JPH06148880A - Optical recorded film and its production - Google Patents
Optical recorded film and its productionInfo
- Publication number
- JPH06148880A JPH06148880A JP4299040A JP29904092A JPH06148880A JP H06148880 A JPH06148880 A JP H06148880A JP 4299040 A JP4299040 A JP 4299040A JP 29904092 A JP29904092 A JP 29904092A JP H06148880 A JPH06148880 A JP H06148880A
- Authority
- JP
- Japan
- Prior art keywords
- film
- optical recording
- recording film
- membrane
- organometallic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000009826 distribution Methods 0.000 claims abstract description 19
- 230000007062 hydrolysis Effects 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000012528 membrane Substances 0.000 claims 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 125000002524 organometallic group Chemical group 0.000 abstract 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000007516 diamond turning Methods 0.000 description 1
- 229940077449 dichromate ion Drugs 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 description 1
- 150000004704 methoxides Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZFLIKDUSUDBGCD-UHFFFAOYSA-N parabanic acid Chemical compound O=C1NC(=O)C(=O)N1 ZFLIKDUSUDBGCD-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Holo Graphy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光記録膜その他の膜、
特に高耐久性を有するホログラム、およびそれを好適に
製造する方法に関する。The present invention relates to an optical recording film and other films,
In particular, the present invention relates to a hologram having high durability and a method for producing the hologram suitably.
【０００２】[0002]
【従来の技術】可干渉性を有する光波が形成する干渉縞
を記録し、再生するホログラフィー技術は、近年、ディ
スプレイホログラムだけでなく、グレーティング、光分
波、集光器及びレーザービームスキャニング素子など各
種光学素子としての応用が研究、開発、実用化がなされ
ている。2. Description of the Related Art In recent years, holographic technology for recording and reproducing interference fringes formed by light waves having coherence has been used not only for display holograms but also for various kinds of gratings, optical demultiplexers, condensers, laser beam scanning elements and the like. The application as an optical element has been researched, developed, and put into practical use.
【０００３】ホログラム記録材料としては、銀塩乳剤、
重クロム酸ゼラチン、フォトレジスト、サーモプラスチ
ック、種々のフォトポリマーなとが開発されている。銀
塩は露光感度が非常に高い市販ホログラム記録材料であ
り、ゼラチン膜を支持体としハロゲン化銀を分散させた
材料が使われている。重クロム酸ゼラチンは回折効率が
非常に高く、ノイズが低い優れた体積位相型ホログラム
記録材料である。この成分はゼラチンに重クロム酸イオ
ンを添加し、感光化した材料である。フォトレジストは
エンボス型のホログラムを大量に複製する際の原盤とな
るもので、複製する材料にはプラスチックが用いられて
いる。サーモプラスチックは繰り返し記録再生ができる
記録材料で、熱可塑性樹脂に表面凹凸として記録する。
いずれのホログラム記録材料においても有機化合物を主
とする物質が用いられている。As a hologram recording material, a silver salt emulsion,
Dichromated gelatin, photoresists, thermoplastics and various photopolymers have been developed. The silver salt is a commercially available hologram recording material with extremely high exposure sensitivity, and a material in which silver halide is dispersed with a gelatin film as a support is used. Dichromated gelatin is an excellent volume phase hologram recording material with extremely high diffraction efficiency and low noise. This component is a material sensitized by adding dichromate ion to gelatin. The photoresist serves as a master when a large number of embossed holograms are copied, and plastic is used as a material for the copy. Thermoplastic is a recording material that can be repeatedly recorded and reproduced, and is recorded on a thermoplastic resin as surface irregularities.
In any hologram recording material, a substance mainly containing an organic compound is used.
【０００４】また一般に化学的に安定な金属酸化物ガラ
ス上に表面凹凸を形成させ回折格子等を加工する技術と
して、電子ビームリソグラフィー、イオンエッチング
や、ダイヤモンドターニングマシンなどの超精密旋盤加
工法がある。Further, generally, as a technique for forming surface irregularities on a chemically stable metal oxide glass to process a diffraction grating and the like, there are an electron beam lithography, an ion etching, and an ultra-precision lathe processing method such as a diamond turning machine. .
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、金属酸
化物ガラスに表面加工する方法は、耐久性に優れた材料
を使用する長所があるが、大量生産、大面積には不向き
である。その点ではホログラフィー露光、フォトリソグ
ラフィーなどの活性放射線に露出する技術を使用すれば
大面積化、大量生産も可能である。しかしながらいずれ
のホログラム記録材料においても有機化合物を主とする
物質が用いられており、そのため一般的に耐久性は良く
ないものばかりである。例えば２５０度以上の温度にな
ると、記録されたホログラム材料そのものが酸化、分解
され、記録された干渉縞は破壊され、光学性能も低下す
る。耐熱温度はせいぜい３００度以下である。また耐候
性の点でも紫外線、水分等の影響により黄変するなどの
欠点を有している。また屈折率の温度変化と体膨張係数
の温度変化が、金属酸化物ガラスに比べ、１桁大きいの
で温度変化による波面収差も生じやすい。However, the method of surface-treating metal oxide glass has the advantage of using a material having excellent durability, but is not suitable for mass production and large area. In that respect, if a technique such as holographic exposure or photolithography is used for exposure to actinic radiation, a large area and mass production are possible. However, in any of the hologram recording materials, substances mainly containing an organic compound are used, and therefore, in general, durability is poor. For example, at a temperature of 250 ° C. or higher, the recorded hologram material itself is oxidized and decomposed, the recorded interference fringes are destroyed, and the optical performance is deteriorated. The heat resistant temperature is at most 300 degrees or less. Further, in terms of weather resistance, it also has a defect that it is yellowed by the influence of ultraviolet rays, moisture and the like. Further, since the temperature change of the refractive index and the temperature change of the body expansion coefficient are one digit larger than those of the metal oxide glass, wavefront aberration due to the temperature change is likely to occur.
【０００６】従って最近、ホログラフィーの分野におい
ては、透過型及び反射型に関わらず高い光学特性はさる
ことながら、その応用用途拡大の観点から湿式処理不要
などのホログラム記録および、ホログラム記録膜の高い
耐熱性、耐環境性が望まれており、それを実現するため
には従来とは抜本的に異なる新しいホログラム記録用材
料の開発が行われている。Therefore, in the field of holography, in recent years, in addition to high optical characteristics regardless of the transmission type and the reflection type, from the viewpoint of expanding the applications thereof, hologram recording such as wet processing is not required and high heat resistance of the hologram recording film is obtained. Property and environment resistance are desired, and in order to realize it, a new hologram recording material radically different from the conventional one is being developed.
【０００７】それらの中で、特願平４−１７２５３４に
おけるホログラム記録材料は、比較的耐熱性が高く、３
００度でも耐え得る性能を有しているが、耐候性の面で
紫外線により黄変してしまうのは避けられない。Among them, the hologram recording material in Japanese Patent Application No. 4-172534 has relatively high heat resistance.
Although it has the ability to withstand even at 00 degrees, it is inevitable that it will turn yellow due to ultraviolet rays in terms of weather resistance.
【０００８】[0008]
【課題を解決するための手段】本発明は上述の従来技術
の課題を克服し、高回折効率、高解像力及び高透過率な
どの優れた光学特性ならびに高感度などを示し、同時に
優れた耐環境性、耐久性を有する光記録膜その他の膜、
およびその光記録膜を簡単な工程において製造する方法
を提供するものである。The present invention overcomes the above-mentioned problems of the prior art and exhibits excellent optical characteristics such as high diffraction efficiency, high resolution and high transmittance, and high sensitivity, and at the same time has excellent environmental resistance. Optical recording film and other films having durability and durability,
And a method for producing the optical recording film in a simple process.
【０００９】すなわち本発明は、（１）内部に多数の微
小空隙を有する無機物質の膜状のネットワークと、
（２）前記空隙の中に存在する気体からなり、前記膜中
の空隙率を膜中の場所によって変化させている光記録膜
である。That is, the present invention provides (1) a film-like network of an inorganic material having a large number of minute voids inside,
(2) An optical recording film, which is made of a gas existing in the voids and has a porosity in the film changed depending on a location in the film.
【００１０】また本発明は、Ａ．（１）光重合性モノマ
ーまたはオリゴマー、（２）光重合開始剤、（３）加水
分解および重縮合が可能である有機金属化合物（４）前
記有機金属化合物のための溶媒、（５）水、および
（６）前記有機金属化合物の加水分解を促進させるため
の触媒、を含む出発溶液を、基材上に塗布し、前記有機
金属化合物を加水分解、重縮合させてゲル化した膜を形
成した後、乾燥により揮発成分を気化させて固体状の光
記録用膜を作製し、Ｂ．前記光記録用膜に、活性放射線
を照射し、ついでＣ．上記光記録用膜中に含まれる有機
成分を除去することからなる、前記金属の酸化物のみか
け密度分布および／または表面凹凸を有する光記録膜の
製造方法である。The present invention also relates to A. (1) Photopolymerizable monomer or oligomer, (2) Photopolymerization initiator, (3) Organometallic compound capable of hydrolysis and polycondensation (4) Solvent for the organometallic compound, (5) Water, And (6) a starting solution containing a catalyst for accelerating the hydrolysis of the organometallic compound is applied onto a substrate, and the organometallic compound is hydrolyzed and polycondensed to form a gelled film. After that, a volatile component is vaporized by drying to prepare a solid optical recording film, and B. The optical recording film is irradiated with actinic radiation, and then C.I. A method for producing an optical recording film having an apparent density distribution and / or surface irregularities of the metal oxide, which comprises removing an organic component contained in the optical recording film.
【００１１】本発明における光記録膜その他の膜の製造
に用いられる出発溶液中の光重合性モノマーとしては、
分子内にアクリロイル基、メタクリロイル基、ビニル
基、アリル基等の重合可能な基を少なくとも１個含有す
るモノマ−が好適に使用することができる。その例とし
て、テトロヒドロフルフリルアクリレート、エチルカル
ビトールアクリレート、ジシクロペンテニルオキシエチ
ルアクリレート、フェニルカルビトールアクリレート、
ノニルフェノキシエチルアクリレート、２−ヒドロキシ
−３−フェノキシプロピルアクリレート、ω−ヒドロキ
シヘキサノイルオキシエチルアクリレート、アクリロイ
ルオキシエチルサクシネート、アクリロイルオキエチル
サクシネート、アクリロイルオキシエチルフタレート、
フェニルアクリレート、ナフチルアクリレート、トリブ
ロモフェニルアクリレート、フェノキシエチルアクリレ
ート、トリブロモフェノキシエチルアクリレート、ベン
ジルアクリレート、ｐ−ブロモベンジルアクリレート、
２，２−ビス（４−メタクリロキシエトキシ−３，５−
ジブロモフェニル）プロパン、イソボルニルアクリレー
ト，２−エチルヘキシルアクリレート、ラウリルアクリ
レート、２，２，３，３−テトラフルオロプロピルアク
リレート等の単官能性アクリレート並びにこれらの単官
能性アクリレートに対応するメタクリレート類；１，６
−ヘキサンジオールジアクリレート、ブタンジオールジ
アクリレート、ＥＯ変成テトラブロモビスフェノールＡ
ジアクリレート、ペンタエリスリトールトリアクリレー
ト、トリメチロールプロパントリアクリレート、ビスフ
ェノールＡジアクリレート、等の多官能アクリレート並
びにこれらの多官能性アクリレートに対応するメタクリ
レート類；スチレン、ｐ−クロロスチレン、ジビニルベ
ンゼン、ビニルアセテート、アクリロニトリル、Ｎ−ビ
ニルピロリドン、ビニルナフタレン、Ｎ−ビニルカルバ
ゾール等のビニル化合物；およびジエチレングリコール
ビスアリルカーボネート、トリアリルイソシアヌレー
ト、ジアリリデンペンタエリスリトール、ジアリルフタ
レート、ジアリルイソフタレート等のアリル化合物など
（混合物を含む）が挙げられる。The photopolymerizable monomer in the starting solution used in the production of the optical recording film and other films in the present invention is
A monomer containing at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group and an allyl group in the molecule can be preferably used. Examples thereof include tetrohydrofurfuryl acrylate, ethyl carbitol acrylate, dicyclopentenyl oxyethyl acrylate, phenyl carbitol acrylate,
Nonylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ω-hydroxyhexanoyloxyethyl acrylate, acryloyloxyethyl succinate, acryloyl oxyethyl succinate, acryloyloxyethyl phthalate,
Phenyl acrylate, naphthyl acrylate, tribromophenyl acrylate, phenoxyethyl acrylate, tribromophenoxyethyl acrylate, benzyl acrylate, p-bromobenzyl acrylate,
2,2-bis (4-methacryloxyethoxy-3,5-
Monofunctional acrylates such as dibromophenyl) propane, isobornyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and methacrylates corresponding to these monofunctional acrylates; 1 , 6
-Hexanediol diacrylate, butanediol diacrylate, EO modified tetrabromobisphenol A
Polyfunctional acrylates such as diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, bisphenol A diacrylate, and methacrylates corresponding to these polyfunctional acrylates; styrene, p-chlorostyrene, divinylbenzene, vinyl acetate, Vinyl compounds such as acrylonitrile, N-vinylpyrrolidone, vinylnaphthalene, and N-vinylcarbazole; and allyl compounds such as diethylene glycol bisallyl carbonate, triallyl isocyanurate, diallylidene pentaerythritol, diallyl phthalate, diallyl isophthalate, etc. Including).
【００１２】本発明で使用される出発溶液中の光重合性
オリゴマーの例としては、上記光重合性モノマーのオリ
ゴマーの他に、ウレタンアクリレ−トオリゴマー、エポ
キシアクリレ−トオリゴマー、エステルアクリレートオ
リゴマー、ポリオールポリアクリレート、変性ポリオー
ルポリアクリレート、イソシアヌル酸骨格のポリアクリ
レートなどの多官能性オリゴアクリレートやこれらのア
クリレートに対応するメタクリレート類など（混合物を
含む）が挙げられるが、これに限定されるものではな
い。Examples of the photopolymerizable oligomer in the starting solution used in the present invention include urethane acrylate oligomers, epoxy acrylate oligomers and ester acrylate oligomers in addition to the oligomers of the above photopolymerizable monomers. Examples include, but are not limited to, polyfunctional oligoacrylates such as polyol polyacrylates, modified polyol polyacrylates, polyacrylates having an isocyanuric acid skeleton, and methacrylates corresponding to these acrylates (including a mixture). Absent.
【００１３】ポリウレタンアクリレートオリゴマーとし
てはポリイソシアネートと２−ヒドロキシアルキル（メ
タ）アクリレートとポリオールの付加反応によって生成
するものが例示される。ここで、ポリイソシアネートと
してはトルエンジイソシアネート、イソホロンジイソシ
アネート、トリメチルヘキサメチレンジイソシアネー
ト、ヘキサメチレンジイソシアネートなどが挙げられ
る。また、ポリオールとしてはポリエチレングリコー
ル、ポリプロピレングリコール、ポリテトラメチレング
リコールなどのポリエーテルポリオール、ポリエステル
ポリオールやポリカーボネートポリオール、ポリシロキ
サンポリオール等が挙げられる。Examples of the polyurethane acrylate oligomer include those formed by the addition reaction of polyisocyanate, 2-hydroxyalkyl (meth) acrylate and polyol. Here, examples of the polyisocyanate include toluene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate. Examples of polyols include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polyester polyols, polycarbonate polyols and polysiloxane polyols.
【００１４】本発明で使用される、光記録膜その他の膜
の製造に用いられる出発溶液中の加水分解および重縮合
が可能である有機金属化合物としては、有機ケイ素化合
物、有機チタン化合物、有機ジルコニウム化合物、およ
び有機アルミニウム化合物のうち少なくとも１種を含む
ものが好ましく、特にアルコキシル基を有する金属アル
コキシドが好ましい。具体的にはシリコン、チタン、ジ
ルコニウム、アルミニウムなどのメトキシド、エトキシ
ド、プロポキシド、ブトキシドなどが単体または混合体
で用いられる。その例としてテトラエトキシシラン、テ
トラメトキシシラン、テトラブトキシシランなどの有機
ケイ素化合物；チタンイソプロポキシド、チタンブトキ
シドなどの有機チタン化合物；ジルコニウムメトキシ
ド、ジルコニウムブトキシドなどの有機ジルコニウム化
合物；アルミニウムエトキシド、アルミニウムブトキシ
ドなどの有機アルミニウム化合物などが挙げられる。ま
たジメチルシロキサン、アミノシラン及びシラノール末
端のポリジメチルシロキサンなどの側鎖に有機部を有す
る化合物、あるいはビニルシラン、アクリルシラン、エ
ポキシシランなどのように他の有機モノマーと重合可能
な官能基を有する化合物で有機的に修飾しても構わな
い。Organometallic compounds capable of being hydrolyzed and polycondensed in the starting solution used in the production of the optical recording film and other films used in the present invention include organosilicon compounds, organotitanium compounds and organozirconium compounds. Compounds and compounds containing at least one kind of organoaluminum compounds are preferable, and metal alkoxides having an alkoxyl group are particularly preferable. Specifically, methoxides such as silicon, titanium, zirconium, and aluminum, ethoxides, propoxides, butoxides, etc. are used alone or in a mixture. Examples thereof include organic silicon compounds such as tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane; organic titanium compounds such as titanium isopropoxide and titanium butoxide; organic zirconium compounds such as zirconium methoxide and zirconium butoxide; aluminum ethoxide, aluminum. Examples include organic aluminum compounds such as butoxide. In addition, a compound having an organic moiety in the side chain such as dimethylsiloxane, aminosilane and silanol-terminated polydimethylsiloxane, or a compound having a functional group capable of polymerizing with other organic monomers such as vinylsilane, acrylsilane, and epoxysilane is used. May be modified as desired.
【００１５】なお、上記金属アルコキシド以外にも金属
アセチルアセトネート、酢酸塩、シュウ酸塩などのカル
ボン酸塩及び硝酸塩、塩化物、オキシ塩化物などの金属
無機化合物を使用しても構わない。In addition to the above metal alkoxides, carboxylates such as metal acetylacetonates, acetates and oxalates, and metal inorganic compounds such as nitrates, chlorides and oxychlorides may be used.
【００１６】上記有機金属化合物は溶液中で加水分解し
重縮合が進むにつれてゾルから無機網目構造が形成され
ゲルとなる。このゲルを高温加熱処理すると金属酸化物
固体を作成することが出来る。The above organic metal compound is hydrolyzed in a solution, and as polycondensation proceeds, an inorganic network structure is formed from the sol to form a gel. When this gel is heated at a high temperature, a metal oxide solid can be produced.
【００１７】また本発明で用いられる前記有機金属化合
物を加水分解および重縮合させるために、溶媒、水、お
よび前記加水分解を促進させるための触媒が必要であ
る。この金属有機化合物を溶解すべき溶媒としては、メ
タノール、エタノール、プロパノール、ブタノールなど
のアルコール類が最も好ましい。また上記触媒として
は、塩酸、酢酸、硫酸、硝酸などの酸およびアンモニア
などの塩基が使用される。Further, in order to hydrolyze and polycondense the organometallic compound used in the present invention, a solvent, water and a catalyst for promoting the hydrolysis are required. Alcohols such as methanol, ethanol, propanol and butanol are most preferable as the solvent for dissolving the metal organic compound. As the catalyst, acids such as hydrochloric acid, acetic acid, sulfuric acid, nitric acid and bases such as ammonia are used.
【００１８】前述の光重合性モノマーまたはオリゴマー
と前述の有機金属化合物の組合わせに関して、特願平４
−１７２５３４においてはそれぞれの重合体の屈折率の
差があること、好ましくはその差が大きい方が高回折効
率を示すが、本発明においては、両者の屈折率とは無関
係に組合せを選択することができる。なぜなら、後で述
べるように、光重合性モノマーまたはオリゴマーが重合
してできた有機ポリマーは後の行程により除去され、光
記録膜中には無機質の網目構造のみを残し、空隙には空
気のような気体を存在させるからである。Regarding the combination of the above-mentioned photopolymerizable monomer or oligomer and the above-mentioned organometallic compound, Japanese Patent Application No.
In -172534, there is a difference in the refractive index of each polymer, and the larger the difference is, the higher the diffraction efficiency is. However, in the present invention, a combination should be selected regardless of the refractive index of both. You can This is because, as will be described later, the organic polymer formed by the polymerization of the photopolymerizable monomer or oligomer is removed by the later process, leaving only the inorganic network structure in the optical recording film and leaving the voids like air. This is because such a gas is present.
【００１９】前述の光重合性モノマーまたはオリゴマー
を活性放射線によって重合させるために、これに光重合
開始剤を添加しておく必要がある。本発明の光重合開始
剤としては以下に示す化合物が挙げられる。例えば、
２，３−ボルナンジオン（カンファーキノン）、２，
２，５，５，−テトラメチルテトラヒドロ−３，４−フ
ラン酸（イミダゾールトリオン）などの環状シス−α−
ジカルボニル化合物、３，３’，４，４’−テトラ−
（ｔ−ブチルパーオキシカルボニル）ベンゾフェノンな
どのベンゾフェノン、ジアセチル、ベンジル、ミヒラー
ズケトン、ジエトキシアセトフェノン、２ーヒドロキシ
ー２ーメチルプロピオフェノン、１ーヒドロキシシクロ
ヘキシルフェニルケトンなどのケトン類、ベンゾイルパ
ーオキサイド、ジ−ｔ−ブチルパーオキサイドなどの過
酸化物、アリルジアゾニウム塩などのアゾ化合物、Ｎ−
フェニルグリシンなどの芳香族カルボン酸、２ークロロ
チオキサントン、２，４−ジエチルチオキサントンなど
のキサンテン類、ジアリルヨードニウム塩、トリアリル
スルホニウム塩、トリフェニルアルキルほう酸塩、鉄ア
レン錯体、ビスイミダゾール類、ポリハロゲン化合物、
フェニルイソオキサゾロン、ベンゾインエチルエーテ
ル、ベンジルジメチルケタールなど（混合物を含む）が
挙げられる。更には助剤として、アミン類、チオール
類、ｐ−トルエンスルホン酸なども挙げられる。In order to polymerize the above-mentioned photopolymerizable monomer or oligomer by actinic radiation, it is necessary to add a photopolymerization initiator to it. Examples of the photopolymerization initiator of the invention include the compounds shown below. For example,
2,3-bornanedione (camphorquinone), 2,
Cyclic cis-α-such as 2,5,5, -tetramethyltetrahydro-3,4-furanic acid (imidazoletrione)
Dicarbonyl compound, 3,3 ', 4,4'-tetra-
Benzophenone such as (t-butylperoxycarbonyl) benzophenone, diacetyl, benzyl, Michler's ketone, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, ketones such as 1-hydroxycyclohexylphenyl ketone, benzoyl peroxide, di-t -Peroxides such as butyl peroxide, azo compounds such as allyldiazonium salts, N-
Aromatic carboxylic acids such as phenylglycine, xanthenes such as 2-chlorothioxanthone and 2,4-diethylthioxanthone, diallyl iodonium salts, triallyl sulfonium salts, triphenylalkylborates, iron allene complexes, bisimidazoles, polyhalogens Compound,
Examples thereof include phenylisoxazolone, benzoin ethyl ether, benzyl dimethyl ketal and the like (including a mixture). Further, examples of the auxiliary agent include amines, thiols, p-toluenesulfonic acid and the like.
【００２０】この光記録膜用出発溶液は主成分で表わし
て、 光重合性モノマーまたはオリゴマーの合計 １０〜８０重量％、 光重合開始剤 ０．０５〜３０重量％、 前記有機金属化合物 ５〜９０重量％、 前記有機金属化合物のための溶媒 ５〜９０重量％、 水 ０．０１〜３０重量％、および 触媒 ０．０５〜３０重量％ を含有していることが好ましい。上記光重合性モノマー
またはオリゴマーの合計が１０重量％未満、または８０
重量％を越えると高い回折効率が得られ難くなる。同様
に上記有機金属化合物が５重量％未満または９０重量％
を超えると高い回折効率が得られない。この組成物は必
要に応じてそれぞれ光増感剤を０．０１〜１０重量％、
可塑剤を０．０１〜１０重量％を含有させることができ
る。The starting solution for the optical recording film is represented by the main component, and the total amount of the photopolymerizable monomer or oligomer is 10 to 80% by weight, the photopolymerization initiator is 0.05 to 30% by weight, and the organometallic compound is 5 to 90%. It preferably contains 5% by weight, a solvent for the organometallic compound 5 to 90% by weight, water 0.01 to 30% by weight, and a catalyst 0.05 to 30% by weight. The total amount of the above photopolymerizable monomers or oligomers is less than 10% by weight, or 80
If it exceeds the weight%, it becomes difficult to obtain high diffraction efficiency. Similarly, the organometallic compound is less than 5% by weight or 90% by weight
If it exceeds, high diffraction efficiency cannot be obtained. This composition contains 0.01 to 10% by weight of a photosensitizer, if necessary.
The plasticizer may be contained in an amount of 0.01 to 10% by weight.
【００２１】使用する光重合性モノマーまたはオリゴマ
ーが低粘性を有する液体である場合には溶媒は必要では
ないが、これが固体であるかまたは高粘性を有する場合
には、それを溶解するための溶媒を使用する。この溶媒
としては例えばトルエン、ジオキサン、クロロホルム、
ジクロロメタン、メチレンクロライド、テトラヒドロフ
ラン等を使用することができる。ただし光重合性モノマ
ーまたはオリゴマーが先に述べた有機金属化合物のため
の溶媒に溶解する場合、例えばイソプロピルアルコール
はテトラエトキシシラン（加水分解および重縮合が可能
である有機金属化合物）の溶媒であると共に、２−ヒド
ロキシ−３−フェノキシヘキシルアクリレート（固体の
光重合性モノマー）の溶媒でもあるので、前記有機金属
化合物のための溶媒であるイソプロピルアルコールは光
重合性モノマーまたはオリゴマーのための溶媒を兼用す
ることができる。No solvent is required if the photopolymerizable monomer or oligomer used is a liquid having a low viscosity, but if it is a solid or has a high viscosity, a solvent for dissolving it. To use. Examples of the solvent include toluene, dioxane, chloroform,
Dichloromethane, methylene chloride, tetrahydrofuran and the like can be used. However, when the photopolymerizable monomer or oligomer is dissolved in the solvent for the organometallic compound described above, for example, isopropyl alcohol is a solvent for tetraethoxysilane (organometallic compound capable of hydrolysis and polycondensation) and Since it is also a solvent for 2-hydroxy-3-phenoxyhexyl acrylate (solid photopolymerizable monomer), isopropyl alcohol, which is a solvent for the organometallic compound, also serves as a solvent for the photopolymerizable monomer or oligomer. be able to.
【００２２】また、加水分解および重縮合反応可能な有
機金属化合物、例えばシリコン系化合物としてジメチル
シロキサン、アミノシラン、及びシラノール末端のポリ
ジメチルシロキサン、γ−メタクリロキシプロピルトリ
エトキシシラン、γ−グルシジロキシプロピルトリエト
キシシランにより無機網目構造を有機修飾して有機無機
複合体としても構わない。すなわち上記化合物のうち例
えばジメチルシロキサン、ポリジメチルシロキサンを、
上記加水分解および重縮合が可能である有機金属化合
物、例えばテトラエトキシシランと組み合わせて、シロ
キサン無機網目構造中に有機基を導入しフレキシビリテ
ィーを付与させることもでき、それにより加熱前の膜の
取扱が容易になる。Organometallic compounds capable of undergoing hydrolysis and polycondensation reactions, such as dimethylsiloxane, aminosilane as a silicon compound, and silanol-terminated polydimethylsiloxane, γ-methacryloxypropyltriethoxysilane, γ-glucidyloxypropyl. The inorganic network structure may be organically modified with triethoxysilane to form an organic-inorganic composite. That is, of the above compounds, for example, dimethyl siloxane, polydimethyl siloxane,
In combination with an organometallic compound capable of hydrolysis and polycondensation, for example, tetraethoxysilane, it is also possible to introduce an organic group into the siloxane inorganic network structure to impart flexibility, whereby the film before heating is heated. Easy to handle.
【００２３】この光記録膜用出発溶液に可塑剤を添加す
ることができる。可塑剤は光記録用組成物中の光重合型
モノマー（またはオリゴマー）に可塑性を付与するため
のものであり、可塑剤の例として、トリエチレングリコ
ールジカプリレート、トリエチレングリコールジアセテ
ート、トリエチレングリコールジプロピオネート、グリ
セリルトリブチレート、テトラエチレングリコールジヘ
プタノエート、ジエチルアジペート、ジエチルセバケー
ト、トリブチルフォスフェートなどを挙げることができ
る。A plasticizer can be added to the starting solution for the optical recording film. The plasticizer is for imparting plasticity to the photopolymerizable monomer (or oligomer) in the optical recording composition, and examples of the plasticizer include triethylene glycol dicaprylate, triethylene glycol diacetate and triethylene. Glycol dipropionate, glyceryl tributyrate, tetraethylene glycol diheptanoate, diethyl adipate, diethyl sebacate, tributyl phosphate and the like can be mentioned.
【００２４】更に、この光記録膜用出発溶液に色素のよ
うな増感剤を添加することができる。これは活性放射線
により効率よく重合反応を起こさせるためである。使用
される色素などとしては以下に示す化合物が挙げられる
が、これに限定されるものではない。例えば、可視光線
を使用する場合にはメチレンブルー、アクリジンオレン
ジ、チオフラビン、ケトクマリン、エリスロシンＣ、エ
オシンＹ、メロシアニン、フタロシアニン、ポルフィリ
ンなど（混合物を含む）の可視光域に吸光を持つ化合物
である。Further, a sensitizer such as a dye can be added to the starting solution for the optical recording film. This is because the active radiation efficiently causes the polymerization reaction. Examples of the dye and the like to be used include the compounds shown below, but the dye is not limited thereto. For example, when using visible light, it is a compound having an absorption in the visible light region such as methylene blue, acridine orange, thioflavin, ketocoumarin, erythrosine C, eosin Y, merocyanine, phthalocyanine, porphyrin (including a mixture).
【００２５】また、本発明の出発溶液に対し、上記成分
に加えてレベリング剤その他の添加剤を追加すること
も、均一な塗膜を作るために非常に有用である。It is also very useful to add a leveling agent and other additives to the starting solution of the present invention in addition to the above components in order to form a uniform coating film.
【００２６】次に本発明の出発溶液を用いて光を記録す
る方法を説明する。光記録材料を調製するには、水、溶
媒、触媒となる酸または塩基を含む有機金属化合物溶液
中に光重合性オリゴマー、モノマー、光重合開始剤、色
素を溶解するのであるが、必要であれば、例えば、メタ
ノ−ル、エタノ−ル、イソプロパノール、トルエン、ジ
オキサン、クロロホルム、ジクロロメタン、メチレンク
ロライド、テトラヒドロフランその他の溶媒（これらの
混合物を含む）が用いられる。これらの溶媒の使用量は
通常、光記録用組成物の主成分１００重量部（溶剤を除
く）に対して、１０〜１０００重量部である。Next, a method of recording light using the starting solution of the present invention will be described. In order to prepare an optical recording material, a photopolymerizable oligomer, a monomer, a photopolymerization initiator and a dye are dissolved in a solution of an organic metal compound containing water, a solvent, an acid or a base serving as a catalyst. For example, methanol, ethanol, isopropanol, toluene, dioxane, chloroform, dichloromethane, methylene chloride, tetrahydrofuran and other solvents (including mixtures thereof) are used. The amount of these solvents used is usually 10 to 1000 parts by weight with respect to 100 parts by weight of the main component (excluding the solvent) of the optical recording composition.
【００２７】その後、上記のような組成比で光記録用出
発溶液を調製した後、この液状物をガラス板、シリコン
基板などの平滑な基材表面上に種々の塗布方法を用いて
コーティングを行う。コーティング方法としてはスピン
コート、ディップコート、バーコート、フローコート
（カーテンコート）などや、ドクターブレード、アプリ
ケーターを用いた方法など種々の方法が適用できる。Thereafter, an optical recording starting solution having the above composition ratio is prepared, and then the liquid material is coated on a smooth substrate surface such as a glass plate or a silicon substrate by various coating methods. . As a coating method, various methods such as spin coating, dip coating, bar coating, flow coating (curtain coating), and a method using a doctor blade or an applicator can be applied.
【００２８】その後、この塗布膜を室温または加温状
態、必要であれば更に減圧状態の下で、一定時間、一定
温度の下に保持して、出発溶液中に含まれた溶媒または
光重合性オリゴマーまたはモノマーを溶解するときに使
用した溶媒、水、触媒などの揮発成分を塗膜の中から蒸
発、除去させて、有機金属化合物が加水分解、重縮合反
応により形成された無機網目構造中に光重合性オリゴマ
ー、モノマー、光重合開始剤、光増感剤などが均一に取
り込まれた固体状の光記録用フィルムが平滑な基材表面
上に被覆された状態で得られる。実際には、これらの揮
発成分は完全に除去されずに、数重量％程度まで残留し
ても、実質的に固体状の膜状体が得られれば問題ない。
光記録用膜の乾燥後の厚みは通常０．０１〜１００μｍ
である。その後、得られた光記録用膜の表面上に、次工
程で照射または露出する活性放射線に対し透明な樹脂フ
ィルムまたはガラス板を適当な方法を用いてカバーす
る。これは本組成物がラジカル重合で重合が進行するた
め酸素による重合阻害作用を防止するためと、塵埃、異
物などの付着を防止するためである。Then, the coating film is kept at room temperature or under heating, or under reduced pressure if necessary, for a certain period of time at a constant temperature, and the solvent or photopolymerizable property contained in the starting solution is maintained. Volatile components such as solvent, water and catalyst used when dissolving the oligomer or monomer are evaporated and removed from the coating film, and the organometallic compound is hydrolyzed into the inorganic network structure formed by polycondensation reaction. A solid optical recording film in which a photopolymerizable oligomer, a monomer, a photopolymerization initiator, a photosensitizer and the like are uniformly incorporated can be obtained in a state of being coated on a smooth base material surface. Actually, even if these volatile components are not completely removed and remain up to several wt%, there is no problem as long as a substantially solid film body is obtained.
The thickness of the optical recording film after drying is usually 0.01 to 100 μm.
Is. Then, on the surface of the obtained optical recording film, a resin film or a glass plate transparent to the actinic radiation to be irradiated or exposed in the next step is covered by an appropriate method. This is to prevent the polymerization inhibiting action of oxygen due to the progress of radical polymerization of the present composition, and to prevent the adhesion of dust and foreign matter.
【００２９】次に上記のカバーされた光記録膜を、活性
放射線に露出する行程を行う。活性放射線とは紫外線、
可視光、赤外線などの輻射線、電子ビーム、イオンビー
ムなど、照射により光重合性オリゴマー、モノマーに重
合反応を生じさせることができる放射線を指す。この行
程として、例えば可干渉性を有する輻射線によって得ら
れる干渉縞に露光させる方法がある。一般的には可干渉
性の光源としてレーザー光源を使用する公知の方法が用
いられる。干渉露光の方法としては既知のホログラフィ
ック露光光学系を使用して実施することができる。通
常、この方法は二光束干渉露光法と呼ばれている。レー
ザ発振器から発振するレーザ光を、ビームスプリッタ
ー，ビームエキスパンダー，コリメーターレンズ等を用
いて、２つの平行光あるいは拡散光に分けられる。そし
てその一方の光束を参照光として光記録材料に入射させ
る。他方の光束は例えば物体像を記録する場合はその物
体に照射され、その物体からの反射光を物体光として光
記録材料に入射させる。このとき参照光と物体光が干渉
縞を形成し、その干渉縞が光記録用膜に記録されて光記
録膜（ホログラム）が得られるのである。Next, the above-mentioned covered optical recording film is exposed to actinic radiation. Actinic radiation is ultraviolet light,
This refers to radiation that can cause a photopolymerizable oligomer or monomer to undergo a polymerization reaction upon irradiation, such as visible light or infrared radiation, electron beam, or ion beam. As this process, there is a method of exposing to interference fringes obtained by radiation having coherence, for example. Generally, a known method using a laser light source as a coherent light source is used. As a method of interference exposure, a known holographic exposure optical system can be used. This method is usually called a two-beam interference exposure method. The laser light emitted from the laser oscillator is divided into two parallel lights or diffused lights by using a beam splitter, a beam expander, a collimator lens, and the like. Then, one of the light fluxes is made incident on the optical recording material as reference light. When recording an object image, for example, the other light flux is applied to the object, and the reflected light from the object is incident on the optical recording material as object light. At this time, the reference light and the object light form interference fringes, and the interference fringes are recorded on the optical recording film to obtain an optical recording film (hologram).
【００３０】また、活性放射線に露出する方法として、
上記干渉露光法の他に、パターニングマスクを用いる方
法でもよい。輻射線を通過させない物質で所定のパター
ンを作成したマスクを前記光記録用膜の上に載置し、例
えば高圧水銀ランプの輻射線をパターニングマスクを通
して露光する方法が挙げられる。さらには一定口径の活
性放射線ビームを走査させる方法でもよい。As a method of exposing to actinic radiation,
In addition to the interference exposure method, a method using a patterning mask may be used. There is a method in which a mask having a predetermined pattern formed of a substance that does not pass radiation is placed on the optical recording film and the radiation of a high pressure mercury lamp is exposed through a patterning mask. Further, a method of scanning an actinic radiation beam having a constant diameter may be used.
【００３１】活性放射線に露出する時間はその活性放射
線の強度、記録面積その他によって異なるが、通常０．
１秒〜３０分であり、全露光量が０．１〜１０００mJ/c
m2になるように露出される。The exposure time to actinic radiation varies depending on the intensity of the actinic radiation, the recording area, etc., but is usually 0.
1 second to 30 minutes, total exposure is 0.1 to 1000 mJ / c
Exposed to m 2 .
【００３２】光記録膜を活性放射線に露出する行程の次
に、該光記録材料中に残存する未重合の光重合性オリゴ
マー、モノマーの重合を完結し、そして未反応の光重合
開始剤及び色素などの光増感剤を失活する工程を経る事
が好ましい。Next to the step of exposing the optical recording film to actinic radiation, polymerization of unpolymerized photopolymerizable oligomers and monomers remaining in the optical recording material is completed, and unreacted photopolymerization initiator and dye are added. It is preferable to go through the step of deactivating the photosensitizer such as.
【００３３】この工程は、活性放射線に露出した後の光
記録膜の全面に対し重合反応を生じさせ得る均一な活性
放射線照射を行なうことができる。この均一照射によっ
て光記録膜中の未重合オリゴマー、モノマーの重合が完
結し、形成されていた組成分布が固定される。この工程
は全露出量が通常約１０〜１００００mJ/cm2になるよう
に行なわれる。ただしこの工程を行わなくても次に述べ
る有機成分を除去する工程により同等の効果が得られ
る。In this step, uniform actinic radiation capable of causing a polymerization reaction can be applied to the entire surface of the optical recording film after being exposed to actinic radiation. This uniform irradiation completes the polymerization of unpolymerized oligomers and monomers in the optical recording film, and fixes the composition distribution formed. This step is performed so that the total exposure is usually about 10-10000 mJ / cm 2 . However, even if this step is not performed, the same effect can be obtained by the step of removing the organic component described below.
【００３４】次の行程として、上述の工程により得られ
た光記録膜より有機成分を除去することを行う。前記有
機成分とは前述した光重合性モノマーまたはオリゴマー
が重合した有機ポリマーだけでなく、未重合のモノマ
ー、オリゴマー、さらに光重合開始剤、色素、溶媒など
の残存物も含まれる。その方法としては、例えば少なく
とも２００度以上の温度に加熱する方法が挙げられる。
加熱処理によって光記録膜中の有機成分が、酸化、分解
され、光記録膜から除去され、その除去された跡は空隙
として残り、そこに空気のような気体が存在する。この
加熱温度は使用した光重合性モノマー、オリゴマーある
いは溶媒などの除去される有機化合物にも依存する。ま
た光記録膜の緻密性を高め、機械的強度を上げるために
も高温まで加熱することが好ましい。したがって加熱温
度範囲は２００℃から１２００℃程度、また加熱時間は
少なくとも１分以上が好ましい。As the next step, the organic components are removed from the optical recording film obtained by the above steps. The organic component includes not only the above-described organic polymer in which the photopolymerizable monomer or oligomer is polymerized, but also unpolymerized monomer or oligomer, and a residual substance such as a photopolymerization initiator, a dye or a solvent. Examples of the method include a method of heating to a temperature of at least 200 degrees or more.
The organic components in the optical recording film are oxidized and decomposed by the heat treatment and removed from the optical recording film, and the removed traces remain as voids, in which a gas such as air exists. This heating temperature also depends on the organic compound to be removed such as the photopolymerizable monomer, oligomer or solvent used. Further, it is preferable to heat to a high temperature in order to increase the denseness of the optical recording film and the mechanical strength. Therefore, it is preferable that the heating temperature range is about 200 ° C. to 1200 ° C. and the heating time is at least 1 minute or more.
【００３５】光記録膜より有機成分を除去する他の方法
として、約１８４ｎｍの紫外線を照射し発生させたオゾ
ンにより有機成分を酸化分解させる方法、または溶媒を
用いて有機成分を溶出する方法等が挙げられる。またこ
れらの行程を併用してもよい。As another method for removing the organic component from the optical recording film, there is a method of oxidatively decomposing the organic component with ozone generated by irradiating ultraviolet rays of about 184 nm, or a method of eluting the organic component with a solvent. Can be mentioned. These steps may be used together.
【００３６】この工程で、光記録された膜中に残存する
水、触媒、有機成分が除去されて空隙となり、、無機成
分（金属酸化物）が残る。その際に光記録によって変調
された無機網目構造と有機高分子の組成分布が、無機網
目構造の変調として記録されたことになる。この工程で
得られた膜は有機成分を含有しないため、耐熱性、耐候
性、耐環境性が非常に優れている。In this step, water, catalyst, and organic components remaining in the optically recorded film are removed to form voids, and inorganic components (metal oxides) remain. At that time, the composition distribution of the inorganic network structure and the organic polymer modulated by the optical recording is recorded as the modulation of the inorganic network structure. Since the film obtained in this step contains no organic component, it has excellent heat resistance, weather resistance and environment resistance.
【００３７】また上記膜の空隙率（逆に表現すれば無機
物質（金属酸化物）のみかけ密度）、例えば、膜の単位
微小体積あたり（１０のマイナス２１乗立方ｍあたり）
の空隙率は上記光記録の変調により膜表面の場所によっ
て変化しるが、上記工程で無機網目構造を構成する無機
物質たとえばシリカが変形し得るような高い温度例えば
約３００℃以上に加熱する場合には、無機物質の表面張
力によって無機物質の密度が相対的に小さい膜状体部分
が相対的に大きい膜状体部分よりも大きく収縮して、膜
状体表面に制御された凹凸が形成される。Further, the porosity of the above-mentioned film (in other words, the apparent density of the inorganic substance (metal oxide)), for example, per unit minute volume of the film (per 10 −21 cubic m)
The porosity of changes depending on the location of the film surface due to the modulation of the above optical recording, but in the above step, when the inorganic substance forming the inorganic network structure such as silica is heated to a high temperature, for example, about 300 ° C. or higher. The surface tension of the inorganic substance causes the film portion having a relatively low density of the inorganic material to shrink more than the film portion having a relatively large density, thereby forming controlled unevenness on the surface of the film. It
【００３８】次に本発明の原理について述べる。Next, the principle of the present invention will be described.
【００３９】溶媒、水、および触媒である酸または塩基
を一定量含む有機金属化合物溶液中に、光重合開始剤、
および必要に応じて光増感剤、可塑剤などの添加剤を含
有した光重合性モノマーまたはオリゴマーを加え、攪
拌、混合する。均一に混合された溶液は基板の上に種々
の方法でコーティングされ膜状体が得られる。この段階
では粘性液体からなる膜状体であるが、コーティングの
後に時間が経過するにつれ、有機金属化合物の加水分
解、重縮合が進行し無機網目構造が形成され、ゾルから
ゲル状態に変化する。更に、強制乾燥または自然乾燥を
進めることによって、無機網目構造中に含まれていた溶
媒、水等の揮発成分が蒸発していき、結果として固体状
の光記録用膜状体が得られる。A photopolymerization initiator is added to a solution of an organic metal compound containing a solvent, water, and a certain amount of a catalyst acid or base.
Then, a photopolymerizable monomer or oligomer containing an additive such as a photosensitizer and a plasticizer is added if necessary, and the mixture is stirred and mixed. The uniformly mixed solution is coated on the substrate by various methods to obtain a film-like body. At this stage, it is a viscous liquid film, but as time passes after coating, hydrolysis and polycondensation of the organometallic compound progress to form an inorganic network structure and change from a sol to a gel state. Further, by proceeding with forced drying or natural drying, volatile components such as a solvent and water contained in the inorganic network structure are evaporated, and as a result, a solid optical recording film-like material is obtained.
【００４０】活性放射線に露出する前の光記録膜中で
は、光重合性モノマーまたはオリゴマーは膜全体に形成
された無機網目構造中に均一に保持されているが、レー
ザなどの二光束干渉露光によって形成された干渉縞への
露光、またはマスクパターン露光などのよる活性放射線
に露出行程中に、光記録膜内部での光強度分布により選
択的に重合が開始される。すなわち光強度が強い部分で
重合が始まりそれにつれモノマーが消費されるので、隣
接した光強度が弱い部分から光強度が強い部分にモノマ
ーが供給され更に重合が促進される。この際に、もとも
と光強度が強い部分に存在していた無機網目構造の一部
分は、光強度が弱い部分から供給されたモノマーにより
体積が大きくなった重合体により押し出されて、光強度
が弱い隣接部分に移動することになり、最終的には光強
度が強い部分である、光重合性モノマー（またはオリゴ
マー）が重合した有機ポリマーリッチ領域と、それとは
逆に光強度が弱い部分である、相対的に無機網目構造リ
ッチ領域とに区分され、その両領域の間に大きな組成差
が生じるものと考えられる。この時に光重合性モノマー
（またはオリゴマー）が重合した有機ポリマーの屈折率
Ｎｐと無機網目構造の屈折率Ｎｍ（前記有機金属化合物
が、加水分解および重縮合してできた無機物質が有する
屈折率）との差を利用した光記録膜が本出願人が出願し
た特願平４−１７２５３４である。In the optical recording film before being exposed to actinic radiation, the photopolymerizable monomer or oligomer is uniformly held in the inorganic network structure formed on the entire film. During the exposure process to actinic radiation such as exposure to the formed interference fringes or exposure to a mask pattern, polymerization is selectively initiated by the light intensity distribution inside the optical recording film. That is, since the polymerization starts in the portion where the light intensity is strong and the monomer is consumed accordingly, the monomer is supplied from the adjacent portion where the light intensity is strong to the portion where the light intensity is strong, and the polymerization is further promoted. At this time, a part of the inorganic network structure, which originally existed in the portion where the light intensity was strong, was extruded by the polymer whose volume was increased by the monomer supplied from the portion where the light intensity was weak, and the adjacent portion where the light intensity was weak. The photopolymerizable monomer (or oligomer) is polymerized with the organic polymer-rich region where the light intensity is finally strong, and the region where the light intensity is weak, on the contrary, the relative It is considered that the region is richly divided into the inorganic network structure rich region, and a large compositional difference occurs between the two regions. At this time, the refractive index Np of the organic polymer in which the photopolymerizable monomer (or oligomer) is polymerized and the refractive index Nm of the inorganic network structure (the refractive index of the inorganic substance formed by hydrolysis and polycondensation of the organometallic compound) An optical recording film utilizing the difference between the above and Japanese Patent Application No. Hei 4-172534 filed by the present applicant.
【００４１】本発明の光記録膜においては、前述の活性
放射線への露出によって有機ポリマー成分と無機網目構
造の組成分布を形成させた記録膜から、内部に含まれる
有機ポリマー、または反応が未完結のオリゴマー、モノ
マーのような有機成分を除去させる。従って、特願平４
−１７２５３４で示したポリマーの屈折率Ｎｐと無機網
目構造の屈折率Ｎｍとの差を利用するのではなく、無機
網目構造の屈折率Ｎｍと前記有機成分が出ていった空間
に存在する空気その他の気体の屈折率との差を利用する
ものであるので、光重合性モノマーまたはオリゴマーと
有機金属化合物の組合せを選定する際、屈折率の制限は
なく、そのためより多くの組合せが可能となる。In the optical recording film of the present invention, the organic polymer contained in the inside of the recording film in which the composition distribution of the organic polymer component and the inorganic network structure is formed by the above-mentioned exposure to actinic radiation, or the reaction is incomplete. The organic components such as oligomers and monomers of are removed. Therefore, Japanese Patent Application No. 4
Instead of utilizing the difference between the refractive index Np of the polymer and the refractive index Nm of the inorganic network structure shown in -172534, the refractive index Nm of the inorganic network structure and the air existing in the space where the organic component has come out, etc. Since the difference between the refractive index of the gas and the refractive index of the gas is used, there is no limitation on the refractive index when selecting the combination of the photopolymerizable monomer or oligomer and the organometallic compound, and therefore more combinations are possible.
【００４２】本発明の有機成分を除去する工程によって
光記録膜は多孔質状となり、全体は厚み方向に約２分の
１〜２０分の１の厚みに収縮する。なおこの膜は平面方
向にも収縮しようとするが、基材に拘束されているため
実際には平面方向の収縮は殆ど生じない。この時、２つ
のタイプの変化が起こり得る。第１のタイプは、有機ポ
リマーリッチ領域において有機成分が除去されることに
より、その領域の空隙率が高くなる。それに対し無機網
目構造リッチ領域は有機ポリマーリッチであった領域よ
り空隙率は低い。そして空隙率の低い部分は空隙率の高
い部分よりも高い見かけの屈折率を有する。すなわちこ
の場合には光強度分布が空隙率の分布となって記録され
たことになる。言い替えれば、強い強度の光があたった
膜部分の無機物質のみかけ密度が低くなり、逆に弱い強
度の光があたった膜部分の無機物質のみかけ密度が高く
なる。加水分解および重縮合が可能である有機金属化合
物として、有機ケイ素化合物を用いるよりも有機チタン
化合物を用いた方が、空隙率の低い部分と空隙率の高い
部分との見かけの屈折率差は大きくなる。それは無機網
目構造を構成する酸化チタンの方が酸化珪素（屈折率＝
１．４６）よりもそれ自体高い屈折率（２．３５）を有
するからである。第２のタイプは、第１のタイプの変化
に続いて、多孔質膜がより緻密化される場合、空隙率の
高い有機ポリマーリッチであった領域は、無機網目構造
リッチ領域よりも相対的に収縮率が大きくなるので記録
膜には表面凹凸が形成される場合である。この時、光強
度の高い領域は凹部を形成し、光強度の低い領域は凸部
を形成する。この凹凸の高さは、記録膜の組成、膜の厚
み、照射する光強度分布、加熱温度などによって異な
り、凹凸が殆ど生じない場合もあるが、通常は０．００
１μｍ〜１０μｍの凹凸高さを生じる。By the step of removing the organic component of the present invention, the optical recording film becomes porous, and the entire film shrinks to a thickness of about 1/2 to 1/20 in the thickness direction. Although this film also tries to shrink in the plane direction, in actuality there is almost no shrinkage in the plane direction because it is constrained by the base material. At this time, two types of changes can occur. In the first type, the organic component is removed in the organic polymer-rich region, so that the porosity of the region is increased. On the other hand, the porosity of the region rich in the inorganic network structure is lower than that of the region rich in the organic polymer. The portion with a low porosity has a higher apparent refractive index than the portion with a high porosity. That is, in this case, the light intensity distribution is recorded as a distribution of porosity. In other words, the apparent density of the inorganic substance in the film portion exposed to the intense light becomes low, and conversely, the apparent density of the inorganic substance in the film portion exposed to the weak light becomes high. As an organometallic compound that can be hydrolyzed and polycondensed, using an organotitanium compound rather than using an organosilicon compound causes a large apparent difference in refractive index between a portion having a low porosity and a portion having a high porosity. Become. Titanium oxide that constitutes the inorganic network structure is more silicon oxide (refractive index =
It has a higher refractive index (2.35) per se than 1.46). In the second type, when the porous film is further densified following the change in the first type, the region having a high porosity and having a high organic polymer content is relatively higher than the inorganic network structure-rich region. This is the case where the surface unevenness is formed on the recording film because the shrinkage ratio increases. At this time, a concave portion is formed in a region with high light intensity, and a convex portion is formed in a region with low light intensity. The height of the unevenness varies depending on the composition of the recording film, the thickness of the film, the distribution of the intensity of the light to be irradiated, the heating temperature, and the like, and the unevenness may hardly occur, but it is usually 0.00
The uneven height of 1 μm to 10 μm is generated.
【００４３】表面凹凸か、空孔分布かは無機成分に用い
る化合物、有機成分と無機成分の濃度、加熱処理温度等
の条件による。極端に加熱処理温度が高い場合には、空
隙率の高い有機ポリマーリッチ領域も、無機網目構造リ
ッチ領域もともに空隙率がゼロになり表面凹凸のみが形
成される。また表面凹凸と空孔分布の両方を形成させる
ことも可能である。表面凹凸と空孔分布の両方を形成さ
せる場合、光記録膜としてはそれらは相加的に働く。Whether the surface is uneven or the pore distribution depends on conditions such as the compound used as the inorganic component, the concentrations of the organic component and the inorganic component, and the heat treatment temperature. When the heat treatment temperature is extremely high, the porosity becomes zero in both the organic polymer rich region having a high porosity and the inorganic network structure rich region, and only surface irregularities are formed. It is also possible to form both surface irregularities and pore distribution. When both surface irregularities and pore distribution are formed, they act additively as an optical recording film.
【００４４】以上は膜の厚み方向には空孔（空隙）分布
が生じないとして説明したが、実際には空孔分布は膜の
厚み方向および平面方向にも生じることが多い。特に可
干渉性を有する輻射線によって得られる干渉縞に露光さ
せる場合にはそれが顕著である。Although the above description has been made on the assumption that no pore (void) distribution occurs in the thickness direction of the film, in reality, the pore distribution often occurs in the thickness direction and the plane direction of the film. This is particularly noticeable when exposing to interference fringes obtained by coherent radiation.
【００４５】[0045]
【発明の効果】本発明によって、化学的に安定な無機成
分から構成される、優れた耐光性、耐熱性、耐環境性な
どの耐久性有し、かつ高回折効率、高解像力及び高透過
率などの優れた光学特性を示す光記録膜を得ることがで
きる。また本発明によって、微細な凹凸加工を施した薄
膜を得ることが可能となる。Industrial Applicability According to the present invention, it is composed of a chemically stable inorganic component and has excellent durability such as light resistance, heat resistance and environment resistance, and also has high diffraction efficiency, high resolution and high transmittance. It is possible to obtain an optical recording film exhibiting excellent optical characteristics such as Further, according to the present invention, it becomes possible to obtain a thin film on which fine unevenness processing has been performed.
【００４６】[0046]
【実施例】以下、この発明の実施例を挙げて説明するが
本発明はこれらの実施例に限定されるものではない。 ＜以下に示す化合物の説明＞ ＴＥＯＳ ：テトラエトキシシラン ＰＤＭＳ ：末端シラノール基ポリジメチルシロキサ
ン ＴＨＦ ：テトラヒドロフラン ｉ−ＰＡ ：イソプロピルアルコール ＨＣｌ ：１Ｎ塩酸 Ｔi(ＯＰr)4：テトライソプロポキシチタン ＨＰＰＡ ：２−ヒドロキシ−３−フェノキシプロピ
ルアクリレート ＥＢＰＡ ：エトキシレートビスフェノールＡジアク
リレート ＢＴＴＢ ：３，３’，４，４’−テトラ−（ｔ−ブ
チルパーオキシカルボニル）ベンゾフェノン（日本油脂
製、純度５０％） ＫＣＤ ：３，３’−カルボニルビス（７−ジエチ
ルアミノクマリン）（日本感光色素研究所製） 実施例１ まず最初に光記録膜用出発溶液を以下の条件で調製し
た。 ＜溶液１＞ ---------------------------------------------------- ＴＥＯＳ（加水分解および重縮合が可能 である有機金属化合物として） ２７ｇ ＰＤＭＳ（同上） ３ｇ ＴＨＦ（溶媒） ５ｃｃ ｉ−ＰＡ（溶媒） ９ｃｃ ------------------------------------------------------ ＜溶液２＞ -------------------------------------------------------------- ｉ−ＰＡ（溶媒） １２ｃｃ Ｈ2Ｏ（ＴＥＯＳ、ＰＤＭＳの加水分解用） ２ｃｃ ＨＣｌ（濃度１Ｎ）（加水分解を促進させるための触媒） ５ｃｃ -------------------------------------------------------------- 溶液１、溶液２を別途調製、攪拌した後、加水分解、重
縮合反応の触媒である溶液２を溶液１に攪拌しつつ滴下
して加え均一な溶液を得た。その後、この溶液を８０℃
で４０分間還流して有機金属化合物の溶液を得た。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. <Description of compounds shown below> TEOS: Tetraethoxysilane PDMS: Terminal silanol group polydimethylsiloxane THF: Tetrahydrofuran i-PA: Isopropyl alcohol HCl: 1N Hydrochloric acid Ti (OPr) 4 : Tetraisopropoxytitanium HPPA: 2-Hydroxy- 3-phenoxypropyl acrylate EBPA: ethoxylate bisphenol A diacrylate BTTB: 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone (Nippon Oil & Fats, 50% purity) KCD: 3,3 '-Carbonylbis (7-diethylaminocoumarin) (manufactured by Japan Photosensitive Dye Research Institute) Example 1 First, a starting solution for an optical recording film was prepared under the following conditions. <Solution 1> ---------------------------------------------- ------ TEOS (as an organometallic compound capable of hydrolysis and polycondensation) 27 g PDMS (same as above) 3 g THF (solvent) 5 cc i-PA (solvent) 9 cc ---------- -------------------------------------------- <Solution 2>- -------------------------------------------------- ---------- i-PA (solvent) 12cc H2O (for hydrolysis of TEOS and PDMS) 2cc HCl (concentration 1N) (catalyst for promoting hydrolysis) 5cc ------ -------------------------------------------------- ------ Solution 1 and Solution 2 were separately prepared and stirred, and then Solution 2 which was a catalyst for hydrolysis and polycondensation reaction was added dropwise to Solution 1 with stirring to obtain a uniform solution. Then, this solution is heated to 80 ° C.
After refluxing for 40 minutes, a solution of the organometallic compound was obtained.
【００４７】次に赤色暗室用ランプ下において、以下の
重量比で、光重合開始剤ＢＴＴＢ、色素ＫＣＤを塩化メ
チレン、メタノール混合溶液に溶解し、光重合モノマー
ＨＰＰＡ，ＥＢＰＡに混合攪拌した溶液３を、上記有機
金属化合物の溶液（溶液１、２の混合物）５．０ｇに導
入し、攪拌混合して均一な光記録用出発溶液を得た。Next, under a red dark room lamp, the photopolymerization initiator BTTB and the dye KCD were dissolved in a mixed solution of methylene chloride and methanol in the following weight ratio, and the solution 3 was mixed and stirred with the photopolymerization monomers HPPA and EBPA. Then, 5.0 g of the above-mentioned solution of the organometallic compound (mixture of solutions 1 and 2) was introduced and mixed by stirring to obtain a uniform starting solution for optical recording.
【００４８】 ＜溶液３＞ ---------------------------------------------------------------- ＨＰＰＡ（光重合モノマー） ４．７５ｇ ＥＢＰＡ（光重合モノマー） ０．２５ｇ ＢＴＴＢ（光重合開始剤） ０．５０ｇ ＫＣＤ（色素） ０．０１ｇ 塩化メチレン／メタノール（=95/5重量％）（溶媒） １．００ｇ ---------------------------------------------------------------- この溶液を赤色暗室用ランプ下で、３００×１５０×２
mmのガラス基板上にアプリケーターを用いてコーティン
グし、３０℃、約２４時間静置し、ゲル化、乾燥させ
て、厚みが約９．５μｍのクラックのない感光層を得
た。その後、厚み１００μｍのポリエチレンテレフタレ
ートのカバーフィルムを上記感光層の上に付着させ、そ
れを切断して、６０×６０mmの大きさのガラス基板-感
光層-ポリエチレンテレフタレートフィルムの積層体か
らなる感光材（光記録用膜）を得た。<Solution 3> ------------------------------------------- --------------------- HPPA (photopolymerization monomer) 4.75 g EBPA (photopolymerization monomer) 0.25 g BTTB (photopolymerization initiator) 0.50 g KCD (Dye) 0.01 g Methylene chloride / methanol (= 95/5 wt%) (Solvent) 1.00 g -------------------------- -------------------------------------- 300X this solution under a red dark room lamp 150 x 2
A glass substrate having a thickness of mm was coated with an applicator, allowed to stand at 30 ° C. for about 24 hours, gelled and dried to obtain a photosensitive layer having a thickness of about 9.5 μm and having no crack. After that, a polyethylene terephthalate cover film having a thickness of 100 μm is adhered onto the photosensitive layer, cut and cut, and a photosensitive material composed of a laminate of a glass substrate of 60 × 60 mm-photosensitive layer-polyethylene terephthalate film ( An optical recording film) was obtained.
【００４９】次に図１に示すような光学系においてアル
ゴンイオンレーザー１から発振した波長５１４．５ｎｍ
の光を、シャッター２を通してビームエキスパンダー
３、コリメータレンズ４により平行光とし、ビームスプ
リッター５により二光束の平行光に分け、ミラー６、
６’を用いて上記の感光材（ガラス基板-光記録層-ポリ
エチレンテレフタレートフィルムの積層体）３枚に対し
て、角度θで入射させ干渉露光を行なった。なお角度θ
の値は、それぞれ５゜，１４゜，４２゜とし、３０〜５
０ｍＪ／ｃｍ2の露光量で作製した。Next, in the optical system as shown in FIG. 1, a wavelength of 514.5 nm oscillated from the argon ion laser 1
Beam of light through the shutter 2 into parallel light by the beam expander 3 and the collimator lens 4, and split into two parallel light beams by the beam splitter 5, and the mirror 6,
Using 6 ', three sheets of the above-mentioned photosensitive material (a laminated body of glass substrate-optical recording layer-polyethylene terephthalate film) were made incident at an angle θ to perform interference exposure. Note that the angle θ
The values of 30 and 5 are 5 °, 14 ° and 42 °, respectively.
It was produced with an exposure dose of 0 mJ / cm 2 .
【００５０】干渉露光の後、感光材を３０Ｗの蛍光灯を
用いて３ｃｍの距離から約１５分間全面露光を行い、未
重合モノマーの重合を完結させ固定化した。After the interference exposure, the entire surface of the photosensitive material was exposed with a fluorescent lamp of 30 W from a distance of 3 cm for about 15 minutes to complete the polymerization of the unpolymerized monomer and immobilize it.
【００５１】以上のようにして感光材に約１７０，４８
０，１４００本／ｍｍの空間周波数を有する干渉縞を用
いて回折格子を作製した。As described above, about 170,48 is applied to the photosensitive material.
A diffraction grating was produced using interference fringes having a spatial frequency of 0.1400 lines / mm.
【００５２】次にこの回折格子よりポリエチレンテレフ
タレートフィルムを剥した後、電気炉中で、５０℃／時
間の昇温速度で５００℃まで加熱した。４時間そのまま
の温度で保った後、約１０時間かけて電気炉内を室温ま
で除冷し、回折格子を取り出した。このようにして空間
周波数１７０，４８０，１４００本／ｍｍを有する回折
格子が記録された膜厚１．２μｍのＳiＯ2膜とガラス基
板の積層体が得られた。このＳiＯ2膜の断面を１千倍〜
５万倍の電子顕微鏡によって観察すると、干渉縞の強弱
に応じて表面凹凸および、わずかながらシリカ粒子の密
度分布が形成されていることが確認された。すなわち、
表面の山脈状凸部の高さは約１μｍ、幅は約１μｍ、凹
凸のピッチ（凸部の中心間の距離）は上記空間周波数に
応じてそれぞれ約６μｍ、約２μｍ、および約０．７μ
ｍであった。そして膜内部では、シリカ粒子（直径約
０．０１〜０．１μｍ）が表面が凸の部分の内部では緊
密に存在し、他方表面が凹の部分は粗く（空隙が多く）
存在していることが確かめられた。回折格子としての機
能は主として膜表面の凹凸によるのである。Next, after peeling off the polyethylene terephthalate film from this diffraction grating, it was heated to 500 ° C. in an electric furnace at a heating rate of 50 ° C./hour. After keeping the same temperature for 4 hours, the inside of the electric furnace was cooled to room temperature over about 10 hours, and the diffraction grating was taken out. In this way, a laminated body of the SiO2 film and the glass substrate having a film thickness of 1.2 μm, on which the diffraction grating having the spatial frequencies of 170, 480 and 1400 lines / mm was recorded, was obtained. The cross section of this SiO2 film is 1,000 times
When observed with an electron microscope at a magnification of 50,000, it was confirmed that surface irregularities and a slight density distribution of silica particles were formed depending on the strength of the interference fringes. That is,
The height of the mountain range convex portion on the surface is about 1 μm, the width is about 1 μm, and the pitch of the irregularities (distance between the centers of the convex portions) is about 6 μm, about 2 μm, and about 0.7 μ depending on the spatial frequency.
It was m. Inside the film, silica particles (diameter of about 0.01 to 0.1 μm) are closely present inside the convex portion of the surface, while the concave portion of the surface is rough (there are many voids).
It was confirmed that it existed. The function as a diffraction grating is mainly due to the unevenness of the film surface.
【００５３】実施例２ 実施例１で用いた感光材の上に、ＵＳＡＦテストターゲ
ット（メレスグリオ社製、空間周波数１〜２２８本／ｍ
ｍ）をマスキング板として載置し、２ｋＷの紫外線ラン
プに、光源からの距離を３０ｃｍとして５秒間露光し
た。ポリエチレンテレフタレートフィルムを剥した後、
電気炉中で、昇温速度５０℃／時間で５００℃まで加熱
した。４時間そのままの温度で保った後、約１０時間か
けて電気炉内を室温まで除冷し、感光材を取り出した。
このＳiＯ2膜の表面を電子顕微鏡によって観察すると、
マスクパターンに応じて表面凹凸が形成されていること
が確認された。Example 2 On the photosensitive material used in Example 1, a USAF test target (manufactured by Melles Griot, spatial frequency 1 to 228 lines / m) was used.
m) was placed as a masking plate and exposed to a 2 kW ultraviolet lamp for 5 seconds at a distance of 30 cm from the light source. After peeling off the polyethylene terephthalate film,
In an electric furnace, it was heated to 500 ° C at a heating rate of 50 ° C / hour. After keeping the same temperature for 4 hours, the inside of the electric furnace was cooled to room temperature over about 10 hours, and the photosensitive material was taken out.
When observing the surface of this SiO2 film with an electron microscope,
It was confirmed that surface irregularities were formed according to the mask pattern.
【００５４】実施例３ 次にＴiＯ2を無機網目構造とする場合の実施例を示す。
以下の方法で光記録膜用出発溶液を調整した。 溶液４、溶液５を別途攪拌した後、加水分解、重縮合の
触媒である溶液５を溶液６に攪拌しつつ、徐々に滴下し
て加え均一な溶液を得た。 ＜溶液６＞ -------------------------------------------------------------- ＨＰＰＡ ４．７５ｇ ＥＢＰＡ ０．２５ｇ ＢＴＴＢ ０．５０ｇ ＫＣＤ ０．０１ｇ 塩化メチレン／メタノール（=95/5重量％） １．００ｇ -------------------------------------------------------------- 次に赤色暗室用ランプ下において、上記溶液６に示す重
量比で、光重合開始剤ＢＴＴＢ、色素ＫＣＤを塩化メチ
レン、メタノール混合溶液に溶解し、光重合モノマーＨ
ＰＰＡ，ＥＢＰＡに混合攪拌した溶液６を、上記有機金
属化合物の溶液（溶液４、５の混合物）１０．０ｇに導
入し、攪拌混合して均一な出発溶液を得た。Example 3 Next, an example in which TiO 2 has an inorganic network structure will be described.
A starting solution for an optical recording film was prepared by the following method. After stirring Solution 4 and Solution 5 separately, Solution 5 as a catalyst for hydrolysis and polycondensation was gradually added dropwise to Solution 6 with stirring to obtain a uniform solution. <Solution 6> ---------------------------------------------- ---------------- HPPA 4.75 g EBPA 0.25 g BTTB 0.50 g KCD 0.01 g Methylene chloride / methanol (= 95/5 wt%) 1.00 g --- -------------------------------------------------- --------- Next, the photopolymerization initiator BTTB and the dye KCD were dissolved in a mixed solution of methylene chloride and methanol at a weight ratio shown in the above solution 6 under a red dark room lamp to prepare a photopolymerization monomer H.
Solution 6 which was mixed and stirred with PPA and EBPA was introduced into 10.0 g of the above-mentioned solution of the organometallic compound (mixture of solutions 4 and 5) and stirred and mixed to obtain a uniform starting solution.
【００５５】実施例１と同様な方法でコーティングを行
い、光記録膜を得て、１４００本／ｍｍの空間周波数を
有する干渉縞を用いて回折格子を記録した。Coating was performed in the same manner as in Example 1 to obtain an optical recording film, and a diffraction grating was recorded using interference fringes having a spatial frequency of 1400 lines / mm.
【００５６】Ｈｅ−Ｎｅレーザより発振する６３２．８
ｎｍのビームを用いて回折効率を測定した。回折効率は
入射光強度に対する１次回折光強度の比として算出し
た。その結果を表１に示す。蛍光灯を用いて全面露光を
行なった時点では、わずかに０．０２２の回折効率であ
ったが、加熱処理を行なうにしたがって次第に上昇し、
４００〜５００度の熱処理により約０．５の回折効率が
得られた。632.8 oscillated from He-Ne laser
The diffraction efficiency was measured using a beam of nm. The diffraction efficiency was calculated as the ratio of the intensity of the first-order diffracted light to the intensity of the incident light. The results are shown in Table 1. When the entire surface was exposed using a fluorescent lamp, the diffraction efficiency was only 0.022, but gradually increased as the heat treatment was performed.
A diffraction efficiency of about 0.5 was obtained by heat treatment at 400 to 500 degrees.
【００５７】このＴiＯ2膜の断面を電子顕微鏡によって
観察すると、干渉縞の強弱に応じて主として空孔分布が
形成され、わずかに表面凹凸も形成されていることが確
認された。このように加熱前よりも加熱後で回折格子の
回折効率が向上するのは、加熱前では、入射光強度分布
による有機ポリマーリッチ領域と無機網目構造リッチ領
域との屈折率の差がポリマー（ＨＰＰＡとＥＢＰＡのコ
ポリマー）の屈折率約１．５５と酸化チタンゲルの屈折
率１．６の差（約０．０５）に起因するのに対して、４
００℃加熱後の回折格子では、酸化チタンの屈折率約
２．３５と空気の屈折率約１．００との差（約１．３
５）が加熱前のものの差に比べて非常に大きいことによ
るものである。When the cross section of the TiO2 film was observed with an electron microscope, it was confirmed that the distribution of vacancies was mainly formed depending on the strength of the interference fringes, and the surface irregularities were slightly formed. In this way, the diffraction efficiency of the diffraction grating is improved after heating as compared with before heating, because the difference in the refractive index between the organic polymer-rich region and the inorganic network structure-rich region due to the incident light intensity distribution is higher than that of the polymer (HPPA) before heating. The difference between the refractive index of about 1.55 for a copolymer of EBPA and EBPA) and the refractive index of 1.6 for a titanium oxide gel (about 0.05) is 4
In the diffraction grating after heating at 00 ° C, the difference between the refractive index of titanium oxide of about 2.35 and the refractive index of air of about 1.00 (about 1.3).
This is because 5) is much larger than the difference before heating.
【００５８】[0058]
【表１】 ----------------------------------------[Table 1] ----------------------------------------
【図１】 本発明の実施例として、透過型回折格子を記
録する場合に用いられる光学系の一例である。FIG. 1 is an example of an optical system used when recording a transmission type diffraction grating as an embodiment of the present invention.
１..レーザー発振器、 ２..シャッター、 ３..ビームエキスパンダー、 ４..コリメーターレンズ、 ５..ビームスプリッター、 ７..感光材、 1 .. Laser oscillator, 2 .. Shutter, 3 .. Beam expander, 4 .. Collimator lens, 5 .. Beam splitter, 7 .. Photosensitive material,
Claims (4)
物質の膜状のネットワークと、 （２）前記空隙の中に存在する気体からなり、前記膜中
の空隙率を膜中の場所によって変化させている光記録
膜。1. A membrane-shaped network of an inorganic substance having (1) a large number of minute voids inside, and (2) a gas existing in the voids, wherein the porosity in the membrane is determined by the location in the membrane. Optical recording film that is changed by.
物質の膜状のネットワークと、 （２）前記空隙の中に存在する気体からなり、前記膜の
空隙率を膜表面の場所によって変化させている膜状体を
高い温度に加熱することにより、前記空隙率が相対的に
大きい膜状体部分が相対的に小さい膜状体部分よりも大
きく膜厚み方向に収縮して、膜状体表面に制御された凹
凸が形成されている膜。2. A membrane-shaped network of an inorganic substance having (1) a large number of minute voids inside, and (2) a gas existing in the voids, wherein the porosity of the membrane depends on the location of the membrane surface. By heating the changing film-like body to a high temperature, the film-like body part having a relatively large porosity contracts in the film thickness direction more than the film-like body part having a relatively small porosity, and A film with controlled irregularities formed on the body surface.
マー、 （２）光重合開始剤、 （３）加水分解および重縮合が可能である有機金属化合
物 （４）前記有機金属化合物のための溶媒、 （５）水、および （６）前記有機金属化合物の加水分解を促進させるため
の触媒、 を含む出発溶液を、 基材上に塗布し、前記有機金属化合物を加水分解、重縮
合させてゲル化した膜を形成した後、乾燥により揮発成
分を気化させて光記録用膜を作製し、 Ｂ．前記光記録用膜に活性放射線を照射し、ついで Ｃ．上記光記録用膜中に含まれる有機成分を除去するこ
とからなる、前記金属の酸化物のみかけ密度分布および
／または表面凹凸を有する光記録膜の製造方法。3. A. (1) Photopolymerizable monomer or oligomer, (2) Photopolymerization initiator, (3) Organometallic compound capable of hydrolysis and polycondensation (4) Solvent for the organometallic compound, (5) Water, And (6) a starting solution containing a catalyst for accelerating the hydrolysis of the organometallic compound is applied onto a substrate, and the organometallic compound is hydrolyzed and polycondensed to form a gelled film. After that, a volatile component is vaporized by drying to produce an optical recording film, and B. The optical recording film is irradiated with actinic radiation, and then C.I. A method for producing an optical recording film having an apparent density distribution and / or surface irregularities of the metal oxide, which comprises removing an organic component contained in the optical recording film.
する輻射線によって得られる干渉縞を露光させることで
ある請求項３記載の膜の製造方法。4. The method for producing a film according to claim 3, wherein the irradiation with actinic radiation is to expose an interference fringe obtained by a coherent radiation.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4299040A JP3039165B2 (en) | 1992-11-10 | 1992-11-10 | Optical recording film and manufacturing method thereof |
| US08/412,021 US6479193B1 (en) | 1992-06-30 | 1995-03-28 | Optical recording film and process for production thereof |
| US09/903,585 US6524771B2 (en) | 1992-06-30 | 2001-07-13 | Optical recording film and process for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4299040A JP3039165B2 (en) | 1992-11-10 | 1992-11-10 | Optical recording film and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06148880A true JPH06148880A (en) | 1994-05-27 |
| JP3039165B2 JP3039165B2 (en) | 2000-05-08 |
Family
ID=17867439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4299040A Expired - Lifetime JP3039165B2 (en) | 1992-06-30 | 1992-11-10 | Optical recording film and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP3039165B2 (en) |
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