JPH07199779A - Hologram recording material and hologram recording medium - Google Patents

Abstract

PURPOSE:To provide a hologram recording material and hologram recording medium which are excellent in weatherability and chemical stability, such as heat resistance and strength, and is excellent in resolution, diffraction efficiency, transparency and reproduction wavelength reproducibility particularly in dry development processing. CONSTITUTION:The hologram recording material and hologram recording medium composed of an arom. thermosetting resin (A) which has at least >=1 pieces of addition polymerizable ethylenic usatd. bonds in its constitutional unit and has at last one substitutent selected from unsubstd. phenyl, substd. phenyl, chlorine and bromine, a radical polymerixable aliphat. monomer (B) and a photopolymn. initiator (C) which activates radical polymn. by exposure are obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram recording material and a hologram recording medium capable of forming a hologram by forming a film on a substrate and exposing in an optical system, and particularly to an argon laser beam and an electron beam. The present invention relates to a hologram recording material and a hologram recording medium having high sensitivity, excellent weather resistance such as heat resistance and storage stability, and excellent hologram characteristics such as resolution, diffraction efficiency, and transparency.

[0002]

2. Description of the Related Art Conventionally, since holograms can reproduce three-dimensional stereoscopic images, they have been used for books, covers for magazines, displays for POPs, gifts, etc. because of their excellent design and decorative effects. . Since holograms can be said to be equivalent to the recording of information in submicron units, they are also used for counterfeit prevention marks such as securities and credit cards.

In recent years, a hologram optical element (H) typified by a head-up display (HUD) mounted on an automobile or the like has been used from one utilizing a fine decoration effect.
Application to OE) is considered.

As described above, holograms are used for displays, optical elements, or multiplex recording of images, so that hologram recording materials having improved resolution, diffraction efficiency, transparency, sensitivity, and weather resistance are desired as the applications are expanded. Has been. Therefore, the hologram recording material is required to be highly sensitive to laser light having a visible oscillation wavelength and exhibit high resolution. In practice, the hologram diffraction efficiency, the reproducibility of the reproduction light wavelength, and the It is necessary that the hologram characteristics such as the bandwidth (half-value width of the reproduction light peak) be compatible with the target hologram.

The hologram recording material for the HOE has a diffraction efficiency of 90 at a spatial frequency of 5000 to 6000.
% Or more, band width (half-width of reproduced light peak) is 20 to 3
0 nm, the peak wavelength of the reproduction wavelength is 5 nm from the shooting wavelength
It is desirable that the content be within the range, and it is also necessary that these holograms have excellent storage stability and weather resistance over a long period of time. In particular, the on-vehicle HUD is resistant to heat pressing when it is incorporated into laminated glass, and
1000 hours at 00 ° C and 100 in fade meter
Even if left for 0 hours, the hologram characteristics should not change.

Up to now, as a hologram recording material,
Light-sensitive materials such as silver halide emulsions and hardened dichromated gelatin have been commonly used. Although dichromated gelatin has high diffraction efficiency and low noise characteristics, it has a short shelf life and is easily deteriorated, and the manufactured hologram has poor weather resistance such as humidity resistance and heat resistance, and hologram recording is possible even in silver halide emulsion. There is a problem in that the manufacturing process of the recording medium and the manufacturing process of the hologram become complicated.

To solve the above problems, a binder resin as a carrier is used as a hologram recording material used in the production of holograms having excellent weather resistance and storage stability, and hologram characteristics such as resolution, diffraction efficiency and transparency. A hologram recording material using poly-N-vinylcarbazole may be mentioned, for example, 1,4,5,6,7,7-hexachloro-5-nobornene-anhydrous described in JP-A-60-227280. Holographic recording material comprising 2,3-dicarboxylic acid and dye, JP-A-60-45283
Patent Document, a hologram recording material comprising a sensitizer and a cyclic cis-α-dicarbonyl compound as a crosslinking agent,
2, 3 described in JP-A-60-260080
There is a hologram recording material composed of bornandione and thioflavin T, and a hologram recording material composed of thioflavin T and iodoform described in JP-A-62-123489.

Further, Japanese Patent Application Laid-Open No. 60-88005 describes a photocurable resin composition material in which a constituent of a photopolymerization initiator is a combination of 3-ketocoumarins and a diaryl iodonium salt as a photocurable material with high sensitivity. Further, a gram recording material in which the photopolymerization initiator is combined with a polymer serving as a carrier and polymethylmethacrylate is disclosed in Japanese Patent Application Laid Open
No. 31590.

[0009]

However, the above-mentioned hologram recording material is a photosensitive resin composition whose main component is poly-N-vinylcarbazole, which has high resolution and high diffraction efficiency. Due to the crystallinity of N-vinylcarbazole itself or the solubility in a solvent, the resulting photosensitive resin composition is liable to become cloudy or white, and is inferior in transparency, which causes a problem in hologram reproducibility.

The latter is chemically stable and has high resolution,
Although it has high sensitivity, in the case of wet treatment, the polymer serving as a carrier causes some dissolution in the solvent in the swelling step,
There is a problem that uneven development is likely to occur, and since there are many voids in the hologram, there is a problem that heat resistance and pressure resistance are poor.

Further, as a hologram recording material when a wet process is not carried out in the developing step after exposure to light, Japanese Patent Application Laid-Open No. 2-3 is referred to.
No. 081, a solvent-soluble thermoplastic resin, a liquid ethylenically unsaturated monomer, a photopolymerization initiator and a plasticizer are used in combination to form a refractive index image only in the exposure process. There is a photopolymerizable composition. However, the sensitivity of this hologram recording material at 488 nm is as low as 30 mJ / cm ² and the plasticizer remains, so that the reproduction light wavelength is likely to shift to a short wavelength when exposed to high temperature,
In addition, there is a problem that the heat resistance of the HUD is poor.

Therefore, the present invention is excellent in heat resistance, weather resistance such as strength, and chemical stability, and is particularly excellent in resolution, diffraction efficiency, transparency and reproduction wavelength reproducibility in dry development processing.
A hologram recording material and a hologram recording medium are provided.

[0013]

The invention according to claim 1 is
Aromatic thermosetting resin having at least one addition-polymerizable ethylenically unsaturated bond in the structural unit and at least one substituent selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine. A hologram recording material comprising (A), a radically polymerizable aliphatic monomer (B), and a photopolymerization initiator (C) that activates radical polymerization by exposure.

A second aspect of the present invention is a hologram recording material based on the first aspect of the invention, wherein the aromatic heat-expensive resin (A) is an epoxy acrylate resin.

According to a third aspect of the present invention, the first aspect of the present invention is provided on a substrate.
The hologram recording medium is characterized in that a recording film made of the hologram recording material is formed, and an oxygen barrier film is formed on the recording film.

[0016]

According to the present invention, at least one ethylenically unsaturated bond capable of addition polymerization is contained in the structural unit, and at least one substituent selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine is used. Aromatic thermosetting resin (A) and radical-polymerizable aliphatic monomer (B)
And a photopolymerization initiator (C) that activates radical polymerization upon exposure, and the radically polymerizable aliphatic monomer (B) is uniformly dispersed in the aromatic heat-expensive resin (A). However, when exposed by laser (laser interference light) irradiation, the radical polymerization of the radical-polymerizable aliphatic monomer (B) at the site of strong light interference causes polymerization of the surrounding radicals by the action of the photopolymerization initiator. The polymerizable aliphatic monomer (B) moves. For this reason, the concentration of the radical-polymerizable aliphatic monomer (B) is high at the laser-irradiated portion where the light interference is strong, and the concentration of the radical-polymerizable aliphatic monomer (B) is high at the portion where the light interference action is weak. Is reduced. As a result, the refractive index is changed due to the difference in density due to the difference in density between the portion with strong optical interference and the portion with weak optical interference, and hologram recording is performed. Further, since the aromatic thermosetting resin (A) which becomes the support also has a cross-linked structure, weather resistance such as strength and chemical stability are improved.

Further, the hologram recording medium of the present invention is excellent in the reproducibility of the peak wavelength of reproduction light and its bandwidth.

[0018]

EXAMPLES The present invention will now be described in detail based on examples. FIG. 1 is a schematic diagram illustrating the configuration of a hologram recording medium made of the hologram recording material of the present invention, and FIG. 2 is a schematic explanatory diagram illustrating a two-beam optical system for hologram imaging.

The aromatic thermosetting resin (A) of the hologram recording material of the present invention has at least one addition-polymerizable ethylenically unsaturated bond in the structural unit, and is unsubstituted phenyl, substituted phenyl, It has at least one substituent selected from chlorine and bromine. For example, as shown in the following chemical formulas 1 to 3, bisphenol A type epoxy acrylate, brominated bisphenol A type epoxy acrylate, novolac type epoxy acrylate, etc. In addition to ether type epoxy acrylates, ester type epoxy acrylates may be mentioned, but the present invention is not limited thereto.

[0020]

[Chemical 1]

[0021]

[Chemical 2]

[0022]

[Chemical 3]

The radical-polymerizable aliphatic monomer (B) has at least one ethylenically unsaturated bond in the structural unit and contains a polyfunctional oligomer in addition to the vinyl monomer having one functional group. Alternatively, it may be a mixture thereof.

Specific examples include (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, and 2-hydroxyethyl (meth).
High boiling vinyl monomers such as acrylates, aliphatic polyhydroxy compounds such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, Examples thereof include di- or poly (meth) acrylic esters such as 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and mannitol. But,
It is not limited to this.

The photopolymerization initiator (C) is one which activates radical polymerization upon exposure to light, and examples thereof include organic peroxides and onium salts, which can be sensitized with an organic dye compound.

Specifically, as an example of the organic peroxide, first, tert-butyl peroxide-iso-butarate, 2,5-dimethyl-2,5-bis- (benzoyldioxy) hexane, 1,4- Bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-
tert-butyl peroxide, 2,5-dimethyl-
2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl)
-Iso-propyl hydroperoxide, 2,5-bis (hydroperoxy) -2,5-dimethylhexane, t
ert-butyl hydroperoxide, 1,1-bis (t
ert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, 2,2′5,5′-tetra (tert-butylperoxycarbonyl) benzophenone, 3, 3 ', 4,
4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t
ert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,
4′-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldioxyisophthalate and the like can be mentioned, but the present invention is not limited thereto.

Examples of onium salts are diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate,
Diphenyliodonium hexafluorophosphate,
Bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (P-Chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, tri (4-
Methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium Examples thereof include, but are not limited to, tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-ethoxyphenyl) phosphonium tetrafluoroborate, and the like.

Further, as the sensitizer of the present invention, organic dye compounds such as cyanine or merocyanine dyes, pyrylium or thiopyrylium salt dyes and coumarin dyes can be used.

Examples of cyanine or merocyanine dyes include fluorescein, rhodamine, 2'7'-dichlorofluorescein, 3,3'-dicarboxyethyl-2.
2'-thiocyanine bromide, anhydro-3,3'-
Dicarboxymethylbenzenes 2,2'-thio cyanine betaine, 1-carboxy-1 '- carboxyethyl -
2,2'-quinocyanine bromide, anhydro-3,
3'-dicarboxyethyl-5,5 ', 9-trimethyl-2,2'-thiacarbocyanine betaine, 3,3'-
Dihydroxyethyl-5,5'-dimethyl-9-ethyl-2,2'-thiacarbocyanine bromide, anhydro-3,3'-dicarboxymethyl-2,2'-thiacarbocyanine betaine, 2- [3- Ethyl-4-oxo-
5- (1-Ethyl-4-quinolinidene) ethylidene-2
-Thiazolinidene-methyl] -3-ethylzenzoxazolium bromide, 3-ethyl-5- [ 2- (3-ethyl-2-benzothiazoylidene) ethylidene] rhodamine, 3-ethyl-5- [2- (3-methyl-2 (3H)
-Thiazolinidene) ethylidene] -2-thio-2,4-
Oxazaridione, 3-ethyl-5- (3-ethyl-zenzothiazolilidene) rhodine, 2- (p-dimethylaminostyryl) -3-ethylbenzothiazolium iodide, 2- (p-dimethylaminostyryl) -1-ethylpyridinium iodide, 1,3'-diethyl-2,2 '
Quinothiacyanine iodide and the like, but are not limited thereto.

Examples of pyrylium or thiopyrylium salt dyes are 2-amino-4,6-bis (4-butoxyphenyl) thiopyrylium perchlorate and 2-hydroxy-4,6-bis (4-dimethylaminostyryl). )
Pyrylium perchlorate, 2-hydroxy-4,6-
Bis (4-dimethylaminostyryl) pyrrinium fluoroborate, 2-hydroxy-4,6-bis (4-dimethylaminostyryl) thiopyrrinium perchlorate, 2-hydroxy-4,6-bis (4-dimethylaminostyryl) ) Thiopyrylium fluoroborate, 2-amino-4,6-bis (4-butoxyphenyl) pyrylium perchlorate, 2-amino-4,6-bis (4-butoxyphenyl) pyrylium fluoroborate, 2-amino Examples thereof include, but are not limited to, -4,6-bis (4-methoxy-β-ethylstyryl) thiopyrylium fluoroborate.

Examples of coumarin dyes include 3- (2 '
-Benzimidazole) -7-N, N-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 3,3'-carbonylbiscoumarin,
3,3'-carbonylbis (7-methoxycoumarin),
3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (6-methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonyl Bis (5,7-di-is
o-propoxycoumarin), 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-
Carbonyl bis (5,7-di-n-butoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 7-diethylamino-5 ′, 7′-dimethoxy-3,3′-carbonylbiscoumarin , 3-benzoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-
Benzoyl-7-methoxycoumarin, 3-benzoyl-
8-methoxycoumarin, 3-benzoyl-8-ethoxycoumarin, 3-benzoyl-6-bromocoumarin, 3-
Benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-
7-hydroaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-acetyl-7-methoxycoumarin, 3-acetyl-5,7-dimethoxycoumarin, 7-
Examples include, but are not limited to, dimethylamino-3- (4-iodobenzoyl) coumarin, 7-diethylamino-3- (4-iodobenzoyl) coumarin, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin and the like. Not something.

As described above, the hologram recording material of the present invention has at least one addition-polymerizable ethylenically unsaturated bond in the structural unit and is selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine. Aromatic thermosetting resin (A) having at least one substituent, a radically polymerizable aliphatic monomer (B), and a photopolymerization initiator (C) that activates radical polymerization by exposure. The respective components are appropriately selected, and the photosensitive liquid obtained by mixing them at an arbitrary ratio and dissolving them in a suitable solvent is coated with a glass plate, a polycarbonate plate, a polymethylmethacrylate plate using a spin coater, a roll coater, a bar coater, or the like. A photosensitive layer 3 is formed by coating the substrate 2 such as a polyester film with a photosensitive layer 3 to obtain the hologram recording medium 1 shown in FIG. It is. A protective layer 4 may be provided on the photosensitive layer 3 to block oxygen. The protective layer 4 is formed by, for example, laminating a plastic such as polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or polyethylene terephthalate, or an optically transparent material such as glass, laminating with an extruder, coating a solution, etc. To be done.

The mixing ratio of each component of the hologram recording material of the present invention is not specified, but it is desirable to adjust the hologram recording material so that the transmittance of irradiation light at the time of hologram photographing is 1% or more. . Further, various additives such as known sensitizers, binders, plasticizers, thermal polymerization inhibitors, antioxidants or chain transfer agents may be added to the hologram recording material of the present invention, if necessary.

As an example of the constitution of the hologram recording material of the present invention, the amount of the radically polymerizable aliphatic monomer (B) is 20 to 200 parts by weight based on 100 parts by weight of the aromatic thermosetting resin (A). It is possible to take a range of parts,
It is preferably 40 to 140 parts by weight. The amount of the photopolymerization initiator (C) that activates radicals by exposure is 0.1 with respect to 100 parts by weight of the aromatic thermosetting resin (A).
To 20 parts by weight, preferably 1 to 10 parts by weight. The sensitizer is aromatic thermosetting resin (A) 1
It can be used in the range of 0.1 to 10 parts by weight with respect to 00 parts by weight, but the amount used is limited by the film thickness of the photosensitive layer film and its optical density (or optical density). It is preferable to use in a range that does not exceed (when the transmittance is set, the range is such that the transmittance of irradiation light at the time of hologram photographing is 1% or more). If it deviates from this range, it becomes difficult to obtain a high diffraction efficiency and the sensitivity characteristic deteriorates.

FIG. 2 is a schematic diagram for explaining a two-beam optical system for hologram photographing. Laser light 6 oscillated from a laser 5 passes through a mirror 7, a beam splitter 8, a spatial filter 9, and a lens 10. The hologram recording medium 1 is irradiated. In this embodiment, dry processing is performed without wet development processing.

In the exposure step of the interference pattern, a light source suitable for the hologram recording material of the present invention includes, but is not limited to, a helium-cadmium laser and an argon laser.

The post-exposure fixing step is carried out by overall exposure or heat treatment using a light source such as a helium-cadmium laser, an argon laser, a high pressure mercury lamp, or a xenon lamp.

When a hologram image is recorded on this hologram recording medium 1, a laser irradiation is applied in accordance with a desired image so that a portion of the laser irradiation portion having a strong optical interference action is an aromatic heat-expensive resin. Radical-polymerizable aliphatic monomer (B) uniformly dispersed in (A)
However, when exposed to laser (laser interference light) irradiation, the photopolymerization initiator acts to polymerize and polymerize, so that the radically polymerizable aliphatic monomer (B) around it is moved. For this reason, the concentration of the radical-polymerizable aliphatic monomer (B) is high at the laser-irradiated portion where the light interference is strong, and the concentration of the radical-polymerizable aliphatic monomer (B) is high at the portion where the light interference action is weak. Therefore, the hologram image recording is performed by the refractive index modulation due to the difference in the refractive index due to the difference in density between the portion of the hologram recording medium 1 having strong optical interference and the portion having weak optical interference. Furthermore, since the aromatic thermosetting resin (A) which becomes the support also has a cross-linked structure, the weather resistance such as the strength of the hologram recording medium 1 and the chemical stability are improved.

Further, the hologram recording material of the present invention will be described with reference to specific examples.

[Examples 1 to 6] (Example 1) ○ It has at least one ethylenically unsaturated bond capable of addition polymerization in its structural unit, and is selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine. Aromatic Thermosetting Resin (A) Bisphenol Epoxy Acrylate Resin Having at least One Substituent to be Used 100 parts by weight (Showa Polymer Co., Ltd. VR-60 theoretical molecular weight: 1950) ○ Radical polymerizable aliphatic Monomer (B) 2,2,2-trifluoroethyl acrylate 100 parts by weight ○ Photopolymerization initiator diphenyliodonium hexafluorophosphate 5 parts by weight ○ Sensitizer 3,3'-carbonylbis (7-diethylamino) coumarin 1 part by weight ○ Solvent: A photosensitive solution consisting of 100 parts by weight of 2-butanone was applied to a glass plate so that the film thickness was about 20 μm, and Further, a hologram recording medium 1 was prepared by coating the same with a polyvinyl alcohol (PVA) film.

The hologram recording medium 1 thus prepared is shown in FIG.
488n using an argon laser as a light source by the device of the two-beam optical system used in the ordinary hologram photographing shown in FIG.
After hologram recording was performed with light of m, a hologram was prepared, and then the entire surface of the photosensitive layer 3 of the hologram recording medium 1 was irradiated with a high pressure mercury lamp to fix the hologram.

The diffraction efficiency of this hologram was measured with a spectrophotometer (manufactured by JASCO Corporation). This device has a width of 3 mm
With a photo multimeter with slits, a width of 0.3 mm can be set on the circumference of a 20 cm radius centering around the sample.
The monochromatic light of was incident on the sample at an angle of 45 °, and the diffracted light from the sample was detected. The ratio of the maximum value other than the specular reflection light and the value when the incident light was received directly without placing the sample was defined as the diffraction efficiency.

Further, Examples 2 to 6 are the same as those of Example 1,
In addition to 2-trifluoroethyl acrylate (TFEA), 1,6-hexanediol diacrylate (HDODA), diethylene glycol diacrylate (DEGDA), neopentyl glycol diacrylate (NPGDA), trimethylolpropane triacrylate (TMPTA) as monomers. ) And pentaerythritol triacrylate (PETA), and a hologram recording medium and a hologram were similarly prepared for each of them, and the diffraction efficiency was measured. The results are shown in Table 1.

[0044]

[Table 1]

[Examples 7 to 12] Bisphenol epoxy acrylate resin (Aromatic thermosetting resin (A) of Example 1 (VR-60 theoretical molecular weight manufactured by Showa High Polymer Co., Ltd .:
1950) except that a bisphenol epoxy acrylate resin (VR-90 theoretical molecular weight: 1100 manufactured by Showa Highpolymer Co., Ltd.) was used, and a hologram recording medium and a hologram were prepared in the same manner as in Examples 1 to 6 and the diffraction efficiency was measured. . The results are shown in Table 2.

[0046]

[Table 2]

Examples 12 to 18 In place of the bisphenol epoxy acrylate resin (VR-60 theoretical molecular weight: 1950 manufactured by Showa High Polymer Co., Ltd.) of the aromatic thermosetting resin (A) of Example 1, diphthalic acid was used. A hologram recording medium and a hologram were prepared in the same manner as in Examples 1 to 6 except that glycidyl ester acrylate (Denacol Acrylate DA-721 manufactured by Nagase & Co., Ltd.) was used, and the diffraction efficiency was measured. The results are shown in Table 3.

[0048]

[Table 3]

[Examples 19 to 24] Tetrabromobisphenol was used instead of the bisphenol epoxy acrylate resin (VR-60 theoretical molecular weight: 1950 manufactured by Showa High Polymer Co., Ltd.) of the aromatic thermosetting resin (A) of Example 1. A hologram recording medium and a hologram were prepared in the same manner as in Examples 1 to 6 except that tetrabromobisphenol A epoxy diacrylate synthesized by the reaction of A with glycidyl methacrylate was used, and the diffraction efficiency was measured. The results are shown in Table 4.

[0050]

[Table 4]

[Examples 25 to 30] 3,3'-carbonylbis (7-diethylamino) which is the sensitizer of Example 1
A hologram recording medium and hologram were prepared in the same manner as in Examples 1 to 6 except that meso-diphenyltetrabenzoporphine was used instead of coumarin, and the diffraction efficiency was measured.
The results are shown in Table 5. However, a krypton laser (647 nm) was used instead of an argon laser at the time of exposure.

[0052]

[Table 5]

[Examples 30 to 36] 2,2 ', 5,5'-tetra (te) was used instead of diphenyliodonium hexafluorophosphate, which is the photopolymerization initiator of Example 1.
A hologram recording medium and hologram were prepared in the same manner as in Examples 1 to 6 except that rt-butylperoxycarbonyl) benzophenone was used, and the diffraction efficiency was measured. The results are shown in Table 6.

[0054]

[Table 6]

In order to evaluate the characteristics of the hologram recording material of the present invention, a photosensitive material made of another substance was prepared,
A hologram recording medium and a hologram were prepared under the same conditions, and the diffraction efficiency was measured. Comparative Example 1 Instead of the bisphenol epoxy acrylate resin (VR-60 theoretical molecular weight: 1950 manufactured by Showa High Polymer Co., Ltd.) of the aromatic thermosetting resin (A) of Example 1, an ethylene glycol epoxy acrylate resin (Kyoeisha Co., Ltd.) was used. A hologram recording medium and a hologram were prepared in the same manner as in Example 1 except that Epolite 40E manufactured by Yushi Kagaku Kogyo Co., Ltd. was used, but the hologram could not be formed.

[Comparative Examples 2 and 3] Phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., viscoat #) instead of the radically polymerizable aliphatic monomer (B) of Example 1.
192) or benzyl acrylate (Biscoat # 160 manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used to prepare a hologram recording medium and hologram in the same manner as in Example 1, but no hologram was formed.

The holograms produced and evaluated in the above Examples 1 to 36 were subjected to an environment of 25 ° C. and 60% RH for 180 days,
Also, the hologram did not change even if left at 150 ° C. for 10 hours, and no decrease in diffraction efficiency was observed.

[0058]

As described above, the present invention has at least one addition-polymerizable ethylenically unsaturated bond in the structural unit.
Aromatic thermosetting resin (A) having one or more and at least one substituent selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine; and radically polymerizable aliphatic monomer (B) , A photopolymerization initiator (C) that activates radical polymerization upon exposure to light, has high sensitivity, high resolution, high diffraction efficiency, high transparency, and heat resistance such as heat resistance, especially in dry processing. A hologram recording material and a hologram recording medium having excellent properties and chemically stable can be provided. Further, it can be used as a hologram recording material for HOE having extremely high performance requirements.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating the configuration of a hologram recording medium made of the hologram recording material of the present invention.

FIG. 2 is a schematic diagram illustrating a two-beam optical system for hologram recording.

[Explanation of symbols]

 1 Medium for Hologram Recording 2 Base Material 3 Photosensitive Layer 4 Protective Layer 5 Laser 6 Laser Light 7 Mirror 8 Beam Splitter 9 Spatial Filter 10 Lens

Claims (3)

[Claims] 1. An aromatic having at least one addition-polymerizable ethylenically unsaturated bond in a structural unit and at least one substituent selected from unsubstituted phenyl, substituted phenyl, chlorine and bromine. Thermosetting resin (A)
And a radical-polymerizable aliphatic monomer (B), and a photopolymerization initiator (C) that activates radical polymerization upon exposure to light. 2. The aromatic thermosetting resin (A) is an epoxy acrylate resin.
The hologram recording material described. 3. A hologram recording medium comprising a substrate on which a recording film made of the hologram recording material of claim 1 is formed, and an oxygen barrier film is formed on the recording film.