JP2733078B2 - ink ribbon - Google Patents
ink ribbonInfo
- Publication number
- JP2733078B2 JP2733078B2 JP63316169A JP31616988A JP2733078B2 JP 2733078 B2 JP2733078 B2 JP 2733078B2 JP 63316169 A JP63316169 A JP 63316169A JP 31616988 A JP31616988 A JP 31616988A JP 2733078 B2 JP2733078 B2 JP 2733078B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- styrene
- heat
- film
- acrylate
- 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 - Lifetime
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 description 54
- 230000001050 lubricating effect Effects 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 16
- 239000005060 rubber Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 239000012778 molding material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- WAOPGHCXGUXHKF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 WAOPGHCXGUXHKF-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- FTIQNMPDOJXJJN-UHFFFAOYSA-N 2-(3-dodecylsulfanylbutyl)-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCSC(C)CCC1=CC(C)=CC(C)=C1O FTIQNMPDOJXJJN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- JOWXNCPELQZFHF-UHFFFAOYSA-N 2-[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoyloxy]ethyl 3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoate Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(CC(=O)OCCOC(=O)CC(C)(C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 JOWXNCPELQZFHF-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65814—Cyclic phosphazenes [P=N-]n, n>=3 n = 3 or 4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J31/00—Ink ribbons; Renovating or testing ink ribbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
- G11B5/7023—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent containing polyesters, polyethers, silicones, polyvinyl resins, polyacrylresins or epoxy resins
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
- G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
- G11B5/702—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the bonding agent
- G11B5/7026—Radiation curable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use 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; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はインクリボンに関し、詳しくはワードプロセ
ッサのプリンターなどに使用されるインクリボンに関す
る。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink ribbon, and more particularly, to an ink ribbon used for a printer of a word processor or the like.
情報,通信量の増加に伴い、職場や家庭における小型
ワードプロセッサの普及には目覚ましいものがある。ワ
ードプロセッサのプリンターに使用されるインクリボン
は、ベースフィルム上にインク層を設けてなるものであ
る。従来、このベースフィルムの基材としてはポリエチ
レンテレフタレート(PET),ポリブチレンテレフタレ
ートなどのポリエステル系樹脂、ナイロン6,ナイロン6
6,ナイロン610,ナイロン12などのポリアミド樹脂、ポリ
イミド樹脂、ポリアミドイミド及び紙類が用いられてお
り、これらのうち、特に、PETフィルムが最適であると
されている。しかし、昇華型インクリボン等の出現によ
り、より耐熱性の優れたベースフィルムが求められてい
る。With the increase in information and communication volume, the spread of small word processors in workplaces and homes has been remarkable. An ink ribbon used in a printer of a word processor has an ink layer provided on a base film. Conventionally, as the base material of this base film, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate, nylon 6, nylon 6
6, polyamide resins such as nylon 610 and nylon 12, polyimide resins, polyamide imides and papers are used, and among these, a PET film is considered to be particularly suitable. However, with the advent of sublimation type ink ribbons and the like, a base film having more excellent heat resistance has been demanded.
そこで本発明者らは、現在使用されているインクリボ
ンの基材に比べて、耐熱性に優れるとともに強靱な性状
を有する基材を開発すべく、鋭意研究を重ねた。Therefore, the present inventors have intensively studied to develop a base material having excellent heat resistance and tough properties as compared with a base material of an ink ribbon currently used.
その結果、主としてシンジオタクチック構造を有する
スチレン系重合体を延伸処理して得たフィルムが、上記
の課題を解決できるものであることを見出した。本発明
は、かかる知見に基いて完成したものである。As a result, they have found that a film obtained by stretching a styrene-based polymer having a syndiotactic structure can solve the above-mentioned problems. The present invention has been completed based on such findings.
すなわち、本発明はベースフィルムとして、主として
シンジオタクチック構造を有するスチレン系重合体を延
伸処理してなるフィルムを使用したことを特徴とするイ
ンクリボンを提供するものである。That is, the present invention provides an ink ribbon using, as a base film, a film obtained by subjecting a styrene-based polymer having a syndiotactic structure to stretching treatment.
本発明において、ベースフィルムとして用いるスチレ
ン系重合体は、主としてシンジオタクチック構造を有す
るものであるが、ここで主としてシンジオタクチック構
造とは、立体化学構造が主としてシンジオタクチック構
造、即ち炭素−炭素結合から形成される主鎖に対して側
鎖であるフェニル基や置換フェニル基が交互に反対方向
に位置する立体構造を有するものであり、そのタクティ
シティーは同位体炭素による核磁気共鳴法(13C−NMR
法)により定量される。13C−NMR法により測定されるタ
クティシティーは、連続する複数個の構成単位の存在割
合、例えば2個の場合はダイアッド,3個の場合はトリア
ッド,5個の場合はペンタッドによって示すことができる
が、本発明に言う主としてシンジオタクチック構造を有
するスチレン系重合体とは、通常はダイアッドで75%以
上、好ましくは85%以上、若しくはペンタッド(ラセミ
ペンタッド)で30%以上、好ましくは50%以上のシンジ
オタクティシティーを有するポリスチレン,ポリ(アル
キルスチレン),ポリ(ハロゲン化スチレン),ポリ
(アルコキシスチレン),ポリ(ビニル安息香酸エステ
ル)およびこれらの混合物、あるいはこれらを主成分と
する共重合体を指称する。シンジオタクティシティーの
低いスチレン系重合体では、延伸処理しても充分な延伸
効果が期待できない。なお、ここでポリ(アルキルスチ
レン)としては、ポリ(メチルスチレン),ポリ(エチ
ルスチレン),ポリ(イソプロピルスチレン),ポリ
(ターシャリーブチルスチレン)などがあり、ポリ(ハ
ロゲン化スチレン)としては、ポリ(クロロスチレ
ン),ポリ(ブロモスチレン),ポリ(フルオロスチレ
ン)などがある。また、ポリ(アルコキシスチレン)と
しては、ポリ(メトキシスチレン),ポリ(エトキシス
チレン)などがある。これらのうち特に好ましいスチレ
ン系重合体としては、ポリスチレン,ポリ(p−メチル
スチレン),ポリ(m−メチルスチレン),ポリ(p−
ターシャリーブチルスチレン),ポリ(p−クロロスチ
レン),ポリ(m−クロロスチレン),ポリ(p−フル
オロスチレン)、更にはスチレンとp−メチルスチレン
との共重合体をあげることができる。In the present invention, the styrene-based polymer used as the base film mainly has a syndiotactic structure. Here, the term "syndiotactic structure" means that the stereochemical structure is mainly a syndiotactic structure, that is, carbon-carbon. It has a steric structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in the opposite direction to the main chain formed from bonds, and its tacticity is determined by nuclear magnetic resonance using isotope carbon ( 13). C-NMR
Method). Tacticity measured by the 13 C-NMR method can be represented by the abundance ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five. However, the styrenic polymer having a predominantly syndiotactic structure as referred to in the present invention is usually 75% or more, preferably 85% or more in a dyad, or 30% or more, preferably 50% in a pentad (racemic pentad). Polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinyl benzoate) having the above syndiotacticity and mixtures thereof, or copolymers containing these as main components Refers to coalescence. A styrene-based polymer having low syndiotacticity cannot be expected to have a sufficient stretching effect even if it is stretched. The poly (alkyl styrene) includes poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene) and the like, and poly (halogenated styrene) includes Examples include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), and poly (p-methylstyrene).
Examples include tertiary butyl styrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.
また、本発明に用いるスチレン系重合体は、分子量に
ついては重量平均分子量が10,000以上のものでなければ
ならず、とりわけ50,000以上のものが好適である。ここ
で、重量平均分子量が10,000未満のものでは、延伸が充
分にできない。さらに、分子量分布についてはその広狭
は制約がなく、様々なものを充当することが可能であ
る。なお、主としてシンジオタクチック構造を有するス
チレン系重合体は融点が160〜310℃であって、従来のア
タクチック構造のスチレン系重合体に比べて耐熱性が格
段に優れている。The styrene-based polymer used in the present invention must have a molecular weight of 10,000 or more, particularly preferably 50,000 or more. Here, if the weight average molecular weight is less than 10,000, stretching cannot be performed sufficiently. Further, regarding the molecular weight distribution, the width is not limited, and various types can be applied. The styrene-based polymer mainly having a syndiotactic structure has a melting point of 160 to 310 ° C., and is much more excellent in heat resistance than a conventional styrene-based polymer having an atactic structure.
このような主としてシンジオタクチック構造を有する
スチレン系重合体は、例えば不活性炭化水素溶媒中また
は溶媒の不存在下に、チタン化合物、及び水とトリアル
キルアルミニウムの縮合生成物を触媒として、スチレン
系単量体(上記スチレン系重合体に対応する単量体)を
重合することにより製造することができる(特開昭62-1
87708号公報)。Such a styrene-based polymer having a predominantly syndiotactic structure is, for example, a styrene-based polymer in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. It can be produced by polymerizing a monomer (a monomer corresponding to the above-mentioned styrene-based polymer) (JP-A-62-1).
No. 87708).
本発明では、上述の主としてシンジオタクチック構造
を有するスチレン系重合体を用いるが、目的とする耐熱
性を保つ範囲内で、成形性,延伸性その他目的とする性
質に応じて、熱可塑性樹脂,ゴム,無機充填剤,酸化防
止剤,核剤,可塑剤,相溶化剤,着色剤,帯電防止剤な
どを添加することができる。In the present invention, the above-mentioned styrene-based polymer having mainly a syndiotactic structure is used, but a thermoplastic resin, a thermoplastic resin, Rubber, inorganic fillers, antioxidants, nucleating agents, plasticizers, compatibilizers, coloring agents, antistatic agents and the like can be added.
熱可塑性樹脂としては、例えばアタクチック構造のポ
リスチレン,アイソタクチック構造のポリスチレン,AS
樹脂,ABS樹脂などのスチレン系重合体をはじめ、ポリエ
チレンテレフタレートなどのポリエステル,ポリカーボ
ネート,ポリフェニレンオキサイド,ポリスルホン,ポ
リエーテルスルホンなどのポリエーテル,ポリアミド,
ポリフェニレンスルフィド(PPS),ポリオキシメチレ
ンなどの縮合系重合体、ポリアクリル酸,ポリアクリル
酸エステル,ポリメチルメタクリレートなどのアクリル
系重合体、ポリエチレン,ポリプロピレン,ポリブテ
ン,ポリ4−メチルペンテン−1,エチレン−プロピレン
系重合体などのポリオレフィン、あるいはポリ塩化ビニ
ル,ポリ塩化ビニリデン,ポリ弗化ビニリデンなどの含
ハロゲンビニル化合物重合体などが挙げられる。Examples of the thermoplastic resin include polystyrene having an atactic structure, polystyrene having an isotactic structure, AS
Resins, ABS resins and other styrene polymers, polyesters such as polyethylene terephthalate, polycarbonate, polyphenylene oxide, polysulfone, polyethers such as polyethersulfone, polyamides,
Condensation polymers such as polyphenylene sulfide (PPS) and polyoxymethylene; acrylic polymers such as polyacrylic acid, polyacrylate and polymethyl methacrylate; polyethylene, polypropylene, polybutene, poly 4-methylpentene-1, ethylene Polyolefins such as propylene-based polymers, and halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride.
またゴムとしては、様々なものが使用可能であるが、
最も好適なものはスチレン系化合物をその一成分として
含むゴム状共重合体で、例えば、スチレン−ブタジエン
ブロック共重合体のブタジエン部分を一部あるいは完全
に水素化したゴム(SEBS),スチレン−ブタジエン共重
合体ゴム(SBR),アクリル酸メチル−ブタジエン−ス
チレン共重合体ゴム,アクリロニトリル−ブタジエン−
スチレン共重合体ゴム(ABSゴム),アクリロニトリル
−アルキルアクリレート−ブタジエン−スチレン共重合
体ゴム(AABS),メタクリル酸メチル−アルキルアクリ
レート−スチレン共重合体ゴム(MAS),メタクリル酸
メチル−アルキルアクリレート−ブタジエン−スチレン
共重合体ゴム(MABS)などが挙げられる。これらのスチ
レン系化合物をその一成分として含むゴム状共重合体
は、スチレン単位を有するため、主としてシンジオタク
チック構造を有するスチレン系重合体に対する分散性が
良好であり、その結果、物性の改善効果が著しい。Also, various rubbers can be used,
Most preferred are rubbery copolymers containing a styrene-based compound as one component, for example, rubber (SEBS) in which the butadiene portion of a styrene-butadiene block copolymer is partially or completely hydrogenated, styrene-butadiene Copolymer rubber (SBR), methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-
Styrene copolymer rubber (ABS rubber), acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber (AABS), methyl methacrylate-alkyl acrylate-styrene copolymer rubber (MAS), methyl methacrylate-alkyl acrylate-butadiene -Styrene copolymer rubber (MABS) and the like. Since the rubbery copolymer containing these styrene compounds as one component has styrene units, it has good dispersibility mainly in styrene polymers having a syndiotactic structure, and as a result, the effect of improving physical properties Is remarkable.
さらに用いることのできるゴムの他の例としては、天
然ゴム,ポリブタジエン,ポリイソプレン,ポリイソブ
チレン,ネオプレン,エチレン−プロピレン共重合体ゴ
ム,ポリスルフィドゴム,チオコールゴム,アクリルゴ
ム,ウレタンゴム,シリコーンゴム,エピクロルヒドリ
ンゴム,ポリエーテル・エステルゴム,ポリエステル・
エステルゴムなどが挙げられる。Other examples of rubbers that can be used include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber. , Polyether / ester rubber, polyester /
Ester rubber and the like can be mentioned.
さらに無機充填剤としては、繊維状のものであると、
粒状,粉状のものであるとを問わない。繊維状無機充填
材としてはガラス繊維,炭素繊維、アルミナ繊維等が挙
げられる。一方、粒状,粉状無機充填材としてはタル
ク,カーボンブラック,グラファイト,二酸化チタン,
シリカ,マイカ,炭酸カルシウム,硫酸カルシウム,炭
酸バリウム,炭酸マグネシウム,硫酸マグネシウム,硫
酸バリウム,オキシサルフェート,酸化スズ,アルミ
ナ,カオリン,炭化ケイ素,金属粉末等が挙げられる。Furthermore, as the inorganic filler, if it is a fibrous thing,
It does not matter whether it is granular or powdery. Examples of the fibrous inorganic filler include glass fiber, carbon fiber, and alumina fiber. On the other hand, talc, carbon black, graphite, titanium dioxide,
Examples include silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, and metal powder.
また酸化防止剤としては様々なものがあるが、特にト
リス(2,4−ジ−t−ブチルフェニル)ホスファイト,
トリス(モノおよびジ−ノニルフェニル)ホスファイト
等のモノホスファイトやジホスファイト等のリン系酸化
防止剤およびフェノール系酸化防止剤が好ましい。ジホ
スファイトとしては、 一般式 〔式中、R1,R2はそれぞれ炭素数1〜20のアルキル
基,炭素数3〜20のシクロアルキル基あるいは炭素数6
〜20のアリール基を示す。〕 で表わされるリン系化合物を用いることが好ましい。Although there are various antioxidants, particularly, tris (2,4-di-t-butylphenyl) phosphite,
Phosphorus antioxidants such as monophosphites and diphosphites such as tris (mono- and di-nonylphenyl) phosphites and phenolic antioxidants are preferred. As the diphosphite, the general formula [Wherein, R 1 and R 2 each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or 6 carbon atoms.
Represents up to 20 aryl groups. It is preferable to use a phosphorus compound represented by the following formula:
上記一般式で表わされるリン系化合物の具体例として
は、ジステアリルペンタエリスリトールジホスファイ
ト;ジオクチルペンタエリスリトールジホスファイト;
ジフェニルペンタエリスリトールジホスファイト;ビス
(2,4−ジ−t−ブチルフェニル)ペンタエリスリトー
ルジホスファイト;ビス(2,6−ジ−t−ブチル−4−
メチルフェニル)ペンタエリスリトールジホスファイ
ト;ジシクロヘキシルペンタエリスリトールジホスファ
イトなどが挙げられる。Specific examples of the phosphorus compound represented by the above general formula include distearyl pentaerythritol diphosphite; dioctyl pentaerythritol diphosphite;
Diphenylpentaerythritol diphosphite; bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite; bis (2,6-di-t-butyl-4-)
Methylphenyl) pentaerythritol diphosphite; dicyclohexylpentaerythritol diphosphite;
また、フェノール系酸化防止剤としては既知のものを
使用することができ、その具体例としては、2,6−ジ−
t−ブチル−4−メチルフェノール;2,6−ジフェニル−
4−メトキシフェノール;2,2′−メチレンビス(6−t
−ブチル−4−メチルフェノール);2,2′−メチレンビ
ス〔4−メチル−6−(α−メチルシクロヘキシル)フ
ェノール〕;1,1−ビス(5−t−ブチル−4−ヒドロキ
シ−2−メチルフェニル)ブタン;2,2′−メチレンビス
(4−メチル−6−シクロヘキシルフェノール);2,2′
−メチレンビス−(4−メチル−6−ノニルフェノー
ル);1,1,3−トリス−(5−t−ブチル−4−ヒドロキ
シ−2−メチルフェニル)ブタン;2,2′−ビス−(5−
t−ブチル−4−ヒドロキシ−2−メチルフェニル)−
4−n−ドデシルメルカプトブタン;エチレングリコー
ル−ビス〔3,3′−ビス(3−t−ブチル−4−ヒドロ
キシフェニル)ブチレート〕;1−1−ビス(3,5−ジメ
チル−2−ヒドロキシフェニル)−3−(n−ドデシル
チオ)−ブタン;4,4′−チオビス(6−t−ブチル−3
−メチルフェノール);1,3,5−トリス(3,5−ジ−t−
ブチル−4−ヒドロキシベンジル)−2,4,6−トリメチ
ルベンゼン;2,2−ビス(3,5−ジ−t−ブチル−4−ヒ
ドロキシベンジル)マロン酸ジオクタデシルエステル;n
−オクタデシル−3−(4−ヒドロキシ−3,5−ジ−t
−ブチルフェニル)プロピオネート;テトラキス〔メチ
レン(3,5−ジ−t−ブチル−4−ヒドロキシハイドロ
シンナメート)〕メタンなどが挙げられる。Known phenolic antioxidants can be used, and specific examples thereof include 2,6-di-
t-butyl-4-methylphenol; 2,6-diphenyl-
4-methoxyphenol; 2,2'-methylenebis (6-t
-Butyl-4-methylphenol); 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol]; 1,1-bis (5-t-butyl-4-hydroxy-2-methyl Phenyl) butane; 2,2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,2 '
-Methylenebis- (4-methyl-6-nonylphenol); 1,1,3-tris- (5-t-butyl-4-hydroxy-2-methylphenyl) butane; 2,2'-bis- (5-
t-butyl-4-hydroxy-2-methylphenyl)-
4-n-dodecylmercaptobutane; ethylene glycol-bis [3,3'-bis (3-t-butyl-4-hydroxyphenyl) butyrate]; 1-1-bis (3,5-dimethyl-2-hydroxyphenyl ) -3- (n-Dodecylthio) -butane; 4,4'-thiobis (6-t-butyl-3)
-Methylphenol); 1,3,5-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene; dioctadecyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate; n
-Octadecyl-3- (4-hydroxy-3,5-di-t
-Butylphenyl) propionate; tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane;
上記の酸化防止剤は、前記の主としてシンジオタクチ
ック構造を有するスチレン系重合体100重量部に対し、
0.0001〜2重量部、好ましくは0.001〜1重量部の割合
で配合される。ここで酸化防止剤の配合割合が0.0001重
量部未満であると分子量低下が著しく、一方、2重量部
を超えると機械的強度に影響があるため、いずれも好ま
しくない。The antioxidant is based on 100 parts by weight of the styrenic polymer having a syndiotactic structure.
0.0001 to 2 parts by weight, preferably 0.001 to 1 part by weight. Here, if the compounding ratio of the antioxidant is less than 0.0001 part by weight, the molecular weight is remarkably reduced, while if it exceeds 2 parts by weight, the mechanical strength is adversely affected.
本発明に用いるフィルムは、各種の方法で成形するこ
とができるが、通常は、次のような操作を行う。即ち、
まず上述のスチレン系重合体あるいはこれに他の成分を
適量配合したものを成形材料として、これを通常はまず
押出成形やカレンダー成形、あるいはブロー成形により
成形して、延伸用原反シート(フィルムまたは予備成形
体)とする。この成形にあっては、上記成形材料の加熱
溶融したものを各種成形機にて所定形状に成形するのが
一般的であるが、成形材料を加熱溶融させずに、軟化し
た状態で成形してもよい。ここで成形材料の溶融温度は
スチレン系重合体がポリスチレンの場合、通常は260〜3
50℃、好ましくは280〜330℃である。温度が高すぎる
と、成形材料が分解するなどの問題が生じ、好ましくな
い。また、ここで成形する原反シートの厚さは任意に選
定すればよいが、一般には5mm以下、好ましくは3mm〜20
μmの範囲で適宜定めればよい。厚さが5mmを超えるも
のでは、内部の結晶化が進みシートが白濁する場合があ
る。原反シート(フィルム)の結晶化度は、30%以下、
好ましくは20%以下、さらに好ましくは10%以下であ
る。The film used in the present invention can be formed by various methods. Usually, the following operation is performed. That is,
First, the above-mentioned styrene-based polymer or a material obtained by blending an appropriate amount of other components with the styrene-based polymer is used as a molding material, which is usually first molded by extrusion molding, calender molding, or blow molding to obtain a raw sheet for stretching (film or film). Preform). In this molding, it is general to mold a heat-melted material of the above molding material into a predetermined shape by various molding machines, but without heating and melting the molding material, molding in a softened state. Is also good. Here, the melting temperature of the molding material is usually 260 to 3 when the styrene-based polymer is polystyrene.
The temperature is 50C, preferably 280-330C. If the temperature is too high, problems such as decomposition of the molding material occur, which is not preferable. Further, the thickness of the raw sheet to be molded here may be arbitrarily selected, but is generally 5 mm or less, preferably 3 mm to 20 mm.
It may be appropriately determined within the range of μm. If the thickness exceeds 5 mm, crystallization may progress inside and the sheet may become cloudy. The crystallinity of the raw sheet (film) is 30% or less,
It is preferably at most 20%, more preferably at most 10%.
なお、なるべく結晶化度の低い原反シートを製造した
場合、特に肉厚の厚いシートを成形する際には、加熱溶
融した上記の成形材料を成形時に急冷することが効果的
である。ここで、急冷にあたっては、冷媒温度を100℃
以下、好ましくは80℃以下、さらに好ましくは50℃以下
に設定する。冷媒温度が高すぎると緩慢冷却となり、一
部結晶化が起こり白濁する。When a raw sheet having as low a crystallinity as possible is produced, particularly when a thick sheet is formed, it is effective to rapidly cool the above-mentioned heat-fused molding material at the time of molding. Here, when quenching, the refrigerant temperature should be 100 ° C.
The temperature is set to preferably 80 ° C. or lower, more preferably 50 ° C. or lower. If the refrigerant temperature is too high, slow cooling will occur, and partial crystallization will occur, resulting in cloudiness.
この原反シートを延伸処理するにあたっては、一般に
は材料のガラス転移温度〜融点以下の温度で一軸あるい
は二軸に延伸する。ここで延伸温度はガラス転移温度以
上融点以下、特に透明なフィルムを得るためにはガラス
転移温度以上低温結晶化温度以下が好ましい。また、延
伸倍率については、一軸延伸の場合は、延伸方向に2倍
以上、好ましくは3倍以上、さらに好ましくは3〜10倍
の延伸倍率で延伸すべきである。また二軸延伸の場合
は、それぞれの延伸方向(二軸方向)に1.5倍以上、好
ましくは2倍以上の延伸倍率で延伸すべきである。延伸
倍率が小さすぎると、得られたフィルムの物性は本発明
のベースフィルムとして適さない。なお、上記二軸延伸
の場合は、縦方向及び横方向に同時に延伸してもよい
が、任意の順序で逐次延伸してもよい。When the raw sheet is stretched, it is generally stretched uniaxially or biaxially at a temperature lower than the glass transition temperature to the melting point of the material. Here, the stretching temperature is preferably from the glass transition temperature to the melting point, and particularly from the glass transition temperature to the low temperature crystallization temperature to obtain a transparent film. Regarding the stretching ratio, in the case of uniaxial stretching, the film should be stretched at a stretching ratio of 2 times or more, preferably 3 times or more, more preferably 3 to 10 times in the stretching direction. In the case of biaxial stretching, the film should be stretched in each stretching direction (biaxial direction) at a stretching ratio of 1.5 times or more, preferably 2 times or more. If the stretching ratio is too small, the physical properties of the obtained film are not suitable as the base film of the present invention. In the case of the biaxial stretching described above, the film may be stretched simultaneously in the longitudinal and transverse directions, but may be sequentially stretched in any order.
また本発明では、上記方法の他に特に二軸延伸を行う
場合には、上述の成形材料を、原反シートまたは予備成
形体とすることなく、直接インフレーション成形するこ
とによっても二軸延伸フィルムとすることができる。こ
のインフレーション成形による場合には、融解時の樹脂
温度を融点よりも20℃以上高くすることが、メルトフラ
クチャー,肌荒れ等を防ぐ上で有効であるが、あまり高
すぎると熱分解が起るため、180〜330℃の範囲に設定す
ることが好ましい。さらに、延伸温度は融点以下10℃で
あればよい。また、このインフレーション成形にあたっ
て、ブローアップ比を小さくすれば、一軸延伸も可能で
ある。In the present invention, in addition to the above-described method, particularly when biaxial stretching is performed, the above-described molding material is not formed into an original sheet or a preformed body, and is directly blown and formed into a biaxially stretched film. can do. In the case of this inflation molding, it is effective to raise the resin temperature at the time of melting by 20 ° C. or more from the melting point in order to prevent melt fracture, rough skin, and the like, but if it is too high, thermal decomposition occurs. It is preferable to set the temperature in the range of 180 to 330 ° C. Further, the stretching temperature may be 10 ° C. or lower than the melting point. In the inflation molding, if the blow-up ratio is reduced, uniaxial stretching is also possible.
このようにして延伸フィルムが得られるが、本発明の
ベースフィルムとして使用する場合、1〜50μm、好ま
しくは3.5〜12μm、特に好ましくは3.5〜6μmの厚さ
のものを用いる。Thus, a stretched film is obtained. When the stretched film is used as the base film of the present invention, a film having a thickness of 1 to 50 μm, preferably 3.5 to 12 μm, particularly preferably 3.5 to 6 μm is used.
上記の延伸処理後に、さらに熱固定を行うこともでき
る。この熱固定は、ガラス転移温度以上、融点以下の温
度範囲でフィルム等の素材を緊張状態にして熱処理すれ
ばよい。この熱固定により、フィルムの耐熱性,寸法安
定性,耐薬品性が一層向上する。After the above stretching treatment, heat setting can be further performed. This heat setting may be performed by heat-treating a material such as a film in a tension state in a temperature range from the glass transition temperature to the melting point. The heat setting further improves the heat resistance, dimensional stability, and chemical resistance of the film.
本発明のインクリボンは、上記のようなスチレン系重
合体の延伸フィルムをベースフィルムとして、その片面
にインク層を有するものである。インク層を形成するた
めに用いるインクは、各種のものであってよく、特に制
限はない。The ink ribbon of the present invention has an ink layer on one side of a stretched film of a styrene polymer as described above as a base film. The ink used to form the ink layer may be of various types, and is not particularly limited.
また、インク層とは反対側の面には、必要に応じて耐
熱滑性層を設けてもよい。この耐熱滑性層は、ベースフ
ィルムにインク層を設けた後に形成しても、あるいはイ
ンク層を設ける前に形成してもよい。しかし、作業性の
観点から、耐熱滑性層を形成した後にインク層を設ける
方法が好適である。また、所望の大きさのベースフィル
ムに、耐熱滑性層を設けた後に、所定の巾に切断してイ
ンクリボンとしてもよく、あるいはインクリボンの大き
さのベースフィルム面に耐熱滑性層を設けてもよい。Further, a heat-resistant lubricating layer may be provided on the surface opposite to the ink layer, if necessary. The heat-resistant lubricating layer may be formed after providing the ink layer on the base film, or may be formed before providing the ink layer. However, from the viewpoint of workability, a method in which the ink layer is provided after forming the heat-resistant lubricating layer is preferable. Also, after providing a heat-resistant lubricating layer on a base film of a desired size, it may be cut into a predetermined width to form an ink ribbon, or a heat-resistant lubricating layer may be provided on a base film surface of an ink ribbon. You may.
耐熱滑性層を形成するには、耐熱性,潤滑性,耐久
性,走行性,耐擦傷性,耐粘着性などの諸性能を向上さ
せうる各種の物質、例えばシリコーン系化合物,硬化性
ホスファゼン系化合物,アクリル系化合物などを主成分
とする組成物を常法で塗布すればよい。To form the heat-resistant lubricating layer, various materials capable of improving various properties such as heat resistance, lubricity, durability, running properties, abrasion resistance, and adhesion resistance, for example, a silicone-based compound and a curable phosphazene-based material What is necessary is just to apply the composition which has a compound, an acrylic compound, etc. as a main component by a normal method.
シリコーン系化合物としては、各種のものを使用で
き、例えばモノメチル又はモノエチルトリクロロシラン
に少量のジメチル,ジエチルジクロロシランを混合し、
反応させて得られた初期縮合物などが挙げられ、このも
のは、通常、適当な溶剤に溶解し、必要に応じて可溶性
脂肪酸塩などの硬化促進剤を添加して用いられる。As the silicone compound, various compounds can be used. For example, a mixture of monomethyl or monoethyltrichlorosilane with a small amount of dimethyl, diethyldichlorosilane,
Examples include an initial condensate obtained by the reaction, which is usually dissolved in an appropriate solvent, and used after adding a curing accelerator such as a soluble fatty acid salt as needed.
また、硬化性ホスファゼン化合物は、一般式 NP(A)a(B)b ・・・〔I〕 〔式中、a,bはa>0,b≧0であり、かつa+b=2を
満たす実数を示し、Aは重合硬化性基を示し、Bは非重
合硬化性基を示す。〕 で表わされる繰返し単位を有し、重合度が3以上である
化合物である。ここで一般式〔I〕は、単一の化合物を
表示するものではなく、数種の化合物の混合物の平均値
としての表示である。したがって、各基の数を示すaお
よびbは必ずしも整数に限定されず、小数をも含む実数
である。また、重合度についても同様に3以上の範囲の
整数のみならず、小数をも含む実数である。The curable phosphazene compound is represented by the general formula NP (A) a (B) b ... [I] wherein a and b are a real numbers that satisfy a> 0, b ≧ 0 and a + b = 2. A represents a polymerization-curable group, and B represents a non-polymerization-curable group. ] It is a compound which has the repeating unit represented by these, and has a degree of polymerization of 3 or more. Here, the general formula [I] does not indicate a single compound but indicates an average value of a mixture of several compounds. Therefore, a and b indicating the number of each group are not necessarily limited to integers, but are real numbers including decimal numbers. Similarly, the polymerization degree is a real number including not only an integer in the range of 3 or more but also a decimal number.
上記一般式〔I〕の繰返し単位をもつホスファゼン化
合物は、各置換基の種類により様々なものがある。There are various phosphazene compounds having a repeating unit of the above general formula [I] depending on the type of each substituent.
式中、Aは重合硬化性基を示すが、この重合硬化性基
とは、紫外線,可視光線や電子線の照射,化学的硬化剤
の使用あるいは加熱等により反応して硬化する官能基を
意味し、通常は反応性二重結合を有する基である。この
反応性二重結合を有する基としては、各種のものがある
が、例えばアクリロイル基,メタクリロイル基あるいは
アリル基を含む官能基があげられる。In the formula, A represents a polymer-curable group, and the polymer-curable group means a functional group that is cured by irradiation with ultraviolet light, visible light or electron beam, use of a chemical curing agent, or heating. However, it is usually a group having a reactive double bond. There are various types of groups having a reactive double bond, and examples thereof include functional groups containing an acryloyl group, a methacryloyl group, or an allyl group.
上記アクリロイル基を含む官能基あるいはメタクリロ
イル基を含む官能基は、アクリロイルオキシ基やメタク
リロイルオキシ基、さらには 一般式 〔式中、R1は水素原子またはメチル基を示し、R2は炭
素数1〜12(好ましくは1〜5)のアルキレン基(分岐
アルキレン基を含む)を示す。〕 で表わされるものである。The functional group containing an acryloyl group or the functional group containing a methacryloyl group is an acryloyloxy group, a methacryloyloxy group, or a compound represented by the general formula: [In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkylene group having 1 to 12 (preferably 1 to 5) carbon atoms (including a branched alkylene group). ].
また、このアクリロイル基やメタクリロイル基を含む
官能基は、上述の一般式〔II〕のもののほかに、 一般式 〔式中、R1及びR2は前記と同じである。〕 で表わされる官能基、すなわちヒドロキシアルキル置換
(メタ)アクリルアミドの水酸基から水素原子を除いた
残基、さらに一般式: 〔式中、R1は前記と同じである。〕 で表わされる官能基、即ちアクリルアミドやメタクリル
アミドのアミノ基から水素原子を一個除いた残基をあげ
ることができる。The functional group containing an acryloyl group or a methacryloyl group may be a compound represented by the general formula [II], Wherein R 1 and R 2 are the same as above. A functional group represented by the following formula, that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkyl-substituted (meth) acrylamide, and a general formula: Wherein R 1 is the same as defined above. ], That is, a residue obtained by removing one hydrogen atom from the amino group of acrylamide or methacrylamide.
さらに、アリル基を含む官能基としては、アリル基そ
のもののほか、例えばアリルオキシ基(CH2=CH-CH2O-)
があるが、このアリルオキシ基に限らず、広く、一般式 〔式中、R1及びR2は前記と同じであり、R3及びR4はそ
れぞれ独立に水素又は炭素数1〜4のアルキル基を示
す。〕 で表わされる官能基、即ち水酸基を一個有するアリル化
合物の水酸基から水素原子を除いた残基をあげることが
できる。Further, as the functional group containing an allyl group, in addition to the allyl group itself, for example, an allyloxy group (CH 2 CHCH—CH 2 O—)
There is, but not limited to this allyloxy group, widely the general formula [Wherein, R 1 and R 2 are the same as described above, and R 3 and R 4 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms. ], That is, a residue obtained by removing a hydrogen atom from a hydroxyl group of an allyl compound having one hydroxyl group.
一方、一般式〔I〕中のBは、前述の如く式: R5M- ・・・〔VIII〕 あるいは一般式: で表わされる基を示す。ここで、式〔VIII〕中Mは酸素
原子,硫黄原子又はイミノ基を示し、R5は炭素数1〜18
のアルキル基あるいは炭素数1〜18のハロゲン化アルキ
ル基を示す。具体的には、メトキシ基,エトキシ基,プ
ロポキシ基,ブトキシ基,ペンチルオキシ基,ヘキシル
オキシ基,ヘプチルオキシ基,オクチルオキシ基などの
アルコキシ基,ハロゲン(例えばフッ素、塩素、臭素な
ど)で置換された同様のアルコキシ基,メチルチオ基,
エチルチオ基,プロピルチオ基,ブチルチオ基,ペンチ
ルチオ基,ヘプチルチオ基,オクチルチオ基などのアル
キルチオ基,ハロゲン(例えばフッ素、塩素、臭素な
ど)で置換された同様のアルキルチオ基,メチルイミノ
基,エチルイミノ基,プロピルイミノ基,ブチルイミノ
基,ペンチルイミノ基,ヘキシルイミノ基,ヘプチルイ
ミノ基,オクチルイミノ基などのアルキルイミノ基,ハ
ロゲン(例えばフッ素、塩素、臭素など)で置換された
同様のアルキルイミノ基等をあげることができる。ま
た、式〔IX〕中Mは前記と同じであり、R6〜R10はそれ
ぞれ独立に水素原子,ハロゲン原子,炭素数1〜4のア
ルキル基又は炭素数1〜4のハロゲン化アルキル基を示
す。式〔IX〕の基は、具体的には、フェノキシ基,チオ
フェニル基,ハロゲン化フェノキシ基(2,4,6−トリブ
ロモフェノキシ基,4−ブロモフェノキシ基,2−クロロフ
ェノキシ基,2,4−ジクロロフェノキシ基など)およびハ
ロゲン化チオフェニル基(4−クロロフェニルチオ基な
ど)、あるいはアニリンおよびハロゲン化アニリン(2
−クロロアニリン,2,4−ジクロロアニリン、2,4,6−ト
リブロモアニリンなど)のアミノ基より水素原子を取り
除いた残基などをあげることができる。On the other hand, B in the general formula [I] represents the formula: R 5 M-... [VIII] or the general formula: Represents a group represented by Here, in the formula [VIII], M represents an oxygen atom, a sulfur atom or an imino group, and R 5 has 1 to 18 carbon atoms.
Or a halogenated alkyl group having 1 to 18 carbon atoms. Specifically, it is substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a halogen (eg, fluorine, chlorine, bromine, etc.). Similar alkoxy, methylthio,
Alkylthio groups such as ethylthio group, propylthio group, butylthio group, pentylthio group, heptylthio group, octylthio group, and similar alkylthio groups substituted with halogens (eg, fluorine, chlorine, bromine, etc.), methylimino group, ethylimino group, propylimino group Butylimino group, pentylimino group, hexylimino group, heptylimino group, octylimino group and the like, and similar alkylimino groups substituted by halogen (for example, fluorine, chlorine, bromine and the like). In the formula [IX], M is the same as described above, and R 6 to R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms. Show. Specific examples of the group of the formula [IX] include a phenoxy group, a thiophenyl group, a halogenated phenoxy group (2,4,6-tribromophenoxy group, 4-bromophenoxy group, 2-chlorophenoxy group, 2,4 -Dichlorophenoxy group) and halogenated thiophenyl group (such as 4-chlorophenylthio group), or aniline and halogenated aniline (2
-Chloroaniline, 2,4-dichloroaniline, 2,4,6-tribromoaniline, etc.), and a residue obtained by removing a hydrogen atom from an amino group.
また、前述の一般式〔I〕中のa,bについては、0<
a≦2,0≦b<2であり、かつa+b=2を満たす実数
であればよいが、好ましくは0.6≦a≦2,0≦b≦1.4で
ある。For a and b in the general formula [I], 0 <
Any real number that satisfies a ≦ 2,0 ≦ b <2 and a + b = 2 is preferable, and preferably 0.6 ≦ a ≦ 2,0 ≦ b ≦ 1.4.
なお置換基Aは、一般式〔I〕のホスファゼン化合物
を主成分とする耐熱滑性層が硬化する際に作用する基で
あり、また置換基Bは、その硬化体の物性を調節すると
ともに、重合性能を調節する作用を示す基である。した
がって、a,bを適宜選定することにより、このホスファ
ゼン化合物を主成分とする耐熱滑性層を有するインクリ
ボンの諸物性が規定されることとなる。The substituent A is a group that acts when the heat-resistant lubricating layer containing the phosphazene compound of the general formula [I] as a main component cures, and the substituent B adjusts the physical properties of the cured product, It is a group having an effect of regulating polymerization performance. Therefore, by appropriately selecting a and b, various physical properties of the ink ribbon having the heat-resistant lubricating layer containing the phosphazene compound as a main component are defined.
但し、a=0のものは硬化性を有しないので、このよ
うなホスファゼン化合物は、本発明の耐熱滑性層の成分
からは除外される。しかし、a=2,b=0のもの、即
ち、 一般式NP(A)2 ・・・〔I′〕 で表わされる繰返し単位を有するホスファゼン化合物
は、本発明の耐熱滑性層の成分として利用できる。However, since a compound having a = 0 does not have curability, such a phosphazene compound is excluded from the components of the heat-resistant lubricating layer of the present invention. However, a phosphazene compound having a = 2 and b = 0, that is, a phosphazene compound having a repeating unit represented by the general formula NP (A) 2 ... [I '] is used as a component of the heat-resistant lubricating layer of the present invention. it can.
本発明におけるホスファゼン化合物は、上述の一般式
〔I〕の繰返し単位を有するものであるが、その重合度
は3以上、好ましくは3〜10,000の範囲、さらに好まし
くは3〜18の範囲であり、とりわけ3あるいは4もしく
はそれらの混合物が最適である。また、一般式〔I〕の
繰返し単位が鎖状の結合(重合)したものもあるが、好
ましくは環状に結合(重合)したものである。The phosphazene compound in the present invention has a repeating unit of the above general formula (I), and has a polymerization degree of 3 or more, preferably 3 to 10,000, more preferably 3 to 18, Particularly, 3 or 4 or a mixture thereof is optimal. In addition, there is a repeating unit of the general formula [I] in which the repeating unit is bonded (polymerized) in a chain form, but is preferably a unit which is bonded (polymerized) in a cyclic manner.
本発明に使用しうるホスファゼン化合物のさらに詳細
については、特願昭63-114738号明細書等に記載されて
いる。Further details of the phosphazene compound which can be used in the present invention are described in Japanese Patent Application No. 63-114738.
さらに、アクリル系化合物としては、光重合性単量体
あるいはプレポリマーが挙げられる。Further, examples of the acrylic compound include a photopolymerizable monomer or a prepolymer.
光重合性単量体としては、例えばメチル(メタ)アク
リレート:2−エチルヘキシル(メタ)アクリレート:2−
ヒドロキシエチル(メタ)アクリレート:2−ヒドロキシ
プロピル(メタ)アクリレートなどの単官能性化合物、
1,3−ブタンジオールジ(メタ)アクリレート:1,6−ヘ
キサンジオールジ(メタ)アクリレート: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(メ
タ)アクリレート:テトラエチレングリコールジ(メ
タ)アクリレート:ネオペンチルグリコールジ(メタ)
アクリレート:ポリエチレングリコールジ(メタ)アク
リレート:ヒドロキシピバリン酸エステルネオペンチル
グリコールジ(メタ)アクリレートなどの2官能性化合
物、トリメチロールプロパントリ(メタ)アクリレー
ト:ペンタエリスリトールトリ(メタ)アクリレート:
ジペンタエリスリトールヘキサ(メタ)アクリレート:
トリアリルイソシアネートなどの3官能性以上の多官能
性化合物を挙げることができる。As the photopolymerizable monomer, for example, methyl (meth) acrylate: 2-ethylhexyl (meth) acrylate: 2-
Hydroxyethyl (meth) acrylate: a monofunctional compound such as 2-hydroxypropyl (meth) acrylate;
1,3-butanediol di (meth) acrylate: 1,6-hexanediol di (meth) acrylate: ethylene glycol di (meth) acrylate: diethylene glycol di (meth) acrylate: triethylene glycol (meth) acrylate: tetraethylene glycol Di (meth) acrylate: neopentyl glycol di (meth)
Acrylate: polyethylene glycol di (meth) acrylate: hydroxypivalic acid ester bifunctional compound such as neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate: pentaerythritol tri (meth) acrylate:
Dipentaerythritol hexa (meth) acrylate:
Examples include trifunctional or higher functional polyfunctional compounds such as triallyl isocyanate.
また、光重合性プレポリマーとしては、例えばポリエ
ステル(メタ)アクリレート,ポリウレタン(メタ)ア
クリレート,エポキシ(メタ)アクリレート,ポリエー
テル(メタ)アクリレート,メラミン(メタ)アクリレ
ート,オリゴ(メタ)アクリレート,アルキド(メタ)
アクリレート,ポリオール(メタ)アクリレート,シリ
コン(メタ)アクリレートなど、(メタ)アクリロイル
基を少なくとも1個有するプレポリマーを挙げることが
できる。Examples of the photopolymerizable prepolymer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, oligo (meth) acrylate, and alkyd ( Meta)
Examples include prepolymers having at least one (meth) acryloyl group, such as acrylate, polyol (meth) acrylate, and silicon (meth) acrylate.
ベースフィルムの裏面に耐熱滑性層を形成するには、
上記のようなシリコーン系,硬化性ホスファゼン系ある
いはアクリル系化合物、さらに場合によりこれらの化合
物と共重合可能な単量体及び常用の添加剤を含有させて
塗布液(コーティング材)を調製し、これをフィルムの
裏面に塗布し、活性エネルギー線を照射したり、加熱す
るなどして硬化させればよい。To form a heat-resistant lubricating layer on the back of the base film,
A coating liquid (coating material) is prepared by containing the above-mentioned silicone-based, curable phosphazene-based or acrylic-based compound, and optionally a monomer copolymerizable with these compounds and a conventional additive. May be applied to the back surface of the film and cured by irradiating active energy rays or heating.
また、添加剤としては、無機充填剤,有機充填剤,潤
滑剤などがあげられる。In addition, examples of the additives include inorganic fillers, organic fillers, and lubricants.
無機充填剤としては、微粉末状のシリカ,アルミナ,
ガラス,セラミック等(溶剤分散型でもよい)を使用す
ることができる。As the inorganic filler, fine powdered silica, alumina,
Glass, ceramic, etc. (solvent dispersion type may be used) can be used.
また、有機充填剤としては、微粉末状のアクリル樹脂
などが挙げられる。In addition, examples of the organic filler include finely divided acrylic resin.
潤滑剤は、液体,固体,グリース状のいかなる性状の
ものでもよく、シリコーン系,フッ素系、その他合成潤
滑剤、あるいはテフロン微粒子,二硫化モリブデンなど
を用いることができる。The lubricant may be in any form of liquid, solid, or grease. Silicone, fluorine, other synthetic lubricants, fine particles of Teflon, molybdenum disulfide, and the like can be used.
また、塗布液は作業性,薄厚制御などのうえから有機
溶剤に希釈して使用することができる。かかる有機溶剤
として、メチルエチルケトン,メチルイソブチルケトン
などのケトン類、2−プロパノール,1−ブタノールなど
のアルコール類、クロロホルム,塩化メチレンなどのハ
ロゲン化炭化水素、セロソルブ類、酢酸エステル類、エ
ーテル類、芳香族炭化水素などを単独あるいは適宜混合
して使用することができる。Further, the coating liquid can be used after being diluted with an organic solvent after controlling workability and controlling the thickness. Examples of such organic solvents include ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as 2-propanol and 1-butanol, halogenated hydrocarbons such as chloroform and methylene chloride, cellosolves, acetates, ethers and aromatics. Hydrocarbons and the like can be used alone or in a suitable mixture.
塗布後の硬化には上述のように活性エネルギー線(可
視光線,紫外線,電子線,X線,γ線など)照射や加熱硬
化、常温硬化などの方法を利用する。As described above, curing after application is performed by irradiation with active energy rays (visible light, ultraviolet rays, electron beams, X-rays, γ-rays, etc.), heat curing, and room temperature curing.
なお、可視光線,紫外線を用いた硬化方法を利用する
場合は、反応開始剤(光増感剤)を使用する。かかる反
応開始剤は塗布液中に添加しておけばよい。反応開始剤
の例としては、1−ヒドロキシシクロヘキシルフェニル
ケトン,ジベンゾイル,ベンゾイル,ベンゾインメチル
エーテル,ベンゾインエチルエーテル,p−クロロベンゾ
フェノン,p−メトキシベンゾフェノン,ベンゾイルパー
オキサイド,ジ−t−ブチルパーオキサイドおよびカン
ファキノンをあげることができ、これらを単独であるい
は組合せて使用することができる。さらには、2−メチ
ル−〔4−(メチルチオ)フェニル〕−2−モルフォリ
ノ−1−プロパノンなども好適に使用することができ
る。When a curing method using visible light or ultraviolet light is used, a reaction initiator (photosensitizer) is used. Such a reaction initiator may be added to the coating solution. Examples of the reaction initiator include 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, benzoyl peroxide, di-t-butyl peroxide and camphor. Quinone can be mentioned, and these can be used alone or in combination. Further, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and the like can also be suitably used.
また、加熱硬化あるいは常温硬化の方法による場合
は、重合開始剤として通常は過酸化物系の化合物および
アミン系の化合物を単独あるいは組合せて使用する。過
酸化物系の化合物の例としては、ベンゾイルパーオキサ
イド;p−クロロベンゾイルパーオキサイド;2,4−ジクロ
ロベンゾイルパーオキサイド;t−ブチルヒドロパーオキ
サイド;ジ−t−ブチルパーオキサイド;ジクミルパー
オキサイド;t−ブチルパーオキシアセテート;t−ブチル
パーオキシベンゾエートなどを挙げることができる。ま
た、アミン系の化合物の例としては、N,N,−ジエタノー
ル−p−トルイジン;ジメチル−p−トルイジン;p−ト
ルイジン;メチルアミン;t−ブチルアミン;メチルエチ
ルアミン;ジフェニルアミン;4,4′−ジニトロジフェニ
ルアミン;o−ニトロアミン;p−ブロモアニリン;2,4,6−
トリブロモアニリンなどを挙げることができる。In the case of heat curing or room temperature curing, a peroxide compound and an amine compound are usually used alone or in combination as a polymerization initiator. Examples of peroxide-based compounds include benzoyl peroxide; p-chlorobenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-t-butyl peroxide; dicumyl peroxide. t-butyl peroxyacetate; t-butyl peroxybenzoate; Examples of amine-based compounds include N, N, -diethanol-p-toluidine; dimethyl-p-toluidine; p-toluidine; methylamine; t-butylamine; methylethylamine; diphenylamine; Diphenylamine; o-nitroamine; p-bromoaniline; 2,4,6-
Tribromoaniline and the like can be mentioned.
さらに、酸化防止剤,紫外線防止剤,可塑剤,帯電防
止剤,熱重合防止剤などの添加剤を添加することもでき
る。Further, additives such as antioxidants, ultraviolet inhibitors, plasticizers, antistatic agents, and thermal polymerization inhibitors can be added.
また、前記のような耐熱滑性層を形成する成分を含む
コーティング材に、必要に応じ、さらに酢酸ビニル,ス
テアリン酸ビニルなどのカルボン酸のビニルエステル
類、フマル酸,マレイン酸,無水マレイン酸,イタコン
酸,無水イタコン酸などのエチレン性二重結合を有する
不飽和ジカルボン酸などの硬化性化合物を併用すること
もできる。Further, if necessary, a coating material containing a component for forming a heat-resistant lubricating layer as described above may further include vinyl esters of carboxylic acids such as vinyl acetate and vinyl stearate, fumaric acid, maleic acid, maleic anhydride, A curable compound such as an unsaturated dicarboxylic acid having an ethylenic double bond such as itaconic acid and itaconic anhydride can also be used in combination.
本発明のベースフィルムに耐熱滑性層を形成するコー
ティング材の組成の一例を次に示す。An example of the composition of the coating material for forming the heat-resistant lubricating layer on the base film of the present invention is shown below.
(a) ホスファゼン化合物 100重量部 (b) 無機充填剤 0〜100重量部 (c) ホスファゼン化合物と共重合可能な単官能性単
量体及び/又は多官能性単量体 0〜100重量部 (d) 潤滑剤 0〜50重量部 〔(a)〜(c)の固形分100重量部に対して〕 (e) 帯電防止剤 0〜10重量部 〔(a)〜(c)の固形分100重量部に対して〕 (f) 有機溶剤 (g) 光開始剤あるいは熱重合開始剤0.05〜5重量部
〔(a)〜(c)の硬化性化合物100重量部に対して〕 有機溶剤は、必ずしも使用する必要はないが、前述の
如く作業性、硬化後の膜厚制御のうえから好ましくは前
記の(a)〜(e)の混合物の重量濃度が0.5〜60%と
なるように有機溶剤に溶解すればよい。(A) 100 parts by weight of a phosphazene compound (b) 0 to 100 parts by weight of an inorganic filler (c) 0 to 100 parts by weight of a monofunctional monomer and / or a polyfunctional monomer copolymerizable with a phosphazene compound ( d) Lubricant 0 to 50 parts by weight [based on 100 parts by weight of solids of (a) to (c)] (e) Antistatic agent 0 to 10 parts by weight [solids of 100 of (a) to (c)] (F) Organic solvent (g) 0.05 to 5 parts by weight of photoinitiator or thermal polymerization initiator [based on 100 parts by weight of curable compound (a) to (c)] Although it is not necessary to use the organic solvent, the organic solvent is preferably used such that the weight concentration of the mixture of (a) to (e) is 0.5 to 60% from the viewpoint of workability and control of the film thickness after curing as described above. May be dissolved.
耐熱滑性層を形成するには、上記のように調製された
コーティング材を所望のインクリボン用のベースフィル
ムの片面(背面、インク層とは反対側の面)に従来公知
の方法、例えば、スピンナー法,スプレー法,ロールコ
ーター法などの塗布方法により塗布した後、溶剤を用い
た場合には、溶剤を除去し、次いで常温硬化,加熱硬
化,あるいは紫外線,電子線,X線,γ線などを照射し、
硬化性化合物を硬化させる。これらの硬化方法の中で、
紫外線を照射して硬化させる方法が好適であり、この場
合には、波長が200〜550nmの範囲内にある紫外線を0.1
秒間以上、好ましくは0.5〜30秒間照射することが好ま
しい。In order to form the heat-resistant lubricating layer, the coating material prepared as described above is applied to one surface (the back surface, the surface opposite to the ink layer) of a desired base film for an ink ribbon by a conventionally known method, for example, After applying by a coating method such as spinner method, spray method, or roll coater method, when a solvent is used, the solvent is removed and then room temperature curing, heat curing, or ultraviolet ray, electron beam, X-ray, γ-ray, etc. Irradiate,
The curable compound is cured. Among these curing methods,
A method of curing by irradiating ultraviolet rays is preferable.In this case, ultraviolet rays having a wavelength in the range of 200 to 550 nm are 0.1%.
Irradiation is preferably performed for at least 0.5 second, preferably for 0.5 to 30 seconds.
この際の照射光線の積算光量は、通常100〜5000ミリ
ジュール/cm2である。また、加熱硬化法を採用する場
合には、通常は、100℃以上の温度で完全に硬化させる
ことが好ましい。At this time, the integrated light quantity of the irradiation light beam is usually 100 to 5000 mJ / cm 2 . When the heat curing method is employed, it is usually preferable to completely cure at a temperature of 100 ° C. or higher.
この耐熱滑性層の厚さは、0.03〜20μmの範囲にある
ことが好ましいが、0.05〜10μmの範囲にあることが、
耐熱滑性効果とインクリボンの使用し易さなどのバラン
スの点から好ましい。The thickness of the heat-resistant lubricating layer is preferably in the range of 0.03 to 20 μm, but in the range of 0.05 to 10 μm,
It is preferable from the viewpoint of the balance between the heat-resistant lubrication effect and the ease of use of the ink ribbon.
このようにして得られた耐熱滑性層は、ベースフィル
ムに対して著しく優れた密着性を有しており、しかも機
械的,熱的,化学的性質などにおいても優れており、イ
ンクリボンの耐粘着性,潤滑性,耐熱性,耐久性,走行
性、耐擦傷性などを著しく向上させることができる。The heat-resistant lubricating layer thus obtained has remarkably excellent adhesion to the base film, and also has excellent mechanical, thermal, and chemical properties. Adhesion, lubricity, heat resistance, durability, running properties, scratch resistance, etc. can be significantly improved.
次に、本発明を実施例および比較例によりさらに詳し
く説明する。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
参考例1(シンジオタクチック構造を有するポリスチレ
ン製延伸フィルムの製造) 反応容器に、溶媒としてトルエン2lと触媒成分として
シクロペンタジエニルチタニウムトリクロリド1ミリモ
ルおよびメチルアルミノキサンをアルミニウム原子とし
て0.8モル加え、20℃においてこれにスチレン3.6lを加
え、1時間重合反応を行なった。Reference Example 1 (Production of stretched film made of polystyrene having a syndiotactic structure) To a reaction vessel, 2 l of toluene as a solvent, 1 mmol of cyclopentadienyltitanium trichloride as a catalyst component and 0.8 mol of methylaluminoxane as aluminum atoms were added. At ℃, 3.6 l of styrene was added thereto and a polymerization reaction was carried out for 1 hour.
反応終了後、生成物を塩酸−メタノール混合液で洗浄
し、触媒成分を分解除去した。ついで乾燥し、スチレン
系重合体(ポリスチレン)330gを得た。次に、この重合
体をメチルエチルケトンを溶媒としてソックスレー抽出
し、抽出残分95重量%を得た。このものの重量平均分子
量は290,000、数平均分子量は158,000であり、融点は27
0℃であった。また、この重合体は、13C-NMRによる分析
(溶媒:1,2−ジクロロベンゼン)から、シンジオタクチ
ック構造に基因する145.35ppmに吸収が認められ、その
ピーク面積から算出したラセミペンタッドでのシンジオ
タクティシティーは96%であった。After the completion of the reaction, the product was washed with a mixed solution of hydrochloric acid and methanol to decompose and remove the catalyst component. Then, it was dried to obtain 330 g of a styrene-based polymer (polystyrene). Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain 95% by weight of an extraction residue. It has a weight average molecular weight of 290,000, a number average molecular weight of 158,000 and a melting point of 27.
It was 0 ° C. Analysis of this polymer by 13 C-NMR (solvent: 1,2-dichlorobenzene) showed an absorption at 145.35 ppm due to the syndiotactic structure, and it was determined by the racemic pentad calculated from its peak area. Syndiotacticity was 96%.
得られたポリスチレンに、酸化防止剤として、ビス
(2,4−ジ−t−ブチルフェニル)ペンタエリスリトー
ルジホスファイト及びテトラキス〔メチレン(3,5−ジ
−t−ブチル−4−ヒドロキシハイドロシンナメー
ト)〕メタンをおのおの0.1重量部ずつ混合し、直径40m
mの二軸押出機にて押出して、ペレット化した。Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) are added to the obtained polystyrene as antioxidants. )] Methane mixed with 0.1 parts by weight each, 40m in diameter
The mixture was extruded by a twin-screw extruder of m and pelletized.
得られたペレットを、直径40mmの一軸押出機の先端に
Tダイを取り付けた装置に供給し、シリンダー温度300
℃、Tダイ温度310℃の条件で押出し、肉厚65μmのシ
ートを得た。このとき、シートの冷却用ロールは表面温
度30℃であった。The obtained pellets were supplied to a device having a T-die attached to the tip of a single-screw extruder having a diameter of 40 mm, and a cylinder temperature of 300 was supplied.
C. and a T-die temperature of 310 ° C. to obtain a sheet having a thickness of 65 μm. At this time, the surface temperature of the sheet cooling roll was 30 ° C.
このようにして得られた延伸用原反シートは、透明で
密度1.04g/m2,ガラス転移温度100℃,結晶化度2%で
あった。The raw sheet for stretching obtained in this manner was transparent, had a density of 1.04 g / m 2 , a glass transition temperature of 100 ° C., and a crystallinity of 2%.
次いでこのシートを、延伸温度120℃で縦横に4倍ず
つ同時延伸を行った。得られた延伸フィルムを格子状の
固定具に固定し、250℃で30秒間熱処理した。この時の
フィルムの厚さは4μmであった。Next, this sheet was simultaneously stretched four times vertically and horizontally at a stretching temperature of 120 ° C. The obtained stretched film was fixed to a grid-like fixture and heat-treated at 250 ° C. for 30 seconds. At this time, the thickness of the film was 4 μm.
実施例1(インク塗布フィルム) トルエン15重量部,エチレン−酢酸ビニル共重合体6
重量部及びカーボンブラック2重量部を調合し、振動ボ
ールミルで3時間振とうし、インクリボン用インクを調
合した。Example 1 (ink-coated film) 15 parts by weight of toluene, ethylene-vinyl acetate copolymer 6
By weight, 2 parts by weight of carbon black and 2 parts by weight of carbon black were mixed and shaken with a vibration ball mill for 3 hours to prepare ink for an ink ribbon.
次に、ロールコーターで参考例1で得た6.0μmのス
チレン系重合体延伸フィルムに4μmの塗布厚に塗布
し、インク塗布フィルムを得た。Next, a 4 μm coating thickness was applied to the 6.0 μm stretched styrene polymer film obtained in Reference Example 1 using a roll coater to obtain an ink-coated film.
実施例2(耐熱滑性層付きインクリボン) 2lのフラスコ内でヘキサクロロシクロトリホスファゼ
ン86.8gを脱水したベンゼン338gに溶解した。このベン
ゼン溶液に110gのピリジンおよび0.23gのヒドロキノン
を加えて撹拌した。Example 2 (Ink ribbon with heat-resistant lubricating layer) In a 2 l flask, 86.8 g of hexachlorocyclotriphosphazene was dissolved in 338 g of dehydrated benzene. To this benzene solution, 110 g of pyridine and 0.23 g of hydroquinone were added and stirred.
別に、2−ヒドロキシエチルメタクリレート200mlを
ベンゼン237mlに溶解し、この溶液を上記のフラスコ中
に滴下し、50℃で30時間かけて反応させた。反応後、濾
過してピリジンの塩酸塩を除去した。Separately, 200 ml of 2-hydroxyethyl methacrylate was dissolved in 237 ml of benzene, and this solution was dropped into the above flask, and reacted at 50 ° C. for 30 hours. After the reaction, filtration was performed to remove the pyridine hydrochloride.
濾液を水洗し、次いで芒硝を用いて乾燥させ、減圧蒸
留により溶剤を除去して、粘稠性の1,1,3,3,5,5−ヘキ
サ(メタクリロイルエチレンジオキシ)シクロトリホス
ファゼン200gを得た。The filtrate was washed with water, then dried using sodium sulfate, and the solvent was removed by distillation under reduced pressure to give 200 g of viscous 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene. Obtained.
得られた1,1,3,3,5,5−ヘキサ(メタクリロイルエチ
レンジオキシ)シクロトリホスファゼン100重量部をメ
チルイソブチルケトン中に溶解し、この溶液に1−ヒド
ロキシシクロヘキシルフェニルケトン(光重合開始剤)
3重量部を添加、溶解させ、耐熱滑性層用コーティング
材とした。100 parts by weight of the obtained 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene is dissolved in methyl isobutyl ketone, and 1-hydroxycyclohexylphenyl ketone (photopolymerization start Agent)
3 parts by weight were added and dissolved to obtain a coating material for a heat-resistant lubricating layer.
次に、実施例1で製造したインク塗布フィルムの、イ
ンク塗布面とは反対側の面に耐熱滑性層用コーティング
材をロールコーターで塗布し、積算光量が1500ミリジュ
ール/cm2になるように紫外線を照射し、膜厚0.8μmの
耐熱滑性層を有するインクリボンを得た。Next, a coating material for a heat-resistant lubricating layer is applied by a roll coater to the surface of the ink-coated film manufactured in Example 1 opposite to the ink-coated surface so that the integrated light amount becomes 1500 mJ / cm 2. Was irradiated with ultraviolet rays to obtain an ink ribbon having a heat-resistant lubricating layer having a thickness of 0.8 μm.
実施例3(耐熱滑性層付きインクリボン) 市販のシリコーン系コーティング材をトルエンで希釈
し、耐熱滑性層用コーティング材とした。実施例1で製
造したインク塗布フィルムの、インク塗布面とは反対側
の面に上記の耐熱滑性層用コーティング材をロールコー
ターで塗布し、90℃で10分間乾燥し、膜厚0.8μmの耐
熱滑性層を有するインクリボンを得た。Example 3 (Ink ribbon with heat-resistant lubricating layer) A commercially available silicone-based coating material was diluted with toluene to obtain a coating material for a heat-resistant lubricating layer. On the surface of the ink-coated film produced in Example 1 opposite to the ink-coated surface, the above-mentioned coating material for a heat-resistant lubricating layer was applied with a roll coater, dried at 90 ° C. for 10 minutes, and dried to a thickness of 0.8 μm. An ink ribbon having a heat-resistant lubricating layer was obtained.
比較例1及び2 市販のポリエステル製フィルム(膜厚5.8μm)に実
施例1と同様の操作により厚さ4μmのインク層を有す
るインク塗布フィルムを得た。Comparative Examples 1 and 2 An ink-coated film having a 4 μm thick ink layer was obtained on a commercially available polyester film (thickness: 5.8 μm) in the same manner as in Example 1.
次に、それぞれ実施例2及び実施例3に用いた耐熱滑
性層用コーティング材をそれぞれ同様の操作により塗布
し、膜厚0.8μmの耐熱滑性層を有するインクリボンを
得た。Next, the coating material for a heat-resistant lubricating layer used in Examples 2 and 3 was applied by the same operation, respectively, to obtain an ink ribbon having a heat-resistant lubricating layer having a thickness of 0.8 μm.
実施例2,3及び比較例1,2で得られたインクリボンの評
価結果を次表に示す。The evaluation results of the ink ribbons obtained in Examples 2 and 3 and Comparative Examples 1 and 2 are shown in the following table.
1) 密着性 耐熱滑性層塗布側にセロテープを貼り、強く引き剥が
した後、インクリボンベースフィルムへの耐熱滑性層の
付着状況を観察した。1) Adhesion A cellophane tape was adhered to the heat-resistant lubricating layer application side, and after strongly peeling off, the adhesion state of the heat-resistant lubricating layer to the ink ribbon base film was observed.
2) 走行性 試料をカセットに巻き取り、走行性,速度のぶれ,巻
き取り後のたるみの程度を評価した。2) Runnability The sample was wound into a cassette, and the runnability, fluctuation in speed, and the degree of sag after winding were evaluated.
3) 耐熱性 サーマルヘッドを用いて同一箇所を印殴し、基板フィ
ルムの状況を評価した。3) Heat resistance The same location was stamped and hit using a thermal head, and the condition of the substrate film was evaluated.
1000回以上:1000回の印殴により基板フィルムの劣化が
認められない。1000 times or more: No deterioration of the substrate film is observed by 1000 times of stamping.
500回以下:400〜500回の印殴により基板フィルムにし
わ、破れが認められる。500 or less: Wrinkles and tears are observed in the substrate film after 400 to 500 stampings.
〔発明の効果〕 以上の如く、本発明のインクリボンは、極めて高い耐
熱性を示すと共に、密着性,走行性などの性能において
も優れている。 [Effects of the Invention] As described above, the ink ribbon of the present invention exhibits extremely high heat resistance, and is also excellent in performance such as adhesion and running properties.
したがって、本発明のインクリボンは、ワードプロセ
ッサ,パーソナルコンピュータ等の各種情報機器,通信
機器などのプリンターのインクリボンとして有効に利用
されるものである。Therefore, the ink ribbon of the present invention is effectively used as an ink ribbon for printers such as various information devices such as word processors and personal computers, and communication devices.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 B29L 7:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location B29L 7:00
Claims (2)
タクチック構造を有するスチレン系重合体を延伸処理し
てなるフィルムを使用したことを特徴とするインクリボ
ン。1. An ink ribbon characterized in that a film obtained by stretching a styrene polymer having a syndiotactic structure is used as a base film.
二軸方向にそれぞれ1.5倍以上の延伸倍率で行ったフィ
ルムを使用した請求項1記載のインクリボン。2. The ink ribbon according to claim 1, wherein the film is subjected to a stretching treatment at a stretching ratio of at least two times in a uniaxial direction or at least 1.5 times in a biaxial direction.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63316169A JP2733078B2 (en) | 1988-12-16 | 1988-12-16 | ink ribbon |
US07/443,937 US5082717A (en) | 1988-12-16 | 1989-11-30 | Styrene-based resin composite material |
EP19890122644 EP0376021B1 (en) | 1988-12-16 | 1989-12-08 | Styrene-based resin composite material and use thereof |
DE1989626339 DE68926339T2 (en) | 1988-12-16 | 1989-12-08 | Styrene-based resin composite and its application |
CA002005675A CA2005675A1 (en) | 1988-12-16 | 1989-12-15 | Styrene-based resin composite material and use thereof |
KR1019890018847A KR940008350B1 (en) | 1988-12-16 | 1989-12-15 | Styrene-based resin composite material and use thereof |
US07/770,171 US5273830A (en) | 1988-12-16 | 1991-10-02 | Magnetic recording medium comprising a syndiotactic styrene-based polymer substrate, a magnetic layer and a backcoat lubricating layer each layer containing a curable phosphazine compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63316169A JP2733078B2 (en) | 1988-12-16 | 1988-12-16 | ink ribbon |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02162083A JPH02162083A (en) | 1990-06-21 |
JP2733078B2 true JP2733078B2 (en) | 1998-03-30 |
Family
ID=18074057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63316169A Expired - Lifetime JP2733078B2 (en) | 1988-12-16 | 1988-12-16 | ink ribbon |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2733078B2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
JP2012206346A (en) * | 2011-03-29 | 2012-10-25 | Dainippon Printing Co Ltd | Heat transfer sheet |
-
1988
- 1988-12-16 JP JP63316169A patent/JP2733078B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH02162083A (en) | 1990-06-21 |
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