JP3075082B2 - Hologram photosensitive recording material, hologram photosensitive recording medium, and hologram manufacturing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hologram photosensitive recording material and a hologram photosensitive recording medium used for forming a volume phase hologram, and a hologram manufacturing method using the same.
Alternatively, a hologram-sensitive recording material and a hologram-sensitive recording medium having high sensitivity to electron beams, excellent weather resistance and storage stability, and having good hologram characteristics such as resolution, diffraction efficiency, and transparency, and the like. The present invention relates to a hologram manufacturing method used.

[0002]

2. Description of the Related Art Conventionally, since holograms can reproduce a three-dimensional stereoscopic image, holograms have been used for covers such as books and magazines, displays such as POPs, and gifts because of their excellent design and decorative effects. . Also, holograms are used for security countermeasures, such as securities and credit cards, because they can be said to be equivalent to recording information in submicron units.

[0003] In particular, a volume phase hologram modulates the phase without absorbing a light beam passing through an image by forming spatial interference fringes having different refractive indices instead of optical absorption in a hologram recording medium. In recent years, in addition to display applications, application to hologram optical elements (HOE) typified by head-up displays (HUD) mounted on automobiles is expected.

Meanwhile, it is required that a volume phase type hologram recording material be sensitive to a laser beam having a visible oscillation wavelength with high sensitivity and exhibit high resolution. Further, when actually used for forming a hologram, it is required that characteristics such as the diffraction efficiency of the hologram, the reproducibility of the wavelength of the reconstructed light, and the bandwidth (half-width of the reconstructed light peak) meet the purpose. In particular, the hologram recording material for HOE has a diffraction efficiency of 90% at a spatial frequency of 5000 to 6000 lines / mm.
As described above, the half width (bandwidth) of the peak of the reproduction light is 20 to 3
0 nm, the peak wavelength of the reproduction wavelength is 5 nm from the photographing wavelength.
It is desirable that the content be within the above range, and further, it is required that the storage stability be excellent over a long period of time.

[0005] The general principle of hologram fabrication is described in several documents and technical books, for example, Chapter 2 of “Holographic Display” (edited by Junpei Tsujiuchi; Sangyo Tosho). According to these, a coherent two-beam, generally, one of the laser beams is irradiated to a recording object, and a photosensitive recording medium, for example, a photographic dry plate is placed at a position where total reflection light from the recording object can be received. The recording medium is irradiated directly with the other coherent light in addition to the reflected light from the object without hitting the object. The light reflected from the object is referred to as target light, and the light directly illuminating the medium is referred to as reference light, and interference fringes between the reference light and the target light are recorded as image information.
Next, when the processed recording medium is exposed to light and observed at an appropriate eye position, the light from the illumination light source emits the wavefront of the reflected light that first arrived at the recording medium from the object during recording. Is diffracted by the hologram so as to reproduce the object, and as a result, an object image similar to the real image of the object is observed three-dimensionally. A hologram formed by causing the reference light and the target light to enter the recording medium from the same direction is known as a transmission hologram. On the other hand, holograms formed by making incident from opposite sides of a recording medium are generally known as reflection holograms. Transmission holograms are disclosed, for example, in US Pat.
No. 06327, U.S. Pat. No. 3,894,787, and the like. Further, the reflection hologram can be produced by a known method disclosed in, for example, US Pat. No. 3,532,406.

A value for comparing a hologram formed as an image is refractive index modulation. This is because when the recording medium is directly irradiated with the two light beams at the same angle to the medium and a diffraction grating is produced, the ratio of the incident light diffracted by the diffraction grating, that is, the diffraction efficiency and the recording medium It is a value specified from the thickness. Refractive index modulation is a quantitative measure of the change in refractive index that occurs in exposed and unexposed areas of a volume hologram, that is, the areas where light interferes and strengthens, and is described by H. Kogelnik. Theoretical formula [Bell. Syst. Tech. J. , 48,2
909, (1969). ]. Generally, reflection phase holograms have higher resolution than transmission holograms, that is, recording is difficult because of the large number of interference fringes formed per mm, and it is difficult to obtain high refractive index modulation.

As a recording material for such a volume phase hologram, a photosensitive material based on a bleached silver salt and a gelatin dichromate has been generally used. This dichromated gelatin-based photosensitive material is the most widely used material for recording volume phase holograms due to its high diffraction efficiency and low noise characteristics. However, this photosensitive material has a short shelf life and must be prepared each time it is produced. In addition, since the wet development is performed, the hologram is deformed in the process of swelling and shrinking the gelatin necessary for producing the hologram. For this reason, there is also a problem that the reproducibility of the hologram is poor. In addition, silver salt sensitive materials
A complicated process is required after recording, and the photosensitive material is not satisfactory from the viewpoint of stability and workability. Furthermore, all of the above photosensitive materials have a problem that they are inferior in environmental resistance properties, for example, moisture resistance and weather resistance.

On the other hand, it has excellent environmental resistance characteristics and
A hologram recording material using poly-N-vinylcarbazole is a material having characteristics that a hologram recording material should have such as high resolution and high diffraction efficiency. For example, a hologram recording material comprising a cyclic cis-α-dicarbonyl compound as a crosslinking agent and a sensitizer (JP-A-60-45)
No. 283), a hologram recording material comprising 1,4,4,5,6,7,7-hexachloro-5-norbornene-anhydro-2,3-dicarboxylic acid and a dye (JP-A-60-2).
No. 27280), a hologram recording material comprising 2,3-bornanedione and thioflavin (JP-A-60-26)
0080), a hologram composed of Thioflavin T and iodoform (Japanese Patent Application Laid-Open No. 62-123489) and the like. However, these hologram recording materials also require complicated processing steps because they require wet development, have the problem of poor reproducibility, and are photosensitive materials containing poly-N-vinylcarbazole as a main ingredient. Although it is chemically stable and has high resolution and excellent environmental resistance, poly-N-vinylcarbazole crystallizes and is very easy to whiten, and the reproducibility of transparency is poor.
There is also a problem that the solvent is limited. In addition, further improvement in sensitivity characteristics is desired.

As a material which can be photocured with high sensitivity, a photocurable resin composition used in combination with a 3-ketocoumarin and a diaryliodonium salt, which are constituents of a photopolymerization initiator (Japanese Patent Application Laid-Open No. 60-88005). Further, a hologram recording material in which the photopolymerization initiator is combined with polymethyl methacrylate as a supported polymer (Japanese Patent Application Laid-Open No. 4-31590) has been proposed, which is chemically stable and has high resolution and high sensitivity. Despite having, to form voids by wet processing, dispersion of the peak wavelength of the reproduction wavelength and expansion of the half-width of the peak wavelength, and, at the time of development, since the bile polymer is slightly dissolved in the swelling solvent, It has the problem that development unevenness is likely to occur, and furthermore, since there are many voids in the hologram, it is inferior in heat resistance and heat pressure resistance. It has.

In order to solve such a problem, a photopolymerizable photosensitive material capable of producing a hologram in one processing step without wet processing is disclosed in US Pat. No. 3,993,485 and US Pat. No. 3,658,526. I have. The former includes two types of photosensitive materials. As a first example, a combination of two polymerizable unsaturated ethylenic monomers having different reactivity and refractive index and a photopolymerization initiator, for example, cyclohexyl methacrylate, N- Consisting of vinyl carbazole and benzoin methyl ether,
This is a photosensitive resin composition that can be hologram-recorded by being held between two glass plates and exposed by a two-beam optical system.
Further, as a second example, a polymerizable unsaturated ethylenic monomer having a similar refractive index, an unsaturated ethylenic monomer acting as a cross-linking agent when polymerized, and a refractive index different from those of the two monomers are used. A photosensitive material which comprises four components of a non-reactive compound and a polymerization initiator, for example, butyl methacrylate, ethylene glycol dimethacrylate, 1-phenylnaphthalene and benzoin methyl ether, and can produce a hologram in the same manner as in the first example. It is a conductive resin composition. No matter which photosensitive resin composition is used,
As the polymerization of the more reactive monomer progresses in the part where the light intensity of the interference fringes formed by the two light fluxes progresses, a monomer concentration gradient occurs, and the highly reactive monomer is placed in the part with the strong light intensity and Low monomers or unreactive compounds diffuse into areas of low light intensity. In this way, the interference fringes are recorded with a difference in the refractive index, and a volume phase hologram is formed.

However, such a conventional photosensitive resin composition for hologram recording has the following problems. That is, in the case of the first example, even a monomer having low reactivity undergoes a certain degree of polymerization, and high refractive index modulation cannot be obtained. In the second example, since 1-phenylnaphthalene, which is a non-reactive compound, exists in the system as a low molecular weight compound even after completion of the hologram, there is no storage stability. Further, in any of the examples, since the mixture is low in molecular weight and low in viscosity, there are many problems in workability and reproducibility such as difficulty in sandwiching between substrates and formation of a thick film.

US Pat. No. 3,658,526 discloses a method for producing a stable hologram comprising a hologram recording material in which a liquid monomer, a photopolymerizable ethylenic monomer and a photopolymerization initiator are mixed in a polymer matrix. A single exposure to actinic radiation results in a permanent volume phase hologram. The hologram formed is fixed by subsequent full irradiation with actinic radiation. The hologram recording material disclosed here is intended to provide many advantages in terms of workability and reproducibility, but its diffraction efficiency is low. In this hologram recording material, the refractive index modulation of the completed hologram ranges from 0.001 to 0.003. As a result, the reproduced image of the formed hologram has only a limited brightness. Although it is possible to provide some brightness by increasing the thickness of the hologram recording layer, this solution has resulted in the manufacturer using a large amount of hologram recording material, and has also resulted in certain media, such as in-vehicle applications. It hinders the case where the device is fixed in a laminated glass such as a head-up display. It should also be noted that the holograms formed by this generally cause a decrease in diffraction efficiency due to long-term storage.

As improved techniques including the method of manufacturing a hologram recording material disclosed in US Pat. No. 3,658,526, US Pat. Nos. 4,942,112 and 5,098,803, and JP-A-2-3081, JP-A-2-3081. It is disclosed in JP-A-2-3082. These have a basic composition of a thermoplastic resin, a polymerizable unsaturated ethylenic monomer, and a photopolymerization initiator, and are used to improve the refractive index modulation by using either a thermoplastic resin or a polymerizable unsaturated ethylenic monomer. The inventor has devised to have a refractive index difference by using a compound having an aromatic ring. However, similar to that disclosed in U.S. Pat. No. 3,658,526, the use of a high molecular weight resin as a binder matrix limits the diffusibility of the monomer during exposure, requiring a large amount of exposure. In addition, high diffraction efficiency cannot be obtained. Further, in order to improve this point, a non-reactive plasticizer is added. However, this use causes a problem in the film strength of the formed hologram and also causes the non-reactive plasticizer to have a non-reactive plasticizer. Even after completion, it is present in the system as a low molecular weight compound and has no storage stability. In addition, since the carrier holding this is a thermoplastic resin, it has a drawback of poor heat resistance.

On the other hand, according to Japanese Patent Application Laid-Open No. 5-107999, which is a technique for improving the above-mentioned disadvantage, a cation polymerizable monomer and a cation polymerization initiator are blended in place of the plasticizer in the above-mentioned patent, and after the hologram is formed, The problem of residual reactive plasticizer is solved.

However, a considerable amount of light irradiation is required for fixing after the hologram is formed, and a low molecular weight cationic polymerizable monomer is diffused during fixing.
Distortion occurs in the formed hologram, and high diffraction efficiency cannot be obtained. Further, similarly to the prior art, since the carrier holding the carrier is a thermoplastic resin, it has a drawback of poor heat resistance. Furthermore, a system that does not use a thermoplastic resin as a carrier for holding has many problems in workability and reproducibility, such as difficulty in sandwiching between substrates due to low viscosity and difficulty in forming a thick film. ing.

Furthermore, a photosensitive resin composition for hologram recording comprising an epoxy resin, a radically polymerizable unsaturated ethylenic monomer and a photoradical polymerization agent is disclosed in Japanese Patent Application Laid-Open No. 5-94.
014. As can be seen from the examples, two types of epoxy resins are used. However, when an ultraviolet curable epoxy resin is used, complicated work such as performing radical polymerization and cationic polymerization with light in different wavelength ranges is required. In addition, in order to adjust the diffusibility of the monomer, fine adjustment such as increasing the viscosity by pre-exposure is required, and workability and reproducibility are difficult. Further, when a thermosetting epoxy resin and a curing agent are used, the workability is extremely poor because a considerable amount of ultraviolet curing and heating time are required for curing the epoxy resin for fixing. In addition, high diffraction efficiency cannot be obtained with the improved technology disclosed herein.

[0017]

As described above, in a photopolymerizable photosensitive material capable of producing a hologram in a single processing step without a wet processing, a polymerizable monomer for obtaining a refractive index modulation is used. In addition, there are problems such as dispersibility, storage stability due to the addition of a monomer-supporting carrier and a non-reactive additive, and the workability of hologram production, diffraction efficiency of the obtained hologram, and transparency. The hologram photosensitive recording material and the hologram recording medium having excellent hologram characteristics such as reproducibility cannot be obtained.
There is still a need for an improved photopolymerizable composition for hologram recording, and it can be said that, in particular, an optical element using the same. Therefore, the present invention provides a hologram photosensitive recording material having excellent chemical stability, for example, environmental resistance, particularly excellent heat resistance, and furthermore, by dry processing, high resolution, high diffraction efficiency, high transparency, and excellent reproduction wavelength reproducibility. An object of the present invention is to provide a hologram photosensitive recording medium and a hologram manufacturing method using the same.

[0018]

Means for Solving the Problems The present invention has been made to solve the above problems, and the invention according to claim 1 has the following features.
(A) represented by the general formula (I),

[0019]

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(Wherein, n is a real number not less than 0, X represents a hydrogen atom, a methyl group or an ethyl group, and R1 represents a hydrogen atom or a bromine atom), or represented by the general formula (II) The

[0021]

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(Wherein, n is a real number equal to or greater than 0, and X represents a hydrogen atom, a methyl group or an ethyl group), or
Represented by the general formula (III),

[0023]

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(Wherein, n represents a real number of 0 or more), a thermosetting epoxy oligomer which is soluble in a solvent, is cationically polymerizable, and is solid at normal temperature and normal pressure; Liquid at normal pressure and boiling point at normal pressure
(C) a polymerizable monomer having at least one radically polymerizable ethylenically unsaturated bond having a temperature of 0 ° C. or higher and having a refractive index different from that of the thermosetting epoxy oligomer (A);
It comprises a photoinitiator that simultaneously generates a radical species and a Brnsted acid or Lewis acid that activate radical and cationic polymerization upon exposure to actinic radiation, and (D) a sensitizing dye that sensitizes the photoinitiator (C). A hologram photosensitive recording material characterized by the following.

According to a second aspect of the present invention, in the hologram photosensitive recording material of the first aspect, the photoinitiator (C) is a diphenyliodonium salt.

According to a third aspect of the present invention, in the holographic photosensitive recording material of the first aspect, the sensitizing dye (D) is selected from cyanine or merocyanine dyes, coumarin dyes, chalcone dyes, and porphyrin dyes. It is an organic dye compound.

According to a fourth aspect of the present invention, there is provided a photosensitive layer prepared by dissolving the hologram photosensitive recording material according to any one of the first to third aspects in a solvent, applying the photosensitive solution on a substrate, and drying the photosensitive layer. And a hologram photosensitive recording medium characterized by comprising:

According to a fifth aspect of the present invention, a holographic exposure is performed on the photosensitive layer of the holographic photosensitive recording medium according to the fourth aspect to form a latent image. A hologram manufacturing method characterized by manufacturing a hologram by performing a heat treatment for 1 to 30 minutes in the range described above.

In the hologram recording using the hologram photosensitive recording material of the present invention, the radically polymerizable polymerizable monomer (B) contains a fluorene derivative which is soluble in a solvent, can be cationically polymerized, and is solid at normal temperature and normal pressure. The recording material is uniformly distributed in the solid phase composed of the thermosetting epoxy oligomer and / or the monomer (A). By irradiating the recording material with the laser interference light, the light interference effect in the laser irradiation part is strong. At the site, the photoinitiator (C) simultaneously generates, by the action of the sensitizer (D), a radical species and a Brnsted acid or Lewis acid that activate radical and cationic polymerization. Due to the radical species generated here, the monomer (B) is polymerized and polymerized, so that a difference in the concentration occurs, so that the monomer (B) diffuses and moves from the surroundings. That is, the monomer concentration is high in a part of the laser irradiation part where the light interference action is strong, and is low in a part of the laser irradiation part where the light interference action is weak. Further, the epoxy oligomer and / or monomer (A) is extruded to a portion of the laser irradiation site where the light interference effect is weak, and the concentration at that portion increases,
The concentration at the site where the light interference effect is strong in the laser irradiation site decreases. As a result, a difference in refractive index occurs between the two portions, and it is presumed that a latent image of the hologram is recorded.
Further, by heating after the hologram exposure, the remaining monomers are fixed by polymerization, and around the interference fringes formed by the concentration difference generated by the polymerization of the polymerizable monomer (B) by the strong acid generated simultaneously with the radical species. The epoxy oligomer and / or monomer (A), which is an existing support, has a crosslinked structure due to cationic polymerization and has a high refractive index, thereby enhancing the refractive index modulation. The crosslinking also improves weather resistance.

Further, the hologram photosensitive recording material of the present invention is a hologram having a large refractive index modulation and a high diffraction efficiency, and is superior in reproducibility of the peak wavelength of reproduction light and the bandwidth thereof to the conventional hologram recording material. In addition, since it has excellent environmental resistance characteristics, it can be applied to a hologram optical element.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. FIG. 1 is a schematic diagram illustrating the configuration of a hologram photosensitive recording medium made of the hologram photosensitive recording material of the present invention, and FIG. 2 is a schematic explanatory diagram illustrating a two-beam optical system for hologram imaging.

The component (A) constituting the hologram photosensitive recording material of the present invention includes, for example, the following general formulas (I) and (II):
(III) is a thermosetting epoxy oligomer which is solvent-soluble, cationically polymerizable, and solid at normal temperature and normal pressure, which can be obtained by a general method for synthesizing an epoxy oligomer. For example, the compound can be synthesized from the corresponding phenol compound and epichlorohydrin by the method described in Chapter 12 of “Experimental Method for Polymer Synthesis” (co-authored by Takayuki Otsu and Masayoshi Kinoshita). Note that the present invention is not limited to these, and any material having the above characteristics can be used.

[0033]

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(Wherein, n is a real number not less than 0, X represents a hydrogen atom, a methyl group or an ethyl group, and R 1 represents a hydrogen atom or a bromine atom.)

[0035]

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(In the formula, n is a real number of 0 or more, and X represents a hydrogen atom, a methyl group or an ethyl group.)

[0037]

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(Where n represents a real number equal to or greater than 0)

In the present invention, two or more kinds of thermosetting epoxy oligomers or monomers can be used as a mixture. Particularly, a mixture of a thermosetting epoxy oligomer and a thermosetting epoxy monomer can be used. it can. Further, an epoxy oligomer or monomer not containing a fluorene derivative can be appropriately added.

Next, as the polymerizable monomer capable of being radically polymerized as the component (B), the structural unit contains at least one ethylenically unsaturated bond in the structural unit and has a refractive index equal to that of the thermosetting epoxy oligomer (A). They are different and contain a polyfunctional vinyl monomer in addition to a monofunctional vinyl monomer, or may be a mixture thereof. K
According to ogelnik's theory, it is desirable that the difference in the refractive index between the component (A) and the component (B) is 0.03 or more. Specifically, (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, high-boiling vinyl monomers such as 2-hydroxyethyl (meth) acrylate, and further, an aliphatic polyhydroxy compound, For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol , 1,5-pentanediol, 1,6-hexanediol, 1,10-
Decanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol,
Di- or poly (meth) acrylates such as mannitol, alicyclic monomers such as dimethylol tricyclodecane monoacrylate, dimethylol tricyclodecane diacrylate, aromatic polyhydroxy compounds such as hydroquinone, resorcin, catechol, Examples thereof include di- or poly (meth) acrylates such as pyrogallol and bisphenol A, and ethylene oxide-modified (meth) acrylates of isocyanuric acid.

As the photoinitiator system for activating radical polymerization and cationic polymerization upon exposure to actinic radiation of the component (C) of the present invention, a diphenyliodonium salt or the like is preferable, and it is also possible to sensitize with an organic dye compound. . Examples of the diphenyliodonium salt used in the present invention include M
acromolecules, 10, 1307 (197
7). For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium Iodonium chlorides, bromides, iodonium salts such as borofluoride salts, hexafluorophosphate salts, hexafluoroarsenate salts, triarylsulfonium salts, triarylphosphonium salts, iron arene complexes, triazine compounds and the like. However, the present invention is not limited to these. It can be used in combination with a sensitizer such as an organic dye compound described below.

Further, as the sensitizing dye (D) of the present invention, organic dye compounds such as cyanine or merocyanine dyes, coumarin dyes, chalcone dyes and porphyrin dyes can be used. A specific example will be described below.

Examples of cyanine or merocyanine dyes include fluorescein, rhodamine, 2'7'-dichlorofluorescein, 3,3'-dicarboxyethyl-2,2
2'-thiocyanine bromide, anhydro-3,3 '
-Dicarboxymethyl-2,2'-thiocyanine betaine, 1-carboxymethyl-1'-carboxyethyl-2,2'quinocyanine bromide, anhydro-3,
3'-dicarboxyethyl-5,5 ', 9-trimethyl-2,2'-thiacarbocyanine betaine, 3,3'
-Dihydroxyethyl-5,5'dimethyl-9-ethyl-2,2'-thiacarbocyanine bromide, anhydro-3,3'-dicarboxymethyl-2,2'-thiacarbocyanine betaine, 2- [3- Ethyl-4-oxo-5- (1-ethyl-4-quinolinidene) -ethylidene-2-thiazolinidene-methyl] -3-ethylzenzoxazolium bromide, 3-ethyl-5- [2- (3
-Ethyl-2-benzothiazolylidene) -ethylidene]
Rhodanine, 3-ethyl-5- [2- (3-methyl-2
(3H) -thiazolinylidene) -ethylidene] -2-thio-2,4-oxazalidione, 3-ethyl-5- (3
-Ethyl-zenzothiazolylidene) rhodanine, 2-
(P-dimethylaminostyryl) -3-ethyl, benzothiazolium iodide, 2- (p-diethylaminostyryl) -1-ethyl pyridinium iodide, 1,
The use of 3′-diethyl-2,2′-quinothiacyanine iodide is preferred, but not limited thereto.

Examples of coumarin dyes include 3- (2 ′
-Benzimidazole) 7-N, N-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), 3,3'-carbonylbiscoumarin,
3,3′-carbonylbis (7-methoxycoumarin),
3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (6-methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonyl Bis (5,7-diisopropoxycoumarin), 3,3′-carbonylbis (5,
7-di-n-propoxycoumarin), 3,3′-carbonylbis (5,7-di-n-butoxycoumarin), 3,
3'-carbonylbis (7-dimethylaminocoumarin), 7-diethylamino-5 ', 7'dimethoxy-
3,3'-carbonylbiscoumarin, 3-benzoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-8-
Methoxycoumarin, 3-benzoyl-8-ethoxycoumarin, 3-benzoyl-6-bromocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-
Hydroxycoumarin, 3-acetyl-7-diethylaminocoumarin, 3-acetyl-7-methoxycoumarin, 3
-Acetyl-5,7-dimethoxycoumarin, 7-dimethylamino-3- (4-iodobenzoyl) coumarin, 7
-Diethylamino-3- (4-iodobenzoyl) coumarin, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin and the like, but are not limited thereto.

Examples of chalcone dyes include, but are not limited to, the following compounds.

[0046]

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As porphyrin dyes, 9,10-
Dihydroporphyrin, 5,9,15,19-tetramethylporphyrin, 4,5,14,15-tetrahydro-4,9,14,19-tetramethyl-2,7,12,
17-tetrazaporphyrin, meso-tetraphenylporphyrin, 4,5,9,10,14,15,19,2
0-octamethylporphyrin, 5,9, diacetyl-
4,10,14,15,19,20-hexamethylporphyrin, 5,9-diacetyl-14-ethyl-4,1
0,15,19,20-pentamethylporphyrin,
4,9,14,19-tetramethyl-5,10,15,
20-tetrapropylporphyrin, 2-amino-4,
5,9,10,14,15,19,20-octaethylporphyrin, 2-nitro-4,5,9,10,14,
15,19,20-octaethylporphyrin, meso-
Diphenyltetrabenzoporphyrin, 4,5-dibromo-9,10-, 14,15-, 19,20-tribenzo-2,7,12,17-terrazaporphyrin, 4,
5,9,10,14,15,19,20-octaphenylporphyrin, tetrakis (3,4-dimethoxyphenyl) porphyrin, 4,5,9,10,14,15,
19,20-octa (p-methoxyphenyl) porphyrins and their copper, cobalt, nickel, zinc, platinum,
Although the use of a metal complex such as magnesium is preferred,
It is not limited to these.

Further, sensitization for sensitizing a photoinitiator (D) such as a (thio) xanthene dye, an azulenium dye, a squarylium dye, a (thio) xanthone dye, a tetrapyrazinoporphyrazine dye, etc. Dyes can be used. These sensitizers can be selected according to the purpose of use so as to match the wavelength of the radiation serving as a light source, and depending on the application, two or more kinds may be used in combination.

The hologram light- and heat-sensitive recording material of the present invention comprises:
As described above, (A) general formulas (I), (II) and (III)
A thermosetting epoxy oligomer containing a fluorene derivative which is a solvent-soluble, cationically polymerizable, and solid at normal temperature and normal pressure selected from the group consisting of: (B) a liquid at normal temperature and normal pressure and a boiling point at normal pressure A polymerizable monomer having at least one ethylenically unsaturated bond capable of undergoing radical polymerization at a temperature of 100 ° C. or higher and having a refractive index different from that of the thermosetting epoxy oligomer (A), and (C) a radical upon exposure to actinic radiation A recording material comprising a photoinitiator which simultaneously generates radical species and a Brnsted acid or Lewis acid which activate polymerization and cationic polymerization, and (D) a sensitizing dye which sensitizes the photoinitiator (C), Is preferably in the range of 20 to 100 parts by weight of the polymerizable monomer (B) based on 100 parts by weight of the epoxy oligomer (A). If the ratio deviates, it becomes difficult to obtain a bright hologram with good reproducibility. The amount of the photoinitiator of the component (C) is 0.1 to 20 parts by weight, preferably 1 to 100 parts by weight based on 100 parts by weight of the component (A). 10 parts by weight. Further, the sensitizer of the component (D) is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the component (A).
It is possible to take a range up to. Since the amount used is limited by the thickness of the photosensitive layer to be formed and the optical density of the film thickness, it is preferable to use the optical density within a range not exceeding 2. It is preferable to set the transmittance of the irradiation light to a range of 1% or more).

Further, various additives such as a known thermal polymerization inhibitor, a chain transfer agent and an antioxidant may be added to the hologram photosensitive and heat-sensitive recording material of the present invention, if necessary.

As described above, the photosensitive solution obtained by appropriately selecting these components and mixing them in an arbitrary ratio is applied to a glass plate or a polycarbonate using a known coating means such as a spin coater, a roll coater, or a bar coater. A hologram photosensitive recording medium 1 for normal hologram photography, in which a hologram shown in FIG. 1 is produced, is applied to a substrate 2, such as a plate, a polymethyl methacrylate plate, or a polyester film, in a film form. Further, a protective layer 4 may be provided on the photosensitive layer 3 as an oxygen blocking film. For the protective layer 4, for example, a plastic such as polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, or polyethylene terephthalate, or an optically transparent material such as glass is laminated, and laminated by an extruder or the like, and a solution is applied. It is formed. When the photosensitive liquid is applied, it may be diluted with an appropriate solvent as necessary, but in that case, drying is required after application on the substrate. Further, it is desirable to adjust the transmittance so that the transmittance of the irradiation light at the time of photographing is 1% or more.

FIG. 2 is a schematic diagram for explaining a two-beam optical system for reflection type hologram photography. A laser beam 6 oscillated from a laser 5 passes through a mirror 7, a beam splitter 8, a spatial filter 9, and a lens 10. The hologram photosensitive recording medium 1 is irradiated through the hologram photosensitive recording medium 1. In the present invention, after the hologram is photographed by exposure, the fixing step is performed by dry processing. Although the present invention is not described in detail and is not shown, the production of a transmission hologram is similarly possible.
A transmission hologram having excellent hologram characteristics can be obtained.

When a hologram image is recorded on the hologram photosensitive recording medium 1, a laser irradiation is performed in accordance with a desired image, so that a thermosetting epoxy oligomer (hereinafter, referred to as a thermosetting epoxy oligomer) is applied to the laser irradiation site where the optical interference effect is strong. A)
The radically polymerizable polymerizable monomer (B), which is uniformly dispersed in the solid phase, is polymerized and polymerized by the action of a photopolymerization initiator when exposed by laser (laser interference light) irradiation. The surrounding radically polymerizable monomer (B) moves. For this reason, the concentration of the polymerizable monomer (B) capable of radical polymerization is high in a portion of the laser irradiation portion where the optical interference is strong, and the concentration of the polymerizable monomer (B) of the radical polymerization is high in a portion where the light interference effect is weak. Decrease. Further, the thermosetting epoxy oligomer (A) is extruded to a portion of the laser irradiation site where the light interference effect is weak, and the concentration at that portion increases,
The concentration at the site where the light interference effect is strong in the laser irradiation site decreases. That is, a refractive index difference is generated between the two portions, and thereby a refractive index modulation is caused by a difference in refractive index from a density difference between a portion of the hologram photosensitive recording medium 1 where the light interference is strong and a portion where the light interference effect is weak, and a hologram image is formed. A record is to be made. Furthermore, heating after hologram exposure (60
加熱 120 ° C., heat treatment for 1 to 30 minutes), while the remaining monomers are fixed by polymerization,
The thermosetting epoxy oligomer (A) which is a support existing around interference fringes formed by the concentration difference generated by the polymerization of the polymerizable monomer (B) by the strong acid generated simultaneously with the radical species has a crosslinked structure by cationic polymerization. And the refractive index increases, and the refractive index modulation is enhanced. Further, weather resistance such as strength of the hologram photosensitive recording medium 1 and chemical stability are improved by the crosslinking.

As a light source suitable for the hologram photosensitive recording material of the present invention in the step of exposing the interference pattern, a helium-cadmium laser, an argon laser, a krypton laser, a helium neon laser, or the like can be used, but is not limited thereto. Not something.

Hereinafter, the present invention will be described in more detail with reference to specific examples. <Example 1> 100 parts by weight of a thermosetting epoxy monomer represented by the following formula (V):

[0056]

Embedded image

Triethylene glycol diacrylate 5
A photosensitive solution was prepared by mixing and dissolving 0 parts by weight, 5 parts by weight of diphenyliodonium hexafluorophosphate, and 1 part by weight of 3,3'-carbonylbis (7-diethylamino) coumarin in 200 parts by weight of 1,4-dioxane. This photosensitive liquid was applied to a glass plate so as to have a thickness of about 15 μm to form a photosensitive layer, and then the photosensitive layer was covered with a polyvinyl alcohol (PVA) film to produce a hologram photosensitive recording medium.

The hologram photosensitive recording medium was exposed to light using an argon laser (514.5 nm) as a light source by a two-beam optical system for hologram photography shown in FIG.
Heat treatment was performed at 30 ° C. for 30 minutes to produce a hologram.

The diffraction efficiency of the obtained hologram was measured with a spectrophotometer manufactured by JASCO Corporation. In this spectrophotometer, a photomultimeter having a slit having a width of 3 mm can be installed on a circumference having a radius of 20 cm around a sample. The measurement conditions were such that 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 ratio between the largest value other than the specular reflection light and the case where the incident light was directly received without placing the sample was defined as the diffraction efficiency. The diffraction efficiency before heating was also measured in the same manner. Table 1 shows the evaluation results. However, D. in the table. E. FIG.
And R. I. C indicates diffraction efficiency and refractive index modulation, respectively.

Example 2-5 Triethylene glycol diacrylate (TEGDA)
Instead of diethylene glycol diacrylate (DE
GDA), neopentyl glycol diacrylate (N
PGDA) Ethyl carbitol acrylate (EK
A), 1,6-hexanediol diacrylate (HD
A hologram was prepared in the same manner as in Example 1, except that DA) was used, and the diffraction efficiency was measured. The diffraction efficiency before heating was also measured in the same manner. Table 1 shows the evaluation results.

[0061]

[Table 1]

TEGDA; Triethylene glycol diacrylate DEGDA; Diethylene glycol diacrylate NPGDA; Neopentyl glycol diacrylate EKA; Ethyl carbitol acrylate HDDA; 1,6-Hexanediol diacrylate

<Examples 6 and 7> Except that the thermosetting epoxy monomers of the following formulas (VI) and (VII) are used instead of the thermosetting epoxy monomer (V) of Example 1, respectively. Prepared a hologram in the same manner as in Example 1, prepared a hologram, and measured the diffraction efficiency. The diffraction efficiency before heating was also measured in the same manner. Table 2 shows the evaluation results.

[0064]

Embedded image

[0065]

Embedded image

[0066]

[Table 2]

<Examples 8-10> Instead of the thermosetting epoxy monomer (V) of Example 1, each of the heats represented by the following formula (VIII), wherein the theoretical value of n is 1, 3 and 5 A hologram was prepared in the same manner as in Example 1 except that a curable epoxy oligomer was used, and a hologram was prepared, and the diffraction efficiency was measured. The diffraction efficiency before heating was also measured in the same manner. Table 3 shows the evaluation results.
Shown in

[0068]

Embedded image

[0069]

[Table 3]

<Examples 11-14> The sensitizer of Example 1, 3,3'-carbonylbis (7-
3-ethyl-5 instead of diethylamino) coumarin
-[2- (3-ethyl-2-benzothiazolylidene)-
[Ethylidene] rhodanine (Dye-1), meso-diphenyltetrabenzoporphyrin (Dye-2), 3-
(2′-benzimidazole) 7-N, N-diethylaminocoumarin (Dye-3), 2-benzoyl-3-
A hologram was prepared in the same manner as in Example 1 except that (p-dimethylaminophenyl) -2-propenenitrile (Dye-4) was used, and the diffraction efficiency was measured. The diffraction efficiency before heating was also measured in the same manner. Table 4 shows the evaluation results. However, upon exposure,
For Dye-1, Dye-3, and Dye-4, 488 nm light was used instead of the 514.5 nm argon laser, and Dye-2 was 647 nm krypton laser.
Was used.

[0071]

[Table 4]

Dye-1; 3-ethyl-5- [2- (3-ethyl-2-benzothiazolylidene) -ethylidene] rhodanine Dye-2; meso-diphenyltetrabenzoporphyrin Dye-3; 3 -(2'-benzimidazole) 7-N, N-diethylaminocoumarin Dye-4; 2-benzoyl-3- (p-dimethylaminophenyl) -2-propenenitrile

The hologram of Example 1-14 was obtained at 25 ° C.
No reduction in diffraction efficiency was observed even when left in an environment of 0% RH for 180 days and at 150 ° C. for 10 hours.

[0074]

As described above, the present invention provides, as described above, a solvent-soluble, cationically polymerizable solvent selected from the general formulas (I), (II) and (III), and a solid at room temperature and pressure. And (B) at least one radically polymerizable ethylenically unsaturated bond which is liquid at normal temperature and normal pressure and has a boiling point of 100 ° C. or higher at normal pressure, and is thermosetting. (C) a polymerizable monomer having a different refractive index from the reactive epoxy oligomer (A), and (C) a light which simultaneously generates radical species and a Bronsted acid or Lewis acid which activate radical polymerization and cationic polymerization when exposed to actinic radiation. Excellent sensitivity, resolution, diffraction efficiency, and transparency in the visible light region, especially in dry processing, by comprising the initiator and (D) a sensitizing dye that sensitizes the photoinitiator (E). Which has excellent weather resistance and heat resistance, and can provide a chemically stable hologram photosensitive recording material and hologram photosensitive recording medium. Further, it can be used as a photosensitive recording material for holograms for HOE, which has extremely high required performance.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating the configuration of a hologram photosensitive recording medium made of the hologram photosensitive recording material of the present invention.

FIG. 2 is a schematic diagram illustrating a two-beam optical system for hologram imaging.

[Description of Signs] 1 Holographic photosensitive recording medium 2 Substrate 3 Photosensitive layer 4 Protective layer 5 Laser 6 Laser beam 7 Mirror 8 Beam splitter 9 Spatial filter 10 Lens 11 Lens

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03H 1/00-5/00 G03F ⁷ /00-7/115

Claims (5)

(57) [Claims] (A) A compound represented by the general formula (I): (In the formula, n is a real number of 0 or more, X represents a hydrogen atom, a methyl group or an ethyl group, and R1 represents a hydrogen atom or a bromine atom.) Or represented by the general formula (II): Formula 2 (In the formula, n is a real number of 0 or more, and X represents a hydrogen atom, a methyl group or an ethyl group.) Or represented by the general formula (III): (In the formula, n represents a real number of 0 or more.) A solvent-soluble, cationically polymerizable, thermosetting epoxy oligomer which is a solid at room temperature and pressure selected from the group consisting of: and (B) room temperature, normal pressure Is liquid and boiling point is 10 at normal pressure
(C) a polymerizable monomer having at least one radically polymerizable ethylenically unsaturated bond having a temperature of 0 ° C. or higher and having a refractive index different from that of the thermosetting epoxy oligomer (A);
A photoinitiator that simultaneously generates radical species and a Bronsted acid or a Lewis acid that activate radical and cationic polymerization upon exposure to actinic radiation, and (D) a sensitizing dye that sensitizes the photoinitiator (C) A hologram photosensitive recording material, comprising: 2. The hologram photosensitive recording material according to claim 1, wherein said photoinitiator (C) is a diphenyliodonium salt. 3. The hologram according to claim 1, wherein the sensitizing dye (D) is an organic dye compound selected from a cyanine or merocyanine dye, a coumarin dye, a chalcone dye, and a porphyrin dye. Photosensitive recording material. 4. A photosensitive layer prepared by dissolving the photosensitive recording material for holograms according to claim 1 in a solvent, coated on a substrate, and dried, and provided with an oxygen blocking film. A holographic photosensitive recording medium, comprising: 5. A holographic exposure of the photosensitive layer of the holographic photosensitive recording medium according to claim 4 to form a latent image. A hologram manufacturing method, wherein a hologram is manufactured by performing a heat treatment for up to 30 minutes.