JPH06266271A - Hologram recording sheet - Google Patents

Abstract

PURPOSE:To provide a hologram recording sheet preventing the generation of unnecessary interference fringes via the refraction factor difference between a photosensitive material and a base film and preventing the regenerated wavelength from being drifted from the recorded wavelength with the lapse of time. CONSTITUTION:IN a hologram recording sheet composed of a base film 10 coated with a hologram recording photosensitive material 20, the base film 10 is made of a film containing a plasticizer, and a barrier layer 40 preventing the transition of the plasticizer is provided between the base film 10 and the hologram recording photosensitive material 20. The refraction factor difference is set within 0.05 between the refraction factor of the base film 10 and the barrier layer 40 and the refraction factor of the hologram recording photosensitive material 20.

Description

Detailed Description of the Invention

[0001]

[Industrial applications]

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram recording sheet having a hologram recording light-sensitive material coated on a supporting film, and it is necessary to selectively reflect or diffract light of a desired wavelength. , For example,
The present invention relates to a hologram recording sheet that can be suitably used as a combiner for a head-up display.

[0003]

2. Description of the Related Art In recent years, holograms have come to be widely used for decoration, forgery prevention, optical elements, etc., and the photosensitive material for such holograms is usually shown in FIG.
As shown in the cross section, a substrate 1 made of PET or the like containing no plasticizer or the like and coated with a photosensitive material 2 such as photoresist or photopolymer in a uniform and single layer is used. Note that FIG. 2 is an example in which the recording sheet is formed in a dry film form, and a protective film 3 made of PET or the like is laminated on the photosensitive material 4.

[0004]

However, in the prior art as described above, the photosensitive material and the support film (PET) are used.
However, there is a problem in that unnecessary interference fringes are recorded due to Fresnel reflection caused by the difference in refractive index between the photosensitive material and the supporting film during hologram recording. In order to remove the unnecessary interference fringes, a film having the same refractive index as that of the photosensitive material may be selected as the supporting film, and many of such films contain a plasticizer. When the photosensitive material directly contacts the film containing the plasticizer, the hologram reproduced image becomes uneven over time after hologram recording. This is because the plasticizer contained in the support film migrates over time to the photosensitive material on which hologram recording was performed,
This is because the distance between the interference fringes changes, which causes a deviation between the recording wavelength and the reproducing wavelength.

The present invention has been made in view of the above problems, and an object thereof is to eliminate the generation of unnecessary interference fringes due to the difference in refractive index between the light-sensitive material and the supporting film, and to reproduce wavelength over time. Is to provide a hologram recording sheet that does not deviate from the recording wavelength.

[0006]

As a result of various investigations for solving the above problems, it was found that the difference in refractive index between the hologram recording photosensitive material and the hologram recording photosensitive material was less than 0.05. The above problems can be solved by forming a layer structure in which a plastic layer having a refractive index difference of 0.05 or less between the hologram recording photosensitive material and a supporting film containing an agent is laminated as a barrier layer. The inventors have found that and completed the present invention.

The hologram recording sheet of the present invention has, for example, a laminated structure of a barrier layer 40, a photosensitive material 20, a barrier layer 40, and a protective film 30 on a support film 10 in this order as shown in the sectional view of FIG. Has been made.

Here, the films 10 and 30 are supporting films which are usually used for a hologram sensitive material in the form of a dry film, and include polypropylene, TAC (triacetyl cellulose), polyvinyl chloride and polyethylene containing a plasticizer. , PMMA (Poromethylmethacrylate), etc. can be used.

As the barrier layer 40, a resin containing no plasticizer may be used, and for example, the polymers shown in the following table, UV curable resins, and ionizing radiation curable resins can be used. The barrier layer 40 may be formed by coating and drying a solution of these resins dissolved in an appropriate solvent. In the case where the hologram recording sheet of the present invention is formed in a dry film form as shown in FIG. 1, the barrier layer 40 includes the films 10, 30.
Alternatively, it is necessary to select a peelable material from the photosensitive material 20.

As the photosensitive material 20, known materials for hologram recording such as photoresist and photopolymer are used.

As a means for obtaining the layer constitution as shown in FIG. 1, for example, printing is performed by a known coating method such as gravure coating, roll coating, blade coating, die coating and the like.

The hologram recording sheet obtained by the above method can prevent the plasticizer contained in the films 10 and 30 on the surface from migrating to the photosensitive material 20 by the barrier layer 40. A wavelength shift can be prevented, and a plasticizer-containing film suitable for various applications such as a plasticizer-containing heat resistant film and a plasticizer-containing solvent resistant film can be used for the films 10 and 30. It has advantages.

A hologram can be produced by irradiating a hologram recording sheet having this layer structure with a laser beam having a wavelength in a photosensitive region peculiar to the photosensitive material 20. Here, various conventionally known lasers such as a helium neon laser, an argon laser, a krypton laser, a helium cadmium laser, and a ruby laser can be used as a recording light source.

Next, in the present invention, the films 10, 3
Polymers that can be typically used as 0, the barrier layer 20, and the photosensitive material 20, the refractive index thereof, and the glass transition temperature are shown below.

Polymer n T _g (K °) ──────────────────────────────────── Polyvinylidene Fluor Ride 1.42 233 Polydimethylsilylene (polydimethylsiloxane) 1.43 146 Polyoxypropylene 1.4495 198 Polyvinyl isobutyl ether 1.4507 254 Polyvinyl ethyl ether 1.4540 230 Polyoxyethylene 1.4563 232 Polyvinyl butyl ether 1.4563 218 Polyvinyl pentyl ether 1.4581 207 Polyvinyl hexyl ether 1.4591 199 Poly (4 -Methyl-1-pentene) 1.459 -1.465 302 Cellulose acetate butyrate 1.46 -1.49 322-388 Polyvinyl octyl ether 1.4613 194 Poly (vinyl 2-ethylhexyl ether) 1.4626 207 Polyvinyl decyl ether 1.4628 211 Poly (2-methoxyethyl acrylate) 1.463 223 Poly Butyl acrylate 1.4631 251 Poly (t-butyl methacrylate) 1.4638 333 Poly (3-ethoxypropyl acrylate) 1.465 218 Polyvinyl propionate 1.4665 283 Polyvinyl acetate 1.4665 305 Polyvinyl methyl ether 1.467 242 Polyethyl acrylate 1.4685 249 Ethylene-vinyl acetate copolymer 1.47 -1.50 (80% -20% vinyl acetate) Cellulose propionate 1.47 -1.49 400 Cellulose triacetate 1.47 -1.48 322-751 Polyvinyl methyl ether (isotactic) 1.4700 242 Poly (3-methoxypropyl acrylate) 1.471 198 Poly ( 2-ethoxyethyl acrylate) 1.471 223 polymethyl acrylate 1.472 -1.480 283 polyisopropyl methacrylate 1.4728 354 poly (1-decene) 1.4730 232 polypropylene (atactic, density 0.85 75 g / cm ³ ) 1.4735 260 Poly (vinyl sec-butyl ether) (isotactic) 1.4740 254 Polydodecyl methacrylate 1.4740 208 Polyoxyethyleneoxysuccinoyl 1.4744 244 (Polyethylene succinate) Polytetradecyl methacrylate 1.4746 201-264 Ethylene -Propylene copolymer (EPR-rubber) 1.4748-1.48 140-260 Polyhexadecyl methacrylate 1.4750 288 Polyvinyl formate 1.4757 310 Polyisobutyl methacrylate 1.477 333 Ethyl cellulose 1.479 316 Polyvinyl acetal 1.48 -1.50 305 Cellulose acetate 1.48 -1.50 322-751 Cellulose Tripropionate 1.48 -1.49 400 Polyoxymethylene 1.48 232 Polyvinyl butyral 1.48 -1.49 322 Poly (n-hexyl methacrylate) 1.4813 268 Poly (n-butyl methacrylate) 1.483 293 Poly (n -Propyl methacrylate) 1.484 308 Polyethyl methacrylate 1.485 338 Poly (1,1-diethylpropyl methacrylate) 1.4889 268 Polymethyl methacrylate 1.4893 378 Poly (2-decyl-1,3-butadiene) 1.4899 220 Polyvinyl alcohol 1.49 -1.53 358 Polyethyl Glycolate Methacrylate 1.4903 328 Methylcellulose (low viscosity) 1.497 423 Polyurethane 1.5 -1.6 200-400 Poly (1,2-butadiene) 1.5000 269 Polyvinyl formal 1.50 Cellulose nitrate 1.50 -1.514 326 Poly (2-heptyl-1,3-) Butadiene) 1.5000 190 Poly (2-isopropyl-1,3 butadiene) 1.5028 221 Polypropylene (density 0.9075 g / cm ³ ) 1.5030 260 Polyisobutene 1.505 -1.51 200 Polybornyl methacrylate 1.5059 383 Poly (2-t-butyl-1,3) -Butadiene) 1.50 60 293 Polyethylene glycol dimethacrylate 1.5063 Polycyclohexyl methacrylate 1.5066 356 Gutta percha (β) 1.509 215 Polyoxyethylene (high molecular weight) 1.51 -1.54 232 Polyethylene (density 0.914 g / cm ³ ) 1.51 148 Poly (2-hydroxyethyl methacrylate) 1.5119 328 Polybutene (isotactic) 1.5125 249 Gutta percha (α) 1.514 215 Poly (1,3-butadiene) 1.5154 269 Poly (2-chloroethyl methacrylate) 1.517 365 Poly (2-diethylaminoethyl methacrylate) 1.5174 289 Natural rubber 1.519 -1.52 200 Polyacrylonitrile 1.52 Polymethacrylonitrile 1.52 Polyisoprene 1.521 200 Polyacrycide 1.527 379 Poly (1-vinyl-2-pyrrolidone) 1.53 327 Cellulose 1.54 243-443 Polyvinyl chloride 1.54 -1.55 354 Poly (2-bromo Ethyl methacrylate) 1.5426 325 Poly (N-allyl methacrylamide) 1.5476 433 Polyisopropyl methacrylate 1.552 354 Poly (p-isopropylstyrene) 1.554 360 Polychloroprene 1.554 -1.558 253 Polybenzyl methacrylate 1.5680 327 Polyphenyl methacrylate 1.5706 383 Poly (oxy-2) , 6-dimethylphenylene) 1.575 482 polyoxyethylene oxyterephthaloyl (amorphous) 1.5750 342 polyvinyl benzoate 1.5775 344 poly (4-methoxy-2-methylstyrene) 1.5868 358 poly (o-methylstyrene) 1.5874 409 polystyrene 1.59 -1.592 373 Poly (o-methoxystyrene) 1.5932 348 Poly (p-methoxystyrene) 1.5967 362 Polyvinylidene chloride 1.60 -1.63 255 Poly (o-chlorostyrene) 1.6098 392 Poly (2,6-dichlorostyrene) 1.6 248 440 Polyvinylnaphthalene 1.6818 432 Polyvinylcarbazole 1.683 423,481 ──────────────────────────────────── In addition to the above polymers Also, an ionizing radiation curable material can be used. As the ionizing radiation curable material, an electron beam curable resin and an ultraviolet curable resin are useful, and the electron beam curable resin and the ultraviolet curable resin are that the latter contains a photopolymerization initiator and a sensitizer. Except for, the composition is the same, generally, as a film-forming component, a polymer having a radically polymerizable active group in its structure, an oligomer, a monomer as a main component, in terms of viscosity, 200
It is preferably 0 cps or less. As such polymers and oligomers, those easily available from commercial products such as urethane acrylate and polyester acrylate are applicable to the present invention. As a monomer,
Ionizing radiation-curable monomers such as commercially available acrylic acid or methacrylic acid derivatives are applicable to the present invention. In order to use the above curable resin as an ultraviolet curable resin, as a photopolymerization initiator therein, acetophenones, benzophenone, Michler benzoyl benzoate, α-aminoxime ester, tetramethyl thiuram monosulfide,
Thioxanthones and n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used as a photosensitizer.

As the ionizing radiation irradiation method, the conventional technique can be applied as it is. For example, in the case of electron beam irradiation, Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, linear type, dynamitron type 50 to 1,000 emitted from various electron beam accelerators such as high frequency type
KeV, preferably, an electron beam having an energy of 100 to 300 KeV is emitted from 0.1 to 100 Mrad. , Preferably 1-10 Mrad. It can be cured by irradiation, and in the case of ultraviolet irradiation, ultraviolet rays emitted from light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, carbon arc, xenon arc, metal halide lamps,
0.1 to 10,000 mJ / cm ² , preferably 10
It can be cured by irradiation of up to 1,000 mJ / cm ² .

The hologram recording sheet of the present invention is
As described above, conventionally known coating methods, for example, roll coating, gravure coating, die coating, because it can be produced by using a blade coating and the like lamination process, new equipment is not required, cost At the same time
It also has an advantage that it is possible to use a plasticizer-containing film having environmental conditions corresponding to the use of holograms, that is, heat resistance and solvent resistance.

The hologram recording sheet of the present invention is
Besides the head-up display combiner,
It can be used for decoration and forgery prevention.

As is apparent from the above description, the hologram recording sheet of the present invention is a hologram recording sheet in which a hologram recording photosensitive material is coated on a supporting film, wherein the supporting film is a film containing a plasticizer, Further, a barrier layer for preventing migration of the plasticizer is provided between the support film and the hologram recording light-sensitive material.

In this case, the support film and the barrier layer are
The difference in the refractive index is 0.
It is desirable to use a material within 05.

In the case of a dry film form, it is desirable that the barrier layer is formed so as to be peelable on the support film or the hologram recording photosensitive material.

[0022]

In the present invention, since the support film is made of a film containing a plasticizer, and a barrier layer for preventing migration of the plasticizer is provided between the support film and the hologram recording light-sensitive material, it is included in the support film. Since it is possible to prevent the plasticizer that is present from migrating to the hologram recording light-sensitive material, it is possible to prevent the deviation between the recording wavelength and the reproduction wavelength, and as a supporting film, in accordance with the environmental conditions of use of the hologram, for example, A heat-resistant and solvent-resistant plasticizer-containing heat-resistant film, a plasticizer-containing solvent-resistant film, and the like can be used according to various applications. At the same time, since many conventionally known hologram recording materials can be used, hologram recording is easy, and it is advantageous in terms of cost.

[0023]

Next, examples of the present invention and comparative examples thereof will be described. Example 1 A triacetyl cellulose (TAC) film (Fujitac: Fuji Photo Film Co., Ltd.) having a refractive index (n _D ) of 1.49 and a thickness of 50 μm was used, and the refractive index was 1.50.
(N _D ) polyvinyl alcohol (K24E manufactured by Denki Kagaku Kogyo KK) dissolved in water at a solid content of 10 wt% was roll-coated to a dry film thickness of 5 μm. On top of this, the following composition has a refractive index of 1.50.
A hologram photosensitive material of (n _D ) dissolved in methyl ethyl ketone at a solid content of 20% was used to obtain a dry film thickness of 30 μm.
The roll coating was performed so that the thickness became m. Further, a TAC film roll-coated on the surface with polyvinyl alcohol dissolved in water as a barrier layer as described above was laminated so that the polyvinyl alcohol layer was in contact with the hologram photosensitive material layer.

When hologram recording was carried out on the hologram recording sheet thus obtained, a hologram having no unnecessary interference fringes and stable with time was obtained.

Holographic photosensitive material composition Polyvinyl acetate (Nippon Gosei Kagaku KK: PV-500) 100 parts Phenoxyethyl acrylate (Sartomer: SR-339) 30 parts Cyanine dye (NK-1420: Nippon Sensitive Dye Co., Ltd.) 1 part 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzene 5 parts Nonylphenyl alcohol ethylene oxide adduct (Emulgen 903: Kao Corporation) 5 parts (Comparative Example 1) The above Example A hologram recording sheet was produced under the same conditions as in Example 1 except that the polyvinyl alcohol barrier layer of No. 1 was not provided.

When hologram recording was performed on the obtained hologram recording sheet, unnecessary interference fringes did not occur, but it was unstable over time, and the reproduction wavelength was shifted to the long wavelength side.

(Comparative Example 2) Instead of the TAC film of Example 1, a PET film (Teijin KK: HP-7, n _D
= 1.66) and without providing a polyvinyl alcohol barrier layer, a hologram recording sheet was produced under the same conditions as in Example 1.

When hologram recording was performed on the obtained hologram recording sheet, unnecessary interference fringes were generated. However, the hologram was stable over time.

[0029]

As is apparent from the above description, according to the hologram recording sheet of the present invention, the supporting film is made of a film containing a plasticizer, and the plasticizer is prevented from migrating between the supporting film and the hologram recording photosensitive material. Since the barrier layer for preventing is provided, it is possible to prevent the plasticizer contained in the support film from migrating to the hologram recording light-sensitive material, and thus it is possible to prevent the deviation between the recording wavelength and the reproduction wavelength. , As the support film, depending on the environmental conditions of use of the hologram, for example, a plasticizer-containing heat-resistant film having heat resistance and solvent resistance, a plasticizer-containing solvent resistant film, etc. according to various uses are used. be able to. at the same time,
Since many conventionally known hologram recording materials can be used, the hologram recording material has an advantage that the hologram recording is easy and also advantageous in cost.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a layer structure of one form of a hologram recording sheet of the present invention.

FIG. 2 is a cross-sectional view showing a layer structure of a conventional hologram recording sheet of one form.

[Explanation of symbols]

 10 ... Support film 20 ... Photosensitive material 30 ... Protective film 40 ... Barrier layer

Claims (4)

[Claims] 1. A hologram recording sheet comprising a supporting film coated with a hologram recording photosensitive material, wherein the supporting film comprises a film containing a plasticizer, and the plasticizer is present between the supporting film and the hologram recording photosensitive material. A hologram recording sheet, which is provided with a barrier layer for preventing migration of the hologram recording sheet. 2. The support film and the barrier layer have a difference in refractive index of 0.
The hologram recording sheet according to claim 1, wherein the hologram recording sheet is made of a material within 05. 3. The hologram recording sheet according to claim 1, wherein the barrier layer is peelably formed on the support film. 4. The hologram recording sheet according to claim 1, wherein the barrier layer is formed so as to be peelable on the hologram recording photosensitive material.