JP2001109360A - Hologram recording material composition, hologram recording medium and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram recording material composition which can eliminate the laboriousness of film making operation while exhibiting the good performance, such as good transparency, diffraction efficiency and resolution, which are the characteristics required for a hologram in the same manner as for the conventional compositions. SOLUTION: This hologram recording material composition consists of an allyl prepolymer A having at least one allyl group in the molecule, a (meth) acrylate component B having at least one polymerizable unsaturated group within the molecule and a photopolymerization initiator C. The allyl prepolymer A and the (meth)acrylate component B are so selected that the difference between the refractive index of the former polymer and the refractive index of the latter attains >=0.005, more preferably >=0.01. The weight ratio A:B of the allyl prepolymer A and the (meth)acrylate component B is preferably 5:95 to 95:5, more preferably 10:90 to 90:10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hologram recording material composition, and more particularly to a hologram recording material composition which can be easily formed into a film when producing a hologram recording medium.
Furthermore, the present invention relates to a hologram recording medium obtained therefrom and a method for producing the same.

[0002]

2. Description of the Related Art A hologram is a hologram in which an interference pattern of coherent light of a laser is recorded on a photosensitive material or the like. It has been used throughout.

As typical conventional hologram recording material compositions, there are known a dichromated gelatin photosensitive material and a bleached silver salt photosensitive material (for example, "Display Holography Handbook", pp. 66-67, Dawn Stamp Library (1985), "Optical Engineering Handbook", No. 351
-353 pages, Asakura Shoten (1986)).

However, although dichromated gelatin has a high diffraction efficiency and bleached silver salt photographic materials have high sensitivity, all of these are complicated in the processing of hologram production, and particularly require wet development. There was a disadvantage that it was required.

A hologram recording material composition containing a photopolymerizable monomer has been proposed as a photosensitive material for overcoming such disadvantages. This is to record a hologram by photopolymerizing a photopolymerizable monomer in a portion of the interference pattern where the amount of light is large, thereby causing a refractive index modulation in that portion. For example, a photopolymerizable recording material containing cyclohexyl methacrylate as a photopolymerizable monomer, N-vinylcarbazole and a photopolymerization initiator as main components, or
Photopolymerizable recording materials mainly containing butyl methacrylate and ethylene glycol dimethacrylate as photopolymerizable monomers, 1-phenylnaphthalene as an inactive component not involved in polymerization and a photoinitiator (Applied Optics (Applied Optics) Appl. Opt.), Volume 15, 534
P. (1976)). However, since these materials are in a liquid state, the composition flows between the two surface materials during hologram recording, which hinders good recording. Also,
Even after the hologram recording, a portion having a small amount of light remains as an unreacted monomer, and it is necessary to stabilize the recording by performing a whole-surface exposure process again.

Incidentally, JP-A-3-36582 and JP-A-3-249885 disclose a hologram containing an allyl monomer and an acrylic monomer having different polymerization reactivity and refractive index of the obtained polymer as main components. A recording material composition is described. After the composition is injected between two surface materials, the composition is subjected to a heat treatment to suppress the fluidity of the composition and solve the above problems.

However, these hologram recording material compositions require heat treatment as described above in order to fix them between the two surface materials, and thus the film forming operation is complicated. There was a disadvantage.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide the hologram with the required characteristics such as good transparency, diffraction efficiency, and resolution in the same manner as the conventional hologram. An object of the present invention is to provide a hologram recording material composition that can eliminate the complicated film forming operation.

[0009]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found the following novel hologram recording material composition and completed the present invention.

That is, the hologram recording material composition according to the present invention comprises an allyl-based prepolymer (A) having at least one allyl group in the molecule and a (meth) acrylate having at least one polymerizable unsaturated group in the molecule. And the allyl-based prepolymer (A) and the (meth) acrylate-based compound (B) contain the compound (B) and the photopolymerization initiator (C), and the refractive index of the former and the refractive index of the polymer of the latter are different. Is selected so that the difference from the above is 0.005 or more.

The allyl prepolymer (A) used in the present invention is a prepolymer having at least one allyl group in the molecule, and a typical example is a diallyl phthalate prepolymer. The allyl-based prepolymer (A)
In addition to a homopolymer of an allyl-based monomer, a copolymer of the same monomer and another copolymerizable monomer may be used.
Examples of other monomers copolymerizable with the diallyl phthalate monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene. In this copolymer, usually, diallyl phthalate-based constitutional units are mainly used. The raw material diallyl phthalate monomer of the diallyl phthalate prepolymer is a compound selected from the group consisting of a diallyl orthophthalate monomer, a diallyl isophthalate monomer, and a diallyl terephthalate monomer, or a combination of two or more thereof.
In order to obtain a diallyl phthalate-based prepolymer by homopolymerization of a diallyl phthalate-based monomer, for example, a known polymerization reaction described in JP-B-35-16035 may be performed. Further, in order to obtain a diallyl phthalate-based prepolymer by copolymerizing a diallyl phthalate-based monomer with a diallyl phthalate-based monomer and another monomer copolymerizable with the monomer, for example, Industrial Chemistry Magazine, Vol. 70, No. 3, pp. 360-364 (19
67)). Examples of the allyl-based prepolymer (A) used in the present invention include a diallyl orthophthalate prepolymer, which is a homopolymer, for example, “Daiso Dap” (registered trademark) manufactured by Daiso Corporation, and a diallyl isophthalate prepolymer, for example, “Daiso Corporation” Isodap "(registered trademark), diallyl terephthalate prepolymer, is preferred. The diallyl terephthalate prepolymer may be a modified product thereof, for example, “Daprene” (registered trademark) manufactured by Daiso Corporation.

Further, the allylic prepolymer (A) is
In the presence of a diallyl phthalate-based monomer and / or a diallyl phthalate-based polymer, a metal atom, a group having an aromatic ring, and a metal alkoxide having a hydrolyzable group are expressed by a sol-gel method, as represented by the following general formula. It may be a transparent homogeneous organic-inorganic composite which is a metal oxide polymer obtained by dehydration-condensation (see WO 99/14274).

A metal alkoxide is a substance represented by the general formula X _mM (Ar) _n R ² _p .

Wherein X is an alkoxyl group represented by the general formula R ¹ O (R ¹ is a monovalent organic group), and M is a metal selected from the group consisting of silicon, titanium, zirconium, germanium and aluminum. An atom, Ar is a group having an aromatic ring, R ² is a monovalent organic group, m and n are numbers of 1 or more, and p is a number of 0 or more (where m + n + p is the valence of the metal atom M). ]

Specific examples of the metal alkoxide having a tetravalent metal atom (Si, Ti, Zr or Ge) include the following.

(CH ₃ O) ₃ MPh, (C ₂ H ₅ O) ₃
M (CH ₂ Ph), (C ₂ H ₃ O) ₃ M (C ₂ H ₄ OP
h), (C ₃ H ₈ NO) ₃ MPh, (C ₄ H ₉ O) ₃ M
(C ₃ H ₄ Ph), (CH ₄ NO) ₂ MPh ₂ , (C _{2
H 5 O) 2 M (CH} 3 MPh) 2, (C 3 H 5 O) 2 M
(C ₄ H ₈ Ph) ₂ , (C ₄ H ₁₀ NO) ₂ M (C ₂ H ₂
O ₂ Ph) ₂ , (CH ₃ O) ₂ M (C ₄ H ₉ NPh)
(C ₄ H ₉ ), (C ₂ H ₅ O) ₂ M (C ₄ H ₆ O ₂ P
h) (C ₃ H ₅ ), (C ₂ H ₃ O) ₂ M (C ₂ H ₄ P)
_{h) (C 2 H 5 O} ), (C 3 H 8 NO) 2 M (CH 2 P
h) (CH ₄ N), (C ₄ H ₉ O) ₂ MPh (C
H ₃ ), (CH ₄ NO) ₂ MPh (C ₂ H ₅ ), (C _{2
H 5 O) 2 M (CH} 2 Ph) (C 3 H 7 O), (C 3 H
₅ O) ₂ M (C ₂ H ₂ Ph) (C ₅ H ₉ O ₂ ), (C ₄
H ₁₀ NO) ₂ MPh (C ₄ H ₁₀ N), (CH ₃ O) ₂ M
(CH ₂ OPh) (C ₃ H ₇ ), (C ₂ H ₅ O) ₂ M
_{(C 5 H 8 O 2 Ph} ) (C 4 H 9), (C 2 H 3 O) 2
MPh (C ₃ H ₈ N), (C ₃ H ₈ NO) ₂ M (C ₂ H
₄ Ph) (C ₂ H ₅ ), (C ₄ H ₉ O) ₂ MPh (C ₂
H ₃ O ₂ ), (CH ₄ NO) ₂ MPh (C ₃ H ₇ ),
(C ₂ H ₅ O) ₂ M (CH ₃ NPh) (C ₃ H
₅ O ₂ ), (C ₃ H ₅ O) ₂ M (C ₄ H ₈ Ph) (C _{2
H 3), (C 4 H} 10 NO) 2 M (C 2 H 2 O 2 Ph)
(CH _3).

As the metal alkoxide, (CH ₃ O) _{3
MPh, (C 2 H 5 O} ) 3 MPh, (C 3 H 7 O) 3 M
Ph, (C ₄ H ₉ O) ₃ MPh, (CH ₃ O) ₂ MPh
_{2, (C 2 H 5 O} ) 2 MPh 2, (C 3 H 7 O) 2 MP
_{h 2, (C 4 H 9} O) phenyl alkoxysilanes are preferred, such as ₂ MPh _2, of which phenyl trimethoxy silane is most preferable.

Preferred examples of the aluminum alkoxide include the following.

(CH ₃ O) ₂ AlPh, (C ₂ H ₅ O)
₂ AlPh, (C ₃ H ₇ O) ₂ AlPh, (C ₄ H
₉ O) ₂ AlPh, (CH ₃ O) AlPh ₂ , (C ₂ H
₅ O) AlPh ₂ , (C ₃ H ₇ O) AlPh ₂ , (C ₄
H ₉ O) AlPh ₂ .

The allylic prepolymer (A) may have a thioether group and / or a halogen atom bonded to the main chain. The thioether group and / or halogen atom can be introduced by a method of adding a thiol compound and / or a halogen to a polymerization system of an allylic monomer, a method of adding a thiol compound and / or a halogen to an allylic prepolymer (A), or the like. Done. Examples of the thiol compound used for introducing a thioether group include thiophenols such as thiophenol, 2-chlorothiophenol, 4-chlorothiophenol, 4-tert-butylthiophenol, and 4-mercaptophenol; Examples thereof include dithiols such as thiodibenzenethiol; and aliphatic thiols such as n-butyl mercaptan and n-lauryl mercaptan. Examples of the halogen used for introducing a halogen atom include bromine and chlorine.

The above allyl-based monomer homopolymer or copolymer, the above-mentioned organic-inorganic composite transparent homogeneous material, and the thioether group (halogen) -containing allyl-based prepolymer may be used alone or in combination of two or more. May be used. Further, the organic-inorganic composite transparent homogeneous material and / or the thioether group (halogen) -containing allyl prepolymer may be used in combination with the allyl monomer homopolymer or copolymer.

The diallyl phthalate prepolymer has a softening temperature of 50 to 110 ° C., an iodine value of 50 to 95 as measured by a Wijs method, and 50% by weight of methyl ethyl ketone.
The solution viscosity (30 ° C.) is 50 to 300 centipoise, and the average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is 100.
00-100,000, preferably 30,000-6000
It is particularly preferred that the postpolymerizable prepolymer is 0.

The (meth) acrylate compound (B) used in the present invention has at least one polymerizable unsaturated group such as a (meth) acrylic group in the molecule, and comprises (meth) acrylic acid Is a compound obtained by esterifying the compound with a monohydric or polyhydric alcohol, or an oligomer such as a dimer or trimer thereof. The (meth) acrylate-based compound (B) may be fluorene (meth) acrylate. Generally, the refractive index of the polymer of the (meth) acrylate compound (B) is smaller than that of the allylic prepolymer (A). However, the polymer of fluorene (meth) acrylate has a refractive index larger than that of the allyl-based prepolymer (A). The (meth) acrylate compound (B) has at least one, preferably one to six, polymerizable unsaturated groups in the molecule.
The molecular weight of the (meth) acrylate compound (B) is preferably 2000 or less, more preferably 1500 or less. The (meth) acrylate-based compound (B) is selected according to the size of the refractive index modulation of the hologram produced, the application, and the like.

The (meth) acrylate compound (B) will be exemplified below. Mono (meth) acrylates include methyl methacrylate, ethyl methacrylate, n
-Butyl methacrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, methoxydiethylene glycol methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl Methacrylate,
2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tert-butyl methacrylate, isostearyl methacrylate,
n-butoxyethyl methacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxyethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, Examples include 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, isooctyl acrylate, isomyristyl acrylate, and isostearyl acrylate. Further, as the di (meth) acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,10-decane Diol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate DOO, tetraethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,
9-nonanediol diacrylate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,1
0-decanediol diacrylate and the like.
Examples of the tri (meth) acrylate include trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. Examples of the tetra (meth) acrylate include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, and tetramethylolmethanetetraacrylate. Examples of hexa (meth) acrylate include dipentaerythritol hexamethacrylate, dipentaerythritol hexaacrylate, and the like.

The oligomer is particularly preferably a dimer or trimer of a compound obtained by esterifying (meth) acrylic acid with a monohydric or polyhydric alcohol.

Examples of the fluorene (meth) acrylate include 9,9-bis (4- (2- (meth) acryloyloxymethoxy) phenyl) fluorene and 9,9-bis (4- (2- (meth) acryloyloxyethoxy). ) Phenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) phenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene and the like.

These exemplified compounds may be used alone or in combination of two or more.

As the (meth) acrylate compound (B), a di (meth) acrylate compound is preferable, and ethylene glycol dimethacrylate, neopentyl glycol diacrylate, nonaethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (n =
14), 9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene are particularly preferred.

In the hologram recording material composition according to the present invention, the allyl-based prepolymer (A) and the (meth) acrylate-based compound (B) have a difference between the refractive index of the former polymer and the refractive index of the latter polymer of 0.1. 005 or more, preferably 0.01
It is selected to be above. If this difference is less than 0.005, hologram formation is substantially impossible.
This difference is about 1.0 at the maximum.

The hologram recording material composition according to the present invention is almost solid and has excellent handleability.
In particular, the weight ratio of the allyl-based prepolymer (A) to the (meth) acrylate-based compound (B) is (A) :( B) = 5: 9.
The composition of 5-95: 5 is closer to a solid and easy to handle. The weight ratio (A) :( B) is more preferably 10:90 to 90:10, most preferably 2:90.
0:80 to 80:20.

Photopolymerization initiator (C) in the composition of the present invention
Include He-Ne (wavelength 633 nm), Ar (wavelength 515,488 nm), He-Cd (wavelength 442 nm)
Those which generate a radical by absorbing a laser beam, such as, for example, are preferably used. As such a photopolymerization initiator,
For example, a carbonyl compound alone or a combination of a carbonyl compound and a photosensitizing dye is preferably used. Also, a combination of an amine compound and a photosensitizing dye and a combination of a borate compound and a photosensitizing dye are effective as a photopolymerization initiator.

Examples of the carbonyl compound include benzyl, benzoin ethyl ether, benzophenone,
Diethoxyacetophenone can be exemplified.

As the photosensitizing dye, Michella ketone, acridine yellow, merocyanine, methylene blue, camphorquinone, eosin, decarboxylated rose bengal and the like are preferably used. The photosensitizing dye may be any as long as it absorbs light in the visible region.In addition to the above, for example, cyanine derivatives, merocyanine derivatives, phthalocyanine derivatives, xanthene derivatives, thioxanthene derivatives, acridine derivatives, porphyrin derivatives, coumarin derivatives , Quinolone derivatives, stilbene derivatives, oxazine derivatives, thiazine dyes and the like can also be used. Further, "Dye Handbook" (edited by Shin Okawara et al., Kodansha, 19
1986), "Functional Dye Chemistry" (Nobuo Ogawara et al., Edited by CMC, 1983), and "Specially Functional Materials" (Edited by Chuzaburo Ikemori et al., Edited by CMC, 1986) Can also be used. These may be used alone or in combination of two or more.

Examples of the amine compound include triethanolamine, triisopropanolamine and 2-dimethylaminobenzoic acid.

Examples of the borate compound include triphenyl-n-butyl borate.

Specific examples of the combination of the carbonyl compound and the photosensitizing dye include benzyl-Michler's ketone and benzyl-acridine yellow. As the photosensitizing dye to be combined with the amine compound, decarboxylated rose bengal is preferable. As the photosensitizing dye to be combined with the borate compound, a cyanine dye such as a cyanine, an isocyanine, and a pseudocyanine is preferable.

Photopolymerization initiator (C) in the composition of the present invention
When a carbonyl compound is used, the addition amount is usually 0.1 to 1 with respect to 100 parts by weight of the total of the allyl-based prepolymer (A) and the (meth) acrylate-based compound (B).
It is about 5% by weight, preferably about 0.3 to 3% by weight. When a photosensitizing dye is combined with a carbonyl compound, an amine compound or a borate compound, the total of the above compound and the photosensitizing dye is the total of the allyl-based prepolymer (A) and the (meth) acrylate-based compound (B). It is usually used in an amount of about 0.1 to 15% by weight, preferably about 0.3 to 3% by weight, based on 100 parts by weight.

The hologram recording material composition according to the present invention comprises a solvent-soluble thermoplastic resin (D) in addition to the allylic prepolymer (A), (meth) acrylate compound (B) and photopolymerization initiator (C). ) May be included.
The weight ratio of the thermoplastic resin (D) is (A) :( D) = 80: 20 to 100:
0, preferably 85:15 to 100-0. The solvent-soluble thermoplastic resin (D) has a refractive index of 1.300.
~ 1.800 are preferably used, and specifically,
Condensation polymer of diphenol compound and dicarboxylic acid compound, resin having carbonate group in molecule,-
A homopolymer or copolymer obtained by polymerizing at least one of a resin having an SO ₂ — group, polyvinylidene chloride, and a monomer having an ethylenically unsaturated double bond is preferable. Each of these polymers can be used alone.
You may use it in combination of types or more.

Examples of the condensation polymer of a diphenol compound and a dicarboxylic acid compound include polyarylate,
Examples of the resin having a carbonate group in the molecule include polycarbonate, and examples of the resin having a -SO ₂ -group in the molecule include polysulfone and polyethersulfone, and an ethylenically unsaturated double Examples of the homopolymer or copolymer of a monomer having a bond include polystyrene, polymethyl methacrylate, ethylene-vinyl acetate copolymer, polymethylpentene, a cyclic olefin polymer, a cyclic olefin and ethylene copolymer, and the like. Is mentioned.

To obtain good diffraction efficiency, polyarylate and polysulfone are preferably used.

The hologram recording material composition according to the present invention can contain additives such as a viscosity modifier, a compatibility modifier, a thermal polymerization inhibitor, a chain transfer agent, etc., and a solvent, if necessary.

As the viscosity modifier and the compatibility modifier,
Diallyl phthalate monomer, styrene, 2,2-bis (4-methacryloyloxyphenyl) propane, 3
-Phenoxy-2-hydroxypropyl acrylate,
Polymerizable monomers such as divinylbenzene and vinyl biphenylcarboxylate, and phthalates such as dimethyl phthalate and diethyl phthalate; aliphatic dibasic acids such as dimethyl adipate, dibutyl adipate, dimethyl sebacate and diethyl succinate Esters; orthophosphates represented by trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; acetates represented by glyceryl triacetate and 2-ethylhexyl acetate; triphenyl phosphite, dibutyl hydrogenene Inactive compounds such as phosphites represented by phosphite are exemplified. Further, polyethylene glycol or silicone oil having a weight average molecular weight of 10,000 or less can also be used.

Further, inorganic fine particles, for example, silica gel fine particles (such as “Daiso Gel SP Series” manufactured by Daiso Corporation) or organic fine particles, for example, Japanese Patent Application Laid-Open No. 10-725.
10, diallyl phthalate-based polymers that can be prepared by the methods described in JP-A-10-310684, or “New Material Series“ Advanced Technology of Ultrafine Polymers ””
(CMC, supervised by Soichi Muroi, 1991), "PB, 200 series" manufactured by Kao Corporation, "Bell Pearl Series" manufactured by Kanebo, "Techpolymer Series" manufactured by Sekisui Plastics, manufactured by Sekisui Fine Chemical "Micropearl series", "MR series" and "MP series" manufactured by Soken Chemical Co., Ltd. can also be used as viscosity modifiers. The particle size of these fine particles may be smaller than the film thickness of the hologram, and is usually preferably in the range of 0.1 to 20 μm.

The addition amount of the viscosity modifier and the compatibility modifier is preferably 0.5 to 30 parts by weight based on 100 parts by weight of the total of the allyl prepolymer (A) and the (meth) acrylate compound (B). It is about.

Examples of the thermal polymerization inhibitor include, for example, hydroquinone which has a function of eliminating generated radicals, and examples of the chain transfer agent include α-methylstyrene dimer.

The solvent is effective not only for adjusting the viscosity and the compatibility but also for improving the film forming property. For example, acetone, xylene, toluene, methyl ethyl ketone, tetrahydrofuran and the like are often used. The amount of solvent used is
0.5 to 10 based on a total of 100 parts by weight of the allyl-based prepolymer (A) and the (meth) acrylate-based compound (B)
It is about 00 parts by weight.

To prepare the hologram recording material composition, for example, an allyl prepolymer (A), a (meth) acrylate compound (B) and a photopolymerization initiator (C) are prepared.
If necessary, the above optional components, for example, a solvent-soluble thermoplastic resin (D), additives, a solvent and the like are placed in an organic solvent-resistant container such as a glass beaker, and the whole is stirred. In this case, in order to promote the dissolution of the solid component, the composition may be heated to, for example, about 40 to 90 ° C. as long as the composition is not denatured.

In order to prepare a hologram recording medium using the hologram recording material composition according to the present invention, the recording material composition is applied to one surface of a substrate, and the resulting coating film, ie, a two-layered recording layer and substrate, is formed. Obtain a recording medium with a structure. Also,
If necessary, a three-layer structure is obtained by covering the recording layer on the substrate with a film-like, sheet-like or plate-like protective material.
It is preferable to use a solvent in the step of preparing the composition. In this case, the allyl-based prepolymer (A), (meth) acrylate-based compound (B), and photopolymerization initiator (C) are dissolved or suspended in a solvent, and the resulting solution or suspension is placed on a substrate. After coating, the solvent is volatilized to form a recording layer. When covering the recording layer with a protective material, it is preferable to remove the solvent by air drying or evaporation under reduced pressure before coating the protective material. The substrate is made of an optically transparent material such as a glass plate or polyethylene terephthalate (hereinafter abbreviated as PET).
It comprises a plate, a polycarbonate plate, a plastic plate such as a polymethyl methacrylate plate, or the like. The thickness of the substrate is preferably 0.5 to 10 mm. The protective material is also made of an optically transparent material like the substrate. The substrate does not need to be flat, but may be bent or curved, or have an uneven structure on the surface. The thickness of the protective material is preferably 0.01 to 10 mm
It is. The application method includes gravure application, roll coating application, bar coat application and the like. It is preferable to apply the coating so that the thickness of the recording layer after removing the solvent is 1 to 100 μm.

For recording a hologram on a hologram recording medium, a usual recording method can be adopted. In other words, the laser beam is split into two beams, one of the beams is irradiated on the object, and the interference between the object beam reflected from the object and the reference beam, which is the laser beam of the other, is generated. The recording medium is set at a position where the stripes can be captured. In this state, when laser light irradiation is performed for several seconds to several minutes, interference fringes serving as holograms are recorded on the recording medium. The light amount of the laser light used is represented by the product of the light intensity and the irradiation time, and is preferably 10 to 10,000 mJ / cm.
^{About 2} . If the amount of light is less than this range, recording is difficult, and if it exceeds this range, the diffraction efficiency of the hologram tends to decrease.

After the hologram is formed, post-processing such as development and fixing is not essential. However, in order to stabilize the formed image, the entire surface is irradiated with light or subjected to a heat treatment, and the remaining unreacted monomer is May be post-polymerized.

Further, a hologram can be copied on a recording medium obtained by using the recording material composition according to the present invention. For example, on the protective material surface of the recording medium having the three-layer structure,
The recorded hologram plates are closely overlapped as an original image, and the original image hologram plate is irradiated from above with a high-pressure mercury lamp. As a result, the light interferes between the reference light entering the recording layer of the unrecorded recording medium without diffracting and the diffracted light of the original image (that is, the object light), and the holograph is copied on the recording medium, and the original image is reproduced. A faithful hologram is obtained.
If a good hologram can be obtained by the copying method,
This proves that a hologram can be produced by laser interference.

The allylic prepolymer (A) remains in the recording medium even after producing a hologram on the recording medium obtained by using the recording material composition according to the present invention. Therefore, it is conceivable to use this functionally. For example, the recording material composition according to the present invention can be firmly attached to a substrate by forming the substrate from an unsaturated polyester resin and chemically bonding the remaining allyl groups of the prepolymer (A) to the unsaturated groups of the substrate resin. Can be fixed. As described above, by utilizing the function of the residual allyl group of the allyl-based prepolymer (A), various variations can be given to the material characteristics of the hologram, and a hologram having physical properties that can be used in various applications can be obtained. .

[0053]

In the recording material composition of the present invention, the allylic prepolymer (A) and the (meth) acrylate compound (B) are completely compatible before exposure, but the (meth) acrylate is irradiated with the laser light. The system compound (B) is polymerized by photopolymerization, and finally becomes a hologram recording layer.

That is, when a two-layer structure obtained by applying the recording material composition according to the present invention on a substrate or a three-layer structure obtained by covering the recording layer with a protective material is exposed to an interference pattern, The (meth) acrylate compound (B), which has high photopolymerization reactivity in a portion having a large amount of light, starts photopolymerization, and the volume shrinks in that portion. The unpolymerized material flows from the portion having a small amount of light into the dent formed by this, and the allyl-based prepolymer (A) has a small amount of light due to phase separation of the allylic prepolymer (A) and the (meth) acrylate compound (B). The (meth) acrylate compound (B) diffuses to a small portion, and diffuses and moves to a large light amount portion, and the photopolymerization further proceeds. On the other hand, the photopolymerization proceeds in a portion with a small light amount with a slight delay from a portion with a large light amount. As a result, the portion with a large amount of light has a low refractive index,
The polymer of the (meth) acrylate-based compound (B) accumulates, while the polymer containing the allyl-based prepolymer (A) having a high refractive index accumulates in a portion where the amount of light is small. However,
When fluorene (meth) acrylate is used as the (meth) acrylate compound (B), a fluorene (meth) acrylate polymer having a high refractive index is accumulated in a portion having a large amount of light, and conversely, in a portion having a small amount of light. A polymer containing an allyl-based prepolymer (A) having a low refractive index accumulates.

Thus, an interference pattern based on the composition distribution according to the amount of light, that is, the interference pattern based on the difference in refractive index between the portion containing a large amount of the allyl-based prepolymer (A) and the portion containing a large amount of the (meth) acrylate-based compound (B) is used as a hologram It is formed.

[0056]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to several embodiments of the present invention. However, these examples do not limit the present invention.

Example 1 1) 8 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Dieso Dap, Type A”) and ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
"NK ester 1G") 2 g, benzyl 0.3 g as a polymerization initiator, Michler's ketone 0.1 g as a photosensitizing dye
And 22 g of acetone were mixed at room temperature to prepare a recording material composition comprising these components.

2) This composition was prepared as follows: 76 × 26 × 1.2 m
m was applied to one side of a glass substrate so as to have a thickness of 10 μm, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

In the recording layer of this recording medium, there is no phase separation or precipitation of the polymer and monomer, and since this recording layer is almost solid, it does not adhere to the hand even if it is touched by hand. Of course, there was no sagging. For this reason, the recording layer was excellent in handleability, did not shift from the substrate, and was easy to carry. Further, this recording layer maintained a constant thickness.

3) Next, the recording layer has a size of 76 × 26 m.
m, covered with a protective material made of PET film with a thickness of 10 μm, 3
A hologram recording photosensitive plate having a layer structure was produced.

4) On the surface of the protective material of the unrecorded photosensitive plate,
Another hologram plate that already records 70 lines / mm (diffraction efficiency: about 60%, resolution: about 2000 lines / mm)
Are closely overlapped as an original image, and the original image hologram plate is irradiated with a light ray from a distance of about 10 cm above the original hologram plate with a 100 W high-pressure mercury lamp (having peak wavelengths near 365 nm, 410 nm and 430 nm, respectively) for 1 to 3 minutes. The hologram was copied on an unrecorded photosensitive plate. When the illuminance was measured using an illuminometer capable of measuring from 330 nm to 490 nm, it was 3.0 m when the irradiation distance from the light source was 10 cm.
The energy was less than W / cm ² . Therefore,
Even if you keep recording for 10 minutes, the energy is 1800 mJ /
It was only about cm ² .

The copy thus obtained has no coloring,
Even without the development and fixing operations, the diffraction efficiency was about 30%, which was bright.

The copied hologram maintained a stable image for a long period of three months or more even after the protective material was peeled off.
This recording was performed only by the refractive index modulation, not the unevenness of the recording layer, and was a transparent hologram having almost no absorption in the visible part.

As described above, since a good hologram was obtained by the above-described copying method, it was proved that a hologram could be produced by laser interference.

Examples 2 to 8 1) A recording material was obtained by performing the same operation as in 1) of Example 1 except that the ratio of diallyl orthophthalate prepolymer to ethylene glycol dimethacrylate was changed as follows. A composition was prepared.

Polymer / monomer = 9/1 (g / g) (Example 2) Polymer / monomer = 7/3 (g / g) (Example 3) Polymer / monomer = 6/4 (g / g) ( Example 4) Polymer / monomer = 5/5 (g / g) (Example 5) Polymer / monomer = 4/6 (g / g) (Example 6) Polymer / monomer = 3/7 (g / g) (Example 7) Polymer / monomer = 2/8 (g / g) (Example 8) 2) to 4) By performing the same operations as in 2) to 4) of Example 1, a hologram recording photosensitive plate was obtained. Was produced and a hologram was copied thereon.

Each of the obtained copies has no coloring,
Even without the development and fixing operations, the diffraction efficiency was about 30%, which was bright.

Each of these copy holograms maintained a stable image for a long period of 3 months or more even when the protective material was peeled off. This recording was performed only by the refractive index modulation, not the unevenness of the recording layer, and was a transparent hologram having almost no absorption in the visible part.

Example 9 1) 3.5 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., "Diso Dap, Type K"), ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "NK ester 1G") 5 g, benzyl 0.1
5 g, Michler's ketone 0.05 g and acetone 11 g
Were mixed at room temperature to prepare a recording material composition comprising these components.

2) to 4) By performing the same operations as in 2) to 4) of Example 1, a hologram recording photosensitive plate was prepared and a hologram was copied thereon.

The obtained copy had no coloring, and was a bright product having a diffraction efficiency of about 30% even without the development and fixing operations.

Further, the copied hologram maintained a stable image for a long period of three months or more even when the protective material was peeled off.
This recording was performed only by the refractive index modulation, not the unevenness of the recording layer, and was a transparent hologram having almost no absorption in the visible part.

Example 10 1) Recording was carried out by performing the same operation as in Example 9 1), except that the diallyl orthophthalate prepolymer was replaced with a diallyl isophthalate prepolymer (manufactured by Daiso Co., Ltd., "Isodap"). A material composition was prepared.

2) to 4) By performing the same operations as in 2) to 4) of Example 1, a hologram recording photosensitive plate was prepared and a hologram was copied thereon.

The obtained copy had no coloring and was bright with a diffraction efficiency of about 30% even without the development and fixing operations.

Further, each of these copy holograms maintained a stable image for a long period of 3 months or more even when the protective material was peeled off. This recording was performed only by the refractive index modulation, not the unevenness of the recording layer, and was a transparent hologram having almost no absorption in the visible part.

Examples 11 to 23 1) The diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., "Dieso Dap, Type K") was replaced by the diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., "Dieso Dup, Type A"). A recording material composition was prepared by performing the same operation as 1) of Example 9 except that ethylene glycol dimethacrylate was changed to the following.

Triethylene glycol dimethacrylate (“NK ester 3G”, manufactured by Shin-Nakamura Chemical Co., Ltd.) (Example 11) 1,3-butanediol dimethacrylate (“NK ester BG”, manufactured by Shin-Nakamura Chemical Co., Ltd.) Example 12) 1,6-hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester HD”) (Example 13) neopentyl glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester NPG”) (Example 14) Tetraethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-200”) (Example 1)
5) Nonaethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-400”) (Example 16) 1,6-hexanediol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., “NK Ester A-HD”) )) (Example 17) Neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester A-NPG”) (Example 18) Trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester TMPT”) (Example 1)
9) Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-TMPT”) (Example 2)
0) Tetramethylolmethanetetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-TMMT”) (Example 21) Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester ADP-6”) ( Example 2
2) 9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene (BPEF, manufactured by Osaka Gas Co., Ltd.)
A ") (Example 23) 2) to 4) By performing the same operations as in 2) to 4) of Example 1, a hologram recording photosensitive plate having a three-layer structure was produced, and a hologram was copied thereon.

Each of the obtained copy products had no coloration, and was a bright product having a diffraction efficiency of about 30% without any operation of development and fixing.

Further, each of these copy holograms maintained a stable image for a long period of 3 months or more even when the protective material was peeled off. This recording was performed only by the refractive index modulation, not the unevenness of the recording layer, and was a transparent hologram having almost no absorption in the visible part.

Example 24 1) 6 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Dieso Dap, Type A”) and ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
4 g of "NK ester 1G"), 0.5 g of benzyl, 0.17 g of Michler's ketone and 22 g of acetone were mixed at room temperature to prepare a recording material composition comprising these components.

2) 50 × 60 × 1.5 m of this composition
m was applied to one side of a glass substrate so as to have a thickness of 10 μm, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, a protective material made of a glass plate of the same size as that described above was covered on the recording layer to produce a sandwich-shaped hologram recording photosensitive plate having a three-layer structure.

4) Next, the subject was irradiated with He-Cd laser light to cause interference between the reference light reflected from the reflector and the object light reflected from the object. The hologram recording photosensitive plate having the three-layer structure was installed at a position where a stripe pattern formed by the interference could be captured. In this state, H
Expose the photosensitive plate with e-Cd laser light for a predetermined time (9 mW /
cm ² ), the exposure time was 15 seconds with only this operation,
Interference fringes serving as holograms could be recorded on the photosensitive plate at any of the following times: 30 seconds, 45 seconds, 1 minute, 2 minutes, 5 minutes, and 10 minutes.

No development or fixing operation was required. Since the recording layer is sandwiched between two glass plates, the thickness of the recording layer is uniform even after exposure, and there is no unevenness between the part where the light hits the recording layer strongly and the part where the light hits the light weakly. Was performed by refractive index modulation. Thus, a transparent and bright hologram (resolution 9
40 / mm) were obtained. Even when the protective material was peeled off, a stable image was maintained.

Example 25 1) 5 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Dieso Dap, Type A”) and ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
5 g of “NK ester 1G”, 0.5 g of benzyl, 0.17 g of Michler's ketone and 22 g of acetone were mixed at room temperature to prepare a recording material composition comprising these components.

2) This composition was placed in a size of 50 × 60 × 1.5 m
m was applied to one side of a glass substrate so as to have a thickness of 10 μm, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, a 50 × 60 layer is formed on the recording layer.
mm, a protective material made of PET film with a thickness of 10 μm,
A hologram recording photosensitive plate having a three-layer structure was produced.

4) Next, the subject was irradiated with He-Cd laser light to cause the reference light reflected from the reflecting mirror to interfere with the object light reflected from the object. The hologram recording photosensitive plate having the three-layer structure was installed at a position where a stripe pattern formed by the interference could be captured. In this state, H
Expose the photosensitive plate with e-Cd laser light for a predetermined time (9 mW /
cm ² ), the exposure time was 15 seconds with only this operation,
Interference fringes serving as holograms could be recorded on the photosensitive plate at any of the following times: 30 seconds, 45 seconds, 1 minute, 2 minutes, 5 minutes, and 10 minutes.

No development or fixing operation was required. Since the recording layer is sandwiched between the glass substrate and the PET film protective material, the thickness of the recording layer is uniform even after exposure, and the portion between the portion where the recording layer surface is strongly exposed to light and the portion where the recording layer surface is weakly exposed is exposed. There were no irregularities, and recording was performed by refractive index modulation. Thus, a transparent and bright hologram (resolution: 940 lines / mm) having almost no absorption in the visible region was obtained. Even when the protective material was peeled off, a stable image was maintained.

Example 26 1) A recording material composition was prepared by performing the same operation as in 1) of Example 1.

2) This composition was placed in a size of 50 × 60 × 1.5 m
m was applied to one side of a glass substrate so as to have a thickness of 10 μm, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, a protective material made of a glass plate having the same size as that described above was covered on the recording layer, and a hologram recording photosensitive plate having a sandwich-like three-layer structure was produced.

4) Next, the subject was irradiated with He-Cd laser light to cause interference between reference light reflected from the reflecting mirror and object light reflected from the object. The hologram recording photosensitive plate having the three-layer structure was installed at a position where a stripe pattern formed by the interference could be captured. In this state, H
Expose the photosensitive plate with e-Cd laser light for a predetermined time (10 mW
/ Cm ² ), an interference fringe to be a hologram could be recorded on the photosensitive plate in a few minutes only by this operation.

No development or fixing operation was required. Since the recording layer is sandwiched between two glass plates, the thickness of the recording layer is uniform even after exposure, and there is no unevenness between the part where the light is strongly applied to the surface of the recording layer and the part where the light is weakly applied. Was performed by refractive index modulation. Thus, a transparent and bright hologram (diffraction efficiency: 60%, resolution: 2000 lines / mm or more) with little absorption in the visible region was obtained. Even when the protective material was peeled off, a stable image was maintained.

Tables 1 and 2 show the recording material compositions obtained in Examples 1 to 23 and whether or not copying was possible using the same.
Are shown together.

[0097]

[Table 1]

[0098]

[Table 2]

Examples 27 to 36 1) 2 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Dieso Dap, Type A”), 3 g of (meth) acrylate monomer shown in Table 3 and 0.1 g of benzyl.
25 g, Michler's ketone 0.085 g and acetone 3.5 g were mixed at room temperature to prepare a recording material composition comprising these components.

2) This composition was used for 60 × 60 × 1.3 m
An appropriate amount was applied to one surface of a glass substrate having a thickness of m, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, 1 mm × 6
A 20-μm-thick PET film cut into 0 mm strips was laid, and a protective material made of a glass plate having the same size as above was placed on the PET film to produce a sandwich-shaped hologram recording photosensitive plate having a three-layer structure.

4) Next, the object light and the reference light were caused to interfere with each other using a He-Cd laser. The hologram recording photosensitive plate having the three-layer structure was installed at a position where a stripe pattern formed by the interference could be captured. In this state, He-C
d Expose the photosensitive plate with laser light for a predetermined time (2.5 mW / c
m ² ), hologram interference fringes could be recorded on the photosensitive plate.

Table 3 summarizes the recording material compositions obtained in Examples 27 to 36 and the results of diffraction efficiency measurements performed using the recording material compositions.

[0104]

[Table 3]

Example 37 1) 2 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “DAISO DAP, type A”) and 3 g of neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester A-NPG”) 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (manufactured by NOF Corporation, "B
TTB-25 ") 1.75 g, 3,3 as photosensitizing dye
0.005 g of 3'-carbonylbis [7- (diethylamino) coumarin] (manufactured by Midori Kagaku Co., Ltd., "BC") and 4 g of acetone were mixed at room temperature to prepare a recording material composition comprising these components.

2) This composition was used for 60 × 60 × 1.3 m
An appropriate amount was applied to one surface of a glass substrate having a thickness of m, and acetone was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, 1 mm × 6
A 20-μm-thick PET film cut into 0 mm strips was laid, and a protective material made of a glass plate having the same size as above was placed on the PET film to produce a sandwich-shaped hologram recording photosensitive plate having a three-layer structure.

4) Next, an Ar laser (wavelength 488 n
m) to cause interference with the object light and the reference light. The above-mentioned 3 is located at a position where a stripe pattern formed by this interference can be captured.
A hologram recording photosensitive plate having a layer structure was provided. In this state, the photosensitive plate is exposed to Ar laser light for a predetermined time (20 mW
/ Cm ² ), hologram interference fringes could be recorded on the photosensitive plate.

The obtained hologram had an exposure amount of 100 mJ /
The diffraction efficiency was 89% in cm ² .

Example 38 1) 2.3 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Dieso Dap, Type A”)
9,9-bis (4- (2-acryloyloxyethoxy) phenyl) fluorene (manufactured by Osaka Gas Co., Ltd., “BPEF
A ") 1.8 g, vinyl biphenylcarboxylate (Nippon Steel Chemical Co., Ltd.) 0.9 g, 3, 3 ', 4, 4'-tetra (te
1.75 g of rt-butylperoxycarbonyl) benzophenone ("BTTB-25" manufactured by NOF Corporation)
0.005 g of 3'-carbonylbis [7- (diethylamino) coumarin] (manufactured by Midori Kagaku Co., Ltd., "BC") and 4 g of tetrahydrofuran were mixed at room temperature to prepare a recording material composition comprising these components.

2) This composition was used for 60 × 60 × 1.3 m
An appropriate amount was applied to one surface of a glass substrate having a thickness of m, and tetrahydrofuran was removed from the coating layer under reduced pressure to produce a recording medium having a two-layer structure including the substrate and the recording layer.

3) Next, 1 mm × 6
Spread a PET film with a thickness of 20 μm cut into 0 mm strips, cover with a glass plate protective material of the same size as above,
A hologram recording photosensitive plate having a sandwich-like three-layer structure was produced.

4) Next, an Ar laser (wavelength 488n)
m) to cause interference with the object light and the reference light. The above-mentioned 3 is located at a position where a stripe pattern formed by this interference can be captured.
A hologram recording photosensitive plate having a layer structure was provided. In this state, the photosensitive plate was exposed to Ar laser light for a predetermined time (2 mW /
cm ² ), hologram interference fringes could be recorded on the photosensitive plate.

The obtained hologram has an exposure amount of 40 mJ / c.
The diffraction efficiency was 47% at m ² .

Example 39 1) 2.3 g of triallyl isocyanurate prepolymer (manufactured by Nippon Kasei Co., Ltd., “Tyke Prepolymer”), neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK Ester A-NPG”) ) 2.7 g, 3,
3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (manufactured by NOF CORPORATION, "BTTB-
25 ") 1.75 g, 3,3'-carbonylbis [7-
(Diethylamino) coumarin] (Midori Chemical Co., Ltd., “B
C ") 0.02 g of acetone and 4 g of acetone were mixed at room temperature to prepare a recording material composition comprising these components.

2) to 4) By performing the same operations as in 2) to 4) of Example 38, a hologram recording photosensitive plate was produced to obtain a hologram.

The hologram obtained had an exposure of 50 mJ /
cm ² , 100 mJ / cm ² and 200 mJ / cm ²
In each case, the recording was possible, and the diffraction efficiency was about 30%.

Example 40 1) 5.5 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Daiso Dap, Type A”) was dissolved in 27.5 ml of acetone. 0.1N HCl was added to 4.5 g of phenyltrimethoxysilane prepared separately.
0.41 g of the aqueous solution was dissolved, and the above solution was mixed with the acetone solution, followed by stirring at 20 ° C. for 1 hour. This solution was heated in an oven at a heating rate of 10 ° C. per hour from 20 ° C. to 80 ° C., and left at 80 ° C. for about 3 days to remove the solvent, by-produced methanol and water, and as a product (Transparent diallyl phthalate resin-inorganic composite transparent homogeneous body) was obtained.

2) 2.5 g of this product, neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “N
K ester A-NPG ") 2.5 g, 3, 3 ', 4,
4'-tetra (tert-butylperoxycarbonyl)
Benzophenone ("BTTB-25", manufactured by NOF Corporation)
1.75 g, 3,3'-carbonylbis [7- (diethylamino) coumarin] ("BC", manufactured by Midori Kagaku)
0.005 g and acetone 4 g were mixed at room temperature to prepare a recording material composition comprising these components.

3) to 5) By performing the same operations as in 2) to 4) of Example 38, a photosensitive plate for hologram recording was produced to obtain a hologram.

The obtained hologram had an exposure amount of 50 mJ /
cm ² , 100 mJ / cm ² and 150 mJ / cm ²
In each case, the recording was possible, and the diffraction efficiency was about 30%.

Example 41 1) 3 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Diso Dap, Type A”), 1 g of thiophenol (manufactured by Sumitomo Seika Co., Ltd., “TP”), and azobisisobutyro as a catalyst 0.02 g of nitrile in 30 of acetone
Dissolved in ml. This solution was refluxed at 70 ° C. for 2 hours, and methanol 2 in which 0.1 g of hydroquinone was dissolved was added.
The resulting product was obtained by adding thiol to diallyl orthophthalate prepolymer.

2) 2.5 g of this product, neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “N
K ester A-NPG ") 2.5 g, 3, 3 ', 4,
4'-tetra (tert-butylperoxycarbonyl)
Benzophenone ("BTTB-25", manufactured by NOF Corporation)
1.75 g, 3,3'-carbonylbis [7- (diethylamino) coumarin] ("BC", manufactured by Midori Kagaku)
0.005 g and acetone 4 g were mixed at room temperature to prepare a recording material composition comprising these components.

3) to 5) By performing the same operations as in 2) to 4) of Example 38, a photosensitive plate for hologram recording was produced to obtain a hologram.

The obtained hologram had an exposure amount of 50 mJ /
cm ² , 100 mJ / cm ² and 150 mJ / cm ²
In each case, the recording was possible, and the diffraction efficiency was about 30%.

Example 42 1) 10 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “Daiso Dap, Type A”) was dissolved in 300 ml of carbon tetrachloride. While stirring the solution at 5 ° C. or lower, 30 ml of bromine was added dropwise over about 1 hour. This solution was added to 1000 g of methanol in which 0.1 g of hydroquinone was dissolved to obtain a product in which bromine was added to the diallyl orthophthalate prepolymer precipitated.

2) 2.5 g of this product, neopentyl glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “N
K ester A-NPG ") 2.5 g, 3, 3 ', 4,
4'-tetra (tert-butylperoxycarbonyl)
Benzophenone ("BTTB-25", manufactured by NOF Corporation)
1.75 g, 3,3'-carbonylbis [7- (diethylamino) coumarin] ("BC", manufactured by Midori Kagaku)
0.005 g and acetone 4 g were mixed at room temperature to prepare a recording material composition comprising these components.

3) to 5) By performing the same operations as in 2) to 4) of Example 38, a hologram recording photosensitive plate was produced to obtain a hologram.

The obtained hologram had an exposure amount of 50 mJ /
cm ² , 100 mJ / cm ² and 150 mJ / cm ²
In each case, the recording was possible, and the diffraction efficiency was about 30%.

In Examples 27 to 42, development and fixing operations were unnecessary. Since the recording layer is sandwiched between two glass plates, the thickness of the recording layer is uniform even after exposure, and there is no unevenness between the part where the light hits the recording layer strongly and the part where the light hits the light weakly. Was performed by refractive index modulation. Thus, a transparent and bright hologram having almost no absorption in the visible region was obtained. Even when the protective material was peeled off, a stable image was maintained.

Example 43 1) 8.5 g of diallyl orthophthalate prepolymer (manufactured by Daiso Co., Ltd., “DAISO DAP, type A”), 10 g of ethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “NK ester 1G”), As a solvent-soluble thermoplastic resin, polyarylate (manufactured by Unitika, "U-
100 ") 1.5 g, benzyl 0.6 as a polymerization initiator
g, 0.2 g of Michler's ketone as a photosensitizing dye and 20 g of methylene chloride were mixed at room temperature to prepare a recording material composition comprising these components.

2) to 4) By performing the same operations as in 2) to 4) of Example 1, a hologram recording photosensitive plate was prepared, and a hologram was copied on the plate.

The obtained copy had no coloring, and was a bright product having a diffraction efficiency of about 35% without any operation of development and fixing.

Example 44 Recording was carried out in the same manner as in Example 43, except that 1.5 g of polysulfone ("Udel P-1700", manufactured by Amo Copolymer) was used as the solvent-soluble thermoplastic resin. A material composition and then a hologram recording photosensitive plate were prepared, and a hologram was copied thereon.

The obtained copy had no coloring and was bright with a diffraction efficiency of about 35% even without the development and fixing operations.

[0136]

Since the hologram recording material composition according to the present invention is almost solid, it does not require a heat treatment for solidifying the fluid composition unlike conventional products. The film forming operation can be simplified and workability is good.

Further, since the recording layer obtained from the hologram recording material composition of the present invention is almost solid as described above, it does not adhere to the hand even if it is touched by hand and does not contaminate the hand. It has excellent handleability. In addition, the recording medium provided with the recording layer is easy to carry because the recording layer does not hang down even when the recording medium is tilted and does not shift from the substrate.

Further, the recording medium after hologram recording is:
High transparency, allyl-based prepolymers (A) and (meth)
Since both the polymer of the acrylate compound (B) and the polymer of the acrylate compound (B) are present as a sufficient high-molecular-weight polymer, the stability is excellent, and there is no disadvantage that the two re-diffuse and the recording becomes unclear. Therefore, development and fixing operations for stabilizing the recorded image are not essential, and a hologram can be produced in real time.

As described above, according to the present invention, while the properties required for the hologram, such as good transparency, diffraction efficiency, and resolution, are exhibited in the same manner as the conventional product, film formation which is a problem of the conventional product is achieved. A hologram recording material composition that can eliminate the complexity of operation can be provided.

 ──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant 598109028 Hideo Tanigawa 3-28-28 Fushiodai, Ikeda-shi, Osaka (74) The above three agents 100060874 Patent Attorney Enosuke Kishimoto (4 other) (72) Invention Person Taichi Ichihashi 1-81-31 Midorioka, Ikeda-shi, Osaka Inside the Industrial Technology Research Institute Osaka Industrial Research Institute (72) Inventor Hideo Tanigawa 1-38-31 Midorioka, Ikeda-shi, Osaka Inside Osaka Institute of Industrial Technology Research Institute (72) Inventor Yutaka Kamada 9 Daitakasu-cho, Amagasaki City, Hyogo Prefecture Daiso Corporation (72) Inventor Masayoshi Nakamura 9 Daitakasu-cho Amagasaki City, Hyogo Prefecture Daiso Corporation (72) Inventor Takashi Matsuo Hyogo 9 Daitakasu-cho, Amagasaki City, Daiso Corporation F-term (reference) 2H025 AA00 AA02 AA11 AA15 AB14 AB20 AC08 AD01 BC13 BC19 BC42 BC49 BC51 BC81 BC82 BC92 CA00 C B51 2K008 AA04 AA06 DD13 EE01 FF07 GG01 HH01 4J027 AA07 AC03 AC06 AJ01 AJ04 AJ06 AJ08 BA02 BA05 BA07 BA08 BA09 BA10 BA11 BA12 BA13 BA18 BA19 BA20 BA21 BA22 BA23 BA24 BA26 BA27 BA28 CA09 CA18 CA10

Claims (16)

[Claims] 1. An allyl-based prepolymer (A) having at least one allyl group in the molecule, a (meth) acrylate-based compound (B) having at least one polymerizable unsaturated group in the molecule, and photopolymerization initiation Including the agent (C), the difference between the refractive index of the former and the refractive index of the polymer of the allylic prepolymer (A) and the (meth) acrylate compound (B) is 0.005 or more. A hologram recording material composition characterized by being selected as follows. 2. Allyl prepolymers (A) and (meth)
The hologram recording material composition according to claim 1, wherein the acrylate-based compound (B) is selected such that the difference between the refractive index of the former and the refractive index of the polymer of the latter is 0.01 or more. 3. Allyl prepolymers (A) and (meth)
When the weight ratio of the acrylate compound (B) is (A):
3. The recording material composition according to claim 1, wherein (B) = 5: 95 to 95: 5. 4. An allylic prepolymer (A) and (meth)
When the weight ratio of the acrylate compound (B) is (A):
4. The recording material composition according to claim 3, wherein (B) = 10: 90 to 90:10. 5. A solvent-soluble thermoplastic resin (D)
To the allylic prepolymer (A) with (A) :( D)
= 80: 20 to 100: 0 by weight.
5. The recording material composition according to any one of 4. 6. The allylic prepolymer (A) is a homopolymer of an allylic monomer or a copolymer of the same monomer and another copolymerizable monomer. Item 7. The recording material composition according to Item 1. 7. The recording material composition according to claim 6, wherein the allyl monomer is a diallyl phthalate monomer. 8. An allylic prepolymer (A) comprising a metal alkoxide having a metal atom, a group having an aromatic ring, and a hydrolyzable group in the presence of a diallyl phthalate monomer and / or a diallyl phthalate polymer.
The recording material composition according to any one of claims 1 to 5, which is a transparent and homogeneous organic-inorganic composite obtained by dehydration-condensation by a sol-gel method. 9. The recording material composition according to claim 1, wherein the allylic prepolymer (A) has a thioether group and / or a halogen atom bonded to a main chain. 10. The recording material composition according to claim 1, wherein the allyl prepolymer (A) is a diallyl phthalate prepolymer. 11. The method according to claim 10, wherein the diallyl phthalate prepolymer is a prepolymer selected from the group consisting of diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer and diallyl terephthalate prepolymer, or a combination of two or more thereof. Recording material composition. 12. The recording material composition according to claim 1, wherein the allylic prepolymer (A) has a molecular weight of 10,000 to 100,000. 13. A (meth) acrylate compound (B)
Has 1 to 6 polymerizable unsaturated groups and a molecular weight of 2
The recording material composition according to any one of claims 1 to 12, which has a molecular weight of 000 or less. 14. A (meth) acrylate compound (B)
Is a di (meth) acrylate. The recording material composition according to claim 1, wherein 15. A hologram recording medium in which a recording layer comprising the hologram recording material composition according to claim 1 is formed on a substrate. 16. In producing the hologram recording medium according to claim 15, at least one allyl group is present in the molecule.
Allyl-based prepolymer (A), (meth) acrylate-based compound (B) having at least one polymerizable unsaturated group in the molecule, and photopolymerization initiator (C), and in some cases, solvent-soluble thermoplastic A method for producing a hologram recording medium in which the resin (D) is dissolved or suspended in a solvent, the resulting solution or suspension is applied on a substrate, and then the solvent is volatilized to form a recording layer.