JPH08190334A - Photosensitive recording material for transparent hologram, photosensitive recording medium for transparent hologram, and method for producing transparent hologram using the same - Google Patents

Abstract

(57) [Summary] [Purpose] It is possible to form holograms by dry processing.
It has high transparency, excellent weather resistance, and high resolution.
A transparent hologram having high diffraction efficiency and excellent reproduction wavelength reproducibility. [Structure] (A) a solvent-soluble resin which is solid at room temperature and atmospheric pressure, and (B) a resin which is liquid at room temperature and atmospheric pressure, and has a boiling point of 1 at atmospheric pressure.
A polymerizable monomer having at least one radically polymerizable ethylenically unsaturated bond at 00 ° C. or higher and having a refractive index different from that of (A), and (C) a photoinitiator that activates radical polymerization when exposed to light. A sensitizing dye having an amino group, and (E) a compound capable of forming a sulfonic acid derivative by an external action such as light or heat. The sensitizing dye remaining in the dye is discolored by the sulfonic acid derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for forming a volume phase hologram, is highly sensitive to visible light, particularly visible light such as argon laser light, and has hologram characteristics such as resolution, diffraction efficiency and transparency. The present invention relates to a transparent hologram photosensitive recording material, a transparent hologram photosensitive recording medium, and a method for producing a transparent hologram using the same, which have good values and excellent weather resistance and storage stability.

[0002]

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

Particularly, the volume phase hologram modulates the phase without absorbing the light beam passing through the image by forming spatial interference fringes having different refractive indexes in the hologram recording medium, not by optical absorption. Therefore, in recent years, in addition to display applications, application to a hologram optical element (HOE) represented by a head-up display (HUD) mounted on an automobile is expected.

By the way, the volume phase hologram recording material is required to be highly sensitive to laser light having a visible oscillation wavelength and exhibit high resolution. Further, when actually used for forming a hologram, it is required that characteristics such as diffraction efficiency of hologram, wavelength reproducibility of reproduced light, band width (half-value width of reproduced light peak) and the like are suitable for the purpose. Especially when used in a head-up display (HUD), etc.
It is important to have higher transparency (light transmission). Further, it is also required to have excellent storage stability for a long period of time.

General principles of hologram production are described in several documents and technical books, for example, "Holographic Display" (Junpei Tsujiuchi; Industrial Books), Chapter 2. According to these, generally, one of two beams of coherent laser light is applied to a recording object, and a photosensitive recording medium, for example, a photographic dry plate, is placed at a position where it can receive the totally reflected light from the recording object. In addition to the reflected light from the object, the recording medium is directly irradiated with the other coherent light without hitting the object. The reflected light from the object is called the object light, and the light directly radiated on the medium is called the reference light, and the interference fringes between the reference light and the object light are recorded as image information.
Then, when the treated recording medium is exposed to light and observed at the proper eye position, the light from the illumination source will cause the reflected light wavefront to first reach the recording medium from the object during recording. As a result, the hologram is diffracted so that the object image similar to the real image of the object is three-dimensionally observed. A hologram formed by making reference light and target light incident on a recording medium from the same direction is known as a transmission hologram. On the other hand, holograms formed by making light incident from opposite sides of a recording medium are generally known as reflection holograms. Transmissive holograms are described, for example, in US Pat. No. 35.
It can be obtained by a known method as disclosed in, for example, No. 06327 and U.S. Pat. No. 3,894,787. Further, the reflection hologram can be produced by a known method disclosed in, for example, US Pat. No. 3,532,406.

As a value for comparing holograms formed as images, there is a refractive index modulation. This is because when a diffraction grating is produced by directly irradiating the recording medium with the same angle formed by the two light fluxes and the medium, 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 by the thickness. Refractive index modulation is a quantitative measure of the change in the refractive index that occurs in exposed and unexposed areas of a volume hologram, that is, in areas where light interferes and strengthens and weakens, and is based on H. Kogelnik's Theoretical formula [Bell. Syst. Tech. J. , 48 , 2
909, (1969). ] It can be obtained by. Generally, a reflection phase hologram has a higher resolution than a transmission hologram, that is, since the number of interference fringes formed per 1 mm is large, recording is difficult and it is difficult to obtain high refractive index modulation.

The following are recording materials for such volume phase holograms. Conventionally, bleached silver salt and dichromate gelatin-based photosensitive materials have been generally used. This dichromate gelatin-based photosensitive material records a volume phase hologram due to its high diffraction efficiency and low noise characteristics. It is the most widely used material for working. By the way, this photosensitive material has a short shelf life,
Since it must be prepared each time it is prepared and wet development is performed, the hologram is deformed in the process of swelling and contracting gelatin required for hologram preparation, resulting in poor hologram reproducibility and a silver salt sensitive material. Requires a complicated process after recording and is not a satisfactory light-sensitive material from the viewpoint of stability and workability. In addition, all of these above-mentioned light-sensitive materials have a problem that they are inferior in environmental resistance characteristics such as humidity resistance and weather resistance.

On the other hand, a hologram recording material using poly-N-vinylcarbazole is a material having excellent environmental resistance and having the characteristics that a hologram recording material should have such as high resolution and high diffraction efficiency. can give. For example, a hologram recording material comprising a cyclic cis-α-dicarbonyl compound as a crosslinking agent and a sensitizer (JP-A-60-45).
283), 1,4,5,6,7,7-hexachloro-5-norbornene-anhydrous-2,3-dicarboxylic acid, and a hologram recording material comprising a dye (JP-A-60-227).
280), a hologram recording material composed of 2,3-bornanedione and thioflavin (JP-A-60-2600).
80), holograms composed of thioflavin T and iodoform (Japanese Patent Laid-Open No. 62-123489), and the like. However, since these hologram recording materials also require wet development, they require complicated processing steps and are inferior in reproducibility. Further, they are photosensitive materials containing poly-N-vinylcarbazole as a main ingredient. Therefore, although it is chemically stable, has high resolution, and is excellent in environmental resistance, poly-N-vinylcarbazole is easily crystallized and whitens easily, reproducibility of transparency is poor, and the solvent is limited. It has the problem of being lost. In addition, further improvement in sensitivity characteristics is desired.

Further, as a material which can be photocured with high sensitivity, a photocurable resin composition which is used in combination with 3-ketocoumarins and a diaryl iodonium salt, which are constituent components of a photopolymerization initiator, is disclosed in JP-A-60-88005. ), And a hologram recording material (JP-A-4-31590) in which the photopolymerization initiator is combined with polymethylmethacrylate as a supporting polymer has been proposed, and is chemically stable and has high resolution and high sensitivity. Although it has a, to form voids by wet processing, the dispersion of the peak wavelength of the reproduction wavelength and the expansion of the half-value width of the peak wavelength, also, at the time of development, because the bile polymer is slightly dissolved in the swelling solvent, There is a problem that uneven development is likely to occur, and moreover, since there are many voids in the hologram, the problem is that heat resistance and heat and pressure resistance are poor. It has.

Therefore, 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. 365.
It is disclosed in Japanese Patent No. 8526. The former has two types of light-sensitive materials, and as a first example, a combination of two polymerizable unsaturated ethylenic monomers having different reactivity and refractive index and a photopolymerization initiator, such as cyclohexyl methacrylate, N-. A photosensitive resin composition composed of vinylcarbazole and benzoin methyl ether, which can be hologram-recorded by sandwiching it between two glass plates and exposing with a two-beam optical system. 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 it is polymerized, and a refractive index different from those of the two monomers are used. Which is composed of four components of a non-reactive compound and a polymerization initiator, such as butyl methacrylate, ethylene glycol dimethacrylate, 1-phenylnaphthalene and benzoin methyl ether, and a hologram can be prepared in the same manner as in the first example. Resin composition. No matter which photosensitive resin composition is used, the polymerization of the more reactive monomer proceeds at the portion where the light intensity of the interference fringes formed by the two light fluxes becomes strong, and a monomer concentration gradient occurs, resulting in a highly reactive monomer. Is diffused into a portion having a high light intensity, and a monomer or non-reactive compound having a low reactivity is diffused into a portion having a low light intensity. In this way, interference fringes are recorded with a difference in refractive index, and a volume phase hologram is formed.

The latter 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 produces a permanent volume phase hologram. The formed hologram is fixed by subsequent blanket irradiation with actinic radiation.

Further, as an improved technique including the method for producing a hologram recording material disclosed in US Pat. No. 3,658,526, US Pat. No. 4,942,112 and US Pat. No. 5,098,803, and JP-A-2-3081 and 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 either a thermoplastic resin or a polymerizable unsaturated ethylenic monomer is added to improve the refractive index modulation. A compound having an aromatic ring is used to obtain a difference in refractive index, and like the one disclosed in US Pat. No. 3,658,526, a high molecular weight resin is used as a binder matrix so that the monomer at the time of exposure can be improved. Due to the limitation of diffusibility, a large amount of exposure is required and high diffraction efficiency cannot be obtained. Therefore, a non-reactive plasticizer is added.

Further, according to Japanese Patent Laid-Open No. 5-107999, there is proposed a composition in which a cationically polymerizable monomer and a cationic polymerization initiator are blended in place of the plasticizer in the above patent. Further, 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 JP-A-5-9.
4014.

[0014]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The above-mentioned volume phase hologram recording materials have problems of polymerizability or dispersibility of a monomer for obtaining a refractive index modulation, and a carrier carrying the monomer and a non-reactive additive. There are problems such as storage stability due to addition, workability in hologram production, hologram efficiency such as hologram obtained, transparency, and reproducibility of hologram characteristics, but especially dry developing method is used. In photopolymerizable photosensitive materials, the problem common to all is that the sensitizing dye used during hologram formation remains in the system as it is, resulting in the problem of colored holograms, and particularly high transmittance is required. This is a serious problem in the application of optical elements such as head-up display (HUD). Therefore, the present invention is capable of forming a hologram by a dry process, is highly transparent, has excellent weather resistance, and has high resolution, high diffraction efficiency, and excellent reproduction wavelength reproducibility. PROBLEM TO BE SOLVED: To provide a method for producing a transparent recording medium and a transparent hologram using the same.

[0015]

The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 uses the same radiation as the reference light which is coherent actinic radiation in the recording medium. In a photosensitive recording material for a transparent hologram, which forms an interference pattern by entering a certain target light to form a hologram, (A) a solvent-soluble resin which is solid at room temperature and atmospheric pressure, and (B) A polymerizable monomer which is liquid at room temperature and pressure and has at least one radically polymerizable ethylenically unsaturated bond having a boiling point of 100 ° C. or higher at normal pressure and having a refractive index different from that of the component (A); , (C) a photoinitiator that activates radical polymerization upon exposure to actinic radiation, (D) a sensitizing dye having an amino group that sensitizes the photoinitiator (C), (E) light or heat, etc. The external action of A photosensitive recording material for the transparent hologram, characterized in that a compound that generates a phosphate derivative.

The invention of claim 2 is characterized in that in the photosensitive recording material for transparent hologram of claim 1, the compound which produces a sulfonic acid derivative is represented by the following general formula (1).

Embedded image (In the formula, R represents that the aromatic ring is substituted with one or more substituents consisting of a hydrogen atom, an alkyl group, a halogen group, a nitro group, a hydroxyl group, a cyano group, an amino group or an alkoxy group.)

According to a third aspect of the present invention, a photosensitive layer prepared by dissolving the photosensitive recording material for transparent hologram according to the first aspect in a solvent is applied onto a substrate and dried, and a protective layer. A photosensitive recording medium for a transparent hologram, characterized by comprising:

According to a fourth aspect of the invention, the photosensitive layer of the transparent hologram photosensitive recording medium according to the third aspect is subjected to holographic exposure to form a latent image, and then externally exposed to light or heat. A method for producing a transparent hologram, characterized in that the sensitizing dye having an amino group is fading or decolored by a sulfonic acid derivative produced from a compound which acts to produce the sulfonic acid derivative.

[0019]

According to the present invention, the radical-polymerizable aliphatic monomer (B) is uniformly distributed in the resin (A) which is soluble in a solvent and solid at room temperature and atmospheric pressure. The radical polymerization active species generated from the photoinitiator (D) by the action of the sensitizing dye (C) by the photoinitiator (D) at the site of strong laser light interference in the laser irradiation site by irradiating with the interference light As a result, as the aliphatic monomer (B) is polymerized and polymerized, a difference in concentration occurs, so that the aliphatic monomer (B) diffuses and moves from the surroundings. That is, the monomer concentration is high in a portion of the laser-irradiated portion having a strong optical interference action, and is low in a portion of the laser-irradiated portion having a weak optical interference action. Further, the resin (A) is extruded to a portion of the laser-irradiated portion where the light interference action is weak, and the concentration thereof is increased, and the concentration of the portion of the laser-irradiated portion where the light interference action is strong is lowered. As a result, a difference in refractive index occurs between the two parts, so that a latent image of the hologram is recorded.

Then, by adding a compound (E) which generates a sulfonic acid derivative by an external action such as light or heat, an external action such as light or heat is given after the hologram is formed, so that the recording medium is subjected to the external action. The residual sensitizing dye (D) having an amino group is discolored / erased by the sulfonic acid derivative. That is, in the sensitizing dye (D) added to the photosensitive recording material, the compound (E) that generates a sulfonic acid derivative added in advance forms the sulfonic acid derivative by an external action such as light or heat. , Because the amino group of the sensitizing dye (D) is quaternized, the sensitizing dye (D)
Since the absorption wavelength region of the above shifts to the short wavelength side and shifts to the ultraviolet wavelength region, fading and decoloring occur in the visible region (400 to 700 nm). Further, the sensitizing dye (D) having a quaternized amino group has excellent weather resistance and storage stability, and does not cause coloration due to decomposition or the like even during storage for a long period of time, and a stable transparent hologram can be obtained.

The photosensitive recording material for transparent hologram of the present invention is excellent in refractive index modulation, diffraction efficiency, reproducibility of reproduction light peak wavelength and its bandwidth, and is also excellent in environment resistance. It can be applied to a hologram optical element such as a head-up display that requires high transparency.

[0022]

The present invention will be described in detail below. FIG. 1 is a schematic diagram for explaining the constitution of a transparent hologram photosensitive recording medium made of the transparent hologram photosensitive recording material of the present invention, and FIG. 2 is a schematic explanation for explaining a two-beam optical system for reflection hologram photographing. It is a figure.

The component (A) resin which is soluble in the solvent and solid at room temperature and atmospheric pressure, which constitutes the photosensitive recording material for transparent holograms of the present invention, is, for example, polymethacrylic acid ester, polyacrylic acid ester, or a portion thereof. Hydrolyzate, polyvinyl acetate, polystyrene, polyvinyl butyral, polyvinyl acetate, polyvinyl formal, polyvinyl acetal, polychloroprene, polyvinyl chloride, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose,
Chlorinated polyethylene, Chlorinated polypropylene, Poly-N
-Vinylcarbazole, poly-N-vinylpyrrolidone,
Polyacetic acid / vinyl acrylate, polyacetic acid / vinyl methacrylate, ethylene / vinyl acetate copolymer and styrene, maleic anhydride, acrylic acid, methacrylic acid, acrylic acid, acrylic acid ester, methacrylic acid ester,
Thermoplastic resins represented by copolymers composed of copolymerizable monomers such as acrylamide and methacrylamide, bisphenol A, bisphenol AD, bisphenol B, bisphenol AF, bisphenol S, novolac, o-cresol novolac, p- A thermosetting resin is typified by an epoxy resin produced by a condensation reaction of various phenol compounds such as alkylphenol novolac and epichlorohydrin. It should be noted that it is possible to use resins other than the resins listed above, and the present invention is not limited to these. Two or more kinds of these resins that are soluble in a solvent and are solid at room temperature and atmospheric pressure may be mixed and used.

Component (B) has at least one radically polymerizable ethylenically unsaturated bond which is liquid at normal temperature and pressure and has a boiling point of 100 ° C. or higher at normal pressure, and as component (A) The polymerizable monomer having a different refractive index includes at least one ethylenic unsaturated bond in the structural unit, and includes a polyfunctional vinyl monomer in addition to the monofunctional vinyl monomer, It may be a mixture of these. Actually, according to the above-mentioned theory of H. Kogelnik, component (A) and component (B)
It is desirable that the difference in the refractive index between and is 0.03 or more.

Specifically, high-boiling vinyl monomers such as (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, and aliphatic poly Hydroxy compounds, such as 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,
Di- or poly (meta) such as pentaerythritol, dipentaerythritol, sorbitol, mannitol
Acrylic esters, or alicyclic polyhydroxy compounds such as dimethylol tricyclodecane monoacrylate and dimethylol tricyclodecane diacrylate, and aromatic polyhydroxy compounds such as hydroquinone, resorcin, catechol, pyrogallol, and bisphenol A. Or poly (meth) acrylic acid ester,
Ethylene oxide-modified (meth) acrylic acid ester of isocyanuric acid, 2-phenoxyethyl methacrylate,
Phenol ethoxylate monoacrylate, p-chlorophenyl acrylate, KAYARAD-R551
(Trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

Component (C) of the present invention is a photoinitiator system that activates radical polymerization upon exposure to actinic radiation.
Macromolecules, 10 , 1307 (19)
77). A compound described in 1. such as diphenyliodonium, ditolyliodonium, phenyl (p-anisyl)
Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium,
Chloride, bromide, or borofluoride of iodonium such as bis (p-chlorophenyl) iodonium,
In addition to iodonium salts such as hexafluorophosphate salts and hexafluoroarsenate salts, triarylsulfonium salts, triarylphosphonium salts, and iron arene complexes, tert-butyl peroxide-i
so-butarate, 2,5-dimethyl-2,5-bis-
(Benzoyldioxy) hexane, 1,4-bis [α-
(Tert-Butyldioxy) -iso-propoxy]
Benzene, di-tert-butyl peroxide, 2,5
-Dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5-bis (hydroperoxy) -2,5-dimethylhexane, tert -Butyl hydroperoxide,
1,1-bis (tert-butyldioxy) -3,3
5-trimethylcyclohexanone, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, 2,2'5,5'-tetra (t
ert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4
4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t
ert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, t
ert-butyl peroxybenzoate, di-tert
-Organic peroxides such as butyldiperoxyisophthalate, quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone , Benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, and other benzoin derivatives.

Further, as the component (D) sensitizing dye having one or more kinds of amino groups for sensitizing the photoinitiator (C) of the present invention, specifically, rhodamine B, crystal violet, malachite green, auramine. O, phosphine R, acridine orange, acridine yellow, cetoflavin T, brilliant claisle blue, neutral red, thionine, methylene blue, indigo, pinacyanol, tetraphenylporphyrin, 3,3'-
Carbonyl bis (7-diethylaminocoumarin), 3-
(2'-benzothiazole) -7-diethylaminocoumarin, 3- (2'-benzimidazole) -7-diethylaminocoumarin, 3,3'-carbonylbis (7-dimethylaminocoumarin), 7-diethylamino-5 ',
7'-dimethoxy-3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3
-Benzoyl-7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 7-dimethylamino-3- (4-iodobenzoyl) coumarin, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 2-benzoyl- 3- (p-dimethylaminophenyl) -2-propenenitrile, 2,5-bis {[4
-(Diethylamino) -phenyl] methylene} -cyclopentanone, 2,5-bis {[4- (dimethylamino)
-Phenyl] methylene} -cyclopentanone, 2,6-
Bis {[4- (diethylamino) -phenyl] methylene} -cyclohexanone, 2,6-bis {[4- (dimethylamino) -phenyl] methylene} -cyclohexanone, 3-ethyl-2-[(3-ethyl-2 -Benzothiazolinylidene) methyl] -3H-benzothiazolinium iodide, 3-ethyl-2-[(1-ethyl-2 (1
H) -quinolilidene) methyl] benzothiazolinium iodide, 3-ethyl-2- [3- (3-ethyl-2-benzoxazolinylidene) -1-propenyl] benzoxazolinium iodide. 3-ethyl-5- [2- (3
-Ethyl-2-benzorialinidene) ethylidene] rhodamine, 2- (p-dimethylaminostyryl) -1-ethylpyridiniodide, 2- (p-dimethylaminostyryl) -1-ethylpyridinium iodide, 2 -(P-
Examples thereof include dimethylaminostyryl) -3-ethylbenzothiazolinium iodide. In addition, many dye compounds having an amino group described in "Dye Handbook" (Shin Okawara, Tejiro Kitao, Tsuneaki Hirashima, Ken Matsuoka, Kodansha 1986) can be used in the present invention. Further, these sensitizing dyes can be selected so as to match the wavelength of the actinic radiation different depending on the intended use of the hologram, and two or more kinds can be used in combination depending on the application.

Next, the component (E) of the present invention, which is a compound which forms a sulfonic acid derivative by an external action such as light or heat, is represented by the following general formula (1) by an external action such as light or heat. Any sulfonic acid derivative can be produced.

Embedded image (In the formula, R represents that the aromatic ring is substituted with one or more substituents consisting of a hydrogen atom, an alkyl group, a halogen group, a nitro group, a hydroxyl group, a cyano group, an amino group or an alkoxy group.)

Specific examples of the compound of component (E) include diphenyliodonium trifluoromesylate and 4-
Methoxydiphenyliodonium trifluoromesylate, bis (4-tert-butylphenyl) iodonium trifluoromesylate, diphenyliodonium mesylate, 4-methoxydiphenyliodonium mesylate, bis (4-tert-butylphenyl) iodonium mesylate, diphenyl Iodonium tosylate,
4-methoxydiphenyliodonium tosylate, bis (4-tert-butylphenyl) iodonium tosylate, bis (bis (4-tert-butylphenyl) iodonium) 1,3-benzenesulfonate, 2,6-
Dinitrobenzyl tosylate, 2,6-dinitrobenzyl mesylate, triphenylsulfonium, trifluoromesylate, 4-methoxytriphenylsulfonium trifluoromesylate, 4-methyltriphenylsulfonium trifluoromesylate, 4-fluorotriphenyl Sulfonium trifluoromesylate, benzoin tosylate, pyrogallol trimesylate, 2-nitrobenzyl tosylate, 4,5-dimethoxy-2-nitrobenzyl tosylate, diphenyldisulfone, di (p
-Tolyl) disulfone, DAM-101 (manufactured by Midori Kagaku), DAM-201 (manufactured by Midori Kagaku), PI-10
5 (made by Midori Kagaku), NDI-105 (made by Midori Kagaku), NAI-105 (made by Midori Kagaku), diphenyliodonium, 9,10-diethoxyanthracene sulfonate, p-nitrobenzyl-9,10-di Ethoxyanthracene-2-sulfonate, p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, benzyl p-chlorobenzene sulfonate, benzyl m-chlorobenzene sulfonate, benzyl p-methoxybenzene sulfonate, benzyl p-cyanobenzene sulfonate, p -Chlorobenzyl, p-chlorobenzene sulfonate, m-chlorobenzyl p-chlorobenzene sulfonate, p-bromobenzyl p-chlorobenzene sulfonate, m-bromobenzyl p-chlorobenzene sulfonate p- ethylbenzyl p- chlorobenzene sulfonate, tosylate, p- hydroxybenzyl tosylate, m- hydroxy tosylate, p- methoxybenzyl tosylate, m- methoxybenzyl tosylate, p- methyl tosylate,
m-methylbenzyl tosylate, p-chlorobenzyl tosylate, m-chlorobenzyl tosylate, p-nitrobenzyl tosylate, m-nitrobenzyl tosylate,
Examples thereof include p-bromobenzyl tosylate, m-bromobenzyl tosylate, p-cyanobenzyl tosylate, and m-cyanobenzyl tosylate.

However, the present invention is not limited to these,
It is also possible to use a sulfonic acid ester generally obtained by reacting a corresponding alcohol with an acid chloride of a sulfonic acid derivative such as p-toluenesulfonyl chloride or methylsulfonyl chloride. You may use these in combination of 2 or more types.

The light and heat sensitive recording material for transparent holograms of the present invention comprises (A) a solvent-soluble resin, a solvent-soluble resin which is solid at room temperature and normal pressure, and (B) a liquid which is liquid at normal temperature and normal pressure. And a polymerizable monomer having at least one radically polymerizable ethylenic unsaturated bond having a boiling point of 100 ° C. or higher under normal pressure and having a refractive index different from that of the resin (A), and (C) actinic radiation Photoinitiator that activates radical polymerization when exposed to light, (D) a sensitizing dye having an amino group that sensitizes the photoinitiator (C), and (E) a sulfonic acid by an external action such as light or heat. The mixture ratio of the resin (A) and the polymerizable monomer (B) is high because the resin (A) and the polymerizable monomer (B) have a high refractive index because the amount of the monomer polymerized by laser holographic exposure is insufficient. Got rate modulation If the polymerizable monomer (B) is excessive, the monomer remaining in the system without being polymerized in the first holographic exposure causes polymerization while diffusing in the manufacturing process, and the hologram once formed Since the interference fringes of 1 may be disturbed and high refractive index modulation may not be obtained, it is necessary to pay attention to the mixing ratio.
Regarding the combination of the resin (A) and the polymerizable monomer (B) for obtaining a bright hologram, for example, the above-mentioned U.S. Pat. No. 4,942,112, U.S. Pat. No. 5,098,803, and Japanese Unexamined Patent Publication (Kokai) No. 2-3081, JP-A-2-3082, JP-A-5-107999, JP-A-5-94014, or Japanese Patent Application No. 6-46742, Japanese Patent Application No. 6-149796, Japanese Patent Application No. 6-149797 by the present applicant. , Japanese Patent Application No. 6-149798, Japanese Patent Application No. 6-148244, Japanese Patent Application No. 6-148245,
It is described in Japanese Patent Application No. 6-178812. The amount of the component (C) photoinitiator is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the component (A). Furthermore, the sensitizing dye of the component (D) can be in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the component (A).

As described above, the respective components of the light and heat sensitive recording material for transparent hologram are appropriately selected, and the photosensitive liquid obtained by mixing them at an arbitrary ratio is used by a known coating means such as a spin coater, a roll coater or a bar coater. As shown in FIG. 1, a substrate 2 such as a glass plate, a polycarbonate plate, a polymethylmethacrylate plate, or a polyester film is coated in a film form.
The transparent hologram photosensitive recording medium 1 for ordinary hologram imaging in which the hologram shown in FIG. Further, a protective layer 4 may be provided as an oxygen blocking film on the photosensitive layer 3. As the protective layer 4, for example, a material equivalent to that of the substrate 2 described above, or an optically transparent material such as polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol or polyethylene terephthalate, or glass, is used to sandwich the photosensitive layer. It is formed by laminating, stacking with an extruder, or coating a solution. When the photosensitive solution is applied, it may be diluted with an appropriate solvent if necessary, but in that case, it is necessary to dry it after applying it on the substrate.

If desired, various additives such as known thermal polymerization inhibitors, chain transfer agents, and antioxidants may be added to the light and heat sensitive recording material for transparent holograms of the present invention.

FIG. 2 is a schematic diagram for explaining a two-beam optical system for reflection type hologram photographing. 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 recording medium 1 is irradiated with the light. In the present invention, after the hologram photographing by exposure, the fixing process is dry-processed (light irradiation and / or
Or heat treatment). Although not described in detail and shown in the drawings, the present invention can be similarly applied to the production of a transmission hologram, and a transmission hologram having excellent hologram characteristics can be obtained.

A helium-cadmium laser, an argon laser, a krypton laser, a helium neon laser, or the like can be used as a light source suitable for the photosensitive recording material for transparent hologram of the present invention in the exposure process of the interference pattern, but it is not limited thereto. It is not something that will be done.

Further, as a means for generating a sulfonic acid derivative by an external action after hologram production, as a whole surface exposure with a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an oven or the like. There is heating by a hot plate or the like, but the heating is not limited to this. Also, two or more of these methods may be combined. The external action is so-called external stimulus, and there is a specific acid in addition to light and heat.

When a hologram image is recorded on this transparent hologram photosensitive recording medium 1, laser irradiation is applied in accordance with a desired image so that a portion of the laser-irradiated portion having a strong optical interference action is soluble in a solvent at room temperature. At least one radically polymerizable ethylenically unsaturated bond that is uniformly dispersed in a resin (A) that is a solid at normal pressure, is a liquid at normal temperature and normal pressure, and has a boiling point of 100 ° C. or higher at normal pressure. When the polymerizable monomer (B) having one or more and different refractive index from the component (A) is exposed to laser (laser interference light) to be exposed to light, it is polymerized and polymerized by the action of the photopolymerization initiator. The movement of the surrounding radically polymerizable polymerizable monomer (B) occurs. Therefore, the concentration of the radical-polymerizable polymerizable monomer (B) is high at the portion of the laser irradiation portion where the light interference is strong, and the concentration of the radical-polymerizable polymerizable monomer (B) is at the portion where the light interference action is weak. Therefore, the refractive index modulation occurs due to the difference in the refractive index due to the difference in the density between the part of the transparent hologram photosensitive recording medium 1 where the light interference is strong and the part where the light interference is weak, and the hologram image is recorded. Is. Further, in the sensitizing dye (D) having the amino group, which remains in the recording medium after the hologram formation, the compound (E) which generates a sulfonic acid derivative added in advance is generated by an external action such as light and heat. Since the amino group of the sensitizing dye (D) is quaternized by the sulfonic acid derivative, the absorption wavelength range of the sensitizing dye (D) shifts to the short wavelength side and shifts to the ultraviolet wavelength range. Discoloration / decoloration at 700 nm) occurs. Further, the sensitizing dye (D) having a quaternized amino group has weather resistance,
It has excellent storage stability, and even when it is stored for a long period of time, it will not be colored due to decomposition and the like, and a stable transparent hologram can be obtained.

Hereinafter, the present invention will be described in more detail with reference to specific examples. <Example 1> Bisphenol A type epoxy resin (trade name "Epicoat 1007" manufactured by Yuka Shell Epoxy Co., Ltd.) 1
00 parts by weight, triethylene glycol diacrylate 5
0 parts by weight, 5 parts by weight of diphenyliodonium hexafluorophosphate, 1 part by weight of 3,3′-carbonylbis (7-diethylamino) coumarin, and 5 parts by weight of 2-nitrobenzyl tosylate were mixed and dissolved in 200 parts by weight of 2-butanone. The obtained solution was used as a photosensitive solution. This photosensitive solution is applied on a glass substrate so as to have a film thickness of about 15 μm to form a photosensitive layer, and then polyvinyl alcohol (PV
A) The film was covered with a film to prepare a photosensitive recording medium 1 for transparent hologram.

The photosensitive recording medium 1 for transparent hologram was used as a light source for the hologram recording two-beam optical system shown in FIG. 2 as an argon laser (514.5 nm, exposure amount 20 mJ).
/ Cm ² ) to expose a hologram image, and then heat treatment was performed at 100 ° C. for 30 minutes. Furthermore, in order to photolyze 2-nitrobenzyl tosylate, light irradiation of 100 mJ / cm ² was performed with a high pressure mercury lamp.

The obtained hologram was recorded in the visible light region (400-
It was 90 when the average transmittance at 700 nm) was measured.
%showed that. Further, when this hologram was heat-treated at 150 ° C. for 1 hour, coloring of the sheet due to oxidation did not occur, and similarly, the visible light range (400 to 70
The average transmittance at 0 nm) was 90%. The transmittance before the treatment with the sulfonic acid derivative is around 60% T. The diffraction efficiency of the hologram was measured with a spectrophotometer manufactured by JASCO Corporation. This spectrophotometer is a photomultimeter having a slit with a width of 3 mm and a radius of 2 with the sample as the center.
It can be installed on the circumference of 0 cm. As the measurement conditions, 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 largest value other than the specularly reflected light and the value obtained when the incident light was directly received without placing the sample. As a result, the diffraction efficiency was 95% and the refractive index modulation was 0.0204.

<Example 2-5> 3- (2'- of Example 1)
Benzothiazole) -7-diethylaminocoumarin (D
3,3′-carbonylbis (7- instead of ye-1)
Diethylaminocoumarin) (Dye-2), 2,5-bis {[4- (diethylamino) -phenyl] methylene}
-Cyclopentanone (Dye-3), 2,6-bis {[4- (dimethylamino) -phenyl] methylene}-
Cyclohexanone (Dye-4), 3-ethyl-5-
[2- (3-Ethyl-2-benzoriazolinylidene) ethylidene] Rhodanine (Dye-5) is used, except that
The same procedure as in Example 1 was performed to measure the average transmittance of the hologram at each time point. This is shown in Table 1 together with the results of Example 1. However, T-1 is the average transmittance of the sheet in the visible light range (400 to 700 nm) after irradiation with light, and T-2 is 150 ° C.
Visible light region (400-700nm) after heating for 1 hour
The average transmittance of the sheet in FIG. In addition, D. E. FIG. And R.A. I. C indicates diffraction efficiency and refractive index modulation, respectively.

[0042]

[Table 1]

Dye-1: 3- (2'-benzothiazole) -7-diethylaminocoumarin Dye-2: 3,3'-carbonylbis (7-diethylaminocoumarin) Dye-3: 2,5-bis {[4 -(Diethylamino)
-Phenyl] methylene} -cyclopentanone Dye-4: 2,6-bis {[4- (dimethylamino)
-Phenyl] methylene} -cyclohexanone Dye-5: 3-ethyl-5- [2- (3-ethyl-2
-Benzodiazolinylidene) ethylidene] rhodamine

<Example 6-10> Bisph of Examples 1-5
Enol A type epoxy resin (trade name "Epicoat 100
7 ”Vinyl acetate instead of Yuka Shell Epoxy Co., Ltd.
With triethylene glycol diacrylate
Instead of KAYARAD-R551 (trade name Nippon Kayaku
Except that the holograms are manufactured in the same manner as in Example 1 except that
Fabricate and measure average transmittance, diffraction efficiency, refractive index modulation
Was. The evaluation results are shown in Table 2. However, T-1 is 1
After heat treatment at 00 ℃ for 30 minutes, use a high pressure mercury lamp for 100
mJ / cm ²Visible light range (400
The average transmittance of the sheet at (-700 nm) was measured.
And T-2 was added at 150 ° C for 1 hour.
Shear in the visible light range (400-700 nm) after heating
The average transmittance of the glass sheet is measured.

[0045]

[Table 2]

<Embodiment 11-15> 2-of Embodiments 1 to 5
A hologram was prepared in the same manner except that p-methoxybenzyl tosylate was used instead of nitrobenzyl tosylate. In addition, p instead of 2-hydroxytosylate
When -methoxybenzyl tosylate was used, heat treatment was carried out at 130 ° C. for 10 minutes instead of light irradiation by a high pressure mercury lamp to generate a sulfonic acid derivative (p-toluenesulfonic acid). Similarly, the average transmittance, diffraction efficiency, and refractive index modulation of the hologram plate were measured. This is shown in Table 3. However, T-1 is the average transmittance of the sheet in the visible light region (400 to 700 nm) when heat-treated at 100 ° C. for 30 minutes and then at 130 ° C. for 10 minutes, and T-2 is a visible light region (400 to 70 after heating at 150 ° C. for 1 hour).
The average transmittance of the sheet at 0 nm) is measured.

[0047]

[Table 3]

<Example 16-20> A hologram was prepared in the same manner as in Example 11 except that 2-phenylethyl tosylate was used instead of p-methoxybenzyl tosylate in Examples 11 to 15, and the average transmittance was obtained. The diffraction efficiency and the refractive index modulation were measured. The evaluation results are shown in Table 4. However,
T-1 is 130 ° C after heat treatment at 100 ° C for 30 minutes
Visible light range (400 ~
The average transmittance of the sheet at 700 nm) was measured, and T-2 was the average transmittance of the sheet in the visible light range (400 to 700 nm) after further heating at 150 ° C. for 1 hour. is there.

[0049]

[Table 4]

<Comparative Example 1-5> In Examples 1 to 5,
A hologram was prepared in the same manner except that 2-nitrobenzyl tosylate was not added, and the average transmittance, diffraction efficiency and refractive index modulation were measured in the same manner. The evaluation results are shown in Table 5. However, T-1 is the average transmittance of the sheet in the visible light range (400 to 700 nm) after heat treatment at 100 ° C. for 30 minutes, and T-2 is 150 ° C. for 1 hour. Visible light range (400-
The average transmittance of the sheet at 700 nm) is measured. Regarding the diffraction efficiency and the refractive index modulation, almost no change was observed even when 2-nitrobenzyl tosylate, which is a compound that produces a sulfonic acid derivative by an external action such as light or heat, was not added, but the transparency was improved. There was a large difference, and the light transmittance was 20 to 30% lower when not added, and further decreased when heated to 150 ° C.

[0051]

[Table 5]

<Comparative Example 6-10> A hologram was similarly prepared in the same manner as in Examples 16 to 20 except that 2-phenylethyl tosylate was not added.
The diffraction efficiency and the refractive index modulation were measured. Table 6 shows the evaluation results.
Shown in However, T-1 is the average transmittance of the sheet in the visible light range (400 to 700 nm) after heat treatment at 100 ° C. for 30 minutes, and T-2
Is a visible light region (4
The average transmittance of the sheet in the range of 0 to 700 nm) is measured. Similar to Comparative Examples 1 to 5, there is almost no change in diffraction efficiency and refractive index modulation even when 2-nitrobenzyl tosylate, which is a compound that produces a sulfonic acid derivative by an external action such as light or heat, is not added. I can not see it, but there is a big difference in transparency,
When it was not added, the light transmittance was 20 to 30% lower, and particularly when it was heat-treated at 150 ° C., it was further lowered.

[0053]

[Table 6]

<Comparative Example 11> A hologram was prepared in the same manner as in Example 1 except that 2-nitrobenzyl tosylate was not added, and light was emitted using a high pressure mercury lamp so that the same degree of fading as that in Example was produced. When irradiation was performed, the average transmittance of the sheet in the visible light range (400 to 700 nm) remained at about 80% even when light energy of 10 J / cm ² was applied.

[0055]

As described above, according to the present invention, (A) a solvent-soluble resin at room temperature and a solid at atmospheric pressure, and (B) room temperature,
At least one radically polymerizable ethylenically unsaturated bond that is liquid at normal pressure and has a boiling point of 100 ° C. or higher at normal pressure
And (C) a photoinitiator that activates radical polymerization upon exposure to actinic radiation, and (D) a photoinitiator (C). By being composed of a sensitizing dye having an amino group to be sensitized and (E) a compound that produces a sulfonic acid derivative by an external action such as light or heat, high transparency in the visible light region is obtained especially in dry processing. As well as getting
It is possible to provide a hologram that is excellent in weather resistance such as heat resistance and is chemically stable. In particular, it can be used as a transparent hologram photosensitive recording material for a hologram optical element (HOE) having extremely high performance requirements such as a head-up display.

[Brief description of drawings]

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

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

[Explanation of symbols]

 1 Transparent Holographic Photosensitive Recording Medium 2 Substrate 3 Photosensitive Layer 4 Protective Layer 5 Laser 6 Laser Light 7 Mirror 8 Beam Splitter 9 Spatial Filter 10 Lens 11 Lens

Claims (4)

[Claims] 1. A photosensitive recording material for a transparent hologram, wherein a reference light, which is coherent chemical action radiation, and a target light, which is the same radiation, are incident on a recording medium to form an interference pattern to form a hologram. Specifically, (A) a solvent-soluble resin that is solid at room temperature and atmospheric pressure, and (B) a radical-polymerizable ethylenic unsaturated that is liquid at room temperature and atmospheric pressure and has a boiling point of 100 ° C. or higher at atmospheric pressure. A polymerizable monomer having at least one bond and having a refractive index different from that of the component (A), (C) a photoinitiator which activates radical polymerization upon exposure to actinic radiation, and (D) a photoinitiator. A sensitizing dye having an amino group for sensitizing (C), and (E)
1. A photosensitive recording material for transparent hologram, comprising a compound which produces a sulfonic acid derivative by an external action such as light or heat. 2. The photosensitive recording material for a transparent hologram according to claim 1, wherein the sulfonic acid derivative produced by an external action such as light or heat is represented by the following general formula (1). Embedded image (In the formula, R represents that the aromatic ring is substituted with one or more functional groups consisting of a hydrogen atom, an alkyl group, a halogen group, a nitro group, a hydroxyl group, a cyano group, an amino group or an alkoxy group.) 3. A photosensitive layer comprising a photosensitive layer prepared by dissolving the photosensitive recording material for transparent hologram according to claim 1 in a solvent and coating the same on a substrate, followed by drying, and a protective layer. A characteristic photosensitive recording medium for transparent holograms. 4. The photosensitive layer of the transparent hologram photosensitive recording medium according to claim 3 is subjected to holographic exposure to form a latent image, and then an external action such as light or heat is applied to the photosensitive layer so that the sulfone is removed. A method for producing a transparent hologram, characterized in that the sensitizing dye having an amino group is fading or decolored with a sulfonic acid derivative produced from a compound producing an acid derivative.