JPH0736354A - Hologram recording photosensitive material - Google Patents

Abstract

PURPOSE:To provide excellent chemical stability and environment resisting characteristic, particularly, heat resistance, sensitive characteristic, resolution, diffraction efficiency and transparency by constituting a hologram recording photosensitive material from respective specified high molecular polymer, com pound, epoxy compound, and a photopolymerization initiator series. CONSTITUTION:A hologram recording photosensitive material is formed of (A) a high molecular polymer substantially containing no aromatic ring nor heterocyclic ring in the molecule; (B) a compound having one or more of polymerizable ethylenic unsaturated groups substantially having no aromatic ring nor heterocyclic ring in the molecule; (C) an epoxy compound having an aromatic ring or heterocyclic ring in the molecule which may have a substituent; and (D) a photopolymerization initiator. As the high molecular polymer (A), solvent-soluble high molecular polymers are used. As the compound (B), unsaturated compounds such as (meth)acrylic acids, and (meth)acrylate compounds are used, and as the epoxy compound (C), epoxy monomers such as phenyl glycidyl ether are used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for hologram recording which is excellent in chemical stability and environmental resistance, particularly in heat resistance, and is excellent in sensitivity characteristics, resolution, diffraction efficiency and transparency.

[0002]

2. Description of the Related Art Conventionally, bleached silver salt and dichromated gelatin type photosensitive materials have been generally used as hologram recording media. However, in the production of holograms using these hologram recording media, the method for producing the photosensitive plate and the process for producing the holograms are complicated, and the produced holograms are inferior in environmental resistance characteristics such as moisture resistance and weather resistance. Moreover, there is a problem that the resolution is limited.

In order to solve such a problem, a hologram recording material using a photopolymer has been proposed. For example, Japanese Patent Publication No. 62-22152 discloses a hologram recording material characterized by a combination of a polyfunctional monomer having two or more ethylenically unsaturated bonds, a non-crosslinkable polymer and an initiator. ing. 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 in the long wavelength region, 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, uneven development caused by voids and cracks generated during the solvent immersion operation, and deterioration of transparency due to whitening. Further, since the polymer used is non-crosslinkable, the strength of the cured film is inferior.

On the other hand, a hologram recording material using a photopolymer (and a hologram recording material using a photopolymer capable of producing 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 production step (and ) Or its manufacturing method is disclosed. For example, JP-A-2-3081, JP-A-2-3082, USP49424212, or USP50.
In Japanese Patent Publication No. 98803, for recording holograms, a thermoplastic polymer characterized in that either a polymer or a monomer has a substituent containing an aromatic ring or a halogen atom, a liquid ethylenic monomer, and a photoinitiator. Photopolymerizable compositions and refractive index imaging elements are disclosed. According to this known technique, the hologram having excellent diffraction efficiency, high resolution, environment resistance and transparency can be manufactured by the SPIE "Practica".
l Holography IV ", Volume 1212, 30.
Page (1990) and "Journal of Ima"
Ging Science ", Vol. 35, p. 19 and 2.
This is demonstrated on page 5 (1991). However, in the hologram recording material, in order to form a refractive index modulation pattern by hologram exposure, it is necessary for the monomer to diffuse in the polymer during hologram exposure, and as a thermoplastic polymer for that purpose, Tg is relatively high.
It is necessary to select a material with low heat resistance, and it is difficult to improve heat resistance. Also, because it essentially uses ethylenically unsaturated monomers, it is an optically transparent inorganic material such as a glass plate. When forming a hologram on the above, there was a defect that adhesion was not improved.

Further, in Japanese Patent Application Laid-Open No. 5-94014, a photosensitive resin composition for hologram is characterized by comprising a radical-polymerizable unsaturated ethylenic monomer, an epoxy resin, a photo-radical initiator and a sensitizer. However, since a binder polymer is not used, when the composition is applied onto a substrate to form a hologram recording medium, the medium may have fluidity and a fine interference pattern. In manufacturing a hologram that needs to be formed, there may be a problem in terms of resolution and the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a photosensitive material for hologram recording which is excellent in chemical stability and environmental resistance, particularly in heat resistance, and is excellent in sensitivity characteristics, resolution, diffraction efficiency and transparency. Is.

[0007]

Means for Solving the Problems In consideration of the above points, the present inventors have made earnest studies to achieve the above object, and as a result,
The present invention has been achieved.

That is, the first invention is a high-molecular polymer (A) essentially having no aromatic ring or heterocycle in the molecule,
Compound (B) having at least one polymerizable ethylenically unsaturated group having essentially no aromatic ring or heterocycle in the molecule, having an aromatic ring or heterocycle optionally having a substituent in the molecule A second aspect of the present invention is a photosensitive material for hologram recording characterized by comprising an epoxy compound (C) and a photopolymerization initiator system (C). The second invention is a photosensitive material having essentially no aromatic ring or heterocycle in the molecule. Molecular polymer (A), compound (B) having at least one polymerizable ethylenically unsaturated group having essentially no aromatic ring or heterocycle in the molecule, aromatic ring which may have a substituent, or A thermopolymerization initiator system (D) of an epoxy compound (C) is added to a hologram recording photosensitive material comprising an epoxy compound (C) having a heterocycle in the molecule and a photopolymerization initiator system (C). Is a photosensitive material for hologram characterized by

The present invention will be described in detail below.
First, a solvent-soluble high-molecular polymer is used as the high-molecular polymer (A) essentially having no aromatic ring or heterocycle in the molecule used in the present invention. Examples of such high molecular weight polymers are given below. For example, cellulose acetate, cellulose butyrate, cellulose-based polymer such as ethyl cellulose, chlorinated rubber, rubber-based polymer such as cyclized rubber,
(Meth) acrylic acid polymer, (meth) acrylic acid ester homopolymer or copolymer of two or more components, polyvinyl acetate, partially saponified polyvinyl acetate, ethylene vinyl acetate copolymer, vinyl chloride vinyl acetate copolymer Polyvinyl ester-based polymer such as coalesce, polyurethane resin,
Examples thereof include polyester resins, polyvinyl butyral, polyvinyl formal, and other polyvinyl acetal resins. These high molecular weight polymers (A) may be used alone, or may be used as a mixture of two or more as required.

Next, the compound (B) having one or more polymerizable ethylenically unsaturated groups essentially having no aromatic ring or heterocycle in the molecule, which is used in the present invention, is exemplified. Specific examples include unsaturated acid compounds such as (meth) acrylic acid, itaconic acid, maleic acid, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. ) Acrylic acid alkyl ester compound, tetrahydrofuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, vinyl monomers of 2-hydroxyethyl (meth) acrylate, and aliphatic polyhydroxy compounds such as ethylene. Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol. Di- or poly (meth) acrylic esters such as trimethylolpropane, pentaerythritol, dipentaerythritol, neopentyl glycol, sorbitol, mannitol, trifluoro Fluorine atom-containing (meth) acrylate compounds such as tyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate Can be mentioned. You may use these individually or in mixture of 2 or more.

Further, as the compound having a polymerizable ethylenic unsaturated bond, an addition-polymerizable compound which is polymerized through ring-opening sigma bond cleavage is also mentioned. Such compounds are described in K. J. Ivin and T.W. Edited by Elsa, Els
first, in 1984, evier, New York
Chapter “General Thermodynamics
nd Mechanistic Aspects of
Ring-Opening Polymerizati
on ", pages 1-82, and Chapter 2," Ring O "
pening Polymerization via
Carbon-Carbon Sigmabond
Cleavage ", pages 83-119, WJB.
A. Airey et al. Macromol. Sci. -Ch
em. , A21, pp. 1611-1639, 19
1984, and I. Cho and K. -D. Ahn J. Polym. Sci. , Polym. Lett. E
d. Vol. 15, pp. 751 to 753, 1977. 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 (EAV
C) etc. are mentioned. You may use these individually or in mixture of 2 or more.

Next, an epoxy compound (C) having an aromatic ring or a heterocycle which may have a substituent in the molecule will be exemplified. For example, phenyl glycidyl ether, o-cresyl glycidyl ether, p-cresyl glycidyl ether,
tert-butylphenyl glycidyl ether, bisphenol-A-diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenol-F-diglycidyl ether, tetrabromobisphenol-F-diglycidyl ether, diglycidyl resorcinol ether, 2- Epoxy monomers such as phenyl ethylene oxide and isophthalic acid diglycidyl ester are included. You may use these individually or in mixture of 2 or more.

Next, the photopolymerization initiator system (C) used in the present invention will be exemplified. 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. To mention a mixed system with at least one initiator (b) which generates a radical and / or a Lewis acid by interaction, or a compound system in which a sensitizer and an initiator are integrated by an ionic bond or a covalent bond. You can

Specific examples of the sensitizer (a) include unsaturated ketones such as chalcone derivatives and dibenzalacetone derivatives, and 1,2-diketone derivatives such as benzyl and camphorquinone. Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xanthone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonol derivative, styryl derivative, base styryl derivative, acridine derivative, Azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetrabenzoporphyrin derivative Tetranaphthoporphyrin derivative, triarylmethane derivative, tetraazaporphyrin derivative, phthalocyanine derivative, naphthalocyanine derivative, tetraazaporphyrazine derivative, tetrapyrazinoporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, tetraphyrin derivative, annulene derivative, Pyrylium derivatives, thiopyrylium derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, organic ruthenium complexes, and the like. Others, edited by Nobu Okawara et al., "Dye Handbook"
(1986, Kodansha), Nobu Okawara et al., “Chemistry of Functional Dyes” (1981, CMC), Tadasaburo Ikemori et al., “Special Functional Materials” (1986, CMC), and Examples thereof include sensitizers and other compounds that absorb at the wavelength of radiation. 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 Well, on the other hand, a cyanine derivative,
In the case of a cationic dye such as an azurenium derivative, a pyrylium derivative or a thiopyrylium derivative, a compound in which a borate anion such as a triarylalkylboron anion is ionically bonded may be used.

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, xanthenes such as 2-chlorothioxanthene and 2,4-diethylthioxanthene, aryldiazinium salts, diaryliodonium salts, sulfonium salts, triphenylalkylborates, metal arene complexes , Bisimidazoles,
Examples thereof include 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.)", Vol. 30, p. 174 (19).
1986) iron arene complex, diphenyliodonium hexafluorophosphate, di (p-tolyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and other diaryliodonium salts, triphenylsulfonium hexafluorophosphate, diphenylphenacylsulfonium hexa Fluoroantimonate, dimethylphenacylsulfonium hexafluorophosphate, benzyl-
Sulfonium salts such as 4-hydroxyphenylmethylsulfonium hexafluoroantimonate, oxosulfonium salts such as tetraphenyloxosulfonium hexafluorophosphate, iodonium such as diphenyliodonium (n-butyl) triphenylborate described in JP-A-3-704. Organoboron complex, diphenylphenacylsulfonium (n-butyl) triphenylborate described in Japanese Patent Application No. 4-89535, Japanese Patent Application No. 4-
Sulfonium organoboron complexes such as dimethylphenacylsulfonium (n-butyl) triphenylborate described in 56831, "Organometallics (Orga)
Noh metallics) ”, vol. 8, p. 2737 (1989) and the like.

For example, tris (trichloromethyl)-
Photopolymerization initiators such as 2,4,6-triazine, iron arene complexes, diphenyliodonium salts, triarylsulfonium salts, and dimethylphenacylsulfonium salts can react with radicals and acids by interacting with a sensitizer in a photoexcited state. Can be generated.

The initiator system (E) for activating the polymerization of the epoxy compound (C) of the present invention includes amines, acid anhydrides, polyamide resins, imidazoles, Lewis acid adducts and dicyandiamide. , Organic acid hydrazides, diaminomaleonitriles, melamine derivatives, amine imide derivatives, polyamine salts, aromatic diazonium salts, diaryl iodonium salts, sulfonium salts, ammonium salts, pyridinium salts, phosphonium salts, polymercaptan curing agents, etc. Resins, compounds described by Hiroshi Kakiuchi, Shokoido (1985), compounds described in "Functional Materials", Vol. 13, No. 5, page 5 (1993), and the like. In particular, boron trifluoride amine complex, organic acid hydrazide, polyamine salt, sulfonium salt, ammonium salt, pyridinium salt and phosphonium salt, etc. act as latent curing agents, so that the pot life of the photosensitive material can be lengthened. It is preferably used.

The hologram recording light-sensitive material used in the present invention comprises a high molecular polymer (A), a compound (B), an epoxy compound (C) and a photopolymerization initiator system (D) at an appropriate concentration. It can be obtained by dissolving in a solvent and applying the obtained solution in the form of a film on a substrate such as a glass plate. There is no particular limitation on the compounding ratio of each of the above components, but it is preferable to adjust the concentration of the photopolymerization initiator system (D) so that the transmittance of the laser light for irradiation is 1% or more. If necessary,
Various additives such as plasticizers, chain transfer agents, antioxidants,
You may add a thermal-polymerization inhibitor, a leveling agent, etc.

The amount of the high molecular weight polymer (A) in the whole photosensitive material is 10 to 90% by weight, preferably 30 to 70% by weight, in order to carry out hologram recording having high diffraction efficiency. The amount of the compound (B) used is 10 to 20 with respect to 100 parts by weight of the high molecular polymer (A) as a support.
The amount of the epoxy compound (C) used is 10 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the high molecular polymer (A) as a support. It is 100 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.

In the photopolymerization initiator system (D) used in the present invention, the amount of the sensitizer (a) used is the high polymer (A) 10
0 to 30 parts by weight, preferably 0.1 to 30 parts by weight,
It is used in the range of 0.5 to 15 parts by weight. The amount used is limited by the film thickness of the photosensitive layer and the optical density of the film thickness. That is, it is preferably used in a range where the optical density does not exceed 2. The amount of the initiator (b) used is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymer (A).

The obtained solution is applied in the form of a film on a base material and used as a hologram recording medium. The applied thickness is preferably 1 μm to 50 μm as a film thickness after drying, more preferably in the range of 4 μm to 20 μm, but the thickness is required to meet required hologram characteristics such as diffraction efficiency or reproduced light half width and refraction. It is necessary to set the optimum thickness depending on the relationship with the rate modulation degree (Δn) or whether the hologram to be manufactured is a reflection hologram or a transmission hologram. For the rationale, see H. Kogelnik, Bell. Syst. T
ech. J. , Vol. 48, p. 2909 (1969)
It is described in.

By using a spin coater, a roll coater, a knife coater, a bar coater, or the like, a photosensitive solution prepared by dissolving the hologram recording photosensitive material having the above composition ratio in an appropriate solvent is directly applied to a glass plate, a plastic film, or the like. A photosensitive film is formed on the base material. Further, a protective layer for blocking oxygen may be formed thereon. The protective layer may be formed by laminating a film or plate made of a plastic such as polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or polyethylene terephthalate, or applying a solution of the polymer. Alternatively, a glass plate may be attached. Further, an adhesive or a liquid substance may be present between the protective layer and the photosensitive film (and / or) or between the substrate and the photosensitive film in order to enhance airtightness.

The photosensitive plate or film formed of the hologram recording photosensitive material obtained as described above is
After fixing to the holder so that it is not affected by vibration, H
Volume phase hologram recording is performed by irradiating various laser lights such as e-Cd laser, Ar ion laser, He-Ne laser, Kr ion laser, and ruby laser. FIG. 1 shows an example of the optical system.

Light and / or heat can be applied to the hologram-recorded photosensitive plate or film for fixing the unexposed portion or the portion having a small exposure amount. In particular, fixing by heating contributes to an improvement in diffraction efficiency and an improvement in physical properties of the photosensitive film, for example, an improvement in heat resistance due to an improvement in Tg. As the light to be used, visible light and / or ultraviolet light such as carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, and tungsten lamp can be used in addition to visible light laser. On the other hand, heat is 40 ℃
It is preferable to heat between 1 and 160 ° C. Light and heat may be applied simultaneously to the hologram-recorded photosensitive plate or film, or light and heat may be applied separately. Further, an operation of peeling the protective film may be performed before and after applying light and / or heat.

[0026]

The photosensitive material for hologram recording of the present invention comprises a polymer (A) having essentially no aromatic ring or heterocycle in the molecule, and a polymer having essentially no aromatic ring or heterocycle in the molecule. From a compound (B) having one or more possible ethylenically unsaturated groups, an epoxy compound (C) having an aromatic ring and a heterocycle which may have a substituent in the molecule (C), and a photopolymerization initiator system (D) It is characterized by being formed. Using a hologram recording medium obtained by forming the hologram recording photosensitive material as a film on a substrate, in interference exposure of a laser light source having high coherence as shown in FIG. Formed in the medium. At that time, at a site having a strong interference action, a radical or / and an acid is generated from the photopolymerization initiator system by the action of light, and the polymerization reaction of the compound (B) is mainly induced. At this time, in the case of an initiator system in which an acid is also generated at the same time, the epoxy compound (C)
Although the polymerization of is also induced, the reaction speed is extremely slow compared to the radical reaction, and therefore the polymerization hardly progresses.

Therefore, at the site having a strong interference action, the compound (B) is aggregated and polymerized by diffusion, so that a layer having a small refractive index is formed. On the other hand, in the area of low interference,
Since the epoxy compound (C) remains, the difference in refractive index between the two parts increases, and a hologram is formed by the refractive index modulation. Particularly in the present invention, the compound (B) does not have an aromatic ring or a heterocyclic ring which may have a substituent in its molecule, while the epoxy compound (C) has a substituent in its molecule. It is presumed that the effect of the above-described refractive index modulation becomes remarkable because of having an aromatic ring and a heterocyclic ring which may have.

[0028]

The present invention will be described in more detail based on the following examples. In the following examples, parts represent parts by weight unless otherwise specified. Table 1 shows the composition of the hologram recording photosensitive materials used in Examples 1 to 10.

Example 1 100 parts of polyvinyl acetate (PVAc) and 50 parts of dimethylol tricyclodecane diacrylate (DCPA)
Part, tetrabromobisphenol A diglycidyl ether (TBBADGE) 50 parts, 3,3′-carbonylbis (7-diethylaminocoumarin) (KCD) 3 parts
Part, 5 parts of diphenyliodonium hexafluorophosphate (DPI) and a photosensitive solution consisting of methyl isobutyl ketone on a glass plate of 100 × 125 × 3 mm,
A 5 mil applicator was applied so that the film thickness after drying the photosensitive solution would be 25 μm, and a hologram recording photosensitive plate was prepared. Further, a 5% aqueous solution of polyvinyl alcohol was applied with a spin coater. Hologram exposure was performed on this photosensitive plate by two-beam interference using the reflection hologram production optical system shown in FIG. At that time, as a laser, 488 nm light of an Ar ion laser was used. Then, this hologram-exposed photosensitive plate was irradiated with a 500 W xenon lamp for 30 seconds, and then placed in an oven at 150 ° C. for 2 hours.

The diffraction efficiency of the hologram obtained as described above was measured by an ART25C spectrophotometer manufactured by JASCO Corporation. The apparatus is a photomultimeter having a slit with a width of 3 mm and a radius of 20 c with the sample as the center.
It can be installed on the circumference of m. Monochromatic light having a width of 0.3 mm was incident on the sample at an angle of 45 degrees, and 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 collectively shows the exposure energy amount (sensitivity characteristic) that gives the maximum diffraction efficiency, the diffraction efficiency, the playback wavelength, and the full width at half maximum of the reproduction light.

[0031] The DPI in Example 2 Example 1, (eta ⁶ - cumene) - except for changing the (eta ⁶ cyclopentadienyl) iron hexafluorophosphate (FeArene) is operated in the same manner as in Example 1 Table 2 shows the sensitivity characteristics, the diffraction efficiency, the playback wavelength, and the full width at half maximum of the reproduced light when the above was performed.

Example 3 Operation was carried out in the same manner as in Example 1 except that DPI in Example 1 was changed to 2,4,6-tris (trichloromethyl) -1,3,5-triazine (TCT). Table 2 shows the sensitivity characteristics, the diffraction efficiency, the playback wavelength, and the full width at half maximum of the reproduced light when the above was performed.

Example 4 The KCD in Example 1 was changed to tetra-tert-butyltetrabenzoporphyrin zinc complex (TBP),
Table 2 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and full width at half maximum of reproduced light when operated in the same manner as in Example 1 except that the light source was changed from the Ar ion laser to the He-Ne laser. Indicated.

Example 5 The photosensitizing solution of Example 1 was prepared by using a boron trifluoride-benzylamine complex (BF) as a thermosetting agent for tetrabromobisphenol A diglycidyl ether, which is an epoxy compound.
Example 1 except that the photosensitizer was added with 3 parts of ( _3- BA).
Table 2 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and full width at half maximum of reproduced light when operated in the same manner as in.

Example 6 PVAc in Example 1 was mixed with polyvinyl butyral (P
Table 2 shows the sensitivity characteristics, diffraction efficiency, playback wavelength, and full width at half maximum of reproduced light when operated in the same manner as in Example 1 except that VB) was used.

Example 7 Sensitivity characteristics, diffraction efficiency, playback wavelength, reproduction light when operated in the same manner as in Example 1 except that PVAc was changed to cellulose acetate butyrate (CAB) in Example 1. The full width at half maximum of is shown in Table 2.

Example 8 In the same manner as in Example 1, phenylglycidyl ether (P
Table 2 shows the sensitivity characteristics, the diffraction efficiency, the playback wavelength, and the full width at half maximum of the reproduction light when operated in the same manner as in Example 1 except that GE) was used.

Example 9 Sensitivity characteristics, diffraction efficiency, playback wavelength, reproduction light when operated in the same manner as in Example 1 except that DCPA in Example 1 was replaced with isobornyl acrylate (IBA). The full width at half maximum of is shown in Table 2.

Example 10 Sensitivity characteristics, diffraction efficiency, playback wavelength, reproduction when operated in the same manner as in Example 1 except that DCPA was changed to triethylene glycol diacrylate (TEGDA) in Example 1. The full width at half maximum of light is summarized in Table 2.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

EFFECTS OF THE INVENTION By using the photosensitive material for hologram recording of the present invention, it is possible to produce a volume phase hologram having a small exposure energy, excellent chemical stability and environmental resistance, high resolution and high diffraction efficiency. Is possible.

[Brief description of drawings]

FIG. 1 shows a block diagram of a two-beam laser exposure apparatus for manufacturing a volume phase hologram.

[Explanation of symbols]

 1: Laser light source 2: Mirror 3: Lens 4: Spatial filter 5: Substrate (glass plate) 6: Hologram photosensitive film 7: Protective film (polyvinyl alcohol film)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yen Yasuike 2-3-13, Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. A polymer (A) having essentially no aromatic ring or heterocycle in the molecule, and a polymerizable ethylenically unsaturated group essentially having no aromatic ring or heterocycle in the molecule. A hologram recording comprising a compound (B) having one or more compounds, an epoxy compound (C) having an aromatic ring or a heterocycle which may have a substituent in the molecule, and a photopolymerization initiator system (D). Photosensitive material. 2. A high molecular weight polymer (A) essentially having no aromatic ring or heterocycle in the molecule, and a polymerizable ethylenically unsaturated group essentially having no aromatic ring or heterocycle in the molecule. A hologram recording photosensitive material comprising a compound (B) having one or more compounds, an epoxy compound (C) having an aromatic ring or a heterocyclic ring which may have a substituent in the molecule, and a photopolymerization initiator system (D), A photosensitive material for hologram recording comprising an initiator system (E) for activating the polymerization of an epoxy compound (C).