JPH075796A - Hologram recording composition, hologram recording medium, and production of hologram using the same - Google Patents

Abstract

PURPOSE:To provide a hologram recording medium excellent in chemical stability and environmental resistance, high in sensitivity, resolution and diffraction efficiency in a wide wavelength region and to provide an easy production method for hologram using this recording medium. CONSTITUTION:This hologram recording compsn. contains a thermosetting oligomer or polymer (A) having at least two oxilane rings, a compd. (B) having at least one polymerizable ethylenic unsatd. bond, a sensitizing dye (C) for visible rays, a photopolymn. initiator (D), and a catalyst (E) for polymn. of epoxy resin. Further, the difference of refractive indices of the oligomer or polymer (A) and the compd. (B) having polymerizable ethylenic unsatd. bonds is specified to be >=0.005.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram recording having excellent chemical stability and environmental resistance, high sensitivity over a wide wavelength range, and excellent resolution, diffraction efficiency and transparency. The present invention relates to a recording medium and a hologram manufacturing method using the medium.

[0002]

2. Description of the Related Art Conventionally, bleached silver salt and dichromated gelatin type photosensitive materials have been generally used as hologram recording materials. However, the hologram materials using this both have the problems that they require complicated wet development processing and that they are inferior in resolution or environmental resistance characteristics such as humidity resistance and weather resistance.

In order to solve such a problem, a hologram recording material using a photopolymer has been proposed. For example, Japanese Patent Publication No. 62-22152 discloses a hologram recording material characterized by a combination of a polyfunctional monomer having two or more ethylenically unsaturated bonds, a non-crosslinkable polymer and an initiator. ing. According to the known technique, it is possible to manufacture a hologram that is excellent in terms of diffraction efficiency, resolution, environment resistance, etc., but it is inferior in sensitivity characteristics and photosensitive wavelength region characteristics, or a wet treatment process is adopted in hologram manufacturing. However, there are drawbacks such as complications in production such as the occurrence of defects, uneven development caused by voids and cracks generated during the solvent immersion operation, and deterioration of transparency due to whitening.

On the other hand, a hologram recording material that does not require a complicated or complicated wet processing step in the hologram manufacturing step and is capable of manufacturing a hologram only by interference exposure is the "Applied Optics". , Vol. 15, No. 2, pp. 534 (1976
Year) as a known technique. It consists of a combination of a low refractive index monomer and a high refractive index non-reactive material. Further, JP-A-3-36582 and JP-A-3-249785 disclose hologram recording materials characterized by combining an allyl monomer and an acrylic monomer having different refractive indexes and polymerizable properties. According to this known technique, it is possible to manufacture a volume phase hologram having a high diffraction efficiency, "Holographic Display Research Group Bulletin", Vol. 10, No. 1,
This is demonstrated on page 3 (1990). However, since all of these known techniques use a monomer having fluidity as a main component, it is necessary to previously perform a treatment for suppressing fluidity of the photosensitive film such as heat treatment before hologram exposure. However, there are drawbacks such as complicated operation and difficulty in controlling the film thickness.

Similarly, there is disclosed a hologram recording material (and) using a photopolymer capable of producing a hologram only by interference exposure, or a method for producing the hologram recording material. For example, in JP-A-2-3081 or JP-A-2-3082, either a polymer or a monomer has an aromatic ring or a substituent containing a halogen atom, and a thermoplastic polymer and liquid ethylene. Disclosed are a photopolymerizable composition for hologram recording and a refractive index imaging element which are composed of a polymerizable monomer and a photoinitiator. However, the sensitivity characteristic of the hologram recording material to Ar ion laser is
It is on the order of several tens of mJ / cm ² , and it is desired to further improve the sensitivity characteristics in order to shorten the exposure time in hologram duplication.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a hologram recording medium which is extremely excellent in chemical stability and environmental resistance and is particularly excellent in high sensitivity characteristics, resolution and diffraction efficiency in a wide wavelength range, and a hologram using the hologram recording medium. The present invention provides a simple production method of.

[0007]

Means for Solving the Problems In consideration of the above points, the present inventors have made earnest studies to achieve the above object, and as a result,
The present invention has been achieved.

That is, in the present invention, the oxirane ring of
Thermosetting oligomer or polymer (A) having at least one, a compound (B) having at least one polymerizable ethylenic unsaturated bond, a visible light sensitizing dye (C),
Photopolymerization initiator (D) and epoxy resin polymerization catalyst (E)
Which has a refractive index difference of 0 between the thermosetting oligomer or polymer (A) containing at least two oxirane rings and the polymer of the compound (B) having at least one polymerizable ethylenic unsaturated bond. The composition for hologram recording characterized by being 0.005 or more, and
The hologram recording composition, relates to a hologram recording medium, characterized in that a photosensitive film is formed on an optically transparent substrate, further, after the hologram recording medium is subjected to hologram exposure, light or It is a method of manufacturing a hologram characterized by applying heat.

First, the thermosetting oligomer or polymer (A) having two or more oxirane rings used in the present invention will be described. This includes bisphenol A
Manufactured by a condensation reaction of and epichlorohydrin,
A so-called bisphenol A type epoxy resin can be used. Examples of this include Epicoat 1001, Epicoat 1004, and Epicoat 1009 of Yuka Shell Epoxy Co., Ltd. Further, there is a so-called brominated bisphenol A type epoxy resin produced by using tetrabromobisphenol A instead of bisphenol A. Examples of this include Epicoat 5050 and Epicoat 5051 of Yuka Shell Epoxy Co., Ltd. Further, a phenol novolac resin, an ortho-cresol novolac epoxy resin in which a glycidyl group is bonded to an ortho-cresol novolac resin, or an ortho-cresol novolac epoxy resin can be given. These include brominated novolac type epoxy resin of No. 7-1287 existing chemical substance, novolac type epoxy resin of No. 7-1285 existing chemical substance, biphenyl type epoxy resin of No. 4-1522 existing chemical substance, etc. To be Other specific examples include the epoxy resins described in "Chemical products of 11892", pages 826 to 834 (1992), published by Kagaku Kogyo Daily.

The advantages of using these epoxy resins are that they are extremely excellent in adhesiveness, toughness, chemical resistance, heat resistance and environmental resistance. Therefore, the environment resistance of the hologram produced is extremely good.

Further, since the epoxy resin has a very small volume contraction due to curing, it gives a good result on the wavelength reproducibility of the hologram produced. Note that the wavelength reproducibility here means how much the wavelength (playback wavelength) that gives the maximum diffraction efficiency when reproducing a hologram differs from the wavelength of the laser (recording wavelength) when recording the hologram. The smaller the deviation between the playback wavelength and the recording wavelength, the better the wavelength reproducibility.

The compound (B) having at least one polymerizable ethylenic unsaturated bond used in the present invention includes an oligomer in addition to a monofunctional or polyfunctional vinyl monomer. Further, it may be a high molecular weight compound. Next, these compounds will be exemplified.

Unsaturated acid compounds such as (meth) acrylic acid, itaconic acid and maleic acid, (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. Acid alkyl ester compound, tetrahydrofuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate,
Vinyl monomers such as dimethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N-vinylcarbazole, and aliphatic poly Hydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Di- or poly (meth) acryl such as 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, sorbitol, mannitol, etc. Fluorine atom-containing (meta) such as esters, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate ) Acrylate compounds,
Bromine atom such as 2,3-dibromopropyl (meth) acrylate, tribromophenoltriethylene oxide (meth) acrylate, p-bromophenoxyethyl (meth) acrylate, tetrabromobisphenol A ethi (propyrene) oxide-modified di (meth) acrylate Containing (meth) acrylate compound, phenyl (meth) acrylate, 4-methoxycarbonylphenyl (meth) acrylate, 4-ethoxycarbonylphenyl (meth)
Acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, benzyl (meth) acrylate, 4
-Phenoxyethyl (meth) acrylate, 4-phenylethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4-phenoxytetraethylene glycol (meth) acrylate, 4-
Aromatic ring-containing (meth) acrylate compounds such as phenoxyhexaethylene glycol (meth) acrylate, 4-biphenylyl (meth) acrylate, and epichlorohydrin phthalate-modified di (meth) acrylate; aromatic polyhydroxy compounds such as hydroquinone and resorcin , Catechol, pyrogallol, and other di- or poly (meth) acrylate compounds, isocyanuric acid eth (propylene) oxide-modified (meth) acrylate, bisphenol A eth (propylene) oxide-modified di (meth) acrylate, (meth) acrylated epoxy resin ,
Examples thereof include heavy metal atom-containing (meth) acrylate compounds such as ferrocenylmethyl (meth) acrylate, ferrocenylethyl (meth) acrylate, and zinc di (meth) acrylate.

However, as a combination of the thermosetting oligomer or polymer (A) having two or more oxirane rings and the compound (B) having at least one polymerizable ethylenic unsaturated bond, an oxirane ring is used. It is necessary that the difference in refractive index between the thermosetting oligomer or polymer (A) having two or more and the polymer of the compound (B) having at least one polymerizable ethylenic unsaturated bond is 0.005 or more. And is preferably 0.01 or more. It is impossible to form a hologram without such a combination.

Therefore, a preferable combination is a relatively low refractive index such as an aliphatic epoxy resin, an alicyclic epoxy resin, or a fluorine-containing epoxy resin (<1.
For the thermosetting oligomer or polymer (A) having two or more oxirane rings such as 50), phenyl (meth) acrylate or a compound (B) having at least one polymerizable ethylenic unsaturated bond is used. Aromatic ring-containing polymerizable compounds such as phenoxyethyl (meth) acrylate and phthalic acid diarylate, and bromine-containing polymerizable compounds such as 2,4,6-tribromophenoxyethyl (meth) acrylate are desired. On the other hand, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin and the like have a relatively high refractive index (> 1.
For the thermosetting oligomer or polymer (A) having two or more oxirane rings such as 53), isobornyl (meth) acrylate or a compound (B) having at least one polymerizable ethylenic unsaturated bond can be used. An aliphatic polymerizable compound such as pentaerythritol triacrylate and a fluorine-containing polymerizable compound such as diacrylate of 2,2-bis (4-hydroxyphenyl) hexafluoropropane are preferable.

Next, the visible light sensitizing dye (C) used in the present invention will be described. These are added for the purpose of absorbing light in the visible region and enhancing activity against light.

Specific examples of such a visible light sensitizing dye (C) include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1,2- represented by benzyl and camphorquinone. Diketone derivative, benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonol derivative, acridine derivative, azine derivative, thiazine Derivative, oxazine derivative, indoline derivative, azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative,
Tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative,
Tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, organic ruthenium complexes, and the like, In addition, more specifically, Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Okawara Nobu et al., "Functional Dye Chemistry" (1981).
Dyes and sensitizers described in “Special Functional Materials” (1986, CMC), edited by Chuzaburo Ikemori, et al., But not limited thereto. Examples thereof include dyes and sensitizers that absorb light. Two or more kinds of these may be used in an arbitrary ratio as needed.

Next, the photopolymerization initiator (D) used in the present invention will be explained. By combining with the visible light sensitizing dye (C) to form a composition, it is added for the purpose of enhancing the activity against light and forming a highly sensitive polymerizable composition.

As the photopolymerization initiator (D) suitable for such purpose, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,1' is used.
-Biimidazole and bis (2,4,5-triphenyl)
Bisimidazole derivatives such as imidazolyl, N-arylglycine derivatives such as N-phenylglycine,
Examples include organic azide compounds such as 4,4′-diazidochalcone, titanocenes described in JP-A-61-151197, and aluminate complexes described in JP-A-3-209477, but are not limited thereto. Not something.

As a preferred photopolymerization initiator (D), tris (trichloromethyl) -2,4,6-described in British Patent 1388492 and JP-A-53-133428.
2,4,6-substituted triazine compounds such as triazine,
JP-A-59-189340 and JP-A-60-7.
3,3'4,4'-tetra (te described in Japanese Patent No. 6503).
organic peroxides such as (rt-butylperoxycarbonyl) benzophenone, JP-A-1-54440, EP 109851, and EP 12671.
Issue 2, "Journal of Imaging Science
(J.Imag.Sci.) ", Volume 30, p. 174 (1986)
The described metal arene complexes, N-alkoxypyridinium salts such as 1-methoxy-4-phenylpyridinium tetraphenylborate described in JP-A-63-142345, diphenyliodonium hexafluorophosphate, di (p-tolyl) iodonium hexafluoro. Diaryl iodonium salts such as phosphate, di (p-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, diphenylphenacylsulfonium hexafluoroantimonate, dimethylphenacylsulfonium hexahydrate Fluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate Sulfonium salts such bets, including onium salts such as oxosulfonium salts such as tetraphenyl-oxo hexafluorophosphate and the like.

Among them, particularly preferred photopolymerization initiator (D)
Examples thereof include an iodonium organic boron complex such as diphenyliodonium (n-butyl) triphenylborate described in JP-A-3-704, diphenylphenacylsulfonium (n-butyl) triphenylborate, dimethylphenacylsulfonium (n-). Examples thereof include sulfonium organic boron complexes such as butyl) triphenylborate.

Further, the polymerizable composition of the present invention may contain a thermal polymerization inhibitor for the purpose of preventing polymerization during storage. Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol,
Examples thereof include tert-butylcatechol and phenothiazine. These thermal polymerization inhibitors are added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having a radically polymerizable ethylenically unsaturated bond. Preferably.

The polymerizable composition of the present invention is used for polymerization accelerators and chain transfer catalysts represented by amines, thiols, and disulfides, and epoxy resins for the purpose of accelerating polymerization during and after hologram exposure. It is possible to add a polymerization catalyst or the like. Specific examples of the polymerization accelerator and the chain transfer catalyst that can be added to the polymerizable composition of the present invention include amines such as triethanolamine and N, N-diethylaniline, USP No. 4414312 and JP-A-64143. Thiols described in JP-A-13144, JP-A-2-
Disulfides described in 291561, USP No. 355
8322 and thiones described in JP-A No. 64-17048, and O-acyl thiohydroxamates and N-alkoxypyridine thiones described in JP-A No. 2-291560.

As the epoxy resin polymerization catalyst (E) of the present invention, in addition to sulfonium salts and iodonium salts, "Crosslinking Agent Handbook", page 606, published by Taisei Co., Ltd.
Examples thereof include amines such as aliphatic polyamines, aromatic amines, polyamidoamines, boron trifluoride complex compounds, ketimines, imidazoles, and acid anhydrides described on page 655 (1981). The polymerizable composition of the present invention further, depending on the purpose, a high molecular weight binder or an oligomer binder, a phosphine, a phosphonate, an oxygen scavenger such as a phosphite or a reducing agent, an antihalation agent, a plasticizer, a leveling agent, an ultraviolet absorber, You may use it, mixing with an antistatic agent.

The polymerizable composition used in the present invention comprises a thermosetting oligomer or polymer (A) having two or more oxirane rings, a compound (B) having at least one polymerizable ethylenic unsaturated bond, The visible light sensitizing dye (C), the photopolymerization initiator (D) and the epoxy resin polymerization catalyst (E) are dissolved in an appropriate solvent at an arbitrary ratio, and the resulting solution is treated with an optically transparent group. It is possible to form a photosensitive film on a material and use it as a hologram recording medium. The compounding ratio of each component of the polymerizable composition used in the present invention is preferably 10 to 90% by weight of the thermosetting oligomer or polymer (A) having two or more oxirane rings, based on the total polymerizable composition. , And more preferably 30 to 7
The compound (B) having 0% by weight and at least one polymerizable ethylenic unsaturated bond is preferably 10 to 90.
% By weight, more preferably 30 to 70% by weight, the visible light sensitizing dye (C) is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight, and the photopolymerization initiator (D) is The amount used is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight, and the epoxy resin polymerization catalyst (E) is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight. .

The visible light sensitizing dye (C) has a transmittance of 10% or more with respect to the laser light for irradiation when it is formed as a photosensitive film on an optically transparent substrate to form a hologram recording medium. It is preferable to adjust the concentration so that By selecting such a compounding ratio, a polymerizable composition having high diffraction efficiency and high sensitivity characteristics can be obtained.

The polymerizable composition having the above composition ratio is dissolved in an appropriate solvent, and the solution is spin coated, roll coated, knife coated, bar coated, or the like to directly form a glass plate, a plastic plate or a plastic film. It is used as a hologram recording medium by being formed as a photosensitive film on an optically transparent substrate such as. The hologram recording medium obtained here may further have a protective layer for blocking oxygen on the photosensitive film. The protective layer is polyolefin, polyvinyl chloride,
Laminate a plastic film or plate such as polyvinylidene chloride, polyvinyl alcohol or polyethylene terephthalate. Alternatively, a glass plate may be attached. Also, between the protective layer and the photosensitive film (and) or,
A pressure-sensitive adhesive or an organic solvent may be present between the substrate and the photosensitive film in order to enhance airtightness. The hologram recording medium obtained as described above is fixed to a holder so as not to be affected by vibration, and then visible light such as a He-Cd laser, an Ar ion laser, a He-Ne laser, a Kr ion laser, and a ruby laser. Irradiate a laser to record a hologram. FIG. 1 shows an example of the optical system.

The present hologram recording medium thus hologram-recorded requires application of light and / or heat for fixing an unexposed portion or a portion having a small exposure amount. In addition to the visible light laser shown above,
Uses visible and / or ultraviolet light such as carbon arc lamps, high pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, and tungsten lamps. Further, it is preferable that the heat is applied between 40 ° C and 160 ° C. Furthermore, on the hologram recording medium in which the hologram is recorded,
Light and heat may be applied simultaneously, or light and heat may be applied separately. Further, an operation of peeling the protective layer may be performed before and after applying light and / or heat.

[0029]

The polymerizable composition used in the present invention comprises a thermosetting oligomer or polymer (A) having two or more oxirane rings, a compound (B) having at least one polymerizable ethylenic unsaturated bond, Visible light sensitizing dye (C),
Photopolymerization initiator (D) and epoxy resin polymerization catalyst (E)
It is characterized by including a combination of.

When hologram exposure is performed on a hologram recording medium prepared by using this polymerizable composition, the visible light sensitizing dye (C) absorbs laser light and is excited, which decomposes the photopolymerization initiator (D). It is considered that the compound (B) having at least one polymerizable ethylenic unsaturated bond is polymerized as a result of inducing a free radical to be generated. At this time, light interference occurs in the hologram recording medium in response to hologram exposure, but at a site having a strong interference action, a polymerization reaction of the compound (B) having at least one polymerizable ethylenically unsaturated bond. Occurs. Here, a refractive index difference occurs between the polymer produced by this polymerization reaction and the thermosetting oligomer or polymer (A) having two or more oxirane rings, and a hologram is formed.

After the hologram exposure, at least one polymerizable unreacted ethylenically unsaturated bond which has not reacted is added by adding a post-treatment step with light and / or heat.
Polymerization of the compound (B) having one or more compounds is promoted, and a hologram that is chemically stable and does not change with time is manufactured. At the same time, since the thermosetting oligomer or polymer (A) having two or more oxirane rings also undergoes a polymerization reaction due to the action of the epoxy resin polymerization catalyst (E), it becomes more chemically stable and has environmental resistance that does not change over time. An excellent hologram is manufactured. In addition, the remaining visible light sensitizing dye (D) is effectively decolorized by this post-treatment step,
This will improve the transparency of the hologram.

[0032]

The present invention will be described in more detail based on the following examples. In the following examples, parts represent parts by weight unless otherwise specified.

Example 1 100 parts of Epicoat 1009 (bisphenol A type epoxy resin) manufactured by Yuka Shell Epoxy Co., Ltd. as a thermosetting oligomer or polymer (A) having two or more oxirane rings, and a polymerizable ethylenic non-polymer 90 parts of dimethylol tricyclodecane diacrylate as the compound (B) having at least one saturated bond, 1 part of the ketocoumarin dye represented by the formula 1 as the visible light sensitizing dye (C), a photopolymerization initiator ( As a D), a photosensitive solution containing 2.5 parts of diphenyliodonium hexafluorophosphate, 1 part of N-dimethylcyclohexylamine as an epoxy resin polymerization catalyst (E), and 500 parts of dichloromethane as a solvent was prepared. Formula 1

[Chemical 1]

This photosensitive solution was applied on a glass plate of 100 × 125 × 3 mm by using a 10 mil applicator and dried in an oven at 50 ° C. for 10 minutes to prepare a hologram recording medium. The film thickness of the photosensitive layer after drying was 15 μm. Further, as a protective layer, a 10% aqueous solution of polyvinyl alcohol was applied to the photosensitive layer side with a 3 mil applicator. Hologram exposure was performed on this hologram recording medium with the exposure amount shown in Table 1 by two-beam interference of 488 nm light of an Ar ion laser using the hologram production optical system shown in FIG. After carrying out the hologram exposure, one of the two light fluxes was further blocked and the hologram was exposed to the same exposure time as the hologram exposure, and then placed in a 100 ° C. oven for 1 hour.

Table 1 ─────────────────────────────── Example Exposure Diffraction Efficiency Playback Preservation 1 ^* Preservation 2 ^** (mJ / cm ² ) (%) Wavelength (nm) (days) (days) ───────────────────────────── ─────────────────────────────────────────────────── ── *) Durability under storage at 25 ℃ and 60% RH **) Durability under storage at 90 ℃

The diffraction efficiency is measured by ART by JASCO Corporation.
It was measured with a 25C type spectrophotometer. In this device, a photomultimeter having a slit with a width of 3 mm can be installed on the circumference of a 20 cm radius centered on the sample. Width 0.3 mm
The monochromatic light of was incident on the sample at an angle of 45 degrees and the diffracted light from the sample was detected. The diffraction efficiency was defined as the ratio between the maximum value other than the specular reflection light and the value when the incident light was received directly without placing the sample. Table 2 shows the diffraction efficiency, playback wavelength, and storage stability test results. In addition, as Comparative Example 1,
The results obtained by using CY-179 manufactured by Nippon Ciba-Geigy Co., Ltd. instead of Epicoat 1009 are also shown. No hologram was observed in the system made using CY-179 having a small refractive index.

Table 2 ─────────────────────────────────── Example Heat having two or more oxirane rings Curable exposure dose Oligomers or polymers (A) (mJ / cm ² ) ─────────────────────────────────── ─ 2 Epicoat 1001 (made by Yuka Shell Epoxy Co., Ltd.) 9 3 Epicoat 1004 (made by Yuka Shell Epoxy Co., Ltd.) 9 4 Epicoat 5050 (made by Yuka Shell Epoxy Co., Ltd.) 8 5 Epicoat 180S50 (made by Yuka Shell Epoxy Co., Ltd.) 9 ─ ───────────────────────────────────

Comparative Example 1 As Comparative Example 1, in the same manner as in Example 1, instead of Epicoat 1009, CY-179 manufactured by Japan Ciba-Geigy Co., Ltd.
Results obtained by using are also shown. C with a small refractive index
No holograms were observed in the system made with Y-179.

Examples 2 to 5 In the same manner as in Example 1, a hologram recording medium containing a thermosetting oligomer or polymer (A) having two or more oxirane rings shown in Table 2 instead of Epicoat 1009 was used. I made a hologram. The results are shown in Table 3. Good holograms were obtained in both cases.

Table 3 ───────────────────────────────── Example Diffraction efficiency Playback storability 1 ^* Storability 2 ^** (%) Wavelength (nm) (days) (days) ────────────────────────────────── 2 65 479>250> 30 3 69 484>250> 30 4 79 481>250> 30 5 63 477>250> 30 ──────────────────────── ────────── *) Durability under storage at 25 ℃ and 60% RH **) Durability under storage at 90 ℃

Examples 6 to 9 In the same manner as in Example 1, compounds having at least one polymerizable ethylenically unsaturated bond shown in Table 4 in place of dimethyloltricyclodecanediacrylate (B ) Was used to prepare a hologram using a hologram recording medium containing 90 parts by weight. The results are shown in Table 5. Good holograms were obtained in both cases.

Table 4 ─────────────────────────────────── Examples Polymerizable ethylenically unsaturated bonds Compound (B) having a refractive index of at least one exposure amount (mJ / cm ² ) ─────────────────────────────── ───── 6 Isobornyl acrylate 1.48 15 7 triethylene glycol 1.468 8 diacrylate 8 pentaerythritol 1.48 7 triacrylate 9 trimethylolpropane 1.47 18 trimethacrylate ─────── ────────────────────────────

Table 5 ───────────────────────────────── Example Diffraction Efficiency Playback Preservation 1 ^* Preservation 2 ^** (%) Wavelength (nm) (days) (days) ───────────────────────────────── 6 72 479>180> 7 7 65 65484>180> 7 8 84 485>180> 7 9 70 488>180> 7 ──────────────────────── ────────── *) Durability under storage at 25 ° C. and 60% RH **) Durability under storage at 90 ° C. Examples 10 to 13 In the same manner as in Example 1, using Formula 1 The visible light sensitizing dye (C) shown in Table 6 was used in place of the ketocoumarin dye represented by 1
A hologram was created using a hologram recording medium containing a part by weight. The results are shown in Table 7. Good holograms were obtained in both cases.

Table 6 ─────────────────────────────────── Example Visible light sensitizing dye (C) Exposure (mJ / cm ² ) ─────────────────────────────────── 10 Rose Bengal 20 11 4, 4′-Dimethylaminochalcone 18 12 4,4′-bis (dimethylamino) benzalacetone 12 13 3,3′-diethyl-2,2′-oxacarbocyanine 18 iodide ─────────── ─────────────────────────

Table 7 ───────────────────────────────── Example Diffraction efficiency Playback storability 1 ^* Storability 2 ^** (%) Wavelength (nm) (days) (days) ────────────────────────────────── 10 67 477>250> 30 11 58 485>250> 30 12 62 485>250> 30 13 76 487>250> 30 ─────────────────────── ────────── *) Durability under storage at 25 ℃ and 60% RH **) Durability under storage at 90 ℃

Examples 14 to 17 In the same manner as in Example 1, using a hologram recording medium containing 2.5 parts by weight of the photopolymerization initiator (D) shown in Table 8 instead of diphenyliodonium hexafluorophosphate. , Created the hologram. The results are shown in Table 9. Good holograms were obtained in both cases.

Table 8 ─────────────────────────────────── Example Photopolymerization Initiator (D) Exposure Amount (mJ / cm ² ) ──────────────────────────────────── 14 Bis (tert-butylphenyl) Iodonium 7 hexafluorophosphate 15 diphenyliodonium-n-butyltriphenyl 2 borate 16 dimethylphenacylsulfonium-n-butyl 4 triphenylborate 17 diphenylphenacylsulfonium-n-butyl 3 triphenylborate ──────── ────────────────────────────

Table 9 ───────────────────────────────── Example Diffraction Efficiency Playback Preservation 1 ^* Preservation 2 ^** (%) Wavelength (nm) (days) (days) ────────────────────────────────── 14 62 484>250> 30 15 63 63486>250> 30 16 66 483>250> 30 17 69 488>250> 30 ─────────────────────── ────────── *) Durability under storage at 25 ℃ and 60% RH **) Durability under storage at 90 ℃

[0049]

EFFECTS OF THE INVENTION By using the hologram recording medium of the present invention, a hologram which is highly sensitive over a wide wavelength range, is extremely chemically stable, and has high resolution, high diffraction efficiency and high transparency is simple. Manufactured to.

[Brief description of drawings]

FIG. 1 shows a block diagram of a two-beam exposure apparatus for hologram production.

[Explanation of symbols]

 1: Laser oscillator 2: Mirror 3: Lens 4: Spatial filter 5: Base material (glass plate) 6: Hologram photosensitive layer 7: Protective layer (polyvinyl alcohol film)

Claims (3)

[Claims] 1. A thermosetting oligomer or polymer (A) having two or more oxirane rings, a compound (B) having at least one polymerizable ethylenic unsaturated bond, a visible light sensitizing dye (C), A thermosetting oligomer or polymer (A) containing a photopolymerization initiator (D) and an epoxy resin polymerization catalyst (E) and having two or more oxirane rings, and at least one or more polymerizable ethylenically unsaturated bond. A composition for hologram recording, wherein the refractive index difference with the polymer of the compound (B) has 0.005 or more. 2. The hologram recording composition according to claim 1,
A hologram recording medium comprising a film formed on an optically transparent substrate. 3. A method of manufacturing a hologram, which comprises subjecting the hologram recording medium of claim 2 to hologram exposure and then applying light or heat.