JPH11161138A - Hologram recording medium and production of hologram - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a hologram recording medium of a volume phase type which is good in adhesiveness to a base material and a hologram layer, is excellent in weather resistance, heat resistance and preservable stability and is good in various characteristic values, such as resolution, diffraction efficiency and transparency and a hologram. SOLUTION: The hologram layer 3 consisting of a resin which is solvent soluble and is solid at and under ordinary temp. and atm. pressure, a polymerizable monomer which has a b.p. of >=100 deg.C under atm. pressure, has at least >=1 radical polymerizable ethylenic unsatd. bond and has the refractive index different from the refractive index of the resin, a photoinitiator, a dyestuff sensitizing agent capable of sensitizing the photoinitiator and a silane coupling agent is formed on a base material 2 at least the surface of which is inorg. As a result, the hologram which obviates the peeling of the hologram layer 3 from the base material 2 is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is sensitive to visible light such as argon laser light with high sensitivity, and is excellent in weather resistance, heat resistance and storage stability, as well as in resolution, diffraction efficiency and transparency. The present invention relates to a hologram recording medium for manufacturing a volume phase hologram having good hologram characteristics and a method for manufacturing a hologram.

[0002]

2. Description of the Related Art A hologram is obtained by recording an interference wavefront of coherent light such as a laser in a recording medium such as a photopolymer as a refractive index distribution or an absorbance distribution. This hologram is capable of reproducing a three-dimensional stereoscopic image. Because of its excellent design and decorative effects, it is used for covers of books and magazines, displays such as POPs, and gifts. In particular, volume phase holograms have a refractive index rather than optical absorption in the hologram recording medium. By forming different spatial interference fringes, it is possible to modulate the phase without absorbing the light beam passing through the image, and in recent years, a hologram optical element (hereinafter, referred to as HOE),
For example, a head-up display (HU)
Application to a combiner for D) is expected.

[0003] The general principle of hologram fabrication is described in several documents and specialized books, for example, Chapter 2 of "Holographic Display" (Junhei Tsujiuchi, Sangyo Tosho). According to these, a recording object is irradiated with one of two bundles of coherent light, generally laser light, on a recording object, and a photosensitive recording medium, for example, a photographic dry plate, is placed at a position where it can receive total reflected light from the object. The coherent light in addition to the reflected light from the object is directly applied to the recording medium without being applied to the object. The light reflected from the target is referred to as target light, and the light directly illuminating the recording medium is referred to as reference light, and interference fringes between the reference light and the target light are recorded as holograms (image information).

[0004] When the recording medium thus treated is exposed to light from an irradiation light source and observed at an appropriate eye position, the light from the irradiation light source emits light from the object during recording to the recording medium. Since the light is diffracted by the hologram that reproduces the wavefront of the reflected light that has arrived first, a three-dimensional object image similar to the real image of the target object is observed. The hologram formed by allowing the reference light and the target light to enter the recording medium from the same direction is a transmission hologram, and the hologram formed by allowing the reference light and the target light to enter from opposite sides of the recording medium is reflected. It is a type hologram. Transmission holograms are disclosed, for example, in US Pat. No. 3,506,327 and US Pat.
787, etc., and the reflection type hologram can be obtained, for example, in US Pat.
It can be obtained by a known method disclosed in US Pat.

[0005] The volume phase hologram recording material constituting such a volume phase hologram is sensitive to laser light having a visible oscillation wavelength with high sensitivity and exhibits high resolution. In use, hologram diffraction efficiency, reproduction light wavelength reproducibility, bandwidth (half width of reproduction light peak) and other characteristics are suitable for the purpose, and the hologram recording material itself is often a commercial product. Chemical stability, e.g. heat resistance, light resistance,
It is required that they have excellent environmental resistance such as moisture resistance and also have excellent transparency.

Heretofore, as a recording material for such a volume phase hologram, a photosensitive material based on bleached silver salt and gelatin based dichromate has been generally used. This dichromated gelatin based photosensitive material is most widely used for recording volume phase holograms due to its high diffraction efficiency and low noise characteristics, but this photosensitive material has a short shelf life,
Problems that must be adjusted each time a hologram is produced, and problems that hologram reproducibility is poor due to deformation of the hologram in the process of swelling and shrinking of gelatin required for hologram production by performing wet development. This method requires complicated processing after recording, and is not a photosensitive material 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.

To solve such problems, a hologram recording material composed of a cationically polymerizable thermosetting epoxy oligomer and a radically polymerizable ethylenic monomer (JP-A-8-1680, JP-A-8-44277) ). This hologram recording material can produce a hologram by a simple production method by dry processing, and the obtained hologram has excellent characteristics, and is excellent in environmental resistance such as light resistance and moisture resistance, high resolution, Has high diffraction efficiency. Also, a hologram recording material comprising a thermoplastic resin and an acrylic monomer (US Pat. No. 4,942,112)
No. 5,098,803, JP-A-2-30
No. 81, JP-A-2-3082, etc.) are also materials which have been improved from the viewpoint of stability and workability as compared with photographic materials based on bleached silver salts and gelatin dichromate.

[0008]

However, the above-mentioned hologram recording material has poor adhesion to a substrate to be applied when producing a hologram, and is formed on a substrate, particularly when the surface of the substrate is inorganic. There is a problem that the hologram layer is easily peeled off from the substrate, such a property is obtained only when the hologram layer is obtained, or after once forming the hologram layer,
It is useful when bonding to another substrate or sandwiching between other substrates, but it is often used to produce a hologram on the hologram layer on the substrate and use it as a hologram itself. It is desired to improve the adhesion between the hologram layer and the hologram layer.

According to the conventional bonding method, (1) after forming the hologram, the hologram layer is once peeled off from the base material, and a liquid adhesive is provided between the hologram layer and the base material, and is bonded.
(2) Before applying the hologram recording material to the substrate, an anchor layer may be applied on the substrate. In such a case, there is no deterioration of hologram characteristics, no distortion of diffracted light due to disorder of smoothness and flatness of the hologram layer due to adhesion, and no defect such as crack in the hologram layer. Has been requested. In the former bonding method (1), adhesives generally include a solvent dilution type, a hot melt type, and a polymerization type.

In the solvent dilution type, a rubber having adhesive properties is dissolved in an organic solvent, and then filled between objects to be bonded, and then solidified by vaporization of the solvent. When used in a hologram, the hologram is in contact with the solvent for a long time. Therefore, there is a risk that defects such as cracks may occur in the hologram and that the hologram characteristics may deteriorate. Furthermore, it is difficult to form a thin and uniform adhesive layer between the base material and the hologram layer, and there is a problem that the hologram product is liable to be optically distorted and the transmittance is reduced.

In the hot-melt type, since the base material and the hologram layer are bonded at a high temperature, deterioration of the hologram layer and deterioration of the hologram characteristics due to heat cannot be ignored. It is difficult to form a thin and uniform adhesive layer, and there is a problem that the hologram product is liable to be optically distorted and the transmittance is reduced.

The polymerization type is used for bonding optical parts and the like, and typically includes an epoxy-based adhesive, a silicone-based adhesive, and a polyester-based adhesive. Epoxy adhesives require high-temperature conditions or the addition of a catalyst such as an amine to cure the epoxy adhesive in a short time. Adhesives have poor adhesion between inorganic and organic materials, and polyester adhesives generally have high viscosity. When diluted with a monomer to improve workability, the monomer permeates the hologram layer and the hologram disappears It is difficult to form an adhesive layer thinly and uniformly between the base material and the hologram layer like other adhesives as a whole.
There is a problem that the hologram product is liable to be optically distorted and the transmittance is reduced.

In recent years, as a transparent adhesive used for optical applications such as a camera lens and an eyeglass lens,
Photopolymerization type (for example, product name "Hard Rock OP-1"
030M "," Hard Rock OP-1050M ", and" Hard Rock OP-1045K "manufactured by Denki Kagaku Kogyo Co., Ltd.). With such an adhesive, there is no problem such as a decrease in permeability. However, similarly to other adhesives, it is difficult to form a thin and uniform adhesive layer between the base material and the hologram layer, and there is a problem that air bubbles easily enter the adhesive layer. In addition, the fact that it is very expensive is one factor that hinders use.

In the latter bonding method (2), a resin coating is generally used as an anchor layer having good adhesion to a hologram layer on a transparent base material having an inorganic surface. However, as it is required to be optically transparent so as not to deteriorate the hologram characteristics and to be able to form uniformly, those containing an additive having a particle size that diffuses light cannot be used, Selection of the hologram recording material is difficult because the usable target is considerably limited, and further, when the hologram recording material is applied on the anchor layer, the anchor layer is slightly dissolved and mixed with the hologram recording material. There is a problem that adversely affects the characteristics. However, the anchor layer has poor adhesion to a transparent base material whose surface is inorganic, so that peeling at the interface is a problem.

Accordingly, the present invention provides good adhesion between the substrate and the hologram layer, excellent weather resistance, heat resistance and storage stability.
It is another object of the present invention to provide a volume phase type hologram recording medium and a method for manufacturing a hologram in which various hologram characteristic values such as resolution, diffraction efficiency, and transparency are good.

[0016]

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) a resin which is soluble in a solvent and is solid at normal temperature and pressure, and (B) a liquid which is liquid at normal temperature and pressure and has a boiling point of 10 at normal pressure.
(D) a polymerizable monomer having at least one radically polymerizable ethylenically unsaturated bond having a temperature of 0 ° C. or higher and having a different refractive index from the resin, (C) a photoinitiator,
A hologram layer comprising a dye sensitizer capable of sensitizing a photoinitiator and (E) a silane coupling agent is formed on a substrate whose surface is at least inorganic, at least for hologram recording. Medium.

According to a second aspect of the present invention, there is provided the hologram recording medium according to the first aspect, wherein the resin (A) is a cationically polymerizable thermosetting epoxy oligomer having at least one glycidyl group in its unit structure. And
(B) The polymerizable monomer is an aliphatic monomer.

According to a third aspect of the present invention, in the hologram recording medium according to the first or second aspect, the silane coupling agent (E) has at least one glycidyl group and an alkoxysilyl group in its structure. It is characterized by having.

According to a fourth aspect of the present invention, there is provided the hologram recording medium according to the first or second aspect, wherein (E) the silane coupling agent has at least one (meth) acryl group and an alkoxy group in its structure. It has a silyl group.

According to a fifth aspect of the present invention, in the hologram recording medium according to the first or second aspect, (E) the silane coupling agent has at least one or more amino groups and alkoxysilyl groups in its structure. It is characterized by having.

The invention according to claim 6 is characterized in that at least (A)
A resin that is solvent-soluble and is solid at normal temperature and pressure,
(B) liquid at normal temperature and pressure and boiling point of 100 ° C. at normal pressure
A polymerizable monomer having at least one or more radically polymerizable ethylenically unsaturated bonds and having a different refractive index from the resin (A), (C) a photoinitiator, and (D)
A hologram layer comprising a dye sensitizer capable of sensitizing a photoinitiator and (E) a silane coupling agent is formed at least on a substrate having an inorganic surface, and subjected to holographic exposure to produce a hologram. A method for producing a hologram, characterized in that:

According to a seventh aspect of the present invention, in the method for manufacturing a hologram according to the sixth aspect, the method comprises:
A hologram is manufactured by performing a heat treatment at 0 to 150 ° C.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
FIG. 1 is a schematic sectional view illustrating the configuration of a hologram recording medium according to the present invention, and FIG. 2 is a schematic view illustrating an optical system for photographing a reflection hologram.

The component (A) constituting the hologram layer of the hologram recording medium of the present invention is solvent-soluble,
Examples of the resin which is solid at normal pressure include, for example, polymethacrylates, polyacrylates and partial hydrolysates thereof, polyvinyl acetate, polyvinyl formal, polyvinyl acetal, polychloroprene, polyvinyl chloride, cellulose acetate, and cellulose. Acetate butyrate, methyl cellulose, ethyl cellulose,
Chlorinated polyethylene, chlorinated polypropylene, Poly N
-Vinyl carbazole, poly-N-vinyl pyrrolidone,
Polyacetic acid / vinyl acrylate, polyacetic acid / vinyl methacrylate, ethylene / vinyl acetate copolymers and copolymers of styrene, maleic anhydride, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamide, methacrylamide, etc. There are thermoplastic resins typified by copolymers of possible monomers, etc., and are solvent-soluble and have at least one glycidyl group in the unit structure.
Bisphenol A, bisphenol A
D, bisphenol B, bisphenol AF, bisphenol S, brominated bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol AD, hydrogenated bisphenol B, hydrogenated bisphenol S, hydrogenated bisphenol AF,
Hydrogenated brominated bisphenol A can be mentioned.
The present invention is not limited thereto, and any epoxy compound produced by a condensation reaction between various phenol compounds and epichlorohydrin can be used.
As described above, two or more of these may be used in combination.

The 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. As a polymerizable monomer having a different refractive index,
It contains at least one ethylenically unsaturated bond in the structural unit, contains a polyfunctional vinyl monomer in addition to a monofunctional vinyl monomer, or may be a mixture thereof. In practice, it is desirable that the difference in the refractive index between the component (A) and the component (B) is 0.03 or more according to the theory of H. Kogelnik described above.

Specifically, high-boiling vinyl monomers such as (meth) acrylic acid, itaconic acid, maleic acid, (meth) acrylamide, diacetone acrylamide, and 2-hydroxyethyl (meth) acrylate; 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) acrylate,
In addition to ethylene oxide-modified (meth) acrylate of isocyanuric acid and the like, 2-phenoxyethyl methacrylate, phenol ethoxylate monoacrylate,
p-chlorophenyl acrylate, KAYARAD-R
551 (trade name, manufactured by Nippon Kayaku Co., Ltd.).

The photoinitiator of the component (C) of the present invention includes
acromolecules, 10 , 1307 (197
7). And 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, iron arene complexes and the like, 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-propylhydroperoxide, 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
tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4
4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t
tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) -4,4′-dicarboxybenzophenone, t
tert-butyl peroxybenzoate, di-tert
Organic peroxides such as -butyldiperoxyisophthalate, and quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; Benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methyl benzoin and α-phenyl benzoin.

Further, the component (D) of the present invention capable of sensitizing the photoinitiator (D) The dye sensitizer includes, specifically, rhodamine B, crystal violet, malachite green, auramine O, phosphine R, acridine. Orange, acridine yellow, setoflavin T, brilliant clayle blue, neutral red, thionine,
Methylene blue, indigo, pinacyanol, tetraphenylporphyrin, 3,3′-carbonylbis (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- (dimethyl Amino) -phenyl] methylene} -cyclohexanone, 3-ethyl-2-
[(3-ethyl-2-benzothiazolinylidene) methyl] -3H-benzothiazolinium iodide, 3-ethyl-2-[(1-ethyl-2 (1H) -quinolylidene)
Methyl] benzothiazolinium iodide, 3-ethyl-
2- [3- (3-ethyl-2-benzoxazolinylidene) -1-propenyl] benzoxazolinium iodide. 3-ethyl-5- [2- (3-ethyl-2-benzorialinidene) ethylidene] rhodanine, 2- (p-dimethylaminostyryl) -1-ethylpyridiniiodide, 2- (p-dimethylamino) Styryl) -1-ethylpyridinium iodide, 2- (p-dimethylaminostyryl) -3-ethylbenzothiazolinium iodide and the like. Other "Dye Handbook" (Shin Okawara, Teijiro Kitao, Tsuneaki Hirashima, Ken Matsuoka)
Many dye compounds described in Kodansha 1986) can be used in the present invention. Further, these dye sensitizers can be selected to suit different wavelengths of actinic radiation depending on the purpose of use of the hologram, and depending on the application, two or more kinds can be used in combination.

As the component (E) silane coupling agent of the present invention, vinyl tris (β-methoxy) silane,
Vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane,
N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like, but are not limited thereto. Any compound can be used as long as it has at least one bond between silicon and an alkoxy (methoxy, ethoxy, etc.) group capable of bonding to the inorganic substance of the base material. These silane coupling agents can be used alone or in combination of two or more.

As the substrate used in the present invention, a transparent substrate having an inorganic surface such as a glass plate, glass or various resin plates, for example, polycarbonate, polymethyl methacrylate, polyether sulfonic acid, polysulfone cellulose, polyethylene terephthalate (PET),
A transparent substrate having a silane compound sol-gel coated on the surface of a polyetherketone or the like, glass or various resin plates, for example, polycarbonate, polymethyl methacrylate, polyether sulfonic acid, polysulfone cellulose, polyethylene terephthalate (PET), poly Aluminum, base material surface made of ether ketone, etc.
And a substrate or the like on which a vapor-deposited layer is formed on the surface of a metal or silicon oxide compound by vapor deposition.

In the present invention, each of the components (A) resin, (B) polymerizable monomer, (C) photoinitiator, (D) dye sensitizer and (E) silane coupling agent of the above-mentioned hologram recording material are used. One or more kinds are appropriately selected, and a photosensitive solution obtained by mixing at an arbitrary ratio is applied to a spin coater, a roll coater,
Using a known coating means such as a bar coater, a hologram layer 3 is formed on the transparent substrate 2, for example, a glass plate, which is applied in a film form and dried to obtain a hologram recording medium 1 shown in FIG. The photoinitiator may be selected and added depending on the light source used for recording the hologram, and is generally selected by a combination of the photoinitiator and the dye sensitizer.

According to the schematic diagram for explaining the optical system for photographing the reflection hologram of FIG. 2 showing the process of forming a hologram by subjecting the hologram recording medium 1 to holographic exposure, the laser 5 oscillates. Laser light 6
The hologram was incident on the hologram recording medium 1 via the mirror 7, the lens 10, the lens 11, and the spatial filter 9 to form interference fringes, and a hologram image was recorded (hologram photographing by exposure). Furthermore, heat treatment or whole-surface light irradiation is performed at 40 to 150 ° C. as necessary.

According to the present invention, the alkoxy portion of the silane coupling agent contained in the hologram recording material by the production of the hologram has the alkoxy surface of the silane coupling agent and the (meth) acrylic group of the silane coupling agent. Since the functional groups such as vinyl group, amino group, and glycidyl group are respectively bonded to the compound in the hologram recording material, the silane coupling agent crosslinks between the hologram layer and the base material, and the adhesion is strong. Becomes

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on specific embodiments. <Example 1> Bisphenol-based epoxy oligomer (trade name "Epicoat 1007" manufactured by Yuka Shell Epoxy)
100 parts by weight, 50 parts by weight of triethylene glycol diacrylate, 5 parts by weight of diphenyliodonium hexafluorophosphate, 1 part by weight of 3- (2′-benzothiazole) -7-diethylaminocoumarin and a silane coupling agent (S1 ~ S6) was mixed and dissolved in 200 parts by weight of 2-butanone to prepare a hologram recording material, which was coated on a glass plate washed with acetone so as to have a thickness of about 15 μm, and dried to form a hologram layer. Then, a hologram recording medium was produced.

The hologram recording medium was subjected to the reflection hologram photographing optical system shown in FIG. 2 using an argon laser (514.5 nm; 20 mJ / cm ² ) as a light source.
After performing holographic exposure from both sides of the hologram recording medium 1 to produce a reflective hologram, a heat treatment was performed at 80 ° C. for 30 minutes.

The characteristics (diffraction efficiency) of the obtained hologram were 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 centering on the sample.
The light was incident at an angle of 5 °, and diffracted light from the sample was detected. The ratio of the largest value other than the specularly reflected light to the value when the incident light was directly received without placing the sample was defined as the diffraction efficiency. At this time, the diffraction efficiency was 95%, and the peak of the reproduction light wavelength was 512 nm (in the case of the silane coupling agent S-1). In addition, the presence or absence of peeling when the hologram layer is in the form of a film,
The adhesion, the reduction in hologram diffraction, and the presence / absence of hologram damage, including hologram image distortion, were examined, and the results are shown in Table 1. Note that, as Comparative Example 1, the hologram recording material of Example 1 was replaced with a silane coupling agent (S1 to S1).
A hologram recording medium was prepared in the same manner except that 6) was not added, and holographic exposure and heat treatment were performed to prepare a hologram. Once this hologram layer is peeled off,
Using a commercially available adhesive (B1 to B4) shown below, the glass plate was again bonded to the glass plate, and the adhesiveness, reduction in hologram diffraction, and damage to the hologram were examined in the same manner. The results are shown in Table 1. Show. Further, as Comparative Example 2, a hologram was produced using a hologram recording material to which no silane coupling agent was added, and the adhesion, the reduction in hologram diffraction, and the presence or absence of hologram damage were similarly examined.
Shown in

The silane coupling agent used in Example 1 S1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane S2: γ-glycidoxypropylmethyldiethoxysilane S3: γ-glycidoxypropyl Triethoxysilane S4: N-β (aminoethyl) -γ-aminopropyltrimethoxysilane S5: γ-aminopropyltrimethoxysilane S6: N-phenyl-γ-aminopropyltrimethoxysilane

○ Adhesive used in Comparative Example 1 B1: Trade name “3062F” manufactured by Su-Bond B2: Trade name “Hard Rock UC3000” manufactured by Denki Kagaku B3: Trade name “UV-3541” manufactured by Toa Gosei Chemical Co. B4: Trade name “INC-92” manufactured by Nippon Kayaku

[0039]

[Table 1]

(Adhesion) ○: The hologram layer cannot be peeled off in the form of a film. ×: The hologram layer can be easily peeled off in the form of a film. (Diffraction efficiency) ○: 90% or more. ：: The difference in the peak of the reproduction light wavelength is smaller than 5 nm as compared with a hologram having no treatment (no silane coupling agent added, no adhesive). X: The difference of the peak of the reproduction light wavelength is 10 nm or more as compared with the unprocessed hologram. (Image distortion) ○: The image seen by the reproduction light is clear ×: The image seen by the reproduction light is unclear

<Example 2> The bisphenol-based epoxy oligomer of Example 1 (trade name "Epicoat 100")
7 "Vinyl acetate instead of Yuka Shell Epoxy Co., Ltd., and KAYARAD-R551 (trade name, manufactured by Nippon Kayaku Co., Ltd.) instead of triethylene glycol diacrylate, the following silane coupling agents (S7 to S1)
A hologram recording medium was prepared in the same manner as in Example 1 except that 0) was used, and holographic exposure and heat treatment were performed to prepare a hologram. The diffraction efficiency of this hologram was 84%, and the peak of the reproduction light wavelength was 511 nm.
(At the time of the silane coupling agent S-1). In the same manner, the adhesiveness, the decrease in diffraction of the hologram, and the presence or absence of breakage of the hologram were examined, and the results are shown in Table 2. As Comparative Example 3, a hologram recording medium was prepared in the same manner as in Example 2, except that the silane coupling agent (S7 to S10) was not added, and holographic exposure and heat treatment were performed. Was performed to produce a hologram. The hologram layer was once peeled off, and again bonded to a glass plate using the same adhesives (B1 to B4) as in Comparative Example 1, similarly having adhesiveness, reduced hologram diffraction, and presence or absence of hologram damage. And the results are shown in Table 2. Further, as Comparative Example 4, a hologram was produced using a hologram recording material to which no silane coupling agent was added, and similarly, adhesion, reduction in hologram diffraction, and whether or not the hologram was damaged were examined. Show.

The silane coupling agent used in Example 2 S7: vinyltris (β-methoxy) silane S8: vinyltriethoxysilane S9: vinyltrimethoxysilane S10: γ-methacryloxypropyltrimethoxysilane

[0043]

[Table 2]

(Adhesion) ○: The hologram layer cannot be peeled off in the form of a film. ×: The hologram layer can be easily peeled off in the form of a film. (Diffraction efficiency) ：: 90% or more. ：: The difference in the peak of the reproduction light wavelength is smaller than 5 nm as compared with a hologram having no treatment (no silane coupling agent added, no adhesive). X: The difference of the peak of the reproduction light wavelength is 10 nm or more as compared with the unprocessed hologram. (Image distortion) ○: The image seen by the reproduction light is clear ×: The image seen by the reproduction light is unclear

As shown in Tables 1 and 2 above, according to the hologram recording medium and the method for producing a hologram of the present invention, the characteristics of the produced hologram are not affected.
It was confirmed that the hologram layer on which the hologram image was recorded and the substrate were firmly adhered. Further, instead of a glass plate, for example, polyvinyl alcohol (PVA) 20 wt%
/ Water 80wt% / isopropyl alcohol (IPA) 2
The same effect can be obtained when a polyethylene terephthalate (PET) film coated with 0 wt% (11 g) + 3-glycidyloxypropyl trimexisilane (0.5 g) by sol-gel coating is used, and the surface of the base material is made of a metal such as aluminum. The same effect was obtained when a transparent substrate having a vapor-deposited layer formed by vapor-depositing a silicon oxide compound or a silicon oxide compound was used.

[0046]

As described above, according to the hologram recording medium and the method for producing a hologram of the present invention, the hologram recording material is added with a silane coupling agent to form a hologram layer and a hologram layer. Adhesion with materials is good, the hologram layer does not peel from the substrate, weather resistance, heat resistance and storage stability are excellent, and various characteristic values of the hologram such as resolution, diffraction efficiency, transparency, etc. A good volume phase hologram can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view illustrating the configuration of a hologram recording medium according to the present invention.

FIG. 2 is a schematic explanatory view illustrating an optical system for photographing a reflection hologram.

[Explanation of symbols]

 Reference Signs List 1 hologram recording medium 2 transparent substrate 3 hologram layer 5 laser 6 laser beam 7 mirror 8 beam splitter 9 spatial filter 10 lens 11 lens

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03H 1/18 G03H 1/18

Claims (7)

[Claims] 1. A resin which is soluble in a solvent and which is solid at ordinary temperature and pressure, and (B) a radically polymerizable ethylene which is liquid at ordinary temperature and pressure and has a boiling point of 100 ° C. or more at ordinary pressure. A polymerizable monomer having at least one or more unsaturated bonds and having a different refractive index from the resin (A);
A hologram layer comprising a photoinitiator, (D) a dye sensitizer capable of sensitizing a photoinitiator, and (E) a silane coupling agent is formed on a substrate having at least the surface thereof being inorganic. A hologram recording medium characterized by the above-mentioned. 2. The resin (A) is a cationically polymerizable thermosetting epoxy oligomer having at least one glycidyl group in its unit structure, and the polymerizable monomer (B) is an aliphatic monomer. The hologram recording medium according to claim 1, wherein: 3. The hologram recording medium according to claim 1, wherein said (E) silane coupling agent has at least one or more glycidyl groups and alkoxysilyl groups in its structure. 4. The hologram recording according to claim 1, wherein the (E) silane coupling agent has at least one or more (meth) acryl groups and alkoxysilyl groups in its structure. Medium. 5. The hologram recording medium according to claim 1, wherein the (E) silane coupling agent has at least one amino group and alkoxysilyl group in its structure. (6) at least (A) a solvent soluble at room temperature,
A resin that is solid at normal pressure, and (B) at least one radically polymerizable ethylenically unsaturated bond that is liquid at normal temperature and normal pressure and has a boiling point of 100 ° C. or higher at normal pressure, and (A) a polymerizable monomer having a different refractive index from the resin;
A hologram layer comprising (C) a photoinitiator, (D) a dye sensitizer capable of sensitizing a photoinitiator, and (E) a silane coupling agent is formed on a substrate whose surface is at least inorganic. And producing a hologram by performing holographic exposure. 7. The method for producing a hologram according to claim 6, wherein after the production of the hologram, a hologram is produced by performing a heat treatment at 40 to 150 ° C.