JPH11338336A - Hologram optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram optical element which is excellent in resolution, diffraction efficiency, transparency and preservable stability and is further excellent in chemical resistance and scratching resistance. SOLUTION: This element 1 is formed by providing the surface of a base material 10 with a hologram layer 20 and laminating a compsn. contg. silicone which has a visible light transmittance of >=80% and a thickness of <=100 μm and is monofunctional or bifunctional in functional unit as a silicone compsn. layer 30. The silicone compsn. layer 30 may also be formed of the silicone compsn. which is cured by addition of a hardener or catalyst and by heating or the silicons compsn. which consists of silicone having at least one among an acryl group, mercapto group, unsatd. double bonds and epoxy group and a photopolymn. initiator and is cured by irradiation with UV light or the compsn. which contains the silicone having the acryl group and is cured by irradiation with electronic beams.

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, when the hologram is formed, the hologram is present in the outermost layer, so that a problem remains if the hologram is not provided with chemical resistance, scratch resistance and the like. Further, the hologram made of such a recording material is in the form of a film having a thickness of about 10 to 40 μm, and when used as an optical element, it was necessary to attach it to a smooth base material. Further, when a hologram is produced from a film-like recording material, a reproduced image is likely to be blurred from the viewpoint of undulation and smoothness of the film. , Blur becomes more 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 display element obtained by peeling off the glass substrate after transferring to another substrate also has a hologram in the outermost layer. However, there is a problem in the case where it does not have chemical resistance, scratch resistance and the like. Further, the substrate to be transferred needs to be transparent, it is necessary to adhere the hologram while maintaining the transparency, and it is necessary to prevent the hologram from being attacked by the adhesive. In many cases, the adhesiveness of the hologram is not sufficient.

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

[0009]

In order to achieve the above object, according to the first aspect of the present invention, a hologram layer is provided on a base material, and a hologram layer is provided thereon with a visible light transmittance of 80% or more. Monofunctional or 2 functional units with a thickness of 1 to 100 μm
A hologram optical element characterized by being laminated with a composition containing a functional silicone.

According to a second aspect of the present invention, there is provided a hologram optical element according to the first aspect, wherein a curing agent or a catalyst is added to the composition containing silicone and the composition is cured by heating. It is.

Further, in the invention according to claim 3, the composition containing the silicone comprises a silicone having at least one of an acrylic group, a mercapto group, an unsaturated double bond and an epoxy group, and a photopolymerization initiator. The hologram optical element according to claim 1, wherein the hologram optical element is cured by irradiation with ultraviolet light.

Further, according to the invention of claim 4, the hologram optical element according to claim 1, wherein the composition containing silicone contains silicone having an acryl group and is cured by electron beam irradiation. It is an element.

[0013]

Embodiments of the present invention will be described below. In the hologram optical element according to the present invention, as shown in FIG. 1, a hologram layer (20) is provided on a substrate (10), and a visible light transmittance of 80% or more and a thickness of 1 ~ 100 μm, the functional unit is monofunctional or 2
This is a hologram optical element (1) obtained by laminating a silicone composition layer (30) containing a functional silicone.

According to a second aspect of the present invention, the silicone composition layer (30) shown in FIG. 1 is cured by adding a curing agent or a catalyst to the composition containing silicone and heating the composition. The hologram optical element (1), wherein the silicone composition layer (30) shown in FIG. 1 has at least one of an acrylic group, a mercapto group, an unsaturated double bond, and an epoxy group. A hologram optical element (1), which is cured by irradiating a composition comprising silicone and a photopolymerization initiator with ultraviolet light,
Furthermore, the invention of claim 4 provides a hologram optical element in which the silicone composition layer (30) shown in FIG. 1 is cured by irradiating the silicone composition containing silicone having an acrylic group with an electron beam. 1).

The above-mentioned silicone composition layer (30)
The hologram optical element (1) laminated on the hologram layer (20) has high resolution, high diffraction efficiency, and high transparency, is excellent in reproduction wavelength reproducibility, storage stability, and is also resistant to chemicals and resistance. Excellent scratch resistance can be obtained.

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

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 silicone composition layer (30) having a visible light transmittance of 80% or more and a thickness of 1 to 100 μm used in the present invention comprises:
Since the functional unit contains a monofunctional or bifunctional silicone compound and is cured by actinic radiation or heat, it is placed on the formed hologram layer (20), so that the hologram layer (20) is not affected. It is necessary. For example, depending on the selected silicone compound or its solvent, the hologram layer (20) swells, and the reproduction hologram changes the reproduction light wavelength, and the transmission hologram changes the diffraction angle.

When the thickness of the silicone composition layer (30) is less than 1 μm, chemical resistance and scratch resistance are poor, and when it exceeds 100 μm, a desired visible light transmittance cannot be obtained. The number of objects is increased more than necessary, which is uneconomical and requires much energy for curing and the like.

The silicone composition layer (3) used here
Examples of the silicone composition that can be used as 0) include silicone for release paper, and examples thereof include a condensation reaction type, an addition reaction type, a solventless type, an ultraviolet curable type, and an electron beam curable type, but are not limited thereto.

The above condensation reaction type silicone is subjected to a dehydrogenation condensation reaction and a methanol removal condensation reaction of a long-chain silanol-functional dimethylsiloxane, methylhydrogenpolysiloxane, methylmethoxypolysiloxane, etc. in the presence of an organotin-based catalyst. Things. Morphologically, solvent type,
An emulsion type is used. Specifically, KS-705F, KS-708 (solvent type), KM-
763, KM-764-E (emulsion type), manufactured by Toray Silicone Co., Syl off23, SD-7206
(Solvent type), Syl off22, SM-7270
(Emulsion type) and the like.

The addition reaction type silicone is a type in which a linear methylvinylpolysiloxane having a vinyl group at both terminals or at both terminals and a chain is reacted with methylhydrogenpolysiloxane in the presence of a platinum-based catalyst. It is. As the addition reaction type, a solvent type or a non-solvent type is used. Specifically, KS-837, KS-778, K
S-847, KS-847H, KS-774A, KS-
839, KS-830 series, KS-775 (solvent type), KN-316, KN-320A (solvent-free type). In this case, CAT-P is used as a crosslinking agent and a catalyst.
L-56. Toray Silicone SRX-3
57, SD-7227, SRX-211, SD-722
0, SRX-345, SRX-370 (solvent type, curing agent: SRX212CAT, etc.), manufactured by Toshiba Silicone Co., Ltd., T
S56-707, TPR-6721, XS56-61
9, XS56-604, TPR-6700 (solvent type, curing agent: CM670) and the like.

The ultraviolet-curable silicone is obtained by adding a photopolymerization initiator to silicone having an acryl group and is disclosed in JP-B-53-36515 and JP-B-57-52371.
JP, JP-B-58-53656, JP-B-61-
No. 17863, a composition obtained by adding a photoinitiator to a polysiloxane having a mercapto group and an unsaturated double bond.
No. 52371, JP-B-62-24017, and a composition obtained by adding an onium salt catalyst to a siloxane having an epoxy group. JP-B-53-48198, JP-B-61-53383, JP-B-64399
No. 1, JP-A-59-180661, JP-A-59-68061
The composition described in JP-A-177029 can be mentioned.

Further, the electron beam-curable silicone is preferably a silicone having a radical polymerizable group. However, if the irradiation amount is increased, even a silicone having no functional group can be cured. Specifically, any acrylic-containing silicone may be used.

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, 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 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) 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 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 sensitizing dyes 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.

As described above, these components are appropriately selected, and the photosensitive solution obtained by mixing them at 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. A photosensitive liquid is applied to the substrate (10) in the same manner. 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 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. Alternatively, a hologram produced on a glass substrate may be transferred to the substrate (10) via an adhesive or the like.

The hologram optical element (1) of the present invention is obtained by spin-coating and dipping the above-mentioned silicone compound on the hologram layer (20). The silicone composition is diluted with an appropriate solvent according to the viscosity. May be

Further, a hard coat layer or an anchor layer may be provided on the hologram layer (20).

The hologram optical element (1) of the present invention described above has chemical resistance, scratch resistance, and stain resistance, and has poor adhesion between the hologram layer (20) and the substrate (10). A hologram optical element (1) capable of suppressing peeling in such a case can be provided.

[0040]

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 used in a blue plate glass (1.
A 1 mm thick, 5 inch square, SiO2 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 with a laser beam (6) using an optical system as shown in FIG.
An argon laser (514.5) was used as a light source on a hologram master recorded and formed on the silver halide photosensitive material (67) according to 1) while being in close contact with the hologram master while being immersed in isooctane.
(nm) from the substrate surface with light spread by using a lens, and then heated at 80 ° C. for 10 minutes, and further fixed by irradiating the entire hologram recording medium with a high-pressure mercury lamp. Thus, a volume phase hologram was obtained.

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, the surface of the hologram layer (20) formed on the blue sheet glass was coated with an optical adhesive hard lock 0P-10.
45K (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) is uniformly applied, and a 2 mm-thick base material (10) molded with a heat-resistant methacrylic resin (Sumipex-BTR, manufactured by Sumitomo Chemical Co., Ltd.) is placed.
Depressurized by depressurization, the UV irradiation device (500 mJ / cm
After being cured in ² ), it was peeled off from the blue glass plate. After diluting solvent-type silicone (KS-3705) manufactured by Shin-Etsu Chemical Co., Ltd. with toluene on the surface of the transferred hologram layer (20), a curing agent (CAT-PL-50T) is added, and the silicone composition is spun. Coated. The mixture was heated in an oven at 100 ° C. for 10 minutes to obtain a hologram optical element (1).

The hologram optical element (1) obtained above
Is the diffraction efficiency of 80% (half-width of the reproduction light peak: 20 n
In m), the transmittance of the baseline at 400 to 600 nm was 90%, and no effect due to image blur was observed. Furthermore, 100 squares of 1 mm square were made on the surface of the hologram layer (20) with a single-edge razor, and a 12 mm width of Nitto cellophane tape was erased with an eraser to completely adhere the pieces, and then the tape was instantaneously peeled off. As a result, no peeling was observed on the hologram surface. Further, when the gauze was rubbed while being pressed, no peeling occurred and no scratch was generated.

<Example 2> A hologram optical element (1) was obtained by the same materials and operations as in Example 1 except that the substrate (10) was a polycarbonate resin (Iupilon, manufactured by Mitsubishi Engineering-Plastics Corporation). .

The hologram optical element (1) obtained above
Means that the diffraction efficiency is 79% (half-width of the reproduction light peak: 22 n
In m), the transmittance of the baseline at 400 to 600 nm was 84%, and no adverse effect due to image blur was observed. Furthermore, 100 pieces of 1 mm square grid were made on the hologram surface with a single-edge razor, and a 12 mm width of Nitto cellophane tape was erased with an eraser to completely adhere the tape, and the tape was instantaneously peeled off. On the surface, no peeling was seen. Further, when the gauze was rubbed while being pressed, no peeling occurred and no scratch was generated.

<Example 3> The hologram optical element (1) was manufactured using the same materials and operations as in Example 1 except that the base material (10) was a polymethylpentene resin (TPX, manufactured by Mitsui Petrochemical Industries, Ltd.). Obtained.

The hologram optical element (1) obtained above
Has a diffraction efficiency of 76% (half-width of the reproduction light peak: 23n).
m), the transmittance of the baseline at 400-600 nm was 85%, and no adverse effect due to image blur was observed. Furthermore, 100 pieces of 1 mm square grid were made on the hologram surface with a single-edge razor, and a 12 mm width of Nitto cellophane tape was erased with an eraser to completely adhere the tape, and the tape was instantaneously peeled off. No peeling was seen on the surface. Further, when the gauze was rubbed while being pressed, no peeling occurred and no scratch was generated.

Example 4 The same procedure as in Example 1 was carried out except that a solvent-curable type (SD-7227) manufactured by Toray Silicone Co., Ltd. was diluted with toluene and a curing agent (SRX212CAT) was added as a silicone composition. A hologram optical element (1) was obtained by the above materials and operation.

Example 5 A silicone composition was prepared in the same manner as in Example 2 except that a solvent-curable type (SD-7227) manufactured by Toray Silicone Co., Ltd. was diluted with toluene and a curing agent (SRX212CAT) was added. A hologram optical element (1) was obtained by the above materials and operation.

Example 6 The same as Example 3 except that a solvent-curable type (SD-7227) manufactured by Toray Silicone Co., Ltd. was diluted with toluene and a curing agent (SRX212CAT) was added as a silicone composition. A hologram optical element (1) was obtained by the above materials and operation.

Table 1 shows the measurement results of the diffraction efficiency and transmittance of the hologram optical element (1) obtained in Examples 4 to 6 above.

[0054]

[Table 1]

As is evident from the diffraction efficiency and transmittance shown in Table 1, no adverse effect of these hologram optical elements (1) due to image blur was observed. Furthermore, 100 pieces of 1 mm square grid were made on the hologram surface with a single-edge razor, and a 12 mm width of Nitto cellophane tape was erased with an eraser to completely adhere the tape, and the tape was instantaneously peeled off. No peeling was seen on the surface. Further, when the gauze was rubbed while being pressed, no peeling occurred and no scratch was generated.

Example 7 Silicone Composition Layer (30)
UV-curable X-62-7028 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing (two-pack type), diluting with toluene, spin-coating the hologram layer (20) surface, and removing the solvent by drying, a handy UV lamp (OHD-320M, manufactured by Oak High Pressure Co., Ltd.) The hologram optical element (1) was obtained by the same material and operation as in Example 1 except that irradiation was performed for about 2 minutes to obtain a silicone composition layer (30).

Example 8 Silicone Composition Layer (30)
UV-curable X-62-7028 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing (two-pack type), diluting with toluene, spin-coating the hologram layer (20) surface, and removing the solvent by drying, a handy UV lamp (OHD-320M, manufactured by Oak High Pressure Co., Ltd.) The hologram optical element (1) was obtained by the same materials and operations as in Example 2 except that the irradiation was performed for about 2 minutes to obtain a silicone composition layer (30).

Example 9 Silicone Composition Layer (30)
UV-curable X-62-7028 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing (two-pack type), diluting with toluene, spin-coating the hologram layer (20) surface, and removing the solvent by drying, a handy UV lamp (OHD-320M, manufactured by Oak High Pressure Co., Ltd.) The hologram optical element (1) was obtained by using the same materials and operations as in Example 3 except that irradiation was performed for about 2 minutes to obtain a silicone composition layer (30).

Example 10 Silicone Composition Layer (3
0): UV-curable X-62-70 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing 28 (two-pack type) and diluting with toluene,
After spin-coating the hologram layer (20) and removing the solvent by drying, irradiation with a handy UV lamp (high pressure mercury lamp, OHD-320M manufactured by Oak Manufacturing Co., Ltd.) is performed for about 2 minutes to form a silicone composition layer (30). Example 4 except that
Holographic optical element (1)
I got

Example 11 Silicone Composition Layer (3
0): UV-curable X-62-70 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing 28 (two-pack type) and diluting with toluene,
After spin-coating the hologram layer (20) and removing the solvent by drying, irradiation with a handy UV lamp (high pressure mercury lamp, OHD-320M manufactured by Oak Manufacturing Co., Ltd.) is performed for about 2 minutes to form a silicone composition layer (30). Example 5 except that
Holographic optical element (1)
I got

Example 12 Silicone Composition Layer (3
0): UV-curable X-62-70 manufactured by Shin-Etsu Chemical Co., Ltd.
After preparing 28 (two-pack type) and diluting with toluene,
After spin-coating the hologram layer (20) and removing the solvent by drying, irradiation with a handy UV lamp (high pressure mercury lamp, OHD-320M manufactured by Oak Manufacturing Co., Ltd.) is performed for about 2 minutes to form a silicone composition layer (30). Example 6 except that
Holographic optical element (1)
I got

Table 2 shows the measurement results of the diffraction efficiency and transmittance of the hologram optical element (1) obtained in Examples 7 to 12 above.

[0063]

[Table 2]

As is evident from the diffraction efficiency and transmittance shown in Table 2, no adverse effect due to image blur was observed in these hologram optical elements (1). Furthermore, 100 pieces of 1 mm square grid were made on the hologram surface with a single-edge razor, and a 12 mm width of Nitto cellophane tape was erased with an eraser to completely adhere the tape, and the tape was instantaneously peeled off. No peeling was seen on the surface. Further, when the gauze was rubbed while being pressed, no peeling occurred and no scratch was generated.

<Comparative Example 1> The hologram optical element (1) was manufactured using the same material and operation as in Example 1 except that a PET film (100 μm thick, Melinex 518, manufactured by ICI) was used instead of the blue plate glass in Example 1. ) Got.

The hologram optical element (1) obtained had a diffraction efficiency of 78%, but the reproduced image appeared distorted.

<Comparative Example 2> A hologram was prepared in the same manner as in Example 1, and a heat-resistant methacrylic resin (Sumipex-
BTR, manufactured by Sumitomo Chemical Co., Ltd.) and attached to a 2 mm thick substrate (10) were not provided with a silicone composition. The hologram display element has a diffraction efficiency of 79% (half-width of the reproduction light peak: 22 nm) and a wavelength of 400 to 600 n.
The transmittance of the baseline at m was 90%, and the effect of blurring of the image was not observed. However, 100 1-mm square grids were formed on the hologram surface with a single-edge razor.
Nitto cellophane tape 12 mm wide was rubbed with an eraser to completely adhere, and then the tape was instantaneously peeled off. As a result, 63 grids were peeled off on the hologram surface. Further, when the gauze was rubbed while being pressed, the gauze was not peeled off but was hurt.

[0068]

As described above, the present invention has the following effects. That is, a hologram layer is provided on a base material, and a visible light transmittance of 80% or more and a thickness of 1 to 1 are formed thereon.
A composition containing a monofunctional or bifunctional silicone having a functional unit of 100 μm as a silicone composition layer, wherein the silicone composition layer is cured by adding a curing agent or a catalyst and heating, or an acrylic group ,
A silicone composition comprising a silicone having at least one of a mercapto group, an unsaturated double bond, and an epoxy group and a photopolymerization initiator, which is cured by irradiation with ultraviolet light, or a silicone containing a silicone having an acryl group When the composition is cured by irradiation with an electron beam, the obtained hologram optical element can have excellent diffraction efficiency and transparency, and can have chemical resistance and scratch resistance.

[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 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 20 hologram layer 30 silicone composition layer 60 laser 61 laser beam 62 mirror 63 half mirror 64 objective lens 65 spey Char filter 66mm lens 67mm silver halide photosensitive material

Claims (4)

[Claims] 1. A hologram layer is provided on a substrate, and a composition containing monofunctional or bifunctional silicone having a monofunctional or bifunctional functional unit having a visible light transmittance of 80% or more and a thickness of 1 to 100 is laminated thereon. A hologram optical element, comprising: 2. The hologram optical element according to claim 1, wherein a curing agent or a catalyst is added to the composition containing silicone, and the composition is cured by heating. 3. The composition containing silicone comprises a silicone having at least one of an acrylic group, a mercapto group, an unsaturated double bond, and an epoxy group, and a photopolymerization initiator, and is irradiated with ultraviolet light. The hologram optical element according to claim 1, wherein the hologram optical element is cured. 4. The hologram optical element according to claim 1, wherein the composition containing silicone contains silicone having an acryl group, and is cured by electron beam irradiation.