JPH09106241A - 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 polymer compd. containing a polysiloxane compd. part in the side 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. 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,
Polyethylene oxide having an average molecular weight of, 000,000, 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, in order to increase the degree of refractive index modulation caused by exposure to the interference pattern of radiation,
Binder polymers having a lower refractive index have been desired.

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,
In the known art, it is necessary to use 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 side chain has a polysiloxane compound part. By using the polymer compound (A) containing, not only 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 also a relatively small refractive index The use of aliphatic monomers is also possible. 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 relates to a polymer compound (A) containing a polysiloxane compound part in the side chain,
A hologram comprising a compound (B) having a polymerizable ethylenically unsaturated bond and a photopolymerization initiator system (C), and having a refractive index modulation degree of 0.005 or more due to interference exposure of laser light. A photosensitive composition for hologram recording, and a photosensitive composition for hologram recording, comprising a photosensitive composition for hologram recording and a chain transfer agent (D) further added to the photosensitive composition for hologram recording. Of a holographic recording medium, characterized in that the functional composition is formed on a base material, and the hologram recording medium is subjected to hologram exposure, and then light or heat is applied to the hologram recording medium. Is the way.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the polymer compound (A) containing a polysiloxane compound portion in the side chain used in the present invention will be described. The polymer compound (A) containing a polysiloxane compound portion in the side chain as used herein is a single or plural polysiloxane compound having a reactive functional group at one end and a monomer unit capable of reacting with the functional group. As a copolymer with one or more kinds, or a polysiloxane compound having a reactive functional group at one end, a single kind or a plurality of kinds, and a line having a reactive functional group capable of reacting with the functional group on the main chain. It is synthesized as a graft copolymer with a polymer.

Examples of the reactive functional group at the end of the polysiloxane compound having a reactive functional group at one end include (meth) acrylic group, hydroxyl group, methylol group, epoxy group, ethyleneimino group, isocyanate group, thioisocyanate. Group, lactone group, ketene group, aldehyde group, vinyl group,
Amino group, amide group, mercapto group, acid hydrazine group,
Examples thereof include a hydroxamic acid group, a sulfonic acid chloride group, an acid azide group, a sulfonic acid group, a carboquinyl group, and an acid anhydride group. Specifically, as one end (meth) acryloxy group-containing polysiloxane compound, Cilaplane FM-0711, FM-0721, FM manufactured by Chisso Corporation is used.
Cilaplane FM manufactured by Chisso Co., Ltd. as a polysiloxane compound containing a hydroxy group at one end such as -0725.
-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.,
As one end epoxy group-containing polysiloxane compound, Cilaplane FM-0511, FM- manufactured by Chisso Corporation
0521, FM-0525, X manufactured by Shin-Etsu Chemical Co., Ltd.
-22-173B, TSF4 manufactured by Toshiba Silicone Co., Ltd.
730, TSF4731, TSL9905, etc. as one-terminal vinyl group-containing polysiloxane compound, 2 Toshiba Silicone Co., Ltd. TSL9705, etc., one-terminal amino group-containing polysiloxane compound, Chisso Corp. Silaplane FM-3331 , FM-3321, FM
-3325, X-22-161 manufactured by Shin-Etsu Chemical Co., Ltd.
AS, X-22-161A, X-22-161B, X-
22-161C, XF42- manufactured by Toshiba Silicone Co., Ltd.
A2645, XF42-A2646, TSF4700,
TSF4701, TSF4702, TSF4703, T
SF4720, TSL9306, TSL9305, TS
Examples include L9346, TSL9386, BX16-853, BY16-853B manufactured by Toray Silicone Co., Ltd., and the like.

Further, the monomer capable of reacting with the functional group of the polysiloxane compound having a reactive functional group at one end is an alkene, a (meth) acrylic acid ester, a polyhydric alcohol depending on the type of the reactive functional group. , Epoxies, ethyleneiminos, isocyanates, thioisocyanates,
It can be selected from lactones, ketene, aldehydes, amines, amides, thiols, acid hydrazines, hydroxamic acids, acid azides, carboxylic acids, and their derivatives, acid anhydrides and the like.

Specifically, as alkenes, butene,
As (meth) acrylic acid esters such as heptene and octene, 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 C1-18 alkyl (meth) acrylates such as methacrylate; glycidyl acrylate,
Glycidyl methacrylate; C2-18 alkoxyalkyl (meth) acrylate such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate;
C2-8 hydroxyalkyl (meth) acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, etc. Aminoalkyl esters of acrylic acid, acrylamide, methacrylamide, etc.
As polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, 3-methyl-1,5-pentanediol and the like, epoxies,
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 di Glycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, hydroquinone diglycidyl ether, etc., ethyleneiminos, triethylenediamine, bisethyleneimine, etc. Isocyanate (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, thioisocyanates, methylenebis (4-phenylthioisocyanate), lactones, γ-crotonolactone, α-angelicalactone, β -Angelicalactone and the like, ketene, diketene and the like, aldehydes such as p-holomethylstyrene, α-cyanomethylacrolein, (meth) acrolein, crotonaldehyde,
As amines such as benzaldehyde, hydroxyaldehyde, aldehyde acid, salicylaldehyde, and anisaldehyde, ethylenediamine, polyoxypropylenediamine, mensendiamine, isophoronediamine, chair (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, Bis (aminomethyl) cyclohexane, N-aminoethylpiperazine,
m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2,5-dimethyl-2,
5-hexanediamine and the like, amides such as phthalimide and succinimide, thiols such as pentamethylene dimercaptan and hexamethylene dimercaptan, and acid hydrazines such as phenylhydrazide,
Hydroxamic acids, such as semicarbazide, formhydroxamic acid, acetohydroxamic acid, etc., Acid azides, o-quinonediazide, carboxylic acids, and their derivatives, malonic acid, maleic acid, succinic acid, adipic acid, sepacic acid, Oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 1,4
-Butanedicarboxylic acid and the like, as an acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, Dodecenyl succinic anhydride,
Examples thereof include polyazelaic acid anhydride and polydodecanedioic acid anhydride.

Further, as a linear polymer having a reactive functional group capable of reacting with a functional group of a polysiloxane compound having a reactive functional group at one end on its main chain, a (meth) acrylic group, a hydroxyl group or a methylol group is used. , Epoxy group, ethyleneimino group, isocyanate group, thioisocyanate group, lactone group, ketene group, aldehyde group, vinyl group, amino group, amide group, mercapto group, acid hydrazine group, hydroxamic acid group, sulfonic acid chloride group , Acid azido group, sulfonic acid group, carboquinyl group, having a reactive functional group such as acid anhydride group, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, other polyvinyl compounds, Poly (meth) acrylic acid, poly (meth) acrylic acid ester, poly Acrylonitrile, polybutadiene, polyisoprene, polyesters, polycarbonates, polyacetals, polyethylene oxides, polyphenylene oxides, polysulfides, polysulfones, polyamides, polyimides, polyurethanes, polyethers,
Linear polymers such as epoxy resin, phenoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin can be used.

Specifically, glycidyl methacrylate
Acrylonitrile copolymer, polyvinylamine, polyethyleneimine, polytrimethyleneimine, polyaminostyrene, polyvinyl hydroxyethyl ether, poly-
p-hydroxystyrene, polyhydroxymethylmethacrylate, poly-N-methylolacrylamide, carboxymethylcellulose, poly (meth) acrylic acid, polyepichlorohydrin, polychloromethylstyrene, polyvinylchloroethyl ether, polyacrylamide,
Examples thereof include styrene / maleic anhydride copolymer, poly (meth) acrolein, polyacetal, polyvinyl isocyanate, polyvinyl alcohol, 1-nylon and the like.

The polymer compound (A) containing a polysiloxane compound part in a series of side chains synthesized by using these is
Since it has a low refractive index, it can have a large difference in refractive index from a compound having a polymerizable ethylenically unsaturated bond, and when hologram recording is performed by a radiation interference pattern, a hologram having a high diffraction efficiency can be obtained. Can be created. 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 polymer compound (A) containing a polysiloxane compound moiety in the side chain can be used as a mixture of two or more kinds. Further, a mixture with a polysiloxane compound or a polymer compound other than the polysiloxane compound can be used. It may be used as a mixture.

As the polysiloxane compound, dimethylpolysiloxane, methylhydrogenpolysiloxane, terminal hydrogenpolysiloxane, methylphenylpolysiloxane, phenylhydrogenpolysiloxane, diphenylpolysiloxane, alkyl-modified polysiloxane, amino-modified polysiloxane, Examples thereof include carboxyl modified polysiloxane, epoxy modified polysiloxane, vinyl group modified polysiloxane, alcohol modified polysiloxane, polyether modified polysiloxane, alkyl / polyether modified polysiloxane, and fluorine modified polysiloxane. Specifically, as dimethylpolysiloxane, TSF451 manufactured by Toshiba Silicone Co.,
XS69-A1753, Toray Silicone Co., Ltd. SH200, BY16-140, etc., as one-end hydrogen dimethyl polysiloxane, Chisso Co., Ltd. silaplane FM1111, FM1121, FM11.
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., Cilaplane 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 Torre Silicone Co., Ltd. such as (meth) acryloyl modified polysiloxane Examples include Silaplane FM0711, FM0721, FM0725 and the like manufactured by Co., Ltd.

As the polymer compound other than the polysiloxane compound, a homopolymer of vinyl monomer or a copolymer of two or more components, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-, etc.
Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, 2-methylbutyl,
3-methylbutyl, 2-ethylbutyl, 1,3-dimethylbutyl, 2-ethylhexyl, 2-methylpentyl,
Chains such as cyclohexyl, adamantyl, isobornyl, dicyclopentanyl, tetrahydrofurfuryl,
Polymers of branched and cyclic alkyl (meth) acrylic acid ester monomers, polymers of (meth) acrylic acid ester monomers having hydroxyl groups such as 2-hydroxyethyl, 2-hydroxypropyl and 4-hydroxybutyl, glycidyl ( A polymer of a (meth) acrylic acid ester monomer containing an epoxy group such as (meth) acrylate,
Polymers of (meth) acrylic acid ester monomer containing an amino group such as N, N-dimethylaminoethyl, N, N-diethylaminoethyl, t-butylaminoethyl and the like,
(Meth) acrylic acid, itaconic acid, maleic acid, 2-
Polymers of vinyl monomers containing carboxyl groups such as (meth) acryloyloxypropylhexahydrophthalic acid, polymers of phosphate group-containing (meth) acrylic acid ester monomers such as ethylene oxide modified phosphoric acid (meth) acrylate, acrylamide Polymers of vinyl monomers such as N-butyl acrylamide, N, N-dimethyl acrylamide, N-vinyl pyrrolidone, acrylonitrile, vinyl acetate, vinyl butyral, vinyl acetal and vinyl formal. Further, copolymers of two or more components of these vinyl monomers, polyacrylonitrile, polybutadiene, polyisobrene, polyester, polycarbonate, polyacetal, polyethylene oxide, polyphenylene oxide, polysulfide, polysulfone, polyamide, polyimide, polyurethane, polyether, etc. can do.

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.

Use of a compound (B) having a polymerizable ethylenically unsaturated bond and having a substituent selected from an aromatic ring or a halogen atom in the molecule to enhance the diffraction efficiency of a 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.

It is also possible to use a non-halogen-based aliphatic compound as the compound (B) having a polymerizable ethylenically unsaturated bond. 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.

Among 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.

The compound (B) having a polymerizable ethylenically unsaturated bond may also be an addition-polymerizable compound which is polymerized through ring-opening sigma bond cleavage. 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 represented by chalcone derivatives and dibenzalacetone derivatives, 1,2-diketone derivatives represented by benzyl and camphorquinone, and the like. 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.

Next, 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 1.0 to 30 with respect to 100 parts by weight of the polymer compound (A) containing a polysiloxane compound part in the side chain.
Parts by weight are preferred.

Next, in the hologram recording photosensitive composition of the present invention, a crosslinking agent can be used for the purpose of more firmly fixing the recording layer after hologram production.
In the cross-linking agent here, the polymer compound (A) containing a polysiloxane compound part in the side chain is a hydroxy group, an amino group,
When it has a reactive group such as an epoxy group, a carboxyl group and a mercapto group, it can be used for crosslinking, and depending on the type of the reactive group, polyhydric alcohols, amines, 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 preferably added in the range of 0.001 to 20 parts by weight with respect to 100 parts by weight of the polymer compound (A) containing a polysiloxane compound part in the side chain having the reactive group.

A thermal polymerization inhibitor may be added to the hologram recording photosensitive composition 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 polymer compound (A) containing a polysiloxane compound moiety in the side chain, a compound (B) having a polymerizable ethylenically unsaturated bond, and photopolymerization. It is possible to dissolve the initiator system (C) in a suitable solvent at an arbitrary ratio, form the resulting solution as a photosensitive film on a substrate, and use it as a hologram recording medium.

In the photosensitive composition for hologram recording used in the present invention, the amount of the polymer compound (A) containing a polysiloxane compound moiety in the side chain in the composition is high diffraction efficiency, high resolution, and high In order to produce a transparent hologram, the content is 10 to 90% by weight, preferably 30 to 70% by weight.
It is. The amount of the compound (B) having a polymerizable ethylenically unsaturated bond used is 10 to 50 with respect to 100 parts by weight of the polymer compound (A) containing a polysiloxane compound part in the side chain.
It is 0 part 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 polymer compound (A) 1 containing a polysiloxane compound part in the side chain.
It is used in an amount of 0.001 to 30 parts by weight, preferably 0.1 to 5 parts by weight, based on 00 parts by weight. The amount used is
It 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. Further, the initiator (b) is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the polymer compound (A) containing a polysiloxane compound part in the side chain. used.

The photosensitive composition for hologram recording having the above composition ratio is dissolved in a suitable 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. In addition, poly vinyl 111111111 alcohol,
A protective film such as polyethylene terephthalate, polyolefin, polyvinyl chloride, polyvinylidene chloride or cellophane film may be further provided and used. As a method of forming the protective film, coating in a solution state,
The hologram recording medium can be laminated on the hologram recording medium by electrostatically adhering, laminating using an extruder, or laminating a film in which an adhesive is applied to the protective film in advance. 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 the heat resistance of the substrate used, the polymer compound (A) containing a polysiloxane compound part in the side chain in the photosensitive composition for photosensitive material for hologram recording of the present invention and polymerizable It is necessary to select a suitable temperature condition in consideration of the heat resistance of the compound (B) having a specific 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. .

[0041]

The photosensitive composition for hologram recording used in the present invention comprises a polymer compound (A) containing a polysiloxane compound moiety in the side chain, a compound (B) having a polymerizable ethylenically unsaturated bond, and a photopolymerization compound. It is characterized by comprising an 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. Also,
The compound (B) having an unreacted 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 enlarged. Then, a hologram is formed by the refractive index modulation. On the other hand, since the polymer compound (A) containing a polysiloxane compound moiety in the side chain used in the present invention has a low refractive index, it has a large difference in refractive index from the compound (B) having an ethylenically unsaturated bond. It is possible to further improve the refractive index modulation effect, and 0.0
When the combination shows a refractive index modulation of 05 or more, it is considered that the effect becomes 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.

[0043]

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 A four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube was placed in a one-terminal methacryloyl-modified polydimethylsiloxane (manufactured by Chisso Corporation, trade name FM-071).
1, 50 parts by weight of molecular weight 1000, 50 parts by weight of methyl methacrylate (MMA, molecular weight 100), and 200 parts by weight of methyl ethyl ketone (MEK) were mixed to prepare a uniform solution. 0.8 parts by weight of azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was reacted at 80 ° C. for about 2 hours in a nitrogen atmosphere, and then 0.2 parts by weight of AIBN was added in a total amount of nitrogen atmosphere. Lower, heating for about 2 hours,
Stirring is continued, a copolymer of FM-0711 and MMA,
Polymer 1 (number average molecular weight of about 19000, MW / MN =
2.03) was synthesized.

100 parts by weight of Polymer 1 as the polymer compound (A) containing a polysiloxane compound portion in the side chain, and phenoxyethyl acrylate (manufactured by Kyoeisha Yushi Co., Ltd.) as the compound (B) having a polymerizable ethylenically unsaturated bond. Brand name PO-A, refractive index = 1.52) 100 parts by weight, 3,3′-carbonylbis (7-diethylaminocoumarin) (KC) as a photopolymerization initiator system (C) sensitizer (a)
D) was prepared in an amount of 0.5 part by weight, the initiator (b) was 5 parts by weight of diphenyliodonium hexafluorophosphate (DPI), and the solvent was 200 parts by weight of methyl ethyl ketone (MEK).

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.

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

Example 2 Using the composition of Example 1 and a hologram recording medium containing 5 parts by weight of 2-mercaptobenzoxazole (MBO) as a chain transfer catalyst, a hologram was prepared in the same manner as in Example 1. did. Table 2 shows the results.

Examples 3 to 6 FM-0711 and MMA were added at 80 parts by weight and 20 parts by weight, respectively.
By weight, 60 parts by weight and 40 parts by weight, 40 parts by weight and 60 parts by weight, 20 parts by weight and 80 parts by weight, respectively, in the same manner as in Example 1, a copolymer of FM-0711 and MMA, polymer 2 (Number average molecular weight of about 14,000, MW / MN = 1.5
6), polymer 3 (number average molecular weight about 14,000, MW /
MN = 1.64), polymer 4 (number average molecular weight about 150)
00, MW / MN = 1.65) and polymer 5 (number average molecular weight about 14,000, MW / MN = 1.58) were synthesized.

A hologram was prepared in the same manner as in Example 2 except that the hologram recording medium containing 100 parts by weight of each of the polymers 2, 3, 4, and 5 was used instead of the polymer 1. Table 2 shows the results.

Examples 7 to 11 Instead of FM-0711, FM-0721 (methacryloyl-modified polydimethylsiloxane modified at one end, manufactured by Chisso Corporation,
Using the trade name FM-0721, molecular weight 5000), FM
The mixing ratios of -0721 and MMA are 80 parts by weight and 20 parts by weight, 60 parts by weight and 40 parts by weight, 50 parts by weight and 50 parts by weight, 40 parts by weight and 60 parts by weight, 20 parts by weight and 8 parts by weight, respectively.
FM-072 in the same manner as in Example 1
Copolymer of 1 and MMA, polymer 6 (number average molecular weight about 14,000, MW / MN = 1.70), polymer 7 (number average molecular weight about 12000, MW / MN = 1.89), polymer 8 (number average Molecular weight about 12000, MW / MN =
1.91), polymer 9 (number average molecular weight of about 10,000,
MW / MN = 2.08) and Polymer 10 (number average molecular weight of about 9000, MW / MN = 2.05) were synthesized.

As in Example 2, instead of the polymer 1, a hologram recording medium containing 100 parts by weight of each of the polymers 6, 7, 8, 9, and 10 was used to prepare a hologram. Table 2 shows the results.

Examples 12 to 14 FM-0711, MMA, and salicyl acrylate (manufactured by Kyoeisha Oil & Fat Co., Ltd., trade name S-A) were each added to 40 parts.
In the same manner as in Example 1, FM was added in a weight ratio of 50 parts by weight to 50 parts by weight, 25 parts by weight to 50 parts by weight to 25 parts by weight, 10 parts by weight to 50 parts by weight to 40 parts by weight. −
Copolymer of 0711, MMA and S-A, polymer 11
(Number average molecular weight of about 14,000, MW / MN = 1.8
9), polymer 12 (number average molecular weight about 12000, MW
/MN=1.72), polymer 13 (number average molecular weight about 1)
2000, MW / MN = 1.74) were synthesized.

As in Example 2, instead of the polymer 1, a hologram recording medium containing 100 parts by weight of each of the polymers 11, 12 and 13 was used to prepare a hologram. Table 2 shows the results.

Example 15 A four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube was charged with glycidyl methacrylate (GM).
A homogeneous solution was prepared by mixing 100 parts by weight of A), 100 parts by weight of acrylonitrile (AN), and 200 parts by weight of tetrahydrofuran (THF). 1.6 parts by weight of azobisisobutyronitrile (AIBN) was added as a polymerization initiator,
After reacting at 64 ° C for about 2 hours in a nitrogen atmosphere, further A
Add 0.4 parts by weight of IBN in total, and add about 4 parts under nitrogen atmosphere.
The heating and stirring are continued for a time to obtain a copolymer of GMA and AN,
A trunk polymer (molecular weight 6000) was synthesized. 1-terminal amino-modified polydimethylsiloxane (manufactured by Chisso Corporation, trade name FM-3311, molecular weight 1000) 1 was added to this polymer solution.
00 parts by weight was added dropwise over 1 hour, and heating and stirring were continued for 1 hour to synthesize a silicone graft copolymer, Polymer 14 (molecular weight 15000).

A hologram was prepared in the same manner as in Example 2 except that the hologram recording medium containing 100 parts by weight of the polymer 14 was used instead of the polymer 1. Table 2 shows the results.

Examples 16 to 19 In the same manner as in Example 2, a hologram was prepared by using a hologram recording medium containing 100 parts by weight of the mixture of the polymers shown in Table 3 instead of the polymer 1. Table 4 shows the results.

Examples 20 to 27 In the same manner as in Example 2, a hologram recording medium containing 100 parts by weight of the compound (B) having an ethylenically unsaturated bond shown in Table 5 instead of phenoxyethyl acrylate was used. Created a hologram. Table 5 shows the results.

Examples 28 to 37 In the same manner as in Example 2, instead of the photopolymerization initiator system comprising KCD and DPI, a hologram recording medium was used instead of the initiator system shown in Table 6 to form a hologram. Created. Table 7 shows the results.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

[Table 5]

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

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 can be easily manufactured.

[0068]

[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 (9)

[Claims] 1. A laser beam comprising a polymer compound (A) having a polysiloxane compound moiety in its side chain, a compound (B) having a polymerizable ethylenically unsaturated bond and a photopolymerization initiator system (C). 1. The photosensitive composition for hologram recording, which has a refractive index modulation degree of 0.005 or more by the interference exposure. 2. A polymer compound (A) having a polysiloxane compound portion in its side chain, which is a copolymer of a polysiloxane compound having a reactive functional group at one end and a monomer capable of reacting with the functional group. The photosensitive composition for hologram recording according to claim 1, which is a united body. 3. A polymer compound (A) having a polysiloxane compound part in its side chain has a main chain of a polysiloxane compound having a reactive functional group at one end and a reactive functional group capable of reacting with the functional group. The photosensitive composition for hologram recording according to claim 1, which is a graft copolymer with the linear polymer above. 4. 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. 5. The photosensitive composition for hologram recording according to claim 1, wherein the compound (B) having a polymerizable ethylenically unsaturated bond is a non-halogen aliphatic compound. 6. 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. 7. The photosensitive composition for hologram recording according to claim 1, further comprising a chain transfer agent (D). 8. A hologram recording medium formed by forming a layer of the photosensitive composition for hologram recording material according to claim 1 on a substrate. 9. The hologram recording medium according to claim 8,
A method for producing a hologram, which comprises applying light or heat after hologram exposure.