JPH11231761A - Hologram display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram display element which has an improved resolution, diffraction efficiency, transparency, regenerative wavelength reproducibility and preservation stability, and further, suitable for mass conduction by using a volume phase type hologram of a little color aberration and which can be molded into an arbitrary shape. SOLUTION: An ultraviolet setting resin layer 20 is formed by setting such a resin on a film base 10 composed of a synthetic resin and a hologram recording member layer 30 capable of producing hologram is provided on the ultraviolet setting resin layer 20. In this case, a hologram display element producing a hologram on the layer 30 is transferred through a transparent adhesive agent 50 formed on the hologram recording member layer 30 onto another colorless transparent base 40 and the hologram display element 1 is provided while being released on the interface between the ultraviolet setting resin layer 20 and the hologram recording member layer 30.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a layer structure when a volume phase hologram recording material is used as a display element, and more particularly to a hologram display element having various shapes.

[0002]

2. Description of the Related Art Holograms, which reproduce a three-dimensional image, are preferred for their excellent design, and are used for covers of books and magazines, POP displays, gifts and the like.
Further, since the hologram is equivalent to recording information on the order of submicron, it is also used to prevent forgery of securities, credit cards and the like. Further, in recent years, in addition to display applications, application to a hologram optical element (HOE) typified by a combiner for a head-up display (HUD) mounted on an automobile or a reflector for a reflective liquid crystal display device is expected. ing.

[0003] The hologram recording material is required to be sensitive to laser light having a visible oscillation wavelength with high sensitivity and to exhibit high resolution. In actual use, it is required that characteristics such as diffraction efficiency of the hologram, reproducibility of the wavelength of the reproduction light, bandwidth (half-width of the reproduction light peak), chromatic aberration (blur), etc. meet the purpose. Specifically, HOE
In order to obtain a recording material for the
90% or more for 000 to 6000 lines, the half width (band width) of the peak of the reproduction light is preferably 10 to 30 nm, and the peak wavelength of the reproduction wavelength is preferably within 5 nm from the photographing wavelength. In addition, durability such as solvent resistance and abrasion resistance is required, and it is also necessary to have excellent storage stability for a long period of time.

Hitherto, as a hologram material, a photosensitive material based on a bleached silver salt and gelatin dichromate has been generally used. However, these hologram recording materials are
In each case, complicated processing is required after the production and recording of the photosensitive plate, and further, there is a problem that environmental resistance properties, for example, moisture resistance and weather resistance are inferior.

On the other hand, it has excellent environmental resistance characteristics and
As a material having characteristics that a hologram recording material should have, such as high resolution and high diffraction efficiency, there is a dry-processed recording material having no voids in a hologram layer, specifically, a solvent-soluble and cationically polymerizable material. Holographic recording materials comprising a thermosetting resin having at least one ethylene oxide ring in its structural unit and a radically polymerizable ethylenic monomer (JP-A-8-1676, JP-A-8-1677,
JP-A-8-1678 and JP-A-8-1679). A hologram made of such a recording material has a thickness of 1
When a hologram is to be formed, a substrate having a smooth surface and being not eroded by a solvent of a photosensitive liquid is required when forming a hologram. A glass substrate is one that satisfies these conditions.

However, if a hologram is produced using a glass substrate, it must be produced in a batch system.
There were problems such as poor mass productivity and high cost. Still further, using a glass substrate as the base material,
Another problem is that it becomes difficult to form the hologram into an arbitrary shape. Therefore, as a method for solving these problems, a method of providing a hologram photosensitive layer on a film substrate without using a glass substrate as a substrate is mentioned. By adopting this method, continuous hologram production can be performed. The above disadvantages can be overcome. Further, after the hologram is formed, the hologram layer is transferred from the film base material to another colorless and transparent base material that can be formed into an arbitrary shape via an adhesive or the like, and then peeled off from the film base material. Therefore, there is an advantage that the base material of the hologram display element can be arbitrarily selected.

However, a hologram produced by providing a hologram recording material layer on the above-mentioned film substrate has too strong an adhesive property between the film substrate and the hologram recording material layer, so that the hologram recording material layer is peeled off from the film substrate. And it is difficult to employ the above method.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has as its object to provide high resolution, high diffraction efficiency, high transparency, reproduction wavelength reproducibility, and storage. It is an object of the present invention to provide a hologram display element which is excellent in mass productivity and can be formed into an arbitrary shape by using a volume phase hologram having excellent stability and less chromatic aberration.

[0009]

In order to achieve the above object, the present invention first provides an ultraviolet curable resin obtained by curing an ultraviolet curable resin on a synthetic resin film substrate. A hologram recording material layer capable of producing a hologram on the ultraviolet curable resin layer, and a hologram display element formed by producing a hologram on the hologram recording material layer. A hologram display element, wherein the hologram display element is transferred onto another colorless and transparent base material via a suitable adhesive and peeled off at the interface between the ultraviolet curable resin layer and the hologram recording material layer.

[0010] In the invention of claim 2, the film substrate made of the synthetic resin is a polyethylene terephthalate resin, a polymethyl methacrylate resin, a polycarbonate resin, a cellulose triacetate resin, a polypropylene resin,
The hologram display element according to claim 1, wherein the hologram display element is made of any one of polyethylene resins.

According to a third aspect of the present invention, the ultraviolet curable resin layer comprises a urethane acrylate oligomer or a polyester acrylate oligomer, a low-viscosity acrylic monomer, and a photoinitiator. This is a display element.

Further, in the invention of claim 4, the colorless and transparent substrate is made of an acrylic resin, a polycarbonate resin, a cellulose triacetate resin, an amorphous polyolefin resin, quartz,
3. The method according to claim 1, wherein the glass is made of any one of glass.
Or a hologram display element according to 3.

[0013]

Embodiments of the present invention will be described below. As shown in FIG. 1, a hologram display element (1) of the present invention comprises an ultraviolet-curable resin layer (2) obtained by curing an ultraviolet-curable resin on a film base (10) made of a synthetic resin.
0), a hologram recording material layer (30) capable of producing a hologram is provided on the ultraviolet curable resin layer (20), and a hologram display element formed by producing a hologram on the hologram recording material layer (30) is a hologram. The transparent adhesive (5) applied on the hologram recording material layer (30) on which
0), and transferred onto another colorless and transparent substrate (40), and the ultraviolet curable resin layer (20) and the hologram recording material layer (3) are transferred.
The hologram display element (1) as shown in FIG. 2 is obtained by peeling off at the interface with (0).

The hologram display element (1) obtained in this way is made of a film base (10) made of a synthetic resin as a base, preferably a web-like film, so that the hologram display element (1) having excellent productivity is obtained. 1) a film substrate made of a synthetic resin (10)
An ultraviolet curing resin layer (20) is provided thereon, and a hologram recording material layer (30) is provided thereon, so that separation at the interface of the hologram recording material layer (30) and the hologram display element (1) can be arbitrarily performed. This facilitates transfer to another colorless and transparent substrate (40) that can be formed into a shape.

Hereinafter, embodiments of the hologram display device of the present invention will be described in more detail including the materials used. The hologram used in the present invention is a reflection hologram called a Lippmann hologram which is a volume phase hologram, and a transmission hologram. That is, the phase distribution in which the interference fringes are recorded becomes a multilayer film having a periodic structure with a large number of layers having different refractive indices. Only when the hologram has a very high reflectance (reflection type), the number of layers is smaller than that of the reflection type, and the hologram has a broader peak of the reproduction light (transmission type). Further, the hologram can have a lens function or a prism function by utilizing the diffraction of light, and by using these characteristics, a display element capable of displaying a virtual image at a long distance can be manufactured. In addition, when used as a display element, it is necessary to have environmental resistance properties such as heat resistance, moisture resistance, light resistance, etc., and holograms produced by wet development with voids having relatively high diffraction efficiency satisfy the specifications. In many cases, the hologram is preferably a hologram formed by dry processing without any voids in the hologram layer.

The hologram used in the present invention may be any hologram produced from a hologram recording material utilizing a difference in refractive index between a polymer serving as a carrier and a monomer polymerized by a polymerization initiation species generated by light. Specifically, a thermosetting resin (component (A)) having at least one solvent-soluble and cationically polymerizable ethylene oxide ring in its structural unit, an ethylenic monomer capable of radical polymerization (component (B)), A photoinitiator (component (C)) that activates radical polymerization and cationic polymerization upon exposure to actinic radiation, and a sensitizing dye (component (D)) that sensitizes the photoinitiator (component (C)) Holograms produced from such hologram recording materials.

The component (A) of the thermosetting resin having at least one ethylene oxide ring soluble in a solvent and capable of cationic polymerization in a structural unit is represented by the general formula:

Embedded image (Where n = 1 to 20)

Or the general formula

Embedded image (In the formula, R represents an alkyl group, and n = 1 to 20.)

Or a general formula

Embedded image Wherein n = 1 to 20. For example, bisphenol A, bisphenol AD, bisphenol B, bisphenol AF, bisphenol S, brominated bisphenol A, novolak, o-cresol novolak, p-alkylphenol novolak Formed by the condensation reaction of various phenol compounds such as hydrogenated bisphenol A, hydrogenated bisphenol AD, hydrogenated bisphenol B, hydrogenated bisphenol AF, hydrogenated bisphenol S and hydrogenated brominated bisphenol A with epichlorohydrin. Epoxy compounds can be mentioned. However, the present invention is not limited to these.

The molecular weight of the thermosetting resin as the component (A) is preferably from 900 to 6000. If the molecular weight is smaller than this, the film-forming property is deteriorated and uniform coating cannot be performed. Further, a molecular weight larger than this range generally makes synthesis difficult.
The epoxy equivalent of the thermosetting resin is preferably in the range of 400 to 6700, otherwise good cationic polymerization does not proceed.

The radically polymerizable ethylenic monomer as the component (B) includes at least one ethylenically unsaturated bond in its structural unit, and may be a monofunctional vinyl monomer. And a polyfunctional vinyl monomer, or a mixture thereof. Specifically, (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, high boiling vinyl monomers such as 2-hydroxyethyl (meth) acrylate, and further, an aliphatic polyhydroxy compound, For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Examples thereof include, but are not limited to, di- or poly (meth) acrylates such as hexanediol, 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and mannitol.

Further, as a photoinitiator system which activates radical polymerization and cationic polymerization when exposed to the actinic radiation which is the component (C), J. Pharm. Photochem. Sc
i. Technol. , 2,283 (1977). Compounds, specifically iron arene complex, trihalogenomethyl-substituted s-triazine, sulfonium salt, diazonium salt, phosphonium salt, selenonium salt,
Arsonium salts, iodonium salts and the like, and examples of iodonium salts include Macromolecule
s, 10 , 1307 (1977). And diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m
-Nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium and the like, iodonium chloride, bromide, or borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic Group sulfonates and the like.

Further, the sensitizing dye which is the component (D) according to the present invention includes organic compounds such as cyanine or merocyanine derivatives, coumarin derivatives, chalcone derivatives, xanthene derivatives, thioxanthene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives and the like. Dye compounds can be used, and in addition, "Dye Handbook" (Shin Okawara et al., Edited by Kodansha 1986), "Chemistry of functional dyes" (Shin Okawara et al., Edited by CMC 1981),
"Specially Functional Materials" (CEM 19 by Chuzaburo Ikemori et al.)
1986) are used. It should be noted that the present invention is not limited to these, and any other dyes and sensitizers that absorb light in the visible region can be used. These may be used in two or more at any ratio as needed.

The amount of component (B) contained in the hologram recording material according to the present invention can be in the range of 20 to 200 parts by weight, preferably 100 parts by weight of component (A). 30 to 100 parts by weight. In addition, the amount of the photoinitiator of the component (C) is 10
0.1 to 20 parts by weight, preferably 1 to 0 parts by weight
To 10 parts by weight. The amount of component (D) depends on the amount of component (A)
It can range from 0.1 to 5 parts by weight per 100 parts by weight, preferably from 0.2 to 0.5 part by weight. The amount used is limited by the thickness of the photosensitive layer and the optical density of the thickness. That is, it is preferable to use the optical density within a range not exceeding 2.

As described above, these components are appropriately selected and mixed at an arbitrary ratio, and the obtained photosensitive solution is coated with a known coating means such as a bar coater, an applicator, a doctor blade, a roll coater, a die coater, and a comma coater. A UV curable resin is applied to a film substrate (10) made of a synthetic resin by using the resin, and cured to form a UV curable resin layer (20), on which a photosensitive liquid is similarly applied. When the photosensitive liquid is applied, it may be diluted with an appropriate solvent as necessary, but in that case, drying is required after application on the substrate. Examples of the solvent include dichloromethane, chloroform, acetone, 2-butanone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate and 2-butoxyethyl acetate.
Methoxyethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2-
(2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, tetrahydrofuran,
1,4-dioxane and the like can be mentioned. After drying, hologram exposure is performed, and if post-processing is required, predetermined processing is performed to obtain a volume phase hologram.

When a volume phase type hologram is produced from the hologram recording material according to the present invention by an optical duplication method, an intermediate liquid may be used to increase the adhesion between the hologram master or mirror and the hologram recording material. Specifically, a material having a relatively high boiling point having a refractive index of about 1.4 to 1.5 without affecting the hologram master or the hologram recording material is preferable. Specific examples include saturated hydrocarbons such as n-heptane, n-octane, isooctane, n-nonane, and n-decane, and isoper which is a mixture thereof, and aromatic hydrocarbons such as toluene and xylene. However, this is not the case.

The film substrate (10) made of a synthetic resin used for the hologram display element (1) of the present invention includes polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, cellulose triacetate resin, polypropylene resin, polyethylene resin And the like. More specifically, Melinex (PET film, ICI Japan Co., Ltd.)
Co., Ltd.), Teijin Tetron film (PET film,
Teijin Limited), Sanduren (PMMA film,
Kanebuchi Chemical Industry Co., Ltd.), Acryprene (PMMA film, manufactured by Mitsubishi Rayon Co., Ltd.), Iupilon film (PC film, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), Panlite sheet (PC film, Teijin Chemical Co., Ltd.), Lonza TAC (TAC film,
Lonza), Toyobo Pyren Film-OT (PP film, Toyobo Co., Ltd.), Super Pure Array (PP film, Idemitsu Petrochemical Co., Ltd.), Hybron film (PE film, Mitsui Toatsu) Platec Corporation
Co., Ltd.), Toyobo Rix film (PE film, manufactured by Toyobo Co., Ltd.) and the like, but are not limited thereto.

The ultraviolet curable resin layer (20) used in the hologram display element of the present invention is cured by ultraviolet rays and has no adverse effect even when a hologram photosensitive liquid is applied, and furthermore, a film substrate (10) made of a synthetic resin. And at the same time, furthermore, a volume phase hologram layer (3
0) should be good. Specifically, urethane acrylate oligomers (for example, M-1100, M-1200, M-1600 manufactured by Toa Gosei Chemical Co., Ltd.)
Or a polyester acrylate oligomer (for example, M-6100, M-6200, manufactured by Toa Gosei Chemical Co., Ltd.)
M-7100, M-8300) were diluted with various low-viscosity acrylic monomers and the viscosity was adjusted.
Hydroxycyclohexyl phenyl ketone, (1-6
η-cumene) (η-cyclopentadienoyl) iron hexafluorophosphate, 2,2′-dimethoxy-2-
The one to which phenylacetophenone or the like is added is used.

As the adhesive (50) used in the hologram display element of the present invention, a liquid-type adhesive or a sheet-tape-like film-type adhesive which is cured by irradiation with actinic radiation may be used. Particularly, in order to perform transfer lamination without any unevenness, it is preferable to cure with actinic radiation. The colorless and transparent substrate (40) and the hologram recording material layer (30) are bonded together, and at the same time, both are cured before curing. It is necessary not to dissolve or swell,
The adhesive before curing has a viscosity of 10 to 100 in order to make it difficult for air bubbles to enter when bonding the colorless and transparent substrate (40).
A range of 0 cps is desirable. Further, it is desirable that the refractive index of the adhesive (50) after curing is close to both.

Specifically, for example, Optomer KR40
0, BYK304 (UV curable epoxy resin, manufactured by Asahi Denka Co., Ltd.), Hard Rock UC-3000, OP-6040,
OP-1045K (UV curable polyene / polythiol type, manufactured by Denki Kagaku Kogyo Co., Ltd.) and OP-3010P (UV curable acrylic type, manufactured by Denki Kagaku Kogyo Co., Ltd.) are not limited thereto. In addition to the above-mentioned commercial products, urethane acrylate oligomers (for example, manufactured by Toa Gosei Chemical Co., Ltd.,
M-1100, M-1200, M-1600 etc.), polyester acrylate oligomer (for example, M-6100, M-6200, M-7100, M-7100, manufactured by Toa Gosei Chemical Co., Ltd.)
-8300) or epoxy acrylate (e.g.,
Showa Polymer Co., Ltd.'s Lipoxy VR60, VR90) was diluted with various low-viscosity acrylic monomers to adjust the viscosity, and 1-hydroxycyclohexyl phenyl ketone, (1-6-η-cumene) (η-cyclopentadiene) was used as an initiator. Noyl) iron hexafluorophosphate, 2,2′-dimethoxy-2-phenylacetophenone, and the like.

As the above film-type adhesive, another colorless and transparent base material (40) is adhered to the hologram recording material layer (30), and at the same time, the film-type adhesive is used for the hologram display element (1). You need transparency,
Furthermore, since it is desired that there is no birefringence, a film type adhesive having no base material is desirable. Also, it is desirable that the refractive index be close to both.

Specifically, HJ-9150W, HJ-3
160 W (transparent, weather-resistant, heat-resistant double-sided tape, manufactured by Nitto Denko Corporation) and UT (ecology-type double-sided tape, manufactured by Sony Chemical Corporation), but are not limited thereto. Further, in order to improve the adhesion between the hologram recording material layer (30) and the other colorless and transparent substrate (40),
Various substances are applied to the surface of another colorless and transparent substrate (40),
Those subjected to easy adhesion treatment by vapor deposition, corona treatment or the like can also be used.

Other colorless transparent substrates (40) that can be formed (including cut) into any shape used in the hologram display element (1) of the present invention include quartz glass, blue plate glass, and the like.
In addition to polyethylene terephthalate resin, polymethyl methacrylate resin, polycarbonate resin, cellulose triacetate (TAC) resin, polypropylene resin and polyethylene resin, polymethylpentene resin or the 5th Polymer Material Forum Abstracts, p. 35 (1996), but not limited thereto. Also,
Various substrates can be arbitrarily used according to the use of the hologram display element.

[0034]

Next, the present invention will be described in detail with reference to examples. <Example 1> Bisphenol epoxy resin epicoat 1007 (degree of polymerization n = 10.8, epoxy equivalent: 175)
0-2100, Yuka Shell Epoxy Co., Ltd.) 100
Parts by weight, 50 parts by weight of triethylene glycol diacrylate and 5 parts by weight of 4,4'-bis (tert-butylphenyl) iodonium hexafluorophosphate, 3,3'-carbonylbis (7-diethylamino)
0.5 parts by weight of coumarin was mixed and dissolved in 100 parts by weight of 2-butanone to prepare a photosensitive solution for the hologram recording material layer (30).

On the other hand, a film substrate (1
0) as a 100 μm-thick polyethylene terephthalate film (Melinex 708, ICI
Japan Co., Ltd.), urethane acrylate oligomer M
1200 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 100 parts by weight of neopentyl glycol diacrylate (NPGD
A) A solution prepared by mixing and dissolving 100 parts by weight (manufactured by Nippon Kayaku Co., Ltd.) and 10 parts by weight of Irgacure 184 (manufactured by Ciba Geigy) in 100 parts by weight of methanol was used to prepare a solution 3 to 3 using a bar coater # 6. After coating with a thickness of 6 μm, the coating was dried in an oven set at 80 ° C. for 10 minutes, and cured with a UV irradiation device (a conveyor type ultraviolet curing device manufactured by Eye Graphics Co., Ltd., a high-pressure mercury lamp, 1 J / cm ² ) and irradiated with ultraviolet light. A cured resin layer (20) was produced.

Subsequently, the photosensitive liquid for the hologram recording material layer (30) obtained above is applied on the ultraviolet curable resin layer (20) with a bar coater # 40 so as to have a film thickness of about 20 μm. Hologram recording material layer (30)
Was given.

The coated surface of the hologram recording material layer (30) was applied to a hologram master for producing a transmission hologram recorded and produced on a silver halide photosensitive material (67) using an optical system as shown in FIG. A hologram was prepared by exposing from the hologram master surface with light spread with an argon laser (514.5 nm) using a lens as a light source, then heated at 80 ° C. for 10 minutes, and further heated with a high-pressure mercury lamp. Established by irradiating the entire surface,
A volume phase transmission hologram was obtained.

HJ-3160W (50 μm thick, transparent, weather-resistant, heat-resistant double-sided tape, manufactured by Nitto Denko Corporation) is evenly attached to the hologram prepared on the ultraviolet curable resin layer (20) using a laminator. After peeling off the cover film on the back side of the adhesive film, place a soda lime glass (1.1 mm thick, 5 inch square, untreated surface) as another colorless transparent substrate (40), and paste it with a laminator. That is, after the transfer, the film substrate (10) made of a synthetic resin was peeled off to obtain a hologram display element.

In the hologram display element obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 2 The neopentyl glycol diacrylate in the ultraviolet curable resin layer (20) of Example 1 was changed to trimethylolpropane triacrylate (TMPTA) (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). Except for the above, a hologram display element was obtained using the same materials and operations as in Example 1.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 3 Neopentyl glycol diacrylate in the ultraviolet curable resin layer (20) of Example 1 was replaced with dipentaerythritol hexaacrylate (DPHA) (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.).
A hologram display element was obtained by using the same materials and operations as in Example 1 except for the above.

In the hologram display element obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 4 A cellulose triacetate film (100 μm
A hologram display element was obtained by the same material and operation as in Example 1 except that the thickness and the thickness were made by Lonza TAC, manufactured by Lonza.

In the hologram display device obtained above, the adhesiveness between the film base (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 5 A cellulose triacetate film (100 μm
Thickness, Lonza TAC, manufactured by Lonza Co., Ltd.), and a hologram display element was obtained using the same materials and operation as in Example 2.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 6 A cellulose triacetate film (100 μm
Thickness, Lonza TAC, manufactured by Lonza Co., Ltd.), and a hologram display element was obtained using the same materials and operation as in Example 3.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 7 Urethane acrylate oligomer M1 in the ultraviolet-curable resin layer (20) of Example 1
200 is a polyester acrylate oligomer M-6
A hologram display element was obtained by using the same materials and operation as in Example 1 except that 100 (manufactured by Toa Gosei Chemical Co., Ltd.) was used.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 8 The urethane acrylate oligomer M1 in the ultraviolet curable resin layer (20) of Example 2
200 is a polyester acrylate oligomer M-6
A hologram display element was obtained by using the same materials and operations as in Example 2 except that 100 (manufactured by Toa Gosei Chemical Co., Ltd.) was used.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 9 The urethane acrylate oligomer M1 in the ultraviolet curable resin layer (20) of Example 3
200 is a polyester acrylate oligomer M-6
A hologram display element was obtained by using the same materials and operations as in Example 3 except that 100 (manufactured by Toa Gosei Chemical Co., Ltd.) was used.

In the hologram display element obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 10 Polyvinyl acetate (molecular weight: 1)
67000, manufactured by Aldrich) 100 parts by weight, phenoxyethyl acrylate (Biscoat # 192, manufactured by Osaka Organic Chemical Industry) 90 parts by weight, and diphenyliodonium hexafluorophosphate 5 parts by weight, 3,3 ′
-Carbonylbis (7-diethylamino) coumarin 0.1.
A hologram display element was obtained by the same materials and operation as in Example 1, except that 5 parts by weight of 2-butanone was mixed and dissolved in 100 parts by weight of the photosensitive liquid for the hologram recording material layer (30).

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

<Example 11> A hologram display element was obtained by using the same material and operation as in Example 2 except that a photosensitive liquid for a hologram recording material layer (30) was used as in Example 10 described above.

In the hologram display device obtained above, the adhesiveness between the film base (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

<Example 12> A hologram display element was obtained by using the same materials and operations as in Example 3 except that the photosensitive liquid for the hologram recording material layer (30) was the same as that in Example 10.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 13 Other Colorless and Transparent Substrate (40)
To a cellulose triacetate film (100 μm thick, Lonza T
A hologram display element was obtained by using the same materials and operations as in Example 1 except that the hologram display element was manufactured by AC (Lonza).

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 14 Other colorless and transparent base material (40)
To a cellulose triacetate film (100 μm thick, Lonza T
A hologram display element was obtained by using the same materials and operations as in Example 2 except that the hologram display element was manufactured by AC, Lonza.

In the hologram display device obtained above, the adhesiveness between the film substrate (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Example 15 Other Colorless and Transparent Substrate (40)
To a cellulose triacetate film (100 μm thick, Lonza T
A hologram display element was obtained by using the same materials and operations as in Example 3 except that the hologram display element was manufactured by AC, Lonza.

In the hologram display device obtained above, the adhesiveness between the film base (10) made of synthetic resin and the ultraviolet curable resin layer (20) is strong, and the hologram recording material layer (30) It could be easily peeled off at the interface of the ultraviolet curable resin layer (20). Further, the surface properties of the hologram display element obtained by peeling were also good.

Comparative Example 1 A 100 μm-thick polyethylene terephthalate film (Melinex 708, ICC) was used as a film substrate (10) made of a synthetic resin.
UV curable resin layer (2 on I Japan Co., Ltd.)
A hologram optical element was manufactured using the same materials and operations as in Example 1 without providing 0).

The hologram display device obtained above has a strong adhesion between the film substrate (10) made of synthetic resin and the hologram recording material layer (30). The hologram display element cannot be peeled off between the material (10) and the hologram recording material layer (30), but peels off between the hologram recording material layer (30) and the adhesive (50). I couldn't do that.

<Comparative Example 2> The film substrate (1
0) polyethylene terephthalate film as
100 μm-thick cellulose triacetate film (Lonza T
A hologram display element was manufactured using the same materials and operation as in Comparative Example 1 except that the hologram display element was manufactured by AC, Lonza.

The hologram display device obtained above has a strong adhesiveness between the film base (10) made of synthetic resin and the hologram recording material layer (30), so that the hologram display element made of synthetic resin can be used. The hologram display element cannot be peeled off between the material (10) and the hologram recording material layer (30), but peels off between the hologram recording material layer (30) and the adhesive (50). I couldn't do that.

<Comparative Example 3> The film base material (1
0) polyethylene terephthalate film as
A hologram display element was produced using the same materials and operations as in Comparative Example 1, except that a 100 μm-thick polymethyl methacrylate film (Acryprene, manufactured by Mitsubishi Rayon Co., Ltd.) was used.

The hologram display element obtained above has a strong adhesiveness between the film base (10) made of synthetic resin and the hologram recording material layer (30). The hologram display element cannot be peeled off between the material (10) and the hologram recording material layer (30), but peels off between the hologram recording material layer (30) and the adhesive (50). I couldn't do that.

<Comparative Example 4> The film substrate (1
0) polyethylene terephthalate film as
A hologram display element was manufactured using the same materials and operations as in Comparative Example 1, except that a 100 μm-thick polycarbonate film (Iupilon film, manufactured by Mitsubishi Engineering-Plastics Corporation) was used.

The hologram display device obtained above has a strong adhesion between the film base (10) made of synthetic resin and the hologram recording material layer (30), so that the hologram display element made of synthetic resin can be used. The hologram display element cannot be peeled off between the material (10) and the hologram recording material layer (30), but peels off between the hologram recording material layer (30) and the adhesive (50). I couldn't do that.

[0076]

As described above, the present invention has the following effects. That is, an ultraviolet curable resin layer obtained by curing an ultraviolet curable resin is provided on a film base made of a synthetic resin, a hologram recording material layer capable of producing a hologram is provided on the ultraviolet curable resin layer, and the hologram recording material layer is provided on the hologram recording material layer. A hologram display element produced by producing a hologram is transferred onto another colorless and transparent base material via a transparent adhesive applied to the hologram recording material layer on which the hologram is produced, and the ultraviolet-curable resin layer and In a hologram display element peeled off at the interface with the hologram recording material layer, a hologram display element superior in productivity is formed by using a film base made of a synthetic resin as a base, preferably a web-like film. Can be.

Further, by providing an ultraviolet curable resin layer on a film substrate made of a synthetic resin and providing a hologram recording material layer thereon, peeling at the interface of the hologram recording material layer, that is, molding into an arbitrary shape is possible. This facilitates transfer to other colorless and transparent substrates.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a hologram display element according to an embodiment of the present invention in a side cross section before transfer.

FIG. 2 is an explanatory view showing a hologram display element after transfer according to an embodiment of the present invention in a side cross section.

FIG. 3 is an explanatory diagram showing an optical system for producing a hologram master for duplicating a hologram display element according to an embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 1 hologram display element 10 film base made of synthetic resin 20 ultraviolet curable resin layer 30 hologram recording material layer 40 other colorless and transparent base material 50 adhesive 60 laser 61 ‥ Laser beam 62 ‥‥ Mirror 63 ‥‥ Half mirror 64 ‥‥ Objective lens 65 ‥‥ Spatial filter 66 ‥‥ Lens 67 ‥‥ Silver halide photosensitive material

Claims (4)

[Claims] An ultraviolet curable resin layer obtained by curing an ultraviolet curable resin is provided on a film substrate made of a synthetic resin, and a hologram recording material layer capable of producing a hologram is provided on the ultraviolet curable resin layer. A hologram display element obtained by forming a hologram on the material layer is transferred onto another colorless and transparent base material via a transparent adhesive formed on the hologram recording material layer, and the hologram recording is performed with the ultraviolet curable resin layer. A hologram display device, which is separated at an interface with a material layer. 2. A film base comprising a synthetic resin, comprising a polyethylene terephthalate resin, a polymethyl methacrylate resin, a polycarbonate resin, a cellulose triacetate resin, a polypropylene resin, or a polyethylene resin. The hologram display device according to any one of the preceding claims. 3. The hologram display device according to claim 1, wherein said ultraviolet-curable resin layer comprises a urethane acrylate oligomer or a polyester acrylate oligomer, a low-viscosity acrylic monomer, and a photoinitiator. 4. The colorless and transparent substrate is made of any one of acrylic resin, polycarbonate resin, cellulose triacetate resin, amorphous polyolefin resin, quartz, and glass. The hologram display device according to any one of the preceding claims.