JPH04142313A - Transparent, three-dimensionally crosslinked resin - Google Patents
Transparent, three-dimensionally crosslinked resinInfo
- Publication number
- JPH04142313A JPH04142313A JP2267165A JP26716590A JPH04142313A JP H04142313 A JPH04142313 A JP H04142313A JP 2267165 A JP2267165 A JP 2267165A JP 26716590 A JP26716590 A JP 26716590A JP H04142313 A JPH04142313 A JP H04142313A
- Authority
- JP
- Japan
- Prior art keywords
- group
- weight
- transparent
- groups
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011347 resin Substances 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 abstract description 3
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 abstract description 2
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000005266 casting Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- SSMDYRHBKZVGNR-UHFFFAOYSA-N 3-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)C1=CC(=O)NC1=O SSMDYRHBKZVGNR-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- -1 maleimide compound Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 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 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- QDEQBRUNBFJJPW-UHFFFAOYSA-N 1-(3-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC(N2C(C=CC2=O)=O)=C1 QDEQBRUNBFJJPW-UHFFFAOYSA-N 0.000 description 1
- YWODHBPFOGXUFX-UHFFFAOYSA-N 1-(3-hydroxyphenyl)pyrrole-2,5-dione Chemical compound OC1=CC=CC(N2C(C=CC2=O)=O)=C1 YWODHBPFOGXUFX-UHFFFAOYSA-N 0.000 description 1
- UNCUTNPWBZKJHD-UHFFFAOYSA-N 1-(3-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC(N2C(C=CC2=O)=O)=C1 UNCUTNPWBZKJHD-UHFFFAOYSA-N 0.000 description 1
- PRZFFHNZHXGTRC-UHFFFAOYSA-N 1-(3-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1 PRZFFHNZHXGTRC-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- XAHCEMQKWSQGLQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(OC)=CC=C1N1C(=O)C=CC1=O XAHCEMQKWSQGLQ-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- XLYBLHPXFJTHBP-UHFFFAOYSA-N 3-(4-nitrophenyl)pyrrole-2,5-dione Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=CC(=O)NC1=O XLYBLHPXFJTHBP-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- LKUOJDGRNKVVFF-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=O)C=CC1=O LKUOJDGRNKVVFF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 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
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 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
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-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
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 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
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Eyeglasses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、耐熱性、透明性および耐溶剤性に優れ、かつ
、複屈折が小さい透明三次元架橋樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a transparent three-dimensional crosslinked resin that has excellent heat resistance, transparency, and solvent resistance, and has low birefringence.
［従来の技術］
一般にプラスチック材料は軽量で、耐衝撃性、加工性お
よび大量生産性に優れることから、近年光学フィルター
、光学レンズおよび光ディスク等の光学素子用材料とし
ての需要が拡大しつつある。[Prior Art] In general, plastic materials are lightweight and have excellent impact resistance, workability, and mass productivity, so demand for them as materials for optical elements such as optical filters, optical lenses, and optical disks has been increasing in recent years.
これらの光学素子用プラスチック材料としては、現在、
ポリメタクリル酸メチル、ポリスチレンおよびポリカー
ボネートなどの透明性樹脂が主に用いられている。Currently, plastic materials for these optical elements include:
Transparent resins such as polymethyl methacrylate, polystyrene and polycarbonate are mainly used.
［発明が解決しようとする課題］
しかるに、ポリメタクリル酸メチルは熱変形温度に代表
される耐熱性が劣る。[Problems to be Solved by the Invention] However, polymethyl methacrylate has poor heat resistance as typified by heat distortion temperature.
ポリスチレンは耐熱性が劣るだけでなく、複屈折が大き
いという欠点がある。Polystyrene has the drawback of not only poor heat resistance but also high birefringence.
また、ポリカーボネートは、耐熱性は優れているものの
、耐溶剤性および弾性率が低いため、板厚０．５１１１
１以下で成形した場合に問題がある。In addition, although polycarbonate has excellent heat resistance, its solvent resistance and elastic modulus are low, so the plate thickness is 0.5111 mm.
There is a problem when molding with less than 1.
また、特開昭５６−１３１６５４号公報および特開昭５
８−１２６１１９号公報においては、マレイミド化合物
を用いたポリマからなる光デイスク基板が示されている
。Also, JP-A No. 56-131654 and JP-A No. 5
No. 8-126119 discloses an optical disk substrate made of a polymer using a maleimide compound.
しかしながら、これらの技術においては、耐溶剤性、耐
薬品性等が劣るといった問題点を有していた。However, these techniques have had problems such as poor solvent resistance and chemical resistance.
本発明は、上記問題を解決しようとするものであり、耐
熱性、透明性および耐溶剤性に優れ、しかも、複屈折が
小さいという特性を有する透明三次元架橋樹脂を提供す
ることを目的とする。The present invention aims to solve the above problems, and aims to provide a transparent three-dimensional crosslinked resin that has excellent heat resistance, transparency, and solvent resistance, and has low birefringence. .
［課題を解決するための手段］
本発明は上記目的を達成するために、下記の構成を有す
る。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.
［一般式（Ｉ）で表される単量体を２０〜９８重量％、
および不飽和基を２個以上有する多官能単量体を２〜８
０重量％含有し、かつ、該一般式（Ｉ）で表される単量
体と、該不飽和基を２個以上有する多官能単量体との合
計重量割合が、３０重量％以上である組成物を共重合し
てなる透明三次元架橋樹脂。[20 to 98% by weight of the monomer represented by general formula (I),
and 2 to 8 polyfunctional monomers having two or more unsaturated groups.
0% by weight, and the total weight ratio of the monomer represented by the general formula (I) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. A transparent three-dimensional crosslinked resin made by copolymerizing a composition.
ＣＲＩ ＝ＣＲ２
Ｏ０
（式中、Ｒは水素および炭素数１〜２０の炭化水素基か
ら選ばれる置換基を表わす。Ｒ１、Ｒ２は水素、メチル
基およびエチル基から選ばれる置換基を表わす。）」
一般式（Ｉ）で表されるマレイミド誘導体化合物につい
て説明する。CRI = CR2 O0 (wherein, R represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R1 and R2 represent a substituent selected from hydrogen, a methyl group, and an ethyl group.) The maleimide derivative compound represented by general formula (I) will be explained.
ＣＲＩ ＝ＣＲ２
Ｏ０
（式中、Ｒは水素および炭素数１〜２０の炭化水素基か
ら選ばれる置換基を表わす。Ｒ１、Ｒ２は水素、メチル
基およびエチル基から選ばれる置換基を表わす。）
Ｒ１とＲ２については、それぞれが同種であっても、異
種であってもよい。CRI = CR2 O0 (wherein, R represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R1 and R2 represent a substituent selected from hydrogen, a methyl group, and an ethyl group.) R1 and R2 may be the same or different.
Ｒが炭化水素基である場合、具体例としては、メチル基
、エチル基、プロピル基、オクチル基、オクタデシル基
などの直鎖状アルキル基、イソプロピル基、５ｅｃ−ブ
チル基、１ｅ「１−ブチル基、イソペンチル基などの分
枝状アルキル基、シクロヘキシル基、メチルシクロヘキ
シル基などの脂環式炭化水素基、フェニル基、メチルフ
ェニル基などのアリール基、ベンジル基、フェネチル基
などのアラルキル基など各種の例を挙げることができる
。When R is a hydrocarbon group, specific examples include linear alkyl groups such as methyl group, ethyl group, propyl group, octyl group, and octadecyl group, isopropyl group, 5ec-butyl group, and 1e"1-butyl group. , branched alkyl groups such as isopentyl groups, alicyclic hydrocarbon groups such as cyclohexyl groups and methylcyclohexyl groups, aryl groups such as phenyl groups and methylphenyl groups, and aralkyl groups such as benzyl groups and phenethyl groups. can be mentioned.
さらに、Ｒ５Ｒ１およびＲ２は、フッ素、塩素、臭素な
どのハロゲノ基、シアノ基、カルボキシル基、スルホン
酸基、ニトロ基、ヒドロキシ基、アルコキシ基などの各
種置換基で置換されたものであってもよい。Furthermore, R5R1 and R2 may be substituted with various substituents such as a halogeno group such as fluorine, chlorine, or bromine, a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxy group, or an alkoxy group. .
一般式（Ｉ）で示される化合物の具体例としては、Ｎ−
メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−フェニ
ルマレイミド、Ｎ−０−メチルフェニルマレイミド、Ｎ
−ｍ−メチルフェニルマレイミド、Ｎ−ｐ−メチルフェ
ニルマレイミド、Ｎ−０−ヒドロキシフェニルマレイミ
ド、Ｎ−ｍ−ヒドロキシフェニルマレイミド、Ｎ−ｐ−
ヒドロキシフェニルマレイミド、Ｎ−メトキシフェニル
マレイミド、Ｎ−ｍ−メトキシフェニルマレイミド、Ｎ
−ｐ−メトキシフェニルマレイミド、Ｎ−ｏ−クロロフ
ェニルマレイミド、Ｎ−ｍ−クロロフェニルマレイミド
、Ｎ−ｐ−クロロフェニルマレイミド、Ｎ−０−カルボ
キシフェニルマレイミド、Ｎ−ｐ−カルボキシフェニル
マレイミド、口ｐ−ニトロフェニルマレイミド、Ｎ−エ
チルマレイミド、Ｎ−シクロへキシルマレイミド、トイ
ソプロビルマレイミドなどが挙げられる。Specific examples of the compound represented by general formula (I) include N-
Methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-0-methylphenylmaleimide, N
-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-0-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-
Hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N
-p-methoxyphenylmaleimide, N-o-chlorophenylmaleimide, N-m-chlorophenylmaleimide, N-p-chlorophenylmaleimide, N-0-carboxyphenylmaleimide, N-p-carboxyphenylmaleimide, p-nitrophenylmaleimide , N-ethylmaleimide, N-cyclohexylmaleimide, toisopropylmaleimide, and the like.
これらの単量体は、１種で、あるいは、２種以上の混合
物として用いてもよい。また、かかるマレイミド化合物
の中でも耐熱性テスト後の黄変、耐候性の点からは、と
くにアルキルマレイミド、シクロアルキルマレイミドが
好ましく、と（にＮ５Ｏ−プロピルマレイミド、Ｎ−シ
クロへキシルマレイミドが好ましい。さらには、キャス
ト重合時のモノマ溶液の調製の容易さ、および前記特性
を満足させ得るという点から、Ｎ−１ｓｏ−プロビルマ
レイミドとＮ−シクロヘキシルマレイミドなどのＮ−ア
ルキルマレイミドとＮ−脂環式アルキルマレイミドの併
用が最も好ましい。併用時のＮ−アルキルマレイミドと
Ｎ−脂環式アルキルマレイミドの比率は、不飽和基を２
個以上有する多官能単量体の種類、量などにより、適宜
、実験的に定められるべきものであるが、通常は併用の
効果を発現させるためには、Ｎ−アルキルマレイミド１
００重量部に対して、Ｎ−脂環式マレイミドを１０重量
部から５００重量部の範囲で使用することが好ましい。These monomers may be used alone or as a mixture of two or more. Among these maleimide compounds, alkylmaleimides and cycloalkylmaleimides are particularly preferred from the viewpoint of yellowing after a heat resistance test and weather resistance, and N5O-propylmaleimide and N-cyclohexylmaleimide are particularly preferred. N-alkylmaleimide such as N-1so-propylmaleimide and N-cyclohexylmaleimide and N-alicyclic alkyl It is most preferable to use maleimide in combination.The ratio of N-alkylmaleimide and N-alicyclic alkylmaleimide when used in combination is such that the unsaturated group is
Although it should be determined experimentally as appropriate depending on the type and amount of the polyfunctional monomer having 1 or more N-alkylmaleimides, it is usually necessary to
It is preferable to use N-alicyclic maleimide in an amount of 10 to 500 parts by weight based on 00 parts by weight.
次いで、不飽和基を２個以上有する多官能単量体につい
て説明する。すなわち、不飽和基を２個以上有する多官
能単量体とは、前記マレイミドと共重合可能な不飽和官
能基を２個以上有するモノマであり、共重合可能な官能
基としては、ビニル基、メチルビニル基、アクリル基、
メタクリル基などが挙げられる。また、−分子中に異な
る共重合可能な官能基が２個以上含まれるモノマも本発
明で言うところの多官能単量体に含まれる。Next, a polyfunctional monomer having two or more unsaturated groups will be explained. That is, the polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide, and the copolymerizable functional groups include vinyl groups, Methylvinyl group, acrylic group,
Examples include methacrylic group. Further, monomers containing two or more different copolymerizable functional groups in the -molecule are also included in the polyfunctional monomers referred to in the present invention.
以上のような不飽和基を２個以上有する多官能単量体の
好ましい具体例としては、エチレングリコールジ（メタ
）アクリレート、ジエチレングリコールジ（メタ）アク
リレート、トリエチレングリコールジ（メタ）アクリレ
ート、グリセロール（ジ／トリ）（メタ）アクリレート
、トリメチロールプロパン（ジ／トリ）（メタ）アクリ
レート、ペンタエリスリトール（ジ／トリ／テトラ）
（メタ）アクリレートなどの多価アルコールのジ−トリ
ー、テトラ−（メタ）アクリレート類、ｐ−ジビニルベ
ンゼン、０−ジビニルベンゼンなどの芳香族多官能モノ
マ、（メタ）アクリル酸ビニルエステル、（メタ）アク
リル酸アリルエステルなどのエステル類、ブタジェン、
ヘキサジエン、ペンタジェンなどのジエン類、ジクロロ
ホスファゼンを原料として重合多官能基を導入したホス
ファゼン骨格を有するモノマ、トリアリルジイソシアヌ
レへトなどの異原子環状骨格を有する多官能モノマなど
が挙げられる。Preferred specific examples of the polyfunctional monomer having two or more unsaturated groups as described above include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and glycerol ( di/tri)(meth)acrylate, trimethylolpropane(di/tri)(meth)acrylate, pentaerythritol(di/tri/tetra)
Di-trily of polyhydric alcohols such as (meth)acrylate, tetra-(meth)acrylates, aromatic polyfunctional monomers such as p-divinylbenzene and 0-divinylbenzene, (meth)acrylic acid vinyl ester, (meth) Esters such as allyl acrylate, butadiene,
Examples include dienes such as hexadiene and pentadiene, monomers having a phosphazene skeleton in which polymerized polyfunctional groups are introduced using dichlorophosphazene as a raw material, and polyfunctional monomers having a heteroatomic cyclic skeleton such as triallyl diisocyanurate.
本発明の透明三次元架橋重合体中には、前述の一般式（
Ｉ）で表わされる単量体が２０〜９８重量％含有されて
いることが必要であるが、２０重量％未満の場合には充
分な耐熱性、機械的強度、低複屈折化などの特性を満足
させることができない。また、９８重量％を越える場合
には、架橋度が低下し、耐溶剤性、低吸水率化などを満
足することかできない。さらに、３０〜８０重量％であ
ることが好ましく、さらに好ましくは４０〜６０重量％
である。The transparent three-dimensional crosslinked polymer of the present invention contains the general formula (
It is necessary that the monomer represented by I) be contained in an amount of 20 to 98% by weight; however, if the content is less than 20% by weight, properties such as sufficient heat resistance, mechanical strength, and low birefringence may not be obtained. I can't satisfy you. Moreover, if it exceeds 98% by weight, the degree of crosslinking decreases, making it impossible to satisfy solvent resistance, low water absorption, etc. Furthermore, it is preferably 30 to 80% by weight, more preferably 40 to 60% by weight.
It is.
一方、もう１つの必須成分である不飽和基を２個以上有
する多官能単量体は、三次元架橋重合体中に２〜８０重
量％の割合で含有されていることが必要であるが、２重
量％未満の場合には三次元架橋が充分に進行せず、耐熱
性、耐溶剤性などの低下が認められる。また、８０重量
％を越えると、耐衝撃性などが低下し、プラスチックと
しての特性低下が著しくなるといった問題が生じてくる
。On the other hand, the polyfunctional monomer having two or more unsaturated groups, which is another essential component, must be contained in the three-dimensional crosslinked polymer in a proportion of 2 to 80% by weight. If the amount is less than 2% by weight, three-dimensional crosslinking will not proceed sufficiently, and a decrease in heat resistance, solvent resistance, etc. will be observed. Furthermore, if the content exceeds 80% by weight, problems such as impact resistance and other properties will decrease, resulting in significant deterioration of the properties of the plastic.
さらに、本発明樹脂中には、機械的強度の向上、低複屈
折化、高屈折率化、低吸水率化、染色性向上、耐熱性向
上、耐衝撃性向上などを目的として、各種の共重合可能
なモノマが好ましく併用される。Furthermore, the resin of the present invention contains various compounds for the purpose of improving mechanical strength, lowering birefringence, increasing refractive index, lowering water absorption, improving dyeability, improving heat resistance, and improving impact resistance. Polymerizable monomers are preferably used in combination.
かかる併用可能なモノマとしては、芳香族ビニル系単量
体、オレフィン系ビニル単量体、（メタ）アクリル酸お
よびそのエステル系単量体、多価カルボン酸無水物など
が挙げられる。かかる芳香族ビニル系単量体の具体例と
しては、スチレン、ａ−メチルスチレン、ｐ−メチルス
チレン、ｐ−１−ブチルスチレン、ビニルトルエン、ク
ロロスチレンおよびブロモスチレンなどが挙げられる。Examples of such monomers that can be used in combination include aromatic vinyl monomers, olefinic vinyl monomers, (meth)acrylic acid and its ester monomers, and polyvalent carboxylic acid anhydrides. Specific examples of such aromatic vinyl monomers include styrene, a-methylstyrene, p-methylstyrene, p-1-butylstyrene, vinyltoluene, chlorostyrene, and bromostyrene.
通常は、性能および工業的に入手し易いなどの点からス
チレン、ａ−メチルスチレンおよびｐ−メチルスチレン
などが用いられる。Usually, styrene, a-methylstyrene, p-methylstyrene, etc. are used from the viewpoint of performance and industrial availability.
その他のビニル系単量体としては、・アクリロニトリル
、メタクリロニトリルなどのシアン化ビニル系単量体、
メタクリル酸メチル、アクリル酸メチル、メタクリル酸
シクロヘキシル、メタクリル酸ｔ−ブチル、メタクリル
酸ベンジル、アクリル酸、メタクリル酸などの（メタ）
アクリル酸（エステル）系単量体、無水マレイン酸など
が好ましい具体例として挙げられる。Other vinyl monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate, benzyl methacrylate, acrylic acid, methacrylic acid, etc. (meth)
Preferred examples include acrylic acid (ester) monomers and maleic anhydride.
さらに、耐光性、耐酸化劣化性、帯電防止性を向上させ
る目的から各種紫外線吸収剤、酸化防止剤、帯電防止剤
を添加することも有用である。とくに耐薬品性や耐熱性
を低下させずに、これらの性能を向上させることが可能
なことから紫外線吸収性、あるいは、酸化防止性を有す
るモノマを共重合することが好ましい。かかるモノマの
好ましい例としては、不飽和二重結合を有するベンゾフ
ェノン系紫外線吸収剤、不飽和二重結合を有するフェニ
ルベンゾエート系紫外線吸収剤、ヒンダードアミノ基を
置換基として有する（メタ）アクリルモノマなどが挙げ
られる。これらの共重合モノマは０． ５〜２０重量％
の範囲で使用されることが好ましい。０．５重量％未満
の場合には添加効果が認められず、また、２０重量％を
越える場合には、耐熱性、機械的強度などが低下する傾
向がある。Furthermore, it is also useful to add various ultraviolet absorbers, antioxidants, and antistatic agents for the purpose of improving light resistance, oxidative deterioration resistance, and antistatic properties. In particular, it is preferable to copolymerize a monomer having ultraviolet absorbing properties or antioxidant properties because these properties can be improved without reducing chemical resistance or heat resistance. Preferred examples of such monomers include benzophenone ultraviolet absorbers having unsaturated double bonds, phenylbenzoate ultraviolet absorbers having unsaturated double bonds, and (meth)acrylic monomers having hindered amino groups as substituents. can be mentioned. These copolymerized monomers are 0. 5-20% by weight
It is preferable to use it within the range of . If it is less than 0.5% by weight, no effect will be observed, and if it exceeds 20% by weight, heat resistance, mechanical strength, etc. tend to decrease.
不飽和二重結合を有するベンゾフェノン系紫外線吸収剤
としては、例えば、下記一般式（ＩＩ）で示される構造
を有するものが挙げられる。Examples of the benzophenone ultraviolet absorber having an unsaturated double bond include those having a structure represented by the following general formula (II).
Ｒ３、Ｒ４、Ｒ５、Ｒ６のうち、少なくとも１基であり
、その他の官能基は水素またはアルキル基、アルケニル
基、アラルキル基、アリール基、アルコキシ基、アラル
コキシ基、アリロキシ基、ヒドロキシ基、ハロゲノ基、
スルホン酸（エステル）基、カルボン酸（エステル）基
、リン酸（エステル）基など特に限定されるものではな
（、同種であっても異種であってもよい。At least one group among R3, R4, R5, R6, and the other functional groups are hydrogen or an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkoxy group, an allyloxy group, a hydroxy group, a halogeno group,
Sulfonic acid (ester) groups, carboxylic acid (ester) groups, phosphoric acid (ester) groups, etc. are not particularly limited (they may be of the same type or different types).
また、不飽和二重結合を有するフェニルベンゾエート系
紫外線吸収剤としては、例えば下記の構造式（ｍ）で示
される化合物が挙げられる。Furthermore, examples of the phenylbenzoate ultraviolet absorber having an unsaturated double bond include a compound represented by the following structural formula (m).
ここでＲ７−Ｒ１２のうち、少なくとも１つは、不飽和
二重結合を有する有機基であり、その他の官能基は、水
素、アルキル基、アルケニル基、アラルキル基、アリー
ル基、アルコキシ基、アラルコキシ基、アリロキシ基、
ヒドロキシ基、ハロゲノ基、スルホン酸（エステル）基
、カルボン酸（エステル）基、リン酸（エステル）基な
ど特に限定されるものではなく、同種であっても、異種
であってもよい。Here, at least one of R7 to R12 is an organic group having an unsaturated double bond, and other functional groups include hydrogen, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, and an aralkoxy group. , allyloxy group,
There are no particular limitations on the hydroxy group, halogeno group, sulfonic acid (ester) group, carboxylic acid (ester) group, phosphoric acid (ester) group, etc., and they may be of the same type or different types.
ヒンダードアミノ基を置換基として有するアクリルモノ
マおよびメタクリルモノマにおいて、ヒンダードアミノ
基としては、例えば下記の構造式（ＩＶ）で示される置
換基が挙げられる。In acrylic monomers and methacrylic monomers having a hindered amino group as a substituent, examples of the hindered amino group include a substituent represented by the following structural formula (IV).
Ｒ”Ｒ１３
（式中Ｒ”、Ｒ”、Ｒ１６およびＲ１７は、炭素数１〜
５の低級アルキル基であり、Ｒ１５は、炭素数１〜５の
低級アルキル基および水素から選ばれる。）かかるヒン
ダードアミノ基を有するアクリルまたはメタクリルモノ
マはヒドロキシヒンダードアミンと各種の（メタ）アク
リル酸とのエステル化あるいは（メタ）アクリル酸クロ
ライドなどとの反応によって調製される。R"R13 (in the formula, R", R", R16 and R17 have 1 to 1 carbon atoms)
5 lower alkyl group, and R15 is selected from a lower alkyl group having 1 to 5 carbon atoms and hydrogen. ) Such acrylic or methacrylic monomers having a hindered amino group are prepared by esterification of hydroxy hindered amine with various (meth)acrylic acids or reaction with (meth)acrylic acid chloride or the like.
かかるヒンダードアミノ基を置換基として有する（メタ
）アクリルモノマの具体例としては、２２６．６−チト
ラメチルー４−ピペリジニルアクリレート、２．２．６
．６−チトラメチルー４−ピペリジニルメタアクリレー
ト、１．２．２．６．６−ベンタメチルー４−ピペリジ
ニル−アクリレート、１．２．２．６．６−ベンタメチ
ルー４−ピペリジニル−メタアクリレートなどのモノマ
が挙げられる。Specific examples of (meth)acrylic monomers having such a hindered amino group as a substituent include 226.6-titramethyl-4-piperidinyl acrylate, 2.2.6
．． Monomers such as 6-titramethyl-4-piperidinyl methacrylate, 1.2.2.6.6-bentamethyl-4-piperidinyl-acrylate, 1.2.2.6.6-bentamethyl-4-piperidinyl-methacrylate are mentioned. It will be done.
本発明樹脂中における必須成分である一般式（Ｉ）で表
されるモノマと、不飽和基を２個以上有する多官能単量
体との合計含有量は、三次元架橋樹脂中、３０重量％以
上であることが必要であり、好ましくは４０重量％以上
である。すなわち、３０重量％未満では、透明性、耐熱
性、耐薬品性、耐衝撃性などに優れたポリマを得ること
かできない。The total content of the monomer represented by general formula (I), which is an essential component in the resin of the present invention, and the polyfunctional monomer having two or more unsaturated groups is 30% by weight in the three-dimensionally crosslinked resin. It needs to be at least 40% by weight, preferably at least 40% by weight. That is, if it is less than 30% by weight, a polymer with excellent transparency, heat resistance, chemical resistance, impact resistance, etc. cannot be obtained.
本発明透明三次元架橋樹脂の重合方法に関しては、特に
制限はなく、通常公知の方法で重合することができる。There are no particular limitations on the method of polymerizing the transparent three-dimensionally crosslinked resin of the present invention, and polymerization can be carried out by commonly known methods.
すなわち、ラジカル発生性開始剤の存在下または非存在
下に上記の単量体混合物を所定の温度条件下に保つこと
によって重合することができる。塊状重合、溶液重合、
懸濁重合および注型重合等各種の方法を用いることがで
きる。That is, polymerization can be carried out by maintaining the above monomer mixture under predetermined temperature conditions in the presence or absence of a radical-generating initiator. bulk polymerization, solution polymerization,
Various methods such as suspension polymerization and cast polymerization can be used.
本発明の透明三次元架橋樹脂の重合度に関しては、特に
制限はないが、重合率は高い方が好ましく、ハードコー
トなどの溶液コーティング、真空蒸着などを考慮すると
９０％以上が好ましい。There is no particular restriction on the degree of polymerization of the transparent three-dimensional crosslinked resin of the present invention, but the higher the polymerization rate, the more preferable it is, and in consideration of solution coating such as hard coating, vacuum deposition, etc., 90% or more is preferable.
本発明の透明三次元架橋樹脂の成形法に関しても特に制
限はないが、効果的な成形法としては、注型重合法が挙
げられる。Although there are no particular limitations on the method of molding the transparent three-dimensional crosslinked resin of the present invention, an effective molding method includes a cast polymerization method.
本発明によって得られる樹脂は、透明性、耐熱性、耐光
性、耐候性、耐衝撃性、グレージング性、耐薬品性など
に優れることから、眼鏡レンズ、サングラスレンズ、カ
メラ用レンズ、ビデオカメラ用レンズ、ゴーグル用レン
ズ、コンタク）・レンズなどの光学レンズ用に、′さら
には、液晶デイスプレィ用基板、液晶デイスプレィの光
拡散板、エレクトロルミネッセンス用基板など各種デイ
スプレィの基板材料に、自動車、航空機などのフロント
、サイド、リヤ、ルーフなどのウィンド用に、また、複
屈折性が優れることから光デイスク基板などにも適用さ
れるものである。The resin obtained by the present invention has excellent transparency, heat resistance, light resistance, weather resistance, impact resistance, glazing property, chemical resistance, etc., so it can be used for eyeglass lenses, sunglass lenses, camera lenses, and video camera lenses. , goggle lenses, contact lens) and other optical lenses, as well as various display substrate materials such as liquid crystal display substrates, liquid crystal display light diffusion plates, electroluminescence substrates, and front panels for automobiles and aircraft. It is also used for side, rear, and roof windows, and because of its excellent birefringence, it is also applied to optical disk substrates.
［実施例］
以下、本発明を実施例をもとにさらに具体的に説明する
。[Examples] Hereinafter, the present invention will be explained in more detail based on Examples.
実施例１
イソプロピルマレイミド ２６．５ｇスチレン
１８．５ｇジビニルベンゼン
５．０ｇアゾビスイソブチロニトリル ０．０
５ｇを混合、溶解させ、キャスト重合により、注型成形
した。キャスト重合は、次のように行った。Example 1 Isopropylmaleimide 26.5g styrene
18.5g divinylbenzene
5.0g Azobisisobutyronitrile 0.0
5 g was mixed, dissolved, and cast-molded by cast polymerization. Cast polymerization was performed as follows.
大きさ１５０＋＋＋ｍＸ １５０ｍｍ、厚さ５ｍｍの２
枚のガラス板の外周辺部を、軟質塩化ビニル製ガスケッ
トで貼り、２枚のガラス板の距離が２ｒｎｍになるよう
に組立てた。この組立てたガラス板の中へ、前記の単量
体混合物を注入し、７０’Ｃで８時間、１００°Ｃで１
時間重合させ、透明な注型板を得た。Size 150+++m x 150mm, thickness 5mm 2
The outer periphery of the two glass plates was pasted with a soft vinyl chloride gasket, and the two glass plates were assembled so that the distance between them was 2 nm. The above monomer mixture was injected into the assembled glass plate, heated at 70'C for 8 hours, and heated at 100°C for 1 hour.
Polymerization was carried out for a period of time to obtain a transparent casting plate.
この注型板の特性（全光線透過率、飽和吸水率、耐溶剤
性、曲げ試験、ガラス転移温度）を測定した。なお、全
光線透過率はＡＳＴＭ Ｄ−６４８に基いて測定した
。飽和吸水率は７０℃温水中にサンプルを１０時間浸漬
した後の重量増加で表わした。耐溶剤性は、アセトンを
含浸させたガーゼで表面をラビングし、その時の光沢変
化を目視により評価した。また、曲げ試験はＪＩＳ
Ｋ−７２０３に基いて測定した。ガラス転移温度は、Ｍ
ｅｔｔｌｅ＋ Ｔ＾３０００を用いて測定した。得られ
た注型板の特性を表１に示した。The properties of this cast plate (total light transmittance, saturated water absorption, solvent resistance, bending test, glass transition temperature) were measured. Note that the total light transmittance was measured based on ASTM D-648. The saturated water absorption rate was expressed as the weight increase after the sample was immersed in 70°C warm water for 10 hours. Solvent resistance was evaluated by rubbing the surface with gauze impregnated with acetone and visually evaluating the change in gloss at that time. In addition, the bending test is JIS
Measured based on K-7203. The glass transition temperature is M
It was measured using ettle+ T^3000. Table 1 shows the properties of the obtained casting plate.
実施例２
実施例１のイソプロピルマレイミドをイソプロピルマレ
イミド５０重量％、シクロへキシルマレイミド５０重量
％からなる混合物２６．５ｇに代えた以外は、実施例１
と同様にして透明な注型板を得た。得られた注型板の特
性を表１に示した。Example 2 Example 1 except that the isopropylmaleimide in Example 1 was replaced with 26.5 g of a mixture consisting of 50% by weight of isopropylmaleimide and 50% by weight of cyclohexylmaleimide.
A transparent casting plate was obtained in the same manner as above. Table 1 shows the properties of the obtained casting plate.
実施例３
実施例１のスチレンをメタアクリル酸メチルに代えた以
外は実施例１と同様にして透明な注型板を得た。得られ
た注型板の性能を表１に示した。Example 3 A transparent casting plate was obtained in the same manner as in Example 1 except that styrene in Example 1 was replaced with methyl methacrylate. Table 1 shows the performance of the obtained casting plate.
実施例４
イソプロピルマレイミド ４５ｇ
ジビニルベンゼン ５ｇ
アゾビスイソブチロニトリル ０．１ｇを混合、溶解
させ、実施例１と同様のキャスト重合により、注型板を
得た。得られた注型板の特性を表１に示した。Example 4 45 g of isopropyl maleimide, 5 g of divinylbenzene, and 0.1 g of azobisisobutyronitrile were mixed and dissolved, and the same cast polymerization as in Example 1 was carried out to obtain a cast plate. Table 1 shows the properties of the obtained casting plate.
比較例１
イソプロピルマレイミド ２６ｇ
スチレン ２４ｇ
アゾビスイソブチロニトリル ０．１ｇを混合、溶解
させ、実施例１と同様のキャスト重合により、透明な注
型板を得た。得られた注型板の特性を表１に示した。Comparative Example 1 26 g of isopropylmaleimide, 24 g of styrene, and 0.1 g of azobisisobutyronitrile were mixed and dissolved, and the same cast polymerization as in Example 1 was performed to obtain a transparent cast plate. Table 1 shows the properties of the obtained casting plate.
比較例２
イソプロピルマレイミド ２５ｇ
スチレン １２．５ｇメタアクリル
酸メチル １２．５ｇアゾビスイソブチロニトリ
ル ０．１ｇを混合、溶解し、実施例１と同様のキャス
ト重合を用いて注型板を作成したが透明板にはならず乳
白色となった。得られた注型板の特性を表１に示した。Comparative Example 2 25g of isopropylmaleimide, 12.5g of styrene, 12.5g of methyl methacrylate, and 0.1g of azobisisobutyronitrile were mixed and dissolved, and a cast plate was prepared using the same cast polymerization as in Example 1. It did not become a transparent plate but became milky white. Table 1 shows the properties of the obtained casting plate.
表１
［発明の効果］
本発明によって得られる透明三次元架橋樹脂は、以下の
効果を有する。Table 1 [Effects of the Invention] The transparent three-dimensional crosslinked resin obtained by the present invention has the following effects.
１、耐熱性に優れる。1. Excellent heat resistance.
２、耐溶剤性、耐薬品性に優れる。2. Excellent solvent and chemical resistance.
３、成型収縮率が小さいため、早期離型などの問題がな
く、外観に優れた成型品が得られる。3. Since the molding shrinkage rate is small, there are no problems such as early release from the mold, and molded products with excellent appearance can be obtained.
Claims (1)
量％、および不飽和基を２個以上有する多官能単量体を
２〜８０重量％含有し、かつ、該一般式（ I ）で表さ
れる単量体と、該不飽和基を２個以上有する多官能単量
体との合計重量割合が、３０重量％以上である組成物を
共重合してなる透明三次元架橋樹脂。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは水素および炭素数１〜２０の炭化水素基か
ら選ばれる置換基を表わす。Ｒ＾１、Ｒ＾２は水素、メ
チル基およびエチル基から選ばれる置換基を表わす。）(1) Contains 20 to 98% by weight of a monomer represented by the general formula (I) and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups, and the general formula A transparent three-dimensional product obtained by copolymerizing a composition in which the total weight ratio of the monomer represented by (I) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. crosslinked resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R^1 and R^2 are hydrogen and a methyl group. and a substituent selected from ethyl group.)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267165A JPH04142313A (en) | 1990-10-03 | 1990-10-03 | Transparent, three-dimensionally crosslinked resin |
| AU86152/91A AU642538B2 (en) | 1990-10-03 | 1991-10-03 | Optical sheet material |
| EP91917324A EP0503097B1 (en) | 1990-10-03 | 1991-10-03 | Optical sheet material |
| PCT/JP1991/001336 WO1992006124A1 (en) | 1990-10-03 | 1991-10-03 | Optical sheet material |
| DE69117925T DE69117925T2 (en) | 1990-10-03 | 1991-10-03 | FILM-SHAPED OPTICAL MATERIAL |
| KR1019920701300A KR927003662A (en) | 1990-10-03 | 1991-10-03 | Optic plate |
| US08/291,353 US5612432A (en) | 1990-10-03 | 1994-08-16 | Sheetlike article for optical use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2267165A JPH04142313A (en) | 1990-10-03 | 1990-10-03 | Transparent, three-dimensionally crosslinked resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04142313A true JPH04142313A (en) | 1992-05-15 |
Family
ID=17441003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2267165A Pending JPH04142313A (en) | 1990-10-03 | 1990-10-03 | Transparent, three-dimensionally crosslinked resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04142313A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06130202A (en) * | 1992-10-15 | 1994-05-13 | Toray Ind Inc | Heat resistant optical resin plate |
| JP2000191640A (en) * | 1998-12-29 | 2000-07-11 | Dainippon Ink & Chem Inc | Bismaleimide containing mesogenic group |
| JP2007052210A (en) * | 2005-08-17 | 2007-03-01 | Nikon-Essilor Co Ltd | Polarizing lens and manufacturing method thereof |
-
1990
- 1990-10-03 JP JP2267165A patent/JPH04142313A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06130202A (en) * | 1992-10-15 | 1994-05-13 | Toray Ind Inc | Heat resistant optical resin plate |
| JP2000191640A (en) * | 1998-12-29 | 2000-07-11 | Dainippon Ink & Chem Inc | Bismaleimide containing mesogenic group |
| JP2007052210A (en) * | 2005-08-17 | 2007-03-01 | Nikon-Essilor Co Ltd | Polarizing lens and manufacturing method thereof |
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