JPH11338337A - Hologram optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram optical element having high resolution and high diffraction efficiency, excellent transparency, reproducing wavelength reproducibility and preservable stability and is further excellent chemical resistance and scratching resistance. SOLUTION: This hologram optical element 1 is formed by providing the surface of a base material 10 with a hologram layer 20, bonding the surface of a chemical reaction type adhesive layer 30, which is formed by applying a colorless and transparent chemical reaction type adhesive having a visible light transmittance of >=80% and a thickness of 1 to 100 μm to a film, onto the front surface 20a of this layer and curing and peeling the hologram layer at the boundary between this chemical reaction type adhesive layer 30 and the film. The chemical reaction type adhesive layer 30 is formed by curing the adhesive by irradiation with UV rays or by adding a hardener or catalyst to this chemical reaction type adhesive and curing the adhesive by heating.

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 protective layer of 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. JP-A-8-1676 and JP-A-8-1676 disclose a hologram recording material comprising a thermosetting resin having at least one ethylene oxide ring in a structural unit and a radically polymerizable ethylenic monomer.
No. 1677, Japanese Unexamined Patent Application Publication No.
No. -1679.

[0006]

However, a hologram made of the above recording material has a thickness of 10 to 4 mm.
It is in the form of a film having a thickness of about 0 μm, and when used as an optical element, it needs to be attached to a smooth substrate. Furthermore, when producing a hologram with a film-like recording material, the reproduced image is likely to be blurred from the viewpoint of undulation and smoothness of the film,
In particular, when used for a HUD combiner or the like, the reproduced image is separated from the viewpoint to some extent, so that the blur is easily noticeable.
Furthermore, since the light from the light source is reflected on the hologram or the base material, it becomes very difficult to see unless the specular reflection component is removed. It was a mess.

From the above, when producing a hologram, a substrate having a smooth surface, having no birefringence, and being not affected by the solvent of the photosensitive liquid is required. No. However, it is difficult to form a hologram made of a glass substrate into an arbitrary shape. Therefore, it is conceivable to transfer a hologram made of a glass substrate to another substrate, but the hologram optical element obtained by peeling off the glass substrate after transferring to another substrate also has a hologram in the outermost layer. However, when it does not have chemical resistance and scratch resistance, there is a problem in its chemical resistance and scratch resistance.

The present invention has been made to solve the above-mentioned problems of the prior art.
It is an object of the present invention to provide a hologram optical element having high diffraction efficiency, excellent transparency, reproduction wavelength reproducibility, excellent storage stability, and excellent chemical resistance and scratch resistance by using a volume phase hologram having less chromatic aberration. .

[0009]

In order to achieve the above object, the present invention first provides a hologram layer on a base material and a thickness of 1 to 100 μm on the layer surface.
m, a colorless and transparent chemical reaction type adhesive having a visible light transmittance of 80% or more is applied to the film, and the surface of the chemical reaction type adhesive layer is bonded and cured, and the interface between the chemical reaction type adhesive layer and the film is cured. The hologram optical element is characterized in that the hologram optical element is separated from the hologram optical element.

According to a second aspect of the present invention, there is provided the hologram optical element according to the first aspect, wherein the chemically reactive adhesive layer is cured by ultraviolet irradiation.

In the invention according to claim 3, the chemical reaction type adhesive layer is formed by heating and curing a material obtained by adding a curing agent or a catalyst to the chemical reaction type adhesive. A hologram display device according to item 1.

According to a fourth aspect of the present invention, there is provided the hologram optical element according to the first, second or third aspect, wherein a release layer is formed on the surface of the film on which the chemically reactive adhesive is applied. It is.

According to a fifth aspect of the present invention, in the hologram optical element according to the fourth aspect, the release layer contains a silicone resin as a main component.

Further, in the invention according to claim 6, the chemical reaction type adhesive layer contains trimethylolpropane triacrylate or dipentaerythritol hexaacrylate. Or a hologram optical element described in 3.

Further, in the invention according to claim 7, the hologram layer comprises a thermosetting resin having at least one solvent-soluble and cationically polymerizable ethylene oxide ring in a structural unit; a radically polymerizable ethylenic monomer; 2. The hologram recording material according to claim 1, wherein the hologram recording material is made of a photoinitiator system that activates radical polymerization and cationic polymerization when exposed to actinic radiation, and a sensitizing dye that sensitizes the photoinitiator. This is a hologram display element.

[0016]

Embodiments of the present invention will be described below with reference to the drawings. In the hologram optical element of the present invention, the invention according to claim 1 includes a substrate (1) as shown in FIG.
2) A hologram layer (20) is provided on the hologram layer (20), and a colorless and transparent chemical reaction having a thickness of 1 to 100 μm and a visible light transmittance of 80% or more is formed on the surface (20a) of the hologram layer (20) as shown in FIG. Although the adhesive layer (30) is applied on the film (40), the surface (30a) of the adhesive layer is bonded and cured, and the adhesive layer (30) and the film (40) are bonded together. 1 peeled off at the interface (40a)
Is a hologram optical element (1) shown in FIG.

The invention according to claim 2 is the one in which the chemically reactive adhesive layer (30) shown in FIG. 2 is cured by irradiation with ultraviolet rays, and the invention according to claim 3 is as shown in FIG. The chemical reaction type adhesive layer (30) is obtained by heating and curing a material obtained by adding a curing agent or a catalyst to the chemical reaction type adhesive.

According to a fourth aspect of the present invention, as shown in FIG. 3, a release layer (50) is applied to a surface (40b) of the film (40) on which a chemically reactive adhesive is applied. The invention according to claim 5 is directed to the release layer (50) shown in FIG.
Are those having a silicone resin as a main component.

According to a sixth aspect of the present invention, the chemically reactive adhesive layer (30) shown in FIGS. 1, 2 and 3 contains trimethylolpropane triacrylate or dipentaerythritol hexaacylate. It becomes.

Further, the hologram layer (20) shown in FIG. 1 is characterized in that the hologram layer (20) shown in FIG. A holographic recording material made of a possible ethylenic monomer, a photoinitiator system that activates radical and cationic polymerization when exposed to actinic radiation, and a sensitizing dye that sensitizes the photoinitiator. .

The above-mentioned chemical reaction type adhesive layer (30)
The hologram optical element (1) laminated on the hologram layer (20) has high resolution, high diffraction efficiency, transparency,
Excellent reproduction wavelength reproducibility, storage stability, chemical resistance,
Excellent scratch resistance can be obtained.

Hereinafter, embodiments of the hologram display device of the present invention will be described in more detail including the materials used.

The chemically reactive adhesive layer (30) used in the hologram optical element (1) of the present invention is cured by actinic radiation, has a thickness of 1 to 100 μm, and has a visible light transmittance of 80 μm.
% Or more, it is necessary to adhere to the surface of the hologram layer (20), not to dissolve or swell both before curing, and to apply to the hologram layer after applying to the film (40) base material. It is desirable that the chemically reactive adhesive before curing has tackiness, so that it does not shift at the time of alignment and air bubbles hardly enter. After curing, it is desirable that the material be hard.

When the thickness of the chemically reactive adhesive layer (30) is less than 1 μm, chemical resistance and abrasion resistance are inferior, and when it exceeds 100 μm, the required light transmittance cannot be obtained, so that it is used. The number of chemically reactive adhesives increases more than necessary, which is uneconomical and requires a lot of energy for curing and the like.

As the chemical reaction type adhesive for forming the above-mentioned chemical reaction type adhesive layer (30), an ultraviolet curing type, an electron beam curing type, and a thermosetting type adhesive may be mentioned. A thermosetting adhesive is desirable.

As the ultraviolet curable adhesive, there is an adhesive obtained by adding a photoinitiator to an acrylic oligomer diluted with a low-viscosity acrylic monomer. In addition, an epoxy resin diluted with an acrylic monomer, an initiator for activating radical polymerization and cationic polymerization is added to the diluted epoxy resin, and an adhesive made of only the cationically polymerizable substance using the initiator. But it doesn't matter.

Specifically, for example, urethane acrylate oligomers M-1100, M-1200 and M-1600
(Manufactured by Toa Gosei Chemical Co., Ltd.), polyester acrylate oligomers M-6100, M-6200, M-7100, M
-8300 (manufactured by Toa Gosei Chemical Co., Ltd.) or epoxy acrylate Lipoxy VR-60, VR-90 (manufactured by Showa Polymer Co., Ltd.) diluted with various low-viscosity acrylic monomers to adjust the viscosity, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-
2-phenylacetophenone, (1-6-η-cumene)
(Η-cyclopentadienoyl) iron hexafluorophosphate and the like are added.

Further, a so-called epoxy resin, which is a condensate of a bisphenol and epichlorohydrin, is added to a so-called epoxy resin, supervised by Shozaburo Yamaguchi, encyclopedia of adhesion and adhesion (Asakura Shoten).
p. In addition to the thermosetting composition to which the curing agent described in 99 is added, a colorless and transparent composition having a visible light transmittance of 80% or more of a phenol resin or the like may be used.

As described above, these components are appropriately selected and mixed at an arbitrary ratio, and the chemically reactive adhesive obtained is mixed with a known adhesive such as a bar coater, an applicator, a doctor blade, a roll coater, a die coater, a comma coater or the like. The film (40) is applied to the substrate by using a coating means. When the chemical reaction type adhesive is applied, the adhesive may be diluted with an appropriate solvent if necessary.
0) After coating on top, drying is required. Examples of the solvent include dichloromethane, chloroform, acetone, 2-butanone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate,
Butoxyethyl acetate, 2-methoxyethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy)
Examples include ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, tetrahydrofuran, and 1,4-dioxane. After drying, it is wound up through a cover film. After laminating the film with the adhesive layer on the hologram layer (20) and curing it according to various prescriptions, the film (4)
Separate only 0) and provide a protective layer

Further, in order to improve the releasability at the interface (40a) between the chemical reaction type adhesive layer (30) and the film (40), the film (40) and the chemical reaction type adhesive layer (30) are removed. It is also possible to use a material in which a variety of substances are applied in between to improve the releasability by coating, vapor deposition, corona treatment, or the like.
In particular, it is preferable that the release layer (50) is formed by applying and curing an ultraviolet or thermosetting silicone compound. Specifically, silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., KNS316,
KNS320A (solvent-free thermosetting type, curing agent; CAT-P
L-56), X62-7574 (solvent-free ultraviolet curing type), KS847H, KS776A, KS776L, K
S778, KS385 (solvent thermosetting type, curing agent; CAT
-PL-56), KS5508 (solvent thermal ultraviolet curing type,
Curing agent; CAT-PL-5000) and the like, but not limited thereto. By providing the release layer (50) between the film (40) and the chemically reactive adhesive layer (30), a separator is not required when applying the chemically reactive adhesive to the film (40). Furthermore, since the unreacted low-molecular silicone slightly migrates to the coated surface when the film is wound up, there is a tendency that the peelability of the cured adhesive is improved.

The hologram used in the present invention is a reflection type hologram called a Lippmann hologram which is a volume phase type hologram and a transmission type 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.
When used as a display element, heat resistance, moisture resistance,
It is necessary to have environmental resistance characteristics such as light resistance, and holograms produced by wet development by forming voids with relatively high diffraction efficiency often do not satisfy specifications.
It is desirable to use a hologram obtained by dry processing without any voids in the hologram layer.

The hologram layer (20) used in the present invention may be made of 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, for example, a thermosetting resin having at least one solvent-soluble and cationically polymerizable ethylene oxide ring in a structural unit (component (A)), a radically polymerizable ethylenic monomer (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)) A hologram produced from a hologram recording material made of, but not limited to, the following.

The thermosetting resin having at least one ethylene oxide ring in the structural unit which is a solvent-soluble and cationically polymerizable component (A) is a compound represented by the following general formula:

Embedded image (Where n = 1 to 20)

Or a general formula

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

Or the 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) is a monomer having at least one ethylenically unsaturated bond in its structural unit, and 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 actinic radiation which is the above-mentioned 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 the 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 the 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.

The photosensitive solution obtained by appropriately selecting these components and mixing them in an arbitrary ratio 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. Is applied to the substrate (10) using 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, 2-methoxy Ethyl 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 layer (20).

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 base material (10) used in the hologram optical element (1) of the present invention may be quartz glass, blue plate glass, polycarbonate plate, acrylic plate, cellulose triacetate (TAC) plate, polymethylpentene resin or the like. ,
Abstracts of 5th Polymer Material Forum Lectures, p. 35
(1966), but not limited thereto. Also, the substrate (10) and the hologram layer (20) may be formed by directly providing a photosensitive layer on the substrate as described above, and then forming a hologram.
After the hologram is formed, the hologram may be replaced with the base material (10).

The hologram optical element (1) of the present invention as described above can be a hologram optical element (1) formed in various shapes, has no image blur, distortion, etc., and has chemical resistance and scratch resistance. Excellent in properties.

[0045]

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 layer (20).

The photosensitive solution obtained above was mixed with blue plate glass (1.
A 1 mm thick, 5 inch square, SiO ₂ surface-treated product) was applied with a doctor blade so as to have a film thickness of about 30 μm, and dried to produce a hologram recording material layer for forming a hologram layer (20).

The hologram recording material layer was coated on the silver halide photosensitive material (67) by a laser beam (61) from a laser (60) using an optical system as shown in FIG.
A hologram is prepared by exposing the hologram master recorded on the hologram master, which is in contact with the hologram master while being immersed in isooctane, with a laser beam of 514.5 nm as a light source from a substrate surface with light spread using a lens. , 80
After heating at 10 ° C. for 10 minutes, the entire surface of the hologram recording medium was irradiated with a high-pressure mercury lamp to fix the hologram recording medium, thereby obtaining a volume phase hologram.

The diffraction efficiency of the obtained volume phase hologram was measured with a spectrophotometer manufactured by Shimadzu Corporation. The transmittance obtained by subtracting the minimum value from the baseline of the absorption peak detected by the apparatus was defined as the diffraction efficiency. Further, the surface reflectance was relatively evaluated based on the transmittance of the hologram optical element at the baseline in the visible region.

Subsequently, an epoxy acrylate lipoxy V was applied to the surface of the hologram layer (20) prepared on the blue plate glass.
100 parts by weight of R60 (manufactured by Showa Polymer Co., Ltd.), 100 parts by weight of 2-hydroxyethyl acrylate HEA (manufactured by Osaka Organic Chemical Industry), 100 parts by weight of Aronix M120 (manufactured by Toa Gosei Chemical Co., Ltd.), and Kayarad TMPTA (Nippon Kayaku) A solution obtained by adding 9 parts by weight of Irgacure 184 (manufactured by Ciba Geigy) to 100 parts by weight of Melinex S (100) as a film (40).
(PET film, manufactured by ICI Co., Ltd.) and dried to form a chemically reactive adhesive layer (30), and this surface was laminated. UV irradiation device (HMW-848- manufactured by Oak Co., Ltd.)
2. After irradiation with high pressure mercury lamp, 500mJ / cm ² ), PE
Only the T film (40) was peeled off to obtain a hologram optical element (1).

The obtained hologram optical element (1) has a diffraction efficiency of 80% (half-width of the reproduction light peak: 20 nm).
90% baseline transmission at 400-600 nm
Is not affected by blurring of the image.
Even when the surface was rubbed with a cloth impregnated with toluene and acetone, the surface was not damaged and the hologram was unchanged.

Example 2 Kayarad TMPTA of the chemically reactive adhesive layer (30) used in Example 1 above
A hologram optical element (1) was obtained by the same materials and operations as in Example 1 except that Kayarad DPHA (manufactured by Nippon Kayaku) was used instead of Nippon Kayaku (manufactured by Nippon Kayaku).

The obtained hologram optical element (1) was not damaged even when its surface was rubbed with a cloth containing ethanol, toluene and acetone, and the hologram was unchanged.

Example 3 Chemical reaction type adhesive layer (30)
50 parts by weight of Epicoat 1007 (trade name, manufactured by Yuka Shell Co., Ltd.) and 50 parts by weight of epoxy acrylate Lipoxy VR60 (trade name, manufactured by Showa Polymer Co., Ltd.)
100 parts by weight of 2-hydroxyethyl acrylate HEA (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M1
20 (100 parts by weight, manufactured by Toa Gosei Chemical Co., Ltd.) and 100 parts by weight of Kayarad TMPTA (trade name, manufactured by Nippon Kayaku Co., Ltd.) dissolved in 100 parts by weight, and 9 parts by weight of Irgacure 184 (trade name, manufactured by Ciba Geigy) 4,4'-bis (ter
A hologram optical element (1) was obtained in the same manner as in Example 1, except that 0.5 parts by weight of (t-butylphenyl) iodonium hexafluorophosphate (synthetic product) was added.

The obtained hologram optical element (1) was not damaged even when its surface was rubbed with a cloth containing ethanol, toluene and acetone, and the hologram was unchanged.

Example 4 Chemical reaction type adhesive layer (30)
25 parts by weight of 4,4′-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 parts by weight of Epicoat 1001 (Yuka Kabushiki Kaisha, trade name) dissolved in 50 parts by weight of methyl ethyl ketone. And Melinex S (100 μm thick PET) as the film (40)
A film, manufactured by ICI, trade name) and dried.
The surface of the chemically reactive adhesive layer (30) was laminated on the surface of the hologram layer (20) produced in the same manner as in Example 1. 10
After heating in an oven at 0 ° C. for 1 hour to cure the adhesive, the PET film (40) was peeled off to obtain a hologram optical element (1).

The obtained hologram optical element (1) has a diffraction efficiency of 75% (half-width of the reproduction light peak: 18 nm).
89% baseline transmission at 400-600 nm
Is not affected by blurring of the image.
Even when the surface was rubbed with a cloth impregnated with toluene and acetone, the surface was not damaged and the hologram was unchanged.

Comparative Example 1 Chemical Reaction Type Adhesive Layer (30)
A hologram optical element having a hologram layer (20) formed on a soda lime glass by the same operation as in Example 1 except that no hologram layer was formed.

The surface of the obtained hologram optical element having no chemical reaction type adhesive layer was rubbed with a cloth containing ethanol, toluene and acetone.
0) The surface was scratched and the reproduction light changed from yellow to red. Over time, the color of the reproduction light approached its original color, but traces of solvent stains remained.

[0059]

As described above, the present invention has the following effects. That is, a hologram layer is provided on a substrate, and the layer surface (10a) has a thickness of 1 to 100 μm.
m, a surface (30a) of a chemically reactive adhesive layer (30) in which a colorless and transparent chemically reactive adhesive having a visible light transmittance of 80% or more is applied on a film (40), and is cured.
A hologram optical element peeled off at the interface (40a) between the chemically reactive adhesive layer (30) and the film (40), wherein the chemically reactive adhesive layer (30) is cured by irradiation with ultraviolet light, or The said chemical reaction type adhesive layer (30),
Since the one obtained by adding a curing agent or a catalyst to the above-mentioned chemical reaction type adhesive is cured by heating, the obtained hologram optical element has excellent diffraction efficiency, transparency, chemical resistance, and scratch resistance. Can have a property.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a hologram optical element according to an embodiment of the present invention in a side cross section.

FIG. 2 is an explanatory view showing a transfer body for transferring a chemically reactive adhesive layer for obtaining a hologram optical element according to an embodiment of the present invention in a side cross section.

FIG. 3 is an explanatory view showing, in a side cross section, another transfer body for transferring a chemically reactive adhesive layer for obtaining a hologram optical element according to an embodiment of the present invention.

FIG. 4 is a schematic diagram showing an optical system for producing a hologram master for replicating a hologram optical element according to an embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 1 hologram optical element 10 base material 20 hologram layer 20a hologram layer surface 30 chemical reaction adhesive layer 30a chemical reaction adhesive layer surface 40 film 40a Interface between chemical reaction type adhesive layer and film 40b {chemical reaction type adhesive coating surface of film 50} release layer 60 laser 61 laser beam 62 mirror 63 half mirror 64 objective lens 65 ‥‥ Spatial filter 66 ‥‥ Lens 67 ‥‥ Silver halide photosensitive material

Claims (7)

[Claims] A hologram layer is provided on a base material, and a colorless and transparent chemically reactive adhesive having a thickness of 1 to 100 μm and a visible light transmittance of 80% or more is coated on a film on the surface of the hologram layer. A hologram optical element, wherein the hologram optical element is obtained by bonding and curing the surfaces of an agent layer and peeling off at the interface between the chemically reactive adhesive layer and the film. 2. The hologram optical element according to claim 1, wherein said chemically reactive adhesive layer is cured by irradiation with ultraviolet rays. 3. The hologram display element according to claim 1, wherein the chemically reactive adhesive layer is formed by heating a material obtained by adding a curing agent or a catalyst to the chemical reactive adhesive. 4. The film according to claim 1, wherein a release layer is formed on the surface of the film to which the chemically reactive adhesive is applied.
Or the hologram optical element according to 3. 5. The hologram optical element according to claim 4, wherein the release layer contains a silicone resin as a main component. 6. The hologram optical element according to claim 1, wherein said chemically reactive adhesive layer contains trimethylolpropane triacrylate or dipentaerythritol hexaacrylate. . 7. A hologram layer comprising: a thermosetting resin having at least one solvent-soluble and cationically polymerizable ethylene oxide ring in a structural unit; a radically polymerizable ethylenic monomer; and radical polymerization upon exposure to actinic radiation. And a photoinitiator system to activate cationic polymerization,
2. The hologram display element according to claim 1, wherein the hologram display element is made of a hologram recording material comprising a sensitizing dye for sensitizing a photoinitiator.