JP2002297005A - Photosensitive composition for volume hologram recording, and photosensitive medium for volume hologram recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a volume hologram recording material and a volume hologram recording medium, in which polymerization reaction can be made to proceed, even if a small amount of photopolymerization initiator is used during interference exposure and to provide a volume hologram film having little or no residue of the photopolymerization initiator or its decomposed product. SOLUTION: The photosensitive composition for volume hologram recording contains a binder polymer and a photopolymerizable compound, having spontaneous photopolymerization reactivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition capable of recording a volume hologram, a volume hologram recording medium using the same, and a volume hologram produced using the recording medium.

[0002]

2. Description of the Related Art As a photosensitive composition for producing a volume hologram, the Omnidex series manufactured by DuPont is the only commercially available mass-produced product. This material contains a radical polymerization monomer, a binder polymer, a photoradical polymerization initiator, and a sensitizing dye as main components, and utilizes a difference in refractive index between the radical polymerization monomer and the binder polymer. That is, when the photosensitive composition formed in the form of a film is subjected to interference exposure, radical polymerization is started in a portion where light is strong, and a concentration gradient of a radical polymerization monomer is generated with the exposure. Diffusion transfer of the polymerized monomer occurs. As a result, depending on the intensity of the interference light, the density of the radical polymerizable monomer is increased and decreased, and appears as a difference in refractive index. Although this material system has the best performance as a currently reported photopolymer for volume holograms, problems have been pointed out with respect to heat resistance and transparency.

Further, a material system using both radical polymerization and cationic polymerization has been reported. For example, Japanese Patent No. 28731
No. 26 discloses a system using a monomer having a diallyl fluorene skeleton as a high refractive index radical polymerizable monomer and a cationic polymerizable monomer having a smaller refractive index than the radical polymerizable monomer. In this system, the high refractive index component is polymerized by radical polymerization at the time of hologram exposure, and then the image is fixed by cationic polymerization at the fixing exposure.

Further, a material system utilizing cationic polymerization is
For example, it is disclosed in US Pat. This material system has the advantage that there is no oxygen inhibition in the radical polymerization system, but the sensitivity of cationic polymerization (Photosp
Eed) is poor, and there is a problem that it is difficult to provide sensitivity in a long wavelength region.

Further, Japanese Patent No. 2953200 discloses a material system using an inorganic substance network and a photopolymerizable monomer in combination. When an inorganic material capable of forming a network is used as a binder, there is an advantage that heat resistance, environmental friendliness, and mechanical strength are excellent, and a large difference in refractive index from a photopolymerizable organic monomer can be obtained. The hologram recording film formed by the system is rather brittle and has poor flexibility, processability, and coating suitability, and poor compatibility between the inorganic binder and the organic monomer. There is a problem that it is difficult to do.

Further, Japanese Patent Application Laid-Open No. 2000-508873 discloses a material in which ultrafine metal particles are dispersed in a solid matrix as a hologram recording material. However, the matrix needs to have fluidity, and the solidity is poor. There is.

Further, as a known example using a combination of a high refractive index aromatic ring-containing binder polymer and a low refractive index fluorine-containing monomer, Japanese Patent Application Laid-Open No. Hei 5-21034 is particularly useful.
3, JP-A-5-210344, JP-A-5-257416
There is. However, in this combination, the sensitivity at the time of interference exposure is not so high because of insufficient polymerization reactivity. Although addition of a polyfunctional acrylate to increase the polymerizability of the fluorine-containing monomer is also described, this method impairs the low refractive index inherent to the fluorine-containing monomer. Furthermore, in this combination,
There is a problem that a strongly exposed portion in which a polymer of a fluorine-containing monomer is present in a high proportion is mechanically brittle, and that yellowing easily occurs because an aromatic ring-containing binder polymer is used.

Further, as a known example using a combination of a low-refractive-index binder polymer composed of a fluorine-containing acrylic monomer and an acrylic monomer containing no fluorine and a high-refractive-index aromatic ring-containing monomer, Japanese Patent Application Laid-Open No.
7588. However, also in this example, the low refractive index of the fluorine-containing acrylic monomer is impaired by copolymerization with the fluorine-free acrylic monomer, and furthermore, yellowing is likely to occur due to the aromatic ring of the aromatic ring-containing monomer. There is.

As an index indicating the performance of the volume hologram, there is a refractive index modulation amount (Δn). This value is calculated by Kogelnik's coupled wave theory. As described above, various volume hologram recording materials are known, but the refractive index modulation amount (Δn) showing the hologram performance is at most about 0.06, and is applied to a new optical element or the like. At this time, there is a demand for further improvement of Δn.

In view of application to a wide range of fields such as optical elements, not only hologram recording performance such as refractive index difference, sensitivity and transparency but also physical properties such as film strength and heat resistance are included. There is a demand for a material system that sufficiently satisfies various performances.

[0011]

Although various material systems as described above have been disclosed for forming a volume hologram, any of these material systems requires a photopolymerization initiator to perform interference exposure. Therefore, the photopolymerization initiator or its decomposition product remains in the finally obtained volume hologram film,
There is a possibility that physical properties or optical characteristics of the volume hologram film are adversely affected. Also, from the viewpoint of cost reduction, it is desired that the use of the photopolymerization initiator be reduced or completely eliminated.

The present invention has been accomplished in view of the above-mentioned circumstances, and a first object of the present invention is to provide a polymerization reaction which uses only a small amount or no photopolymerization initiator at the time of interference exposure. Is to obtain a volume hologram recording material and a volume hologram recording medium which can be advanced.

A second object of the present invention is to obtain a volume hologram having little or no residual photopolymerization initiator or its decomposition product in the finally obtained volume hologram film.

[0014]

In order to achieve the above object, the photosensitive composition for volume hologram recording provided by the present invention comprises, as an essential component, a binder polymer,
And a photopolymerizable compound having spontaneous photopolymerization reactivity.

[0015] The photosensitive medium for volume hologram recording provided by the present invention comprises a binder polymer and a photopolymerizable compound having spontaneous photopolymerization reactivity as essential components. It is characterized in that a material layer is provided on a substrate.

The photosensitive composition for volume hologram recording and the photosensitive medium for volume hologram recording of the present invention can be used as a refractive index modulating component in a strongly exposed area even when a photopolymerization initiator is not present at the time of interference exposure. Since a compound capable of spontaneously polymerizing is used, a volume hologram can be formed without reducing or using any photopolymerization initiator.

Therefore, the cost can be reduced and the economy is excellent. In addition, when the hologram recording material layer of the photosensitive composition for volume hologram recording or the hologram recording material layer of the photosensitive medium for volume hologram recording is in contact with the skin of a human or animal, there is little possibility that the photopolymerization initiator adversely affects, or ,
When no photopolymerization initiator is used, such a fear is completely eliminated.

Further, the volume type hologram film finally obtained using the volume type hologram recording photosensitive composition and the volume type hologram recording photosensitive medium has little residual photopolymerization initiator or its decomposition product. Or not at all,
The photopolymerization initiator or its decomposed product is less likely to adversely affect the film physical properties and optical characteristics of the volume hologram film, or if no photopolymerization initiator is used, such a risk is completely eliminated. .

In the present invention, a hologram recording material layer of a photosensitive medium for volume hologram recording is formed by using a photosensitive composition for volume hologram recording substantially not containing a photopolymerization initiator, and the layer is formed after interference exposure. It is preferable to obtain a volume hologram film substantially free of a photopolymerization initiator or a decomposition product thereof.

The spontaneous photopolymerizable compound preferably contains a combination of a donor compound belonging to a donor / acceptor photopolymerization system and an acceptor compound.

In particular, in a combination using a compound having a vinyl dioxolane skeleton represented by the following formula 1 as the donor compound and a compound having a maleimide skeleton represented by the following formula 2 as the acceptor compound, polymerization shrinkage is small. This is useful because a volume hologram film having excellent dimensional stability can be obtained.

[0022]

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[0023]

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When a compound having two or more maleimide skeletons in one molecule is used as the compound having a maleimide skeleton, a cross-linking can be formed by photopolymerization of a donor / acceptor system.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive composition for volume hologram recording provided by the present invention contains a binder polymer and a photopolymerizable compound having spontaneous photopolymerization reactivity as essential components. It is characterized by the following.

In the present invention, the binder polymer used in the present invention has general properties required for a volume hologram, namely, transparency, film physical properties, and a refractive index of a polymer of a photopolymerizable compound generated in a strongly exposed portion during interference exposure. A material that satisfies the physical properties such as the difference and does not inhibit the progress of the spontaneous polymerization reaction of the photopolymerizable compound during interference exposure is used.

Specific examples of the binder polymer include polymethacrylate or a partial hydrolyzate thereof; polyvinyl acetate or a hydrolyzate thereof; polyvinyl alcohol or a partially acetalized product thereof; triacetyl cellulose; polyisoprene; polybutadiene; Chloroprene; silicone rubber; polystyrene; polyvinyl butyral; polychloroprene; polyvinyl chloride; chlorinated polyethylene; chlorinated polypropylene; poly-N-vinylcarbazole or a derivative thereof; poly-N-vinylpyrrolidone or a derivative thereof; Acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, vinyl acetate Copolymer and at least one polymerizable component copolymerizable monomers groups such as Le; can be used a mixture containing the two or more of each binder polymer alone. Preferably, polyisoprene, polybutadiene, polychloroprene, polyvinyl alcohol, polyvinyl acetal which is a partially acetalized product of polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, etc. Or a mixture thereof.

As a step of promoting the refractive index modulation caused by the interference exposure or stabilizing the recorded hologram, there is a step of moving a polymerizable component by heating. For this purpose, these matrix polymers are completely cured. It is necessary that the glass transition temperature be relatively low before the reaction, and that the monomer transfer be facilitated. Specifically, the glass transition temperature is preferably 180 ° C. or lower.

In the present invention, the photopolymerizable compound having spontaneous photopolymerization reactivity (spontaneous photopolymerizable compound) is a component for forming interference fringes by modulating the refractive index of a strongly exposed portion during interference exposure. (Refractive index modulating component), which has a refractive index of a polymer obtained by polymerizing the spontaneous photopolymerizable compound different from that of the binder polymer.
The spontaneous photopolymerizable compound may have a larger or smaller refractive index than the binder polymer when it becomes a polymer, but it is preferable that the difference between the two is at least 0.01 or more.

In the photopolymerization reaction, the polymerizable compound directly acquires the activity of the polymerization reaction by light irradiation and spontaneously initiates and initiates polymerization. Is a polymerizable compound that does not activate, and a photopolymerization initiator that generates active species such as radicals and cations by light irradiation coexist, and generates an active species from the photopolymerization initiator by light irradiation, and the action of the active species There is a broad sense of photopolymerization reaction in which the polymerization reaction of the polymerizable compound is started and progressed.

The spontaneous photopolymerizable compound used in the present invention is a compound capable of causing a photopolymerization reaction in a narrow sense in the above-mentioned classification, and is itself photopolymerizable when irradiated with light in a visible region or an invisible region. Directly,
It is a component that can spontaneously initiate and progress photopolymerization even when no photopolymerization initiator is present.

The type of reaction of the spontaneous photopolymerizable compound is not particularly limited. For example, a compound which spontaneously causes radical polymerization or cationic polymerization by light irradiation may be used. Further, the sensitivity wavelength of the spontaneous photopolymerizable compound is not limited to the visible region, and in the present invention, those having sensitivity to light irradiation in an invisible region including ionizing radiation such as ultraviolet rays and electron beams,
It can be used as a spontaneous photopolymerizable compound.

As the spontaneous photopolymerizable compound, specifically, a donor compound and an acceptor compound belonging to a donor / acceptor photopolymerization system can be used in combination.

In the donor / acceptor photopolymerization system, a hydrogen-donating (electron-donating) donor compound and a hydrogen-accepting (electron-accepting) acceptor compound spontaneously initiate a polymerization reaction by interaction with light. The photopolymerization initiator does not need to be used.

As the donor compound, triethylene glycol divinyl ether, furfuryl vinyl ether,
Examples thereof include vinyl ethers such as 4-propenyloxymethyl-1,3--2-dioxolanone and N-vinylpyrrolidone.

As the acceptor compound, maleimide, N-methylmaleimide, N-phenylmaleimide, p-carbomethoxyphenylmaleimide, N, N '
Maleimides such as -alkylenedimaleimide, N, N'-oxyalkylenedimaleimide, dimethyl fumarate,
Examples include diallyl maleate and dimethyl maleate.

In a combination using a compound having a vinyl dioxolane skeleton represented by the following formula 1 as a donor compound and a compound having a maleimide skeleton represented by the following formula 2 as an acceptor compound, polymerization shrinkage is small and dimensional stability is low. This is useful because a volume hologram film excellent in the above can be obtained.

[0038]

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[0039]

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As the compound having a vinyl dioxolane skeleton represented by the formula 1, a vinyl dioxolane compound represented by the following formula 1a can be exemplified.

[0041]

Embedded image (Wherein R ¹ and R ² are hydrogen, halogen, hydroxyl group, alkyl group such as methyl or butyl, alkylene oxide group, aromatic group such as phenyl or naphthyl, alicyclic group such as cyclohexyl or cyclooctyl, Heterocyclic groups such as furan, pyrrole, pyran and thiopyran, and groups derived therefrom.) On the other hand, as the compound having a maleimide skeleton represented by the formula 2,
The maleimide compound represented by a can be exemplified. Among the compounds having a maleimide skeleton, those having two or more maleimide skeletons in one molecule are polyfunctional, and are preferred because they can form cross-linking by donor / acceptor photopolymerization. Examples of the polyfunctional maleimide compound include, among the compounds included in Formula 2a, those in which R ^{1 as} an N-substituent is a maleimide-N′-substituted product. Specifically, N, N ′ N, N'-dimaleimides such as -alkylenedimaleimide and N, N'-oxyalkylenedimaleimide are included.

[0042]

Embedded image (Wherein, R ¹ is hydrogen, a hydroxyl group, an alkyl group such as methyl or butyl, an alkylene oxide group, an aromatic group such as phenyl or naphthyl, an alicyclic group such as cyclohexyl or cyclooctyl, furan, pyrrole, pyran, Heterocyclic groups such as thiopyran, maleimide-N'-substituted products thereof, and groups derived therefrom.)

As the spontaneous photopolymerizable compound, an oligomer or polymer containing a photopolymerizable group can be used. However, at the time of interference exposure, the smaller the molecular weight of the refractive index modulating component is in the hologram recording material layer, the smaller the molecular weight is. It is preferable to use a monomer because it is considered that the monomer easily moves to the strongly exposed portion.

In the present invention, a compound capable of spontaneously polymerizing in a strongly exposed portion even when a photopolymerization initiator is not present at the time of interference exposure is used as a refractive index modulation component of the photosensitive composition for volume hologram recording. Since it is used, a volume hologram can be formed with a reduced or no photopolymerization initiator. Therefore, the cost can be reduced,
Excellent economy. Further, when the photosensitive composition for volume hologram recording comes into contact with human or animal skin, there is little possibility that the photopolymerization initiator has an adverse effect, or when no photopolymerization initiator is used, the Such fear is completely eliminated. The volume hologram film finally obtained using the photosensitive composition for volume hologram recording has little or no residual photopolymerization initiator or its decomposed product, so the photopolymerization initiator or its decomposed product Is less likely to adversely affect the physical properties and optical properties of the volume hologram film, or if no photopolymerization initiator is used, such a risk is completely eliminated.

In the present invention, a hologram recording material layer of a photosensitive medium for volume hologram recording is formed using a photosensitive composition for volume hologram recording substantially not containing a photopolymerization initiator, and the layer is formed after interference exposure. It is preferable to obtain a volume hologram film substantially free of a photopolymerization initiator or a decomposition product thereof. However, a small amount of a photopolymerization initiator can be added to the photosensitive composition for volume hologram recording of the present invention, if necessary, for the purpose of improving the sensitivity during interference exposure.

When a photopolymerization initiator is used, one that generates an active species capable of promoting the reaction mode is appropriately selected according to the reaction mode of the spontaneous photopolymerizable compound. For the above donor / acceptor photopolymerization system,
For example, as a photoradical polymerization initiator, 1,3-di (t
-Butyldioxycarbonyl) benzophenone, 3,
3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, N-phenylglycine, 2,
4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers can be used. As a cationic photopolymerization initiator, Aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt, aromatic phosphonium salt, mixed ligand metal salt (for example, (η ⁶ -benzene) (η ⁵ -cyclopentadienyl) iron (II), silanol -Aluminum complex) and the like. The photopolymerization initiator is preferably decomposed after recording the hologram from the viewpoint of stabilizing the recorded hologram.

The most common application of holograms is holograms as visible images. In order to record a hologram as such a visible image, a visible laser beam, for example, an argon ion laser (458n
m, 488 nm, 514.5 nm), krypton ion laser (647.1 nm), YAG laser (532)
nm) or when it is desired to broaden the wavelength band in which a photopolymerization reaction can occur in order to improve the sensitivity of interference exposure, with the aim of improving the sensitivity at each laser light wavelength. And a visible light sensitizing dye. A visible light sensitizing dye does not generate an active species for initiating polymerization like a photopolymerization initiator, but has an absorption wavelength in a visible light region and is a component that improves the reactivity of a polymerization system. is there.

Examples of the visible light sensitizing dye include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes,
Examples thereof include cyanine dyes, rhodamine dyes, and pyrylium salt dyes. When high transparency such as an optical element is required for the visible light sensitizing dye, it is preferable that the dye be colorless due to decomposition or the like by a post-process after heating the hologram or irradiation with ultraviolet rays.

The photosensitive composition for volume hologram recording of the present invention may optionally contain components other than those described above. For example, a relatively small amount of a binder component can be compounded in addition to the binder polymer for the purpose of improving the film strength of a hologram film product.

The spontaneous photopolymerizable compound as the refractive index modulating component is 10 to 10 parts by weight of the binder polymer.
It is used in a proportion of 1000 parts by weight, preferably 10 to 100 parts by weight. When a donor / acceptor photopolymerization system is used as the spontaneous photopolymerizable compound, the total amount of the donor compound and the acceptor compound is 10 to 1000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder polymer. So that the ratio is The mixing ratio of the donor compound and the acceptor compound may be usually adjusted so as to be 1: 1 or around the equivalent of the reaction equivalent of the two, but is appropriately adjusted in consideration of the reactivity of the two.

Although a photopolymerization initiator is not required in the present invention, when it is used for improving the sensitivity of interference exposure, a relatively small amount is used.
0.1 to 8 parts by weight, preferably 0.1 to 8 parts by weight
Used in a proportion of 5 parts by weight.

The visible light sensitizing dye is a binder polymer 1
It is used in an amount of 0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 00 parts by weight.

Each of the above-mentioned materials was subjected to acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, , 4-dioxane,
By dissolving in 1,2-dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, or the like, or a mixed solvent thereof, a coating liquid as a photosensitive composition for volume hologram recording according to the present invention can be prepared. it can. However, when the spontaneous photopolymerizable compound is liquid at room temperature, the amount of the coating solvent used can be reduced, and the coating solvent may not be needed at all.

The hologram recording material layer is formed by applying the above coating solution to a suitable support such as a base film or a glass substrate by a method such as a spin coater, a gravure coater, a comma coater or a bar coater and drying. Thus, a photosensitive medium for volume hologram recording is obtained. The thickness of the volume hologram recording material layer is 1 to 100 μ
m, preferably 10 to 40 μm.

The base film of the photosensitive medium for volume hologram recording has transparency, and is a polyethylene film, a polypropylene film, a polyethylene fluoride film, a polyvinylidene fluoride film,
Polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol film, polyvinyl alcohol film, polymethyl methacrylate film, polyether sulfone film, polyether ether ketone film, polyamide film, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer film And a resin such as a polyester film such as a polyethylene terephthalate film and a polyimide film, and has a thickness of 2 to 200 μm, preferably 10 to 50 μm.

When the volume hologram recording material layer after drying is tacky, a film exemplified as the above-mentioned base film can be laminated as a protective film. In this case, the contact surface of the laminate film with the volume hologram recording material layer may be subjected to a release treatment so as to be easily peeled off later.

The thus obtained photosensitive medium for volume hologram recording has a hologram recording material layer provided on a base film, and the hologram recording material layer comprises, as essential components, a binder polymer and a spontaneous material. It contains a photopolymerizable compound having high photopolymerization reactivity. Further, the hologram recording material layer also contains a visible light sensitizing dye as necessary.

The volume hologram can be formed on the photosensitive medium for volume hologram recording according to the present invention by performing interference exposure by a conventionally known method.

For example, a hologram master is faced to and adhered to a hologram recording material layer of a photosensitive medium for volume hologram recording, and visible light or ionizing radiation such as ultraviolet light or an electron beam is used from the transparent base film side. A volume hologram is formed by performing the interference exposure.

Further, in order to promote the refractive index modulation by interference exposure or to complete the polymerization reaction, after the interference exposure, treatment such as overall exposure with ultraviolet light and heating can be appropriately performed.

It is considered that the volume hologram recording mechanism of the photosensitive composition for volume hologram recording in the present invention is basically the same as the mechanism conventionally known. That is, when the photosensitive composition formed in the form of a film is subjected to interference exposure, photopolymerization is started at a portion where light is strong, and a concentration gradient of a spontaneous photopolymerizable compound is thereby generated, and the portion where light is weak is strong. Spontaneous diffusion transfer of the photopolymerizable compound occurs in the portion. However, in the present invention, the spontaneous photopolymerizable compound starts and proceeds polymerization in a state where only a small amount or ideally no photopolymerization initiator coexists. As a result, the spontaneous photopolymerizable compound and / or its polymer can be made dense and dense depending on the intensity of the interference light, and appear as a difference in refractive index. This refractive index difference becomes an interference fringe, and a volume hologram is formed.

The Δn calculated from Kogelnik's theory indicates the difference in the refractive index in the refractive index distribution formed in response to the interference light incident on the light-sensitive material. Become. In the present invention, this
With Δn calculated from Kogelnik's theory, it is possible to evaluate the difference in the refractive index between the strongly exposed portion and the weakly exposed portion or the non-exposed portion of the interference exposure. Regarding the difference in refractive index between the strongly exposed portion and the weakly exposed portion or the non-exposed portion of the interference exposure, any of the refractive indices may be large, but it is preferable that the difference between the two is at least 0.01 or more.

As described above, the hologram recording material layer of the photosensitive medium for volume hologram recording according to the present invention forms interference fringes by interference exposure and becomes a hologram layer, and a volume hologram is obtained.

Further, as is apparent from the above description, the hologram recording material layer of the photosensitive medium for volume hologram recording in the present invention comprises a spontaneous photopolymerizable compound which does not require a photopolymerization initiator and has a refractive index modulation. The photopolymerization initiator or its residue is present in a small amount or not at all in the hologram film finally used as a component. Therefore, the physical properties and optical properties of the volume hologram film are less likely to be adversely affected by the photopolymerization initiator or its residue, or when no photopolymerization initiator is used,
There is no fear of such adverse effects.

[0065]

Next, the present invention will be described with reference to examples.

(Example 1) (1) Preparation of photosensitive composition solution for volume hologram recording The following components and solvent were mixed to prepare a photosensitive composition solution for volume hologram recording.

<Composition of the photosensitive composition solution for volume hologram recording> Polymethyl methacrylate (Elvacite 20)
41, manufactured by DuPont): 100 parts by weight ・ 4,4′-dimaleimidobisphenol: 30 parts by weight ・ p-glycidyloxystyrene: 30 parts by weight ・ 3-ethyl-5-[(3-ethyl-2 (3H)- Benzothiazolylidene) ethylidene] -2-thioxo-4-
Oxazolidinone (NK-1473, manufactured by Hayashibara Biochemical Laboratory): 0.02 parts by weight ・ Methanol: 30 parts by weight ・ Methyl ethyl ketone: 30 parts by weight

(2) Production of photosensitive medium for volume hologram recording The above solution was treated with 38 μm polyethylene terephthalate (P
ET) film (Lumirror T-60 manufactured by Toray Industries, Inc.) was applied using a bar coater so as to have a dry film thickness of 20 μm to prepare a photosensitive medium for volume hologram recording.

Next, the hologram recording material layer side of the photosensitive medium for volume hologram recording is laminated on a mirror,
514.5 nm argon ion laser light was incident from the ET side to perform interference exposure to record a volume hologram.

Next, the interference fringes were fixed by heating and UV polymerization to obtain a volume hologram. As a result of calculation from the spectral evaluation result, the refractive index modulation amount Δn was 0.027.

[0071]

As described above, the photosensitive composition for volume hologram recording and the photosensitive medium for volume hologram recording of the present invention can be used as a refractive index modulating component even if a photopolymerization initiator is not present at the time of interference exposure. Since a compound capable of spontaneously polymerizing is used in the part, a volume hologram can be formed without reducing or using any photopolymerization initiator.

Therefore, the cost can be reduced and the economy is excellent. In addition, when the hologram recording material layer of the photosensitive composition for volume hologram recording or the hologram recording material layer of the photosensitive medium for volume hologram recording comes into contact with human or animal skin, there is little possibility that the photopolymerization initiator has an adverse effect, or ,
When no photopolymerization initiator is used, such a fear is completely eliminated.

Further, the volume hologram film finally obtained by using the volume hologram recording photosensitive composition and the volume hologram recording photosensitive medium has little residual photopolymerization initiator or its decomposition product. Or not at all,
The photopolymerization initiator or its decomposed product has little risk of adversely affecting the film physical properties and optical properties of the volume hologram film, or when no photopolymerization initiator is used, such a risk is completely eliminated. .

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Claims (12)

[Claims] 1. A binder polymer as an essential component,
A photosensitive composition for volume hologram recording, comprising a photopolymerizable compound having spontaneous photopolymerization reactivity. 2. The volume type hologram recording photosensitive composition according to claim 1, wherein the photosensitive composition does not substantially contain a photopolymerization initiator. 3. The photosensitive composition for volume hologram recording according to claim 1, further comprising a visible light sensitizing dye. 4. The method according to claim 1, wherein the photopolymerizable compound contains a donor / acceptor photopolymerization system in combination with a donor compound and an acceptor compound.
4. The photosensitive composition for volume hologram recording according to claim 1. 5. A method comprising: a compound having a vinyl dioxolane skeleton represented by the following formula 1 as the donor compound; and a compound having a maleimide skeleton represented by the following formula 2 as the acceptor compound.
The volume type hologram recording photosensitive composition according to claim 4. Embedded image Embedded image 6. The volume hologram recording photosensitive composition according to claim 5, wherein the compound having a maleimide skeleton contains a compound having two or more maleimide skeletons in one molecule. 7. A binder polymer as an essential component,
Further, a photosensitive medium for volume hologram recording, wherein a volume hologram recording material layer containing a photopolymerizable compound having spontaneous photopolymerization reactivity is provided on a substrate. 8. The volume hologram recording photosensitive medium according to claim 7, wherein the volume hologram recording material layer does not substantially contain a photopolymerization initiator. 9. The photosensitive medium for volume hologram recording according to claim 7, wherein the volume hologram recording material layer further contains a visible light sensitizing dye. 10. The volume hologram recording material layer,
10. The photopolymerizable compound contains a donor / acceptor photopolymerizable system in combination with a donor compound and an acceptor compound.
A photosensitive medium for volume hologram recording according to any one of the above. 11. A compound having a vinyl dioxolane skeleton represented by the following formula 1 as the donor compound:
The photosensitive medium for volume hologram recording according to claim 10, comprising a compound having a maleimide skeleton represented by the following formula 2 as the acceptor compound. Embedded image Embedded image 12. The photosensitive medium for volume hologram recording according to claim 11, wherein the compound having a maleimide skeleton contains a compound having two or more maleimide skeletons in one molecule.