JPH04170425A - Hydrogenated norbornene-based ring-opening polymer, production thereof, and disc substrate and disc prepared therefrom - Google Patents
Hydrogenated norbornene-based ring-opening polymer, production thereof, and disc substrate and disc prepared therefromInfo
- Publication number
- JPH04170425A JPH04170425A JP2295438A JP29543890A JPH04170425A JP H04170425 A JPH04170425 A JP H04170425A JP 2295438 A JP2295438 A JP 2295438A JP 29543890 A JP29543890 A JP 29543890A JP H04170425 A JPH04170425 A JP H04170425A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogenated
- polymer
- norbornene
- opening polymer
- based ring
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 title claims abstract description 27
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 title 1
- 230000003287 optical effect Effects 0.000 claims abstract description 46
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000012778 molding material Substances 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000002848 norbornenes Chemical class 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 acyclic olefin Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000003749 cleanliness Effects 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- IWDIGJWJZKSMAO-UHFFFAOYSA-N pentacyclo[7.5.1.02,7.011,15.012,14]pentadec-1-ene Chemical compound C12C(C3C4C(CC5C(=C14)CCCC5)C3)C2 IWDIGJWJZKSMAO-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ノルボルネン系開環重合体水素添加物、その
製造方法、それで作られたディスク基板、及びディスク
に関する。更に詳しくは、異物含有量が少なく、記録信
号再生時のノイズの少ない光学式記録媒体用光学材料と
して好適なノルボルネン系開環重合体水素添加物、その
製造方法、それで作られたディスク基板、及びディスク
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrogenated norbornene-based ring-opening polymer, a method for producing the same, a disk substrate made from the same, and a disk. More specifically, a hydrogenated norbornene-based ring-opening polymer suitable as an optical material for optical recording media with low foreign matter content and low noise during reproduction of recorded signals, a method for producing the same, a disk substrate made from the same, and Regarding discs.
テトラシクロドデセン、そのアルキル置換体、エステル
型置換体などに代表されるノルボルネン系モノマーの開
環重合体水素添加物は光学材料として好ましい性質を有
している。 （例えば特開昭６０−２６０２４号、特開
昭６３−３１７５２０号、特開平１−１３２６２６号な
ど）、とくに数平均分子：ｌ（Ｍｎ）が２０ 、０００
〜ｓｏ、ｏｏｏ、重量平均分子１ （ＭＶ）が４０，０
００〜ｇｏ、ｏｏｏ、分子量分布（Ｍｗ／Ｍｎ）が２．
５以下であり、かつポリマー中の揮発成分が０．３重量
％以下である場合には、射出成形の際にボイドやシルバ
ーストリークを発生することがなく、光学用材料として
きわめて優れた特性を有している（特願平２−１５０６
８４号）。Hydrogenated ring-opening polymers of norbornene monomers, typified by tetracyclododecene, its alkyl-substituted products, ester-type substituted products, etc., have favorable properties as optical materials. (For example, JP-A-60-26024, JP-A-63-317520, JP-A-1-132626, etc.), especially when the number average molecule: l (Mn) is 20,000
~so, ooo, weight average molecule 1 (MV) is 40,0
00~go, ooo, molecular weight distribution (Mw/Mn) is 2.
5 or less, and if the volatile component in the polymer is 0.3% by weight or less, no voids or silver streaks will occur during injection molding, and the material will have extremely excellent properties as an optical material. (Patent application Hei 2-1506)
No. 84).
このような水素添加物を製造するに当たっては、一般に
ノルボルネン、系開環重合体を溶媒中で触媒を用いて水
素添加し、触媒を除去し１次いで重合体溶液に溶媒と同
量以上の貧溶媒、通常２〜３倍のケトンまたはアルコー
ルと接触させることによって析出単離させ、乾燥する方
法が採用されている（例えば特開平１−１３８２５７号
）。In producing such hydrogenated products, generally, norbornene-based ring-opening polymers are hydrogenated in a solvent using a catalyst, the catalyst is removed, and then the polymer solution is added with at least the same amount of poor solvent as the solvent. Usually, a method is employed in which the product is brought into contact with 2 to 3 times as much ketone or alcohol to precipitate, isolate, and dry (for example, JP-A-1-138257).
しかし、この方法の場合には、処理時間が長い。However, this method requires a long processing time.
、操作が複雑であるといった問題に加え、水素添加物中
に異物が混入しやすいという問題がある。異物混入の原
因として、ポリマーの析出に用いる溶剤中の異物がポリ
マーに混入する、析出したポリマーを分離・乾燥する工
程での移動操作時に塵が異物として混入する１重合触媒
や水素添加触媒の除去が不完全であることなどが挙げら
れる。In addition to the problem of complicated operation, there is also the problem that foreign substances are likely to be mixed into the hydrogenated product. The cause of foreign matter contamination is that foreign matter in the solvent used for polymer precipitation gets mixed into the polymer, and dust gets mixed in as foreign matter during the transfer operation in the process of separating and drying the precipitated polymer.1 Removal of polymerization catalysts and hydrogenation catalysts. For example, it is incomplete.
光学材料として、中でも光ディスクのごとき情報記録媒
体として使用する場合は、特に、樹脂中の異物が記録信
号の不良と密接な相関があることが公知である。 （特
開昭６ｌ−９０３４５）異物含有量が多いポリマーを光
学式記録媒体用光学材料に使用すると記録信号再生時の
ノイズや信号エラーの原因となるため好ましくないが、
従来の方法では異物の混入を避けられず、より異物含量
の少ないポリマー及びその製法の実現が望まれていた。When used as an optical material, especially as an information recording medium such as an optical disk, it is known that foreign matter in the resin has a close correlation with defects in recorded signals. (Japanese Patent Application Laid-Open No. 61-90345) It is undesirable to use a polymer with a high content of foreign substances as an optical material for an optical recording medium because it causes noise and signal errors during reproduction of recorded signals.
Conventional methods cannot avoid contamination of foreign matter, and it has been desired to realize a polymer with a lower foreign matter content and a method for producing the same.
本発明は、記録信号再生時のノイズや信号エラーの少な
い光学式記録媒体用光学材料として優れたノルボルネン
系開環重合体水素添加物及び該添加物の製造に適したノ
ルボルネン系開環重合体水素添加物の製造方法を提供す
る。The present invention relates to a hydrogenated norbornene-based ring-opening polymer which is excellent as an optical material for optical recording media with less noise and signal errors during reproduction of recorded signals, and a hydrogenated norbornene-based ring-opened polymer suitable for the production of the additive. A method for producing an additive is provided.
本発明によれば、ｊｌｌの発明としてノルボルネン系モ
ノマーの開環重合体の水素添加物であって、該水素添加
物の高速液体クロマトグラフィにより□ 測定シタ数平
均分子量（Ｍｎ）−が２０，０００〜５０，０００、重
量平均分子量 （Ｎｕ）が４０．０００〜８０，０００
、分子、１分布（Ｍｎ／Ｍｗ）が２．５以下、該水素添
加物中に含まれる揮発成分０．３重量゛％以下であり、
かつ０．５縄以上の異物量が１ｘｌｏ５／ｇ以下である
成形用材料が提供され、第２の発明として該成形材料を
成形したディスク基板が提供され、第３の発明として該
ディスク基板に金属反射膜を蒸着した光学式記録媒体デ
ィスクが提供され、さらにＩＩ４の発明としてノルボル
ネン系開環重合体を溶液中そ水素添加触媒の存在下で水
素添加反応した後の反応混液を孔径が０．５．以下のフ
ィルターで渡通した後、濾液中の揮発成分を減圧下の加
熱により蒸発させることを特徴とするノルボルネン系開
環重合体水素添加物の製造方法が提供される。According to the present invention, as an invention of Jll, there is provided a hydrogenated product of a ring-opening polymer of a norbornene monomer, which has a measured number average molecular weight (Mn) of 20,000 to 20,000 by high performance liquid chromatography of the hydrogenated product. 50,000, weight average molecular weight (Nu) 40,000 to 80,000
, the molecular weight distribution (Mn/Mw) is 2.5 or less, and the volatile component contained in the hydrogenated product is 0.3% by weight or less,
A molding material is provided in which the amount of foreign matter of 0.5 rope or more is 1xlo5/g or less, a second invention provides a disk substrate molded with the molding material, and a third invention provides a disk substrate having a metal content on the disk substrate. An optical recording medium disk having a reflective film deposited thereon is provided, and furthermore, as invention II4, a reaction mixture obtained by subjecting a norbornene-based ring-opening polymer to a hydrogenation reaction in the presence of a hydrogenation catalyst in a solution with a pore diameter of 0.5 is provided. ．． There is provided a method for producing a hydrogenated norbornene-based ring-opening polymer, which comprises passing the filtrate through the following filter and then evaporating volatile components in the filtrate by heating under reduced pressure.
以下、本発明の構成について詳述する。Hereinafter, the configuration of the present invention will be explained in detail.
（ノルボルネン系モノマーの開環重合体の水素添加物）
本発明のベースポリマーは、ノルボルネン系モノマーの
開環重合体の水素添加物である。(Hydrogenated ring-opening polymer of norbornene monomer) The base polymer of the present invention is a hydrogenated ring-opening polymer of norbornene monomer.
該水素添加物は、高速液体クロマトグラフィーにより測
定した数平均分子量（Ｍｎ）が２０ 、０００〜ｓｏ、
ｏｏｏ、重量平均分子量（Ｍりが４０，０００〜ｇｏ
、ｏｏｏ、分子量分布（Ｍ％ｌ／Ｍ１１）が２．５以下
テアリ、かつ、該水素添加物中に含まれる揮発成分が０
゜３重量％以下であり、かつ０．５．以上の異物量が１
×１０５個／ｇ以下のものである。The hydrogenated product has a number average molecular weight (Mn) of 20,000 to so, measured by high performance liquid chromatography.
ooo, weight average molecular weight (M 40,000~go
, ooo, the molecular weight distribution (M%l/M11) is 2.5 or less, and the volatile components contained in the hydrogenated product are 0.
°3% by weight or less, and 0.5. The amount of foreign matter is 1
×105 pieces/g or less.
数平均分子量（Ｍｎ）および重量平均分子量（Ｍｗ）が
上記範囲より大きいと、複屈折が劣り、かつ、成形性が
悪くなり、グループ転写性も不良となる。If the number average molecular weight (Mn) and weight average molecular weight (Mw) are larger than the above ranges, birefringence will be poor, moldability will be poor, and group transferability will also be poor.
数平均分子量（Ｍｎ）が小さいと、機械的強度が劣り、
また、分子量分布（Ｍ％＋／Ｍｎ）が大きいと、複屈折
が大きくなる。When the number average molecular weight (Mn) is small, mechanical strength is poor;
Moreover, when the molecular weight distribution (M%+/Mn) is large, the birefringence becomes large.
揮発成分の含有量が上記範囲より多いと、投影面積が大
きく、厚みの薄い光デイスク基板などを射出成形により
成形した場合に、ボイドやシルバーストリークの発生が
見られる。If the content of volatile components is higher than the above range, voids and silver streaks will occur when a thin optical disk substrate with a large projected area is molded by injection molding.
さらに異物量が多くなると光学式記録媒体ディスクとし
たときの記録再生時のノイズや信号エラーを起こしやす
くなる。Furthermore, when the amount of foreign matter increases, noise and signal errors are more likely to occur during recording and reproduction when used as an optical recording medium disk.
また、本発明における水素添加物は、耐熱性および射出
成形性の観点から、ガラス転移温度（Ｔｇ）が１００℃
以上、好ましくｉ、ｔ１２０〜２００”Ｃ１さらに好ま
しくは１３０〜１８０”Ｃであることが望ましい。Furthermore, from the viewpoint of heat resistance and injection moldability, the hydrogenated material in the present invention has a glass transition temperature (Tg) of 100°C.
As mentioned above, it is desirable that i and t are preferably 120 to 200''C1, and more preferably 130 to 180''C.
ノルボルネン系モノマーとしては、例えば、ノルボルネ
ン、ジメタノオクタヒドロナフタレン、トリメタノドデ
カヒドロアントラセン、およびそれらの置換体；ジシク
ロペンタジェン、２，３−ジヒドロジシクロベンタジエ
ン、ジメタノオクタヒドロベンゾインデン、ジメタノデ
カヒドロベンゾインデン。ジメタノデカヒドロフルオレ
ン、およびそれらの置換体等を挙げることができる。置
換基は、従来から周知のものであれば、炭化水素基、極
性基のいずれでもよく、例えば、アルキル基、アルキリ
デン基、アリール基、シアノ基、ハロゲン原子、アルコ
キシカルボニル基、ピリジル基などが例示される。Examples of norbornene monomers include norbornene, dimetanooctahydronaphthalene, trimetanododecahydroanthracene, and substituted products thereof; dicyclopentadiene, 2,3-dihydrodicyclobentadiene, dimetanooctahydrobenzoindene, Dimethanodecahydrobenzoindene. Dimethanodecahydrofluorene, substituted products thereof, etc. can be mentioned. The substituent may be a hydrocarbon group or a polar group as long as it is conventionally well known, such as an alkyl group, an alkylidene group, an aryl group, a cyano group, a halogen atom, an alkoxycarbonyl group, a pyridyl group, etc. be done.
これらのノルボルネン系モノマーは、それぞれ単独で使
用してもよいが、二種以上組合わせて使用することもで
きる。目的とする開環重合体水素添加物のＴ、を１００
℃以上とするためには、これらのノルボルネン系モノマ
ーの中でも四環体または五環体のものを使用するか、あ
るいはこれらを主成分とし、二環体や二環体のモノマー
と併用することが好ましい。These norbornene monomers may be used alone, or in combination of two or more. T of the target ring-opening polymer hydrogenated product is 100
In order to achieve a temperature above ℃, it is necessary to use tetracyclic or pentacyclic monomers among these norbornene monomers, or to use these as the main component in combination with bicyclic or bicyclic monomers. preferable.
′ 特に、複屈折率の点では、四環体の低級アルキル
置換体またはアルキリデン置換体、中でもエチル置換体
、エチリデン置換体およびプロピル置換体が好ましく、
とりわけエチル置換体またはエチリデン置換体のホモボ
ノリマーまたはこれを５０重量％以上、好ましくは７０
重量％以上重合成分として含むコポリマーが望ましい。' In particular, from the point of view of birefringence, lower alkyl or alkylidene substituted tetracyclics are preferred, especially ethyl, ethylidene and propyl substituted products,
In particular, homobonolimers of ethyl- or ethylidene-substituted products or 50% by weight or more, preferably 70% by weight of these
A copolymer containing at least % by weight as a polymerization component is desirable.
また、共重合成分として、他のシクロオレフィン類、例
えば、シクロプロペン、シクロブテン、シクロペンテン
、シクロヘプテン、シクロオクテン、５，６−シヒドロ
ジシクロペンタンジエン等を本発明の目的を損なわない
範囲、通常、３０重量％以下の範囲で用いることができ
る。In addition, as a copolymerization component, other cycloolefins such as cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, 5,6-cyhydrodicyclopentanediene, etc. may be used within the range that does not impair the purpose of the present invention, usually. It can be used in a range of 30% by weight or less.
また、分子′ＩｋｉＩＩ節剤として、非環式オレフィン
をψ量（通常、１０モル％まで）用いてもよく、その中
でも、特に、１−ブテン、１−ペンテン、１−ヘキセン
等のα−オレフィンが好ましい。In addition, as a molecular 'IkiII moderator, an acyclic olefin may be used in an amount of ψ (usually up to 10 mol%), and among them, α-olefins such as 1-butene, 1-pentene, 1-hexene, etc. is preferred.
このような重合体は、例えば、四ハロゲン化チタンなど
の遷移金属化合物と有機アルミニウム化合物などの有機
金属および第三級アミンから成る触媒系を用いて、チタ
ン成分とモノマーとを逐次添加する方法で得ることがで
きる。もちろん、他の触媒系でＩ［Ｉｌシたものでも、
上記の各要件に合致するものであればよい。Such polymers can be produced, for example, by the sequential addition of a titanium component and a monomer using a catalyst system consisting of a transition metal compound such as titanium tetrahalide, an organometallic such as an organoaluminium compound, and a tertiary amine. Obtainable. Of course, even with other catalyst systems,
Any material that meets each of the above requirements may be used.
開環＊命は、溶媒を用いなくても可能であるが、通常は
、ベンゼン、トルエン、キシレンなどの芳香族炭化水素
、ヘキサン、ヘプタンなどの脂肪族炭化水素、シクロヘ
キサンなどの脂環族炭化水素。Ring-opening is possible without using a solvent, but it is usually carried out using aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane. .
ジクロルエタンなどのハロゲン化炭化水素等の不活性有
機溶媒中で実施される。また、通常、重合温度は、−２
０℃〜１００℃、重合圧力は、０〜５０ｋｇ／ｃ鳳２以
下の範囲から選択される。It is carried out in an inert organic solvent such as a halogenated hydrocarbon such as dichloroethane. Moreover, the polymerization temperature is usually -2
The temperature and polymerization pressure are selected from the range of 0 to 50 kg/c and 2 or less.
ノルボルネン系モノマーの開環重合体の水素添加物は、
周知の水素添加触媒を使用することにより製造される。Hydrogenated ring-opening polymers of norbornene monomers are
Produced by using well-known hydrogenation catalysts.
水添触媒としては、オレフィン化合物の水素化に際して
一般に使用されているものであれば使用可能であり、例
えば、ウィルキンソン錯体、酢酸コバルト／トリエチル
アルミニウム、ニッケルアセチルアセトナート／トリイ
ソブチルアルミニウム、パラジウム−カーボン、ルテニ
ウム−カーボン、ニッケルーけいそう土等を挙げられる
が、次工程での触媒残液の除去の容易さの見地から固形
触媒であることが必要である。As the hydrogenation catalyst, any catalyst commonly used in the hydrogenation of olefin compounds can be used, such as Wilkinson complex, cobalt acetate/triethylaluminum, nickel acetylacetonate/triisobutylaluminum, palladium-carbon, Examples include ruthenium-carbon and nickel-diatomaceous earth, but from the viewpoint of ease of removing catalyst residual liquid in the next step, it is necessary to use a solid catalyst.
水素化反応は、不均一系で、１〜２００気圧の水素圧下
、０〜２５０℃で行なわれる。The hydrogenation reaction is carried out in a heterogeneous system under a hydrogen pressure of 1 to 200 atmospheres and at a temperature of 0 to 250°C.
水素添加率は、耐熱劣化性、耐光劣化性などの観点から
、９０％以上、好ましく９５％以上、特に好ましくは９
９％以上とする。The hydrogenation rate is 90% or more, preferably 95% or more, particularly preferably 9
9% or more.
（異物の濾過工程）
本発明においては水素添加物の溶液を濾過することによ
り異物を除去する異物除去工程が必要である。(Foreign Matter Filtration Step) The present invention requires a foreign matter removal step of removing foreign matter by filtering the hydrogenated solution.
この異物除去工程以降の処理は、新たな異物の混入を防
ぐため、クリーン・ルーム中等、クリーン度の高い環境
下、クリーン度クラス１０００以下で行うことが好まし
く、特にクリーン度クラス１００以下で行うことが好ま
しい。Processing after this foreign matter removal step is preferably carried out in a clean room or other highly clean environment in a cleanliness class of 1000 or less, particularly in a cleanliness class of 100 or less, in order to prevent the contamination of new foreign matter. is preferred.
孔径が０．５７ｍ以下、好ましくは０．３．以下のフィ
ルターで濾過することにより、異物を除去する。The pore diameter is 0.57 m or less, preferably 0.3 m. Remove foreign substances by filtering with the following filter.
孔径が０．５．より大きいフィルターを用いると水素添
加物溶液中の異物含有量が減ジ・せず光学記録式光学材
料として記録再生時のノイズレベルが増大する。The pore diameter is 0.5. If a larger filter is used, the content of foreign substances in the hydrogenated solution will not be reduced, and as an optical recording type optical material, the noise level during recording and reproduction will increase.
フィルターの種類は特に限定されない。一般に、カート
リッジフィルターやメンブランフィルタ−が用いられる
。濾過の効率を上げるため、減圧、または加圧してもよ
い。珪藻土、シリカ、アルミナ等を濾過助剤として使用
することもできる。The type of filter is not particularly limited. Generally, cartridge filters and membrane filters are used. In order to increase the efficiency of filtration, the pressure may be reduced or increased. Diatomaceous earth, silica, alumina, etc. can also be used as filter aids.
濾過の際の溶液濃度は５〜４０重量％、好ましくは１０
〜２５重量％である。濃度が低いと大量の溶液を処理す
る必要があり、濃度が高いと濾過性が低下し、共に生産
性が劣り工業的に不利となる。通常、反応後の溶液濃度
は１０〜２５重景％であるので、濃縮や希釈をすること
なく濾過すればよい。The solution concentration during filtration is 5 to 40% by weight, preferably 10
~25% by weight. When the concentration is low, it is necessary to process a large amount of solution, and when the concentration is high, filtration performance decreases, and both result in poor productivity and are industrially disadvantageous. Usually, the concentration of the solution after the reaction is 10 to 25%, so it may be filtered without concentration or dilution.
（揮発成分除去工程）
本発明においては、異物除去工程に続いて、揮発成分除
去工程でポリマー溶液中の揮発分が除去される。揮発成
分としては、水添反応に用いた溶剤や、重合工程の反応
液を直接水素添加反応に供した場合に含有される未反応
モ人、マーなどがある。(Volatile component removal step) In the present invention, following the foreign matter removal step, volatile components in the polymer solution are removed in the volatile component removal step. Volatile components include the solvent used in the hydrogenation reaction and unreacted monomers and polymers contained when the reaction solution of the polymerization step is directly subjected to the hydrogenation reaction.
揮発成分の含有量が上記範囲より多いと、投影面積が大
きく、厚みの薄い光デイスク基板（とくに大型の光デイ
スク基板）などを射出成形により成形した場合に、ボイ
ドやシルバーストリークの発生が見られる。If the content of volatile components is higher than the above range, voids and silver streaks may occur when injection molding is used to mold optical disk substrates with large projected areas and thin thickness (especially large optical disk substrates). .
揮発成分の除去はポリマー溶液を減圧下に加熱すること
により行われる。このための装置としてはコントロ（日
立製作所社製）、スミス式（神鋼ファウドラー社製）な
どの遠心薄膜連続蒸発器型乾燥器、ボテーター（ケメト
ロン社製）、オンレータ−（桜製作所社ｍｌ）などの蓋
面熱交換型連続反応器型乾燥器、ＳＣＲ（三菱重工社製
）などの高粘度リアクタ装置などが挙げられる。Removal of volatile components is carried out by heating the polymer solution under reduced pressure. Equipment for this purpose includes centrifugal thin film continuous evaporator type dryers such as CONTROL (manufactured by Hitachi, Ltd.), Smith type (manufactured by Shinko Faudler), Votator (manufactured by Kemetron), and Onrator (manufactured by Sakura Manufacturing Co., Ltd.). Examples include a lid surface heat exchange type continuous reactor dryer, a high viscosity reactor device such as SCR (manufactured by Mitsubishi Heavy Industries, Ltd.), and the like.
これらの装置の操作条件は適宜選択しうるが、通常は２
００ｔｏｒｒ以下、好ましくは１００ｔｏｒｒ以下、特
に好ましくは３０ｔｏｒｒ以下で、また、 ２００℃〜
３００’Ｃ，好ましくは２５０℃〜２７０℃で、少なく
とも１０分間行う。圧力が高いと、蒸発速度が遅く生産
性が悪い。また、温度が３００℃より高いとポリマーの
熱分解反応が生じ、 ２００℃未満では揮発成分が残留
し易い、この際、窒素、アルゴンなどの不活性ガス雰囲
気下で処理することが望ましい。The operating conditions for these devices can be selected as appropriate, but usually 2
00 torr or less, preferably 100 torr or less, particularly preferably 30 torr or less, and 200°C to
It is carried out at 300'C, preferably between 250C and 270C for at least 10 minutes. If the pressure is high, the evaporation rate is slow and productivity is poor. Further, if the temperature is higher than 300°C, a thermal decomposition reaction of the polymer occurs, and if it is lower than 200°C, volatile components tend to remain.In this case, it is preferable to perform the treatment under an inert gas atmosphere such as nitrogen or argon.
水素添加物は酸素存在下で加熱すると、熱劣化により着
色しやすく、光学記録式光学材料に対する処理として好
ましくない。When hydrogenated substances are heated in the presence of oxygen, they tend to become colored due to thermal deterioration, which is not preferable for treatment of optical recording materials.
この工程では必要に応じて酸化防止剤、熱安定性剤、滑
剤、紫外線吸収剤などを添加してもよい。In this step, antioxidants, heat stabilizers, lubricants, ultraviolet absorbers, etc. may be added as necessary.
このような方法によれば、 ０．５−以上の異物量がｌ
Ｘ１０５個／ｇ以下、好ましくは８Ｘ］Ｏ’個／ｇ以下
、とくに好ましくは７Ｘ１０’個／ｇ以下のポリマーを
得ることができる。According to such a method, the amount of foreign matter of 0.5- or more is
A polymer having not more than 105 X/g, preferably not more than 8X]O' pieces/g, particularly preferably not more than 7X10' pieces/g can be obtained.
これらの方法によって製造されたポリマー（水素添加物
）は、実質的に非品性であり、透明性、寸法安定性、耐
熱性、吸水性に優れ、透湿性がほとんど認められない。Polymers (hydrogenated products) produced by these methods are substantially immaculate, have excellent transparency, dimensional stability, heat resistance, and water absorption, and exhibit almost no moisture permeability.
（１ｍ化防止剤）
本発明において、前記水素添加物１００重量部に対して
、酸化防止剤を０，０１〜５重量部の割合で配合すると
、成形加工時のポリマーの分解や着色を効果的に防止す
ることができる。(1M inhibitor) In the present invention, when an antioxidant is blended at a ratio of 0.01 to 5 parts by weight to 100 parts by weight of the hydrogenated material, decomposition and coloring of the polymer during molding can be effectively prevented. can be prevented.
酸化防止剤としては、２０℃における蒸気圧が１Ｏ−６
Ｐａ以下、特に好ましくは１０−”Ｐａ以下の酸化防止
剤が望ましい。蒸気圧が１０−’Ｐａより高いものは、
射出成形時に蒸発し、金型や光デイスク基板表面を汚染
する。そして、例えば、記録薄膜形成のための金属蒸着
時、高真空に達しにくくなり、また、装置内部を汚染す
る等の問題の他に、蒸着金属膜の膨れや剥離といった問
題も発生し易くなる。As an antioxidant, the vapor pressure at 20℃ is 1O-6
Antioxidants having a vapor pressure of less than 10 Pa, particularly preferably less than 10-'Pa, are desirable.
It evaporates during injection molding and contaminates the mold and optical disk substrate surface. For example, during metal vapor deposition for forming a recording thin film, it becomes difficult to reach a high vacuum, and in addition to problems such as contamination of the inside of the apparatus, problems such as blistering and peeling of the vapor-deposited metal film are also likely to occur.
本発明で使用できる酸化防止剤としては、例えば、ペン
タエリスリチル−テトラキス［３−（３゜５−ジ−ｔ−
ブチル−４−ヒドロキシフェニル）プロピオネート］、
１，３．５−）リメチル−２゜４．６−）リス（３，５
−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン
、３，９−ビス［２−（３−（３−ｔ−ブチル−４−ヒ
ドロキシ−５−メチルフェニル）プロピオニルオキシ）
−１゜１−ジメチルエチルコー２． ４． ８． １０
−テトラオキサスピロ［５，５］ウンデカンなどのごと
きヒンダードフェノール系を挙げることができる。Examples of antioxidants that can be used in the present invention include pentaerythrityl-tetrakis [3-(3°5-di-t-
butyl-4-hydroxyphenyl)propionate],
1,3.5-)limethyl-2゜4.6-)lis(3,5
-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)
-1゜1-dimethylethylco2. 4. 8. 10
Mention may be made of hindered phenols such as -tetraoxaspiro[5,5]undecane and the like.
（ディスク基板及び光記録媒体）
本発明の成形材料は、通常の成形法により各種成形物に
成形できるが、特に射呂成形により光デイスク基板を作
成するのに適している。(Disc Substrate and Optical Recording Medium) The molding material of the present invention can be molded into various molded products by ordinary molding methods, but is particularly suitable for producing optical disc substrates by molding.
射呂成形によって得られた成形物は、常法に従ってさら
に真空蒸着やスパッタリング等の方法によって、金属、
金属酸化物、金属窒化物、金属硫化物、金属ハロゲン化
物等を目的に応じ、単層または多層に成膜することがで
きる。The molded product obtained by Yaro molding is further processed by conventional methods such as vacuum deposition and sputtering to form metal,
Metal oxides, metal nitrides, metal sulfides, metal halides, etc. can be formed into a single layer or multiple layers depending on the purpose.
透明基板上に、光学的に記録および／または読み出し可
能な反射膜や記録薄膜を設けて、記録媒体を製造するこ
とができる。A recording medium can be manufactured by providing a reflective film or a recording thin film that can be optically recorded and/or read out on a transparent substrate.
金属反射膜としてはＡ１、Ｎｉ、・Ａυなどが使用され
る。記録膜としては、孔形成型としてＴｅ−Ｃ１＾５−
Ｔｅ−５ｅ、Ｔｅ−５ｅ−Ｃ系など、相変化型としてＴ
ｅ帆、５ｎ−Ｔｅ−Ｓｅ、 Ｔｅ−５ｂ−Ｇｅ、 ５ｂ
−５ｅ／Ｂ１−Ｔｅ系など、光磁気型としてＴｂ−Ｆｅ
、 Ｔｂ−Ｆｅ−Ｃｏ、Ｎｂ−Ｄｙ−Ｆｅ、Ｎｂ−Ｄ
ｙ−Ｆｅ−Ｃｏ、 Ｎｂ−Ｄｙ−Ｃｏ、Ｐｔ−Ｔｂ−
Ｆｅ−Ｃｏ系などが使用される。しかし、ここで例示し
たちの以外の反射膜や記録膜が適用されても差し支えな
い。A1, Ni, .Aυ, etc. are used as the metal reflective film. As a recording film, Te-C1^5- is used as a hole-forming type.
T as a phase change type such as Te-5e, Te-5e-C system, etc.
e sail, 5n-Te-Se, Te-5b-Ge, 5b
Tb-Fe as a magneto-optical type such as -5e/B1-Te system
, Tb-Fe-Co, Nb-Dy-Fe, Nb-D
y-Fe-Co, Nb-Dy-Co, Pt-Tb-
Fe--Co type etc. are used. However, reflective films and recording films other than those exemplified here may be applied.
（用途）
本発明の成形材料は、射呂成形、プレス成形、押出成形
、回転成形など一般的な熱可塑性樹脂の加工方法が可能
である。(Applications) The molding material of the present invention can be processed by common thermoplastic resin processing methods such as molding, press molding, extrusion molding, and rotary molding.
そして、本発明の成形材料は、光デイスク基材（基板、
ハブ、スペーサー等）、レンズ、光ファイバー、光学ミ
ラー、プリズム、発光ダイオード用封止材、各種カバー
用ガラス、窓ガラス、アイロンの水タンク、電子レンジ
用品、液晶表示用基板、プリント基板、透明導電性シー
トおよびフィルム、注射器、ピペット、アニマルゲージ
、ハウジング類、フィルム、ヘルメット、スピーカーコ
ーン等に用いることができる。また、光記録媒体として
は、光ディスク、ＣＤ、ＣＤ−ＲＯＭ、レーザーディス
ク、光カード、光フロッピー、光テープ等を挙げること
ができる。The molding material of the present invention can be used as an optical disk base material (substrate,
hubs, spacers, etc.), lenses, optical fibers, optical mirrors, prisms, encapsulants for light emitting diodes, various cover glasses, window glasses, water tanks for irons, microwave oven supplies, LCD display substrates, printed circuit boards, transparent conductive materials It can be used for sheets and films, syringes, pipettes, animal gauges, housings, films, helmets, speaker cones, etc. Further, examples of the optical recording medium include an optical disk, a CD, a CD-ROM, a laser disk, an optical card, an optical floppy disk, an optical tape, and the like.
以下、本発明について、実施例および比較例を挙げて具
体的に説明するが、本発明は、これらの実施例のみに限
定されるものではない。また、以下の実施例および比較
例において、特に断りのない限り、部および％は重量基
準である。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, in the following Examples and Comparative Examples, unless otherwise specified, parts and percentages are based on weight.
〔参考例１〕
６−エチル−１，４：５，８−ジメタノ−１，４，４ａ
、５゜６．７，８，８ａ−オクタヒドロナフタレン（以
下、ＥＴＤという）３０部をシクロヘキサン２００部に
溶解し、分子量調節剤として１−ヘキセンを１部、トリ
エチルアルミニウムの１５％シクロヘキサン溶液１０部
、およびトリエチルアミン５部を添加した。この溶液を
、３０℃に保ちなからＥＴＤ３０部、および四塩化チタ
ンの２０％シクロヘキサン溶液１０部を１時間にわたっ
て連続的に反応系に添加して、開環重合を行った。[Reference Example 1] 6-ethyl-1,4:5,8-dimethano-1,4,4a
, 5゜ 30 parts of 6.7,8,8a-octahydronaphthalene (hereinafter referred to as ETD) was dissolved in 200 parts of cyclohexane, 1 part of 1-hexene as a molecular weight regulator, and 10 parts of a 15% solution of triethylaluminum in cyclohexane. , and 5 parts of triethylamine were added. While this solution was maintained at 30° C., 30 parts of ETD and 10 parts of a 20% cyclohexane solution of titanium tetrachloride were continuously added to the reaction system over 1 hour to carry out ring-opening polymerization.
ＥＴＤと四塩化チタンの全量を添加し、３０分後、転化
率８５％の時点で六塩化タングステンの０．８％シクロ
ヘキサン溶液５部を添加し、更に３０分間攪拌した。The entire amount of ETD and titanium tetrachloride were added, and 30 minutes later, when the conversion rate was 85%, 5 parts of a 0.8% cyclohexane solution of tungsten hexachloride was added, and the mixture was stirred for an additional 30 minutes.
ｓ、ｊ１体の重合体への転化率は９８％であった。The conversion rate of s, j1 body into a polymer was 98%.
〔実施例１〕
（水添工程）
参考例１の方法で得られた重合体溶液１００部に、イソ
プロピルアルコール１部を添加し、室温で１゜分間攪拌
した。さらに蒸留水を１部添加して、８０℃で１時間攪
拌した。反応終了後、無水硫酸マグネシウム３部を添加
して撹拌しながら溶液を室温まで冷却し、珪藻土（ラジ
オライト＄８００昭和化学製）を渡過層として不溶化物
を含んだ溶液を２．５ｋｇ／ｃＢ２加圧渡過し、淡黄色
透明のポリマー溶液６を得た。[Example 1] (Hydrogenation step) 1 part of isopropyl alcohol was added to 100 parts of the polymer solution obtained by the method of Reference Example 1, and the mixture was stirred at room temperature for 1°. Further, 1 part of distilled water was added, and the mixture was stirred at 80°C for 1 hour. After the reaction was completed, 3 parts of anhydrous magnesium sulfate was added and the solution was cooled to room temperature while stirring, and the solution containing insolubilized substances was added at 2.5 kg/cB2 using diatomaceous earth (Radiolite $800 manufactured by Showa Kagaku) as a transition layer. The pressure was passed, and a pale yellow transparent polymer solution 6 was obtained.
上記のポリマー溶液１００部に、ニッケルー珪藻土触媒
１部を添加して、オートクレーブ中に入れ、攪拌混合後
に中の空気を水素で置換して、水素圧を４５ｋｚ／ ｃ
ｍ２にて攪拌しながら温度１９０℃まで加温した後、４
時間不均一系で反応させた。Add 1 part of nickel-diatomaceous earth catalyst to 100 parts of the above polymer solution, place it in an autoclave, and after stirring and mixing, replace the air inside with hydrogen and raise the hydrogen pressure to 45 kHz/c.
After heating to a temperature of 190°C while stirring at m2,
The reaction was performed in a time-heterogeneous system.
（１！過工程）
不溶化物を含んだポリマー含量２０％の反応液をラジオ
ライト＃８００をろ適法として、加圧ろ過器（フンダフ
ィルター、石川島播磨重工社製）を使用し、圧力Ｌ５ｋ
ｇ／ｃ■２で加圧渡過して、無色透明な溶液を得た。こ
の溶液１００部に酸化防止剤としてペンタエリスリチル
−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒ
ドロキシフェニル）プロピオネート］ ０．０１部を加
えて溶解し、クリーン度クラス１００の環境下で、この
液液をさらに０．２−のフィルターにて液適し、異物を
除去した。(1! Over-step) A reaction solution with a polymer content of 20% containing insolubilized substances was filtered using a pressure filter (Fundafilter, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.) using Radiolite #800 as a suitable method, and the pressure was L5k.
A colorless and transparent solution was obtained by passing the pressure at g/c 2. To 100 parts of this solution, 0.01 part of pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] as an antioxidant was added and dissolved, and a cleanliness class 100 was obtained. This liquid was further filtered through a 0.2-filter to remove foreign substances.
（揮発成分除去工程）
上記溶液１００部を用いて、揮発成分であるシクロヘキ
サン及び残留モノマーの蒸発を縦置円筒型濃縮器日立コ
ントロ（日立製作所製）によって行った。運転条件は、
ポリマー溶液温度２５１℃、圧力５７ｔｏｒｒ、ポリマ
ー溶液流量５．９ｋｇ／ｈｒにて行い、水素添加物１９
部を得た。残留溶剤およびモノマーは水素添加物を１０
％含むトルエン溶液をガスクロマトグラフィで分析した
結果、得られた水素添加物中のシクロヘキサン含量０．
０８ｗｔ％、残留モノマー水素添加物含量０．７３％で
あった。(Volatile Component Removal Step) Using 100 parts of the above solution, cyclohexane as a volatile component and residual monomer were evaporated using a vertical cylindrical concentrator Hitachi Control (manufactured by Hitachi, Ltd.). The operating conditions are
The polymer solution temperature was 251°C, the pressure was 57 torr, and the polymer solution flow rate was 5.9 kg/hr.
I got the department. Residual solvents and monomers are hydrogenated at 10%
As a result of gas chromatography analysis of a toluene solution containing 0.0% cyclohexane content in the hydrogenated product obtained.
08 wt%, and the residual monomer hydrogenated content was 0.73%.
この回収した水素添加物溶融物１００部を同濃縮器を用
いて、水素添加物溶融物温度２６０℃、圧力５ ｔｏｒ
ｒ、水素添加物溶融物流！ １６．８ｋｇ／ ｈｒで処
理した。溶融物をダイから押し出し、ペレタイザー（Ｏ
８Ｐ−２、長円製作所製）でカッティングし、ペレット
７３部（ポリマーＡ）を得た。得られたペレットを１０
％含むトルエン溶液をガスクロマトグラフィで分析した
結果、残留シクロヘキサン量、残留モノマー水素添加物
量共に、測定限界以下であった。最終的に回収された水
素添加物は、無色透明で、Ｋｎは２９，０００、ｈは５
９，５００． 阿ｎ／Ｍｗは ２．０５であった。ま
た、示差走査熱量分析（ＤＳＣ）により測定したＴＫは
１４０℃であった。さらに、四塩化炭素溶液としてＩＨ
−ＮＭＲスペクトルにより測定したを水素添加率はほぼ
１００％であった。得られた水素添加物を０．１ カ
ートリッジフィルターにて液適精製したシクロヘキサン
を用いて０．２％溶液に調整し、光散乱式粒子検比器（
ＫＳ−５８、リオン社製）を用いて異物個数を測定した
結果、１．１ｍ以上の異物量２１０個／ｇ、０．５津以
上の異物ｆｆ１６Ｘ１０’個／ｇであった。Using the same concentrator, 100 parts of the recovered hydrogenate melt was heated at a temperature of 260°C and a pressure of 5 torr.
r, Hydrogenated melt logistics! It was treated at 16.8 kg/hr. The melt is extruded through the die, and the pelletizer (O
8P-2, manufactured by Choen Seisakusho) to obtain 73 parts of pellets (Polymer A). 10 of the obtained pellets
As a result of gas chromatography analysis of the toluene solution containing 1.5%, both the amount of residual cyclohexane and the amount of residual monomer hydrogenated material were below the measurement limit. The hydrogenated product finally recovered is colorless and transparent, Kn is 29,000, and h is 5.
9,500. An/Mw was 2.05. Further, the TK measured by differential scanning calorimetry (DSC) was 140°C. Furthermore, IH as a carbon tetrachloride solution
-The hydrogenation rate measured by NMR spectrum was approximately 100%. The obtained hydrogenated product was adjusted to a 0.2% solution using cyclohexane that had been purified with a 0.1% cartridge filter, and the solution was purified using a light scattering particle analyzer (
KS-58, manufactured by Rion Corporation), the number of foreign particles was measured, and the number of foreign particles was 210 pieces/g of 1.1 m or more, and 16 x 10' pieces/g of foreign particles of 0.5 m or more.
〔実施例２〕
揮発成分除去工程の装置を縦置円筒型濃縮器に代えて高
粘度リアクタ装置ＳＣＲ（三菱重工社製）とし、操作条
件を水素添加物溶融物温度２５０℃、圧力１ｔｏｒｒ、
水素添加物溶融物流量３．２２ｋｚ／ ｈｒで１段で処
理を行った以外は実施例１と同様に処理して、水素添加
物１００部からペレット１２部（ポリマーＢ）を得た。[Example 2] A high viscosity reactor device SCR (manufactured by Mitsubishi Heavy Industries, Ltd.) was used instead of a vertical cylindrical concentrator as the device for the volatile component removal process, and the operating conditions were a hydrogenated melt temperature of 250°C, a pressure of 1 torr,
12 parts of pellets (polymer B) were obtained from 100 parts of the hydrogenate by carrying out the same treatment as in Example 1 except that the treatment was performed in one stage at a hydrogenate melt flow rate of 3.22 kHz/hr.
得られた水素添加物は無色透明であり、Ｍｎは２８，８
００． Ｍｕは５９，０００、Ｍｗ／Ｋｎは２．０５
、Ｔには１４０℃であった。残留シクロヘキサン量、残
留モノマー水素添加物量は検出限界以下であった。The obtained hydrogenated product is colorless and transparent, and has an Mn of 28.8
00. Mu is 59,000, Mw/Kn is 2.05
, T was 140°C. The amount of residual cyclohexane and the amount of residual monomer hydrogenated substances were below the detection limit.
水素添加物中の１声以上の異物量は２９０個／ｇ、０−
５．以上の異物量はＩＸＩＱ’個／ｇであった。The amount of foreign matter with one or more voices in the hydrogenated material is 290 pieces/g, 0-
5. The above amount of foreign matter was IXIQ' pieces/g.
〔実施例３〕
千ツマ−として６−メチル−１，４：５，８−ジメタノ
−１，４，４ａ、５，６，７，８，８ａ−オクタヒドロ
ナルタレンを使用する以外は参考例１、実施例１と同様
にして、開環重合体水素添加物ペレット（ポリマーＣ）
を得た。 得られた水素添加物のペレットは無色透明で
、Ｍｎは３１，０００、阿りは６３，０００、阿ｗ／Ｍ
ｎは２゜０３、Ｔｇは１４９℃であり水素添加率はほぼ
１００％であった。[Example 3] Reference example except that 6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaltalene was used as the compound. 1. Ring-opened polymer hydrogenated pellets (Polymer C) in the same manner as in Example 1
I got it. The obtained hydrogenated pellets were colorless and transparent, had an Mn of 31,000, an alium of 63,000, and an aw/M
n was 2°03, Tg was 149°C, and the hydrogenation rate was approximately 100%.
また残留シクロヘキサン量、残留モノマー水素添加物量
は検出限界以下であった６ 水素添加物中の１部ｍ以上
の異物量は３２０個／ｇ、０．５μｇ以上の異物量は６
Ｘ１０’個／ｇであった。In addition, the amount of residual cyclohexane and the amount of residual monomer hydrogenated substances were below the detection limit.6 The amount of foreign substances in the hydrogenated substance of 1 part m or more was 320 pieces/g, and the amount of foreign substances of 0.5 μg or more was 6.
It was X10' pieces/g.
〔実施例４〕
液適工程において酸化防止剤を添加しないこと以外は実
施例１と同様にしてペレットを得た。得られた水素添加
物のペレットは、ごくわずかに黄色味を帯びていたが、
ＭｎＧ、ｔ ２９，０００− Ｍｗｉ、ｔ ５９，５
００、Ｍ１１／Ｍｎは２．０５、Ｔ、は１４１℃であっ
た。残留シクロヘキサン量、残留モノマー水素添加物量
は検出限界以下であった。水素添加物中の１１ｍ以上の
異物は３４０個／ｇ、 ０−５−以上の異物量は９Ｘ
１０’個／ｇであった。[Example 4] Pellets were obtained in the same manner as in Example 1 except that no antioxidant was added in the pouring step. The obtained hydrogenated pellets were slightly yellowish, but
MnG, t 29,000- Mwi, t 59,5
00, M11/Mn was 2.05, and T was 141°C. The amount of residual cyclohexane and the amount of residual monomer hydrogenated substances were below the detection limit. The number of foreign particles of 11m or more in the hydrogenated material is 340 pieces/g, and the amount of foreign particles of 0-5- or more is 9X
It was 10' pieces/g.
〔実施例５〕
減退工程において用いる酸化防止剤をイルガノックス１
３３０ （チバガイギー社製）に代えること以外は実施
例１と同様にしてペレットを得た。得られた水素添加物
のペレットは、無色透明で、Ｍｎは２９．０００．
Ｍｗは５９ 、５００、Ｍｗ／Ｍｎは２−０５． Ｔ
ｇは１４０℃であった。残留シクロヘキサン量、残留モ
ノマー水素添加物量は検出限界以下であった。水素添加
物中の１岸以上の異物は２４０個／ｇ、 ０．５部１ｍ
以上の異物量は６Ｘ１０’個／ｇであった。[Example 5] The antioxidant used in the reduction step was Irganox 1.
Pellets were obtained in the same manner as in Example 1, except that 330 (manufactured by Ciba Geigy) was used. The obtained hydrogenated pellets were colorless and transparent, and had an Mn of 29.000.
Mw is 59,500, Mw/Mn is 2-05. T
g was 140°C. The amount of residual cyclohexane and the amount of residual monomer hydrogenated substances were below the detection limit. 240 particles/g, 0.5 parts 1m
The above amount of foreign matter was 6×10' pieces/g.
〔比較例１〕
実施例１における水添工程終了後、実施例１と同様にし
て減退、引き続き精密液適して、無色透明な溶液を得た
。クリーン度クラス１０００のクリーンルーム内に設置
したクリーンベンチ内のクリーン度クラス１００の環境
下で、この溶液を０．１フイルターにて減退＊ｉ＊ｔ、
たシクロヘキサンを用いて水素添加物濃度５．０％に希
釈した溶液１００部を、３００部のイソプルピルアルコ
ール中に注ぎ入れ、撹拌して水素添加物を析出させた。[Comparative Example 1] After completion of the hydrogenation step in Example 1, the solution was reduced in the same manner as in Example 1, and then applied to a precision liquid to obtain a colorless and transparent solution. This solution was reduced with a 0.1 filter *i*t under a cleanliness class 100 environment in a clean bench installed in a clean room with a cleanliness class 1000.
100 parts of a solution diluted with cyclohexane to a hydrogenate concentration of 5.0% was poured into 300 parts of isopropyl alcohol and stirred to precipitate the hydrogenate.
析出した水素添加物と溶剤とは４００メツシユステンレ
スフイルターにて分離し、回収された水素添加物はクリ
ーンルーム内に設置した真空乾燥器にて１２０℃、 １
ｔｏｒｒ以下で２４時間乾燥し、水素添加物４．２部
を得た。得られた水素添加物１００部に実施例１に使用
したのと同じ酸化防止剤０．０５部を配合し、クリーン
ルーム内に設置したスクリュー径４０ｍｍの単軸押し出
し器（ＳＶ−４０、田辺プラスチックス機械社製）にて
２４０℃で溶融押し出しし、ペレタイザーでカッティン
グしてペレット９１部（ポリマーＤ）を得た。得られた
水素添加物は無色透明で、Ｍｎは２９，０００、阿讐は
５９，７００、Ｍｗ／Ｍｎは２、ｏ６、Ｔｇは１３７℃
であった。得られた水素添加物中の揮発成分は０．５％
であり、異物個数は、１部ｍ以上で７３０個／ｇ、０．
５メ以上で３×１０５個／ｇであった。The precipitated hydrogenated product and solvent were separated using a 400-mesh stainless steel filter, and the recovered hydrogenated product was heated at 120°C in a vacuum dryer installed in a clean room.
It was dried for 24 hours at less than torr to obtain 4.2 parts of hydrogenated product. 0.05 parts of the same antioxidant used in Example 1 was mixed with 100 parts of the obtained hydrogenated product, and a single screw extruder (SV-40, Tanabe Plastics) with a screw diameter of 40 mm was installed in a clean room. The mixture was melt extruded at 240°C using a machine (manufactured by Kikai Co., Ltd.) and cut using a pelletizer to obtain 91 parts of pellets (Polymer D). The obtained hydrogenated product is colorless and transparent, Mn is 29,000, Ani is 59,700, Mw/Mn is 2, o6, and Tg is 137°C.
Met. The volatile component in the obtained hydrogenated product is 0.5%
The number of foreign particles is 730 pieces/g for 1 part m or more, and 0.
It was 3 x 105 pieces/g for 5 or more pieces.
〔比較例２〕
比較例１と同様にして得られた。１度だけ凝固したのち
、乾燥した水素添加物をシクロヘキサンに５％濃度に再
溶解して得られた溶液１００部を０゜２−のフィルター
にて渡通し比較例１と同様にして再度凝固・乾燥−ペレ
ット化して揮発成分含量０．２％のポリマー（ポリマー
Ｅ）を得た。[Comparative Example 2] Obtained in the same manner as Comparative Example 1. After coagulating only once, 100 parts of the solution obtained by redissolving the dried hydrogenated product in cyclohexane to a concentration of 5% was passed through a 0°2-filter and coagulated again in the same manner as in Comparative Example 1. Drying-pelletization gave a polymer (Polymer E) with a volatile content of 0.2%.
乾燥した水素添加物（ポリマーＥ）を、 ０．１フイル
ターにて液適精製したシクロヘキサンを用いて０．５％
溶液に調整し、パーティクルカウンターにて異物個数を
測定した結果、１−以上の異物量８９０個／ｇ、 ０．
５部以上の異物量４×１０５個／にであった。The dried hydrogenated product (polymer E) was purified to 0.5% using cyclohexane, which was purified using a 0.1 filter.
As a result of adjusting the solution and measuring the number of foreign particles with a particle counter, the amount of foreign particles of 1- or more was 890 pieces/g, 0.
The amount of foreign matter of 5 parts or more was 4 x 105 pieces/piece.
以上の結果から１本発明の方法で回収したノルボルネン
系開環重合体水素添加物は、従来法と比較して０．５４
以上の異物の量が少ないことが判る。From the above results, 1. the norbornene ring-opening polymer hydrogenated product recovered by the method of the present invention was 0.54% compared to the conventional method.
It can be seen that the amount of foreign matter is small.
〔実施例６〕
（光デイスク基板の作成）
前記の各ペレットを用い、射出成形機（住人重機械工業
社製、ＤＩＳＣ５ＭＩＩＩ）により、樹脂温度３３０℃
、金型温度１１０℃の条件で射出成形を行ない、直径１
３０ｍｍ、厚さ１．２璽■の光デイスク基板を成形した
。波長８３０ｎｍにおける光線透過率はいずれも９０％
以上であった。[Example 6] (Preparation of optical disk substrate) Using each of the pellets described above, the resin temperature was adjusted to 330° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., DISC5MIII).
, injection molding was performed at a mold temperature of 110°C, and the diameter was 1.
An optical disk substrate having a thickness of 30 mm and a thickness of 1.2 mm was molded. Light transmittance at wavelength 830nm is 90%
That was it.
この光デイスク基板について、目視検査による外観、分
子量（Ｍｕ）変化率、顕微鏡観察によるボイドの有無、
複屈折値（半径：２５〜６０■の範囲）、オーブン中で
、１１０℃、４８時間加熱した後の着色の状況（目視検
査）を測定した。結果を第１表に示した。Regarding this optical disk substrate, the appearance by visual inspection, the rate of change in molecular weight (Mu), the presence or absence of voids by microscopic observation,
The birefringence value (radius: range of 25 to 60 square centimeters) and the state of coloration (visual inspection) after heating in an oven at 110 DEG C. for 48 hours were measured. The results are shown in Table 1.
Ｉｌ１表から明らかなように１本発明の光デイスク基板
は、複屑折が小さく、ミクロボイドやシルバーストリー
クの発生がない、また、酸化防止剤を配合すると、成形
時の分子量低下がなく、長期にわたって着色を生じない
。これに対して、揮発成分の含有量が多い対照例のもの
は、光デイスク基板の外周部にミクロボイドが発生し、
気泡を伴うこともあり、特に大型の光デイスク基板を作
成するときに重大な障害となる。As is clear from Table Il1, the optical disk substrate of the present invention has small double chipping, no micro voids or silver streaks, and when an antioxidant is added, there is no molecular weight reduction during molding, and it can be used for a long time. Does not cause coloring. On the other hand, in the control example with a high content of volatile components, microvoids were generated at the outer periphery of the optical disk substrate.
This may be accompanied by bubbles, which is a serious problem especially when producing large optical disk substrates.
〔実施例７〕
！２表に示す材料を用いて得た光デイ−スフ基板を、ク
リーンルーム内でイソプロピルアルコールで超音波洗浄
を行なった後、フレオン蒸気で乾燥を行なった。その後
、日本真空技術社製ＲＦマグネトロンスパッタリング装
置を用い記録膜として５ｉ３Ｎａ／丁ｂＦｅｃｏｌｓｉ
３Ｎａ ３層膜（ＩＩ厚は各層とも５００オングスト
ローム）を成膜した。[Example 7]! Optical display substrates obtained using the materials shown in Table 2 were ultrasonically cleaned with isopropyl alcohol in a clean room and then dried with Freon vapor. After that, using RF magnetron sputtering equipment manufactured by Japan Vacuum Technology Co., Ltd., 5i3Na/dbFecolsi was used as a recording film.
A three-layer 3Na film (II thickness of each layer was 500 angstroms) was formed.
得られた光ディスクについて、各種物性試験を行ない、
その結果を１Ｎ２表に示す。Various physical property tests were conducted on the obtained optical disc.
The results are shown in Table 1N2.
１１１淀
＜Ｃ／Ｎ比〉
光ディスクのＣ／Ｎ値（ｄＢ）の測定は二 次の条件で
行なった。111 <C/N ratio> The C/N value (dB) of the optical disc was measured under the following conditions.
書き込みレーザーパワー ５．５ ｍＷ再生レーザ
パワー １−０ｍＷディスク回転数
１８０Ｏｒｐｍキャリア周波数 ２ Ｍ
Ｈｚ印加磁界 ３０００ｅ
レーザー波長 ８３０ｎｍ
〈耐久性試験〉
光ディスクを６０℃、８０％ＲＨの恒温高湿槽に投入し
、一定時間後のＣ／Ｎ値、およびソリを測定した。Writing laser power 5.5 mW Reproducing laser power 1-0 mW Disk rotation speed
180Orpm carrier frequency 2M
Hz applied magnetic field: 3000e Laser wavelength: 830 nm <Durability test> An optical disk was placed in a constant temperature and high humidity bath at 60° C. and 80% RH, and the C/N value and warpage after a certain period of time were measured.
くソリの測定〉
日本光学社製反り角自動測定器を使用してソリ（ｍｒａ
ｄ）を測定した。Measurement of warpage〉 Measurement of warp (mra
d) was measured.
〈機械強度〉
機械強度は、１ｍの高さから光ディスクの落下試験を行
ない、割れや欠けの有無を観察した。<Mechanical strength> Mechanical strength was determined by performing a drop test of the optical disc from a height of 1 m and observing the presence or absence of cracks and chips.
くエラー発生状況〉
耐久性試験を行う前に＋ Ｃ／Ｎ比の測定と同条件で
測定した。Error Occurrence Situation> Before carrying out the durability test, measurements were made under the same conditions as those used for measuring the C/N ratio.
ｊＩ２表
〔発明の効果〕
本発明により、光学用材料として優れた性能を有する成
形材料が提供される。特に、本発明の成形材料は、光学
用透明基板を射出成形により成形した場合に、機械的強
度の劣化がなく、ボイドやシルバーストリークなどの発
生がない。また本発明の成形材料から得た透明基板を用
いて耐久性に優れ、かつ記録再生時のノイズの少ない光
記録媒体を製造することができる。Table jI2 [Effects of the Invention] The present invention provides a molding material that has excellent performance as an optical material. In particular, when the molding material of the present invention is molded into an optical transparent substrate by injection molding, there is no deterioration in mechanical strength and no generation of voids or silver streaks. Further, by using a transparent substrate obtained from the molding material of the present invention, it is possible to manufacture an optical recording medium that has excellent durability and has little noise during recording and reproduction.
さらに本発明の方法により、異物含量の少ないポリマー
を効率よく製造することができる。Furthermore, by the method of the present invention, polymers with low foreign matter content can be efficiently produced.
特許出願人 日本ゼオン株式会社Patent applicant: Zeon Corporation
Claims (1)
であって、該水素添加物の高速液体クロマトグラフィに
より測定した数平均分子量（Ｍｎ）が２０，０００〜５
０，０００、重量平均分子量（Ｍｗ）４０，０００〜８
０，０００、分子量分布（Ｍｎ／Ｍｗ）が２．５以下、
該水素添加物中に含まれる揮発成分０．３重量％以下で
あり、かつ０．５μｍ以上の異物量が１×１０＾５／ｇ
以下であることを特徴とする成形用材料。 ２、請求項１記載の成形用材料を成形したディスク基板
。 ３、請求項２記載のディスク基板に金属反射膜を蒸着し
た光学式記録媒体ディスク。 ４、ノルボルネン系開環重合体を溶液中で水素添加触媒
の存在下で水素添加反応する過程（Ａ）、前記過程（Ａ
）の反応液を孔径が０．５μｍ以下のフィルターで濾過
し、水素添加物を濾液として分離する過程（Ｂ）、該濾
液を減圧下に加熱して揮発成分を蒸発させることにより
水素添加物を取得する過程（Ｃ）から成ることを特徴と
するノルボルネン系開環重合体水素添加物の製造方法。[Scope of Claims] 1. A hydrogenated product of a ring-opening polymer of a norbornene monomer, which has a number average molecular weight (Mn) of 20,000 to 5 as measured by high performance liquid chromatography.
0,000, weight average molecular weight (Mw) 40,000-8
0,000, molecular weight distribution (Mn/Mw) is 2.5 or less,
The volatile component contained in the hydrogenated material is 0.3% by weight or less, and the amount of foreign matter of 0.5 μm or more is 1×10^5/g
A molding material characterized by the following: 2. A disk substrate formed from the molding material according to claim 1. 3. An optical recording medium disk comprising a metal reflective film deposited on the disk substrate according to claim 2. 4. Process (A) of hydrogenating a norbornene-based ring-opening polymer in the presence of a hydrogenation catalyst in a solution;
) The reaction solution of step (B) is filtered through a filter with a pore size of 0.5 μm or less to separate the hydrogenated product as a filtrate. A method for producing a hydrogenated norbornene-based ring-opening polymer, comprising the step of obtaining (C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02295438A JP3092937B2 (en) | 1990-11-02 | 1990-11-02 | Norbornene-based ring-opening polymer hydrogenated product, method for producing the same, disk substrate and disk made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02295438A JP3092937B2 (en) | 1990-11-02 | 1990-11-02 | Norbornene-based ring-opening polymer hydrogenated product, method for producing the same, disk substrate and disk made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04170425A true JPH04170425A (en) | 1992-06-18 |
| JP3092937B2 JP3092937B2 (en) | 2000-09-25 |
Family
ID=17820598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02295438A Expired - Fee Related JP3092937B2 (en) | 1990-11-02 | 1990-11-02 | Norbornene-based ring-opening polymer hydrogenated product, method for producing the same, disk substrate and disk made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3092937B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998014499A1 (en) * | 1996-09-30 | 1998-04-09 | Nippon Zeon Co., Ltd. | Norbornene polymer and process for preparing the same |
| US6991863B2 (en) | 2000-09-04 | 2006-01-31 | Zeon Corporation | Magnetic disk substrate and magnetic disk |
| WO2008004573A1 (en) | 2006-07-07 | 2008-01-10 | Jsr Corporation | Cyclic olefin addition copolymer, method for producing the same, and retardation film obtained from the copolymer |
| WO2017164345A1 (en) | 2016-03-25 | 2017-09-28 | 阪本薬品工業株式会社 | Thermoplastic resin composition |
-
1990
- 1990-11-02 JP JP02295438A patent/JP3092937B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998014499A1 (en) * | 1996-09-30 | 1998-04-09 | Nippon Zeon Co., Ltd. | Norbornene polymer and process for preparing the same |
| US6310160B1 (en) | 1996-09-30 | 2001-10-30 | Nippon Zeon Co., Ltd. | Norbornene polymer and process for preparing the same |
| US6991863B2 (en) | 2000-09-04 | 2006-01-31 | Zeon Corporation | Magnetic disk substrate and magnetic disk |
| WO2008004573A1 (en) | 2006-07-07 | 2008-01-10 | Jsr Corporation | Cyclic olefin addition copolymer, method for producing the same, and retardation film obtained from the copolymer |
| US8084563B2 (en) | 2006-07-07 | 2011-12-27 | Jsr Corporation | Cyclic olefin addition copolymer, process for production thereof, and retardation film obtained from the copolymer |
| WO2017164345A1 (en) | 2016-03-25 | 2017-09-28 | 阪本薬品工業株式会社 | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3092937B2 (en) | 2000-09-25 |
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