JPH0216107A - Poly(n-vinylcarbazole) - Google Patents
Poly(n-vinylcarbazole)Info
- Publication number
- JPH0216107A JPH0216107A JP16508688A JP16508688A JPH0216107A JP H0216107 A JPH0216107 A JP H0216107A JP 16508688 A JP16508688 A JP 16508688A JP 16508688 A JP16508688 A JP 16508688A JP H0216107 A JPH0216107 A JP H0216107A
- Authority
- JP
- Japan
- Prior art keywords
- pvcz
- molecular weight
- hologram
- weight
- average molecular
- 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.)
- Pending
Links
- -1 Poly(n-vinylcarbazole) Polymers 0.000 title claims abstract description 18
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 title claims abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract 2
- 239000002904 solvent Substances 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 230000008961 swelling Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000002366 halogen compounds Chemical class 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical class [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- FXDUOKLAEGQUOS-UHFFFAOYSA-N 1,1,1,2,2,2-hexaiodoethane Chemical compound IC(I)(I)C(I)(I)I FXDUOKLAEGQUOS-UHFFFAOYSA-N 0.000 description 1
- AYIIQQPELFMEOI-UHFFFAOYSA-N 1,1,1,2,2-pentaiodoethane Chemical compound IC(I)C(I)(I)I AYIIQQPELFMEOI-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QOACTULVIZXIHU-UHFFFAOYSA-N C=C.Br.Br.Br.Br Chemical compound C=C.Br.Br.Br.Br QOACTULVIZXIHU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- AXMKEYXDFDKKIO-UHFFFAOYSA-N bilane Chemical compound C=1C=C(CC=2NC(CC=3NC=CC=3)=CC=2)NC=1CC1=CC=CN1 AXMKEYXDFDKKIO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 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
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Holo Graphy (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は高分子量ポリ(N−ビニルカルバゾール)(以
下PVCzと略称する)に関し、更に詳しくは体積位相
型ホログラム記録媒体用の材料として有用な高分子量及
び分子量分布の狭いpvCzに関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to high molecular weight poly(N-vinylcarbazole) (hereinafter abbreviated as PVCz), and more specifically, to a material useful as a material for volume-phase hologram recording media. Concerning pvCz with high molecular weight and narrow molecular weight distribution.
(従来の技術)
従来、体積位相型ホログラムが新しい光学素子と云われ
て久しく、近年、例えば、ヘッドアップデイスプレィの
結合素子としての有用性が注目され、その地位を確立し
つつある。(Prior Art) Volume phase holograms have long been considered a new optical element, and in recent years, their usefulness as a coupling element for head-up displays, for example, has attracted attention, and they are beginning to establish themselves as such.
従来、高性能の体積位相型ホログラムを記録し得る記録
媒体としては、重クロム酸で増感したゼラチンが広く知
られ且つ用いられている。Conventionally, gelatin sensitized with dichromic acid has been widely known and used as a recording medium capable of recording high-performance volume phase holograms.
この重クロム酸ゼラチン系記録媒体は、確かに高性能ホ
ログラムを記録し得るという点では優れた記録媒体であ
るが、耐熱性や耐環境性、特に耐湿性に劣り、吸湿によ
って容易に記録が失われるという問題がある。そのため
、ホログラムを防湿性にするために十分な対策が要求さ
れ、例えば、レーザーから眼を保護するためのレーザー
保護眼鏡、自動車用ヘッドアップデイスプレィ装置等に
応用する場合には、ホログラムをガラス板や各種シーラ
ントで密封することが必要となり、加工性、安全性、重
量等の点から実用上の難点があった。Although this dichromate gelatin-based recording medium is certainly an excellent recording medium in that it can record high-performance holograms, it is inferior in heat resistance, environmental resistance, and especially moisture resistance, and recordings are easily lost due to moisture absorption. There is a problem of being exposed. Therefore, sufficient measures are required to make holograms moisture-proof.For example, when applying holograms to laser safety goggles to protect eyes from lasers, head-up display devices for automobiles, etc. It is necessary to seal with various types of sealants, which poses practical difficulties in terms of processability, safety, weight, etc.
上記の如き重クロム酸ゼラチン系記録媒体の欠点を解決
するために、新たな記録媒体としてpvCz等の如く芳
香族化合物を分子鎮構成単位に含むポリマーに沃素化合
物を増感剤として用いるホログラム作成技術が提案され
ている(例えば、特公昭62−14831号公報参照)
。更にこれらを改良して高性能ホログラムを得る技術も
提案されている(例えば、特開昭54−101343号
公報参照)。In order to solve the above-mentioned drawbacks of dichromate gelatin-based recording media, a hologram creation technology using an iodine compound as a sensitizer in a polymer containing an aromatic compound in the molecular weight unit, such as pvCz, has been developed as a new recording medium. has been proposed (for example, see Japanese Patent Publication No. 62-14831)
. Furthermore, techniques for obtaining high-performance holograms by improving these have also been proposed (see, for example, Japanese Patent Application Laid-Open No. 101343/1983).
(発明が解決しようとしている問題点)上記のPVCz
系記録黒記録媒体性、耐光性等に著しく優れた体積位相
型ホログラムを与えることができる。しかしながら、前
記重クロム酸ゼラチン系記録媒体においては99.9%
の回折効率を有し、且つ90%以上の透過率を有する体
積位相型ホログラムが作成されているのに対して、上記
PVCz系記録黒記録媒体には通常90%、改良された
としても98%程度の最大回折効率を達成したに過ぎず
、しかも常に安定した性能が得られる訳でもなく生産性
にも問題がある。(Problem to be solved by the invention) The above PVCz
It is possible to provide a volume phase type hologram that is extremely excellent in recording black recording medium properties, light resistance, etc. However, in the dichromate gelatin recording medium, 99.9%
Volume phase type holograms have been created that have a diffraction efficiency of However, only a certain maximum diffraction efficiency has been achieved, and stable performance is not always obtained, and productivity is also a problem.
又、PVCz系の記録媒体の場合には、重クロム酸ゼラ
チン系記録媒体に比較して、このPvCzの性質に由来
してホログラム現像時に細かいヒビ割れがホログラムに
全体的に発生し易く、透過率が低下する傾向がある。特
に回折ピーク幅が狭いタイプのブラック格子像を形成さ
せる時は、記録媒体の厚さも理論的に示唆される如く必
然的に厚くなるため、上記のヒビ割れの問題が一層顕著
になり、全体の透過率が低下するという問題がある。In addition, in the case of PVCz-based recording media, compared to dichromate gelatin-based recording media, due to the properties of PvCz, fine cracks are more likely to occur throughout the hologram during hologram development, resulting in lower transmittance. tends to decrease. In particular, when forming a type of black grating image with a narrow diffraction peak width, the thickness of the recording medium will inevitably increase as suggested by theory, so the above problem of cracking will become even more prominent, and the overall There is a problem that the transmittance decreases.
又、PVCz系記録黒記録媒体した体積位相型ホログラ
ムを長時間高温(ガラス転移点以下の温度であワても)
にさらされると、回折光ピークが非可逆的に短波長側に
シフトする傾向が認められ、特定光に対して回折光の波
長を合致させるべく、熱履歴に伴うピークのシフトを設
計上予め考慮しなければならないという困難もある。In addition, volume phase holograms using PVCz recording media can be exposed to high temperatures for long periods of time (even at temperatures below the glass transition point).
It has been observed that the peak of diffracted light tends to irreversibly shift toward shorter wavelengths when exposed to There is also the difficulty of having to do so.
従って本発明の目的は、上記の如きPVCz系ホログラ
ム記録媒体の利点を保持しつつ、それらの欠点を解決し
たPVCz系記録黒記録媒体るPVCzを提供すること
である。Accordingly, an object of the present invention is to provide a PVCz-based recording black recording medium that maintains the advantages of the PVCz-based holographic recording medium as described above and solves the drawbacks thereof.
(問題点を解決するための手段) 上記目的は以下の本発明によって達成される。(Means for solving problems) The above objects are achieved by the present invention as described below.
すなわち、本発明は、重量平均分子量が100万以上で
あり、且つその分子量分布が3以下であることを特徴と
するPVCzである。That is, the present invention is a PVCz characterized by having a weight average molecular weight of 1 million or more and a molecular weight distribution of 3 or less.
(作 用)
本発明者らは本発明の目的を達成すべく研究の結果、従
来のPVCz系ホログラム記録媒体において、高回折効
率、高透明性、低ヘイズ、回折ピーク波長のシフト抑制
、高い生産性等を達し得ない原因が、記録媒体を形成す
るPVCzの性質に起因することを見い出した。(Function) As a result of research to achieve the object of the present invention, the present inventors have found that conventional PVCz-based hologram recording media have high diffraction efficiency, high transparency, low haze, suppressed shift of diffraction peak wavelength, and high productivity. It has been found that the reason why the characteristics cannot be achieved is due to the properties of PVCz forming the recording medium.
すなわち、体積位相型ホログラムの記録は、レーザー光
の如きコヒーレント光による干渉波で記録層を露光し、
次に記録層の良溶媒にて記録層を膨摺させ、次いで同記
録層を貧又は非溶媒にて収縮させることによって行われ
ている。In other words, volume phase hologram recording involves exposing the recording layer to interference waves from coherent light such as laser light.
Next, the recording layer is expanded with a good solvent for the recording layer, and then the same recording layer is contracted with a poor or non-solvent.
この際PVCzは増感剤の存在下で光照射によって架橋
を生じ、良溶媒中では膨潤するが、この時にPVCzの
分子量が低かったり、或いは低分子量分を多く含有する
と、未架橋の低分子量物及び光分解ポリマーが溶出する
。この時に溶解するポリマーは、用いる溶剤のポリマー
溶解度、温度及び溶剤の種類等に強く依存する。At this time, PVCz is crosslinked by light irradiation in the presence of a sensitizer and swells in a good solvent, but at this time, if the molecular weight of PVCz is low or it contains a large amount of low molecular weight components, uncrosslinked low molecular weight products and photodegradable polymers are eluted. The polymer dissolved at this time strongly depends on the polymer solubility of the solvent used, the temperature, the type of solvent, etc.
特に得られるホログラムの回折効率を高め膨潤度を大き
くするべく、良溶媒として溶解性の高い溶媒を用いると
、未架橋及び分解ポリマーの溶出が著しくなり、その結
果として次の貧溶媒による収縮処理において、高分子科
学で云ういわゆるボイドが形成され、このボイドが光散
乱の原因となってホログラム中に見た目の白濁を生じる
。In particular, if a highly soluble solvent is used as a good solvent to increase the diffraction efficiency and swelling degree of the resulting hologram, the elution of uncrosslinked and decomposed polymers will be significant, and as a result, during the subsequent shrinkage treatment with a poor solvent, , so-called voids in polymer science are formed, and these voids cause light scattering, resulting in a cloudy appearance in the hologram.
従って、高分子量であり、しかも分子量分布の狭いPV
Czを記録材料として用いることによって、前記の従来
技術の多くの問題点が同時に解決された。Therefore, PV with high molecular weight and narrow molecular weight distribution
By using Cz as a recording material, many of the problems of the prior art mentioned above were solved at the same time.
更に、PVCzに限らず、高分子は分子量が高い程機械
的強度が大となる。又、体積位相型ホログラム形成の主
たる機構はポリマー中に歪みを生しさせてこれを凍結す
ることであるので、現像時の膨拐及び収縮により生じる
ポリマー中の歪を凍結するには、PVCzの分子量が高
いことが必要である。そして、PVCz中に低分子量分
が多く存在するとこれの可塑作用により歪の緩和を促進
させることから、混在する低分子量分が少ない程歪の凍
結に有効であることを見い出した。Furthermore, the higher the molecular weight of a polymer, not limited to PVCz, the higher its mechanical strength. In addition, the main mechanism of volume phase hologram formation is to create strain in the polymer and freeze it, so in order to freeze the strain in the polymer caused by expansion and contraction during development, PVCz It is necessary that the molecular weight is high. They have also found that the presence of a large amount of low molecular weight components in PVCz promotes the relaxation of strain due to their plasticizing action, and therefore, the smaller the amount of low molecular weight components present, the more effective it is in freezing strain.
これに対して従来ホログラム記録媒体として使用されて
いたPVCzは、ポリスチレン換算の重量平均分子量が
高くても70乃至95万であり、その分子量分布は4.
5乃至5.5の広がりを有するものであり、このような
重量平均分子量及び分子量分布を有するか故に前記様々
の問題を生じるものであった。On the other hand, PVCz, which has been conventionally used as a hologram recording medium, has a polystyrene equivalent weight average molecular weight of 700,000 to 950,000 at most, and its molecular weight distribution is 4.
5 to 5.5, and because it has such a weight average molecular weight and molecular weight distribution, it causes the various problems mentioned above.
(好ましい実施態様)
次に好ましい実施態様を挙げて本発明を更に詳しく説明
する。(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.
本発明におけるPVCzはN−ビニルカルバゾールの重
合によって得られるものであり、通常の方法によって得
られるPVCz或いは市場から入手できるPVCzは前
述の如き重囲平均分子量及び分子量分布を有しているの
で、これらの従来のPVCzを精製、例えば、溶媒によ
る分子■分別によって精製し、低分子量分を除去するこ
とによって本発明の目的たる特定のff1ffi平均分
子皿と分子量分布とを有するPVCzを得ることができ
る。尚、本発明で云う重量平均分子量とは、ポリスチレ
ン換算分子量であり、テトラヒドロフランを溶媒とし、
カラム温度27℃でゲルパーミェーションクロマトグラ
フ(Gel PermeationChrromato
graph )により求めた値である(用いたカラムは
、ショウデックスKF−807、KF80M 、排除限
界2X108、3X]O’を連結し、 zx+o’75
至1.2X to3までのポリスチレンを標準として較
正しである)。PVCz in the present invention is obtained by polymerizing N-vinylcarbazole, and PVCz obtained by a conventional method or commercially available has the above-mentioned weight range average molecular weight and molecular weight distribution. PVCz having a specific ff1ffi average molecular plate and molecular weight distribution, which is the object of the present invention, can be obtained by purifying conventional PVCz, for example, by molecular fractionation using a solvent and removing low molecular weight components. In addition, the weight average molecular weight referred to in the present invention is the molecular weight in terms of polystyrene, and when tetrahydrofuran is used as a solvent,
Gel Permeation Chromatograph (Gel Permeation Chromatograph) with column temperature of 27°C.
graph) (The columns used were Showdex KF-807, KF80M, exclusion limits 2X108, 3X]O' were connected, zx+o'75
Calibrated using polystyrene as a standard up to 1.2X to3).
分子量の分別は、PVCzに対して溶解性の異なる種々
の溶媒を用いる方法や濃度を変える方法等従来公知のい
ずれの分別方法を用いてもよい。For the molecular weight separation, any conventionally known separation method may be used, such as a method using various solvents having different solubility for PVCz or a method of changing the concentration.
1例としてPVCzに対する良溶媒と貧又は非溶媒の混
合比を変化させ、PVCzに対する混合溶媒の溶解性を
変化させて分別を行い低分子量を除去した。As an example, the mixing ratio of a good solvent and a poor or non-solvent for PVCz was changed, and the solubility of the mixed solvent for PVCz was changed to perform fractionation and remove low molecular weight.
分子量分別において、PVCzに対する良溶媒としては
、例えば、ピリジン、キノリン及びこれらの誘導体、ジ
オキサン、テトラヒドロフラン等の環状エーテル、ベン
ゼン、トルエン、キシレン(オルト体、メタ体、バラ体
及びそれらの混合物)、エチルベンゼン、n−プロピル
ベンゼン、クメン、フェノール、クレゾール、クロルベ
ンゼン、ジクロルベンゼン、ニトロベンゼン、ベンジル
アルコール、ベンジルクロライド、ベンジルブロマイド
、α−メチルナフタリン、α−クロルナフタリン等のベ
ンゼン及びナフタリンの誘導体、ビラン、ジクロルメタ
ン、クロロホルム、トリクロルエチレン、トリクロルエ
タン、ジクロルエタン、ブロモホルム等のハロゲン置換
の飽和又は不飽和の炭化水素、アセトン、メチルエチル
ケトン、メチルイソブチルケトン、シクロヘキサノン等
のケトン類、酢酸エチル、蟻酸エチル等のエステル類、
その他のアミン類、アミド類等が挙げられ、これらの中
から適当なものを選択又は組合せて使用する。In molecular weight fractionation, good solvents for PVCz include, for example, pyridine, quinoline and their derivatives, dioxane, cyclic ethers such as tetrahydrofuran, benzene, toluene, xylene (ortho form, meta form, bulk form and mixtures thereof), ethylbenzene. , n-propylbenzene, cumene, phenol, cresol, chlorobenzene, dichlorobenzene, nitrobenzene, benzyl alcohol, benzyl chloride, benzyl bromide, α-methylnaphthalene, α-chlornaphthalene and other benzene and naphthalene derivatives, bilane, dichloromethane , halogen-substituted saturated or unsaturated hydrocarbons such as chloroform, trichloroethylene, trichloroethane, dichloroethane, and bromoform; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate and ethyl formate;
Other amines, amides, etc. may be mentioned, and appropriate ones are selected or used in combination from these.
又、分子量分別に使用する非又は貧溶媒としては、例え
ば、n−ペンタン、n−ヘキサン、n−へブタン、n−
オクタン、イソオクタン、シクロヘキサン等のアルカン
、シクロアルカン類、メチルアルコール、エチルアルコ
ール、n−プロピルアルコール、イソプロピルアルコー
ル、n−ブチルアルコール、tert−ブチルアルコー
ル、n−アミルアルコール、イソアミルアルコール等の
アルコール類、ジエチルエーテル、メチルエチルエーテ
ル、ジイソプロピルエーテル等のエーテル類等が挙げら
れ、これらから適当なものを選択又は組合せて使用する
。In addition, examples of non- or poor solvents used for molecular weight fractionation include n-pentane, n-hexane, n-hebutane, n-
Alkanes such as octane, isooctane, cyclohexane, cycloalkanes, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, diethyl Examples include ethers such as ether, methyl ethyl ether, diisopropyl ether, etc., and appropriate ones are selected or used in combination from these.
以上の如き良溶媒と貧溶媒とを、その混合物を昇温した
時にPVCzを十分に溶解し、これを冷却した時に高分
子囲範囲のPVCzが析出する比率に混合して特製溶媒
とし、この中にPVCzを加熱溶解し、次いで冷却する
。この時高分子量分のPVCzは析出し、低分子量分は
溶解状態にあるので溶液相を分離することにより、重量
平均分子量が100万以上のPVCzに富んだものが得
られ、これらの操作を、必要に応じて溶媒の種類、混合
比等を変化させて行うことにより、低分子量P V C
zの含有量が少なく且つ分子量分布の狭いPVCzが得
られる。A special solvent is prepared by mixing the above-mentioned good solvent and poor solvent in such a ratio that PVCz is sufficiently dissolved when the mixture is heated and that PVCz in the polymer range is precipitated when the mixture is cooled. PVCz is melted by heating and then cooled. At this time, the high molecular weight PVCz is precipitated and the low molecular weight content is in a dissolved state, so by separating the solution phase, a product rich in PVCz with a weight average molecular weight of 1 million or more can be obtained. By changing the type of solvent, mixing ratio, etc. as necessary, low molecular weight P V C
PVCz with a low z content and a narrow molecular weight distribution can be obtained.
本発明者の詳細な研究によれば、精製PVCzの重量平
均分子量が100万以上であり、且つその分子量分布が
3以下である時に、これを体積位相型ホログラム記録媒
体として用いることにより、前述の如き種々の問題が有
利に解決されることを見い出した。特に、分子量分布が
2以下であるもの、重量平均分子量が20万以下のPV
Czの含有量が1重量%以下であるもの、更に100万
以上の重量平均分子量のPVCzが全ポリマーの50重
量%以上を占めるものが更に本発明の目的を有利に達成
することができる。According to detailed research by the present inventor, when the weight average molecular weight of purified PVCz is 1 million or more and its molecular weight distribution is 3 or less, by using it as a volume phase type hologram recording medium, the above-mentioned It has been found that various problems such as the following can be advantageously solved. In particular, those with a molecular weight distribution of 2 or less, and PV with a weight average molecular weight of 200,000 or less
The objects of the present invention can be advantageously achieved by a polymer in which the content of Cz is 1% by weight or less, and in which PVCz having a weight average molecular weight of 1 million or more accounts for 50% by weight or more of the total polymer.
以上本発明のPVCzを得るための分別方法の1例を説
明したが、本発明のPVCzは上記分別方法以外の任意
の精製方法でも容易に得られることは自明である。Although one example of the fractionation method for obtaining the PVCz of the present invention has been described above, it is obvious that the PVCz of the present invention can be easily obtained by any purification method other than the above-mentioned fractionation method.
上記本発明のPVCzの用途の1例としてホログラム記
録に用いる場合を説明する。As an example of the use of the PVCz of the present invention, a case where it is used for hologram recording will be described.
PVCzは400万mより長波長側には光吸収帯を有し
ていないので、ホログラム記録媒体として用いる時には
、予めハロゲン化合物、好ましくは沃素化合物及び/又
は臭素化合物によって輻射線に対して活性にされている
必要がある。Since PVCz does not have an optical absorption band on the wavelength side longer than 4 million m, when used as a hologram recording medium, it must be activated in advance to radiation with a halogen compound, preferably an iodine compound and/or a bromine compound. need to be.
かかるハロゲン化合物は、PVCz中に共存して、可視
波長域にも充分な感度を持つ記録層を構成するものであ
り、好ましいものとして具体的には、四状化炭素、ヨー
ドホルム、四状化エチレン、トリヨードエタン、テトラ
ヨードエタン、ペンタヨードエタン、ヘキサヨードエタ
ン、四臭化炭素、四臭化エチレン等の沃素化合物及び臭
素化合物が挙げられる。これらのハロゲン化合物は前記
PVCzlOO重量部に対して、例えば、100乃至1
重量部の割合で添加する。Such a halogen compound coexists in PVCz and constitutes a recording layer having sufficient sensitivity even in the visible wavelength range, and specifically, preferable ones include carbon tetramonide, iodoform, and ethylene tetramonide. , triiodoethane, tetraiodoethane, pentaiodoethane, hexaiodoethane, carbon tetrabromide, ethylene tetrabromide, and other iodine and bromine compounds. These halogen compounds are used in an amount of, for example, 100 to 1 part by weight of the PVCzlOO.
Add in parts by weight.
以上の如きハロゲン化合物の添加量が少なすぎると得ら
れる記録媒体の感度が低く、露光に長時間を要するので
好ましくなく、又、重量比で1を越えて使用すると、記
録媒体中に未分解のハロゲン化合物が残り、後にこれら
を全部除去する必要があるため、記録媒体中にボイドを
生じる要因となるので好ましくない。If the amount of the halogen compound added is too small, the sensitivity of the resulting recording medium will be low and exposure will take a long time, which is not preferable. This is not preferable because the halogen compounds remain and it is necessary to remove all of them later, which causes voids to occur in the recording medium.
更に本発明においては記録媒体の作成に際して可塑剤は
用いない方がよく、例えば、可塑剤を混合すると、現像
時の膨潤・収縮工程において、溶出されずに残った可塑
剤はPVCzと同様に膨潤・収縮作用を受けねばならな
いし、又、収縮後は記録媒体中にブラッグ条件を満たす
屈折率の変調以外の屈折率分布が生じる恐れがあるため
である。勿論上記の如き不都合を生じない範囲において
は必ずしも使用できないと云うことではない。Furthermore, in the present invention, it is better not to use a plasticizer when creating a recording medium. For example, if a plasticizer is mixed, the plasticizer remaining without being eluted will swell in the same way as PVCz during the swelling and shrinking process during development. - This is because the material must be subjected to a shrinkage action, and after shrinkage, there is a possibility that a refractive index distribution other than the refractive index modulation that satisfies the Bragg condition may occur in the recording medium. Of course, this does not necessarily mean that it cannot be used as long as it does not cause the above-mentioned inconveniences.
本発明のPVCzからなる記録媒体は、上述のPVCz
、ハロゲン化合物及び他の必要な添加剤を所定の割合で
適宜溶媒に溶解させるか分散液とした後、ガラス板やプ
ラスチックフィルムの如き適当な基材上に塗膜を形成す
ることによって得られる。The recording medium made of PVCz of the present invention is the above-mentioned PVCz
It can be obtained by dissolving a halogen compound and other necessary additives in a suitable solvent in a predetermined ratio or forming a dispersion, and then forming a coating film on a suitable substrate such as a glass plate or a plastic film.
以上の如くして形成した記録媒体に560rv+迄のコ
ヒーレントな可視光である物体光と参照先の2光束の可
干渉性レーザーを用いて第1図示の如き光学系で露光を
行う。The recording medium formed as described above is exposed to light using an optical system as shown in the first diagram using an object beam which is coherent visible light of up to 560 rv+ and a coherent laser beam of two beams as a reference.
露光工程に続いて、記録層を構成しているPvCzは勿
論のこと、光反応により生成するPvCzの架橋物を殆
ど溶出させることのない溶媒中に浸漬して、記録層中か
ら未反応のハロゲン化合物のみをほぼ完全に溶出除去し
て着色を除く。Following the exposure process, the unreacted halogen is removed from the recording layer by immersing it in a solvent that hardly dissolves the PvCz constituting the recording layer, as well as the cross-linked PvCz produced by the photoreaction. The compound is almost completely eluted and removed to remove coloring.
尚、この工程は下記の膨潤工程を兼ねることができる。Note that this step can also serve as the swelling step described below.
次いで行う現像工程は膨潤工程及び収縮工程の2ステツ
プからなる。The subsequent development process consists of two steps: a swelling process and a shrinking process.
すなわち、上記露光工程によりホログラム潜像が形成さ
れ、且つハロゲン化合物が除去された記録層を、第一の
溶媒である膨a液で処理して、形成されたホログラムパ
ターンに応じた膨潤を引き起すものであり、その後の第
二の溶媒による処理は、膨潤状態の記録層を収縮させて
、上記膨潤状態に応じたホログラムの増幅及び固定化を
行うものである。That is, the recording layer from which a hologram latent image has been formed through the exposure step and from which the halogen compound has been removed is treated with a swelling a liquid, which is a first solvent, to cause swelling in accordance with the formed hologram pattern. The subsequent treatment with the second solvent shrinks the swollen recording layer and amplifies and immobilizes the hologram according to the swollen state.
ホログラム現像工程における第一の溶媒である膨潤液と
は、PVCzとハロゲン化合物との光反応の結果生成さ
れるPVCzの架橋物及び未架橋物に対し、短時間で殆
ど溶出させることのない溶媒である。かかる溶媒として
は、前記本発明において特製溶剤として挙げた良溶媒か
ら適度な膨潤力のものを選択或いは組合せて使用する。The swelling liquid, which is the first solvent in the hologram development process, is a solvent that hardly dissolves crosslinked and uncrosslinked PVCz products produced as a result of the photoreaction between PVCz and a halogen compound in a short period of time. be. As such a solvent, those having an appropriate swelling power are selected from among the good solvents listed as special solvents in the present invention, or used in combination.
又、第二の溶媒である収縮液は、記録層に対して膨潤又
は溶解作用を有せず、且つ上記膨潤液と相溶性のある溶
媒は全て使用可能であり、例えば、前記した非又は貧溶
媒の中から適当なものを選択或いは組合せて使用する。The shrinking liquid, which is the second solvent, can be any solvent that does not have a swelling or dissolving effect on the recording layer and is compatible with the swelling liquid. Appropriate solvents are selected or used in combination.
又、夫々の工程の温度や時間等の処理条件は夫々使用す
る記録層の種類及び溶媒の種類等によって変化し一概に
は規定できないが、−数的にはいずれの工程も10℃乃
至70℃程度の温度で数秒間乃至数分間の処理で十分な
効果を挙げることができる。In addition, processing conditions such as temperature and time for each step vary depending on the type of recording layer and solvent used, and cannot be unconditionally defined, but numerically, the temperature and time for each step are 10°C to 70°C. A sufficient effect can be achieved by treatment for several seconds to several minutes at a moderate temperature.
尚、以上の如くして得られるホログラムフィルムは基板
に接着したままで使用できることは当然であり、更に本
発明において使用したPVCzは高分子量であることか
ら、基板から剥離した状態でも十分な強度を有するので
、基板から剥離したホログラムフィルムとしても十分に
各種用途で使用可能である。It goes without saying that the hologram film obtained as described above can be used while being adhered to the substrate, and furthermore, since the PVC used in the present invention has a high molecular weight, it has sufficient strength even when it is peeled off from the substrate. Therefore, it can be used for various purposes even as a hologram film peeled from a substrate.
(効 果)
以上の如き本発明の特定の重量平均分子量及び分子量分
布を有するPVCzを用いて得られた体積位相型ホログ
ラムは、従来のPVCzを用いた体積位相型ホログラム
の最大回折効率が98%であるのに対して99.9%に
まで向上しており、透A率は600nmにおいて80%
であったものが92%に、ヘイズは10μmの厚みで1
2%であったものが2%以下に夫々改善され、更に14
0℃2時間放置後に20r+mブルーシフトしたものが
lnm以内のシフトであった。(Effect) The volume phase hologram obtained using PVCz having the specific weight average molecular weight and molecular weight distribution of the present invention as described above has a maximum diffraction efficiency of 98% of the volume phase hologram using conventional PVCz. , it has improved to 99.9%, and the A transmittance is 80% at 600 nm.
The haze was 92%, and the haze was 1 at a thickness of 10 μm.
2% improved to below 2%, and an additional 14%
The blue shift of 20 r+m after being left at 0° C. for 2 hours was within 1 nm.
(実施例)
次に実施例及び比較例を挙げて本発明を更に具体的に説
明する。(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples.
実施例I
PVCZ(ルビカンM−170、BASF社製)20g
をジオキサン/イソプロピルアルコール混合液(重量比
3/1)に加えて加温して溶解し、均になった後、室温
に冷却した。沈澱したPVCzをデカンテーションで分
離し、分離したPVCzをジオキサン/イソプロピルア
ルコール混合液(重量比3/1)に加え攪拌してポリマ
ーを数回洗浄して本発明のPVCzを得た。Example I PVCZ (Rubican M-170, manufactured by BASF) 20g
was added to a dioxane/isopropyl alcohol mixture (weight ratio 3/1) and dissolved by heating, and after being homogenized, it was cooled to room temperature. The precipitated PVCz was separated by decantation, and the separated PVCz was added to a dioxane/isopropyl alcohol mixture (weight ratio 3/1) and stirred to wash the polymer several times to obtain the PVCz of the present invention.
その一部をテトラヒドロフランに溶解し、カラム温度2
7℃でゲルパーミェーションクロマトグラフを用い、カ
ラムはショウデックス(shodex、昭和電工@)K
F−807、KF80Mを接続し、ポリスチレンを基準
にして重量平均分子量及び分子量分布を求めたところ、
重量平均分子量は152万、分子量分布は1.48であ
った。又、分子量20万以下のPVCzの含有量は0.
8重量%であり、分子■100万以上のPVCzの含有
量は62重量%であった。A part of it was dissolved in tetrahydrofuran, and the column temperature was 2.
Using a gel permeation chromatograph at 7°C, the column was Shodex (Showa Denko @) K.
When F-807 and KF80M were connected and the weight average molecular weight and molecular weight distribution were determined based on polystyrene,
The weight average molecular weight was 1.52 million, and the molecular weight distribution was 1.48. In addition, the content of PVCz with a molecular weight of 200,000 or less is 0.
8% by weight, and the content of PVCz with molecules (1) of 1,000,000 or more was 62% by weight.
上記PVCz2.5g及び四沃素炭素をクロルヘンゼン
に暗所で溶解し、洗浄したガラス板上にスピナー(協和
セミコンダクター製)を用いて塗工及び¥1.燥して7
.2μmの記録層を形成した。2.5 g of the above PVCz and tetraiodine carbon were dissolved in chlorhenzene in a dark place, and coated on a cleaned glass plate using a spinner (manufactured by Kyowa Semiconductor) for ¥1. dry 7
.. A recording layer of 2 μm was formed.
この記録層をArレーザー(488nm)を用いる第1
図に示した光学系で露光してホログラムを記録した。This recording layer was removed using an Ar laser (488 nm).
A hologram was recorded by exposure using the optical system shown in the figure.
露光後、35℃のトルエンに2分間、35℃のキシレン
に2分間浸漬し、更に20℃のへブタンに2分間浸漬処
理後乾燥させて体積位相型ホログラムを得た。After exposure, it was immersed in toluene at 35°C for 2 minutes, xylene at 35°C for 2 minutes, and further immersed in hebutane at 20°C for 2 minutes, followed by drying to obtain a volume phase hologram.
上記ホログラムの反射回折効率を反射装置を有する分光
光度計(日立u−3400)で測定したところ、518
nmの光で最大反射回折効率99%を示し、又、600
nmの光での透過率は87%をボし、更にヘイズ(全ヘ
イズ値)はJISK7105に基づきヘイズメーター(
日本重色■製)で測定したところ1,7%であった。When the reflection diffraction efficiency of the above hologram was measured using a spectrophotometer (Hitachi U-3400) equipped with a reflection device, it was found to be 518
It shows a maximum reflection diffraction efficiency of 99% for light of 600 nm.
The transmittance of nm light is 87%, and the haze (total haze value) is measured using a haze meter (based on JIS K7105).
When measured using a Nippon Juishiki (trade name), it was 1.7%.
次に窒素雰囲気中140℃に約5時間保持後、ホログラ
ムの特性を前記光学系で測定したところ、最大回折効率
のピークシフトは認められず、且つ最大回折効率及びヘ
イズ値の変化は全く認められなかった。Next, after holding the hologram at 140°C for about 5 hours in a nitrogen atmosphere, the characteristics of the hologram were measured using the optical system, and no peak shift in the maximum diffraction efficiency was observed, and no change in the maximum diffraction efficiency or haze value was observed. There wasn't.
実施例2
PVCZC)L/ビカンM−170) 20 gをジオ
キサン/イソプロピルアルコール混合液(重量比3/1
)に加えて加温して溶解し、28℃で放置して冷却した
。沈澱したPVCzをデカンテーションで分離し、分離
したPVCzをジオキサン/イソプロピルアルコール混
合液(重量比371.2)に加え攪拌してポリマーを数
回洗浄して本発明のPVCzを得た。Example 2 20 g of PVCZC) L/Bican M-170) was mixed with a dioxane/isopropyl alcohol mixture (weight ratio 3/1).
), the mixture was heated and dissolved, and the mixture was allowed to cool at 28°C. The precipitated PVCz was separated by decantation, and the separated PVCz was added to a dioxane/isopropyl alcohol mixture (weight ratio 371.2) and stirred to wash the polymer several times to obtain the PVCz of the present invention.
その一部を実施例1と同様にして重囲平均分子量及び分
子量分布を測定したところ、重量平均分子量は176万
、分子量分布は1.51であった。又、分子量20万以
下のPVCzの含有量は0.2重量%であり、分子ff
1100万以上のpvCzの含有量は53重量%であっ
た。When a part of it was measured for weight average molecular weight and molecular weight distribution in the same manner as in Example 1, the weight average molecular weight was 1,760,000, and the molecular weight distribution was 1.51. In addition, the content of PVCz with a molecular weight of 200,000 or less is 0.2% by weight, and the molecule ff
The content of pvCz of 11 million or more was 53% by weight.
上記PVCzを用いて膜厚を10.2μmにしたことを
除き、実施例1と同様にして記録層を形成し同様に露光
及び現像を行って得た体積位相型ホログラムの反射回折
効率は99.9%、透過率は92%、ヘイズは1.6%
であり、特に記録層の膜厚を50%増加させたにも拘ら
ずヘイズは同等であった。又、加熱保存試験においても
実施例1と同様の結果が得られた。The reflection diffraction efficiency of a volume phase type hologram obtained by forming a recording layer in the same manner as in Example 1 and performing exposure and development in the same manner as in Example 1, except that the film thickness was 10.2 μm using the above PVCz, was 99. 9%, transmittance is 92%, haze is 1.6%
In particular, the haze was the same even though the thickness of the recording layer was increased by 50%. Also, the same results as in Example 1 were obtained in the heat storage test.
比較例1
実施例1における特製前のPVCz (ルビカンM−1
70(BASF社製、商標名))2.5gを用いて、他
は実施例1と同様にして記録層の形成、露光及び現像を
行って比較例の体積位相型ホログラムを得た。このホロ
グラムを実施例1と同様に測定したところ、回折効率は
僅か4%であり、透過率は68%と悪く明らかに白濁し
ており、ヘイズ値は測定する必要が無かった。又、実施
例1と同様な加熱試験後は回折が全く失われていた。Comparative Example 1 PVCz (Rubican M-1) before special production in Example 1
A volume phase hologram of a comparative example was obtained by forming a recording layer, exposing and developing in the same manner as in Example 1 using 2.5 g of 70 (manufactured by BASF, trade name). When this hologram was measured in the same manner as in Example 1, the diffraction efficiency was only 4%, the transmittance was poor at 68%, and it was clearly cloudy, so there was no need to measure the haze value. Moreover, after the same heating test as in Example 1, diffraction was completely lost.
又、上記において現像条件を20℃のトルエン中に2分
間、25℃のキシレン中に2分間浸漬し、次いで20℃
のへブタン中に2分間浸漬し、現像を低温で行ったとこ
ろ、回折効率は12%で透過率は77%であり、140
℃で5時間の加熱試験後には回折効率性が消失した。In addition, the development conditions in the above were immersion in toluene at 20°C for 2 minutes, immersion in xylene at 25°C for 2 minutes, and then immersion in 20°C
When the film was immersed in hebutane for 2 minutes and developed at low temperature, the diffraction efficiency was 12% and the transmittance was 77%.
The diffraction efficiency disappeared after a 5 hour heating test at °C.
上記の特製前のPVCzを実施例1と同一条件で測定し
たところ、重量平均分子量は92万であり1分子量分布
は5.4であった。When the above-mentioned PVCz before special production was measured under the same conditions as in Example 1, the weight average molecular weight was 920,000 and the molecular weight distribution was 5.4.
比較例2
実施例1における特製PVCzに代えて未精製のPVC
Z (ツビコール2105P (亜南香料■製))2.
5gを使用し、他は実施例1と同様にして記録層の形成
、露光及び現像を行って比較例の体積位相型ホログラム
を得た。このホログラムも最大回折効率は23%(52
0万m)、透過率73%及びヘイズ21%であり、又、
140℃5時間の加熱試験後はピーク波長が501 n
mにシフトし、最大回折効率は6%に低下した。Comparative Example 2 Unrefined PVC instead of special PVCz in Example 1
Z (Tubicol 2105P (manufactured by Anan Kaori ■)) 2.
A volume phase hologram of a comparative example was obtained by forming a recording layer, exposing and developing in the same manner as in Example 1, using 5 g. This hologram also has a maximum diffraction efficiency of 23% (52
00,000 m), transmittance of 73% and haze of 21%, and
After a heating test of 140°C for 5 hours, the peak wavelength was 501 nm.
m, and the maximum diffraction efficiency decreased to 6%.
上記の特製前のPVCzを実施例1と同一条件で測定し
たところ、重量平均分子量は78万であり、分子量分布
は4.6であった。When the above-mentioned PVCz before special production was measured under the same conditions as in Example 1, the weight average molecular weight was 780,000, and the molecular weight distribution was 4.6.
第1図は実施例で用いたホログラム記録光学系を示す。 FIG. 1 shows a hologram recording optical system used in Examples.
Claims (3)
分子量分布が3以下であることを特徴とするポリ(N−
ビニルカルバゾール)。(1) Poly(N-
vinyl carbazole).
カルバゾール)の含有量が、全体の1重量%以下である
請求項1に記載のポリ(N−ビニルカルバゾール)。(2) The poly(N-vinylcarbazole) according to claim 1, wherein the content of poly(N-vinylcarbazole) having a weight average molecular weight of 200,000 or less is 1% by weight or less of the total weight.
ルカルバゾール)の含有量が、全体の50重量%以上で
ある請求項1に記載のポリ(N−ビニルカルバゾール)
。(3) The poly(N-vinylcarbazole) according to claim 1, wherein the content of poly(N-vinylcarbazole) having a weight average molecular weight of 1 million or more is 50% by weight or more of the total weight.
.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16508688A JPH0216107A (en) | 1988-07-04 | 1988-07-04 | Poly(n-vinylcarbazole) |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16508688A JPH0216107A (en) | 1988-07-04 | 1988-07-04 | Poly(n-vinylcarbazole) |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0216107A true JPH0216107A (en) | 1990-01-19 |
Family
ID=15805613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16508688A Pending JPH0216107A (en) | 1988-07-04 | 1988-07-04 | Poly(n-vinylcarbazole) |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0216107A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009057528A (en) * | 2007-09-04 | 2009-03-19 | Nippon Shokubai Co Ltd | Carbazole group-containing polymer with high molecular weight |
-
1988
- 1988-07-04 JP JP16508688A patent/JPH0216107A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009057528A (en) * | 2007-09-04 | 2009-03-19 | Nippon Shokubai Co Ltd | Carbazole group-containing polymer with high molecular weight |
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