JP2000132072A - Volume hologram laminated body and label for manufacture of same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide volume hologram laminated body capable of extending the reproduction band of diffracted light and capable of giving a bright hologram and to provide a label used for manufacturing the volume hologram laminated body. SOLUTION: A 1st adhesive layer 3, a volume hologram layer 5, a 2nd adhesive layer 4 and a surface protective film 6 are successively laminated on a substrate 2 to obtain the objective volume hologram laminated body 1. A (meth) acrylic monomer is contained in the 1st adhesive layer 3 and/or the 2nd adhesive layer 4. When the volume hologram layer 5 is subjected to hologram recording with monochromatic light, the half-width of its reproduction wavelength region is >=30 nm. When the volume hologram layer 5 is subjected to color hologram recording with polychromatic light which is a mixture of light of more than two different wavelengths, the half-width of each reproduction wavelength region is >=20 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a volume hologram laminate and a label for producing the volume hologram laminate, which enable the reproduction band of diffracted light to be widened. The present invention relates to a volume hologram laminate suitable for use as a color filter and a label for producing a volume hologram laminate.

[0002]

2. Description of the Related Art Conventionally, a volume hologram laminate generally comprises an adhesive layer, a volume hologram layer, an adhesive layer,
It has a configuration in which a transparent protective film is laminated in order, and records a face image on a volume hologram layer on an identification card or the like as a base material, and is also being applied as a color filter in a liquid crystal optical element. When reproducing the hologram recorded in the volume hologram layer, there is a problem that if the reproduction band of the diffracted light is narrow, the illumination light source used for reproducing the hologram is limited. By providing such a layer adjacent to the volume hologram layer, the reproduction band of the diffracted light is widened, but there is a problem that the film thickness of the volume hologram laminate increases.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a volume hologram laminate and a label for producing the volume hologram laminate, which make it possible to widen the reproduction band of diffracted light and obtain a bright hologram. And

[0004]

A volume hologram laminate according to the present invention is a volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a substrate. In the body, the first and / or second
The pressure-sensitive adhesive layer contains a (meth) acrylic monomer, the volume hologram layer is hologram-recorded with single-wavelength light, and the half-width of the reproduction wavelength range is 30 nm or more.

[0005] The volume hologram laminate of the present invention comprises:
In a volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a base material, the first and / or second pressure-sensitive adhesive layers may have 3.) Acrylic monomer is contained, and the volume hologram layer is color hologram-recorded with two or more wavelengths of light, and the half width of each reproduction wavelength range is 20 nm or more.

The above-mentioned pressure-sensitive adhesive layer is characterized in that it is a two-part cross-linking type pressure-sensitive adhesive which adds a cross-linking agent at the time of use to cross-link.

The above-mentioned volume hologram layer is made of a photopolymerizable compound, and is characterized in that it is hologram-recorded.

The label for producing a volume hologram laminate of the present invention is a label for producing a volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a release sheet. In the label, the (meth) acrylic monomer is contained in the first and / or second pressure-sensitive adhesive layers, and the half width of the reproduction wavelength range of the hologram recorded in the volume hologram layer is 30 nm or more. Features.

The label for producing a volume hologram laminate of the present invention is a volume hologram laminate in which a first adhesive layer, a volume hologram layer, a second adhesive layer, and a surface protection film are sequentially laminated on a release sheet. In the production label, the first and / or second pressure-sensitive adhesive layers contain a (meth) acrylic monomer, and the volume hologram layer is recorded with a color hologram with two or more wavelengths of light. It is characterized in that the half width of the wavelength range is 20 nm or more.

[0010]

FIG. 1 is a cross-sectional view of a volume hologram laminate according to the present invention. In the figure, 1 is a volume hologram laminate, 2 is a substrate, 3 is a first adhesive layer, 4 is a second adhesive layer, 5 is a volume hologram layer, and 6 is a surface protection film.

As the substrate 2 in the volume hologram laminate of the present invention, a film or a sheet made of paper, synthetic paper, synthetic resin or metal can be used.
In addition, it can take various forms such as a card shape such as an ID card and a booklet such as a passport. You. When a color filter of a liquid crystal display element is used, a glass substrate or an electrode layer in a liquid crystal cell is a base material.

Further, the volume hologram laminate of the present invention comprises:
FIG. 1 illustrates a configuration in which a volume hologram layer 5 is laminated on a base material 2 via a first adhesive layer 3.
A structure in which the volume hologram layer 5 is laminated thereon via a double-sided adhesive tape may be adopted.

In the volume hologram layer 5, after a volume hologram recording material is applied on a support film, interference fringes corresponding to the wavefront of light from an object are recorded in the layer in the form of transmittance modulation and refractive index modulation. It can be a color hologram that reproduces two or more colors, or a monochromatic hologram. Also, when copying, it is easily manufactured by closely contacting a volume hologram master and exposing and developing it. You can do it.

The volume hologram layer 5 comprises a matrix polymer, a photopolymerizable compound, a photopolymerization initiator, a sensitizing dye,
And a dry-type volume phase hologram recording photosensitive material comprising a plasticizer and a surfactant, if necessary.

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

Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and their halogen-substituted unsaturated carboxylic acids such as chlorinated unsaturated carboxylic acids. , Brominated unsaturated carboxylic acids, fluorinated unsaturated carboxylic acids, and the like. The salts of unsaturated carboxylic acids include the sodium and potassium salts of the aforementioned acids.

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

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3 -Methacryloxy-2- Mud propoxy) phenyl] dimethyl methane, bis - [p- (acryloxy ethoxy phenyl] dimethyl methane, 2,2-bis (4-methacryloyloxy) propane, methacrylate -2
-Naphthyl and the like.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate, and the like.

As the crotonic acid ester, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
And sorbitol tetracrotonate.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate and the like.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

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

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

As another example, see JP-B-48-417.
No. 08-208, a polyisocyanate compound having two or more isocyanate groups in one molecule, represented by the following general formula: CH ₂ CC (R) COOCH ₂ CH (R ′) OH (where R and R ′ are hydrogen or And a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl-containing vinyl monomer represented by the following formula:

Also, urethane acrylates described in JP-A-51-37193, JP-A-48-641
No. 83, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 5
Polyester acrylates, epoxy resins and (meth) as described in JP-A-2-30490, respectively.
Examples include polyfunctional acrylates and methacrylates such as acrylic acid.

Further, the Journal of the Adhesion Society of Japan, Vol. 20, N
o7, those introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used.

Other monomers containing phosphorus include mono (2-acryloyloxyethyl) acid phosphate (trade name: Light Ester PA, manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and mono (2-methacryloikiethyl) Acid Phosphate (trade name: Light Ester PM, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.); epoxy acrylate-based trade name: Lipoxy VR-60 (manufactured by Showa Polymer Co., Ltd.); trade name: Lipoxy VR-90 (manufactured by Showa Polymer Co., Ltd.) and the like.

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

Further, triacrylates having the following structural formula:

[0031]

Embedded image

(Toa Gosei Chemical Industry Co., Ltd., trade name, Aronix M-315)

[0033]

Embedded image

(Trade name, Aronix M-325, manufactured by Toa Gosei Chemical Industry Co., Ltd.), and 2,2'-bis (4-
Acryloxy diethoxyphenyl) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, NK ester A-BPE-4), tetramethylolmethanetetraacrylate (Shin-Nakamura Chemical)
(Trade name, NK Ester A-TMMT), and the like. In the present invention, the acrylic monomer and the methacrylic monomer are referred to as (meth) acrylic monomers.

[0035] Plasticizers added as needed include
Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, and trimethylolpropane, and derivatives in which terminal hydroxyl groups of these polyhydric alcohols are blocked by etherification, acetylation,
Weight average molecular weight 200 to 2,000, preferably 200
Polyethylene glycol of ~ 600, weight average molecular weight 3
00 to 2,000, preferably 300 to 1,000, polyalkylene glycols such as polypropylene glycol, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), heptyl nonyl phthalate (HNP), phthalate 2-Ethylhexyl acid (DOP), di-n-octyl phthalate (DNO
P), di-i-octyl phthalate (DCapP), (79 alkyl) phthalate (D79P), di-i-phthalate
Decyl (DIDP), ditridecyl phthalate (DTD)
P), phthalate plasticizers such as dicyclohexyl phthalate (DCHP), butylbenzyl phthalate (BDP), ethylphthalylethyl glycolate (EPEG) and butylphthalylbutyl glycolate (BPBG); -2-ethylhexyl (DOA), di- (methylcyclohexyl) adipate, diisodecyl adipate (DIDA), di-n-hexyl azelate (DNNZ), di-2-ethylhexyl azelate (DOZ), sebacine Dibasic acid ester plasticizers such as dibutyl citrate (DBS) and di-2-ethylhexyl sebacate (DOS), and triethyl citrate (TE
C), citrate ester plasticizers such as tributyl citrate (TBC), triethyl acetyl citrate (ATEC) and acetyl tributyl citrate (ATBC), epoxy plasticizers such as epoxidized soybean oil, and tributyl phosphate (TBP) ), Polyester plasticizers such as phosphate ester plasticizers such as triphenyl phosphate (TPP), tricresyl phosphate (YCP), and tripropylene glycol phosphate.

Next, as a photopolymerization initiator in the initiator system, 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-
(Butyldioxycarbonyl) benzophenone, N-phenylglycine, 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers Etc. are exemplified. The photopolymerization initiator is
From the viewpoint of stabilization of the recorded hologram, it is preferable that the hologram is decomposed after recording the hologram. For example, organic peroxides are preferable because they are easily decomposed by irradiation with ultraviolet rays.

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

Examples of the matrix polymer include polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate, polyvinyl alcohol or its partial acetalized product, triacetyl cellulose, polyisoprene, polybutadiene, polychloroprene, Silicone rubber, polystyrene, polyvinyl butyral, polychloroprene, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, poly-N-vinyl carbazole or its derivatives, poly-N-vinyl pyrrolidone or its derivatives, styrene and maleic anhydride Polymer or its half ester, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, vinyl acetate Copolymers or mixtures thereof, are used to at least one polymerizable component copolymerizable monomers set forth. Preferably polyisoprene,
Polybutadiene, polychloroprene, polyvinyl alcohol, and polyvinyl acetal which is a partially acetalized product of polyvinyl alcohol, polyvinyl butyral,
Examples include polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, and the like, and mixtures thereof.

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

The photopolymerizable compound is a binder resin 1
It is used in an amount of 10 parts by weight to 1000 parts by weight, preferably 10 parts by weight to 100 parts by weight based on 00 parts by weight.

The photopolymerization initiator is used in an amount of 1 to 10 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The sensitizing dye is used in an amount of 0.01 to 1 part by weight, preferably 0.0 to 1 part by weight, based on 100 parts by weight of the binder resin.
It is used in a proportion of 1 part by weight to 0.5 part by weight.

Other photosensitive material components include various nonionic surfactants, cationic surfactants, and anionic surfactants.

These hologram recording materials include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve,
Ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol or the like, or a mixed solvent thereof, is used. % ~
It is a 25% coating liquid. The thickness of the hologram recording layer after drying is 0.1 μm to 50 μm, preferably 5 μm.
２０20 μm. As such a hologram recording material, for example, Omnidex 352 manufactured by DuPont,
706.

Next, the pressure-sensitive adhesive layers 3 and 4 will be described.
Examples of the pressure-sensitive adhesive layer include an acrylic resin, an acrylate resin, or a copolymer thereof, a styrene-butadiene copolymer, a natural rubber, a casein, a gelatin, a rosin ester, a terpene resin, a phenolic resin, a styrene resin, and a chroman resin. Indene resins, polyvinyl ethers, silicone resins and the like, as well as alpha-cyanoacrylate, silicone, maleimide, styrene, polyolefin, resorcinol, polyvinyl ether, and silicone adhesives. In addition, the pressure-sensitive adhesive layer can be formed using a so-called two-component cross-linking pressure-sensitive adhesive that is cross-linked by adding an isocyanate-based cross-linking agent, a metal chelate-based cross-linking agent, or the like at the time of use. Further, a heat sealant may be used as the pressure-sensitive adhesive layer.
Vinyl acetate copolymer resin, polyamide resin, polyester resin, polyethylene resin, ethylene-isobutyl acrylate copolymer resin, butyral resin, polyvinyl acetate and its copolymer resin, cellulose derivative, polymethyl methacrylate resin, polyvinyl ether resin, polyurethane resin, Polycarbonate resin, polypropylene resin,
Epoxy resin, phenol resin, SBS, SIS, SE
Examples thereof include thermoplastic elastomers such as BS and SEPS, and reactive hot melt resins. The thickness of the pressure-sensitive adhesive layer is preferably 4 μm to 20 μm.

The volume hologram laminate of the present invention is characterized in that a (meth) acrylic monomer is added to at least one of the pressure-sensitive adhesive layers 3 and 4. As the (meth) acrylic monomer, a low molecular weight component having a molecular weight of 100 to 5,000, and particularly preferably having a molecular weight of 100 to 2,000. If the molecular weight is less than 100, it becomes volatile, which is not preferable. If it exceeds 5,000, the mobility to the adjacent layer decreases, and the purpose of addition may not be achieved.

Examples of the (meth) acrylic monomer include the acrylic monomers and methacrylic monomers described in the section of the volume hologram layer. Preferably, methoxypolyethylene glycol methacrylate (weight average molecular weight 400), methoxydiethylene glycol (meth ) Acrylate, polyethylene glycol di (meth)
Acrylate (weight average molecular weight 200), trimethylolpropane tri (meth) acrylate and the like are exemplified.

As the (meth) acrylic monomer, it is preferable to select a substance compatible with the components constituting the volume hologram layer. In addition, it is required that the interference fringes transferred to and recorded in the volume hologram layer are not completely destroyed and that recording and reproduction are not disabled.

The (meth) acrylic monomer is dissolved and dispersed in an organic solvent together with the above-mentioned pressure-sensitive adhesive, for example, coated on a release paper and dried to form a pressure-sensitive adhesive layer. The content is 20% by weight, preferably 5% by weight to 15% by weight, and if it exceeds 20% by weight, the tackiness is impaired.

In the present invention, when the pressure-sensitive adhesive layer to which the (meth) acrylic monomer is added is laminated on the volume hologram layer, the detailed reason is unknown, but the (meth) acrylic monomer is It has the function of shifting to the hologram-recorded volume hologram layer and swelling the volume hologram layer, and the obtained reproduction wavelength can be shifted to a longer wavelength side than the recording wavelength. It is possible to control the wavelength.

The relationship between the content of the recording wavelength shifting substance in the pressure-sensitive adhesive layer and the reproduction wavelength in the volume hologram layer may be determined by the following experimental method.

(Dependence of Wavelength Shift Amount on Addition of Photopolymerizable Compound) Hologram recording film: PET film / volume hologram layer / polyvinyl chloride film (“Omn” manufactured by DuPont)
idex 706 ") Adhesive film: The following composition-Acrylic adhesive (" Nissetsu PE-118 "manufactured by Nippon Carbide Co., Ltd.)-100 parts by weight-Methyl ethyl ketone-30 parts by weight-Toluene-15 parts by weight-Acetic acid Ethyl... 15 parts by weight of trimethylolpropane triacrylate (TMPTA) added in different amounts to add various T
An adhesive having an MPTA concentration is prepared and applied to a PET film in a dry film thickness of 15 μm to prepare an adhesive film.

First, 488n was added to the hologram recording film.
After recording the hologram with an argon laser having a specific wavelength of m, the polyvinyl chloride film is peeled off, and the adhesive film is adhered to the hologram surface from the side of the adhesive layer.

The obtained PET film / volume hologram layer / pressure-sensitive adhesive layer / PET film was baked at 140 ° C., which is a condition in an actual processing process, for 15 minutes, and then “UV-2100PC” manufactured by Shimadzu Corporation was used. , The spectral transmittance was measured, the peak wavelength was measured, and the shift amount from the recording wavelength of 488 nm (peak wavelength -488)
nm = Δλ).

FIG. 3 shows the measurement results. In FIG. 3, the unit of the TMPTA concentration is 10 ⁻⁴ mol, which is the amount added per 1 g of the acrylic pressure-sensitive adhesive. As shown in FIG. 3, when the amount of TMPTA added to the pressure-sensitive adhesive layer is 0, Δλ
Is negative, indicating that unreacted monomers, plasticizers, and the like move from the volume hologram layer to the pressure-sensitive adhesive layer, the volume hologram layer shrinks, and the reproduction wavelength shifts to the shorter wavelength side.
When the amount of TMPTA added increases, Δλ increases, and the reproduction wavelength shifts to the longer wavelength side.

Further, in the present invention, when the pressure-sensitive adhesive layer to which the (meth) acrylic monomer is added is laminated on the volume hologram layer, the detailed reason is unknown, but the control of the reproduction wavelength is not known. At the same time as having the effect of expanding the reproduction wavelength band. That is, even if the bright line of the illumination light source has a sharp wavelength, the volume hologram laminate of the present invention can cope with the sharp wavelength, and a bright hologram can be stably obtained.

In the volume hologram laminate of the present invention, the content of the moving component added to the first pressure-sensitive adhesive layer and / or the second pressure-sensitive adhesive layer is balanced with the content in the volume hologram layer. If the moving components other than the (meth) acrylic monomer are not moved between the pressure-sensitive adhesive layers and the volume hologram layer, the reproduction wavelength can be further stabilized.

Examples of these moving components include photopolymerizable compounds and plasticizers described as constituent materials of the volume hologram layer. These moving components are the same as or different from those of the volume hologram layer. However, when a (meth) acrylic monomer is selected as the transfer component, it may be added in consideration of the amount of the (meth) acrylic monomer that is the additive component in the present invention described above.

Further, examples of the transfer component include a tackifier (tackifier), a surfactant, and a polyalkylene glycol. These mobile components have a molecular weight of 1
It is a low molecular weight component having a molecular weight of 100 to 5,000, and particularly preferably a component having a molecular weight of 100 to 2,000. If the molecular weight is less than 100, it becomes volatile, which is not preferable.
If it exceeds 5,000, mobility to the adjacent layer decreases,
The purpose of the addition may not be achieved. Further, it is preferable to select a substance having compatibility with the components constituting the volume hologram layer as the moving component to be contained in the pressure-sensitive adhesive layer, and to completely remove interference fringes transferred to and recorded in the volume hologram layer. It is required that it not be destroyed or make recording / reproduction impossible.

Further, the moving components contained in the pressure-sensitive adhesive layer include:
The adhesive layer is preferably contained in such an amount as not to impair the adhesiveness thereof in combination with the (meth) acrylic monomer which is the above-mentioned additive component, and the total amount is preferably 20% by weight or less. May be set as appropriate from the relationship with the content of the moving component in the volume hologram layer and the relationship with the desired reproduction wavelength.

Next, the surface protective film 6 has transparency, and is a polyethylene film, a polypropylene film,
Polyethylene fluoride film, polyvinylidene fluoride film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, polyether sulfone film, polyether ether ketone film, polyamide Examples of the film include a resin such as a polyester film such as a film, a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer film and a polyethylene terephthalate film, and a polyimide film. The film thickness is 2 μm to 200 μm, and preferably 10 μm to 50 μm.

When the volume hologram layer has adhesiveness in the volume hologram laminate, an adhesive layer, a volume hologram layer, and a surface protection film may be formed on the substrate.
Generally, the surface protective film contains a plasticizer, and in this case, the balance between the pressure-sensitive adhesive layer, the volume hologram layer, and the surface protective film may be adjusted in consideration of the moving components.

Although not shown, the surface protective film may be subjected to a hard coat treatment as required for the purpose of enhancing the protection of the surface protective film surface.
The hard coat treatment is performed, for example, by dipping, spraying, or roll coating a silicone-based, fluorine-containing silicone-based, melamine alkyd-based, urethane-acrylate (ultraviolet-curable) coating, or the like to a film thickness of 1 μm to 5 μm.
The coating may be applied at 0 μm, preferably 3 μm to 25 μm.

Similarly, although not shown, the surface of the surface protective film 6 or the surface of the hard coat treatment may be subjected to a release treatment. The release treatment may be performed by dipping, spraying, or roll coating a fluorine-based release agent, a silicone-based release agent, a stearate-based release agent, a wax-based release agent, or the like.

The volume hologram layer in the volume hologram laminate of the present invention may record holograms at a single recording wavelength, or may record color holograms at two or more wavelengths. Further, by adding a (meth) acrylic monomer to the pressure-sensitive adhesive layer, the reproduction wavelength can be shifted with respect to the recording wavelength.

When recording a hologram with a single wavelength,
The half-value width of the obtained reproduction wavelength range can be 30 nm or more, preferably 35 nm or more. When color hologram recording is performed at two or more wavelengths, the half-value width of each obtained reproduction wavelength range is 20 nm or more. Preferably, it can be 25 nm or more.

The volume hologram laminate of the present invention can control and adjust the reproduction wavelength to the emission line wavelength of the illumination light source, and can widen the reproduction band. Therefore, a bright hologram image can be obtained under the illumination light source. Can be played.

Next, FIG. 2 shows the layer structure of the cross section of the label for producing a volume hologram laminate of the present invention. In the figure, 10 is a label for producing a volume hologram laminate, 11 is a release paper, and the same reference numerals as those in FIG. 1 indicate the same contents.

The label for producing a volume hologram laminate of the present invention is used for producing the above-described volume hologram laminate, and as shown in FIG. A hologram layer 5, a second adhesive layer 4, and a surface protection film 6 are laminated.

As the release paper 11, a release film obtained by subjecting a polyethylene terephthalate film surface to release treatment with a fluorine-based release agent or a silicone-based release agent may be used in addition to a commonly used release paper. Further, the surface of the release paper which is not on the side of the adhesive layer may be subjected to a release treatment in order to avoid blocking by the adhesive protruding from the side of the label. Further, the laminate may be so-called "semi-punched" so that the laminate can be peeled off from the release paper in an appropriate size, or a cutout such as a perforation may be formed in the release paper. .

After releasing the release paper 11, the label 10
The volume hologram laminate shown in FIG. 1 is produced by laminating on the substrate from the first pressure-sensitive adhesive layer 3 side.

[0072]

The present invention will be described below with reference to examples. (Example 1) (Preparation of transparent protective film / second pressure-sensitive adhesive layer / silicon separator) Silicon separator ("SP-" manufactured by Tokyo Cellophane Co., Ltd.)
PET05 ”film thickness 50 μm) and the following composition ・ Acrylic adhesive (“ Nissetsu PE-118 ”manufactured by Nippon Carbide Co., Ltd.) ・ ・ ・ 100 parts by weight ・ Methyl ethyl ketone ・ ・ ・ 30 parts by weight ・ Toluene ・ ・ ・ 15 parts by weight・ Ethyl acetate ・ ・ ・ 15 parts by weight ・ Isocyanate type crosslinking agent (“Nissetsu CK-101” manufactured by Nippon Carbide Co., Ltd.) Was applied. A polyethylene terephthalate film (Lumirror T-6 manufactured by Toray Industries, Inc.)
0, and a film thickness of 50 μm).

(Silicone separator A / first pressure-sensitive adhesive layer /
Production of Silicon Separator B) Silicon Separator A ("SP" manufactured by Tokyo Cellophane Co., Ltd.
-PET05 "film thickness of 50 μm) and the following composition: Acrylic adhesive (" Nissetsu PE-118 "manufactured by Nippon Carbide Co., Ltd.) ... 100 parts by weight -Methyl ethyl ketone ... 30 parts by weight -Toluene ... 15 parts by weight Part: Ethyl acetate: 15 parts by weight Methoxy polyethylene glycol methacrylate (weight average molecular weight: 400, manufactured by Shin-Nakamura Chemical Co., Ltd.): 10 parts by weight of the adhesive solution was immediately dried to a film thickness of 15 μm. Was applied with a comma coater. A silicon separator B ("SP-PET02" film thickness 50 μm, manufactured by Tokyo Cellophane Co., Ltd.) was laminated on this.

(Preparation of Hologram Recording Film) Polyethylene terephthalate film (PET film: 50)
μm) / hologram recording material / polyvinyl chloride film A lipogram hologram was recorded with a 488 nm argon laser on a hologram recording film (Omnidex 706; manufactured by DuPont).

(Preparation of Hologram Laminate) The polyvinyl chloride film of the hologram recording film obtained above was peeled off, and the silicon separator A / first pressure-sensitive adhesive layer / silicon separator B obtained above was replaced with silicon separator A.
And the two are laminated, and the PET film / volume hologram layer / first pressure-sensitive adhesive layer / silicon separator B
I got

The PET film is peeled from the laminate,
Further, the transparent protective film / second pressure-sensitive adhesive layer / silicon separator of the above-obtained transparent protective film / second silicon pressure-sensitive adhesive layer was peeled off, and the two were laminated to form a transparent protective film / second pressure-sensitive adhesive layer / hologram recording material / first pressure-sensitive adhesive layer / A volume hologram laminate label of the present invention comprising a silicon separator B was obtained.

This label was heated at 140 ° C. for 15 minutes, and its spectral characteristics were evaluated. The reproduction wavelength was 498 nm, Δλ from the recording wavelength was +10 nm, and the half width was 43 nm.

(Comparative Example) A label for preparing a volume hologram laminate was prepared in the same manner as in Example 1 except that methoxypolyethylene glycol methacrylate was omitted from the material for forming the first pressure-sensitive adhesive layer, and the spectral characteristics were similarly measured. As a result of the evaluation, the reproduction wavelength was 472 nm, and the half width was 26 nm.

(Example 2) Instead of the hologram recording film in Example 1, a hologram recording film (HRF800x001; manufactured by DuPont) consisting of PET film / hologram recording material / PET film was used.
Color Lippmann holograms were recorded using lasers having respective wavelengths of 6 nm, 532 nm and 647 nm.

Using the obtained hologram recording film, the volume hologram of the present invention comprising a transparent protective film / second pressure-sensitive adhesive layer / hologram recording material / first pressure-sensitive adhesive layer / silicon separator B as in Example 1 A laminate label was obtained.

The label was heated at 140 ° C. for 15 minutes and its spectral characteristics were evaluated.
487 nm, 544 nm, and 655 nm, and Δλ with the recording wavelength is +12 nm, +12 nm, and +8 nm.
The half widths are 21 nm, 23 nm, and 27 n, respectively.
m.

[0082]

The volume hologram laminate and the label for producing the volume hologram laminate according to the present invention can be controlled to a desired reproduction wavelength and can have a wide reproduction band, so that a bright hologram can be obtained under an illumination light source. The image can be reconstructed.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a volume hologram laminate of the present invention in a sectional view thereof.

FIG. 2 is a diagram for explaining a label for producing a volume hologram laminate of the present invention in a sectional view thereof.

FIG. 3 is a diagram for explaining the relationship between the addition amount of trimethylolpropane triacrylate in the pressure-sensitive adhesive layer and the amount of wavelength shift from the recording wavelength in the obtained volume hologram layer.

[Explanation of symbols]

1 is a volume hologram laminate, 2 is a substrate, 3 is a first pressure-sensitive adhesive layer, 4 is a second pressure-sensitive adhesive layer, 5 is a volume hologram layer, 6 is a surface protective film, 10 is a label for producing a volume hologram laminate, Reference numeral 11 denotes a release sheet.

Claims (6)

[Claims] 1. A volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a base material, wherein the first and / or second pressure-sensitive adhesive is used. A volume hologram laminate comprising a layer containing a (meth) acrylic monomer, a hologram recording of a volume hologram layer with a single wavelength light, and a half-value width of a reproduction wavelength range of 30 nm or more. 2. A volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a base material, wherein the first and / or second pressure-sensitive adhesive is used. The layer contains a (meth) acrylic monomer, and the volume hologram layer is color hologram-recorded with two or more wavelengths of light, and the half width of each of the reproduction wavelength ranges is 20 nm or more. Volume hologram laminate. 3. The volume hologram laminate according to claim 1, wherein the pressure-sensitive adhesive layer is a two-component cross-linkable pressure-sensitive adhesive that is cross-linked by adding a cross-linking agent at the time of use. 4. The volume hologram laminate according to claim 1, wherein the volume hologram layer is made of a photopolymerizable compound and is hologram-recorded. 5. A label for producing a volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a release sheet,
The (meth) acrylic monomer is contained in the first and / or second pressure-sensitive adhesive layers, and a half-value width of a reproduction wavelength range of the hologram recorded in the volume hologram layer is 30 nm or more. Label for producing volume hologram laminate. 6. A label for producing a volume hologram laminate in which a first pressure-sensitive adhesive layer, a volume hologram layer, a second pressure-sensitive adhesive layer, and a surface protection film are sequentially laminated on a release sheet,
The first and / or second pressure-sensitive adhesive layers contain a (meth) acrylic monomer, and the volume hologram layer is color hologram-recorded with two or more wavelengths of light, and the half-width of each of these reproduction wavelength ranges. Is 20 nm or more.