JPH09106240A - Hologram recording photosensitive composition, hologram recording medium and production of hologram by using the medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hologram recording photosensitive compsn. and a hologram recording medium which are chemically stable and have high sensitivity for a wide wavelength region and excellent resolution, diffraction efficiency, transparency, light resistance and heat resistance, and to provide a production method of a hologram by using the medium. SOLUTION: This compsn. consists of a block copolymer having at least each one kind of siloxane compd. part and an org. compd. part in the main chain, a compd. having polymerizable ethylene-type unsatd. bonds, and a photopolymn. initiator, and the compsn. gives >=0.005 refractive index modulation degree by holographic exposure. The layer of the compsn. is formed on a base material to obtain a hologram recording medium. Then the hologram recording medium is hologram-exposed and then applied with light or heat to produce a volumetric phase type hologram.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition for hologram recording which has high sensitivity over a wide wavelength range, is chemically stable, is excellent in resolution, diffraction efficiency, transparency and is excellent in light resistance. The present invention relates to an object, a hologram recording medium, and a hologram manufacturing method using the same.

[0002]

2. Description of the Related Art Holograms are capable of recording and reproducing three-dimensional stereoscopic images. Therefore, by utilizing their excellent design and decorative effects, they can be used as covers for books, magazines, displays for POPs, gifts, etc. Has been done. Moreover, since it is possible to record minute information in submicron units, it is also applied to counterfeit prevention marks such as securities, credit cards, and prepaid cards. In particular, the volume phase hologram can modulate light passing through the formed hologram by forming spatial interference fringes having different refractive indexes in the hologram recording medium. , POS scanners and holographic optical elements (HOE) represented by head-up displays (HUD) are expected.

In response to such industrial demands for volume phase holograms, volume phase hologram recording materials using photopolymers have been proposed so far. For example, as a method for producing a hologram using a photopolymer, a method has been proposed in which a hologram recording medium made of a photopolymer is exposed to a radiation interference pattern and then subjected to a developing treatment with a developing solution. For example, Tokiko Sho 6
No. 2-22152, a photosensitive material obtained by combining a polymer to be a carrier with a polyfunctional monomer having two or more ethylenically unsaturated bonds and a photopolymerization initiator is used as a radiation interference pattern. The first step of exposing the photosensitive material is the first step.
And a third step of swelling the light-sensitive material by treatment with a solvent, and a third step of shrinking the light-sensitive material by treatment with a second solvent having a poor swelling action. A method of making a hologram using a polymer is disclosed. According to the known technique, it is possible to manufacture a hologram that is excellent in terms of diffraction efficiency, resolution, environment resistance, etc., but it is inferior in sensitivity characteristics and photosensitive wavelength region characteristics, or a wet treatment process is adopted in hologram manufacturing. However, there are drawbacks such as complications in production such as the occurrence of defects and problems such as uneven development due to voids and cracks generated during the solvent immersion operation and deterioration of transparency due to whitening.

On the other hand, a hologram recording material using a photopolymer and a hologram recording material using a photopolymer capable of manufacturing a hologram only by interference exposure as the only processing step which does not require a complicated or complicated wet processing step in the hologram manufacturing step. A manufacturing method is disclosed. For example, U.S. Pat. No. 3,658,526 proposes a hologram recording photosensitive layer characterized by comprising an aliphatic polymer binder, an aliphatic acrylic monomer and a photopolymerization initiator. In the art, the refractive index of the high molecular polymer used and the aliphatic acrylic monomer are close to each other, so that the refractive index modulation degree obtained by hologram exposure is in the range of 0.001 to 0.003. There is a drawback that high diffraction efficiency cannot be obtained. In order to solve the problems in the art, in US Pat. No. 4,942,112, a solvent-soluble thermoplastic polymer having a boiling point of 10
A photopolymerizable composition for hologram recording and a refractive index imaging element comprising a liquid ethylenic monomer having a temperature of 0 ° C. or higher, a solid ethylenic monomer and a photopolymerization initiator are also disclosed in US Pat. No. 5,098,803. Is
Solvent-soluble thermoplastic polymer, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted heterocyclic group, or a liquid ethylenic monomer having a chlorine atom or a bromine atom and a boiling point of 100 ° C. or higher, and photopolymerization A photopolymerizable composition for hologram recording and an element for refractive index imaging, which are characterized by comprising an initiator, are disclosed, and the fact that a high refractive index modulation degree of 0.005 or more is actually obtained is described in SPIE "Practical Holgrr".
aphy IV ", Volume 1212, p. 30 (1990)
Year) and “J of Imaging Science
e ", 35, 19 and 25 (1991).

In these photopolymerizable compositions for hologram recording, either the polymer or the monomer contains an aromatic ring or a halogen atom in order to increase the degree of refractive index modulation caused by exposure to the radiation interference pattern. It is characterized by being composed of a combination of materials having a substituent, and in particular, from a combination of a non-aromatic thermoplastic resin having a low refractive index and a liquid ethylenic acrylic monomer having an aromatic group or a halogen atom. The following so-called monomer orientation type composition is preferably used. Non-aromatic (halogen) thermoplastic polymers used in the art include polymethylmethacrylate, polyethylmethacrylate, polyvinylacetate, polyacetic acid /
Vinyl acrylate, polyacetic acid / vinyl methacrylate, hydrolyzable polyvinyl acetate, ethylene / vinyl acetate copolymers, saturated and unsaturated polyurethanes, butadiene and isoprene polymers and copolymers, 4,000 to 1,000
Polyethylene oxide having an average molecular weight of 10,000, an oxydide having an acrylate or methacrylate group, N-methoxymethyl polyhexamethylene adipamide, cellulose acetate, cellulose acetate succinate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, polyvinyl butyral. , Polyvinyl formal, all of which have a refractive index of 1.46 or more, and a binder polymer having a smaller refractive index is desired in order to further increase the refractive index modulation degree caused by exposure to the interference pattern of radiation. It was

Generally, a high molecular compound having a unit of a polysiloxane compound in the molecule has a smaller refractive index than the above-mentioned general-purpose thermoplastic polymer, and therefore a polymerization capable of increasing the refractive index modulation degree in hologram exposure. It is possible to widen the selection range of the volatile monomer. That is,
The known art requires the use of an aromatic group (aromatic heterocyclic group) having a large refractive index or a monomer substituted with a halogen atom such as chlorine and bromine, but the siloxane compound part and the organic compound part are By using the block copolymer (A) having at least one kind in the main chain skeleton,
It is possible to use not only an aromatic group having a high refractive index (aromatic heterocyclic group) or a monomer substituted with a halogen atom such as chlorine and bromine but also an aliphatic monomer having a relatively low refractive index. Also, by having an organic compound unit in the molecule at the same time, it becomes possible to impart thermal stability to the hologram.

[0007]

The present invention has high sensitivity over a wide wavelength range, is chemically stable, is excellent in resolution, diffraction efficiency, reproduction wavelength reproducibility, and transparency, and has light resistance. An excellent photosensitive composition for hologram recording, a hologram recording medium, and a simple method for producing a hologram using the same are provided.

[0008]

Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above object in consideration of the above points, and
This has led to the present invention. That is, the present invention provides a block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton, a compound (B) having a polymerizable ethylenic unsaturated bond, and a photopolymerization initiator. A hologram recording photosensitive composition comprising the system (C) and having a refractive index modulation degree of 0.005 or more by interference exposure of laser light, and the hologram recording photosensitive composition, A photosensitive composition for hologram recording, characterized in that a chain transfer agent (D) is added, characterized in that the photosensitive composition for hologram recording is formed into a layer on a substrate. The hologram recording medium is a hologram recording medium, and the hologram recording medium is subjected to hologram exposure, and then light or heat is applied to the hologram recording medium.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the block copolymer (A) having at least one type of siloxane compound portion and at least one type of organic compound portion in the main chain skeleton used in the present invention will be described. At least 1 part of the siloxane compound part and the organic compound part here
The block copolymer (A) having each kind in the main chain skeleton is
Block copolymer of a single type or a plurality of types of polysiloxane compounds having reactive functional groups at both ends or one end and a single type or a plurality of types of organic compounds having reactive functional groups capable of reacting with the functional groups Is synthesized as.

Examples of the reactive functional group at the end of the polysiloxane compound having a reactive functional group at the terminal include vinyl group, amino group, hydroxy group, carboxyl group, epoxy group,
(Meth) acryloxy group and the like. Specifically, as a polysiloxane compound containing vinyl groups at both ends,
Cilaplane FM-2231, FM manufactured by Chisso Corporation
-2241, FM-2242, FP-2231, FP-
2241, FP-2242, XF40-A1987, TSL9706, TSL964 manufactured by Toshiba Silicone Co., Ltd.
6, TSL9686, etc. TS as a polysiloxane compound containing vinyl group at one end, manufactured by Toshiba Silicone Co., Ltd.
As a polysiloxane compound containing amino groups at both ends, such as L9705, Cilaplane FM-3 manufactured by Chisso Corporation
311, FM-3321, FM-3325, Shin-Etsu Chemical Co., Ltd. X-22-161AS, X-22-161.
A, X-22-161B, X-22-161C, Toshiba Silicone XF42-A2645, XF42-
A2646, TSL9306, TSL9346, TSL
9386, BX16-8 manufactured by Toray Silicone Co., Ltd.
53, BY16-853B, and the like, as one end amino group-containing polysiloxane compound, Cilaplane FM-3311, FM-3321, FM-332 manufactured by Chisso Corporation.
5, X-22-161AS, X manufactured by Shin-Etsu Chemical Co., Ltd.
-22-161A, X-22-161B, X-22-1
61C, XF42-A264 manufactured by Toshiba Silicone Co., Ltd.
5, XF42-A2646, TSF4700, TSF4
701, TSF4702, TSF4703, TSF47
20, TSL9306, TSL9305, TSL934
6, TSL9386, B manufactured by Torre Silicone Co., Ltd.
X16-853, BY16-853B, and the like, as both-end hydroxy group-containing polysiloxane compounds, manufactured by Chisso Corporation, Cilaplane FM-4411, FM-44.
21, FM-4425, X-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-160AS, KF6001, KF6002, KF6
003, XF3905, YF manufactured by Toshiba Silicone Co., Ltd.
3800, YF3057, YF3807, YF380
2, YF3897, YF3804, TSF4751, BY16-801, BY1 manufactured by Toray Silicone Co., Ltd.
6-817, BY16-873, PRX413, BY1
6-848, BY16-848B, BX16-001,
BX16-002, BX16-003, BX16-00
4, BX16-005, BX16-006, BX16-
007, BX16-008, BX16-009, BX1
6-010, BX16-011, BX16-012, S
A silaplane FM manufactured by Chisso Corporation as a polysiloxane compound containing a hydroxy group at one end such as F8427.
-0411, FM-0421, FM-0425, X-22-170B, X-22-50 manufactured by Shin-Etsu Chemical Co., Ltd.
02, TSF4750 manufactured by Toshiba Silicone Co., Ltd.,
TSF4770, TSF manufactured by Toshiba Silicone Co., Ltd.
4771, TSF410, TSF411, and the like, as the both-end epoxy group-containing polysiloxane compound, manufactured by Chisso Corporation, Silaplane FM-5511, FM-55.
21, FM-5525, XF made by Toshiba Silicone Co., Ltd.
42-A2262, XF42-A2263, TSL99
06, TSL9946, TSL9986, BX16-854, BX16-854 manufactured by Toray Silicone Co., Ltd.
B, BY16-855, BY16-855B, etc. can be illustrated. As a polysiloxane compound containing an epoxy group at one end, Cilaplane F manufactured by Chisso Corporation
M-0511, FM-0521, FM-0525, X-22-173B manufactured by Shin-Etsu Chemical Co., Ltd., TSF4730, TSF4731, TSL manufactured by Toshiba Silicone Co., Ltd.
As the polysiloxane compound containing one terminal (meth) acryloxy group, such as 9905, Cilaplane FM-0711, FM-0721, FM-072 manufactured by Chisso Corporation.
5 etc. can be illustrated.

Further, the organic compound having a reactive functional group capable of reacting with the functional group of the polysiloxane compound having a reactive functional group at the terminal includes alkenes, amines, amides and polyvalent compounds depending on the type of the reactive group. It can be selected from alcohols, polymer diols, carboxylic acids, acid anhydrides, epoxies, isocyanates, (meth) acrylic acid esters and the like. Specifically, as alkenes,
As amines such as butene, heptene, octene, ethylenediamine, polyoxypropylenediamine, isophoronediamine, iso (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine , M-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2,
As polyhydric alcohols and polymer diols such as 5-dimethyl-2,5-hexanediamine, 1,9-nonanediol, 2-methyl-1,8-octanediol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol , Dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, 3-methyl-1,5-pentanediol,
Poly (1,4-butanediol adipate), poly (β
-Methyl-δ-valerolactone), poly (nonanediol adipate), poly (3-methyl-1,5-pentamethylene carbonate), poly (nonanediol carbonate), poly (methylpentanediol adipate),
As carboxylic acids such as polytetramethylene ether glycol, malonic acid, maleic acid, succinic acid, adipic acid, sepacic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,2,4-trimethyladipic acid, 2, As acid anhydrides such as 4,4-trimethyladipic acid and 1,4-butanedicarboxylic acid, phthalic acid anhydrides, trimellitic acid anhydrides, pyromellitic acid anhydrides, benzophenonetetracarboxylic acid anhydrides, methyltetrahydrophthalic anhydrides Acids, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenyl succinic anhydride, polyazelaic anhydride, polydodecanedioic anhydride and the like, as epoxy compounds, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, ethylene glycol Diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ester , O-phthalic acid diglycidyl ester, hydroquinone diglycidyl ether, and the like, as the isocyanates, tolylene diisocyanate (including various isomer ratios), diphenylmethane-4,4′-diisocyanate, naphthylene-
1,5-diisocyanate, 3,3′-dimethyl-4,
4'-biphenylene diisocyanate, xylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate, diisocyanate, etc.,
As (meth) acrylic acid esters, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate and other C1-18 alkyl (meth) acrylates; glycidyl acrylate, glycidyl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate C2-18 alkoxyalkyl (meth) acrylates such as ethoxybutyl acrylate and ethoxybutyl methacrylate; 2-8 hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; dimethylamino Examples thereof include aminoalkyl (meth) acrylates such as ethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate, acrylamide, methacrylamide; acrylic acid and methacrylic acid.

Further, synthetic polymer polyols derived from these organic compounds may be used. As the polyester polyol, for example, Curapol P manufactured by Kuraray Co., Ltd.
-510, P-1010, P-1510, P-201
0, P-3010, P-4010, P-5010, P-
6010, P-2011, CPM-1000, F-10
10, F-2010, F-3010, PMIPA-20
00, PKA-A, MPD / IPA, MPD / TPAL
-1010, L-2010, L-3010, A-101
0, A-1510, A-2010, PNA-2000,
PNOA-1010, PNOA-2010, PTG-L-1000, L-2000, manufactured by Hodogaya Chemical Co., Ltd.
L-3000, Adeka Polyether P-400, P-700, P-1000, P-200 manufactured by Asahi Denka Co., Ltd.
0, P-3000, BPX-11, BPX-33, BP
X-55, G-300, polyester polyols described in JP-B-05-31570, and the like.

The block copolymer (A) having a series of at least one siloxane compound portion and at least one organic compound portion in the main chain skeleton synthesized by using these siloxane compound and organic compound has a low refractive index. Therefore, a large difference in refractive index with a compound having a polymerizable ethylenically unsaturated bond can be obtained, and a hologram having high diffraction efficiency can be created when hologram recording is performed by a radiation interference pattern. . In addition, since it has extremely high optical transparency and extremely low yellowing, it is possible to extremely enhance the light resistance of the formed hologram, and further, due to its thermal stability, extremely increase the heat resistance of the formed hologram. You can

The block copolymer (A) having at least one siloxane compound portion and at least one organic compound portion in the main chain skeleton can be used as a mixture of two or more kinds, and a mixture with a polysiloxane compound, Alternatively, it is used as a mixture with an oligomer or a polymer having no siloxane compound part, which is soluble in a solvent and has compatibility with the block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton. It doesn't matter.

As the polysiloxane compound, dimethylpolysiloxane, methylhydrogenpolysiloxane, hydrogenpolysiloxane at both ends, methylphenylpolysiloxane, phenylhydrogenpolysiloxane, diphenylpolysiloxane, alkyl-modified polysiloxane, amino-modified polysiloxane. , Carboalkyl modified polysiloxane, epoxy modified polysiloxane, vinyl group modified polysiloxane, alcohol modified polysiloxane, polyether modified polysiloxane, alkyl / polyether modified polysiloxane, fluorine modified polysiloxane and the like. Specifically, as dimethylpolysiloxane, TSF451 manufactured by Toshiba Silicone Co.,
XS69-A1753, Toray Silicone Co., Ltd. SH200, BY16-140, etc. are used as hydrogen dimethyl polysiloxanes at both ends, and Cilaplane FM1111, FM1121, FM11 as Chisso Co., Ltd.
25, XF40-A260 manufactured by Toshiba Silicone Co., Ltd.
6, TSX manufactured by Toshiba Silicone Co., Ltd. as methyl hydrogen polysiloxane such as XF40-A0153.
F484, TSF483, SH1107 manufactured by Toray Silicone Co., Ltd., BY16-805, etc. YF3800, YF3905, YF305 manufactured by Toshiba Silicone Co., Ltd.
7, YF3807, YF3802, YF3897, BY16-801, BY16 manufactured by Toray Silicone Co., Ltd.
-817, BY16-873, PRX413 and the like, as a methylphenyl polysiloxane, TSF431, TSF433, TSF43 manufactured by Toshiba Silicone Co., Ltd.
4, TSF437, TSF4300, YF3804, SH510, SH550 manufactured by Toray Silicone Co., Ltd.
As an alkyl-modified polysiloxane such as SH710,
TSF4421, TSF44 manufactured by Toshiba Silicone Co., Ltd.
22, TSF4420, XF42-A3160, XF4
2-A3161, SH2 manufactured by Torre Silicone Co., Ltd.
03, SH230, SF8416, BX16-811
As amino-modified polysiloxanes such as F and BY16-846, TSF4700, T manufactured by Toshiba Silicone Co., Ltd.
SF4701, TSF4702, TSF4703, TS
F4704, TSF4705, TSF4706, XF4
2-A2645, XF42-A2646, SF8417, BY16-828, B manufactured by Toray Silicone Co., Ltd.
Y16-849, BY16-850, BX16-85
9, BX16-860, BX16-853, BX16-
853B, Cilaplane FM331 made by Chisso Corporation
1, as a carboxyl-modified polysiloxane such as FM3321, FM3325, manufactured by Toshiba Silicone Co., Ltd.
As an epoxy-modified polysiloxane such as SF4700, TSF4771, SF8418 manufactured by Toray Silicone Co., Ltd., TSF473 manufactured by Toshiba Silicone Co., Ltd.
1, YF3965, XF42-A4439, TSF47
30, TSF4732, XF42-A4438, XF4
2-A5041, TSL9906, TSL9946, T
SL9986, XF42-A2262, XF42-A2
263, SF8411 manufactured by Toray Silicone Co., Ltd.,
SF8413, BY16-839, BX16-861,
BX16-862, SF8421EG, BY16-84
5, BX16-863, BX16-864, BX16-
865, BX16-866, BY16-855, BY1
6-855B, Cilaplane FM0 manufactured by Chisso Corporation
511, FM0521, FM0525, FM5511,
As an alcohol-modified polysiloxane such as FM5521, FM5525, TSF4 manufactured by Toshiba Silicone Co., Ltd.
750, TSF4751, and SF8428, SH3771, SH3746, BY1 manufactured by Torre Silicone Co., Ltd.
1-954, BY16-036, BY16-027, B
Y16-038, BX16-018, BY16-84
8, BX16-848B, BX16-001, BX16
-002, BX16-003, BX16-004, BY
16-005, BX16-009, BX16-010,
BX16-011, BX16-012, SF8427,
Silane plane FM4411, FM4 manufactured by Chisso Corporation
421, FM4425, FM0411, FM0421,
As a polyether modified polysiloxane such as FM0425, TSF4440, TS manufactured by Toshiba Silicone Co., Ltd.
F4425, TSF4426, TSF4452, TSF
4460, TSF4441, TSF4453, TSF4
480, TSF4450, SH3749, BX16-033, SH3748, B manufactured by Torre Silicone Co., Ltd.
X16-034, BX16-035, SF8400, S
As a higher fatty acid modified polysiloxane such as F8410 and SF8419, TSF41 manufactured by Toshiba Silicone Co., Ltd.
0, TSF411, and other higher alcohol ester-modified polysiloxanes such as S manufactured by Toray Silicone Co., Ltd.
As a vinyl group-containing polysiloxane such as F8422,
Toshiba Silicone Co., Ltd. XF40-A1987, TS
L9646, TSL9686, BX16-867, BX16-868, manufactured by Toray Silicone Co., Ltd., Silaplane FM2231, FM224, manufactured by Chisso Corporation.
1, FM2242, FP2231, FP2241, FP
2242 and the like as fluorine-modified polysiloxane, FQF501 manufactured by Toshiba Silicone Co., Ltd., FS1265 manufactured by Toray Silicone Co., Ltd., and mercapto-modified polysiloxane BX1 manufactured by Toray Silicone Co., Ltd.
6-838A, BX16-838 and other chloroalkyl modified polysiloxanes such as TSL9236 and TSL9276 manufactured by Toshiba Silicone Co., Ltd. and BX16-835 manufactured by Toray Silicone Co., Ltd. such as (meth) acryloyl modified polysiloxane and Chisso Examples include Silaplane FM0711, FM0721, FM0725 and the like manufactured by Co., Ltd.

A block copolymer (A) having no siloxane compound part, soluble in a solvent and having at least one siloxane compound part and at least one organic compound part in the main chain skeleton.
Examples of the oligomers or polymers having compatibility with the above include homopolymers of vinyl monomers or copolymers of two or more components, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, te.
rt-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl, 1,3-dimethylbutyl, 2-ethylhexyl, 2-methylpentyl, cyclohexyl, adamantyl, Polymers of chain, branched and cyclic alkyl (meth) acrylic acid ester monomers such as isobornyl, dicyclopentanyl, tetrahydrofurfuryl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, etc. Polymers of (meth) acrylic acid ester monomer having a hydroxyl group, polymers of (meth) acrylic acid ester monomer containing an epoxy group such as glycidyl (meth) acrylate, N, N-dimethylaminoethyl, N, N-diethylamino Ethyl, t- Containing an amino group such as chill aminoethyl (meth) polymers of acrylic acid ester monomers, (meth) acrylic acid, itaconic acid, maleic acid, 2
A polymer of a vinyl monomer containing a carboxyl group such as (meth) acryloyloxypropylhexahydrophthalic acid, a polymer of a phosphoric acid group containing (meth) acrylic acid ester monomer such as ethylene oxide modified phosphoric acid (meth) acrylate, Examples thereof include polymers of vinyl monomers such as acrylamide, N-butylacrylamide, N, N-dimethylacrylamide, N-vinylpyrrolidone, acrylonitrile, vinyl acetate, vinyl butyral, vinyl acetal, and vinyl formal. Furthermore, copolymers of two or more components of these vinyl monomers can be exemplified.

Next, the compound (B) having a polymerizable ethylenically unsaturated bond used in the present invention will be explained. The compound (B) having a polymerizable ethylenically unsaturated bond herein is a compound having one or more radically polymerizable ethylenically unsaturated groups as a functional group.

Among the compounds (B) having a polymerizable ethylenically unsaturated bond, a compound having a substituent selected from an aromatic ring or a halogen atom in the molecule is used to enhance the diffraction efficiency of the hologram. You can Examples of such compounds include styrene, α-methylstyrene, styrenes such as 4-meth (eth) oxystyrene, phenyl (meth) acrylate, 4-phenylethyl (meth) acrylate, and 4-methoxycarbonylphenyl (meth) acrylate. , 4-ethoxycarbonylphenyl (meth) acrylate, 4-butoxycarbonylphenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyhydroxypropyl (meth) Acrylate, 4-phenoxyethyl (meth) acrylate, 4-phenoxydiethylene glycol (meth) acrylate, 4-phenoxytetraethylene glycol (meth) acrylate, 4-
Phenoxyhexaethylene glycol (meth) acrylate, EO-modified phenoxyphosphoric acid (meth) acrylate, EO-modified phthalic acid (meth) acrylate, 4-biphenylyl (meth) acrylate, aromatic polyhydroxy compound such as hydroquinone, resorcin, catechol , Di- or poly (meth) acrylate compounds such as pyrogallol, bisphenol A di (meth) acrylate, eth (propiylene) oxide-modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, eth (propene) lenoxide Modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, eth (propylene) oxide modified bisphenol S di (meth) acrylate, epichlorohydrin An aromatic group such as sexual phthalate (meth) acrylate (meth) acrylate compounds, p- chlorostyrene, p- bromostyrene, p-
Chlorophenoxyethyl (meth) actrate, p-bromophenoxyethyl (meth) actrate, trichlorophenol eth (propylene) oxide modified (meth) acrylate, tribromophenol eth (propylene) oxide modified (meth) acrylate, tetrachlorobisphenol A eth (Propylene) oxide-modified di (meth)
Acrylate, tetrabromobisphenol A eth (propy) lene oxide modified di (meth) acrylate, tetrachlorobisphenol S eth (propyrene) oxide modified di (meth) acrylate, tetrabromobisphenol S eth (propyrene) oxide modified di (meth) acrylate, etc. Styrenes having aromatic groups substituted with halogen atoms having an atomic weight greater than that of chlorine and (meth)
Acrylate compounds, vinyl compounds having heteroaromatic groups such as N-vinylcarbazole, 3-me (e) tyl-N-vinylcarbazole, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-bromo-2- Examples thereof include hydroxypropyl (meth) acrylate, 2,3-dichloropropyl (meth) acrylate, and 2,3-dibromopropyl (meth) acrylate, which are substituted with a halogen atom having an atomic weight of chlorine or more. To be

Further, a compound having an aromatic ring or a halogen atom and a sulfur atom in the molecule is more preferable for improving the diffraction efficiency of the hologram. Examples of such compounds include phenylthio (meth) acrylate, 4-phenylethylthio (meth) acrylate, 4-methoxycarbonylphenylthio (meth) acrylate, 4-ethoxycarbonylphenylthio (meth) acrylate, 4-butoxycarbonylphenylthio. (Meth) acrylate, 4-te
rt-Butylphenylthio (meth) acrylate, benzylthio (meth) acrylate, 4-phenoxydiethylene glycol thio (meth) acrylate, 4-phenoxytetraethylene glycol thio (meth) acrylate, 4-phenoxyhexaethylene glycol thio (meth) acrylate , 4-biphenylylthio (meth) acrylate, aromatic polyhydroxy compounds, for example, dithio or polythio (meth) acrylate compounds such as hydroquinone, resorcin, catechol, and pyrogallol,
Bisphenol A dithio (meth) acrylate, eth (propyrene) oxide modified bisphenol A dithio (meth) acrylate, bisphenol F dithio (meth) acrylate, eth (propylene) oxide modified bisphenol F dithio (meth) acrylate, bisphenol S dithio ( Thio (meth) acrylate compounds having aromatic groups such as (meth) acrylate, eth (propyylene) oxide modified bisphenol S dithio (meth) acrylate, epichlorohydrin modified phthalic acid dithio (meth) acrylate, trichlorophenol eth (propylene) oxide modified Thio (meth) acrylate, tribromophenol eth (propyrene) oxide-modified thio (meth) acrylate, tetrachlorobisphenol A eth (propy) le Oxide-modified dithio (meth) acrylate, tetrabromobisphenol A eth (propy) lene oxide-modified dithio (meth) acrylate, tetrachlorobisphenol S eth (propi) lene oxide-modified dithio (meth) acrylate, tetrabromobisphenol S eth (propyrene) oxide A thio (meth) acrylate compound having an aromatic group substituted with a halogen atom having an atomic weight of chlorine or more such as dithio (meth) acrylate, 3-chloro-2-hydroxypropylthio (meth) acrylate, 3-bromo-2 −
Hydroxypropylthio (meth) acrylate, 2,3
-Dichloropropylthio (meth) acrylate, 2,3
Examples thereof include a thio (meth) acrylate compound substituted with a halogen atom having an atomic weight of chlorine or more such as dibromopropylthio (meth) acrylate.

As the compound (B) having a polymerizable ethylenic unsaturated bond, it is possible to use a non-halogen type aliphatic compound. As such a compound, as a monofunctional type, unsaturated acid compounds such as (meth) acrylic acid, itaconic acid and maleic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth)
Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Isodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate,
Alkyl (meth) acrylate types such as 2 (2-ethoxyethoxy) ethyl (meth) acrylate, n-butoxyethyl (meth) acrylate, morpholinoethyl (meth) acrylate, methoxydiethyl (propylene) glycol (meth) acrylate, methoxy Triethy (propyylene) glycol (meth) acrylate, Methoxytetraeth (propyylene) glycol (meth) acrylate, Methoxypoly (propylenene) glycol (meth) acrylate, Ethoxydieth (propyylene) glycol (meth) acrylate, Ethoxytri Alkoxyalkylene glycol (meth) acrylate type such as eth (propyylene) glycol (meth) acrylate, ethoxypoly (ethylene) (propylene) glycol (meth) acrylate, cyclo Xyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclopentanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, pinanyl (meth ) Alicyclic (meth) acrylate type such as acrylate, amine type such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide (Meth) acrylate, allyl (meth) acrylate, glycidyl (meth)
Examples include functional group-containing (meth) acrylates such as acrylates.

Next, as a polyfunctional type, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol. Di (meth) acrylate, bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayarad R-167, hydroxy Pivalic acid neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: alkyl type (meth) acrylates such as Nippon Kayaku Kayarad HX series, ethylene glycol Ruji (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin-modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin-modified prolene glycol (Meth) acrylate: Alkylene glycol type (meth) acrylate such as Nagase & Co. Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane di (Meth) acrylate: Kayarad R-604 manufactured by Nippon Kayaku, ethylene oxide-modified trimethylolpropane tri (meth) acrylate:
Sartomer SR-454, propylene oxide-modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku's TPA-310, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type such as Nagase & Co. DA (M) -321 (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate: Toagosei Aronix M
-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl modified dipentaerythritol poly (meth) acrylates: Nippon Kayaku Kayarad D-310, 320, 330, etc., caprolactone Modified dipentaerythritol poly (meth) acrylates: Kayarad DPCA-20, 30, 6 manufactured by Nippon Kayaku
Pentaerythritol type (meth) acrylates such as 0 and 120, glycerol di (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate: glycerol type such as Nagase & Co. Denacol DA (M) -314 and triglycerol di (meth) acrylate (Meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl di (meth) acrylate,
Methoxylated cyclohexyl di (meth) acrylate: alicyclic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toagosei Aronix M-315, tris (methacryloxyethyl) isocyanurate, Caprolactone-modified tris (acryloxyethyl) isocyanurate,
Examples thereof include isocyanurate type (meth) acrylates such as caprolactone-modified tris (methacryloxyethyl) isocyanurate.

Of the non-halogenated aliphatic compounds,
The compound which further contains a sulfur atom in a molecule is illustrated.
For example, as a monofunctional type, methoxydiethyl (propylene) glycolthio (meth) acrylate, methoxytriethyl (propylene) glycolthio (meth) acrylate, methoxytetraethyl (propylene) glycolthio (meth) acrylate, methoxypoly (meth) acrylate Propylene) glycol thio (meth) acrylate, ethoxydiethyl (prop) len glycol thio (meth) acrylate, ethoxy triethyl (prop) len glycol thio (meth) acrylate, ethoxy polyethylene (prop) len glycol thio (meth) acrylate Alkoxyalkylene glycol thio (meth) acrylate type,
Cyclohexylthio (meth) acrylate, tetrahydrofurylthio (meth) acrylate, isobornylthio (meth) acrylate, dicyclopentanylthio (meth) acrylate, tricyclopentanylthio (meth)
Examples thereof include alicyclic thio (meth) acrylate types such as acrylate, dicyclopentadienylthio (meth) acrylate, and pinanylthio (meth) acrylate.

Next, as a polyfunctional type, 1,3-propanediol dithio (meth) acrylate, 1,4-butanediol dithio (meth) acrylate, 1,6-hexanediol dithio (meth) acrylate, neopentyl glycol. Dithio (meth) acrylate, bis (thioacryloxy neopentyl glycol) adipate, bis (thiomethacryloxy neopentyl glycol) adipate, epichlorohydrin-modified 1,6-hexanediol dithio (meth) acrylate, hydroxypivalic acid neopentyl glycol dithio ( (Meth) acrylate,
Alkyl-type thio (meth) acrylates such as caprolactone-modified hydroxypivalic acid neopentyl glycol dithio (meth) acrylate, ethylene glycol dithio (meth) acrylate, diethylene glycol dithio (meth) acrylate, triethylene glycol dithio (meth) acrylate, tetraethylene glycol Dithio (meth) acrylate, polyethylene glycol dithio (meth) acrylate, epichlorohydrin modified ethylene glycol dithio (meth) acrylate, epichlorohydrin modified diethylene glycol dithio (meth) acrylate, propylene glycol dithio (meth) acrylate, dipropylene glycol dithio (meth) acrylate, Tripropylene glycol dithio (meth) acrylate, tet Propylene glycol dithio (meth) acrylate, polypropylene glycol dithio (meth) acrylate, epichlorohydrin-modified prolene glycol dithio (meth) acrylate and other alkylene glycol type thio (meth) acrylates, trimethylolpropane trithio (meth) acrylate, ditrimethylolpropane Trithio (meth) acrylate, neopentyl glycol modified trimethylolpropane dithio (meth) acrylate, ethylene oxide modified trimethylolpropane trithio (meth) acrylate, propylene oxide modified trimethylolpropane trithio (meth) acrylate, epichlorohydrin modified trimethylol Trimethylolpropane-type thio (meth) acrylates such as propanetrithio (meth) acrylate Acrylate, pentaerythritol trithio (meth) acrylate, pentaerythritol tetrathio (meth) acrylate, stearic acid modified pentaerythritol dithio (meth) acrylate, dipentaerythritol hexathio (meth) acrylate, dipentaerythritol monohydroxypentathio (meth) ) Acrylate, alkyl-modified dipentaerythritol polythio (meth) acrylate, caprolactone-modified dipentaerythritol polythio (meth) acrylates, etc. pentaerythritol-type thio (meth) acrylate, glycerol dithio (meth) acrylate, epichlorohydrin-modified glycerol trithio ( Glycerol-type thio (meth), such as (meth) acrylate and triglyceroldithio (meth) acrylate Acrylate, dicyclopentanyldithio (meth) acrylate, tricyclopentanyldithio (meth) acrylate, cyclohexyldithio (meth)
Acrylate, alicyclic thio (meth) acrylates such as methoxylated cyclohexyldithio (meth) acrylate, tris (thioacryloxyethyl) isocyanurate, tris (thiomethacryloxyethyl) isocyanurate, caprolactone modified tris (thioacryloxyethyl) Examples thereof include isocyanurate-type thio (meth) acrylates such as isocyanurate and caprolactone-modified tris (thiomethacryloxyethyl) isocyanurate. You may use these individually or in mixture of 2 or more.

Further, as the compound (B) having a polymerizable ethylenically unsaturated bond, an addition-polymerizable compound which is polymerized through ring-opening sigma bond cleavage is also mentioned. Such compounds are described in K. J. Ivin and T.W. Saegusa edition,
In Elsevier, New York, 1984,
Chapter 1 "General Thermodynamics"
s and Mechanical Aspects
ofRing-Opening Polymeriz
ation ”pages 1-82 and chapter 2“ Rin
g Opening Polymerization
via Carbon-Carbon Sigmabo
nd Clear ", pp. 83-119, W.N.
J. Bailey et al. Macromol. Sci.
-Chem. , A21, pp. 1611-1639.
P., 1984, and I.M. Cho and K. -D. A
hn's J. Polym. Sci. , Polym. Let
t. Ed. Volume 15, Pages 751 to 753, 197
It is described in 7 years. Specific examples include vinylcyclopropane such as 1,1-dicyano-2-vinylcyclopropane, 1,1-dichloro-2-vinylcyclopropane, diethyl-2-vinylcyclopropane-1,1-dicarboxylate (EVCD). ), Ethyl-1-acetyl-2-vinyl-1-cyclopropanecarboxylate (EAVC), ethyl-1-benzoyl-2-vinyl-
1-cyclopropanecarboxylate (EBVC) and the like. These may be used alone or as a mixture of two or more, or may be used as a mixture with the above-mentioned (meth) acrylic compound or vinyl compound.

Next, the photopolymerization initiator system (C) used in the present invention will be explained. As such a photopolymerization initiator system, at least one kind of sensitizer (a) having absorption in a wavelength range from ultraviolet to near infrared and a sensitizer (a) exposed to actinic radiation are used. A mixture system with at least one initiator (b) that generates an active species that induces polymerization of the compound (B) having a polymerizable ethylenically unsaturated bond by interaction, or a sensitizer and an initiator Mention may be made of compound systems integrated by ionic or covalent bonding.

Specific examples of the sensitizer (a) include unsaturated ketones such as chalcone derivatives and dibenzalacetone derivatives, and 1,2-diketone derivatives such as benzyl and camphorquinone. Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, thioketocoumarin derivative, cyanine derivative, ketocyanine derivative, merocyanine derivative, oxonol derivative, styryl derivative, acridine Derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetrabe Zone porphyrin derivatives, tetra-naphthoquinone topo Qualification phosphorus derivatives, triarylmethane derivatives, tetraazaporphyrin derivatives, phthalocyanine derivatives,
Naphthalocyanine derivative, tetraazaporphyrazine derivative, tetrapyrazinoporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, tetraphyrin derivative, anulene derivative, pyrylium derivative, thiopyrylium derivative, pyran derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran Derivatives, organic ruthenium complexes and the like can be mentioned. In addition to these, "Dye Handbook" (1986, Kodansha), edited by Nobu Okawara, edited by Nobu Okawara, "Chemistry of Functional Dyes" (1981).
Dyes and sensitizers described in "Special Functional Materials" (1986, CMC), edited by T. Saburo Ikemori et al., U.S. Pat. No. 3,652,275, U.S. Pat.
62, 162, U.S. Pat. No. 4,268,667, U.S. Pat. No. 4,351,893, U.S. Pat. No. 4,454,218, U.S. Pat. No. 4,535,052, JP-A-2-85858, JP-A-2-216154, and JP-A-2-216154. Examples thereof include compounds having absorption in the wavelength of radiation, such as the unsaturated ketone sensitizers described in 5-27436. These sensitizers (a) may be used as a mixture of two or more kinds in an arbitrary ratio if necessary. Further, among these sensitizers (a), in the case of an anionic dye such as a xanthene derivative, a thioxanthene derivative or an oxonol derivative, an aryldiazonium cation, a diaryliodonium cation, a triarylsulfonium cation, a dialkylphenacylsulfonium cation, Even a compound having an ionic bond with an onium cation such as a dialkylphenacylsulfoxonium cation, an alkylarylphenacylsulfoxonium cation, an alkylarylphenacylsulfoxonium cation, a diarylphenacylsulfonium cation or a diarylphenacylsulfoxonium cation Good, on the other hand, such as cyanine derivative, azurenium derivative, pyrylium derivative or thiopyrylium derivative For thione dyes, it may be a compound borate anions such as triaryl alkyl boron anion is ionically bound.

The following compounds can be exemplified as the initiator (b). For example, cyclic cis-α-dicarbonyl compounds such as 2,3-bornanedione (camphorquinone) and 2,2,5,5-tetramethyltetrahydro-3,4-furanic acid (imidazoletrione), benzophenone, diacetyl, benzyl. , Michler's Ketone,
Ketones such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone, peroxides such as benzoyl peroxide and di-tert-butyl peroxide, diazonium salts such as aryldiazonium, N-
Aromatic carboxylic acids such as phenylglycine, 2-chlorothioxanthene, xanthenes such as 2,4-diethylthioxanthene, onium salts such as diaryl iodonium salts and sulfonium salts, triphenylalkylborates, metal arene complexes, bis Examples thereof include imidazoles, polyhalogen compounds, phenylisoxazolone, benzoin ethyl ether and benzyl dimethyl ketal. These photopolymerization initiator systems (C) may be used as a mixture of two or more kinds in an arbitrary ratio, if necessary.

Preferred photopolymerization initiators are 2,4,6-substituted triazine compounds such as tris (trichloromethyl) -2,4,6-triazine described in British Patent 1388492 and JP-A-53-133428. JP-A-59-189340 and JP-A-60-76.
3,3'-4,4'-tetra (te
organic peroxides such as (rt-butylperoxycarbonyl) benzophenone, JP-A-1-54440, EP 109851, and EP 12671.
No. 2 and "Journal of Imaging Science (J.Imag.Sci.)", Volume 30, No. 17
Iron arene complex described on page 4 (1986), diphenyliodonium hexafluorophosphate, di (p-tolyl) iodonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, diphenylphena Sylsulfonium hexafluoroantimonate, dimethylphenacylsulfonium hexafluorophosphate,
Sulfonium salts such as benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate,
Oxosulfonium salts such as tetraphenyloxosulfonium hexafluorophosphate, JP-A-3-70
No. 4, diphenyliodonium (n-butyl)
Iodonium organic boron complexes such as triphenylborate, diphenylphenacylsulfonium (n-butyl) triphenylborate described in Japanese Patent Application No. 5-255347, and dimethylphenacylsulfonium (n-butyl) tri described in JP-A-5-213861. Sulfonium organoboron complexes such as phenylborate, "Organometallics", Volume 8,
Iron arene organic boron complexes described on page 2737 (1989) and the like can be mentioned.

Next, in the present invention, the chain transfer agent (D) is effective for increasing the diffraction efficiency of the hologram. Preferred chain transfer agents are thiols, such as 2
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole,
4,4-thiobisbenzenethiol, p-bromobenzenethiol, thiocyanuric acid, 1,4-bis (mercaptomethyl) benzene, p-toluenethiol, and the like, and US Pat. No. 4,414,312 and JP-A-64-1314.
No. 4, thiols, disulfides described in JP-A-2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, JP-A-2-291.
560 O-acyl thiohydroxamate and N-
Alkoxy pyridine thiones are also included. The amount of the chain transfer agent used is preferably 1.0 to 30 parts by weight with respect to 100 parts by weight of the block copolymer (A) having at least one siloxane compound part and one organic compound part in the main chain skeleton.

Next, in the photosensitive composition for hologram recording of the present invention, a crosslinking agent can be used for the purpose of more firmly fixing the recording layer after hologram production.
The cross-linking agent as used herein is a block copolymer (A) having at least one type of siloxane compound part and one type of organic compound part in the main chain skeleton, and reacts with a hydroxy group, an amino group, an epoxy group, a carboxyl group, a mercapto group, or the like. When it has a functional group, it can be used for crosslinking,
Depending on the type of reactive group, polyhydric alcohols, amines,
It can be selected from amides, polyfunctional carboxylic acids, acid anhydrides, isocyanates, epoxies and the like. Specific compounds include compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita et al. (1981, Taiseisha), "Adhesion Handbook" edited by The Japan Adhesive Association (1980, Nikkan Kogyo Shimbun). be able to. These crosslinking agents are added in an amount of 0.001 with respect to 100 parts by weight of the block copolymer (A) having at least one kind of the siloxane compound part having the reactive group and at least one organic compound part in the main chain skeleton.
It is preferably added in the range of 20 to 20 parts by weight.

A thermal polymerization inhibitor may be added to the photosensitive composition for hologram recording of the present invention for the purpose of preventing polymerization during storage. Specific examples include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol,
Examples thereof include phenothiazine. These thermal polymerization inhibitors are added in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the compound (B) having a polymerizable ethylenically unsaturated bond. Is preferred.

The photosensitive composition for hologram recording of the present invention further comprises phosphine, phosphonate, and
It may be used as a mixture with an oxygen scavenger such as phosphite, a reducing agent, an antihalation agent, a plasticizer, a leveling agent, an ultraviolet absorber, an antistatic agent and the like.

The photosensitive composition for hologram recording used in the present invention comprises a block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton, and a polymerizable ethylenically unsaturated bond. The compound (B) having the formula (1) and the photopolymerization initiator system (C) are dissolved in a suitable solvent at an arbitrary ratio, and the resulting solution is used as a hologram recording medium by forming a photosensitive film on a substrate. It is possible to

In the photosensitive composition for hologram recording used in the present invention, the amount of the block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton in the composition is To produce a hologram with high diffraction efficiency, high resolution and high transparency,
It is 10 to 90% by weight, preferably 30 to 70% by weight. The amount of the compound (B) having a polymerizable ethylenically unsaturated bond used is 10 to 100 parts by weight of the block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton. It is 500 parts by weight, preferably 30 to 300 parts by weight. If it deviates from the above range, it becomes difficult to maintain high diffraction efficiency and improve sensitivity characteristics, which is not preferable.

Among the photopolymerization initiator systems used in the photosensitive composition for hologram recording of the present invention, the sensitizer (a) is a block having at least one siloxane compound part and at least one organic compound part in the main chain skeleton. 0.001 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the copolymer (A).
Used in the range of up to 5 parts by weight. The amount used is limited by the film thickness of the photosensitive layer and the optical density of the film thickness. That is, it is preferably used in a range where the optical density does not exceed 2.
The initiator (b) is 0.1 to 30 parts by weight, preferably 0 to 100 parts by weight of the block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton. It is used in the range of 0.5 to 20 parts by weight.

The photosensitive composition for hologram recording having the above composition ratio is dissolved in an appropriate solvent, and this is applied in a film form on a substrate to be used as a hologram recording medium. The applied thickness is 1 μm to 100 μ as the film thickness after drying.
m is more preferable, and the range of 5 μm to 50 μm is more preferable, but the thickness is not limited to the relationship between required hologram characteristics such as diffraction efficiency or half-value width of reproduced light and the refractive index modulation degree (Δn), or It is necessary to set the optimum thickness depending on whether the hologram to be used is a reflection hologram or a transmission hologram. For the rationale, see H. Kogelnik, Bell. Sy
st. Tech. J. , Vol. 48, p. 2909 (19
1969).

Examples of the substrate include a glass plate, a polymethylmethacrylate plate, a polycarbonate film, a cellulose triacetate film or a polyester film. Further, a protective film such as polyvinyl alcohol, polyethylene terephthalate, polyolefin, polyvinyl chloride, polyvinylidene chloride or cellophane film can be further provided and used. As the method for forming the protective film, coating in a solution state, electrostatic adhesion, lamination using an extruder, or laminating a film in which an adhesive is applied to the protective film in advance is used to form the hologram recording medium. Can be laminated on top. As described above, when the hologram recording medium is used by being sandwiched between two substrates, at least one is required to be optically transparent.

Next, a method of manufacturing a hologram using the hologram recording medium of the present invention will be described. That is, the hologram recording medium produced by the above-mentioned method is used, for example, in the reflection hologram photographing optical system shown in FIG. 1 and the transmission hologram optical system shown in FIG.
Luminous flux interference exposure is performed. Further, it is possible to perform interference exposure by an optical system (so-called Denisiku system) for reflection hologram imaging with one light flux as shown in FIG. The photosensitive composition for hologram recording according to the present invention can complete the production of the hologram by such a single hologram exposure, but the polymerizable ethylenic non-reaction which is unreacted only by the hologram exposure. In order to further accelerate the polymerization of the compound (B) having a saturated bond, it is possible to perform heating or (and) whole surface exposure treatment.
Even if such processing is performed, the hologram characteristics are not impaired. As a heat source for heat treatment, a heat circulation type oven or a heating roll is generally preferably used, but the heat source is not limited to this. The heat treatment temperature is not particularly limited, but it is a block having at least one kind of siloxane compound part and at least one organic compound part in the main chain skeleton in the photosensitive composition for photosensitive material for hologram recording of the present invention. It is necessary to select suitable temperature conditions in consideration of the heat resistance of the copolymer (A) and the compound (B) having a polymerizable ethylenically unsaturated bond. Usually, a temperature between 40 ° C and 150 ° C is preferable. As the light source used for the entire surface exposure, in addition to the laser light used for the interference exposure, visible light and / or ultraviolet light such as carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, etc. are used. .

[0039]

The photosensitive composition for hologram recording used in the present invention comprises at least one siloxane compound part and at least one organic compound part.
A block copolymer (A) having a main chain skeleton for each type, a compound (B) having a polymerizable ethylenic unsaturated bond,
It is characterized by comprising a photopolymerization initiator system (C). Using a hologram recording medium obtained by forming the composition as a film on a substrate, an interference pattern is formed in the recording medium by interference exposure with a laser light source having high coherence as shown in FIG. To be done. At that time, at a site having a strong interference action, a free radical is generated from the photopolymerization initiator system by the action of light (a Lewis acid is also generated at the same time depending on the selection of the initiator), and a polymerizable ethylenic unsaturated bond is generated. The polymerization reaction of the compound (B) having On the other hand, such a polymerization reaction is not induced at the site where the interference action is low, and a density gradient caused by the volume contraction accompanying the polymerization reaction is formed at both sites. In addition, the unreacted compound (B) having an ethylenically unsaturated bond is aggregated by diffusive transfer to the site having a strong interference action, so that the density is further increased and the difference in refractive index from the site having a low interference action is expanded. As a result, a hologram is formed by the refractive index modulation. On the other hand, the block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton used in the present invention has a low refractive index.
A large difference in refractive index from the compound (B) having an ethylenically unsaturated bond can be obtained, and the refractive index modulation effect can be further improved. In the case of a combination exhibiting a refractive index modulation of 0.005 or more. , It is interpreted that the effect became remarkable.

After the hologram exposure, a post-treatment step with light or heat is added to promote polymerization and diffusion of the unreacted compound (B) having an ethylenically unsaturated bond, which is chemically stable. Moreover, a hologram that does not change with time is manufactured. In addition, the post-treatment process effectively erases the remaining photopolymerization initiator system (C) sensitizer and improves the transparency of the hologram.

[0041]

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

Example 1 Isophorone diisocyanate (IPDI, molecular weight 22
2) A solution prepared by dissolving 9 parts by weight of 200 parts by weight of methyl ethyl ketone (MEK) is heated at 80 ° C. under a nitrogen atmosphere,
After stirring and adding 2 to 3 drops of di-n-butyltin dilaurate as a catalyst, both ends amino-modified polydimethylsiloxane (trade name BY16-853B, manufactured by Toray Silicone Co., Ltd., while continuing heating and stirring). Amino equivalent 250
0) A solution in which 100 parts by weight of MEK was dissolved in 100 parts by weight of MEK was added dropwise at a rate of 10 g per minute, and heating and stirring were continued for about 2 hours, and the terminal IPDI-modified dimethylsiloxane polymer, polymer 1 (number average molecular weight of about 6000, MW / MN
= 1.35) was synthesized.

As a block copolymer (A) having at least one siloxane compound part and at least one organic compound part in the main chain skeleton, 100 parts by weight of Polymer 1 is used as a compound (B) having a polymerizable ethylenically unsaturated bond. 100 parts by weight of dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Yushi Co., Ltd., trade name DCP-A, refractive index = 1.50), cyclopentanone as a photopolymerization initiator system (C) sensitizer (a) 0.5 parts by weight of 2,2,5-bis {[4- (diethylamino) phenyl] methylene} (DEAW), 5 parts by weight of diphenyliodonium hexafluorophosphate (DPI) as an initiator (b), and methyl ethyl ketone as a solvent. A photosensitive solution containing 200 parts by weight of (MEK) was prepared.

This photosensitive solution was applied on a glass plate of 100 × 125 × 3 mm by using a 5 mil applicator,
It was dried in an oven at 60 ° C for 10 minutes to prepare a hologram recording medium. The film thickness of the photosensitive layer after drying was 15 μm. Further, a polyethylene terephthalate film as a protective layer was attached to the photosensitive layer side. Hologram exposure was performed on this hologram recording medium at an exposure amount of 30 mJ / cm ² by ^two- beam interference of 514.5 nm light of an Ar ion laser, using the hologram production optical system shown in FIG. After performing the hologram exposure, one of the two light beams is further blocked and exposed to the same exposure amount as the hologram exposure,
Then, it was left in an oven at 100 ° C. for 1 hour.

Diffraction efficiency is ART by JASCO Corporation
It was measured with a 25C type spectrophotometer. In this device, a photomultimeter having a slit with a width of 3 mm can be installed on the circumference of a 20 cm radius centered on the sample. Width 0.3 mm
The monochromatic light of was incident on the sample at an angle of 45 degrees, and the diffracted light from the sample was detected. The diffraction efficiency was defined as the ratio between the maximum value other than the specular reflection light and the value when the incident light was received directly without placing the sample. Table 2 shows the results of the diffraction efficiency, the refractive index modulation degree, and the playback wavelength of the obtained hologram.

Example 2 9 parts by weight of IPDI was added to methyl ethyl ketone (MEK) 20
The solution dissolved in 0 parts by weight was heated and stirred at 80 ° C., and 2 to 3 drops of di-n-butyltin dilaurate as a catalyst was added, and then while heating and stirring were continued, polyethylene glycol (PEG, molecular weight) was added. About 2000) 40 parts by weight MEK4
The solution dissolved in 0 part by weight was added dropwise at a rate of 10 g / min, and heating and stirring were continued for about 2 hours. In that solution,
A solution prepared by dissolving 100 parts by weight of BY16-853B in 100 parts by weight of MEK was added dropwise at a rate of 10 g / min, and the mixture was further heated and stirred for about 2 hours and continued for 2 hours to block polyethylene glycol / isophorone diisocyanate / polydimethylsiloxane block polymer, polymer 2 ( Number average molecular weight 170
00, MW / MN = 1.70) was synthesized.

As in Example 1, a hologram was prepared by using a hologram recording medium containing 100 parts by weight of Polymer 2 instead of Polymer 1. Table 2 shows the results.

Example 3 Using the composition of Example 2 and a hologram recording medium containing 10 parts by weight of 2-mercaptobenzoxazole (MBO) as a chain transfer agent, a hologram was prepared in the same manner as in Example 1. did. Table 2 shows the results.

Example 4 Instead of PEG, polypropylene glycol (PPG,
Using a molecular weight of about 2000) and in the same manner as in Example 2,
Block polymer of polypropylene glycol / isophorone diisocyanate / polydimethylsiloxane, polymer 3 (number average molecular weight of about 17,000, MW / MN = 1.
69) was synthesized.

As in Example 3, a hologram was prepared using a hologram recording medium containing 100 parts by weight of Polymer 3 instead of Polymer 2. Table 2 shows the results.

Example 5 Instead of PEG, a polyester polyol (Kuraray Co., Ltd., trade name CLAPOL P-2010, molecular weight 2000,
A block polymer of polyester polyol / isophorone diisocyanate / polydimethylsiloxane, polymer 4 (number average molecular weight about 20,000, MW) using 3-methyl-1,5-pentanediol adipate) in the same manner as in Example 2. /MN=1.51) was synthesized.

A hologram was prepared in the same manner as in Example 3 except that the hologram recording medium containing 100 parts by weight of the polymer 4 was used in place of the polymer 2. Table 2 shows the results.

Example 6 Instead of PEG, Japanese Patent Publication No. 05-31570, Example 1
In the same manner as in Example 2, using the hexahydrophthalic anhydride / phenyl glycidyl ether / ethylene glycol polyester polyol described in 1., a block polymer of polyester polyol / isophorone diisocyanate / polydimethylsiloxane, polymer 5 (number average molecular weight of about 9000, MW / MN = 1.72) was synthesized.

As in Example 3, a hologram was prepared by using a hologram recording medium containing 100 parts by weight of the polymer 5 instead of the polymer 2. Table 2 shows the results.

Examples 7 to 10 As in Example 3, holograms were prepared using a hologram recording medium containing 100 parts by weight of the polymer mixture shown in Table 1 instead of the polymer 2. Table 2 shows the results.

Examples 11 to 20 As in Example 3, a holographic recording medium containing 100 parts by weight of the compound (B) having an ethylenically unsaturated bond shown in Table 3 in place of dimethyloltricyclodecane diacrylate. Was used to create a hologram. Table 3 shows the results.

Examples 21 to 30 In the same manner as in Example 3, instead of the photopolymerization initiator system consisting of DEAW and DPI, hologram recording media were replaced with the initiator system shown in Table 4 to form holograms. Created.
Table 5 shows the results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

EFFECT OF THE INVENTION By using the hologram recording photosensitive composition used in the present invention, the hologram recording medium, and the method for producing a hologram using the same, it is possible to chemically react with high sensitivity over a wide wavelength range. A volume phase hologram that is stable, has high resolution, high diffraction efficiency, high transparency, and is excellent in light resistance and heat resistance can be easily manufactured.

[0064]

[Brief description of the drawings]

FIG. 1 is a block diagram of a two-beam exposure apparatus for creating a reflection hologram.

FIG. 2 shows a block diagram of a two-beam exposure apparatus for producing a transmission hologram.

FIG. 3 shows a block diagram of a one-beam exposure apparatus for producing a reflection hologram.

[Explanation of symbols]

1: substrate (glass plate) 2: photosensitive layer for hologram recording 3: protective film (polyester film) 4: collimated laser light obtained through a spatial filter 5: reflection mirror (or master hologram)

Claims (7)

[Claims] 1. A block copolymer (A) having at least one siloxane compound part and at least one organic compound part in a main chain skeleton, a compound (B) having a polymerizable ethylenically unsaturated bond, and a photopolymerization initiator system. A photosensitive composition for hologram recording, which comprises (C) and has a refractive index modulation degree of 0.005 or more by interference exposure of laser light. 2. The photosensitive composition for hologram recording according to claim 1, wherein the compound (B) having a polymerizable ethylenically unsaturated bond is a compound having an aromatic ring or a halogen atom in the molecule. 3. The photosensitive composition for hologram recording according to claim 1, wherein the compound (B) having a polymerizable ethylenic unsaturated bond is a non-halogen aliphatic compound. 4. The photosensitive composition for hologram recording according to claim 1, wherein the compound (B) having a polymerizable ethylenically unsaturated bond is a compound containing a sulfur atom in the molecule. 5. The photosensitive composition for hologram recording according to claim 1, which further contains a chain transfer agent (D). 6. A hologram recording medium formed by forming a layer of the photosensitive composition for hologram recording material according to claim 1 on a substrate. 7. The hologram recording medium according to claim 6,
A method for producing a hologram, which comprises applying light or heat after hologram exposure.