhodamine dyes, pyrylium dyes, cyclopentanone dyes, cyclohexanone dyes, and the like can be used.

  Examples of cyanine dyes and merocyanine dyes include 3,3′-dicarboxyethyl-2,2′-thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1, 3'-diethyl-2,2'-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidelidene) ethylidene] -2-thioxo-4-oxazolidine, etc. Is mentioned. Examples of the coumarin dyes and ketocoumarin dyes include 3- (2′-benzimidazole) 7-N, N-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin), and 3,3′-. Examples include carbonylbiscoumarin, 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), and the like.

  Visible light active sensitizing dyes are those that become colorless by being decomposed by heating or ultraviolet irradiation in the post-process after recording interference fringes when high transparency is required as in optical elements. preferable. As such a sensitizing dye, the above-mentioned cyanine dye is preferably used.

  Such a volume hologram recording material includes essential components and optional components as they are, or as required, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aromatic solvents such as toluene and xylene, methyl cellosolve, etc. It is prepared by mixing with a cellosolve solvent such as methanol, an alcohol solvent such as methanol, an ether solvent such as tetrahydrofuran or dioxane, or a halogen solvent such as dichloromethane or chloroform and mixing in a cool and dark place using, for example, a high-speed stirrer. After the coating liquid is formed, it may be applied onto the substrate and the resin layer by using an applicator with a dry film thickness of 1 μm to 50 μm, preferably 3 μm to 40 μm, particularly preferably 5 μm to 30 μm.

  When the volume hologram transfer foil is used, the volume hologram layer should have a glass transition point (Tg) of 100 ° C. or higher (about 200 ° C. at the maximum). Even when heat is applied, volume hologram recording can be made stable. The glass transition point (Tg) is measured based on JISK 7121.

Next, the manufacturing method of the volume hologram laminated body of this invention is demonstrated.
The volume hologram laminate of the present invention first contains a radically polymerizable monomer and a cationically polymerizable monomer adjacent to each other on the substrate and the resin layer, after partially forming a resin layer on the substrate. A volume hologram recording material layer is applied and formed into a laminate.

  (1) An aging treatment is performed on the obtained laminate. The aging treatment is performed by leaving the laminate at room temperature or heating at 40 to 80 ° C. for 1 to 48 hours. By this treatment, in the layer structure of the base material / resin layer / volume hologram recording material layer, the monomers and the like in the volume hologram recording material layer are transferred into the resin layer. As will be described later in Example 1, when the resin layer after the aging treatment is subjected to IR analysis, it is confirmed that the radical polymerizable monomer or the cationic polymerizable monomer in the volume hologram recording material layer has moved into the resin layer. .

  (2) Next, after aging treatment of the laminate, the hologram master was brought into close contact with the volume hologram recording material layer side, and then hologram exposure was performed by laser irradiation from the substrate side of the laminate, and the hologram was recorded. Layer.

  The volume hologram records a hologram image by fixing a photopolymerizable material with interference fringes generated by light interference as fringes having different refractive indexes. Therefore, as a method of recording a volume hologram in this step, for example, reference light is incident from the base material side of the volume hologram forming substrate, object light is incident from the volume hologram layer side, In this method, the hologram hologram is disposed on the volume hologram layer, and the light is incident from the substrate side, whereby the incident light and the reflected light reflected by the hologram original are converted into the volume hologram. The method of making it interfere in a layer etc. can be mentioned. Among them, the method using the hologram original plate described above is preferable, and thus, a volume hologram can be easily recorded.

(3) After hologram exposure, the hologram original plate is peeled off, and a PET film is laminated on the peeled surface. Then, the laminate 50 ° C. to 150 DEG ° C., was heated for 5 minutes to 120 minutes, irradiated with ultraviolet light at ^{500mJ / cm 2 ~5,000mJ / cm 2} . In the heat treatment step, it is considered that a part of the polymerizable monomer remaining after the hologram exposure is diffused again, and other monomers are fixed by the heat treatment-ultraviolet irradiation treatment to form a stable hologram.

  In the present invention, when the resin layer is formed using a polymethyl methacrylate resin or a polyvinyl acetate resin, the substrate / resin layer / volume hologram layer can be compared with the portion where the resin layer is not provided in the volume hologram laminate. It has been found that the reproduction center wavelength is different on the longer wavelength side in the laminated portion. Although the detailed reason is unknown, the interference fringe period (interference fringe interval) in the volume hologram layer is larger than the interference fringe period (interference fringe interval) in the resin layer from an electron microscope cross-sectional photograph of Example 1 described later. Therefore, the re-transfer of the monomer from the resin layer to the volume hologram layer occurs in the heating step (3) above, and thereby the reproduction center wavelength in the laminated portion of the substrate / resin layer / volume hologram layer However, it is considered that the difference is on the long wavelength side compared to the reproduction center wavelength in the laminated portion of the base material / volume hologram layer where the resin layer is not provided.

  Moreover, when the resin layer is formed using polyvinyl butyral resin or polyvinyl acetal resin, the reproduction center wavelength is not provided in the portion where the resin layer is not provided in the laminated portion of the base material / resin layer / volume hologram layer in the volume hologram laminate. It has been found that the difference is on the short wavelength side. Although the detailed reason is unknown, in the polyvinyl butyral resin layer and the polyvinyl acetal resin, it is considered that the movement of the monomer different from the PMMA resin layer is caused by the heating step (3) described above. It is considered that the reproduction center wavelength in the resin layer / volume hologram layer laminated portion is different from the reproduction center wavelength in the substrate / volume hologram layer laminated portion where no resin layer is provided.

  As described above, the volume hologram laminate of the present invention can be a volume hologram laminate partially having a portion with a different reproduction center wavelength. Moreover, even if the volume hologram recording material obtained is used as an original plate, the volume hologram recording material layer is adhered to this, and even when contact copying is attempted with a single wavelength laser beam, the portion where the reproduction center wavelength is different becomes dark, It is impossible to copy well, and a volume hologram laminate excellent in forgery prevention can be obtained.

  Next, the volume hologram transfer sheet of the present invention will be described with reference to FIGS. FIG. 2 shows a first volume hologram transfer sheet in which an adhesive layer 4 is provided on the volume hologram layer 3 in the volume hologram laminate of FIG. The adhesive layer 4 is a pressure-sensitive adhesive layer or a heat seal layer. In particular, FIG. 2 illustrates a case where a peelable sheet 5 is further laminated in the case of forming a pressure-sensitive adhesive layer, which is a volume hologram transfer label. Is the case. In the case of a heat seal layer, the peelable sheet 5 can be omitted and a volume hologram transfer foil is obtained.

  4 is a second volume hologram transfer sheet, in which a second substrate 7 is provided on the volume hologram layer of the volume hologram laminate of FIG. 1 so as to be peelable, and the substrate of the volume hologram laminate of FIG. An adhesive layer 4 is provided on the resin layer 2 and the volume hologram layer 3 that are exposed by peeling 1. The adhesive layer 4 is a pressure-sensitive adhesive layer or a heat seal layer. In particular, FIG. 4 shows a case where a peelable sheet 5 is further laminated in the case of forming a pressure-sensitive adhesive layer, and is a volume hologram transfer label. Is the case. In the case of a heat seal layer, the peelable sheet 5 can be omitted and a volume hologram transfer foil is obtained.

  Adhesives in volume hologram transfer labels include acrylic resins, acrylic ester resins, or copolymers thereof, styrene-butadiene copolymers, natural rubber, casein, gelatin, rosin esters, terpene resins, phenolic resins, styrene Illustrative examples include resin, chroman indene resin, polyvinyl ether, and silicone resin, and alpha-cyanoacrylate, silicone, maleimide, styrene, polyolefin, resorcinol, and polyvinyl ether adhesives are used. The pressure-sensitive adhesive is a coating solution using ethyl acetate, toluene, methyl ethyl ketone, butyl acetate or the like as a solvent. After the pressure-sensitive adhesive layer is formed on the peelable sheet with a dry film thickness of 0.5 μm to 20 μm, a volume hologram is formed. It is good to laminate on the layer 3 with a peelable sheet. As the release sheet, in addition to the commonly used release paper, a film obtained by releasing a polyethylene terephthalate resin film or polypropylene resin film with a fluorine release agent, a silicone release agent, etc. is used. May be.

  In addition, the heat sealant in the volume hologram transfer foil is a thermoplastic resin that has heat sealability, and the resin that can form a heat seal layer as an organic solvent solution includes ethylene-vinyl acetate copolymer resin and polyamide resin. , Polyester resins, polyethylene resins, ethylene-isobutyl acrylate copolymer resins, butyral resins, polyvinyl acetate resins, vinyl chloride vinyl acetate copolymer resins, cellulose derivatives, acrylic resins such as polymethyl methacrylate resins, polyvinyl ether resins, polyurethane resins, Examples include polycarbonate resins, polypropylene resins, epoxy resins, phenol resins, thermoplastic elastomers such as SBS, SIS, SEBS, and SEPS, or reactive hot melt resins. Examples of the organic solvent include toluene, methyl ethyl ketone, and the like. The organic solvent may be applied and formed on the volume hologram layer 3 with a dry film thickness of 2 to 10 μm by a comma coater, a die coater, a gravure coater or the like.

  The volume hologram sticking body of this invention is demonstrated using FIG. 3, FIG. As shown in FIG. 3, the volume hologram sticking body of the present invention is peeled off from the peelable sheet 5 in the volume hologram transfer sheet shown in FIG. 2 and then stuck to the adherend 6 from the adhesive layer 4 side. In addition, the substrate 1 is peeled and removed, or left to be a protective layer for the volume hologram layer.

  Moreover, the other volume hologram sticking body of this invention shown in FIG. 5 peels the peelable sheet 5 in the volume hologram transfer sheet | seat shown in FIG. 4 mentioned above, Then, it adheres to the adherend 6 from the adhesive layer 4 side. The second substrate 7 is peeled off and left or left to serve as a protective layer for the volume hologram layer.

  Examples of the adherend 6 in the volume hologram sticking body of the present invention include transparent or opaque ones such as glass and plastic. Examples of the plastic include a vinyl resin, an acrylic resin, a polystyrene resin, a polyester resin such as polyethylene terephthalate, and a polycarbonate resin. The plastic is particularly suitable for a card, sheet, or film made of a polyester resin. The volume hologram transfer sheet may be attached to a sheet such as an ID card, an examination card, a card such as an ID card, or a booklet such as a passport. It is suitable for use as a certificate showing the above grades or as a certificate of taking measures for it. In addition, in the past, for applications where a paper certificate is pasted and sealed, and the target article is transparent and substantially flat or has a quadratic curved surface, it can be replaced with a certificate in principle. Can be used. Further, the volume hologram transfer sheet can be widely used for articles having a part made of paper, synthetic paper, synthetic resin, a film or sheet made of metal, or a glass plate. Further, by utilizing the unique and three-dimensional characteristics of volume holograms, it can be used as a label to be attached to magazines such as books and saddle-stitched weekly magazines, glass windows of automobiles, premium products, and the like.

  Hereinafter, the present invention will be specifically described with reference to examples.

(Example 1)
(1) Production of volume hologram laminate Polyethylene terephthalate (PET) film (Lumirror 50T60; manufactured by Toray Industries, Inc.) having a thickness of 50 μm is used as a base material, and the weight average molecular weight is 100,000 on the base material. Using a resin layer forming working solution dissolved in a methyl ethyl ketone solvent of methyl methacrylate, the resin layer was applied and formed in a pattern by a gravure printing method to form a patterned resin layer having a dry film thickness of 2 μm.

Next, on the resin layer, a volume hologram layer forming coating solution having the following composition was directly applied using an applicator so as to have a dry film thickness of 10 μm to form a volume hologram layer.
(Volume hologram layer forming coating solution)
Polyvinyl acetate (Denkasacnol SN-08H: Degree of polymerization 800; manufactured by Denki Kagaku Kogyo Co., Ltd.)
... 35 parts by weight- 1,6-hexanediol diglycidyl ether (Denacol EX-212; manufactured by Nagase ChemteX Corporation)
・ ・ ・ 25 parts by weight • Diphenoxyethanol full orange acrylate (BPEFA; manufactured by Osaka Gas Chemical Co., Ltd.)
... 35 parts by weight / diaryliodonium salt (PI2074; manufactured by Rhodia)
... 4 parts by weight ・ 2,5-bis (4-diethylaminobenzylidene) cyclopentanone
・ ・ ・ Single child part ・ Methyl isobutyl ketone 100 parts by weight ・ 1-Butanol 100 parts by weight

(2) Aging process The obtained volume hologram laminate was aged for 24 hours at room temperature. After the aging treatment, the resin layer was analyzed with an IR analyzer (FT / IR-610 manufactured by JASCO Corporation). As a result, it was found that 1,6-hexanediol diglycidyl ether and diphenoxyethanol full orange acrylate were contained. confirmed.

(3) Hologram imaging process A hologram master was laminated on the volume hologram layer in the volume hologram laminate, and a volume hologram was recorded by injecting 532 nm laser light at 80 mJ / cm ² from the substrate side. After recording, the hologram master was peeled off and a 50 μm thick PET film was laminated on the volume hologram layer.

(4) Heat treatment-ultraviolet irradiation treatment process The volume hologram laminate after hologram recording was heat-treated at 100 ° C. for 10 minutes, and then irradiated with ultraviolet rays (3,000 mJ / cm ² ) to fix the hologram. A volume hologram laminate was obtained.

  FIG. 7 is a 70% reduced copy of a scanning electron micrograph (magnified 15,000 times) of the longitudinal section at the location where the resin layer is laminated in the obtained volume hologram laminate. In FIG. 7, 1 is a substrate, 2 is a resin layer, 3 is a volume hologram layer, and interference fringes are recorded on the resin layer 2 at an interval of 116 nm, and interference fringes are recorded on the volume hologram layer 3 at an interval of 186 nm. You can see that

  FIG. 8 shows a spectral transmittance curve as a result of measuring the transmittance with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) for a portion where the resin layer is patterned and a portion where the resin layer is not patterned. .

  The reproduction center wavelength of the spectral transmittance curve (A) of the portion where the resin layer was patterned was 544 nm, and the reproduction center wavelength of the spectral transmittance curve (B) of the portion where the resin layer was not patterned was 527 nm.

(Forgery prevention)
The volume hologram layer forming coating solution described above is applied to a dry film thickness of 10 μm on a 50 μm-thick PET film to obtain a laminate, and the volume hologram recording material layer side thereof From the above, the volume hologram laminate on which the volume hologram was recorded as described above was pasted onto the PET film, and then the volume hologram was photographed using a laser beam of 532 nm. As a result, the portion where the resin layer was patterned was dark. The hologram could not be taken well.

(Example 2)
A volume hologram is recorded in the same manner as in Example 1 except that a methyl acetalone solution of polyvinyl acetal resin (ESREC BH-6: weight average molecular weight of about 92,000, manufactured by Sekisui Chemical Co., Ltd.) is used as the resin layer coating solution. A volume hologram laminate was obtained.

  The transmittance is measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) for the portion where the resin layer is patterned and the portion where the resin layer is not patterned, and FIG. 9 shows a spectral transmittance curve.

  The reproduction center wavelength of the spectral transmittance curve (C) of the portion where the resin layer was patterned was 490 nm, and the reproduction center wavelength of the spectral transmittance curve (D) of the portion where the resin layer was not patterned was 527 nm.

  As for the anti-counterfeiting property, as in Example 1, when a volume hologram was photographed using the volume hologram laminate on which the volume hologram was recorded as an original, the portion where the resin layer was patterned was darkened, and the hologram was successfully formed. I could not shoot.

(Example 3)
A volume hologram laminate in which volume holograms are recorded in the same manner as in Example 1 except that a methyl ethyl ketone solution of polyvinyl acetate resin (weight average molecular weight of about 500,000; manufactured by ALDRICH) is used as the resin layer coating liquid. Got.

  When the transmittance was measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) for a portion where the resin layer was patterned and a portion where the resin layer was not patterned, the reproduction center of the portion where the resin layer was patterned The wavelength was 554 nm, and the reproduction center wavelength of the spectral transmittance curve of the unpatterned portion was 527 nm.

  As for the anti-counterfeiting property, as in Example 1, when a volume hologram was photographed using the volume hologram laminate on which the volume hologram was recorded as an original, the portion where the resin layer was patterned was darkened, and the hologram was successfully formed. I could not shoot.

Example 4
A volume hologram on which a volume hologram is recorded in the same manner as in Example 1 except that a methyl ethyl ketone solution of polyester resin (Byron 270: weight average molecular weight 40,000; manufactured by Toyobo Co., Ltd.) is used as the coating liquid for the resin layer. A laminate was obtained.
When the transmittance was measured with a spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) for a portion where the resin layer was patterned and a portion where the resin layer was not patterned, the reproduction center of the portion where the resin layer was patterned The wavelength was 556 nm, and the reproduction center wavelength of the spectral transmittance curve of the unpatterned portion was 527 nm.
As for the anti-counterfeiting property, as in Example 1, when a volume hologram was photographed using the volume hologram laminate on which the volume hologram was recorded as an original, the portion where the resin layer was patterned was darkened, and the hologram was successfully formed. I could not shoot.

(Example 5)
On the volume hologram layer in the volume hologram laminate produced in Example 1, the following composition and acrylic pressure-sensitive adhesive (Nissetsu PE-118; manufactured by Nippon Carbide Industries Co., Ltd.)
・ ・ ・ 100 parts by mass ・ Isocyanate-based crosslinking agent (Nissetsu CK-101; manufactured by Nippon Carbide Industries Co., Ltd.)
... 2 parts by mass · Solvent (Methyl ethyl ketone / toluene / ethyl acetate = 2/1/1 (mass ratio)
The adhesive solution consisting of 60 parts by mass was applied with an applicator so as to have a film thickness of 20 μm after drying, and then dried in an oven to form an adhesive layer. Then, a peelable sheet (SPPET (75 μm); manufactured by Tosero Co., Ltd.) was laminated on the adhesive layer to obtain a volume hologram transfer label which is the first volume hologram transfer sheet of the present invention.

  After peeling off the peelable sheet in the volume hologram transfer label, it was stuck on the PVC card as the adherend from the pressure-sensitive adhesive layer side using a handler terminator to obtain the volume hologram sticking body of the present invention. . In the volume hologram, a reproduction center wavelength is different in a pattern shape between a portion where the resin layer is provided and a portion where the resin layer is not provided, and an excellent design is obtained.

(Example 6)
On the untreated PET film {Lumirror T60 (25 μm); manufactured by Toray Industries, Inc.}, the following composition: Polymethylmethacrylate (weight average molecular weight 100,000)
・ ・ ・ 97 parts by mass ・ Polyethylene wax (weight average molecular weight 10,000)
... 3 parts by mass-Solvent (Methyl ethyl ketone / toluene / ethyl acetate = 2/1/1 (mass ratio))
・ ・ ・ 60 parts by mass of a peelable protective layer forming solution was applied with a bar coater so that the film thickness after drying was 1 μm, and then dried in an oven to obtain a laminate of PET film / peelable protective layer Got.

  Using the volume hologram laminate (PET film / resin layer / volume hologram layer / PET film) before being treated in the heat treatment-ultraviolet irradiation treatment step in the method for producing a volume hologram laminate of Example 1, After the PET film on the volume hologram layer side was peeled off, and passed through a roller at 80 ° C. facing the peelable protective layer surface in the PET film / peelable protective layer laminate obtained above from the volume hologram layer side, The whole surface was irradiated with ultraviolet rays to obtain a volume hologram laminate composed of PET film / peelable protective layer / volume hologram layer / resin layer / PET film.

After the PET film on the resin layer side in the obtained volume hologram laminate was peeled off, the following composition on the resin layer partially provided with the volume hologram layer: Polyester resin (Vylonal MD1985; manufactured by Toyobo Co., Ltd.)
... 100 parts by mass-Solvent (water / isopropyl alcohol = 1/1 (mass ratio))
・ ・ ・ A heat seal layer forming solution consisting of 100 parts by mass was applied with a bar coater so that the film thickness after drying was 4 μm, and then dried in an oven to obtain a PET film / peelable protective layer / volume hologram layer A volume hologram transfer foil which is a second volume hologram transfer sheet of the present invention comprising: / resin layer / heat seal layer was obtained.

Using the hot stamping machine (V-08: manufactured by Navitas), the obtained volume hologram transfer foil is placed on the PVC card as the adherend from the heat seal layer side, the transfer temperature is 150 ° C., and the transfer time is 0.5 sec. And a press pressure of 125 kgf / cm ² , and then the PET film was peeled off to obtain a volume hologram sticking body comprising peelable protective layer / volume hologram layer / resin layer / heat seal layer / PVC card. In the volume hologram, a reproduction center wavelength is different in a pattern shape between a portion where the resin layer is provided and a portion where the resin layer is not provided, and an excellent design property is obtained.

It is sectional drawing of the volume hologram laminated body of this invention. It is sectional drawing of the 1st sheet | seat for volume hologram transfer of this invention. It is sectional drawing of the volume hologram sticking body produced using the 1st sheet | seat for volume hologram transfer of this invention. It is sectional drawing of the 2nd sheet | seat for volume hologram transfer of this invention. It is sectional drawing of the volume hologram sticking body produced using the 2nd volume hologram transfer sheet of this invention. It is a figure for demonstrating the method of calculating a diffraction efficiency, a half value width, and a reproduction center wavelength from a spectral transmittance curve. The volume hologram laminate obtained in Example 1 is a 70% reduced copy of a scanning electron micrograph (15,000 times) of a longitudinal section in a resin layer laminate. The spectral transmittance curve of the part by which the resin layer in the volume hologram laminated body obtained in Example 1 was patterned, and the part which is not patterned is shown. The spectral transmittance curve of the part by which the resin layer in the volume hologram laminated body obtained in Example 2 was patterned, and the part which is not patterned is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Resin layer 3 ... Volume hologram layer 4 ... Adhesive layer 5 ... Release sheet 6 ... Adhering body 7 ... 2nd base material 8 ... Primer layer

Claims (14)

  A volume hologram laminate in which a resin layer is partially provided on a base material, and is adjacent to the resin layer and a volume hologram layer is laminated on the base material. The volume hologram laminate is characterized in that the reproduction center wavelength is different between a portion where the resin layer is provided and a portion where the resin layer is not provided in the volume hologram laminate.   The volume hologram laminate according to claim 1, wherein the resin layer and the base material are adjacent to each other.   The volume hologram laminate according to claim 1, wherein a primer layer is formed between the resin layer and the substrate.   The volume hologram layer is a volume hologram layer derived from a volume hologram recording material containing a radical polymerizable monomer and a cationic polymerizable monomer, and the volume hologram based on the migration of the polymerizable monomer from the volume hologram recording material adjacent to the resin layer The volume hologram laminate according to any one of claims 1 to 3, wherein the volume hologram laminate is formed.   The resin layer is made of a resin selected from polymethyl methacrylate resin, polyvinyl acetate resin, and polyester resin, and the reproduction center wavelength of the portion provided with the resin layer in the volume hologram laminate is the portion where the resin layer is not provided. The volume hologram laminate according to any one of claims 1 to 4, wherein the volume hologram laminate is located on a longer wavelength side than the reproduction center wavelength.   The resin layer is made of a resin selected from polyvinyl butyral resin and polyvinyl acetal resin, and the reproduction center wavelength of the portion provided with the resin layer in the volume hologram laminate is compared with the reproduction center wavelength of the portion where the resin layer is not provided. The volume hologram laminate according to any one of claims 1 to 4, wherein the volume hologram laminate is on the short wavelength side.   The difference between the reproduction center wavelength of the portion where the resin layer is provided in the volume hologram laminate and the reproduction center wavelength of the portion where the resin layer is not provided is at least 10 nm or more. The volume hologram laminate as described. After the resin layer was partially applied and formed on the base material, a volume hologram recording material layer adjacent to the resin layer and containing a radical polymerizable monomer and a cationic polymerizable monomer was applied and formed on the base material. Later, the resulting laminate is
(1) A step of transferring the polymerizable monomer in the volume hologram recording material layer to the resin layer by performing an aging treatment,
(2) Hologram exposure process by laser exposure from the substrate side,
(3) A step of applying heat treatment and ultraviolet irradiation treatment to move the polymerizable monomer between the resin layer and the volume hologram recording material layer and fixing the hologram;
The resin layer is formed with a volume hologram based on a polymerizable monomer transferred from an adjacent volume hologram recording material layer, and is provided with a resin layer portion and a resin layer in the laminate. A method for producing a volume hologram laminate, characterized in that the reproduction center wavelength is different from that of a non-existing portion.   A volume hologram transfer sheet, wherein an adhesive layer is provided on the volume hologram layer in the volume hologram laminate according to any one of claims 1 to 7.   A second base material is provided on the volume hologram layer in the volume hologram laminate according to claim 1 or 3 so as to be peelable, and an adhesive layer is provided on a surface of the volume hologram laminate from which the base material has been peeled off. A volume hologram transfer sheet characterized by the above.   A second substrate is detachably provided on the volume hologram layer in the volume hologram laminate according to claim 2, and the resin layer and the volume hologram layer are exposed by peeling the substrate in the volume hologram laminate. A volume hologram transfer sheet provided with an adhesive layer.   The volume hologram transfer sheet is a volume hologram transfer foil having the adhesive layer as a heat seal layer, or a volume hologram transfer label having the adhesive layer as an adhesive layer. The volume hologram transfer sheet according to any one of claims 1 to 11.   The volume hologram transfer sheet according to claim 9 is adhered to the adherend from the adhesive layer side, and the substrate is peeled off or left to be a protective layer for the volume hologram layer. A featured volume hologram sticker.   The volume hologram transfer sheet according to claim 10 or 11, wherein the volume hologram layer is adhered to the adherend from the adhesive layer side, and the second base material is peeled off or left so as to protect the volume hologram layer. The volume hologram sticking body characterized by being made into a layer.

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