JP3408293B2 - Hologram with reduced indentation defects - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram which is capable of reducing dent-like defects due to foreign substances mixed in during hologram production (including duplication).

[0002]

2. Description of the Related Art A hologram original plate and a photosensitive material are brought into close contact with each other, and a laser beam is irradiated to cause the diffracted light from the original plate and the incident light to interfere with each other in the photosensitive material to record a hologram image of the original plate in the photosensitive material. The hologram original plate has been duplicated. In this case, in order to prevent the image distortion due to the back surface reflection component, an optical contact liquid having a substantially equal refractive index is interposed between the original plate and the photosensitive material to improve adhesion and prevent back surface reflection to duplicate the hologram image. I am trying to do it.

[0003]

By the way, the optical contact liquid interposed between the glass and the photosensitive material film has fluidity,
It is difficult to obtain a uniform thickness due to vibration, etc., and especially when the amount of the contact liquid is large, it may take some time for the flow to subside and stabilize after application, which poses a problem of hindering hologram production. there were. In addition, even if holograms are produced or copied in a clean room, foreign matter (dust) with a diameter of about 10 μm that is brought in from the outside and adhered to the film or glass when the workers enter the room or bring in the materials is completely removed. It is impossible to remove. Such foreign matter lifts up the film, and the hologram recording part is generated due to the flow of the optical contact liquid around the foreign matter, or the reproduced image of the hologram produced or duplicated by the film being pressed by the foreign matter. There has been a problem that a large number of portions (hollow-shaped defects) that appear to have hollows with a diameter of several hundreds of μm to several mm are generated.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a hologram in which the occurrence of dent-like defects is reduced due to the inclusion of foreign matter and no defects are visually recognized in the reproduced image.

[0005]

SUMMARY OF THE INVENTION According to the present invention, a light-sensitive material film is brought into close contact with an antireflection-coated glass via an optical contact liquid, or ND (Neutral Den).
A hologram produced by irradiating a recording portion adhered to glass or ND glass coated with antireflection with a laser beam divided into two light beams,
A cushion layer containing a highly elastic polymer as a main component is provided on the side of the non-reflective coated glass or ND glass or the non-reflective coated ND glass that comes into contact with the film or the surface of the film that comes into contact with the glass. It is characterized in that the occurrence of recessed defects due to the pressure of the film embedded in the film is reduced.

Further, according to the present invention, an original plate portion in which a protective glass is adhered to the upper surface of an original plate hologram supported by a support, and a photosensitive material film for duplication are adhered to a glass which is antireflection coated through an optical contact liquid. N adhered to ND glass or non-reflection-coated ND glass, or adhered to non-reflection-coated glass via an optical contact liquid
D is a duplicate hologram that is brought into close contact with a duplicated portion that is brought into close contact with D glass and is recorded on a duplication material film by laser light irradiation, and is a duplication portion side of an original protective glass or an original side of a duplication material film, A cushion layer containing a highly elastic polymer as a main component is provided, and foreign matters mixed in at the time of duplication are embedded in the cushion layer to reduce occurrence of dent-like defects due to compression of the film.

[0007]

In the hologram of the present invention, a glass and a film are formed by providing a cushion layer on the side of the glass with antireflection coating, ND glass or original protective glass which is in contact with the photosensitive material film, or the side of the photosensitive material film which is in contact with the glass. Even if foreign matter is mixed in between, it is wrapped inside the cushion layer, and the flow of the optical contact liquid and the lifting of the photosensitive material film due to the pressure of the foreign matter are prevented,
Although traces of the recorded foreign matter can be observed by an optical microscope, no defects are visually recognized in the reproduced image.

[0008]

EXAMPLE FIG. 1 shows the case of using ND glass with a flexible antireflection (AR) coat. The original plate supporting glass 3 is brought into close contact with the AR coated ND glass 1 through the optical contact liquid 2, the original plate film 4 is supported by the supporting glass 3, and the original plate protective glass 6 is further adhered by the optical adhesive 5 to form the original plate portion. To form. Cushion layer 1 on this original
6. The duplicating photosensitive material film 8, the optical contact liquid 9, the cushion layer 15, and the ND glass 13 with the AR coat are stacked with the optical contact liquid 7 interposed therebetween to form a duplicated portion. As described above, according to the present invention, the adhesive cushion layer 15 is provided on the inner surface side of the ND glass 13 with the AR coat, and the original plate protective glass 6 is provided.
Cushion layer 16 is provided on the side of the optical contact liquid, and as the cushion layers 15 and 16, gelatin for photography, casein used for semiconductors, adhesive polymer materials, etc. are used. A uniform force is applied to the liquid to make the optical contact liquid uniform and thin, and even if dust is mixed in, it is held inside to prevent the flow of the contact liquid and floating of the film due to foreign matter, thus making a copy. It can be done without any problems. The cushion layer 15
The same effect can be obtained even if a similar cushion layer is provided on the upper surface of the photosensitive material film instead of, and on the lower surface of the photosensitive material film instead of the cushion layer 16.

Various types of cushion layers can be used as follows. Regarding the polymer layer in which the cushion layer is a binder polymer or a binder polymer containing a plasticizer, the binder polymer is a protein in a natural polymer, albumin, globulin, casein, collagen, gelatin, elastin, keratin, fibroin, etc. Examples include agar (agarose, agaropectin), alginic acid, chitin, chitosan, cellulose, starch, lignin, and natural rubber.

Of these, particularly preferred are:
Examples include casein, gelatin, and natural rubber, which have excellent optical properties and coating properties.

As the synthetic polymer, acrylate-styrene-acrylonitrile (AAS) copolymer, acrylonitrile-butadiene-styrene (ABS) copolymer, chlorinated polyethylene-acrylonitrile-styrene (AC
S) copolymer, acrylic ester copolymer, olefin-vinyl alcohol copolymer, alkyd resin, amino resin, bismaleimide-triazine resin, cellulose acetate (CA), cellulose butyrate acetate (CAB), ethyl cellulose (EC) , Hydroxyethyl cellulose, carboxymethyl cellulose, chlorinated polyether, coumarone resin, chlorinated polyethylene, allyl resin, ethylene-
α-olefin copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, epoxy resin,
Furan resin, fluororesin, ionomer, ketone resin,
Methacrylate-butadiene-styrene (MBS) copolymer, methacryl-styrene copolymer, nitrile resin,
Oxybenzoyl polyester, petroleum resin, phenol resin, polyacetal, polyamide, polyamideimide, polyarylate, polyallylsulfone, polyputadiene, thermosetting polybutadiene, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, water-crosslinkable polyethylene, Polyethylene terephthalate, polyimide, polyamino bismaleimide, methacrylic resin (PMMA), polymethylpentene, polypropylene, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polystyrene, styrene-acrylonitrile (SAN) copolymer, styrene copolymer, butadiene -Styrene copolymer, polyurethane, vinyl acetate resin, polyvinyl acetate Tar, polyvinyl alcohol, polyvinyl chloride, vinyl acrylic modified polyvinylidene chloride, polyvinylidene chloride, silicone, xylene resins, urethane acrylate resins.

In the present invention, polymers that can be typically used, their refractive indexes and glass transition temperatures are shown below. Polymer n T _g (K °) ──────────────────────────────────── Polyvinylidene fluoride 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 Polybutyl Acry 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 poly (methyl acrylate) 1.472 -1.480 283 poly isopropyl methacrylate 1.4728 354 poly (1-decene) 1.4730 232 polypropylene (atactic, density of 0.8575g / 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 Ethylcellulose 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) Crylate) 1.484 308 Polyethylmethacrylate 1.485 338 Poly (1,1-diethylpropylmethacrylate) 1.4889 268 Polymethylmethacrylate 1.4893 378 Poly (2-decyl-1,3-butadiene) 1.4899 220 Polyvinyl alcohol 1.49 -1.53 358 Polyethylglycolate 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) ) 1.5060 293 Polyethylene Lenglycol 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-chloroethylmethacrylate) 1.517 365 Poly (2-diethylaminoethylmethacrylate) 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-bromoethylmethacryl) Rate) 1.5426 325 poly (N-allylmethacrylamide) 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-2,2) 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) 1.6248 440 Polyvinyl As Le naphthalene 1.6818 432 polyvinylcarbazole 1.683 423,481 particularly preferred among these, relatively Tg is high cushioning low, polyvinyl acetate, polybutadiene, polyvinyl butyral, urethane-acrylic Leto resins.

Examples of the plasticizer include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, and trimethylolpropane, which are phthalate ester plasticizers such as dimethyl phthalate (DM).
P), diethyl phthalate (DEP), dibutyl phthalate (DBP), heptylnonyl phthalate (HNP), di-2-ethylhexyl phthalate (DOP), di-phthalate
n-octyl (DNOP), di-i-octyl phthalate (DCapP), phthalic acid (79 alkyl) (D79
P), di-i-decyl phthalate (DIDP), ditridecyl phthalate (DTDP), dicyclohexyl phthalate (DCHP), butylbenzyl phthalate (BDP), ethylphthalylethyl glycolate (EPEG), butylphthalylbutyl. It is a fatty acid dibasic ester plasticizer such as glycolate (BPBG).

Di-2-ethylhexyl adipate (DO
A), di (methylcyclohexyl) adipate, diisodecyl adipate (DIDA), di-n- azelaate
Hexyl (DNHZ), di-2-ethylhexyl azelate (DOZ), dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS) and other citric acid ester plasticizers.

Triethyl citrate (TEC), tributyl citrate (TBC), acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATB)
C) Epoxidized soybean oil (ESO) as epoxy plasticizer
As isophosphoric acid ester plasticizer, tributyl phosphate (T
BP), triphenyl phosphate (TPP), tricresyl phosphate (YCP), tripropylene glycol phosphate and the like.

The thickness of the cushion layer is 1 to 1000 μm.
m, preferably 20 to 100 μm. If it is too thin, the cushioning property is low, and if it is too thick, it adversely affects the optical properties (haze, transmittance, etc.).

The amount of plasticizer contained in the binder is 0.
It is -80%, preferably 10-50%. If it is too small, the effect on plasticity is low, and if it is too large, the strength of the coating film decreases.

Regarding the polymer layer in which the cushion layer is made of an adhesive, the adhesive polymer layer may be prepared by coating a glass substrate with a solution form or by laminating a film form. It can be used in the present invention.

Solution coating method A method in which a solvent-type pressure-sensitive adhesive is applied in a state of being dissolved in a solvent and dried and used, and there are rubber-based, acrylic-based and silicone-based pressure-sensitive adhesives.

As the rubber type, natural rubber, styrene-butadiene rubber, polyisobutylene rubber, isoprene rubber, etc. Acrylic type, copolymer polymer having 2-ethylhexyl acrylate as a main monomer, etc. Silicone type, rubbery siloxane , A silicone polymer containing resinous siloxane as a main component, and the like.

As the coating solvent, toluene, trichlene, normal hexane, ethyl acetate, toluene, methyl ethyl ketone, etc. are used.

Emulsion type adhesives and hot melt type adhesives can also be used.

Film laminating method A commercially available film-type double-sided adhesive in which the above-mentioned adhesive is formed into a support film can be used.
This double-sided pressure-sensitive adhesive is preferably only the pressure-sensitive adhesive as shown in FIG. In FIG. 2A, protective films 22 are attached to both surfaces of the adhesive layer. In addition, as shown in FIG. 2B, when the adhesive layer 21 is attached to both sides of the support film 20, it is necessary to use a film of polypropylene, polyvinyl chloride or the like that has no or almost no polarized light. When the support film has polarized light like PET, striped unevenness or the like occurs in the duplicated product.

In addition to the above polymers, ionizing radiation curable materials 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 similar, 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, It is preferably 2000 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 the monomer, an ionizing radiation curable monomer such as a commercially available acrylic acid or methacrylic acid derivative can be applied to the present invention. In order to make the above curable resin an ultraviolet curable resin, as a photopolymerization initiator therein, acetophenones,
Benzophenone, Michler benzoyl benzoate, α
-Aminoxime ester, tetramethyl thiuram monosulfide, thioxanthones, and as a photosensitizer, n
-Butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used.

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 copying apparatus of the present invention will be described with reference to FIG.
As shown in FIG. 3, the duplication photosensitive material film 21 is sent out from the supply roller 22 and wound by the winding roller 23. The original layer 26 is a support 24 that moves up and down.
The close contact liquid dropping device 25 drops the close contact liquid and raises the support table 24 to bring it into close contact with the duplication photosensitive material film 21. Excess liquid is roller 2
Remove by squeezing with 7. Next, the contact liquid is dropped onto the recording film 21 by the contact liquid dropping device 28,
It is brought into close contact with the AR-coated ND layer 29. Also at this time, the excess liquid is squeezed out by a roller or the like, and the pressing device 32 presses the liquid to bring it into close contact. At this time, when the ND layer is thick and cannot be squeezed by the roller, the thickness is set to 0.1 to 1.5 mm, and the material is a polymeric material having no optical birefringence and an equal refractive index. Is used to give flexibility and allow excess liquid to be squeezed out. Also, AR coated ND layer 2
By providing a cushion layer on 9, the vibration of the contact liquid can be suppressed during the exposure replication.

A laser beam 30 which is conjugated with the original layer is made incident on the replication system thus formed to perform exposure replication. After replication is complete, the AR-coated ND layer is removed and the recording film 21 is separated from the replication system by processing the original layer. The separated recording film 12 enters the drying chamber 31 and is dried in order to remove the adhered contact liquid. The dried film is collected by the take-up roller 23. These move as a series of operations and are continuously copied. It is also possible to improve productivity by attaching a plurality of these exposure units and drying units.

The central portion of the hollow defect of the hologram reproduced without using the cushion layer is examined by an optical microscope (OLYMPU).
SHL company MHL100 type), when observed by epi-illumination and dark-field observation at a magnification of 50 to 200 times, the foreign substance itself (<about 10 μm) or the foreign substance of the replicated film locally pressed by the foreign substance. Distortion in the vicinity (Equation 1)
It can be seen that a crater-like dark portion having a diameter of 0 to about 200 μm) is holographically recorded. In addition, when observing a portion of the hologram reproduced by using the cushion layer 5 that cannot be determined only by the dented defect, the same foreign matter itself or the distortion of the cushion layer surface layer due to the foreign matter is recorded. FIG. 4 is a photograph of a reproduced image of the foreign substance itself observed in this way (magnification: 200, film: F
UJI FP-3000B SUPER, ISO320
0, exposure time 12.25 seconds), and FIG. 5 is a photograph of a reproduced image of a portion where the cushion layer is distorted by foreign matter on the film (magnification 2).
00, film same as above, exposure time 13.37 seconds).
When copying is performed without using the cushion layer, such foreign matter presses the film to be replicated, and the reproduced image is several hundred μm to several mm.
Although a dented defect of about the diameter occurs, if a cushion layer is used, even if a foreign substance is present, it is not embedded in the cushion layer and does not press the film, preventing the occurrence of a dented defect. be able to. However, in the hologram reproduced by using the cushion layer, as shown in FIGS. 4 and 5, there is a trace of a foreign substance microscopically in a portion where there is no dent defect visually, as shown in FIGS. Will be recorded.

[0029]

As is apparent from the above description, a polymer having a high elasticity is provided on the side of the glass with antireflection coating, ND glass or original protective glass which comes into contact with the photosensitive material film, or the side of the photosensitive material film which comes into contact with the glass. By providing a cushion layer containing as a main component, even if foreign matter is mixed between the glass and the film, the foreign matter is caught inside the cushion, and the flow of the optical contact liquid and the lifting of the photosensitive material film due to the pressure of the foreign matter. Although a microscopic trace of a foreign substance which is prevented and can be confirmed by an optical microscope is recorded, a hologram having no defect in a reproduced image can be obtained visually.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an example of a duplication method for obtaining a hologram of the present invention.

FIG. 2 is a diagram illustrating a film bonding method.

FIG. 3 is a diagram illustrating a duplication device.

FIG. 4 is a photograph showing an image in which a foreign substance itself is recorded.

FIG. 5 is a photograph showing an image in which distortion of a film due to pressing of a foreign matter is recorded.

[Explanation of symbols]

1 ... ND glass with AR coating, 2 ... Optical contact liquid, 3 ...
Original support glass, 4 ... Original film, 5 ... Optical adhesive,
6 ... Original protective glass, 7 ... Optical contact liquid, 8 ... Photosensitive material film for reproduction, 9 ... Optical contact liquid, 13 ... AR coated ND glass, 15, 16 ... Cushion.

Claims (2)

(57) [Claims] 1. A non-reflective glass, ND glass, or non-reflective co-coating a light-sensitive material film through an optical contact liquid.
A hologram produced by irradiating a recording portion, which is in close contact with any of the coated ND glasses, with a laser beam divided into two light beams, which is non-reflection coated glass, ND glass, non-reflection coat
Between the exposed ND glass and the photosensitive material film layer
In addition, a cushion layer composed mainly of a highly elastic polymer is provided, and foreign substances mixed in are embedded in the cushion layer, and the occurrence of dent defects due to pressure on the film is reduced. Hologram with reduced dent defects. 2. An original plate part in which an original plate protective glass is adhered to the upper surface of an original plate hologram supported by a support, and a duplicating photosensitive material film are non-reflective through an optical contact liquid.
Coated glass, ND glass, anti-reflection coated
Either the ND glass is brought into close contact with it, or the non-reflective coated glass is brought into close contact with the duplication portion brought into close contact with the ND glass through an optical contact liquid, and then recorded on the duplication photosensitive material film by laser light irradiation. A duplication hologram, in which a cushion layer composed mainly of a highly elastic polymer is provided between the original protective glass and the photosensitivity material film for duplication, and foreign substances mixed during duplication are embedded in the cushion layer.
A hologram with reduced pit defects, characterized in that the occurrence of dent defects due to pressure on the film is reduced.