JP5284866B2 - Photosensitive composition containing vinylcyclopropane compound - Google Patents

Description

The present invention relates to a photosensitive composition containing a vinylcyclopropane compound.
The photosensitive composition containing the vinylcyclopropane compound of the present invention is particularly suitable as a material for a hologram optical recording medium.

  Conventionally, development of a holographic optical recording medium using a holographic principle has been advanced. Information is recorded on these hologram optical recording media by superimposing information light including image information and reference light in a recording layer made of a photosensitive composition, and writing interference fringes formed at that time on the recording layer. Is done by. Then, by making the reference light incident on the recording layer on which information is recorded at a predetermined angle, light diffraction of the reference light by the formed interference fringes occurs, and the information light is reproduced.

  In recent years, volume holograms have been developed in practical use for ultra-high density optical recording, and are attracting attention. Volume hologram is a method of writing interference fringes in three dimensions by actively utilizing recording in the thickness direction of the optical recording medium, increasing the diffraction efficiency by increasing the thickness, and recording using multiple recording There is a feature that the capacity can be increased.

  In such volume hologram optical recording media, a high recording density is an important factor. However, in a recording system using a normal photopolymer, distortion of recording interference fringes is caused by volume contraction that occurs during polymerization of a photopolymerizable monomer. Occurs, and there is a serious problem that an error is caused at the time of data input / output (Non-Patent Document 1). As a method for reducing the volume shrinkage, there is a method of adding a filler to the volume hologram recording medium. In this case, since the filler does not participate in polymerization that causes volume shrinkage, the recording layer as a whole has an effect of suppressing volume shrinkage during polymerization. However, there is a demerit that the recording capacity is reduced as the amount of filler added is increased.

  In addition, a monomer compound has been proposed in which a vinylcyclopropane structure, which is said to have a relatively small volume shrinkage, is incorporated to reduce volume shrinkage associated with polymerization. As an example of a compound capable of suppressing volume shrinkage, a polymerizable monomer having a phenyl ester group or adamantyl ester group-substituted vinylcyclopropane structure and expanding in volume at the time of polymerization is disclosed (Non-Patent Documents 2 and 3).

Journal of Japan Printing Society, 2004, 41, 279-285 Macromolecules, 1994, 27, p. 5543-5546 Macromolecules, 1996, 29, p. 1943-1950

Since these polymerizable monomers listed in Non-Patent Document 2 and Non-Patent Document 3 are solid at room temperature, they are not suitable for practical use from the viewpoint of highly convenient low polymerization shrinkable monomers required in various industrial fields. The problem remains.
The present invention is a photosensitive composition having a small volume shrinkage by using a compound having a low viscosity at room temperature before polymerization and having a small volume shrinkage when polymerized using heat and a photo radical initiator. It is an object to provide a photosensitive composition having a large recording capacity when used as a volume hologram recording composition.

As a result of intensive studies to achieve the above object, the present inventors have used a specific vinylcyclopropane compound having a cycloalkyl group in the molecule as a polymerizable monomer in the photosensitive composition, so that The present invention has been completed by finding out that it is liquid and can exhibit an effect of suppressing polymerization shrinkage.
That is, the present invention provides (a) Formula (1) as a first aspect.

(In the formula (1), X and Y may be the same as or different from each other, and C (═O) R ¹ , C (═O) OR ¹ , OC (═O) R ¹ , C ( = O) SR ¹ , SC (= O) R ¹ , C (
= O) represents NR ¹ R ² , SO ₂ R ¹ or R ¹ ,
R ¹ is unsubstituted or a linear alkyl group having 1 to 12 carbon atoms, or 3 to 12 carbon atoms.
Substituted by a substituent selected from the group consisting of a cycloalkyl group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, and a hydroxy group. Represents a cycloalkyl group having 3 to 18 carbon atoms,
R ² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. It is related with the photosensitive composition containing the vinylcyclopropane compound represented by this.
As a 2nd viewpoint, based on the volume of the said photosensitive composition, it is related with the photosensitive composition as described in a 1st viewpoint in which the said vinyl cyclopropane compound occupies 50 volume% or more.
As a third aspect, the composition further comprises (b) a photopolymerization initiator and (c) inorganic fine particles, and when this is subjected to pattern exposure, mutual diffusion occurs in the composition, and a spatial refractive index modulation pattern is formed. The photosensitive composition according to the first aspect or the second aspect is characterized by being formed.
As a fourth aspect, the present invention relates to the photosensitive composition according to any one of the first to third aspects, wherein the vinylcyclopropane compound has a viscosity of 10 to 3,000 mPa · s.
As a fifth aspect, the present invention relates to the photosensitive composition according to any one of the first to fourth aspects, wherein the vinylcyclopropane compound has a refractive index of 1.45 to 1.55.
As a sixth aspect, the present invention relates to the photosensitive composition according to any one of the first aspect to the fifth aspect, wherein X and Y in the formula (1) represent C (═O) OR ¹ .
As a seventh aspect, in the formula (1), R ¹ is unsubstituted or a linear alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 1 to 12 carbon atoms. A cycloalkyl group having 5 to 8 carbon atoms substituted with a substituent selected from the group consisting of an alkoxy group of the above, an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, and a hydroxy group. The present invention relates to the photosensitive composition according to any one of the first to sixth aspects.
As an eighth aspect, the present invention relates to a hologram recording layer comprising the photosensitive composition according to any one of the first aspect to the seventh aspect.
As a ninth aspect, the present invention relates to a hologram recording medium in which the hologram recording layer according to the eighth aspect is formed on a support and the hologram recording layer is covered with a protective material.

Since the photosensitive composition of the present invention is in a liquid state before polymerization and its viscosity is low, it is easy to handle in actual use situations. And since the vinylcyclopropane compound represented by Formula (1) to contain has a small volume shrinkage accompanying superposition | polymerization compared with the conventional polymerizable monomer, the use as a low shrinkage | contraction material can be anticipated. Furthermore, since the photosensitive composition of the present invention has a low refractive index, it can be expected to be used as a material particularly for optical applications.
Therefore, the photosensitive composition of the present invention can be used as, for example, an adhesive, a cement, a dental material, a veneer material, a composite material, or a molded body by utilizing the property that the volume shrinkage after curing is small. Furthermore, in addition to low volume shrinkage, its characteristics such as low refractive index, high transparency, low viscosity before polymerization, etc., for example, camera prism, coating material, optical window material, nonlinear optical element, optical recording It can be used as an optical material such as a material, a gap fill material, and a volume hologram.

In particular, since the photosensitive composition of the present invention has a low viscosity as described above, a volume having low diffraction loss and high diffraction efficiency can be obtained by uniformly dispersing inorganic fine particles in a polymerizable monomer (vinylcyclopropane compound). The composition is useful as a photosensitive composition for a phase hologram recording material.
And since the hologram recording layer of the present invention contains the above photosensitive composition having a small volume shrinkage, distortion of interference fringes to be recorded hardly occurs, and errors that occurred during data input / output can be greatly suppressed. And high multiplex characteristics can be realized. Further, the recording capacity is not reduced by the filler used conventionally for suppressing the volume shrinkage.
Therefore, the hologram recording medium of the present invention including the recording layer has a low light scattering loss, a high diffraction efficiency, a small error at the time of data input / output, a large recording capacity, a high density and a high recording sensitivity. it can.

FIG. 1 is a conceptual diagram of an apparatus that performs two-beam interference exposure on a volume hologram recording medium. FIG. 2 is a graph showing the exposure time change of the diffraction efficiency of the volume hologram recording medium in Example 6. FIG. 3 is a graph showing a change in exposure time of the diffraction efficiency of the volume hologram recording medium in Comparative Example 3.

Hereinafter, the present invention will be described in more detail.
The (a) vinylcyclopropane compound contained in the photosensitive composition of the present invention is a compound represented by the formula (1).
The present invention is characterized in that a vinylcyclopropane compound having a cycloalkyl group in the structure is used as a polymerizable monomer. Since the structure of the cycloalkyl group is flexible, it has been realized that the photosensitive composition containing the vinylcyclopropane compound becomes a low-viscosity liquid. Further, the vinylcyclopropane compound is composed of only a carbon atom, a hydrogen atom, or an oxygen atom depending on the choice of the substituent, and therefore, the photosensitive composition containing the compound can have a low refractive index. Yes.

In the formula (1), X and Y may be the same or different from each other, and C (═O) R ¹ , C (═O) OR ¹ , OC (═O) R ¹ , C ( = O) SR ¹ , SC (= O) R ¹ , C (= O) NR ¹ R ² , SO ₂ R ¹ , or R ¹ . X and Y preferably represent C (═O) OR ¹ .
R ¹ represents an optionally substituted cycloalkyl group having 3 to 18 carbon atoms, and R ² represents any one of a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group. Here, the substituent of the cycloalkyl group in R ¹ is a linear alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or the number of carbon atoms. It is selected from the group consisting of an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, and a hydroxy group.

Specific examples of R ¹ include various groups. Among them, an unsubstituted cycloalkyl group having 5 to 8 carbon atoms substituted by the above substituent is preferable, particularly a cyclopentyl group, A cyclohexyl group, a cycloheptyl group or a cyclooctyl group is preferred.

Specific examples of R ² include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, phenyl group. , Naphthyl group, anthracenyl group, furyl group, thienyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, furazanyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, pyridyl Group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, benzofuranyl group, isobenzofuranyl group, benzo [b] thienyl group, indolyl group, isoindolyl group, 1H-indazolyl group, benzimidazolyl group, benzoxazolyl group Ben Thiazolyl group, 1H-benzotriazolyl group, quinolyl group, isoquinolyl group, cinnolyl group, quinazolyl group, quinoxalinyl group, phthalazinyl group, naphthyridinyl group, purinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenoxazinyl group, phenothiazinyl group Phenazinyl group, phenoxathiinyl group, thiantenyl group, indolizinyl group, morpholino group and the like.

  The vinylcyclopropane compound represented by the above formula (1) usually exists as a stereoisomer mixture, particularly as a racemic compound.

  The vinylcyclopropane compound represented by the above formula (1) preferably has a viscosity of 3,000 mPa · s or less at 25 ° C. When the viscosity is high, it is not easy to disperse and mix other components when the photosensitive composition is used. For example, when the composition is a hologram recording composition described later, the inorganic fine particles to be added are not easily moved. Problem will occur.

  In addition, the vinylcyclopropane compound represented by the above formula (1) preferably has a refractive index of 1.45 to 1.55 at the wavelength to be sensitized, and further has an aromatic ring group to avoid coloring. It is more preferable that the compound is not contained.

  Based on the volume of the photosensitive composition of the present invention, it is preferable that (a) the vinylcyclopropane compound occupies 50% by volume or more. When the occupation ratio of the vinylcyclopropane compound is small, the effect of suppressing shrinkage during polymerization cannot be obtained sufficiently. When used as a composition for hologram recording, there may be a problem that sufficient diffraction efficiency cannot be obtained during hologram recording.

The photosensitive composition of the present invention preferably contains a photopolymerization initiator that initiates (co) polymerization of the vinylcyclopropane compound represented by the formula (1). Examples of such a photopolymerization initiator include 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- ( 2-carboxyethyl) -2-methylpropionamidine], dimethyl 2,2′-azobisisobutyrate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2 '
-Azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propion Amido}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] Hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] sulfate, 2 , 2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] hydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2- Imidazolin-2-yl] pro } -Hydrochlorides, azo compounds such as 2,2′-azobis [2- (2-imidazolin-2-yl) propane]; p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azide Benzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide, 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidostilbene, etc. 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, and 1-diazo-4-N, Diazo compounds such as N-diethylaminobenzeneborofluoride; 1,2-naphthoquinone-diazide (2) -4-sulfonic acid sodium salt O-quinonediazide compounds such as 1,2-naphthoquinone-diazide (2) -5-sulfonic acid ester and 1,2-naphthoquinone-diazide (2) -4-sulfonyl chloride; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin propyl ether and benzoin isobutyl ether; benzophenone, 4,4′-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4 -Benzophenones such as benzoyl biphenyl, 4-benzoyl diphenyl ether and benzyl; 3,3'-carbonylbis (7- (diethylamino) -2H-chromen-2-one) (BC (CAS [63226] manufactured by Midori Chemical Co., Ltd.) 13-1])) and the like; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) In addition to biimidazole compounds such as -1,2'-biimidazole and 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole; Organic peroxides, titanocene compounds, thiol compounds, halogenated hydrocarbon compounds, trichloromethyltriazine compounds, or onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used. Of these, a titanocene compound and a thiol compound are preferably used in combination.
These polymerization initiators may be used alone or in combination of two or more as required.

  The photosensitive composition of the present invention preferably contains (b) a photopolymerization initiator and (c) inorganic fine particles in addition to (a) the vinylcyclopropane compound represented by the formula (1). When the photosensitive composition containing these components (a) to (c) is subjected to pattern exposure, mutual diffusion occurs in the composition, and a spatial refractive index modulation pattern is formed, that is, a volume hologram can be obtained. it can. Hereinafter, the photosensitive composition containing the components (a) to (c) is also referred to as a volume hologram forming composition.

In the volume hologram forming composition, the above-mentioned photopolymerization initiators are used, and a titanocene compound and a thiol compound are particularly preferably used in combination.
Specific examples of the titanocene compound are not particularly limited, and various conventionally known titanocene photopolymerization initiators can be used. Among these, bis (cyclopentadienyl) bis [2,6-difluoro -3- (1H-pyrrol-1-yl) phenyl] titanium is preferred.

  Specific examples of the thiol compound are not particularly limited, and various thiol compounds generally used as a chain transfer agent for radical polymerization reaction can be used. Among them, 1-dodecanethiol, pentaerythritol tetrakis (3-mercapto) Propionate) and 2-benzothiazole thiol are preferred, and pentaerythritol tetrakis (3-mercaptopropionate) is more preferred.

In the volume hologram forming composition, the addition amount of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (a) vinylcyclopropane compound.
In particular, when a titanocene compound and a thiol compound are used as a photopolymerization initiator, the addition amount of the titanocene compound and the thiol compound is 0.01 parts by mass to 100 parts by mass of the component (a) vinylcyclopropane compound. 10 parts by mass is preferable, and 0.1 to 5 parts by mass is more preferable.
When the titanocene compound is less than 0.01 parts by mass, the polymerizability is remarkably reduced. When the titanocene compound is more than 10 parts by mass, the composition and the polymer are colored, the light transmittance in the depth direction is decreased, and the resulting polymer There is a risk of problems such as a decrease in strength.
Moreover, when the amount of the thiol compound is less than 0.01 parts by mass, the polymerizability is remarkably reduced, and when it exceeds 10 parts by mass, the transparency of the composition or the polymer is decreased, the viscosity of the composition is increased, and the strength of the obtained polymer There is a possibility that a problem such as a decrease in the amount of the problem occurs.

In the volume hologram forming composition, since the inorganic fine particles need to reduce light scattering loss, fine particles having an average particle diameter of 400 nm or less are preferable, 200 nm or less is more preferable, and 20 nm or less is preferable. Is more preferable. The smaller the particle size, the better. However, the smaller the particle size, the more difficult it is to manufacture.
The proportion of the inorganic fine particles in the volume hologram formation is preferably 3% by volume or more, more preferably 5% by volume or more, with respect to the total volume of the inorganic fine particles and the resin component in the polymerization state. preferable. However, there is a limit to the amount of inorganic fine particles that can be dispersed in the composition, and if it is too large, it becomes difficult to disperse, and therefore it is preferably 50% by volume or less.

  Specifically, the inorganic fine particles are preferably inorganic oxide fine particles such as silica, zirconia, and titania. The form of the inorganic fine particles used may be a powder or a sol dispersed in water or an organic solvent, but it is used as a sol dispersed in an organic solvent from the viewpoint of dispersibility and stability in the volume hologram forming composition. Is preferred. Examples of the organic solvent include methanol, isopropanol, butanol, ethylene glycol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, xylene, dimethylacetamide, and toluene, and a polymerizable monomer (vinyl represented by the formula (1)) There is no particular limitation as long as it can be uniformly dispersed in the cyclopropane compound).

The inorganic fine particles are preferably enhanced in dispersibility in the polymerizable monomer (vinylcyclopropane compound represented by the formula (1)) by using a method such as encapsulation, surface treatment, or hybridization. Among them, modification using a surface treatment agent is preferable because it is industrially simple.
As the surface treatment agent, an agent having an affinity for the surface of the inorganic fine particles and having a surface functional group and a hydrophobic group in order to enhance dispersibility in the polymerizable compound is preferable.
Examples of the surface reactive functional group include alkylsilanes such as methylsilane and ethylsilane, alkoxysilanes such as methoxysilane and ethoxysilane, and reactive silane compounds such as halogenated silanes such as chlorosilane, titanium chloride, methoxytitanium, ethoxy Examples thereof include a reactive titanium compound such as alkoxytitanium such as titanium, a carboxyl group, a phosphoric acid group, a sulfonic acid group, or an ester thereof.

In the case of using the photosensitive composition, particularly the composition in a hologram recording layer and a volume phase hologram recording medium, in addition to the above components, a sensitizer, a chain transfer agent, a plasticizer, a coloring agent, if necessary. An additive such as an agent may be added. In addition, when used as a volume hologram forming composition, a binder resin may be added as a binder in order to have a uniform film thickness and to allow a hologram formed by polymerization by light irradiation to exist stably. good.

  Binder resins preferably have good compatibility with functional monomers. Specific examples thereof include chlorinated polyethylene, polymethyl methacrylate, copolymers of methyl methacrylate and other (meth) acrylic acid alkyl esters, vinyl chloride and acrylonitrile. Examples of the copolymer include polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, and acetyl cellulose.

  To make a volume phase hologram recording medium using the photosensitive composition (volume hologram forming composition) of the present invention, a polymerizable monomer (vinyl cyclopropane compound represented by the formula (1)), a photopolymerization initiator The inorganic fine particles may be mixed with a sensitizer and a binder resin, if necessary, and coated on the transparent support without solvent, or may be mixed by adding a solvent or an additive to these mixtures. This is coated on a support and dried to form a recording layer. Subsequently, a transparent support or a protective layer for blocking oxygen can be provided on the recording layer.

  As the transparent support, a transparent glass plate, an acrylic plate, a transparent resin film, or the like is used. As the transparent resin film, a polyethylene terephthalate film, a polyethylene film, or the like is used. As a coating method, in addition to the direct dropping method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating can be used.

  As the protective layer, a known technique for preventing adverse effects such as a decrease in sensitivity due to oxygen and deterioration in storage stability, for example, application of a water-soluble polymer or the like can be used. Here, a water-soluble polymer or the like that forms a transparent resin film is employed.

  The hologram recording method of the hologram recording medium using the photosensitive composition (for volume hologram formation) is as follows. First, when two mutually coherent laser beams are simultaneously irradiated on the medium, interference fringes are formed on the medium in which bright and dark portions are arranged in stripes. Then, the polymerizable monomer starts to polymerize in the bright part of the medium, and the concentration of the polymerizable monomer in the bright part decreases. Accordingly, a concentration gradient of the polymerizable monomer is generated in the dark part and the bright part, and the polymerizable monomer is moved and supplied from the dark part to the bright part, and further polymerization proceeds. On the other hand, it is considered that the inorganic fine particles move from the bright part to the dark part as the polymerizable monomer moves.

  When a certain amount of time has passed, the polymerization of the polymerizable monomer finally proceeds even in the dark part, and the entire recording layer of the medium becomes a polymer. In this way, a striped distribution of the relative density difference between the polymerizable monomer and the inorganic fine particles is formed in the polymer of the polymerizable monomer. Since the refractive index of the inorganic fine particles is different from the refractive index in the polymerization state of the polymerizable monomer, a refractive index distribution is formed in the recording layer, and a hologram is recorded. At the time of reproduction, if the region where the hologram is formed is irradiated with reproduction light, diffraction occurs and a hologram image is reproduced.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.

[Device used]
In addition, the analyzers and conditions used in the examples are as follows.
[1] Melting point measuring instrument: Mettler Toledo Co., Ltd. automatic melting point measuring device, FP62
[2] Mass spectrometry Model: ZQ2000 manufactured by Nippon Waters Co., Ltd.
Detection method: ESI method [3] ¹ H NMR
Model: JNM-ECX300 manufactured by JEOL Ltd.
Measuring solvent: CDCl ₃
[4] ¹³ C NMR
Model: JNM-ECX300 manufactured by JEOL Ltd.
Measuring solvent: CDCl ₃
[5] Viscosity (E-type viscometer)
Model: VISCONIC EMD manufactured by Tokimec Co., Ltd.
[6] Gel filtration chromatography (GPC)
Model: HLC-8220GPC manufactured by Tosoh Corporation
Column: SHODEX GPC-8051 x 2 + guard column (SHODEX GPC KF-G)
Reference column: SHODEX GPC KF-800RH x 2 Column temperature: 40 ° C
Detector: UV (254 nm) and RI
Eluent: THF
Column flow rate: 1.0 ml / min
Reference column flow rate: 0.2 ml / min
[7] Refractive index Model: Refractometer RA-520N manufactured by Kyoto Electronics Industry Co., Ltd.
Measurement wavelength: 633 nm
[8] Density Model: Accupic 1330 manufactured by Shimadzu Corporation
Model: Density / specific gravity meter DA-500 manufactured by Kyoto Electronics Industry Co., Ltd.

[Volume shrinkage]
The density at 25 ° C. of the monomer before polymerization (d monomer) and the density at 25 ° C. of the polymerized cured product obtained by polymerization (d polymer) are respectively measured, and the volume shrinkage (%) is obtained by the following formula. It was.
Volume shrinkage (%) = {(d polymer-d monomer) / d polymer} × 100

[Synthesis Example 1] Synthesis of dicyclopentyl 2-vinylcyclopropane-1,1-dicarboxylate

5.08 g (32.5 mmol) of 2-vinylcyclopropane-1,1-dicarboxylic acid obtained by the method described in Tetrahedron Letters 1974, Vol. 15, p 1393, 4.31 g of cyclopentanol ( 50.0 mmol) and 4-dimethylaminopyridine (DMAP) 0.61 g (5.0 mmol) were put into a reaction vessel, 22 g of dichloromethane was added and stirred under a nitrogen atmosphere, dissolved, and then cooled to 0 ° C. did. Among them, N, N′-dicyclohexylcarbodiimide (D
(CC) 14.4 g (70.0 mmol) dissolved in 4 g of dichloromethane was added dropwise while paying attention to heat generation. After completion of dropping, the mixture was further stirred at room temperature for 12 hours. The solid precipitated from the reaction mixture was removed by filtration, and then the solvent was distilled off. The resulting crude product was purified with a silica gel column (hexane: ethyl acetate = 98: 2) to give a desired product which was a colorless and transparent liquid. Was obtained in a yield of 5.9 g (81% yield). The results of mass spectrometry, ¹ H NMR and ¹³ C NMR of the target product are shown below.
M / z: 315 (M + Na ⁺ ) (calculated value 315.16 (M + Na ⁺ ))
¹ H NMR (300 MHz, CDCl ₃ ): 1.49 (1H, q, J = 4.5 Hz), 1.55-1.90 (17H, m), 2.53 (1H, q, J = 8) .1 Hz), 5.12 (1 H, dd, J = 1.8 Hz, 9.9 Hz), 5.17 to 5.22 (2 H, m), 5.28 (1 H, dd, J = 1.8 Hz, 17.1 Hz), 5.36-5.48 (1 H, m) ppm
¹³ C NMR (75 MHz, CDCl ₃ ): 20.2 (s), 23.7 (t), 30.
8 (s), 32.4 (t), 36.1 (s), 78.3 (d), 118.1 (s), 133.2 (s), 167.2 (s), 169.5 (S) ppm

The obtained dicyclopentyl 2-vinylcyclopropane-1,1-dicarboxylate had a density at 25 ° C. of 1.069 g / cm ³ , a refractive index of 1.489, and a viscosity at 25 ° C. of 35 mPa · s. It was.

[Synthesis Example 2] Synthesis of dicyclohexyl 2-vinylcyclopropane-1,1-dicarboxylate

Charge 40.6 g (260 mmol) of 2-vinylcyclopropane-1,1-dicarboxylic acid, 40.1 g (400 mmol) of cyclohexanol, and 4.89 g (40 mmol) of 4-dimethylaminopyridine (DMAP) to the reaction vessel, Under a nitrogen atmosphere, 200 g of dichloromethane was added, stirred and dissolved, and then cooled to 0 ° C. A solution prepared by dissolving 115.5 g (560 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 40 g of dichloromethane was dropped therein while paying attention to heat generation. After completion of dropping, the mixture was further stirred at room temperature for 12 hours. The solid precipitated from the reaction mixture was removed by filtration, and then the solvent was distilled off. The resulting crude product was purified with a silica gel column (hexane: ethyl acetate = 98: 2) to give a desired product which was a colorless and transparent liquid. Was obtained in a yield of 28 g (44% yield). The results of mass spectrometry, ¹ H NMR and ¹³ C NMR of the target product are shown below.
M / z: 343 (M + Na ⁺ ) (calculated value 343.19 (M + Na ⁺ ))
¹ H NMR (300 MHz, CDCl ₃ ): 1.23-1.90 (22H, m), 2.55 (1H, q, J = 8.1 Hz), 4.78-4.82 (2H, m ), 5.11 (1H, dd, J = 1.8 Hz, 9.9 Hz), 5.28 (1H, dd, J = 1.8 Hz, 17.1 Hz), 5.37-5.49 (1H, m) ppm
¹³ C NMR (75 MHz, CDCl ₃ ): 20.2 (s), 23.6 (t), 25.
3 (d), 30.7 (s), 31.4 (t), 36.2 (s), 73.9 (d), 118.1 (s), 133.3 (s), 167.0 (S), 169.2 (s) ppm

The obtained dicyclohexyl 2-vinylcyclopropane-1,1-dicarboxylate had a density at 25 ° C. of 1.056 g / cm ³ , a refractive index of 1.492, and a viscosity at 25 ° C. of 450 mPa · s. .

Synthesis Example 3 Synthesis of dicycloheptyl 2-vinylcyclopropane-1,1-dicarboxylate

2-vinylcyclopropane-1,1-dicarboxylic acid 5.08 g (32.5 mmol), cycloheptanol 5.71 g (50.0 mmol), and 4-dimethylaminopyridine (DMAP) 0.61 g (5.0 mmol) Was added to a reaction vessel, and 29 g of dichloromethane was added and stirred under a nitrogen atmosphere to dissolve, and then cooled to 0 ° C. A solution obtained by dissolving 14.4 g (70.0 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 6 g of dichloromethane was added dropwise thereto while paying attention to heat generation. After completion of dropping, the mixture was further stirred at room temperature for 12 hours. The solid precipitated from the reaction mixture was removed by filtration, and then the solvent was distilled off. The resulting crude product was purified with a silica gel column (hexane: ethyl acetate = 98: 2) to give a desired product which was a colorless and transparent liquid. Was obtained in a yield of 5.5 g (yield 63%). The results of mass spectrometry, ¹ H NMR and ¹³ C NMR of the target product are shown below.
M / z: 371 (M + Na ⁺ ) (calculated value 371.22 (M + Na ⁺ ))
¹ H NMR (300 MHz, CDCl ₃ ): 1.45 to 1.77 (22H, m), 1.80 to 1.98 (4H, m), 2.54 (1H, q, J = 8.1 Hz) ), 4.92 to 5.01 (2H, m), 5.11 (1H, dd, J = 1.8 Hz, 9.9 Hz), 5.27 (1H, dd, J = 1.8 Hz, 17. 1 Hz), 5.36-5.46 (1 H, m) ppm · ¹³ C NMR (75 MHz, CDCl ₃ ): 20.2 (s), 22.8 (t), 28.
3 (t), 30.7 (s), 33.6 (t), 36.3 (s), 76.4 (s), 118.1 (s), 133.4 (s), 166.9 (S), 169.2 (s) ppm

The obtained dicycloheptyl 2-vinylcyclopropane-1,1-dicarboxylate had a density at 25 ° C. of 1.052 g / cm ³ , a refractive index of 1.498, and a viscosity at 25 ° C. of 166 mPa · s. there were.

[Synthesis Example 4] Synthesis of dicyclooctyl 2-vinylcyclopropane-1,1-dicarboxylate

2-vinylcyclopropane-1,1-dicarboxylic acid 5.08 g (32.5 mmol), cyclooctanol 6.41 g (50.0 mmol), and 4-dimethylaminopyridine (DMAP) 0.61 g (5.0 mmol) The reaction vessel was charged, 32 g of dichloromethane was added under a nitrogen atmosphere, stirred and dissolved, and then cooled to 0 ° C. A solution prepared by dissolving 14.4 g (70.0 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 6 g of dichloromethane was added dropwise thereto while paying attention to heat generation. After completion of dropping, the mixture was further stirred at room temperature for 12 hours. The solid precipitated from the reaction mixture was removed by filtration, and then the solvent was distilled off. The resulting crude product was purified with a silica gel column (hexane: ethyl acetate = 98: 2) to give a desired product which was a colorless and transparent liquid. Was obtained in a yield of 6.0 g (64% yield). The results of mass spectrometry, ¹ H NMR and ¹³ C NMR of the target product are shown below.
M / z: 399 (M + Na ⁺ ) (calculated value 399.25 (M + Na ⁺ ))
¹ H NMR (300 MHz, CDCl ₃ ): 1.42-1.89 (30H, m), 2.53 (1H, q, J = 8.1 Hz), 4.92-5.03 (2H, m ), 5.11 (1H, dd, J = 1.8 Hz, 9.9 Hz), 5.27 (1H, dd, J = 1.8 Hz, 17.1 Hz), 5.36-5.48 (1H, m) ppm
¹³ C NMR (75 MHz, CDCl ₃ ): 20.2 (s), 22.9 (q), 25.
3 (d), 27.0 (s), 27.1 (t), 30.7 (s), 31.3 (q), 36.2 (s), 76.4 (s), 118.1 (S), 133.4 (s), 166.9 (s), 169.2 (s) ppm

Further, the density of dicyclooctyl 2-vinylcyclopropane-1,1-dicarboxylate at 25 ° C. was 1.043 g / cm ³ , the refractive index was 1.500, and the viscosity at 25 ° C. was 724 mPa · s.

[Example 1] Photoradical polymerization of a photosensitive composition containing dicyclopentyl 2-vinylcyclopropane-1,1-dicarboxylate and measurement of volume shrinkage thereof Dicyclopentyl 2-vinylcyclo prepared in Synthesis Example 1 20 mg of benzoin ethyl ether was mixed with 1.0 g of propane-1,1-dicarboxylate. This composition was dropped on a glass substrate to prepare a sample for irradiation. Using a LIGHTTENINGS series LC5 manufactured by Hamamatsu Photonics Co., Ltd., a 35 W metal halide lamp was used as a light source, an irradiation sample was placed at a position 20 cm from the light source, and a polymerized cured product was obtained by performing 30 spectral irradiation at 25 ° C. As a result of measuring the density at 25 ° C. of the cured product, it was 1.134 g / cm ³ , and the volumetric shrinkage calculated therefrom was 5.7%. The results of weight average molecular weight Mw and ¹ H NMR by GPC of the obtained polymerized cured product are shown.
Mw (GPC): 63,000
¹ H NMR (300 MHz, CDCl ₃ ): 1.4 to 1.9 (16H, brs), 2.47 (4H, brs), 5.15 (2H, brs), 5.33 (2H, brs) ppm

[Example 2] Photoradical polymerization of a photosensitive composition containing dicyclohexyl 2-vinylcyclopropane-1,1-dicarboxylate and measurement of volume shrinkage thereof Dicyclohexyl 2-vinylcyclopropane- prepared in Synthesis Example 2 20 mg of benzoin ethyl ether was mixed with 1.0 g of 1,1-dicarboxylate. The composition was irradiated with light in the same manner as in Example 1 to obtain a polymerized cured product. As a result of measuring the density of the cured product at 25 ° C., it was 1.102 g / cm ³ , and the volumetric shrinkage calculated therefrom was 4.2%. Weight average molecular weight Mw and ¹ H N by GPC of the resulting polymerized cured product
The result of MR is shown.
Mw (GPC): 85,000
¹ H NMR (300 MHz, CDCl ₃ ): 1.2 to 1.9 (20H, brs), 2.54 (4H, brs), 4.77 (2H, brs), 5.34 (2H, brs) ppm

[Example 3] Photoradical polymerization of a photosensitive composition containing dicycloheptyl 2-vinylcyclopropane-1,1-dicarboxylate and measurement of volume shrinkage thereof Dicycloheptyl 2-prepared in Synthesis Example 3 2- 20 mg of benzoin ethyl ether was mixed with 1.0 g of vinylcyclopropane-1,1-dicarboxylate. The composition was irradiated with light in the same manner as in Example 1 to obtain a polymerized cured product. As a result of measuring the density of the cured product at 25 ° C., it was 1.148 g / cm ³ , and the volumetric shrinkage calculated therefrom was 8.4%. Weight average molecular weight Mw and ¹ H N by GPC of the resulting polymerized cured product
The result of MR is shown.
Mw (GPC): 133,000
¹ H NMR (300 MHz, CDCl ₃ ): 1.4 to 1.9 (24H, brs), 2.48 (4H, brs), 4.93 (2H, brs), 5.33 (2H, brs) ppm

Example 4 Photocyclopolymerization of Photosensitive Composition Containing Dicyclooctyl 2-vinylcyclopropane-1,1-dicarboxylate and Measurement of Volume Shrinkage Dicyclooctyl 2-prepared in Synthesis Example 4 20 mg of benzoin ethyl ether was mixed with 1.0 g of vinylcyclopropane-1,1-dicarboxylate. The composition was irradiated with light in the same manner as in Example 1 to obtain a polymerized cured product. As a result of measuring the density of the cured product at 25 ° C., it was 1.128 g / cm ³ , and the volumetric shrinkage calculated therefrom was 7.5%. Weight average molecular weight Mw and ¹ H N by GPC of the resulting polymerized cured product
The result of MR is shown.
Mw (GPC): 218,000
¹ H NMR (300 MHz, CDCl ₃ ): 1.4 to 1.9 (28H, brs), 2.47 (4H, brs), 4.93 (2H, brs), 5.33 (2H, brs) ppm

[Comparative Synthesis Example 1] Synthesis of diisopropyl 2-vinylcyclopropane-1,1-dicarboxylate

Under a nitrogen flow, 9.89 g (227 mmol) of 55% sodium hydride and 22.03 g (103 mmol) of 1,4-dibromo-2-butene were added to 110 mL of anhydrous tetrahydrofuran at room temperature and stirred. Thereafter, the solution was cooled to 0 ° C., and a solution obtained by dissolving 19.39 g (103 mmol) of diisopropyl malonate in 22 mL of anhydrous tetrahydrofuran was dropped therein while paying attention to heat generation and foaming. After completion of dropping, the mixture was stirred for 1 hour and further stirred at room temperature for 88 hours. Thereafter, 58 g of water was slowly dropped into the reaction system and stirred. Thereafter, extraction was performed three times with 200 mL of diisopropyl ether, and the obtained organic layer was washed with 100 mL of 5% aqueous sodium hydrogen carbonate. Anhydrous magnesium sulfate was added to the organic layer after the separation, and the mixture was allowed to stand, followed by filtration. The solvent was distilled off with an evaporator to obtain 21.78 g of a crude product. Then, 9.37 g was taken out and purified by a silica gel column (hexane: ethyl acetate = 95: 5 to 90:10) to obtain 6.16 g (yield 58%) of the objective product as a colorless transparent oil. ¹ H NMR and ¹³ C NMR of the obtained target product are shown below.
¹ H NMR (300 MHz, CDCl ₃ ): 1.20 to 1.29 (12H, m), 1.49 (1H, q, J = 4.5 Hz), 1.64 (1H, q, J = 4) .5 Hz), 2.55 (1 H, q, J = 8.1 Hz), 5.00 to 5.14 (3 H, m), 5.28 (1 H, d, J = 17.1 Hz), 5.31 ~ 5.49 (1H, m) ppm
¹³ C NMR (75 MHz, CDCl ₃ ): 20.0 (s), 21.6 (q), 30.
6 (s), 36.1 (s), 68.8 (s), 69.1 (s), 118.1 (s), 133.2 (s), 166.9 (s), 169.2 (S) ppm

[Comparative Synthesis Example 2] Synthesis of ditertiary butyl 2-vinylcyclopropane-1,1-dicarboxylate

Under nitrogen flow, 8.64 g (198 mmol) of 55% sodium hydride and 19.25 g (90 mmol) of 1,4-dibromo-2-butene were added to 110 mL of anhydrous tetrahydrofuran at room temperature and stirred. Thereafter, the solution was cooled to 0 ° C., and a solution obtained by dissolving 19.47 g (90 mmol) of ditertiary butyl malonate in 22 mL of anhydrous tetrahydrofuran was dropped therein while paying attention to heat generation and foaming. After completion of dropping, the mixture was stirred for 1 hour and further stirred at room temperature for 9 hours. Thereafter, 58 g of water was slowly dropped into the reaction system and stirred. Thereafter, extraction was performed three times with 200 mL of diisopropyl ether, and the obtained organic layer was washed with 100 mL of 5% aqueous sodium hydrogen carbonate. Anhydrous magnesium sulfate was added to the organic layer after the separation and the mixture was allowed to stand and then filtered, and the solvent was distilled off with an evaporator to obtain 29.12 g of a crude product. Then 5.68 g was taken out and purified with a silica gel column (hexane: ethyl acetate = 95: 5-90: 10) to obtain 2.50 g of white crystals. 7.50 g of heptane was added and dissolved at room temperature, and then cooled to −70 ° C., and the precipitated crystals were washed and dried to obtain 1.81 g (yield 38%) of the desired product as white crystals. It was. Melting point 52.9 ° C. (average value measured twice). ¹ H NMR and ¹³ C NMR of the obtained target product are shown below.
¹ H NMR (300 MHz, CDCl ₃ ): 1.23 to 1.55 (20H, m), 2.42 to 2.50 (1H, m), 5.09 to 5.30 (2H, m), 5.37-5.49 (1H, m) ppm
¹³ C NMR (300 MHz, CDCl ₃ ): 19.7 (s), 28.0 (s), 29
. 9 (s), 37.6 (s), 81.2 (s), 81.7 (s), 117.7 (s), 133.5 (s), 166.8 (s), 169.1 (S) ppm

[Reference Example 1]
Macromolecules, 1993, 26, p. The density of diethyl 2-vinylcyclopropane-1,1-dicarboxylate described in 1818-1824 at 25 ° C. is 1.020 g / cm ³ , and the density of the polymer of this compound is 1.
134 g / cm ³ . The volume shrinkage of the polymer calculated from these values is 10.1%.

[Comparative Example 1] Photoradical polymerization of diisopropyl 2-vinylcyclopropane-1,1-dicarboxylate and measurement of volume shrinkage thereof Diisopropyl 2-vinylcyclopropane-1,1-dicarboxy prepared in Comparative Synthesis Example 1 30 mg of benzoin ethyl ether was mixed with 1.0 g of the rate (liquid, density 1.104 g / cm ^{3 at} 25 ° C.). The composition was irradiated with light in the same manner as in Example 1 to obtain a polymerized cured product. As a result of measuring the density of the cured product, it was 1.213 g / cm ³ , and the volumetric shrinkage calculated therefrom was 9.0%.

Thus, each vinylcyclopropane compound prepared in Synthesis Example 1 to Synthesis Example 4 is a low-viscosity liquid, and the photosensitive compositions of Examples 1 to 4 containing the compound are obtained after photopolymerization. It was confirmed that there was little volume shrinkage of hardened | cured material.
Further, from the results of Reference Example 1 and Comparative Example 1, the vinyl cyclopropane compound in which the substituent in the compound is an ethyl ester group or an isopropyl ester group is insufficient in the effect of suppressing the volume shrinkage of the polymer. It was confirmed that the vinylcyclopropane compound having a tertiary butyl ester group prepared in 2 was solid at room temperature and was not suitable for the preparation of a photosensitive composition.

[Example 5] Preparation of photosensitive composition 1,1-bis (cyclohexyloxycarbonyl) -2-vinylcyclopropane 300 mg, zirconia sol (manufactured by Sumitomo Osaka Cement Co., Ltd., product name: nano zirconia toluene dispersion) 1 914 g, dicyclopentadienyl-titanium-bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) (manufactured by Ciba Japan, trade name: Irgacure 784), 3 mg, pentaerythritol 3 mg of tetra (3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and dispersed uniformly to prepare a photosensitive composition.

[Example 6] Measurement of diffraction efficiency A polyethylene terephthalate film having a thickness of 50 µm was attached as a spacer to both ends of a slide glass, and the photosensitive composition prepared in Example 5 was placed in the center of the slide glass (a region sandwiched between the spacers). This was dropped and covered with a slide glass to produce a volume phase hologram recording medium. The recording medium was subjected to two-beam interference exposure with the apparatus shown in FIG. 1 to record a volume hologram.
First, two-beam interference exposure (grating spacing 1 μm) was performed on the hologram recording medium 1 using an Nd: YVO ₄ laser 2 having a wavelength of 532 nm at an exposure power density of 100 mW / cm ² . The light emitted from the Nd: YVO ₄ laser 2 is split into two by a half mirror 13 through a beam expander 3, and irradiated onto the hologram recording medium 1 through mirrors 8 and 9, respectively, and interference fringes of both lights are recorded. A hologram will be formed.
At the same time, the hologram forming process is monitored by irradiating the hologram recording medium 1 with a helium-neon (He-Ne) laser 4 having a wavelength of 632.8 nm, which the hologram recording medium 1 is not sensitive to, and detecting the diffracted light with the photodetectors 18-20. And diffraction efficiency was evaluated.
A graph showing the change of the diffraction efficiency of this sample with time is shown in FIG. As shown in FIG. 2, it was confirmed that a volume phase hologram having a diffraction efficiency close to 100% was formed.

[Comparative Example 2] Preparation of photosensitive composition To 500 mg of tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name A-DCP), zirconia sol (manufactured by Sumitomo Osaka Cement Co., Ltd., product name: Nano) Zirconia toluene dispersion) 3.05 g, dicyclopentadienyl-titanium-bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) (Ciba Japan Co., Ltd., trade name: Irgacure 784) 5 mg was mixed and dispersed uniformly to prepare a photosensitive composition.

[Comparative Example 3] Measurement of diffraction efficiency Using the photosensitive composition prepared in Comparative Example 2, a volume hologram was recorded in the same manner as in Example 6. A graph showing the change of the diffraction efficiency of this sample with time is shown in FIG. The diffraction efficiency was about 50%.

  From the above, it was confirmed that the photosensitive composition of the present invention containing a vinylcyclopropane compound into which a cycloalkyl ester group was introduced would be a hologram recording medium having excellent recording characteristics.

1 hologram recording medium 2 Nd: YVO ₄ laser 3 beam expander 4 the He-Ne laser 5,6,7,8,9,10,11 mirror 12 the beam sampler 13 half mirrors 14 and 15 half-wave plates 16 and 17 polarizing prism 18, 19, 20 Photodetector

Claims (9)

(A) Formula (1)

(In the formula (1), X and Y may be the same as or different from each other, and C (═O) R ¹ , C (═O) OR ¹ , OC (═O) R ¹ , C ( = O) SR ¹ , SC (= O) R ¹ , C (
= O) represents NR ¹ R ² , SO ₂ R ¹ or R ¹ ,
R ¹ is unsubstituted or a linear alkyl group having 1 to 12 carbon atoms, or 3 to 12 carbon atoms.
Substituted by a substituent selected from the group consisting of a cycloalkyl group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, and a hydroxy group. Represents a cycloalkyl group having 3 to 18 carbon atoms,
R ² represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The photosensitive composition containing the vinylcyclopropane compound represented by this. The photosensitive composition of Claim 1 in which the said vinylcyclopropane compound occupies 50 volume% or more based on the volume of the said photosensitive composition. Furthermore, it is a composition containing (b) a photopolymerization initiator and (c) inorganic fine particles, and when this is subjected to pattern exposure, mutual diffusion occurs inside the composition, and a spatial refractive index modulation pattern is formed. The photosensitive composition according to claim 1, wherein the photosensitive composition is characterized. The photosensitive composition according to any one of claims 1 to 3, wherein the vinylcyclopropane compound has a viscosity of 10 to 3,000 mPa · s. The photosensitive composition according to claim 1, wherein the vinylcyclopropane compound has a refractive index of 1.45 to 1.55. In the formula (1), X and Y represent C (= O) OR ^1, photosensitive composition according to any one of claims 1 to 5. In the formula (1), R ¹ is unsubstituted or a linear alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, carbon The cycloalkyl group having 5 to 8 carbon atoms substituted with a substituent selected from the group consisting of an acyl group having 1 to 12 atoms, an acyloxy group having 1 to 12 carbon atoms, and a hydroxy group. The photosensitive composition as described in any one of Claims 6 thru | or 6. A hologram recording layer comprising the photosensitive composition according to any one of claims 1 to 7. A hologram recording medium, wherein the hologram recording layer according to claim 8 is formed on a support, and the hologram recording layer is covered with a protective material.

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