WO1992020016A1

WO1992020016A1 - Hologram and its formation method

Info

Publication number: WO1992020016A1
Application number: PCT/JP1992/000585
Authority: WO
Inventors: Tsuguo Yamaoka; Shuichi Namai
Original assignee: Nissan Motor Co., Ltd.; Dai Nippon Printing Co., Ltd.
Priority date: 1991-05-09
Filing date: 1992-05-08
Publication date: 1992-11-12
Also published as: DE4291301T1; JPH0643797A

Abstract

A hologram shown in the figure, wherein a photopolymer in a matrix polymer produces interference fringes (10), and a photopolymer or thermal polymer (20) having a refractive index different from that of the photopolymer exists between the fringes, thereby forming a diffraction grating. A recording medium consisting of a matrix polymer, a photopolymerizable compound and a photopolymerization initiator is exposed to an interference pattern of light, and is then dipped into a developing solution containing a polymer of the photo-polymerizable compound and a photo- or thermally-polymerizable compound having a different refractive index after curing from that of the polymer of the photo-polymerizable compound. The recording medium is then cured by heat or light. In this way, non-uniformity of diffraction efficiency and reproduction wavelength and whitening can be prevented, the reproduction wavelength can be controlled, and a hologram having high diffraction efficiency and high brightness can be obtained.

Description

Specification

Hologram and method for forming the same

Technical field

The present invention relates to a hologram, in particular, to a configuration and a material of a volume phase type photogram and a method of forming the same.

Background art

Holography is a technique for recording interference fringes generated using a light source with good coherence such as a laser on a recording medium. Photoresist, gelatin dichromate, silver halide emulsion, etc. are known as recording materials, but all have problems in resolution, cost, moisture resistance, etc. Has not yet been obtained.

As a recording material, a hologram recording material comprising poly (vinyl carbazole), a polyfunctional monomer, and a photopolymerization initiator has been known (Japanese Patent Application Laid-Open Nos. 2-216180, 2-221). However, the development is performed by the swelling and shrinking steps, and the reproducibility of the hologram greatly depends on the temperature and humidity at that time, making it difficult to maintain the same reproduction wavelength and diffraction efficiency. In addition, at low exposure energy, the crosslink density of the polymer was low, and it was difficult to avoid the occurrence of whitening due to rapid film shrinkage. Each of the above recording media is composed of a matrix recording medium and interference fringes, and the space between the interference fringes is composed of only a matrix composition.

The present invention firstly provides a novel hologram configuration and a hologram-forming material. Second, it is to provide a hologram having a high diffraction efficiency and no variation in the diffraction efficiency and reproduction wavelength depending on the developing conditions, and a method of forming the hologram.

Third, there is a need to provide a hologram free from whitening and a method for forming the hologram.

Fourth, it is to provide a hologram capable of controlling a reproduction color and a method of forming the hologram.

Disclosure of the invention

In the hologram of the present invention, interference fringes due to a photopolymer are formed in the matrix polymer, and light or a heat polymer having a different light refractive index from that of the photopolymer is present between the interference fringes. A diffraction grating is formed.

More specifically, the photopolymer or the ripened polymer replaces the photopolymerized component in the interference of the photopolymer with another polymerized component, and has a photorefractive index different from that of the photopolymer. The feature is.

Further, one of the photopolymer and the light or heat polymer is a polymerization product of an aromatic (meth) acrylate that may be halogenated, and the other may be halogenated. It is characterized by being a polymerization product of an aliphatic (meth) acrylate.

The method for forming a hologram of the present invention comprises exposing a recording carrier comprising a matrix polymer, a photopolymerizable compound (hereinafter referred to as a host monomer), and a photopolymerization initiator to a light interference pattern. Polymerizing the photopolymerizable compound with the record carrier Light or heat polymerizable compound with different refractive index after curing

(Hereinafter referred to as a guest monomer) in a developing solution having the same, and then the recording medium is cured by heat or light.

A volume phase hologram using a photopolymer greatly depends on the composition of the recording carrier and the developing method.In the conventional production of this kind of hologram, the developing process involves two steps of swelling and shrinking. Therefore, reproducibility was difficult to obtain, and clouding due to film shrinkage and drying process was an inevitable problem. According to the present invention, it has been found that a hologram image can be formed by inserting a polymerized component different from the polymerized component in the record carrier into the unpolymerized region of the interference fringe dark portion, and the refractive index difference.

The volume phase hologram has the property of reflecting and reproducing only specific light, and its wavelength depends on the interval between interference fringes recorded in the hologram layer. By developing with a developer containing a photocurable or thermosetting polymerizable component and then curing the record carrier, it is possible to fix the interference fringes without changing the distance between the interference fringes due to swelling and shrinkage. Thus, a hologram having a uniform reproduction wavelength can be produced with good reproducibility, and the reproduction wavelength can be controlled by selecting a solvent and a combination of a host monomer and a guest monomer. Further, the hologram can be formed as a transparent hologram that does not cause any whitening phenomenon due to cracks or the like generated when a conventional swollen record carrier is contracted. It is.

In addition, by making the photorefractive index of the polymerization component in the record carrier, that is, the host monomer, different from that of the polymerization component in the developing solution, that is, the guest monomer, the diffraction efficiency can be obtained, and the brightness can be improved.ぃ It can be a hologram.

According to the present invention, a reproduction wavelength can be controlled and a hologram having a 髙ぃ diffraction index can be produced with good reproducibility, so that a hologram can be used for, for example, a light control device.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic diagram of a Lippmann hologram forming apparatus.

FIG. 2 is a schematic view of a denishook type hologram forming apparatus.

FIG. 3 is a diagram showing the relationship between the difference in the optical refractive index between the host monomer and the guest monomer and the maximum diffraction efficiency of the hologram produced according to the present invention.

FIG. 4 is a diagram showing a configuration of a hologram of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

First, the components constituting the record carrier in the present invention will be described.

Matrix polymers include polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolysate, polystyrene, polyvinyl butyral, poly (c-prene), polyvinyl chloride, chlorinated polyethylene, Chlorinated polypropylene, poly (N-vinylcarbazole) or its derivative N-vinylpyrrolidone or a derivative thereof, a copolymer of styrene and maleic anhydride or a half ester thereof, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylic acid A copolymer containing a monomer selected from a group of copolymerizable monomers such as luamide and acrylonitrile as a polymerization component is used.

Particularly preferred are poly (N-vinyl carbazole) and derivatives thereof. For example, poly (N-vinyl carbazole), vinyl carbazo-l-vinyl styrene copolymer, vinyl carbazo-l-vinyl chloride copolymer, vinyl carbazo-l-methyl methacrylate Relate copolymer, vinylcarbazole-pynylanthracene copolymer, vinylcarbazole-vinylpyridine copolymer

, Vinyl carbazole monoacrylate copolymer, vinyl carbazole monoethyl acrylate copolymer, vinyl carbazole monoethyl acrylate copolymer, vinyl carbazole monobutyl acrylate copolymer, vinyl Carbazole 22-port vinyl carbazole copolymer, nitrated poly-N-vinyl carbazole, poly-vinyl carbazole, vinyl carbazole mono-N-methylamino vinyl carbazole copolymer, Haguchigen-substituted poly-N-vinylcarbazole, vinylcarbazole-dibromovinylcarbazole copolymer, polyvinylvinylcarbazole, polybenzylidenevinylcarbazole, polypro Zinc carbazole and the like. When these poly-N-vinyl carbazoles are used as a matrix polymer, a hologram having good moisture resistance can be obtained. Ma Also preferred are poly (N-vinylpyrrolidone) and derivatives thereof. For example, copolymers of poly (N-butylpyrrolidone) with butyl acetate, glycidyl methacrylate, alkyl (meth) acrylate, styrene, etc. And the like.

Next, the photopolymerizable compound having an ethylenically unsaturated bond (host monomer) will be described.

Examples of the host monomer include photopolymerization, photocrosslinkable monomers, oligomers, prepolymers, and mixtures thereof having at least one ethylenically unsaturated double bond in one molecule, and examples of the monomer and its copolymer. Examples include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds, etc. .

Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, oxalic acid, isocrotonic acid, maleic acid, and halogen-substituted unsaturated carboxylic acids such as chlorinated acids. And unsaturated carboxylic acids, brominated unsaturated carboxylic acids, fluorinated unsaturated carboxylic acids and the like. Examples of the salts of unsaturated carboxylic acids include the sodium salts and potassium salts of the aforementioned acids.

Further, specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diethanolate, and the like. 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, B Pirenguri co Rujiaku Li rate, neopentyl Legris co over Rujiaku Li rate, Application Benefits Mechirorupu D pan Application Benefits Ryouku Li rate, Application Benefits Mechirorupuroha ⁰ down Application Benefits (§ click Li Roy Ruokishipuro pills) ether, Trimethy sigma —luentant acrylate, hexanediol diatalylate, 1,4 —cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol Penta-erythrate, penta-erythritol, tri-acrylate, dipenta-erythritol, penta-erythritol, tri-acrylate, dipenta-erythritol , Dipentaerythritol tetraatrate, dipentaerythrate Toll hex rate, sorbitol toll rate, sorbitol-lute tollate rate, sorbitol pentaacrylate rate, sorbitol tox rate, trill rate (Acriroy Loquischetil) There are several types of products, such as Polyester Acrylate and oligomas.

Methacrylates include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. Tactylate, trimethicone methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate Rate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, dipentaerythrate Retort Rudimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [P- (3-methacryloxyl-2-hydroxypropoxy) f: ϋ Nyl] dimethylmethane, bis- [ρ- (acryloxyethoxyphenyl) dimethylmethane, 2,2-bis (4-methacryloyloxyphenyl) propane, methacrylic acid-2-naphthyl, and the like.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol. Diitaconate, sorbitol tetritaconate and the like.

Examples of croton acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate.

Isoku The Tonsan esters, ethylene glycidyl Koruji Isokuro Tone DOO, Pentaerisu Li Torujii Sokuro TONNAY one DOO, as the _c maleic phosphate ester sorbitol Te tri Sokuro Tone one bets, and the like, ethylene glycol di maleate over preparative, preparative Riechiren Glycolymate, pentaerythritol and maleic acid, sorbitol tetramarate and the like can be mentioned.

As the halogenated unsaturated carboxylic acids, 2, 2, 3, 3- Tetrafluoropropyl pyratarate, 1H, 1H, 2H, 2H—Heptadecafluorodecylatarate, 2,2,3,3—Tetrafluoropropylpyramethacrylate, 1H, 1H , 2H, 2H—Heptadecafluoro σ-decyl methacrylate, methacrylic acid mono 2,4,6—Tripromophanil, Jib σ-moneopentyl dimethacrylate (trade name: Κ Κester D Β Nakamura Chemical Co., Ltd.), dibromopropyl acrylate (trade name: Ester-DBP, Shin-Nakamura Chemical Co., Ltd.), dipromopropyl methacrylate (trade name: NK ester DBP, manufactured by Shin-Nakamura Chemical Co., Ltd.), methacrylic acid chloride, 1,2,4,6-methacrylic acid triphenyl mouth, p-chlorostyrene, methyl-2-chloroacrylate , Le one 2 _ Kuroroaku Li rate, n- Puchiru 2 Black Roata Li rate, preparative Ripuromofuweno Ruata Li rate, Te preparative Raburomofu Noruaku Li rate, and the like.

Specific examples of amide monomers of an unsaturated carboxylic acid and an aliphatic polyamine compound include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1, 6—Hexamethylene bismethacrylamide, diethylene triammonium triacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, N-phenylmethacrylamide, die And acrylamide.

As another example, a polymer described in Japanese Patent Publication No. 48-41708, which has two or more isocyanate groups in one molecule, may be used. Isocyanate compound, the following general formula

CH ₈ = C (R) C00CH ₂ CH (R ') 0H

(In the formula, R and R 'each represent an amino or methyl group.)

And a vinylurethane compound having a polymerizable vinyl group on a rigid substrate in one molecule to which a vinyl monomer having a permanent acid group represented by the formula (1) is added.

Also, urethane acrylates described in JP-A-51-371193, JP-A-48-64183, JP-B-49-43191 Polyester acrylates such as polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-B-52-34090 Rate can be mentioned.

Furthermore, those described as photocurable monomers and oligomers in the Journal of the Adhesion Society of Japan, Vo1.20. No? .300-308, can also be used.

In addition, the monomers containing the signal include mono (2-atalyi kishechil) acid phosphate (trade name: Lightester PA, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and mono (2-methacrylic acid ethyl). Dofosphate (trade name: Liteester PM, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.); and epoxy acrylate-based product name: Lipposi VR-60 (manufactured by Showa Kogyo Co., Ltd.) ), Trade name: Lipoxy VR-90 (manufactured by Showa Kagaku (铢)).

Trade name: NK ester M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), Trade name: NK ester 23G (Shin-Nakamura Chemical Industry Co., Ltd.).

Further, triarylates having the following structural formula,

CH ₂ = CHCOOCH ₂ CH CH ₂ COOCH = CH ₂

CH ₂ CH ₂ C00CH = CH ₂

(Toagosei Chemical Industry Co., Ltd., trade name, ARONIX M3 15)

CH ₂ CH ₂₀ (CH ₂ ) ₅ OCOCH = CH _: (Toagosei Chemical Industry Co., Ltd., trade name, ARONIX M—

3 2 5), and 2,2'-bis-U-acryloxy-diethoxy-nil) propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, NK ester A-BPB-4), Tet Lamethylol methane acrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name, NK ester A-II) and the like.

Preferably, aromatic (meth) acrylate in which 0 to 10 bromine or iodine atoms are present in one molecule, or vinyl ether, Or an epoxy compound, an aliphatic (meth) acrylate which has 0 to 20 fluorine or silicon atoms in one molecule, or a vinyl ether, or an epoxy compound. Particularly preferred is a halogenated compound. Examples include good aromatic (meth) acrylates and optionally halogenated aliphatic (meth) acrylates.

These host monomers are used in an amount of 1 to 3 parts by weight, preferably 0.3 to 1.5 parts by weight, based on 1 part by weight of the matrix polymer.

Next, the photopolymerization initiator and sensitizer were 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethyl ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Butyl benzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, Isoamyl 4-dimethylaminobenzoate, 2,2-Diethoxyacetatophenone, Penzyldimethylketal, Benziru-β-Methoxyxacetal, 1-Phenyl-1-, 2-propanedione-2- (0-ethoxycarbonyl) oxam, benzophenone, 0-methyl benzoylbenzoate, Michler's skeleton, 4,4'-Bisethylamino benzo Phenonone, 4,4 'dicyclo benzophenone, dibenzoyl (1,2-diphenyl Tandione), benzoin (2-phenyl 2-hydrogen-terminated), benzoin methyl, benzoin ethyl j, benzoin ethyl teryl, benzoin isobutyl butyl ether, benzoin thiobutyl ether The benzo Benzoin butyl ether, benzoin butyl ether (50:50 mixture of n and is 0), benzoin alkyl ether, 4'-isopropyl-12-hydroxy-12-methyl loop mouth piofenonone, 2-hi Droxy-l 2-methyl methyl piophenonone, p-dimethylamino acetophenone, pt-butyl trichloride D-loacetophenone, p-t-buty J regichloroacetone phenone, p- Azidopenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalcetocetphenon, p-azidobenzalaceton, 4,4'-diazidochalcone, 1,3-bis 1 (4,1 azidopenzal) —aceton, 2,6-bis (4'-dibenzo) 1 cyclohexanone, 2,6-bis (4,1 dicisben) (Monkey) 1-Methylcyclohexanone, 4,4'-diazidostyrpene 1,2,2,1-disulfonic acid, 1,3-bis- (4,1-azidobenzal) 1-2-propanone 1,2-sulfone Acid, 1,3-bis- (4'-azidobenzal) 1-2-propanone 1,2,2,1-sodium sodium sulfonate, 1,3-bis (4'-iso-docinnasiliden) 1 2 —Propanone, azidopyrene, 3-sulfonylazide benzoic acid, 4-sulfonylazidobenzoic acid, 2,6-bis- (4′-one-didopenzal) 2,6-bis- (4'-azidobenzal) monomethyl-cyclohexanone 2,2'-disulfonic acid (sodium salt), 4-diazodiphenylamine Sulphate, 4'4'-methoxy Rua Mi emissions sulfuric acid salt, 4 temporary Ryozo one 3-menu butoxy one Ziff et Niryomin, naphthoquinone (1,2) diazide (2) — 4-—Sulfonate sodium salt, naphthoquinone (1,2) diazide (2) — 5-—Sulfonate sodium Salt, naphthoquinone (1,2) dihydrozide (2) — 5-sulfonate (1), naphthoquinone (1,2) diazide (2) — 5 — sulfonate ester, naphthoquinone (1,2) diazide (2)-5-sulfonate (3) -nopolak resin ester, diazo resin (sulfate of diazodiphenylamine, paraform aldehyde condensate and Zinc chloride double salt), triphenylpyrium perchlorate, 4-methoxyphenyl-1,2,6-diphenylpyrium perchlorate, 4-butoxyphenyl 2,2,6-diphenylpyrium perchlorate Acid salt, triphenylthiopyri perm Acid salt, 4-methoxyphenyl 2,6-diphenylthiopyrimidine perchlorate, thioxanthone, 2-methylthioxanthone (2-methyl-9H-thioxancene-1 9-one), (2-chloro-one 9H-thioxanthone-one-one), 2-isopropylpyrthioxanthone (2-iso-propyl-one nine-H-thioxancene-one-one), dibenzosuberon, 2,5 —Bis (4,1 getylaminobenzal) cyclopentanone, 1-acetylamino 412 tronaphtalene, 5-nitroacenaphthene, 1-nitropyrene, or dicyclo mouth, 4-phenoxyacetophenone, 1-hydroxy Doxycyclohexyl phenyl ketone, trade name: Kayakua MBP (manufactured by Nippon Kayaku Co., Ltd.), trade name: UVE CRYLP 36 (UCB), etc. Luo alone, also Kiyoshi Can be used in combination.

In addition, a coumarin compound and an organic peroxide represented by the following general formula (1) can be mentioned.

General formula (1)

1

(Wherein,, R ₂ and R _{3 each} independently represent a chromium atom, a chloro atom, a lower alkoxy group, a lower dialkylamino group, a lower dialkenylamino group or an alicyclic group. X represents a heterocyclic group having a total number of carbon atoms and hetero atoms of 5 to 9 or a COY group, wherein Y represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Represents a lower alkoxy group, a substituted or unsubstituted fuunyl group, a substituted or unsubstituted steryl group, or a substituted or unsubstituted 3 ′ coumarino group, and Z represents a hydrogen atom or a cyano group.

0)

In the formula, R 1, R ₂ , and R ₃ are preferably a hydrogen atom, a carbonyl atom, a lower alkoxy group such as methoxy, ethoxy, butoxy, dimethylamino, getylamino, N-methyl-N-propyl. Lower dialkylamino groups such as pyrinomino; alicyclic amino groups such as N-morpholino and N-piperidino; lower groups such as dipropidinylamino and di (monomethylprobenyl) amino groups; And dialkylamine.

The heterocyclic group represented by X is 2 — imidazole, 2 — N— Methylimidazole, 2-benzimidazole, 2- (4-phenyl) -imidazole, 2-oxazole, 2-benzoxazole, 2- (4-phenyl) oxazole, 2-thiazole, 2-butyl N-thiazole, 2- (4-phenyl) thiazole, 2- (5-phenyl) thiadiazole, 2- (5-tolyl) thiadiazole, 2- (5-biphenyl) thiazyl, 2- ( 5—Phenyl) oxaziazole, 2— (5-p-methoxyphenyl) oxazine, 2- (5-p-chlorophenyl) oxazine, etc.

In addition, Y in one COY group is a substituted or unsubstituted group such as methyl, ethyl, propyl, hexyl, β-silinoethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, etc.

C1-Cs alkyl group, phenyl, ρ-cyanophenyl, Ρ-methylphenyl, ρ-methoxyphenyl, m-hydroxycarbonylphenyl, etc. A steryl group such as methoxisteryl, p-cyanosteryl and m-chlorsteryl, and a 3-coumarino group represented by the following general formula:

(Where R,, R ₂ , R ₃ , and Z are the same as those in the general formula (1))

And the like.

Specific examples of coumarin compounds include 3-cetyl-7-dimethylaminocoumaline, 3-benzoyl-17-dimethyl-aminocoumarin, 3-benzoyl-15, 7-dimethoxycoumarin, methyl, methyl, 7—Jetylamino-1-3-coumarinyl acetate, 3-cinnamoyl-1 7—Jetylaminoc, malin, 3,3,1-carbonylbis (7-jetylamino) coumarin, 3,3′-carbonyl Bis (5,7-dimethoxyamino) coumarin, 7-Jethylamino-5,7'-Dimethoxy-1,3,3,1-biscoumarin, 3- (2'-Benzimidazoline) -17, Jethylamino bear Lin, 3 -— (2'-Benzoxazolyl) -1 7-Jetil-L-minocumaline, 3- (5'-Phenylthiadiazol-1 2,)-7-Jetilamino-coumarin, 3-( 2'-benzthiazolyl-17-getylaminocoumarin, 3,3'-carbonylbis (4-synono-17-getylamino) coumarin and the like. .

Preferred compounds of the organic peroxide used in admixture with the tamarin compound include methyl ketone peroxide, cyclohexanone peroxide, acetyl aceton peroxide, t-butyl peroxide, and methoxide. Nhai de ¹ p Paoki rhino de, diisopropyl Sopuro Pirubenzen Ichipa one Okisai de, t chromatography Bed Chiruku Mirupaokisai de, dichloroethylene Mirupaokisai de, Do, one-bis (t-Buchiruku Mirupa one Okishii Sopuro pill) Baie Benzene, tert-butyl peroxy isopropyl propylate, ponates, benzoyl peroxyside, di (t-butyl peroxy) disophthalate, di (t-butyl peroxy) terephthalate, di (t-butyl peroxy) phthalate, t Monobutyloxybenzoate, 3,3 ', 4,4, -tetra (t-butylperoxycarbonyl) benzophenone, 2,5-dimethyl-2,5- (dibenzoylperoxy) hexane, etc. are used. You.

Among them, particularly preferred are di (t-butyloxy) isophthalate, di (t-butyloxy) terephthalate, di (t-butylperoxy) phthalate, 3,3 ′, 4; 4′—tetral (T-butyloxycarbonyl) benzophenone.

The proportion of the organic peroxide added to the coumarin compound is 1 part by weight to 100 parts by weight, preferably 1 part by weight to 50 parts by weight, based on 1 part by weight of the bear'J compound.

These photopolymerization initiators are used in an amount of 1 part by weight to 80 parts by weight, preferably 1 part by weight to 20 parts by weight, based on 100 parts by weight of the total amount of the above-mentioned matrix polymer and host monomer. Is performed.

A composition for forming a recording carrier is prepared by adding a thermal polymerization inhibitor, a plasticizer, and the like in addition to the above composition.

The record carrier according to the present invention comprises the above composition, for example, benzene, black J-lebenzene, tetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, The film is dissolved in a film or the like and coated on a support such as a glass or a transparent resin film. As a coating method, the film is applied to a film thickness of 0.5 m to 50 m after drying by a spinner coating, a blade coating, a roll coating, or the like. The film itself may be formed by utilizing the supportability of the matrix polymer itself.

The record carrier thus obtained is sensitive to laser light having a bright line at, for example, 4579 A, 488 A, 515 A, 528 A, etc. For example, it provides diffraction efficiency in a practical range with an energy of 1 to 500 mJ / cm ² for an argon laser having a wavelength of 488 A, for example.

Next, a method for forming a mouth gram according to the present invention will be described.

The hologram forming method of the present invention comprises a step of exposing a record carrier to radiation, a step of using a developer containing a guest monomer, and a step of light or heat curing the record carrier after development.

Radiation that can be used in the step of exposing the recording unit to radiation is preferably radiation using a laser beam, a mercury lamp, or the like as a light source.

At the time of hologram formation, a Lippmann hologram forming apparatus that forms a volume phase hologram by irradiating the subject with two coherent bundles of radiation as shown in FIG. 1 at a predetermined offset angle, or As shown in Fig. 2, a denier-type hologram forming device that forms a volume phase hologram by interference between irradiation light and reflected light from a subject is used. 1 Next, the development step is performed by immersing the record carrier on which the hologram latent image is formed in a developer having a guest monomer.

This development step shows the features of the present invention, and causes the record carrier 5 to swell or shrink according to the formed hologram pattern, and to elute unreacted photosensitive components in the unexposed portions. At the same time, a developer having a guest monomer in the unexposed area is permeated to replace the host monomer in the unexposed area with the guest monomer, or to add a guest 0 monomer to the host monomer.

The solvent in the developer has a function of causing a swelling or shrinking action in a short time to a polymer crosslinked product generated by a photopolymerization reaction of a photosensitive component, and a function of eluting an unreacted photosensitive component. For example, swelling liquids include benzene, toluene, 5-xylene, ethylpentene, Ti-propylbenzene, cumene, phenosole, cresolene, chlorylbenzene, dichlorobenzene, nitrobenzene, and benzyl alcohol. And benzene and naphthalene derivatives such as benzyl chloride, benzyl butylamide, monomethylnaphthalene and α-chloronaphthaline, and a mixed solvent thereof may be used. The contracting liquid is a solvent that does not dissolve or swell the recording material, such as η-pentane, hexane, η-heptane, n-octane, isooctane, and cyclohexane. Alcohols, cycloalkanes, methyl alcohol, ethyl alcohol, n-propyl, alcohol, isopropyl alcohol, n Alcohols such as t-butyl alcohol, t-butyl alcohol, T1—amyl alcohol, iso-amyl alcohol, etc., ethyl alcohol, methyl ethyl ether, diisopropyl ether, etc. Ethers, ketones such as acetate and methylethyl ketone and the like, esters such as ethyl acetate, methyl acetate, ethyl formate and methyl propionate, and a mixed solvent thereof may be used.

In the present invention, guest monomers are allowed to enter between interference fringes.

Two

It is necessary to use a solvent having an —1 swelling action. The distance between interference fringes can be controlled by appropriately selecting the solvent in the developer.

Next, the photo- or heat-polymerizable compound (guest monomer) in the developer will be described.

First, as the guest monomer capable of being photopolymerized or thermally polymerized, those described as the host monomer may be used, and the same compound as the host monomer may be used, but the guest monomer and the host monomer are used in the light monomer. By using a monomer having a refractive index difference, a high diffraction efficiency can be obtained when a hologram is formed, and a hologram having a high diffraction efficiency can be obtained as the difference in the light refractive index increases.

Therefore, preferably, one of the host monomer and the guest monomer is an aromatic (meth) acrylate containing 0 to 10 bromine or iodine atoms in one molecule thereof, or a vinyl ether.

Or an epoxy compound, and the other is an aliphatic (meth) acrylate having 0 to 20 fluorine or silicon atoms in one molecule thereof. Or a vinyl ether or epoxy compound.

Particularly preferably, one of the host monomer and the guest monomer is an aromatic (meth) acrylate which may be halogenated, and the other is an aliphatic (meth) acrylate which may be halogenated. ) Atari rate.

As the guest monomer, it is preferable to use a liquid having a molecular weight (viscosity) of 25: 100, which is liquid and soluble in a solvent in a developing solution. Furthermore, if the molecular weight of the guest monomer is too low, it flows out of the unexposed portion during the hologram production step, and as a result, the refractive index difference required for the hologram cannot be obtained, and the obtained π-gram tends to gradually disappear. .

In the development step, the recording carrier is directly immersed in the developing solution, but the photosensitive component in the unexposed portion of the recording carrier is first removed using only a solvent, and then immersed in the developing solution. Good. The concentration of the guest monomer in the developer is appropriately set, but is preferably at least 1% by weight or more.

The record carrier thus developed is then subjected to a curing step.

In the curing step, the record carrier is irradiated with light such as ultraviolet rays or heated to cure the guest monomer in the unexposed portion and fix the record carrier.

The hologram obtained in this manner is composed of a host monomer polymer 10 and a guest monomer polymer 20 as shown in FIG. The surface of the obtained mouth gram can be used as it is. However, glass or plastic film may be attached. Hereinafter, the present invention will be described with reference to specific examples.

Example 1

The following composition

'' Poly N-vinyl carbazole (manufactured by Anan Sangyo Co., Ltd., Tsubikol No. 210 (trade name) average molecular weight 400,000 to 500,000)

· · · 1.0 g

• Tripromophenol methacrylate (trade name: BR-31, manufactured by Dai-Ichi Kogyo Pharmaceutical Co., Ltd.) · 0.5 g · 3, 3 ', 4, 4, 1 tera Benzofuyunone 0.08 g

• 3, 3'—Carbonylbis (7—Jetil R)

A composition having 0.03 g was dissolved in 10 g of 1,4-dioxane, and after a 0.25 μm filtration, a photosensitive solution was obtained.

This photosensitive solution was applied on a 3 mm thick glass plate using a replicator so that the film thickness after drying was 9 m, dried at 70: for 45 minutes, and then dried with a polyvinyl alcohol. (Kuraray Co., Ltd., degree of polymerization: 500, degree of polymerization: 88%) A 10% permanent solution was applied with a spin coater at 200 rpm. This was dried at 60 t for 10 minutes to obtain a record carrier.

Next, the record carrier was exposed to light using a wavelength of 488 Tim from a Lugon laser using the Lippmann type diffraction grating photographing optical system shown in FIG. Exposure was performed at a light intensity ratio of 1: 1 and an exposure energy of 2 O mJ / cm ² . In the figure, 1 is an argon laser, and 2 is Neuf mirror, 3 is a mirror, 4 is a spatial filter, and 5 is a photosensitive plate.

After exposure by Lugon laser, the whole surface was exposed for 60 seconds using a chemical lamp (FL-20BL, manufactured by Toshiba Hayashi). At this time, only a visible light of 400 nm or more was irradiated using a sharp cut filter L39. After exposure, the record carrier is washed for 1 minute in running water to remove the polyvinyl alcohol layer. After drying, the record carrier is washed in a 10% by weight acetone solution of trimethylolpropane acrylate (developer). For 3 minutes.

Next, the record carrier was taken out of the developer and irradiated with a xenon lamp to be cured to produce a hologram.

In the above specific example, each of the holograms was produced using the guest monomers shown in the following table instead of the guest monomer, ie, trimethicone monocyclic panacrylate. In the table below, the difference in the optical refractive index between the guest monomer and the host monomer and the maximum diffraction efficiency of the obtained holegram are also shown in the following table.

Table 1

Two

Five

The above product name: ACTICRYL are all made by France SNPE, and ACTICRY CL959 has the following structural formula

CH ₂ = CHCOCH ₂ CH ₂ N- CH ₂

C CH;

// \ /

It is indicated by 0 0, and the ACTICRY CL960 has the following structural formula

0 0

CH ₂ = CHCOCH ₂ CH ₂ NHCOCH (CH ₃ ) And ACTICRYL CL993 has the following structural formula (wherein R and R ₂ represent alkylene groups)

0 0 0 0

II II II II

CH ₂ = CHC0Ri0C0R20C0R, 0CCH = CH _:

The ACTICRYL CL1039 has the following structural formula

It is shown by.

Further, in the above specific example, a hologram was produced 10 times under the same conditions for a record carrier using Tri-Mn-phenol-methacrylate as the guest monomer, and the reproducibility was examined. At 10%, the reproduction wavelength (^ _χ ) changed only ± 10%.

Further, for a hologram using peptadecafluoropropyl as a guest monomer in the above-described record carrier, the dendritic hologram forming apparatus shown in FIG. Exposure was performed using light with a wavelength of nm. The exposure energy is 2 OmJ / cm ² . In the drawing, the same reference numerals as those in FIG. 1 indicate the same contents, and 6 indicates a subject.

The diffraction grating obtained by performing the same processing as above is the maximum number of times A hologram similar to that of the Lippmann type was obtained with an index of 50% ^. The relationship between the refractive index difference in the above table and its maximum diffraction efficiency is shown in FIG.

From the above table and Fig. 3, it can be seen that the higher the difference in the refractive index between the guest monomer and the host monomer, the higher the diffraction efficiency is obtained, and the reproduction wavelength is changed by the combination of the guest monomer and the host monomer. It can be seen that it can be done.

Comparative Example 1

The record carrier in the above example was immersed in toluene as a developing solution for 3 minutes to remove the tourist component, dried, and further immersed in a mixed solvent of toluene: xylene = 1: 1 for 1 minute to swell. , N-Peptide immersed for 1 minute to shrink, then forcibly dried with a drier to form a hologram, whitening phenomenon occurred.Also, the hologram was made 10 times under the same conditions and reproduced. As a result, the maximum diffraction efficiency fluctuated between 0 and 80%, and the reproduction wavelength (i _max ) fluctuated between 400 nm and 800 rim. there were.

Example 2

In the specific example 1 above, a specific example was made by using a polyurethane monomer ACT I CRY SH CL960, a product of SNPE, France, as a guest monomer, and a host monomer shown in the following table as a guest monomer. A record carrier was prepared in the same manner as in 1 and developed in the same manner as in Example 1 to produce a Lippmann hologram. Hologram The following table also shows the evaluation as a room. The sensitivity of this gram was 5 mJZcm ² , which was a low sensitivity.

Table 2

Two

8

From the above table, it can be seen that the reproduction wavelength changes depending on the host monomer.

Example 3

In the above specific example 1, while using triatalylate (ALONIX M-315 (trade name) manufactured by Toagosei Co., Ltd.) as a host monomer in the same manner as in the specific example 1 using the guest monomer shown in the table below. Similarly, a record carrier was prepared and developed in the same manner as in Example 1 to produce a Lippmann-type hologram, and the evaluation as a hologram is shown in the following table.

Table 3 Guest monomer Refractive index difference Maximum diffraction efficiency maK j Trimethi ii Atarilate 0.034

Product name: ACTICRYL CL959 0.028 36 620 i Product name: ACTICRYL CL960 0.053 42 610 Product name: ACTICRYL CL993 0.043 40 600 Product name: ACTICRYL CL1039 0.052 42 i

! 610! (Note that the guest monomers in the above trade names are the same as those used in Example 1.)

From the above table, it can be seen that the use of a guest monomer having a large difference in light refractive index can improve the diffraction efficiency.

Industrial applicability

As exemplified above, the hologram of the present invention provides a diffraction efficiency by providing a difference between the optical refractive index of the polymer in the interference fringe portion and the optical refractive index of the polymer in the portion between the interference fringes. It is possible to improve it.

The hologram forming method of the present invention can control the hologram reproduction wavelength, has high diffraction efficiency, and can produce a hologram with high brightness with good reproducibility. The obtained hologram is used for an information recording medium, a light control device, and the like.

Claims

The scope of the claims

(1) An interference clog by a photopolymer is formed in the matrix polymer, and a diffraction grating is formed due to the presence of light or a heat polymer having a different refractive index from the photopolymer between the interference fringes. A hologram characterized by being formed.

(2) The light or heat polymer replaces the photopolymer component between the interference fringes of the photopolymer with another polymer component, and has a different light refractive index from that of the photopolymer. The hologram according to claim 1, characterized in that:

(3) Either the photopolymer or the photopolymer or the thermal polymer is a polymerization product of an aromatic (meth) acrylate which may be halogenated, and the other is halogenated. 3. The hologram according to claim 1, wherein the hologram is a polymerization product of an aliphatic (meta) acrylate.

(4) After exposing a recording carrier comprising a matrix polymer, a photopolymerizable compound, and a photopolymerization initiator to a light interference pattern, the recording carrier is subjected to the photopolymerizable compound. A hologram forming method comprising: immersing the recording medium in a developing solution containing a light or heat polymerizable compound having a different light refractive index after curing from the polymer; and then curing the recording carrier by heat or light. .

(5) One of the photo-polymerizable compound and the photo- or heat-polymerizable compound is an aromatic (meth) acrylate which may be halogenated, and the other may be halogenated. 5. The hologram forming method according to claim 4, wherein the hologram is an aliphatic (meth) acrylate.