CN1259660C - Optical disk substrate - Google Patents
Optical disk substrate Download PDFInfo
- Publication number
- CN1259660C CN1259660C CNB028111095A CN02811109A CN1259660C CN 1259660 C CN1259660 C CN 1259660C CN B028111095 A CNB028111095 A CN B028111095A CN 02811109 A CN02811109 A CN 02811109A CN 1259660 C CN1259660 C CN 1259660C
- Authority
- CN
- China
- Prior art keywords
- styrene
- acrylate
- rubber
- optical disc
- resin
- 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.)
- Expired - Fee Related
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 115
- 230000003287 optical effect Effects 0.000 title claims abstract description 109
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229920005989 resin Polymers 0.000 claims abstract description 94
- 239000011347 resin Substances 0.000 claims abstract description 94
- 229920001577 copolymer Polymers 0.000 claims abstract description 56
- 239000011342 resin composition Substances 0.000 claims abstract description 53
- 150000003440 styrenes Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 56
- 239000000314 lubricant Substances 0.000 claims description 50
- 229920001971 elastomer Polymers 0.000 claims description 36
- 229920000578 graft copolymer Polymers 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 33
- 239000000806 elastomer Substances 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 claims 3
- 239000000155 melt Substances 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract description 5
- 238000001746 injection moulding Methods 0.000 description 41
- 239000004925 Acrylic resin Substances 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000004816 latex Substances 0.000 description 21
- 229920000126 latex Polymers 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 20
- 239000008188 pellet Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000001506 calcium phosphate Substances 0.000 description 14
- 229910000389 calcium phosphate Inorganic materials 0.000 description 14
- 235000011010 calcium phosphates Nutrition 0.000 description 14
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- 229920001890 Novodur Polymers 0.000 description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 10
- 235000021355 Stearic acid Nutrition 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- -1 Methoxyethyl Chemical group 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229940096992 potassium oleate Drugs 0.000 description 4
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- LWZNQGJGMBRAII-UHFFFAOYSA-N 2-methylhexyl prop-2-enoate Chemical compound CCCCC(C)COC(=O)C=C LWZNQGJGMBRAII-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 206010020880 Hypertrophy Diseases 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- TWBUVVYSQBFVGZ-UHFFFAOYSA-N tert-butyl butanoate Chemical compound CCCC(=O)OC(C)(C)C TWBUVVYSQBFVGZ-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
- G11B7/2536—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polystyrene [PS]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract
本发明提供一种光盘基板，该光盘基板的强度、成形性、脱模性及复制性优良，而且能以较低的制造成本获得。该光盘基板由选自特定的苯乙烯-丙烯腈共聚树脂(A)、苯乙烯-(甲基)丙烯酸酯系共聚物(B)及橡胶改性苯乙烯系树脂组合物(C)的至少1种苯乙烯系树脂(X)构成。The present invention provides an optical disc substrate which is excellent in strength, formability, releasability and reproducibility, and which can be obtained at relatively low manufacturing cost. The disc substrate is made of at least 1 selected from specific styrene-acrylonitrile copolymer resins (A), styrene-(meth)acrylate copolymers (B) and rubber-modified styrene resin compositions (C). A styrene-based resin (X) constitutes.
Description
技术领域technical field
本发明涉及脱模性和成形后的弯曲变形优良的光盘基板。The present invention relates to an optical disc substrate excellent in mold release properties and bending deformation after forming.
背景技术Background technique
随着信息化社会的发展，市场上的信息记录媒体也从以前的磁带、磁盘发展成了集成度更高的光盘。With the development of the information society, the information recording media on the market have also developed from the previous magnetic tapes and magnetic disks to more integrated optical discs.
要广泛应用就必须降低价格，为此实现了材料的低廉化及生产率的提高。It is necessary to reduce the price in order to be widely used, and for this purpose, the material cost has been reduced and the productivity has been improved.
这里所说的光盘是LD(激光视盘)、VCD(视频CD)、音乐CD、CD-ROM、CD-R、DVD-ROM、DVD-RAM、DVD-R等由激光读取通过变化有无凹纹将声音、影像等的数字化信号存储在塑料基板面的信息的存储介质。The optical disc mentioned here is LD (Laser Video Disc), VCD (Video CD), Music CD, CD-ROM, CD-R, DVD-ROM, DVD-RAM, DVD-R, etc., which are read by laser through changing whether there is a concave or not. It is an information storage medium that stores digital signals such as sound and video on the surface of a plastic substrate.
凹纹的形成方式有采用压模的机械方式及利用光的作用使预先存在于盘面的有机色素发生反应的方式，但对没有特别的限定。The method of forming the grooves includes a mechanical method using a stamper and a method of reacting organic pigments pre-existing on the disk surface by using the action of light, but there is no special limitation.
以往，以聚苯乙烯树脂为代表的芳族乙烯系树脂由于其易成形性，被应用于各种领域。在电子学领域，由于其要求高，采取了添加增塑剂及提高芳族乙烯系树脂的分子量等措施。例如，日本专利特开昭59-140207号中所述的添加特定的矿物油，虽然确认了流动性有一定程度的提高，可是仍不充分，存在成形性的问题，而且还会产生导致成形品的机械强度和耐热性降低的问题。在日本专利特开平3-33142号公布了一种苯乙烯树脂组合物，它可以在保持机械强度和耐热性的情况下，提高流动性，但脱模性及复制性不充分。Conventionally, aromatic vinyl resins typified by polystyrene resins have been used in various fields due to their easy formability. In the field of electronics, due to its high requirements, measures such as adding plasticizers and increasing the molecular weight of aromatic vinyl resins have been taken. For example, the addition of a specific mineral oil described in Japanese Patent Application Laid-Open No. 59-140207 confirmed that the fluidity was improved to a certain extent, but it was still not sufficient, and there was a problem of moldability, and it also caused molded products to be damaged. The problem of reduced mechanical strength and heat resistance. Japanese Patent Application Laid-Open No. 3-33142 discloses a styrene resin composition which can improve fluidity while maintaining mechanical strength and heat resistance, but has insufficient mold releasability and reproducibility.
该技术还存在问题，即由于获得这种苯乙烯系树脂组合物需要有较高的制造技术和较高的成本，因此成本会大大增加。此外还研究了将聚苯乙烯作为光盘基板用材料的技术，但存在下述问题，在成形工序中，由于抗冲击强度变小，起模时成形品易断裂，以及由于耐热性差，因此要获得不弯曲的成形品必须延长冷却时间，从而使成形周期变长，导致生产率低下，而且复制性差。This technique also has a problem in that the cost will be greatly increased due to the high manufacturing technique and high cost required to obtain such a styrenic resin composition. In addition, the technology of using polystyrene as a material for optical disk substrates has been studied, but there are following problems. In the molding process, due to the low impact strength, the molded product is easy to break when the mold is ejected, and due to poor heat resistance, it is necessary to To obtain a molded product that does not bend, it is necessary to prolong the cooling time, thereby making the molding cycle longer, resulting in low productivity and poor reproducibility.
发明的揭示disclosure of invention
本发明者为了解决上述问题进行了各种研究，结果获得了新的发现，即由特定的苯乙烯系树脂(X)构成的光盘基板可提高强度、耐热性和复制性，并由此最终完成了本发明。The inventors of the present invention conducted various studies to solve the above-mentioned problems, and as a result, obtained a new finding that the optical disk substrate composed of a specific styrene-based resin (X) can improve the strength, heat resistance, and reproducibility, and thus finally The present invention has been accomplished.
即，本发明具有以下的构成，That is, the present invention has the following configurations,
(1)光盘基板，由苯乙烯系树脂(X)构成，该基板的特征是，该苯乙烯系树脂(X)为选自下述(A)、(B)及(C)的至少1种苯乙烯系树脂：(1) An optical disk substrate comprising a styrene-based resin (X), wherein the substrate is characterized in that the styrene-based resin (X) is at least one selected from the following (A), (B) and (C) Styrenic resins:
(A)苯乙烯-丙烯腈共聚树脂，(A) styrene-acrylonitrile copolymer resin,
(B)苯乙烯-(甲基)丙烯酸酯系共聚物，它是苯乙烯系单体、(甲基)丙烯酸酯系单体及根据需要添加的可与这些单体共聚的乙烯系单体共聚而形成的，(B) Styrene-(meth)acrylate copolymer, which is a copolymer of styrene-based monomers, (meth)acrylate-based monomers, and vinyl monomers that can be copolymerized with these monomers and formed,
(C)橡胶改性苯乙烯系树脂组合物，它的主成分是苯乙烯-(甲基)丙烯酸酯系共聚物和接枝共聚物，苯乙烯-(甲基)丙烯酸酯系共聚物是苯乙烯系单体、(甲基)丙烯酸酯系单体及根据需要添加的可与这些单体共聚的乙烯系单体共聚而形成的，接枝共聚物是在二烯烃系橡胶状弹性体的存在下，由苯乙烯系单体、(甲基)丙烯酸酯系单体及根据需要添加的可与这些单体共聚的乙烯单体共聚而形成的，且该组合物中的可溶于THF(四氢呋喃)的组分的重均分子量(Mw)为50,000～100,000，橡胶量为2～20％，橡胶粒径为0.1～0.5μm。(C) rubber-modified styrenic resin composition, its main component is styrene-(meth)acrylate copolymer and graft copolymer, styrene-(meth)acrylate copolymer is benzene It is formed by the copolymerization of vinyl monomers, (meth)acrylate monomers, and vinyl monomers that can be copolymerized with these monomers. The graft copolymer is formed in the presence of diene-based rubber-like elastomers. It is formed by the copolymerization of styrene monomers, (meth)acrylate monomers and vinyl monomers that can be copolymerized with these monomers, and the THF (tetrahydrofuran) soluble ) has a weight average molecular weight (Mw) of 50,000-100,000, a rubber content of 2-20%, and a rubber particle size of 0.1-0.5 μm.
(2)进一步限定(1)所述的光盘基板，该基板的特征是，苯乙烯系树脂(A)满足在200℃、5kg载荷下的MFR(熔体流动速度)≥1.0g/10分，以及在5kg载荷下的VSP(维卡软化点)≥105℃的条件。(2) Further define the optical disc substrate described in (1), wherein the substrate is characterized in that the styrene-based resin (A) satisfies an MFR (melt flow rate) ≥ 1.0 g/10 minutes at 200° C. under a load of 5 kg, And the condition of VSP (Vicat softening point) ≥ 105°C under a load of 5kg.
(3)进一步限定(1)所述的光盘基板，该基板的特征是，苯乙烯系树脂(B)满足在200℃、5kg载荷下的MFR≥1.0g/10分，以及在5kg载荷下的VSP≥95℃的条件。(3) Further define the optical disc substrate described in (1), wherein the substrate is characterized in that the styrene-based resin (B) satisfies an MFR ≥ 1.0 g/10 minutes at 200°C under a load of 5 kg, and an MFR under a load of 5 kg The condition of VSP≥95℃.
(4)进一步限定(1)所述的光盘基板，该基板的特征是，苯乙烯系树脂(C)满足在200℃、5kg载荷下的MFR≥2.0g/10分，以及在5kg载荷下的VSP≥90℃的条件。(4) Further define the optical disc substrate described in (1), wherein the substrate is characterized in that the styrene-based resin (C) satisfies MFR ≥ 2.0 g/10 minutes at 200°C under a load of 5 kg, and the MFR under a load of 5 kg The condition of VSP≥90℃.
(5)进一步限定(1)或(4)所述的光盘基板，该基板的特征是，苯乙烯系树脂(C)中的苯乙烯-(甲基)丙烯酸酯系共聚物和接枝共聚物的折射率近似。(5) Further define the optical disc substrate described in (1) or (4), which is characterized in that the styrene-(meth)acrylate copolymer and graft copolymer in the styrene resin (C) approximate refractive index.
(6)进一步限定(1)、(4)或(5)所述的光盘基板，该基板的特征是，苯乙烯系树脂(C)中的可共聚的乙烯系单体是丙烯腈。(6) Further, the optical disk substrate described in (1), (4) or (5), wherein the copolymerizable vinyl monomer in the styrene-based resin (C) is acrylonitrile.
(7)进一步限定(1)～(6)中任一项所述的光盘基板，该基板的特征是，在100质量份的选自(A)、(B)及(C)的至少1种苯乙烯系树脂(X)中混合10～200ppm的润滑剂而形成。(7) Further define the optical disc substrate according to any one of (1) to (6), wherein the substrate is characterized in that at least one selected from (A), (B) and (C) is used in 100 parts by mass. It is formed by mixing 10 to 200 ppm of a lubricant into the styrene-based resin (X).
(8)进一步限定(7)所述的光盘基板，该基板的特征是，润滑剂为选自脂肪酸、脂肪酸金属盐及脂肪酰胺的至少1种以上。(8) The optical disc substrate described in (7) is further characterized in that the lubricant is at least one selected from fatty acids, fatty acid metal salts, and fatty acid amides.
(9)进一步限定(1)～(8)中任一项所述的光盘基板，该基板的特征是，光盘基板用于VCD或CD-ROM。(9) Further define the optical disk substrate described in any one of (1) to (8), wherein the optical disk substrate is used for a VCD or a CD-ROM.
实施发明的最佳方式The best way to practice the invention
以下，详细说明本发明。Hereinafter, the present invention will be described in detail.
苯乙烯系树脂(A)Styrene resin (A)
苯乙烯-丙烯腈共聚树脂所用的苯乙烯系单体包括苯乙烯、α-甲基苯乙烯、叔丁基苯乙烯、氯代苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯等芳族乙烯单体及其取代物，其中苯乙烯效果特别好。Styrenic monomers used in styrene-acrylonitrile copolymer resins include styrene, α-methylstyrene, tert-butylstyrene, chlorostyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene Aromatic vinyl monomers such as phenylstyrene and its substitutes, among which styrene is particularly effective.
丙烯腈系单体包括丙烯腈、甲基丙烯腈、α-氯代丙烯腈等氰化乙烯单体，其中丙烯腈效果特别好。Acrylonitrile-based monomers include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, among which acrylonitrile is particularly effective.
苯乙烯-丙烯腈共聚树脂中，能够根据需要使用可与上述单体共聚的乙烯单体，这种乙烯单体包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸缩水甘油酯等，它们即可以单独使用，也可以并用。在本发明中，(甲基)丙烯酸甲酯表示丙烯酸甲酯或甲基丙烯酸甲酯。In the styrene-acrylonitrile copolymer resin, vinyl monomers that can be copolymerized with the above-mentioned monomers can be used as needed, such vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, (meth) Butyl acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate, hydroxyethyl (meth)acrylate, ( Methoxyethyl meth)acrylate, glycidyl (meth)acrylate, and the like may be used alone or in combination. In the present invention, methyl (meth)acrylate means methyl acrylate or methyl methacrylate.
对苯乙烯-丙烯腈共聚树脂的制造方法没有特别的限定，例如可以采用乳化聚合法、悬浮聚合法、本体聚合法、溶液聚合法等聚合方法。The method for producing the styrene-acrylonitrile copolymer resin is not particularly limited, and polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization may be used.
本发明所用的苯乙烯系树脂(A)的特性最好满足在200℃、5kg载荷下的MFR≥1.0g/10分，且在5kg载荷下的VSP≥105℃的条件。The properties of the styrene-based resin (A) used in the present invention preferably satisfy the conditions of MFR≥1.0g/10min at 200°C under a load of 5kg and VSP≥105°C under a load of 5kg.
苯乙烯系树脂(B)Styrenic resin (B)
苯乙烯-(甲基)丙烯酸酯系共聚物中的苯乙烯系单体包括苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、乙基苯乙烯、对叔丁基苯乙烯等，较好的是苯乙烯。这些苯乙烯系单体即可以单独使用，也可以2种以上并用。Styrenic monomers in styrene-(meth)acrylate copolymers include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethyl Styrene, p-tert-butylstyrene, etc., preferably styrene. These styrene-based monomers may be used alone or in combination of two or more.
(甲基)丙烯酸酯系单体包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯等甲基丙烯酸酯，丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-甲基己酯、丙烯酸2-乙基己酯、丙烯酸癸酯等丙烯酸酯，较好的是(甲基)丙烯酸甲酯或丙烯酸正丁酯，效果特别好的是(甲基)丙烯酸甲酯。这些(甲基)丙烯酸酯系单体既可以单独使用，也可以2种以上并用。(Meth)acrylate-based monomers include methacrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate , methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate and other acrylates, preferably (meth)methyl acrylate or acrylic acid Of the n-butyl esters, methyl (meth)acrylate works particularly well. These (meth)acrylate-based monomers may be used alone or in combination of two or more.
还有，根据需要使用的可与这些单体共聚的乙烯系单体包括丙烯酸、甲基丙烯酸、丙烯腈、甲基丙烯腈、N-苯基马来酰亚胺、N-环己基马来酰亚胺等。Also, vinyl monomers that can be copolymerized with these monomers include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, N-phenylmaleimide, N-cyclohexylmaleimide, and imine etc.
对苯乙烯-(甲基)丙烯酸酯系共聚物的制造方法没有特别的限定，例如可以采用乳化聚合法、悬浮聚合法、本体聚合法、溶液聚合法等聚合方法。The method for producing the styrene-(meth)acrylate copolymer is not particularly limited, and polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization may be used.
本发明所用的苯乙烯系树脂(B)的特性最好满足在200℃、5kg载荷下的MFR≥1.0g/10分，以及在5kg载荷下的VSP≥95℃的条件。The properties of the styrene-based resin (B) used in the present invention preferably satisfy the conditions of MFR≥1.0g/10min at 200°C under a 5kg load and VSP≥95°C under a 5kg load.
苯乙烯系树脂(C)Styrene resin (C)
橡胶改性苯乙烯系树脂组合物的主成分之一的苯乙烯-(甲基)丙烯酸酯系共聚物是苯乙烯系单体、(甲基)丙烯酸酯系单体及根据需要添加的可与这些单体共聚的乙烯系单体共聚而形成的共聚物。The styrene-(meth)acrylate copolymer, one of the main components of the rubber-modified styrenic resin composition, is a styrene-based monomer, a (meth)acrylate monomer, and optionally added A copolymer formed by copolymerizing vinyl monomers of these monomers.
本发明的橡胶改性苯乙烯系树脂组合物的主成分之一的接枝共聚物是在二烯烃系橡胶状弹性体的存在下，由苯乙烯系单体、(甲基)丙烯酸酯系单体及根据需要添加的可与这些单体共聚的乙烯系单体共聚而形成的接枝共聚物。The graft copolymer, which is one of the main components of the rubber-modified styrenic resin composition of the present invention, is prepared from styrene-based monomers, (meth)acrylate-based monomers in the presence of diene-based rubber-like elastomers. Graft copolymers formed by copolymerization of vinyl monomers and vinyl monomers that can be copolymerized with these monomers.
本发明所用的苯乙烯系单体包括苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、乙基苯乙烯、对叔丁基苯乙烯等，较好的是苯乙烯。这些苯乙烯系单体即可以单独使用，也可以2种以上并用。Styrenic monomers used in the present invention include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, p-tert-butylstyrene, etc. , preferably styrene. These styrene-based monomers may be used alone or in combination of two or more.
本发明所用的(甲基)丙烯酸酯系单体包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己基酯等甲基丙烯酸酯，丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-甲基己酯、丙烯酸2-乙基己酯、丙烯酸癸酯等丙烯酸酯，效果较好的是(甲基)丙烯酸甲酯或丙烯酸正丁酯，效果特别好的是(甲基)丙烯酸甲酯。这些(甲基)丙烯酸酯系单体既可以单独使用，也可以2种以上并用。The (meth)acrylate monomers used in the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. Methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate and other acrylates, the better effect is (meth) Methyl acrylate or n-butyl acrylate, methyl (meth)acrylate works particularly well. These (meth)acrylate-based monomers may be used alone or in combination of two or more.
还有，根据需要使用的可与这些单体共聚的乙烯系单体包括丙烯酸、甲基丙烯酸、丙烯腈、甲基丙烯腈、N-苯基马来酰亚胺、N-环己基马来酰亚胺等。Also, vinyl monomers that can be copolymerized with these monomers include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, N-phenylmaleimide, N-cyclohexylmaleimide, and imine etc.
本发明所用的二烯烃系橡胶状弹性体包括聚丁二烯、苯乙烯-丁二烯嵌段共聚物及苯乙烯-丁二烯无规共聚物等。The diene-based rubber-like elastomer used in the present invention includes polybutadiene, styrene-butadiene block copolymers, styrene-butadiene random copolymers, and the like.
还有，本发明的橡胶改性苯乙烯系树脂组合物中的苯乙烯-(甲基)丙烯酸酯系共聚物和接枝共聚物的折射率接近，其差较好是在0.05以下，特别好的是在0.002以下，这样有利于获得良好的透明度。Also, the refractive index of the styrene-(meth)acrylate copolymer and the graft copolymer in the rubber-modified styrene resin composition of the present invention are close to each other, and the difference is preferably at most 0.05, particularly preferably It is below 0.002, which is conducive to obtaining good transparency.
再有，对构成苯乙烯-(甲基)丙烯酸酯系共聚物的各单体的比例没有特别的限定，比较好的是苯乙烯系单体单元20～70质量％，(甲基)丙烯酸酯系单体单元30～80质量％，根据需要使用的可与这些单体共聚的乙烯系单体单元0～10质量％。单体比在上述范围内，且与接枝共聚物的折射率之差接近则更佳。In addition, there is no particular limitation on the ratio of each monomer constituting the styrene-(meth)acrylate copolymer, but preferably 20 to 70% by mass of the styrene monomer unit, and the (meth)acrylate 30 to 80% by mass of vinyl monomer units, and 0 to 10% by mass of vinyl monomer units copolymerizable with these monomers as needed. It is more preferable that the monomer ratio is within the above range and close to the difference in refractive index of the graft copolymer.
还有，对构成接枝共聚物的二烯烃橡胶状弹性体及苯乙烯-(甲基)丙烯酸酯系共聚物的各单体的量没有特别的限定，但最理想的是，接枝共聚物由苯乙烯-(甲基)丙烯酸酯系共聚物20～70质量份与二烯烃橡胶状弹性体30～80质量份接枝形成，上述苯乙烯-(甲基)丙烯酸酯系共聚物由苯乙烯系单体单元20～70质量％、(甲基)丙烯酸酯系单体单元30～80质量及根据需要使用的可与这些单体共聚的乙烯系单体单元0～10质量％构成，单体比在上述范围内，且进行接枝的苯乙烯-(甲基)丙烯酸酯系共聚物和橡胶状弹性体的折射率之差接近则更佳。In addition, the amount of each monomer of the diene rubber-like elastomer and the styrene-(meth)acrylate copolymer constituting the graft copolymer is not particularly limited, but the graft copolymer is most preferably It is formed by grafting 20 to 70 parts by mass of styrene-(meth)acrylate copolymer and 30 to 80 parts by mass of diene rubber-like elastomer. The above-mentioned styrene-(meth)acrylate copolymer is composed of styrene 20-70% by mass of monomeric units, 30-80% by mass of (meth)acrylate-based monomeric units, and 0-10% by mass of vinylic monomeric units copolymerizable with these monomers as needed. It is more preferable that the ratio is within the above range and that the difference in refractive index between the grafted styrene-(meth)acrylate copolymer and the rubber-like elastomer is close.
本发明的橡胶改性苯乙烯系树脂组合物的制造可以采用本体聚合法、溶液聚合法、悬浮聚合法及本体-悬浮聚合法、乳化聚合法等公知的技术。还可以采用间歇式聚合法或连续式聚合法。The rubber-modified styrene-based resin composition of the present invention can be produced by known techniques such as bulk polymerization, solution polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. A batch polymerization method or a continuous polymerization method may also be employed.
效果比较好的是，含接枝共聚物的树脂采用乳化聚合法制造，苯乙烯-(甲基)丙烯酸酯系树脂采用本体聚合法、溶液聚合法、悬浮聚合法及本体-悬浮聚合法中的任一种聚合法制造，将该含接枝共聚物的树脂和该苯乙烯-(甲基)丙烯酸酯系树脂熔融混合制得橡胶改性苯乙烯系树脂组合物，这样得到的树脂组合物的耐冲击性及透明度特别优良。The better effect is that the resin containing graft copolymer is manufactured by emulsion polymerization, and the styrene-(meth)acrylate resin is produced by bulk polymerization, solution polymerization, suspension polymerization and bulk-suspension polymerization. Manufactured by any polymerization method, the resin containing the graft copolymer and the styrene-(meth)acrylate resin are melt-mixed to obtain a rubber-modified styrene-based resin composition, and the resin composition obtained in this way Especially excellent in impact resistance and transparency.
本发明所说的可溶于THF(四氢呋喃)的组分除包括作为主要成分的苯乙烯-(甲基)丙烯酸酯系共聚物外，还包含所有其他的可溶于THF的成分。不溶于THF的组分除包含作为主要成分的接枝共聚物外，还包含所有其他的不溶于THF的成分。The THF (tetrahydrofuran) soluble component mentioned in the present invention includes all other THF soluble components except the styrene-(meth)acrylate copolymer as the main component. The THF-insoluble component comprises, in addition to the graft copolymer as the main component, all other THF-insoluble components.
本发明所用的橡胶改性苯乙烯系树脂组合物中的可溶于THF(四氢呋喃)的组分的重均分子量(Mw)最好为50,000～100,000。如果小于50,000，则抗冲击强度差，如果超过100,000，则成形周期长。这里所说的重均分子量是采用凝胶渗透色谱(GPC)法测定了橡胶改性苯乙烯系树脂组合物中的可溶于THF的组分并经聚苯乙烯换算得到的重均分子量。The weight-average molecular weight (Mw) of the THF (tetrahydrofuran)-soluble component in the rubber-modified styrenic resin composition used in the present invention is preferably 50,000 to 100,000. If it is less than 50,000, the impact strength is poor, and if it exceeds 100,000, the forming cycle is long. The weight-average molecular weight referred to here is a weight-average molecular weight obtained by measuring the THF-soluble component in the rubber-modified styrene-based resin composition by gel permeation chromatography (GPC) in terms of polystyrene.
还有，橡胶改性苯乙烯系树脂组合物的橡胶量最好是2～20％。如果小于2％则抗冲击强度差，如果超过20％则成形周期长，复制性也变差。而且，该橡胶改性苯乙烯系树脂组合物的橡胶粒径最好为0.1～0.5μm。如果小于0.1μm则抗冲击强度差，超过0.5μm则复制性差。In addition, the rubber content of the rubber-modified styrene resin composition is preferably 2 to 20%. If it is less than 2%, the impact strength will be poor, and if it exceeds 20%, the molding cycle will be long and the reproducibility will also be poor. Furthermore, the rubber particle size of the rubber-modified styrene-based resin composition is preferably 0.1 to 0.5 μm. If it is less than 0.1 μm, the impact strength will be poor, and if it exceeds 0.5 μm, the reproducibility will be poor.
本发明所使用的苯乙烯系树脂(C)的特性最好满足在200℃、5kg载荷下的MFR≥2.0g/10分，以及在5kg载荷下的VSP≥90℃的条件。The properties of the styrene-based resin (C) used in the present invention preferably satisfy the conditions of MFR≥2.0g/10min at 200°C under a load of 5kg and VSP≥90°C under a load of 5kg.
在不损害本发明的橡胶改性苯乙烯系树脂组合物的性能的前提下，可以在本发明的橡胶改性苯乙烯系树脂组合物中混合公知的耐候剂、润滑剂、增塑剂、着色剂、防带电剂、矿物油等添加剂。Under the premise of not impairing the performance of the rubber-modified styrene-based resin composition of the present invention, known weather-resistant agents, lubricants, plasticizers, coloring agents, etc. can be mixed in the rubber-modified styrene-based resin composition of the present invention agent, antistatic agent, mineral oil and other additives.
对本发明的橡胶改性苯乙烯系树脂组合物的混合·熔融挤压的方法没有特别的限定，可以采用公知的方法。例如，预先将各种原料用转鼓混合器及搅拌器等混合均匀，送入单轴挤压机或双轴挤压机熔融混炼后制成颗粒的方法。The method of mixing and melt-extruding the rubber-modified styrene-based resin composition of the present invention is not particularly limited, and known methods can be employed. For example, a method in which various raw materials are uniformly mixed in advance with a drum mixer and agitator, and then fed into a single-screw extruder or a twin-screw extruder for melting and kneading to form pellets.
这样得到的本发明的热塑性树脂组合物可以采用注射成形、压缩成形或者挤压成形等方法加工成各种成形体，以供实用。The thus-obtained thermoplastic resin composition of the present invention can be processed into various molded articles by injection molding, compression molding, or extrusion molding for practical use.
在本发明所用的苯乙烯系树脂(X)中最好混合润滑剂。润滑剂的混合量对应于100质量份的苯乙烯系树脂(X)，最好为10～200ppm。如果小于10ppm，则脱模时易断裂，如果超过200ppm，则透明度降低，效果不佳。这里，苯乙烯系树脂(X)为选自苯乙烯系树脂(A)、苯乙烯系树脂(B)或苯乙烯系树脂(C)的1种。A lubricant is preferably mixed with the styrene-based resin (X) used in the present invention. The compounding quantity of a lubricant corresponds to 100 mass parts of styrene-type resin (X), Preferably it is 10-200 ppm. If it is less than 10ppm, it will be easy to break when demoulding, and if it exceeds 200ppm, the transparency will decrease and the effect will be poor. Here, the styrene-based resin (X) is one selected from the styrene-based resin (A), the styrene-based resin (B) or the styrene-based resin (C).
本发明所用的润滑剂的种类有脂肪酸、脂肪酸金属盐及脂肪酰胺等。脂肪酸有硬脂酸、山萮酸、芥酸等。脂肪酰胺有亚乙基双硬酯酰胺等。脂肪酸金属盐有硬脂酸锌(St-Zn)、硬脂酸镁(St-Mg)、硬脂酸钙(St-Zn)等，效果特别好的是硬脂酸锌。The types of lubricants used in the present invention include fatty acids, fatty acid metal salts, and fatty acid amides. Fatty acids include stearic acid, behenic acid, and erucic acid. Fatty amides include ethylene bis stearamide and the like. Fatty acid metal salts include zinc stearate (St-Zn), magnesium stearate (St-Mg), calcium stearate (St-Zn), etc. Zinc stearate is particularly effective.
以下，通过实施例对本发明的具体内容作进一步地说明，但本发明并不限于以下的实施例。还有，在实施例中所用的[份]及[％]都是以质量为基准表示的。Hereinafter, the specific content of the present invention will be further described through examples, but the present invention is not limited to the following examples. In addition, [part] and [%] used in an Example are shown on the basis of mass.
评价方法Evaluation method
1)MFR.按照JIS K-6874，在200℃、5kg载荷的条件下进行测定。1) MFR. Measured in accordance with JIS K-6874 under the conditions of 200°C and 5kg load.
2)VSP：按照JIS K-7206，在5kg载荷的条件下进行测定。2) VSP: Measured under a load of 5 kg according to JIS K-7206.
3)刚性：在成形工序中，作为脱模时成形品不会断裂所需的刚性的尺度的弯曲强度为100MPa以上(参照ASTM D790)。3) Rigidity: In the molding process, the bending strength, which is a measure of the rigidity required for the molded product not to break when demoulding, is 100 MPa or more (see ASTM D790).
4)成形性：成形周期在6秒以下的为生产性优良的材料。4) Moldability: A material with a molding cycle of 6 seconds or less is excellent in productivity.
5)脱模性：因起模不良使成形品产生裂纹前的注射次数，注射100次以上的为脱模性优良的材料。5) Mold release property: The number of injections before the molded product cracks due to poor mold ejection. If the injection is more than 100 times, it is a material with excellent mold release property.
6)复制性：采用凹槽160nm用模子成形时的凹槽深度在100nm以上的为复制性优良的材料。6) Reproducibility: A material with excellent reproducibility has a groove depth of more than 100nm when molded with a groove of 160nm.
7)落锤强度：落锤试验采用保安帽试验时所用的钢制锤(JIS M7608)进行测定。7) Drop weight strength: The drop weight test is measured using a steel hammer (JIS M7608) used in the helmet test.
苯乙烯系树脂(A)的实施例Examples of Styrenic Resin (A)
实施例1Example 1
在装有搅拌机的反应釜中加入苯乙烯70份、丙烯腈30份、磷酸钙2.5份、叔十二烷硫醇0.5份、过氧化苯甲酰0.2份及水250份，升温至100℃开始进行聚合。聚合开始7小时后将温度升至120℃，保持3小时完成聚合。聚合率达到了97％。用盐酸中和得到的反应液，脱水干燥后，得到白色珠状共聚物。将它定为共聚物AS①。Add 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of calcium phosphate, 0.5 parts of tert-dodecyl mercaptan, 0.2 parts of benzoyl peroxide and 250 parts of water into the reaction kettle equipped with a stirrer, and heat up to 100 ° C to start to aggregate. Seven hours after the start of the polymerization, the temperature was raised to 120° C. and kept for 3 hours to complete the polymerization. The polymerization rate reached 97%. The obtained reaction solution was neutralized with hydrochloric acid, dehydrated and dried to obtain a white bead-shaped copolymer. It will be designated as the copolymer AS ①.
在此共聚物中添加混合在作为润滑剂的St-Zn 50ppm，用螺杆直径40mm的单轴挤压机在料筒温度220℃、螺杆转数100rpm的条件下形成颗粒后，用注射成形机(名机社制MDM-I)在成形温度250℃、金属模温度60℃的条件下注射成形，由此得到了直径180mm、中心孔15mm、厚1.2mm的光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。Add and mix St-Zn 50ppm as a lubricant in this copolymer, use a uniaxial extruder with a screw diameter of 40mm to form particles under the conditions of a barrel temperature of 220°C and a screw speed of 100rpm, and then use an injection molding machine ( MDM-I manufactured by Meiki Co., Ltd.) was injection molded at a molding temperature of 250° C. and a mold temperature of 60° C. to obtain an optical disk substrate with a diameter of 180 mm, a center hole of 15 mm, and a thickness of 1.2 mm. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例2Example 2
在装有搅拌机的反应釜中加入苯乙烯70份、丙烯腈30份、磷酸钙2.5份、叔十二烷硫醇0.2份、过氧化苯甲酰0.2份及水250份，升温至100℃开始进行聚合。聚合开始7小时后将温度升至120℃，保持3小时完成聚合。聚合率达到了97％。用盐酸中和得到的反应液，脱水干燥后，得到了白色珠状共聚物。将它定为共聚物AS②。Add 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of calcium phosphate, 0.2 parts of tert-dodecyl mercaptan, 0.2 parts of benzoyl peroxide and 250 parts of water into the reaction kettle equipped with a stirrer, and heat up to 100°C to start to aggregate. Seven hours after the start of the polymerization, the temperature was raised to 120° C. and kept for 3 hours to complete the polymerization. The polymerization rate reached 97%. The obtained reaction liquid was neutralized with hydrochloric acid, and dehydrated and dried to obtain a white bead-shaped copolymer. It will be designated as the copolymer AS②.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50 ppm of St-Zn was added and mixed as a lubricant to this copolymer, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例3Example 3
在装有搅拌机的反应釜中加入苯乙烯80份、丙烯腈20份、磷酸钙2.5份、叔十二烷硫醇0.5份、过氧化苯甲酰0.2份及水250份，升温至100℃开始进行聚合。聚合开始7小时后将温度升至120℃，保持3小时完成聚合。聚合率达到了97％。用盐酸中和得到的反应液，脱水干燥后，得到了白色珠状共聚物。将它定为共聚物AS③。Add 80 parts of styrene, 20 parts of acrylonitrile, 2.5 parts of calcium phosphate, 0.5 parts of tert-dodecyl mercaptan, 0.2 parts of benzoyl peroxide and 250 parts of water into the reaction kettle equipped with a stirrer, and heat up to 100 ° C to start to aggregate. Seven hours after the start of the polymerization, the temperature was raised to 120° C. and kept for 3 hours to complete the polymerization. The polymerization rate reached 97%. The obtained reaction liquid was neutralized with hydrochloric acid, and dehydrated and dried to obtain a white bead-shaped copolymer. It is designated as the copolymer AS③.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50 ppm of St-Zn was added and mixed as a lubricant to this copolymer, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例4Example 4
在实施例1得到的共聚物AS①中不添加润滑剂，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。The copolymer AS① obtained in Example 1 was injection-molded with pellets in the same manner as in Example 1 without adding a lubricant, and an optical disc substrate was obtained. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例5Example 5
在实施例1得到的共聚物AS①中添加混合作为润滑剂的St-Zn250ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。250 ppm of St-Zn as a lubricant was added and mixed to the copolymer AS① obtained in Example 1, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例6Example 6
在实施例1得到的共聚物AS①中添加混合作为润滑剂的EBP50ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50 ppm of EBP was added and mixed as a lubricant to the copolymer AS① obtained in Example 1, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例7Example 7
在实施例1得到的共聚物AS①中添加混合作为润滑剂的St-Mg50ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50 ppm of St-Mg as a lubricant was added and mixed to the copolymer AS① obtained in Example 1, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disk substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例8Example 8
在实施例1得到的共聚物AS①中添加混合作为润滑剂的St-Ca50ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50 ppm of St-Ca was added and mixed as a lubricant to the copolymer AS① obtained in Example 1, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
实施例9Example 9
在实施例1得到的共聚物AS①中添加混合硬脂酸150ppm，和实施例1相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。150 ppm of stearic acid was mixed with the copolymer AS① obtained in Example 1, and injection molding was performed with pellets in the same manner as in Example 1 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
比较例1Comparative example 1
在装有搅拌机的反应釜中加入苯乙烯100份、磷酸钙2.5份、叔十二烷硫醇0.5份、过氧化苯甲酰0.2份及水250份，升温至100℃开始进行聚合。聚合开始7小时后将温度升至120℃，保持3小时完成聚合。聚合率达到了97％。用盐酸中和得到的反应液，脱水干燥后，得到了白色珠状共聚物。将它定为共聚物PS①。Add 100 parts of styrene, 2.5 parts of calcium phosphate, 0.5 parts of tert-dodecyl mercaptan, 0.2 parts of benzoyl peroxide and 250 parts of water into a reactor equipped with a stirrer, and heat up to 100°C to start polymerization. Seven hours after the start of the polymerization, the temperature was raised to 120° C. and kept for 3 hours to complete the polymerization. The polymerization rate reached 97%. The obtained reaction liquid was neutralized with hydrochloric acid, and dehydrated and dried to obtain a white bead-shaped copolymer. It is designated as copolymer PS①.
在此共聚物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表1。50ppm of St-Zn was added as a lubricant to this copolymer, and an optical disc substrate was obtained by injection molding. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 1.
表1
注：复制性的评价为凹槽深度≥100nm：○，凹槽深度＜100nm：×Note: The evaluation of reproducibility is groove depth ≥ 100nm: ○, groove depth < 100nm: ×
由表1可知，实验No.1～9的光盘基板具有优良的刚性、成形性、脱模性及复制性等特性，但实验No.10的光盘基板的特性差。It can be seen from Table 1 that the optical disc substrates of Experiment Nos. 1 to 9 have excellent properties such as rigidity, formability, releasability and reproducibility, but the optical disc substrate of Experiment No. 10 has poor properties.
苯乙烯系树脂(B)的实施例Examples of Styrenic Resin (B)
实施例10Example 10
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯40kg，甲基丙烯酸甲酯60kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇200g，在转数150rpm的搅拌下使混合液分散。在温度100℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状共聚物。将它定为共聚物MS①。100kg of pure water, 0.5g of sodium dodecylbenzenesulfonate, 250g of calcium phosphate, 40kg of styrene, and 60kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 200 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 100°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After the reaction was finished, it was washed, dehydrated and dried to obtain a bead-shaped copolymer. It is designated as copolymer MS①.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，用螺杆直径40mm的单轴挤压机在料筒温度220℃、螺杆转数100rpm的条件下形成颗粒。接着，用注射成形机(名机社制MDM-I)在成形温度240℃、金属模温度60℃的条件下注射成形，由此得到了直径180mm、中心孔15mm、厚1.2mm的光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。St-Zn 50ppm was added and mixed as a lubricant to this copolymer, and pellets were formed under the conditions of a barrel temperature of 220°C and a screw rotation speed of 100rpm using a single-screw extruder with a screw diameter of 40mm. Next, an optical disk substrate with a diameter of 180 mm, a center hole of 15 mm, and a thickness of 1.2 mm was obtained by injection molding with an injection molding machine (MDM-I manufactured by Meiki Co., Ltd.) at a molding temperature of 240° C. and a mold temperature of 60° C. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例11Example 11
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯40kg，甲基丙烯酸甲酯60kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇100g，在转数150rpm的搅拌下使混合液分散。在温度100℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状共聚物。将它定为共聚物MS②。100kg of pure water, 0.5g of sodium dodecylbenzenesulfonate, 250g of calcium phosphate, 40kg of styrene, and 60kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 100 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 100°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After the reaction was finished, it was washed, dehydrated and dried to obtain a bead-shaped copolymer. It is designated as copolymer MS②.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。50 ppm of St-Zn was added and mixed as a lubricant to this copolymer, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例12Example 12
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯60kg，甲基丙烯酸甲酯40kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇200g，在转数150rpm的搅拌下使混合液分散。在温度100℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状共聚物。将它定为共聚物MS③。100kg of pure water, 0.5g of sodium dodecylbenzenesulfonate, 250g of calcium phosphate, 60kg of styrene, and 40kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 200 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 100°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After the reaction was finished, it was washed, dehydrated and dried to obtain a bead-shaped copolymer. It is designated as copolymer MS③.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。50 ppm of St-Zn was added and mixed as a lubricant to this copolymer, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例13Example 13
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯25kg，甲基丙烯酸甲酯70kg及丙烯腈5kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇200g，在转数150rpm的搅拌下使混合液分散。在温度100℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状共聚物。将它定为共聚物MS④。100kg of pure water, 0.5g of sodium dodecylbenzenesulfonate, 250g of calcium phosphate, 25kg of styrene, 70kg of methyl methacrylate and 5kg of acrylonitrile were added to an autoclave with a capacity of 250 liters. 100 g of tert-butyl perisobutyrate and 200 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 100°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After the reaction was finished, it was washed, dehydrated and dried to obtain a bead-shaped copolymer. It is designated as copolymer MS④.
在此共聚物中添加混合作为润滑剂的St-Zn 50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。50 ppm of St-Zn was added and mixed as a lubricant to this copolymer, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例14Example 14
在实施例10得到的共聚物MS①中不添加润滑剂，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。The copolymer MS① obtained in Example 10 was injection-molded with pellets in the same manner as in Example 10 without adding a lubricant, and an optical disk substrate was obtained. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例15Example 15
在实施例10得到的共聚物MS①中添加混合作为润滑剂St-Zn250ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。The copolymer MS① obtained in Example 10 was added and mixed as a lubricant St-Zn 250 ppm, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例16Example 16
在实施例10得到的共聚物MS①中添加混合作为润滑剂St-Mg50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。50 ppm of a lubricant St-Mg was added and mixed to the copolymer MS① obtained in Example 10, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例17Example 17
在实施例10得到的共聚物MS①中添加混合作为润滑剂St-Ca50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。To the copolymer MS① obtained in Example 10, 50 ppm of St-Ca was added and mixed as a lubricant, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例18Example 18
在实施例10得到的共聚物MS①中添加混合作为润滑剂EBP50ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。50 ppm of lubricant EBP was added and mixed to the copolymer MS① obtained in Example 10, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
实施例19Example 19
在实施例10得到的共聚物MS①中添加混合作为润滑剂的硬脂酸150ppm，和实施例10相同，用颗粒进行注射成形，得到了光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表2。150 ppm of stearic acid as a lubricant was added and mixed to the copolymer MS① obtained in Example 10, and injection molding was performed with pellets in the same manner as in Example 10 to obtain an optical disc substrate. Next, the characteristics of the obtained optical disc substrates were evaluated, and the results are shown in Table 2.
表2
注：复制性的评价为凹槽深度≥100nm：○，凹槽深度＜100nm：×Note: The evaluation of reproducibility is groove depth ≥ 100nm: ○, groove depth < 100nm: ×
由表2可知，实验No.11～20的光盘基板具有优良的刚性、成形性、脱模性及复制性等特性，但实验No.10的光盘基板的特性差。It can be seen from Table 2 that the optical disc substrates of Experiment Nos. 11 to 20 have excellent properties such as rigidity, formability, mold release and reproducibility, but the optical disc substrate of Experiment No. 10 has poor properties.
苯乙烯系树脂(C)的实施例Examples of Styrenic Resin (C)
(1)苯乙烯-(甲基)丙烯酸酯系树脂的制造(1) Manufacture of styrene-(meth)acrylate resin
参考例1：苯乙烯-(甲基)丙烯酸酯系树脂(A-1)Reference Example 1: Styrene-(meth)acrylate resin (A-1)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯24kg，甲基丙烯酸甲酯76kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇800g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-1)。100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of calcium phosphate, 24 kg of styrene, and 76 kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 800 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-1).
参考例2：苯乙烯-(甲基)丙烯酸酯系树脂(A-2)Reference Example 2: Styrene-(meth)acrylate resin (A-2)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯24kg，甲基丙烯酸甲酯76kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇600g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-2)。100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of calcium phosphate, 24 kg of styrene, and 76 kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 600 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-2).
参考例3：苯乙烯-(甲基)丙烯酸酯系树脂(A-3)Reference Example 3: Styrene-(meth)acrylate resin (A-3)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯24kg，甲基丙烯酸甲酯76kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇700g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-3)。100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of calcium phosphate, 24 kg of styrene, and 76 kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 700 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-3).
参考例4：苯乙烯-(甲基)丙烯酸酯系树脂(A-4)Reference Example 4: Styrene-(meth)acrylate resin (A-4)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯24可g，甲基丙烯酸甲酯76kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇950g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-4)。100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of calcium phosphate, 24 g of styrene, and 76 kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters. 100 g of tert-butyl butyrate and 950 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-4).
参考例5：苯乙烯-(甲基)丙烯酸酯系树脂(A-5)Reference Example 5: Styrene-(meth)acrylate resin (A-5)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯24kg，甲基丙烯酸甲酯76kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇450g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-5)。100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of calcium phosphate, 24 kg of styrene, and 76 kg of methyl methacrylate were added to an autoclave with a capacity of 250 liters, and perisobutyric acid was added as a polymerization initiator. 100 g of tert-butyl ester and 450 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-5).
参考例6：苯乙烯-(甲基)丙烯酸酯系树脂(A-6)Reference Example 6: Styrene-(meth)acrylate resin (A-6)
在容量250升的高压釜中加入纯水100kg，十二烷基苯磺酸钠0.5g，磷酸钙250g，苯乙烯23kg，甲基丙烯酸甲酯73kg，丙烯腈4kg，再添加作为聚合引发剂的过异丁酸叔丁酯100g和叔十二烷硫醇700g，在转数150rpm的搅拌下使混合液分散。在温度90℃加热聚合此混合液8小时，在温度130℃加热聚合此混合液2.5小时。反应结束后，洗涤、脱水并干燥，得到了珠状苯乙烯-(甲基)丙烯酸酯系树脂(A-6)。100kg of pure water, 0.5g of sodium dodecylbenzenesulfonate, 250g of calcium phosphate, 23kg of styrene, 73kg of methyl methacrylate, and 4kg of acrylonitrile were added to an autoclave with a capacity of 250 liters, and then added as a polymerization initiator 100 g of tert-butyl perisobutyrate and 700 g of tert-dodecyl mercaptan were dispersed under stirring at a rotation speed of 150 rpm. The mixed solution was heated and polymerized at a temperature of 90°C for 8 hours, and the mixed solution was heated and polymerized at a temperature of 130°C for 2.5 hours. After completion of the reaction, it was washed, dehydrated, and dried to obtain a bead-shaped styrene-(meth)acrylate resin (A-6).
(2)橡胶状弹性体胶乳的制造(2) Manufacture of rubber-like elastomer latex
参考例7：橡胶状弹性体胶乳(G-1)Reference Example 7: Rubber-like elastomer latex (G-1)
在容积200升的高压釜中加纯水60kg，油酸钾400g，玫瑰酸钾1200g，碳酸钠1.2kg，过硫酸钾400g，在搅拌下均匀溶解。接着，加入丁二烯80kg，叔十二烷硫醇400g，边搅拌边在60℃聚合30小时，然后升温至70℃，放置20小时完成聚合，得到了平均粒径0.3μm的橡胶状弹性体胶乳(G-1)。Add 60kg of pure water, 400g of potassium oleate, 1200g of potassium roseate, 1.2kg of sodium carbonate, and 400g of potassium persulfate into an autoclave with a volume of 200 liters, and dissolve evenly under stirring. Next, add 80kg of butadiene and 400g of tert-dodecyl mercaptan, polymerize at 60°C for 30 hours while stirring, then raise the temperature to 70°C, and leave it for 20 hours to complete the polymerization, and a rubber-like elastomer with an average particle size of 0.3 μm is obtained. Latex (G-1).
参考例8：橡胶状弹性体胶乳(G-2)Reference Example 8: Rubber-like elastomer latex (G-2)
在容积200升的高压釜中加纯水115kg，油酸钾500g，焦磷酸钠75g，硫酸亚铁1.5g，乙二胺四乙酸钠2.2g及雕自粉22g，在搅拌下均匀溶解。接着，加入丁二烯50kg，叔十二烷硫醇148g，二乙烯基苯30g及过氧化氢二异丙苯96g，边搅拌边在50℃进行反应16小时，完成聚合，得到了橡胶状胶乳。在得到的橡胶状聚合物胶乳中添加磺基琥珀酸钠45g，待充分稳定后，从不同的注料嘴添加0.2％盐酸水溶液和2％苛性钠水溶液，将胶乳的pH值保持在8～9，使胶乳凝集肥大，得到了平均粒径0.4μm的橡胶状弹性体胶乳(G-2)。Add 115kg of pure water, 500g of potassium oleate, 75g of sodium pyrophosphate, 1.5g of ferrous sulfate, 2.2g of sodium ethylenediaminetetraacetate and 22g of diaozi powder into an autoclave with a volume of 200 liters, and dissolve them evenly under stirring. Then, 50 kg of butadiene, 148 g of tert-dodecyl mercaptan, 30 g of divinylbenzene and 96 g of dicumyl hydroperoxide were added, and the reaction was carried out at 50° C. for 16 hours while stirring, and the polymerization was completed to obtain a rubbery latex. . Add 45g of sodium sulfosuccinate to the obtained rubbery polymer latex, and after it is fully stabilized, add 0.2% hydrochloric acid aqueous solution and 2% caustic soda aqueous solution from different injection nozzles to keep the pH value of the latex at 8-9 , the latex was agglomerated and enlarged to obtain a rubber-like elastomer latex (G-2) with an average particle diameter of 0.4 μm.
参考例9：橡胶状弹性体胶乳(G-3)Reference Example 9: Rubber-like elastomer latex (G-3)
改变参考例8的凝集肥大的条件，除平均粒径为0.6μm之外，其他操作都和制造橡胶状弹性体胶乳(G-2)相同，制得了橡胶状弹性体胶乳(G-3)。The conditions for agglomeration and hypertrophy in Reference Example 8 were changed, except that the average particle size was 0.6 μm, and other operations were the same as those for the production of the rubbery elastomer latex (G-2), to obtain the rubbery elastomer latex (G-3).
参考例10：橡胶状弹性体胶乳(G-4)Reference Example 10: Rubbery Elastomer Latex (G-4)
在容积200升的高压釜中加纯水85kg，油酸钾1200g，氢氧化钾200g及过硫酸钾50g，在搅拌下均匀溶解。接着，加入丁二烯50kg和叔十二烷硫醇100g，边搅拌边在50℃进行反应16小时，完成聚合，得到了平均粒径0.08μm的橡胶状弹性体胶乳(G-4)。Add 85kg of pure water, 1200g of potassium oleate, 200g of potassium hydroxide and 50g of potassium persulfate into an autoclave with a volume of 200 liters, and dissolve evenly under stirring. Next, 50 kg of butadiene and 100 g of t-dodecyl mercaptan were added and reacted at 50° C. for 16 hours while stirring to complete the polymerization, thereby obtaining a rubbery elastomer latex (G-4) with an average particle diameter of 0.08 μm.
含接枝共聚物的树脂的制造Manufacture of resins containing graft copolymers
参考例11：含接枝共聚物的树脂(B-1)Reference Example 11: Graft Copolymer-Containing Resin (B-1)
以固体成分换算称量参考例7的橡胶弹性体胶乳(G-1)30kg，将其装入容积200升的高压釜中，再加纯水80kg，边搅拌边在氮气流下升温至50℃。然后，在其中加入硫酸亚铁1.25g，乙二胺四乙酸钠2.5g及溶有雕白粉100g的纯水2kg，分别用6小时的时间连续添加由苯乙烯7.2Kg、甲基丙烯酸甲酯22.8Kg及叔十二烷硫醇60g组成的混合物，以及将过氧化氢二异丙苯120g分散于含油酸钾450g的纯水8kg中而形成的溶液。添加完毕后，升温至70℃，再添加过氧化氢二异丙苯30g，放置2小时完成聚合。Weighed 30 kg of the rubber elastomer latex (G-1) of Reference Example 7 in terms of solid content, put it into an autoclave with a volume of 200 liters, added 80 kg of pure water, and raised the temperature to 50° C. under nitrogen flow while stirring. Then, 1.25g of ferrous sulfate, 2.5g of sodium ethylenediaminetetraacetate and 2kg of pure water dissolved with 100g of Glyph white powder were added therein, and 7.2Kg of styrene and 22.8 kg of methyl methacrylate were continuously added in a period of 6 hours respectively. Kg and 60 g of tert-dodecanemercaptan, and a solution formed by dispersing 120 g of dicumyl hydroperoxide in 8 kg of pure water containing 450 g of potassium oleate. After the addition was completed, the temperature was raised to 70° C., and 30 g of dicumyl hydroperoxide was added, and left to stand for 2 hours to complete the polymerization.
在得到的乳化液中加入抗氧剂，用纯水将固体成分稀释到15％后升温至60℃，边快速搅拌边加入稀硫酸及硫酸镁进行盐析，然后，升温至90℃使其凝固，接着脱水、水洗并干燥，得到粉末状的含接枝共聚物的树脂(B-1)。Add an antioxidant to the obtained emulsion, dilute the solid content to 15% with pure water, then raise the temperature to 60°C, add dilute sulfuric acid and magnesium sulfate while stirring rapidly to carry out salting out, and then raise the temperature to 90°C to solidify , followed by dehydration, water washing and drying to obtain a powdery graft copolymer-containing resin (B-1).
参考例12：含接枝共聚物的树脂(B-2)Reference Example 12: Graft Copolymer-Containing Resin (B-2)
除将参考例11中的橡胶状弹性体胶乳换成参考例8的橡胶状弹性体胶乳(G-2)之外，其他操作和制造含接枝共聚物的树脂(B-1)相同，制得了粉末状的含接枝共聚物的树脂(B-2)。Except that the rubber-like elastomer latex in Reference Example 11 was replaced with the rubber-like elastomer latex (G-2) of Reference Example 8, other operations were the same as in the manufacture of the graft copolymer-containing resin (B-1). A powdery graft copolymer-containing resin (B-2) was obtained.
参考例13：含接枝共聚物的树脂(B-3)Reference Example 13: Graft Copolymer-Containing Resin (B-3)
除将参考例11中的橡胶状弹性体胶乳换成参考例9的橡胶状弹性体胶乳(G-3)之外，其他操作和制造含接枝共聚物的树脂(B-1)相同，制得了粉末状的含接枝共聚物的树脂(B-3)。Except that the rubber-like elastomer latex in Reference Example 11 was replaced with the rubber-like elastomer latex (G-3) of Reference Example 9, other operations were the same as in the manufacture of the graft copolymer-containing resin (B-1). A powdery graft copolymer-containing resin (B-3) was obtained.
参考例14：含接枝共聚物的树脂(B-4)Reference Example 14: Graft Copolymer-Containing Resin (B-4)
除将参考例11中的橡胶状弹性体胶乳换成参考例10的橡胶状弹性体胶乳(G-4)之外，其他操作和制造含接枝共聚物的树脂(B-1)相同，制得了粉末状的含接枝共聚物的树脂(B-4)。Except that the rubber-like elastomer latex in Reference Example 11 was replaced with the rubber-like elastomer latex (G-4) of Reference Example 10, other operations were the same as in the manufacture of the graft copolymer-containing resin (B-1). A powdery graft copolymer-containing resin (B-4) was obtained.
实施例20Example 20
在参考例1制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-1)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(1)。20 parts of the graft copolymer-containing resin (B-1) produced in Reference Example 11 was mixed with 80 parts of styrene-(meth)acrylate resin (A-1) produced in Reference Example 1 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (1).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，用名机社制注射成形机MDM-I在成形温度250℃的条件下进行注射成形，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。50 ppm of St-Zn as a lubricant was added to this rubber-modified resin composition, and injection molding was performed at a molding temperature of 250°C using an injection molding machine MDM-I manufactured by Meiki Co., Ltd., to obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例21Example 21
在参考例1制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-2)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(2)。20 parts of the resin (B-1) containing the graft copolymer produced in Reference Example 11 was mixed with 80 parts of the styrene-(meth)acrylate resin (A-2) produced in Reference Example 1 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (2).
在此橡胶改性树脂组合物(2)中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。To this rubber-modified resin composition (2), 50 ppm of St-Zn was added as a lubricant, and an optical disc substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例22Example 22
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)92份中混合参考例11制造的含接枝共聚物的树脂(B-1)8份，得到了树脂组合物。将它定为橡胶改性树脂组合物(3)。8 parts of the graft copolymer-containing resin (B-1) produced in Reference Example 11 were mixed with 92 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (3).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例23Example 23
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)64份中混合参考例11制造的含接枝共聚物的树脂(B-1)36份，得到了树脂组合物。将它定为橡胶改性树脂组合物(4)。36 parts of the graft copolymer-containing resin (B-1) produced in Reference Example 11 were mixed with 64 parts of the styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (4).
在此橡胶改性树脂组合物(4)中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。To this rubber-modified resin composition (4), 50 ppm of St-Zn was added as a lubricant, and an optical disk substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例24Example 24
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)80份中混合参考例12制造的含接枝共聚物的树脂(B-2)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(5)。20 parts of the graft copolymer-containing resin (B-2) produced in Reference Example 12 was mixed with 80 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (5).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例25Example 25
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(6)。20 parts of the graft copolymer-containing resin (B-1) produced in Reference Example 11 was mixed with 80 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (6).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例26Example 26
在参考例6制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-6)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(7)。20 parts of the resin (B-1) containing the graft copolymer produced in Reference Example 11 was mixed with 80 parts of styrene-(meth)acrylate resin (A-6) produced in Reference Example 6 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (7).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例27Example 27
在实施例25得到的橡胶改性树脂组合物(6)中添加作为润滑剂的硬酯酸250ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。250 ppm of stearic acid was added as a lubricant to the rubber-modified resin composition (6) obtained in Example 25, and an optical disc substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例28Example 28
在实施例25得到的橡胶改性树脂组合物(6)中添加作为润滑剂的EBP 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。EBP 50 ppm was added as a lubricant to the rubber-modified resin composition (6) obtained in Example 25, and an optical disk substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例29Example 29
在实施例25得到的橡胶改性树脂组合物(6)中添加作为润滑剂的硬酯酸50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表3。50 ppm of stearic acid was added as a lubricant to the rubber-modified resin composition (6) obtained in Example 25, and an optical disc substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 3.
实施例30Example 30
在实施例25得到的橡胶改性树脂组合物(6)中添加作为润滑剂的St-Mg 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性讦价，其结果见表4。50 ppm of St-Mg as a lubricant was added to the rubber-modified resin composition (6) obtained in Example 25, and an optical disc substrate was obtained by injection molding. Next, evaluation of the characteristics of the obtained optical disk substrates was carried out, and the results are shown in Table 4.
实施例31Example 31
在实施例25得到的橡胶改性树脂组合物(6)中添加作为润滑剂的St-Ca 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。To the rubber-modified resin composition (6) obtained in Example 25, 50 ppm of St-Ca was added as a lubricant, and an optical disc substrate was obtained by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
实施例32Example 32
在实施例25得到的橡胶改性树脂组合物(6)中不添加润滑剂，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。An optical disc substrate was obtained by injection molding without adding a lubricant to the rubber-modified resin composition (6) obtained in Example 25. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例2Comparative example 2
在参考例4制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-4)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(8)。20 parts of the resin (B-1) containing the graft copolymer produced in Reference Example 11 was mixed with 80 parts of styrene-(meth)acrylate resin (A-4) produced in Reference Example 4 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (8).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例3Comparative example 3
在参考例5制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-5)80份中混合参考例11制造的含接枝共聚物的树脂(B-1)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(9)。20 parts of the resin (B-1) containing the graft copolymer produced in Reference Example 11 was mixed with 80 parts of the styrene-(meth)acrylate resin (A-5) produced in Reference Example 5 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (9).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例4Comparative example 4
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)98份中混合参考例11制造的含接枝共聚物的树脂(B-1)2份，得到了树脂组合物。将它定为橡胶改性树脂组合物(10)。2 parts of the resin (B-1) containing the graft copolymer produced in Reference Example 11 were mixed with 98 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (10).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例5Comparative Example 5
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)56份中混合参考例11制造的含接枝共聚物的树脂(B-1)44份，得到了树脂组合物。将它定为橡胶改性树脂组合物(11)。44 parts of the graft copolymer-containing resin (B-1) produced in Reference Example 11 were mixed with 56 parts of the styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. things. This was designated as a rubber-modified resin composition (11).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例6Comparative example 6
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)80份中混合参考例13制造的含接枝共聚物的树脂(B-3)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(12)。20 parts of the graft copolymer-containing resin (B-3) produced in Reference Example 13 was mixed with 80 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (12).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
比较例7Comparative Example 7
在参考例3制造的苯乙烯-(甲基)丙烯酸酯系树脂(A-3)80份中混合参考例14制造的含接枝共聚物的树脂(B-4)20份，得到了树脂组合物。将它定为橡胶改性树脂组合物(13)。20 parts of the graft copolymer-containing resin (B-4) produced in Reference Example 14 was mixed with 80 parts of styrene-(meth)acrylate resin (A-3) produced in Reference Example 3 to obtain a resin combination. thing. This was designated as a rubber-modified resin composition (13).
在此橡胶改性树脂组合物中添加作为润滑剂的St-Zn 50ppm，通过注射成形得到光盘基板。接着，对得到的光盘基板进行特性评价，其结果见表4。Add 50 ppm of St-Zn as a lubricant to this rubber-modified resin composition, and obtain an optical disc substrate by injection molding. Next, the characteristics of the obtained optical disk substrates were evaluated, and the results are shown in Table 4.
表3
注：复制性的评价为凹槽深度≥100nm：○，凹槽深度＜100nm：×Note: The evaluation of reproducibility is groove depth ≥ 100nm: ○, groove depth < 100nm: ×
表4
注：复制性的评价为凹槽深度≥100nm：○，凹槽深度＜100nm：×Note: The evaluation of reproducibility is groove depth ≥ 100nm: ○, groove depth < 100nm: ×
由表3、表4可知，实验No.21～33的光盘基板具有优良的强度、成形性、脱模性及复制性等特性。实验No.34～40的光盘基板的特性不佳。It can be seen from Table 3 and Table 4 that the optical disc substrates of Experiment Nos. 21 to 33 have excellent characteristics such as strength, formability, mold release property and reproducibility. The characteristics of the optical disc substrates of Experiment Nos. 34 to 40 were not good.
产业上利用的可能性Possibility of industrial use
本发明的光盘基板的强度、成形性、脱模性及复制性优良，而且能以较低的制造成本获得，在工业上极有应用价值。The optical disc substrate of the present invention is excellent in strength, formability, mold release and replicability, and can be obtained at relatively low manufacturing cost, so it has great application value in industry.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP167859/2001 | 2001-06-04 | ||
| JP2001167859 | 2001-06-04 | ||
| JP2001247151 | 2001-08-16 | ||
| JP247151/2001 | 2001-08-16 |
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|---|---|
| CN1513177A CN1513177A (en) | 2004-07-14 |
| CN1259660C true CN1259660C (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028111095A Expired - Fee Related CN1259660C (en) | 2001-06-04 | 2002-05-31 | Optical disk substrate |
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| Country | Link |
|---|---|
| JP (1) | JP4162591B2 (en) |
| KR (1) | KR20040020913A (en) |
| CN (1) | CN1259660C (en) |
| WO (1) | WO2002099799A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100854388B1 (en) * | 2006-12-29 | 2008-08-26 | 제일모직주식회사 | Compact disc using methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin |
| WO2010082613A1 (en) * | 2009-01-16 | 2010-07-22 | 電気化学工業株式会社 | Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same |
| TW202222961A (en) * | 2020-09-25 | 2022-06-16 | 日商電化股份有限公司 | resin composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5888843A (en) * | 1981-11-19 | 1983-05-27 | Asahi Chem Ind Co Ltd | Optical high density information recording medium resin and optical high density information recording medium |
| JPS61163950A (en) * | 1985-01-16 | 1986-07-24 | Dainippon Ink & Chem Inc | thermoplastic resin composition |
| JPS61246210A (en) * | 1985-04-25 | 1986-11-01 | Toray Ind Inc | Optical disk base |
| JPS63162707A (en) * | 1986-12-26 | 1988-07-06 | Mitsubishi Rayon Co Ltd | Optical material |
| JPH0826105B2 (en) * | 1989-11-22 | 1996-03-13 | 株式会社日本触媒 | Optical material having low specific gravity and excellent impact resistance, optical molded article using the optical material, and methods for producing the same |
| JPH05117330A (en) * | 1991-10-28 | 1993-05-14 | Sanyo Chem Ind Ltd | Styrene-acrylic resin and its production |
| JPH05179089A (en) * | 1991-12-26 | 1993-07-20 | Dainippon Ink & Chem Inc | Aromatic vinyl resin composition and method for producing hollow molded article thereof |
| JP3672945B2 (en) * | 1994-05-23 | 2005-07-20 | 奇美実業股▲分▼有限公司 | Styrenic resin composition |
| JP3730694B2 (en) * | 1995-11-24 | 2006-01-05 | 旭化成ケミカルズ株式会社 | Dripping flame retardant styrene resin composition |
| JP4416190B2 (en) * | 1996-06-28 | 2010-02-17 | Ｄｉｃ株式会社 | Rubber-modified copolymer resin composition and process for producing the same |
-
2002
- 2002-05-31 KR KR10-2003-7015792A patent/KR20040020913A/en not_active Application Discontinuation
- 2002-05-31 WO PCT/JP2002/005344 patent/WO2002099799A1/en active Application Filing
- 2002-05-31 CN CNB028111095A patent/CN1259660C/en not_active Expired - Fee Related
- 2002-05-31 JP JP2003502828A patent/JP4162591B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1513177A (en) | 2004-07-14 |
| JPWO2002099799A1 (en) | 2004-09-24 |
| JP4162591B2 (en) | 2008-10-08 |
| WO2002099799A1 (en) | 2002-12-12 |
| KR20040020913A (en) | 2004-03-09 |
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