JP2014034169A - Eraser - Google Patents
Eraser Download PDFInfo
- Publication number
- JP2014034169A JP2014034169A JP2012177420A JP2012177420A JP2014034169A JP 2014034169 A JP2014034169 A JP 2014034169A JP 2012177420 A JP2012177420 A JP 2012177420A JP 2012177420 A JP2012177420 A JP 2012177420A JP 2014034169 A JP2014034169 A JP 2014034169A
- Authority
- JP
- Japan
- Prior art keywords
- plasticizer
- dicarboxylic acid
- cyclohexane
- eraser
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004014 plasticizer Substances 0.000 claims abstract description 91
- -1 cyclohexanedicarboxylic acid ester Chemical class 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 abstract description 11
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 14
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 10
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 2
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- FTQQZEVRNWXZBS-UHFFFAOYSA-N bis(3-methylbutyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCOC(=O)C1CCCCC1C(=O)OCCC(C)C FTQQZEVRNWXZBS-UHFFFAOYSA-N 0.000 description 2
- NSRZVPYAJXTHBK-UHFFFAOYSA-N bis(5-methylhexyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCOC(=O)C1CCCCC1C(=O)OCCCCC(C)C NSRZVPYAJXTHBK-UHFFFAOYSA-N 0.000 description 2
- WZEFLOBFCQPVHR-UHFFFAOYSA-N bis(8-methylnonyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCC(C)C WZEFLOBFCQPVHR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000004806 diisononylester Substances 0.000 description 2
- GGLHXZYMYYBBHT-UHFFFAOYSA-N dinonyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCC GGLHXZYMYYBBHT-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000004064 dysfunction Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000001850 reproductive effect Effects 0.000 description 2
- 230000000241 respiratory effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 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 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 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
- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 description 2
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- FWQYPEXCXNSGSD-UHFFFAOYSA-N 2-(2,2-dimethylhexan-3-yloxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound C(C)(C)(C)C(CCC)OC(=O)C1C(CCCC1)C(=O)O FWQYPEXCXNSGSD-UHFFFAOYSA-N 0.000 description 1
- ZAKMYQRXQRPPAW-UHFFFAOYSA-N 2-(2-methylheptan-4-yloxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound C(CC)C(CC(C)C)OC(=O)C1C(CCCC1)C(=O)O ZAKMYQRXQRPPAW-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- LOWWBIJGJHWQPB-UHFFFAOYSA-N 2-dodecan-4-yloxycarbonylcyclohexane-1-carboxylic acid Chemical compound CCCCCCCCC(CCC)OC(=O)C1CCCCC1C(O)=O LOWWBIJGJHWQPB-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- PSEHGJUUOFMCNV-UHFFFAOYSA-N 2-heptadecan-4-yloxycarbonylcyclohexane-1-carboxylic acid Chemical compound CCCCCCCCCCCCCC(CCC)OC(=O)C1CCCCC1C(O)=O PSEHGJUUOFMCNV-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- UHAYHWBCVHYGFB-UHFFFAOYSA-N 2-tridecan-4-yloxycarbonylcyclohexane-1-carboxylic acid Chemical compound CCCCCCCCCC(CCC)OC(=O)C1CCCCC1C(O)=O UHAYHWBCVHYGFB-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ILYWGWPJRBBODC-UHFFFAOYSA-N bis(10-methylundecyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCC(C)C ILYWGWPJRBBODC-UHFFFAOYSA-N 0.000 description 1
- RYZDRFARYDZAKG-UHFFFAOYSA-N bis(16-methylheptadecyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCCCCCCCC(C)C RYZDRFARYDZAKG-UHFFFAOYSA-N 0.000 description 1
- RRDGKBOYQLLJSW-UHFFFAOYSA-N bis(2-ethylhexyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)CC2OC21 RRDGKBOYQLLJSW-UHFFFAOYSA-N 0.000 description 1
- QUKHPBOCBWDYMW-UHFFFAOYSA-N bis(2-methylpropyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)COC(=O)C1CCCCC1C(=O)OCC(C)C QUKHPBOCBWDYMW-UHFFFAOYSA-N 0.000 description 1
- OIDQOTHCTOVWOF-UHFFFAOYSA-N bis(6-methylheptyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1CCCCC1C(=O)OCCCCCC(C)C OIDQOTHCTOVWOF-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ANSWCYTXKAIJOK-UHFFFAOYSA-N dibutyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1CCCCC1C(=O)OCCCC ANSWCYTXKAIJOK-UHFFFAOYSA-N 0.000 description 1
- ITKVMAXLADRPIZ-UHFFFAOYSA-N didecyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCC ITKVMAXLADRPIZ-UHFFFAOYSA-N 0.000 description 1
- CZJVCYXDYKIZRK-UHFFFAOYSA-N diicosyl cyclohexane-1,2-dicarboxylate Chemical class CCCCCCCCCCCCCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCCCCCCCCCCCC CZJVCYXDYKIZRK-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- GVAAKRNEKNTVRW-UHFFFAOYSA-N dioctadecyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCCCCCCCCCC GVAAKRNEKNTVRW-UHFFFAOYSA-N 0.000 description 1
- FUXJJBJXVZIIMV-UHFFFAOYSA-N dioctyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCC FUXJJBJXVZIIMV-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- AYCHZURENQEYAC-UHFFFAOYSA-N ditert-butyl cyclohexane-1,2-dicarboxylate Chemical compound CC(C)(C)OC(=O)C1CCCCC1C(=O)OC(C)(C)C AYCHZURENQEYAC-UHFFFAOYSA-N 0.000 description 1
- OACQFHLGZUHNQE-UHFFFAOYSA-N diundecyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCCCCCC OACQFHLGZUHNQE-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([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
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100001081 no carcinogenicity Toxicity 0.000 description 1
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 210000002824 peroxisome Anatomy 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000281 testicular toxicity Toxicity 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、字消しに関し、更に詳しくは、消字率が高く、耐折れ性に優れ（すなわち、折れ難い）、可塑剤の耐移行性にも優れる（すなわち、可塑剤の移行量が少ない）、人体及び環境に対する負荷が少ない安全な字消しに関する。 The present invention relates to erasing, and more specifically, has a high erasing rate, excellent folding resistance (that is, difficult to break), and excellent plasticizer migration resistance (that is, a small amount of plasticizer is transferred). It relates to safe erasing with little impact on the human body and the environment.
字消し（通称、消しゴム）は、高い消字性を有することから、筆記具の消去に欠かせないものとして、広範に使用されている。字消しは、一般に基材樹脂に可塑剤及び充填剤を配合し、更に必要に応じて安定剤、着色料、香料等の字消し材料を適宜添加して混合攪拌した後、プレス成形、押出成形、射出成形などの成形方法により加熱、成形して製造されている。 Erasers (commonly known as erasers) are widely used as indispensable for erasing writing instruments because of their high erasability. Erasing is generally done by blending plasticizers and fillers into the base resin, and optionally adding eraser materials such as stabilizers, colorants, and fragrances, and mixing and stirring, followed by press molding and extrusion molding. It is manufactured by heating and molding by a molding method such as injection molding.
字消し用の基材樹脂としては、塩化ビニル樹脂、塩化ビニリデン樹脂、酢酸ビニル樹脂などが挙げられるが、基材樹脂の主流は、高い消字性を有することから、塩化ビニル樹脂である。 Examples of the erasing base resin include vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, and the like, but the mainstream of base resin is vinyl chloride resin because it has high erasability.
一方、可塑剤は、基材樹脂に柔軟性、耐久性、耐寒性、電気特性等を付与するために用いられているが、字消しにおいては、消字性の側面から、消字対象物質である黒鉛等に親和性のある可塑剤が多用されている。 On the other hand, plasticizers are used to impart flexibility, durability, cold resistance, electrical properties, etc. to the base resin. A plasticizer having an affinity for graphite or the like is frequently used.
可塑剤としては、従来フタル酸系のものが多用されていたが、近年、人体及び環境への影響を考慮し、プラスチック製品、特に玩具や食品用の包装容器などへの可塑剤の使用は控えられる傾向にある。字消しも例外ではなく、従来使用されてきた可塑剤の使用を抑制すべく、消字率など性能面では従来の可塑剤と同等もしくはそれ以上の性能を有し、かつ、人体、環境への影響の少ない、安全な可塑剤を用いた字消しが望まれている。 In the past, phthalic acid-based plasticizers have been widely used. However, in recent years, considering the impact on the human body and the environment, the use of plasticizers in plastic products, especially toys and food packaging containers, has been refrained. It tends to be. Erasing is no exception, and it has the same or better performance than conventional plasticizers in terms of performance such as the erasure rate, in order to suppress the use of plasticizers that have been used in the past, and to the human body and the environment. There is a need for erasure using a safe plasticizer with little impact.
例えば、ＢＡＳＦ社製の「Ｈｅｘａｍｏｌｌ（登録商標）ＤＩＮＣＨ」は、食品包装用フィルム、キャップ、王冠コルク、人工ワインコルク、パッキン、調理用手袋などの食品接触製品に使用され、ＥＦＳＡ承認、ＥＵ指令２００２／７２／ＥＣ、ドイツＢｆＲ（ドイツ連邦リスク評価研究所）−食品接触用途のプラスチックに関する勧告、ＪＨＰＡ（日本塩ビ食品衛生協議会）承認を受けている。 For example, “Hexamol (registered trademark) DINCH” manufactured by BASF is used for food contact products such as food packaging films, caps, crown corks, artificial wine corks, packing, cooking gloves, etc., and EFSA approval, EU directive 2002 / 72 / EC, German BfR (German Federal Risk Assessment Institute)-Recommendations on plastics for food contact applications, JHPA (Japan PVC Food Sanitation Council) approval.
医療では、呼吸器チューブ、カテーテル、呼吸マスクなどに使用され、生殖障害性なし、精巣毒性なし、生殖機能障害なし、催奇形性なし、内分泌撹乱作用なし、ペルオキシソーム増殖作用なし、発ガン性なし、環境的危険性なしとなっている。更に、玩具にあたる工作用粘土、人形、ベビー用品などにも使用され、ＥＵ指令２００５／８４／ＥＣ（改定２２版）：欧州、カリフォルニア、ブラジル（３歳以下の子供用玩具に適用）、理事会指令７６／７６９§ＥＮ７１−３ §ＥＮ７１−５ §ＥＮ７１−９、ＥＦＳＡ承認など安全性は高いことが確認されている。これに類似するシクロヘキサンポリカルボン酸及びその誘導体は、モノエステル、ジエステル、トリエステル、テトラエステルならびに無水エステルがあり、これらも安全性が高いという報告がされている。 In medicine, it is used for respiratory tubes, catheters, respiratory masks, etc., no reproductive dysfunction, no testicular toxicity, no reproductive dysfunction, no teratogenicity, no endocrine disrupting effect, no peroxisome proliferative effect, no carcinogenicity, There is no environmental danger. Furthermore, it is also used for clay, dolls, and baby goods for toys. EU Directive 2005/84 / EC (Revised 22nd edition): Europe, California, Brazil (applicable to children's toys under 3 years old), Board of Directors Directive 76/769 § EN71-3 § EN71-5 § EN71-9, EFSA approval, etc. have been confirmed to have high safety. Similar cyclohexane polycarboxylic acids and derivatives thereof include monoesters, diesters, triesters, tetraesters and anhydrous esters, which are reported to be highly safe.
特許文献１及び特許文献２には、ジイソノニルフタレートの水素添加によって得られる、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルをプラスチック製造のための可塑剤や、字消しの可塑剤として使用することが記載されている。そして、特許文献２には、シクロヘキサン−１，２−ジカルボン酸エステルは、ゲル化温度が高く、１４０℃でもペースト状のプラスチゾルの状態を維持しているので、塩化ビニル樹脂と可塑剤とがゲル化しない状態で均一になる利点を有しており、この可塑剤を塩化ビニル樹脂に配合した字消しは、消し屑のまとまり性に優れていることが記載されている。 Patent Document 1 and Patent Document 2 describe that cyclohexane-1,2-dicarboxylic acid diisononyl ester obtained by hydrogenation of diisononyl phthalate is used as a plasticizer for plastic production or as an eraser plasticizer. Has been. In Patent Document 2, cyclohexane-1,2-dicarboxylic acid ester has a high gelation temperature and maintains a paste-like plastisol state even at 140 ° C., so that a vinyl chloride resin and a plasticizer are gelled. It is described that the eraser in which this plasticizer is blended with a vinyl chloride resin is excellent in the sizing property.
しかしながら、可塑剤としてシクロヘキサン−１，２−ジカルボン酸エステルを単体で配合した字消しは、折れ易い欠点がある。 However, the eraser in which cyclohexane-1,2-dicarboxylic acid ester is blended alone as a plasticizer has a drawback that it easily breaks.
本発明は、消字率及び耐折れ性に優れ、更にはプラスチックに対する可塑剤の耐移行性に優れる、人体や環境に対する負荷が極めて少ない安全な字消しを提供することを課題とする。 An object of the present invention is to provide a safe erasure that is excellent in erasure rate and folding resistance, and further excellent in migration resistance of a plasticizer to a plastic and has a very low load on the human body and the environment.
上記課題を解決するため、本発明者は鋭意検討を行い、シクロヘキサンジカルボン酸エステルからなる可塑剤（Ａ）と、特定の可塑剤（Ｂ）とを併用することにより、上記目的を達成できることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventor has intensively studied and found that the above object can be achieved by using a plasticizer (A) comprising a cyclohexanedicarboxylic acid ester and a specific plasticizer (B) in combination. The present invention has been reached.
すなわち、本発明は、基材樹脂に、一般式（１）で表わされるシクロヘキサンジカルボン酸エステルからなる可塑剤（Ａ）と、ガラス転移点（Ｔｇ）が０℃以下の液状アクリルポリマー、ポリエステル系可塑剤から選ばれる少なくとも１種の可塑剤（Ｂ）とを配合してなることを特徴とする字消しを提供する。
［式中、Ｒ１、Ｒ２は互いに独立して、炭素数１〜２０のアルキル基を表す。］
That is, the present invention provides a base resin comprising a plasticizer (A) comprising a cyclohexanedicarboxylic acid ester represented by the general formula (1), a liquid acrylic polymer having a glass transition point (Tg) of 0 ° C. or lower, and a polyester plastic. There is provided an eraser characterized by comprising at least one plasticizer (B) selected from agents.
[In formula, R < 1 >, R < 2 > represents a C1-C20 alkyl group mutually independently. ]
本発明の字消しにおいては、可塑剤（Ｂ）の重量平均分子量が８００〜８，０００であることが好ましく、全可塑剤中に占める可塑剤（Ｂ）の割合が、５０質量％以下であることが好ましい。
ポリエステル系可塑剤としては、炭素数４〜１２の脂肪族ジカルボン酸の少なくとも１種と、多価アルコールの少なくとも１種と、一価アルコール又は一価カルボン酸から選ばれた少なくとも１種とを縮合して得られるポリエステル系可塑剤が好ましい。
In the eraser of the present invention, the weight average molecular weight of the plasticizer (B) is preferably 800 to 8,000, and the proportion of the plasticizer (B) in the total plasticizer is 50% by mass or less. It is preferable.
As a polyester plasticizer, at least one aliphatic dicarboxylic acid having 4 to 12 carbon atoms, at least one polyhydric alcohol and at least one selected from monohydric alcohol or monohydric carboxylic acid are condensed. Polyester plasticizers obtained in this way are preferred.
以上のとおり、本発明によれば、可塑剤として、シクロヘキサンジカルボン酸エステルと、液状アクリルポリマーやポリエステル系可塑剤とを配合することにより、消字率及び耐折れ性に優れるとともに、プラスチックに対する可塑剤の耐移行性に優れる字消しが提供される。また、本発明の字消しは、人体、環境に対する負荷が極めて少なく、安全性が高く、耐環境汚染性に優れるものである。 As described above, according to the present invention, by adding a cyclohexanedicarboxylic acid ester and a liquid acrylic polymer or polyester plasticizer as a plasticizer, the plasticizer for plastic is excellent in erasure rate and folding resistance. An eraser with excellent resistance to migration is provided. Further, the eraser of the present invention has very little burden on the human body and the environment, has high safety, and is excellent in resistance to environmental pollution.
本発明の字消しに用いられる基材樹脂としては、塩化ビニル系樹脂、酢酸ビニル系樹脂、エチレン−酢酸ビニル共重合樹脂、アクリル酸エステル系樹脂、ポリイソプレン（天然ゴム）、スチレン系、ブタジエン系、イソプレン系、エチレン−プロピレン系、ニトリル系、クロロプレン系、ウレタン系、アクリル系、ポリエステル系、オレフィン系のエラストマー等が挙げられる。これらの基材樹脂は単独で、又は必要に応じて２種類以上組み合わせて用いられる。これらの樹脂の中でも、可塑剤との混和が容易で消字力に優れる塩化ビニル系樹脂が特に好ましい。 The base resin used for the eraser of the present invention includes vinyl chloride resin, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, acrylic ester resin, polyisoprene (natural rubber), styrene, butadiene , Isoprene-based, ethylene-propylene-based, nitrile-based, chloroprene-based, urethane-based, acrylic-based, polyester-based, and olefin-based elastomers. These base resins are used alone or in combination of two or more as required. Among these resins, a vinyl chloride resin that is easily mixed with a plasticizer and excellent in erasing power is particularly preferable.
塩化ビニル系樹脂としては、従来用いられている塩化ビニル系樹脂を全て用いることができ、例えば、重合度４００〜３，０００程度のポリ塩化ビニルの他、塩化ビニル−酢酸ビニル共重合体、塩化ビニリデン、塩化ビニル−アクリル酸メチル共重合体、塩化ビニル−メタクリル酸メチル共重合体、及び塩化ビニル−アクリル酸オクチル共重合体が挙げられる。これらは単独で又は必要に応じて２種類以上組み合わせて用いられる。塩化ビニル系樹脂としてはペーストレジンが可塑剤等との混和、加工が容易な点で好ましい。 As the vinyl chloride resin, all conventionally used vinyl chloride resins can be used. For example, in addition to polyvinyl chloride having a polymerization degree of about 400 to 3,000, a vinyl chloride-vinyl acetate copolymer, chloride Examples include vinylidene, vinyl chloride-methyl acrylate copolymer, vinyl chloride-methyl methacrylate copolymer, and vinyl chloride-octyl acrylate copolymer. These may be used alone or in combination of two or more as required. As the vinyl chloride resin, a paste resin is preferable because it can be easily mixed and processed with a plasticizer.
本発明において、可塑剤（Ａ）として用いられるシクロヘキサンジカルボン酸エステルは、下記式（１）で表わされる。
［式中、Ｒ１、Ｒ２は互いに独立して、炭素数１〜２０のアルキル基を表す。］
In the present invention, the cyclohexanedicarboxylic acid ester used as the plasticizer (A) is represented by the following formula (1).
[In formula, R < 1 >, R < 2 > represents a C1-C20 alkyl group mutually independently. ]
Ｒ１、Ｒ２は、同じ又は異なっていてよい。Ｒ１、Ｒ２は、直鎖又は分岐鎖である炭素数１〜２０のアルキル基、好ましくは炭素数３〜１８のアルキル基、特に好ましくは炭素数７〜１３のアルキル基である。このようなアルキル基としては、例えば、メチル、エチル、ｎ−プロピル、イソ−プロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−オクチル及び２−エチルヘキシル、ｎ−ノニル、イソ−ノニル、ｎ−デシル、イソ−デシル、ｎ−ウンデシル、イソ−ウンデシル、ｎ−ドデシル、イソ−ドデシル、ｎ−トリデシル、イソ−トリデシル、ステアリル及びｎ−エイコシル等が挙げられる。Ｒ１、Ｒ２は、シクロアルキル基、アルコキシアルキル基であってもよい。 R 1 and R 2 may be the same or different. R 1 and R 2 are linear or branched alkyl groups having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 18 carbon atoms, and particularly preferably an alkyl group having 7 to 13 carbon atoms. Examples of such an alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tridecyl, stearyl and n-eicosyl, etc. Is mentioned. R 1 and R 2 may be a cycloalkyl group or an alkoxyalkyl group.
シクロヘキサンジカルボン酸エステルは、シクロヘキサンジカルボン酸のジエステルである。シクロヘキサンジカルボン酸エステルは、アルキル基が異なる２以上のエステルからなる混合物であってよく、アルキル基の異なるアルコールとシクロヘキサンジカルボン酸との混合エステルであってもよい。また、シクロヘキサンジカルボン酸エステルには、本発明による効果を阻害しない範囲で、無水物等が含まれていてもよい。 Cyclohexane dicarboxylic acid ester is a diester of cyclohexane dicarboxylic acid. The cyclohexanedicarboxylic acid ester may be a mixture of two or more esters having different alkyl groups, or may be a mixed ester of an alcohol having different alkyl groups and cyclohexanedicarboxylic acid. Further, the cyclohexanedicarboxylic acid ester may contain an anhydride or the like as long as the effects of the present invention are not impaired.
シクロヘキサンジカルボン酸エステルは、シクロヘキサン−１，２−ジカルボン酸エステル、シクロヘキサン−１，３−ジカルボン酸エステル及びシクロヘキサン−１，４−ジカルボン酸エステルである。本発明では、シクロヘキサン−１，２−ジカルボン酸エステルが好ましい。 Cyclohexane dicarboxylic acid esters are cyclohexane-1,2-dicarboxylic acid ester, cyclohexane-1,3-dicarboxylic acid ester and cyclohexane-1,4-dicarboxylic acid ester. In the present invention, cyclohexane-1,2-dicarboxylic acid ester is preferable.
シクロヘキサン−１，２−ジカルボン酸エステルの具体例としては、例えば、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｔｅｒｔ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソブチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソペンチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソヘプチルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−オクチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソオクチルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−２−エチルヘキシルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−ノニルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−デシルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソデシルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−ウンデシルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソドデシルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−オクタデシルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソオクタデシルエステル、シクロヘキサン−１，２−ジカルボン酸ジ−ｎ−エイコシルエステル等のエステル；シクロヘキサン−１，２−ジカルボン酸−ｔｅｒｔ−ブチル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸イソブチル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸−ｎ−ヘキシル−ｎ―ブチルエステル、シクロヘキサン−１，２−ジカルボン酸−ｎ−オクチル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸−ｎ−ノニル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸イソノニル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸イソドデシル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸−ｎ−トリデシル−ｎ−ブチルエステル、シクロヘキサン−１，２−ジカルボン酸イソトリデシル−ｎ−ブチルエステル等の混合エステルが挙げられる。 Specific examples of the cyclohexane-1,2-dicarboxylic acid ester include, for example, cyclohexane-1,2-dicarboxylic acid di-n-butyl ester, cyclohexane-1,2-dicarboxylic acid di-tert-butyl ester, cyclohexane-1 , 2-dicarboxylic acid diisobutyl ester, cyclohexane-1,2-dicarboxylic acid diisopentyl ester, cyclohexane-1,2-dicarboxylic acid diisoheptyl ester, cyclohexane-1,2-dicarboxylic acid di-n-octyl ester, cyclohexane -1,2-dicarboxylic acid diisooctyl ester, cyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl ester, cyclohexane-1,2-dicarboxylic acid di-n-nonyl ester, cyclohexane-1,2-dicarboxylic acid Diiso Nyl ester, cyclohexane-1,2-dicarboxylic acid di-n-decyl ester, cyclohexane-1,2-dicarboxylic acid diisodecyl ester, cyclohexane-1,2-dicarboxylic acid di-n-undecyl ester, cyclohexane-1,2- Dicarboxylic acid diisododecyl ester, cyclohexane-1,2-dicarboxylic acid di-n-octadecyl ester, cyclohexane-1,2-dicarboxylic acid diisooctadecyl ester, cyclohexane-1,2-dicarboxylic acid di-n-eicosyl ester Esters such as: cyclohexane-1,2-dicarboxylic acid-tert-butyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid isobutyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid-n-hexyl- n-bu Ester, cyclohexane-1,2-dicarboxylic acid-n-octyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid-n-nonyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid isononyl-n- Butyl ester, cyclohexane-1,2-dicarboxylic acid isododecyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid-n-tridecyl-n-butyl ester, cyclohexane-1,2-dicarboxylic acid isotridecyl-n-butyl ester And mixed esters.
シクロヘキサン−１，４−ジカルボン酸エステル、シクロヘキサン−１，３−ジカルボン酸エステルの場合も、シクロヘキサン−１，２−ジカルボン酸エステルと同様のアルキル基を有するエステル、ならびに混合エステルを挙げることができる。 In the case of cyclohexane-1,4-dicarboxylic acid ester and cyclohexane-1,3-dicarboxylic acid ester, esters having the same alkyl group as cyclohexane-1,2-dicarboxylic acid ester, and mixed esters can be exemplified.
上記のシクロヘキサンジカルボン酸エステルの中でも、Ｒ１、Ｒ２が、炭素数７〜１３のアルキル基であるのが好ましく、例えば、シクロヘキサン−１，２−ジカルボン酸ジイソペンチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソヘプチルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステル、シクロヘキサン−１，２−ジカルボン酸ジノニルエステル、シクロヘキサン−１，２−ジカルボン酸ジイソデシルエステル、シクロヘキサン−１，２−ジカルボン酸のジ（Ｃ７−１１）アルキルエステル、シクロヘキサン−１，２−ジカルボン酸のジ（Ｃ９−１１）アルキルエステル、シクロヘキサン−１，２−ジカルボン酸のジ（Ｃ７−９）アルキルエステル、シクロヘキサン−１，２−ジカルボン酸のジ（Ｃ８−１３）アルキルエステル等である。市販品としては、ＢＡＳＦ社製の「Ｈｅｘａｍｏｌｌ（登録商標）ＤＩＮＣＨ」が挙げられる。 Among the above cyclohexane dicarboxylic acid esters, R 1 and R 2 are preferably an alkyl group having 7 to 13 carbon atoms. For example, cyclohexane-1,2-dicarboxylic acid diisopentyl ester, cyclohexane-1,2 -Dicarboxylic acid diisoheptyl ester, cyclohexane-1,2-dicarboxylic acid diisononyl ester, cyclohexane-1,2-dicarboxylic acid dinonyl ester, cyclohexane-1,2-dicarboxylic acid diisodecyl ester, cyclohexane-1,2-dicarboxylic acid Di (C7-11) alkyl ester of dicyclohexane-1,2-dicarboxylic acid, di (C9-11) alkyl ester of cyclohexane-1,2-dicarboxylic acid, cyclohexane-1, 2-dicarboxylic acid di ( 8-13) alkyl esters. Commercially available products include “Hexamol (registered trademark) DINCH” manufactured by BASF.
また、本発明において、可塑剤（Ｂ）は、ガラス転移点（Ｔｇ）が０℃以下の液状アクリルポリマー、ポリエステル系可塑剤から選ばれる少なくとも１種の可塑剤である。ガラス転移点（Ｔｇ）は、ＤＳＣ法によって測定される。 In the present invention, the plasticizer (B) is at least one plasticizer selected from a liquid acrylic polymer having a glass transition point (Tg) of 0 ° C. or lower and a polyester plasticizer. The glass transition point (Tg) is measured by the DSC method.
可塑剤（Ｂ）は、基材樹脂との相溶性に優れており、可塑剤（Ａ）とともに配合して成形することにより、字消しの消字率を阻害することなく、可塑剤の耐移行性において優れた性能を示す傾向が見られるようになり、加えて字消しの強度と耐折れ性が向上する。可塑剤（Ｂ）は、重量平均分子量が８００〜８，０００であることが好ましく、重量平均分子量が８００以下では、効果が発現し難くなり、８，０００以上では、ハンドリングに難が生じる。重量平均分子量は８００〜６，０００がより好ましく、８００〜３，０００が特に好ましい。 The plasticizer (B) is excellent in compatibility with the base resin. By blending and molding with the plasticizer (A), the plasticizer (B) is resistant to migration without inhibiting the erasing rate. As a result, a tendency to show excellent performance is observed, and in addition, the erasing strength and folding resistance are improved. The plasticizer (B) preferably has a weight average molecular weight of 800 to 8,000. When the weight average molecular weight is 800 or less, the effect is hardly exhibited, and when it is 8,000 or more, handling is difficult. The weight average molecular weight is more preferably 800 to 6,000, and particularly preferably 800 to 3,000.
可塑剤（Ｂ）の粘度は特に限定されるものではないが、液状アクリルポリマーの場合は３００〜２２，０００（ｍＰａ・ｓ／２５℃）であることが好ましく、より好ましくは３００〜５，０００、特に好ましくは３００〜２，０００である。ポリエステル系可塑剤の場合は２２０〜１７，０００（ｍＰａ・ｓ／２５℃）であることが好ましく、より好ましくは２２０〜３，０００、特に好ましくは２２０〜１，０００である。可塑剤（Ｂ）の粘度が高すぎると、混練攪拌時におけるハンドリング性が低下し、成形もし難くなる。 The viscosity of the plasticizer (B) is not particularly limited, but in the case of a liquid acrylic polymer, it is preferably 300 to 22,000 (mPa · s / 25 ° C.), more preferably 300 to 5,000. Particularly preferred is 300 to 2,000. In the case of a polyester plasticizer, it is preferably 220 to 17,000 (mPa · s / 25 ° C.), more preferably 220 to 3,000, and particularly preferably 220 to 1,000. When the viscosity of the plasticizer (B) is too high, the handling property at the time of kneading and stirring is lowered, and molding becomes difficult.
液状アクリルポリマーはガラス転移点（Ｔｇ）が低い程、混練攪拌時のハンドリング、及び字消しの成形が容易であるため、−３０℃以下程度のものが特に好ましい。液状アクリルポリマーとしては、具体的には、ＡＲＵＦＯＮ ＵＰ−１０００、ＵＰ−１０１０、ＵＰ−１０２０、ＵＰ−１０２１、ＵＰ−１０６１、ＵＰ−１０８０、ＵＰ−１１１０、ＵＰ−１１７０、ＵＰ−１１９０（以上いずれも商品名、東亞合成(株)）等が挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。 As the liquid acrylic polymer has a lower glass transition point (Tg), the handling at the time of kneading and stirring and the forming of the eraser are easier. Specific examples of the liquid acrylic polymer include ARUFUON UP-1000, UP-1010, UP-1020, UP-1021, UP-1061, UP-1080, UP-1110, UP-1170, UP-1190 Product name, Toagosei Co., Ltd.) and the like. These may be used alone or in combination of two or more as required.
ポリエステル系可塑剤は、炭素数４〜１２の脂肪族ジカルボン酸の少なくとも１種と、多価アルコールの少なくとも１種と、一価アルコール又は一価カルボン酸から選ばれた少なくとも１種とを縮合して得られるポリエステル系可塑剤が好ましい。かかる脂肪族ジカルボン酸としては、例えば、コハク酸、マレイン酸、フマル酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸等が挙げられ、１種又は２種以上が使用される。 The polyester plasticizer condenses at least one kind of aliphatic dicarboxylic acid having 4 to 12 carbon atoms, at least one kind of polyhydric alcohol, and at least one kind selected from monohydric alcohol or monovalent carboxylic acid. Polyester plasticizers obtained are preferred. Examples of such aliphatic dicarboxylic acids include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid, and one or more are used.
多価アルコールとしては、例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，２−ブタンジオール、１，３−ブタンジオール、２−メチル−１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、２，２−ジメチル−１，３−プロパンジオール、２，２−ジエチル−１，３−プロパンジオール、２−ｎ−ブチル−２−エチル−１，３−プロパンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２−メチル−１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、１，１２−オクタデカンジオール等の炭素数２〜１８の脂肪族グリコールならびにジエチレングリコール、ジプロピレングリコール等のポリアルキレングリコールが挙げられる。これらの多価アルコールは、１種又は２種以上の混合物が使用される。 Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl- 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol , 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc. Number 2-18 aliphatic glycols and diethylene glycol, include polyalkylene glycols such as dipropylene glycol. These polyhydric alcohols are used singly or as a mixture of two or more.
一価アルコールとしては、例えば、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ヘキサデカノール、オクタデカノール等の炭素９〜１８の一価アルコールが挙げられ、１種又は２種以上の混合物が使用される。一価カルボン酸としては、例えば、ノナン酸、カプリン酸、ウンデシル酸、ラウリン酸等の炭素数９〜１８のカルボン酸が挙げられ、１種又は２種以上の混合物が使用される。ポリエステル系可塑剤は、３価又はそれ以上の多価アルコール及び多塩基酸を変性剤として使用したものでもよい。 Examples of monohydric alcohols include monohydric alcohols of carbon 9-18 such as nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol, etc., one or more kinds A mixture is used. As monovalent carboxylic acid, C9-C18 carboxylic acids, such as nonanoic acid, capric acid, undecyl acid, lauric acid, are mentioned, for example, 1 type, or 2 or more types of mixtures are used. The polyester plasticizer may use a trivalent or higher polyhydric alcohol and a polybasic acid as a modifier.
ポリエステル系可塑剤としては、具体的には、アデカサイザーＰＮ−９３０２、ＰＮ−１５０、ＰＮ−１７０、ＰＮ−２３０、ＰＮ−１０１０、ＰＮ−１０２０、Ｐ−２００、ＰＮ−８５０、ＰＮ−２６０、ＰＮ−６５０、ＰＮ−１０３０、ＰＮ−１４３０、ＰＮ−３０３０、ＨＰＮ−３１３０、ＰＮ−４００、Ｐ−５０４０、ＰＮ−２２０、ＰＮ−２５０、ＰＮ−４４６、ＰＮ−３１０、Ｐ−３００、ＰＮ−２８０、ＰＮ−３５０、ＰＮ−７１６０、ＰＮ−７２３０、ＰＮ−７６５０、ＰＮ−７５５０、ＰＮ−７３１０（以上いずれも商品名、(株)ＡＤＥＫＡ）、ポリサイザーＷ−２３０−ＥＬ、Ｗ−１０２０−ＥＬ、Ｗ−１４１０−ＥＬ、Ｗ−１６４１−Ｓ、Ｗ−２３００−ＥＬ、Ｗ−２３４０−Ｓ、Ｗ−２６４０−Ｓ、Ｗ−４０１０（以上いずれも商品名、ＤＩＣ(株)）等が挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。 Specific examples of polyester plasticizers include Adekasizer PN-9302, PN-150, PN-170, PN-230, PN-1010, PN-1020, P-200, PN-850, PN-260, PN-650, PN-1030, PN-1430, PN-3030, HPN-3130, PN-400, P-5040, PN-220, PN-250, PN-446, PN-310, P-300, PN- 280, PN-350, PN-7160, PN-7230, PN-7650, PN-7550, PN-7310 (all are trade names, ADEKA Corporation), Polycizer W-230-EL, W-1020-EL , W-1410-EL, W-1641-S, W-2300-EL, W-2340-S, W-2640-S, W-4010 ( Above all trade names, DIC (Ltd.)), and the like. These may be used alone or in combination of two or more as required.
本発明の字消しにおける可塑剤（Ａ）及び可塑剤（Ｂ）の配合量は、基材樹脂１００質量部に対し、合計で８０〜２００質量部とすることが好ましく、より好ましくは１００〜１８０質量部である。可塑剤の配合量が８０質量部以上であれば、字消しが硬くなりすぎることで消字率が低下するおそれがなく、一方２００質量部以下であれば、字消しが柔らかくなりすぎることで良好な字消し性能が発現しなくなるおそれがない。 The blending amount of the plasticizer (A) and the plasticizer (B) in the eraser of the present invention is preferably 80 to 200 parts by mass in total with respect to 100 parts by mass of the base resin, more preferably 100 to 180 parts. Part by mass. If the blending amount of the plasticizer is 80 parts by mass or more, there is no fear that the erasing rate will decrease because the erasing becomes too hard, whereas if it is 200 parts by mass or less, the erasing becomes too soft and good. There is no risk of erasing performance disappearing.
また、可塑剤（Ａ）と可塑剤（Ｂ）の割合（質量比）は、９９／１〜１／９９の範囲であれば良いが、より好ましくは９９／１〜５０／５０の範囲、さらに好ましくは、８５／１５〜５０／５０の範囲である。可塑剤（Ｂ）の割合を１５以上とすることにより、耐折れ性及び耐可塑剤移行性に優れる字消しとなり、５０以下とすることにより、可塑剤（Ａ）が本来有している消字率を低下させることなく、耐折れ性に優れる字消しを得ることができ、また字消しの成形も容易となる。これらの特性が発現する理由は明らかではないが、シクロヘキサンジカルボン酸エステルは基材樹脂との相溶性がやや劣るが、可塑剤（Ｂ）を併用することにより、可塑剤と基材樹脂との親和性が高まるものと推察される。字消しの成形性を考慮すると、全可塑剤中の可塑剤（Ｂ）の割合は５０質量％以下とすることが好ましく、可塑剤（Ａ）及び可塑剤（Ｂ）に他の可塑剤を配合した場合も同様である。 Further, the ratio (mass ratio) of the plasticizer (A) and the plasticizer (B) may be in the range of 99/1 to 1/99, more preferably in the range of 99/1 to 50/50, Preferably, it is in the range of 85/15 to 50/50. By setting the ratio of the plasticizer (B) to 15 or more, the eraser has excellent folding resistance and plasticizer migration, and by setting it to 50 or less, the eraser originally possessed by the plasticizer (A). It is possible to obtain an eraser with excellent folding resistance without reducing the rate, and it becomes easy to form the eraser. The reason why these properties are manifested is not clear, but cyclohexanedicarboxylic acid ester is slightly incompatible with the base resin, but by using the plasticizer (B) in combination, the affinity between the plasticizer and the base resin It is presumed that the nature will increase. Considering the formability of the eraser, the proportion of the plasticizer (B) in the total plasticizer is preferably 50% by mass or less, and other plasticizers are added to the plasticizer (A) and the plasticizer (B). The same applies to the case.
上記の可塑剤（Ａ）及び可塑剤（Ｂ）には、本発明の効果を阻害しない範囲で、他の可塑剤を配合することもできる。他の可塑剤の配合量は、基材樹脂１００質量部に対し、０〜６０質量部であることが好ましい。
配合する可塑剤としては、例えば、トリ−２−エチルヘキシルトリメリテート（ＴＯＴＭ）、トリイソデシルトリメリテート（ＴＩＤＴＭ）、トリイソオクチルトリメリテート（ＴＩＯＴＭ）、トリイソノニルトリメリテート等のトリメリット酸系可塑剤；トリオクチルピロメリット酸（ＴＯＰＭ）等のピロメリット酸系可塑剤；ジ−２−エチルヘキシルアジペート（ＤＯＡ）、ジイソノニルアジペート（ＤＩＮＡ）、ジイソデシルアジペート（ＤＩＤＡ）等のアジピン酸系可塑剤；ジ−２−エチルヘキシルセバケート（ＤＯＳ）、ジブチルセバケート（ＤＢＳ）等のセバシン酸系可塑剤；ジ−２−エチルヘキシルアゼレート（ＤＯＺ）等のアゼライン酸系可塑剤；トリクレジルフォスフェート（ＴＣＰ）、トリ−２−エチルヘキシルフォスフェート（ＴＯＰ）等のリン酸系可塑剤；トリエチルシトレート、アセチルトリ−ｎ−ブチルシトレート、トリ−ｎ−ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ−（２−エチルヘキシル）シトレート等のクエン酸系可塑剤；エポキシ化トリグリセリド、エポキシ化脂肪酸モノエステル、エポキシ化大豆油、エポキシ化アマニ油、エポキシ化脂肪酸エステル、エポキシヘキサヒドロフタル酸ジ−２−エチルヘキシル（Ｅ−ＰＳ）、エポキシヘキサヒドロフタル酸ジ−ｎ−オクチル（ｎＥ−ＰＳ）、エポキシヘキサヒドロフタル酸ジエポキシステアリル（Ｅ−ＰＯ）等のエポキシヘキサヒドロフタル酸エステル等のエポキシ系可塑剤；が挙げられる。これらは単独で又は必要に応じ２種以上組み合わせて用いられる。
Other plasticizers can be added to the plasticizer (A) and the plasticizer (B) as long as the effects of the present invention are not impaired. It is preferable that the compounding quantity of another plasticizer is 0-60 mass parts with respect to 100 mass parts of base resin.
Examples of the plasticizer to be blended include tri-2-ethylhexyl trimellitate (TOTM), triisodecyl trimellitate (TIDTM), triisooctyl trimellitate (TIOTM), and triisononyl trimellitate. Mellitic acid plasticizer; pyromellitic acid plasticizer such as trioctyl pyromellitic acid (TOPM); adipic acid plasticizer such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA) Agents; sebacic acid plasticizers such as di-2-ethylhexyl sebacate (DOS) and dibutyl sebacate (DBS); azelaic acid plasticizers such as di-2-ethylhexyl azelate (DOZ); tricresyl phosphate (TCP), tri-2-ethylhexylphos Phosphate plasticizers such as phosphate (TOP); citrates such as triethyl citrate, acetyl tri-n-butyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate Acid plasticizers: epoxidized triglycerides, epoxidized fatty acid monoesters, epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid esters, epoxy hexahydrophthalate di-2-ethylhexyl (E-PS), epoxy hexahydrophthalate And epoxy plasticizers such as epoxy hexahydrophthalate such as di-n-octyl acid (nE-PS) and diepoxy stearyl (E-PO) of epoxy hexahydrophthalate. These may be used alone or in combination of two or more as required.
本発明の可塑剤をゴム及びエラストマーに配合する場合には、石油系油、液状ゴム、液状オリゴマー等の軟化剤を併用することもできる。石油系油としては、パラフィン系炭化水素油、ナフテン系炭化水素油、芳香族系炭化水素油の混合物であるエクステンダーオイルや、プロセス油、スピンドル油、マシン油、流動パラフィン、塩素化パラフィン等が挙げられる。液状ゴムとしては、液状ポリブタジエン、液状ポリイソプレン等が挙げられる。液状オリゴマーとしては、液状ポリブテン、液状α−オレフィンオリゴマー等が挙げられる。軟化剤の配合量は特に限定されないが、基材樹脂１００質量部に対し、３０〜３００質量部であることが好ましい。 When the plasticizer of the present invention is blended with rubber and elastomer, softening agents such as petroleum oil, liquid rubber, and liquid oligomer can be used in combination. Examples of petroleum oils include extender oil, which is a mixture of paraffinic hydrocarbon oil, naphthenic hydrocarbon oil, and aromatic hydrocarbon oil, process oil, spindle oil, machine oil, liquid paraffin, and chlorinated paraffin. It is done. Examples of the liquid rubber include liquid polybutadiene and liquid polyisoprene. Examples of the liquid oligomer include liquid polybutene and liquid α-olefin oligomer. Although the compounding quantity of a softening agent is not specifically limited, It is preferable that it is 30-300 mass parts with respect to 100 mass parts of base resin.
本発明の字消しには、硬度や使用時の消去感を調整するために充填剤を配合することもできる。充填剤としては、珪石粉あるいは石灰石粉（重質炭酸カルシウム）を用いるのが一般的であり、これらの無機粉体は、筆記面を痛めないように微粉化して用いられる。他に珪藻土、タルクあるいはシラス粉末、酸化珪素の微粉末であるアエロジル、無機及び有機の中空粒子等を使用することができる。これらの充填剤を配合する場合の配合量は、基材樹脂によって異なるが、基材樹脂１００質量部に対して、３０〜３００質量部であることが好ましい。 In the eraser of the present invention, a filler can be blended in order to adjust the hardness and erasure feeling during use. As the filler, silica stone powder or limestone powder (heavy calcium carbonate) is generally used, and these inorganic powders are used after being finely divided so as not to damage the writing surface. In addition, diatomaceous earth, talc or shirasu powder, aerosil which is a fine powder of silicon oxide, inorganic and organic hollow particles, and the like can be used. Although the compounding quantity in the case of mix | blending these fillers changes with base resin, it is preferable that it is 30-300 mass parts with respect to 100 mass parts of base resin.
また、必要に応じて基材樹脂、特に塩化ビニル系樹脂の成形時による高温劣化防止のため、安定剤を用いる。光安定性向上のため、紫外線吸収剤等の光安定剤を配合することもできる。その他、粘度調整剤、滑剤、溶剤、着色剤、防腐剤、防黴剤、香料等の添加剤を含有することもできる。これらの添加剤は、本発明による効果を阻害しない範囲内であれば、配合量も特に制限されない。 Further, if necessary, a stabilizer is used in order to prevent high temperature deterioration due to molding of the base resin, particularly vinyl chloride resin. In order to improve the light stability, a light stabilizer such as an ultraviolet absorber can be blended. In addition, additives such as viscosity modifiers, lubricants, solvents, colorants, preservatives, antifungal agents, and fragrances can also be contained. The amount of these additives is not particularly limited as long as the effects of the present invention are not impaired.
以下、実施例及び比較例を用いて本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example and a comparative example, this invention is not limited to a following example.
以下の実施例及び比較例で用いた材料を表１に示す。以下の記載において、「部」は特に断らない限り「質量部」を表す。 The materials used in the following examples and comparative examples are shown in Table 1. In the following description, “part” means “part by mass” unless otherwise specified.
また、以下の実施例、比較例において、得られた字消しの消字率及び移行性は、下記の方法により測定又は評価した。 In the following examples and comparative examples, the erasure rate and transferability of the obtained erasure were measured or evaluated by the following methods.
［消字率の測定方法（ＪＩＳ法）］：
ＪＩＳ Ｓ ６０５０：２００２ ６．４に準拠した。
（１）字消しを厚さ５ｍｍの板状に切り、着色紙と接触する先端部分を半径６ｍｍの円弧に仕上げたものを試験片とした。
（２）画線機を用いて、ＪＩＳ Ｓ ６００６に規定する鉛筆のＨＢと、坪量９０ｇ／ｍ２以上、白色度７５％以上の上質紙を使用して着色紙を作成し、この着色紙に対して、試験片を垂直に、しかも着色線に対して直角になるように接触させ、試験片におもりとホルダの質量の和が０．５ｋｇとなるようにおもりを載せ、１５０±１０ｃｍ／ｍｉｎの速さで着色部を４往復摩消させた。
（３）濃度計によって、着色紙の非着色部分の濃度を０として、着色部及び摩消部の濃度をそれぞれ測定した。
（４）消字率は次の式によって算出し、３回の平均値を求めた。
消字率（％）＝（１−（摩消部の濃度÷着色部の濃度））×１００
[Measurement method of erasure rate (JIS method)]:
Conforms to JIS S 6050: 2002 6.4.
(1) The test piece was prepared by cutting the eraser into a plate having a thickness of 5 mm and finishing the tip portion in contact with the colored paper into an arc having a radius of 6 mm.
(2) Using a drawing machine, create colored paper using pencil HB specified in JIS S 6006 and fine paper with a basis weight of 90 g / m 2 or more and whiteness of 75% or more. The test piece is brought into contact with the test piece perpendicularly and at a right angle to the colored line, and a weight is placed on the test piece so that the sum of the weight of the weight and the holder is 0.5 kg. The colored part was brushed back and forth 4 times at a speed of min.
(3) Using a densitometer, the density of the non-colored part of the colored paper was set to 0, and the density of the colored part and the wear part was measured.
(4) The erasure rate was calculated by the following formula, and the average value of three times was obtained.
Erase rate (%) = (1− (density of wear part ÷ density of colored part)) × 100
［移行性の評価方法］：
字消しをプラスチックの板に挟み、６０±２℃の恒温器の中に入れ、２４時間後に取り出し、可塑剤が試験片に付着した量を測定した。
[Evaluation method for migration]:
The eraser was sandwiched between plastic plates, placed in a 60 ± 2 ° C. incubator, taken out after 24 hours, and the amount of plasticizer adhered to the test piece was measured.
［折れ試験］
字消しを片手で把持し折り曲げた際に、折れるまでに要した回数を測定した。
[Bending test]
When the eraser was held and folded with one hand, the number of times required to fold was measured.
（実施例１〜６、比較例１〜３）
表２に示す配合割合（数字は質量部）で配合した組成物を減圧下にて攪拌した後、１３０〜１５０℃で成形して、字消しを作成した。各字消しについて消字率及び移行性を上記方法で測定した結果を表２に示す。
(Examples 1-6, Comparative Examples 1-3)
After stirring the composition mix | blended by the compounding ratio (a number is a mass part) shown in Table 2 under reduced pressure, it shape | molded at 130-150 degreeC, and created the eraser. Table 2 shows the results of measuring the erasure rate and transferability of each erasure by the above method.
表２より、鉛筆で作成した画線に対する消字率に関して、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単独で用いた場合と、ほぼ同等の結果が得られた。 From Table 2, with respect to the erasure rate with respect to the image line created with a pencil, almost the same result as that obtained when cyclohexane-1,2-dicarboxylic acid diisononyl ester was used alone was obtained.
可塑剤の移行量に関しては、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単独で用いるよりも、液状アクリルポリマーを併用することによって減少した。 The amount of plasticizer transferred was reduced by using the liquid acrylic polymer in combination rather than using cyclohexane-1,2-dicarboxylic acid diisononyl ester alone.
また、液状アクリルポリマーとシクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを併用することにより、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単体で配合した場合に比べて、耐折れ性が向上したが、液状アクリルポリマーの割合を多くすると可塑化に必要な温度が高くなり、成形できないものが生じた。 In addition, the combined use of the liquid acrylic polymer and cyclohexane-1,2-dicarboxylic acid diisononyl ester improved the folding resistance compared to the case where cyclohexane-1,2-dicarboxylic acid diisononyl ester was blended alone, When the ratio of the liquid acrylic polymer was increased, the temperature required for plasticization was increased, resulting in some that could not be molded.
一方、液状アクリルポリマーの替わりにアジピン酸ジエステルを併用した場合、消字率に変化は見られなかったが、はほぼ同等の結果が得られたが、移行量及び耐折れ性に改善効果が見られなかった。 On the other hand, when adipic acid diester was used in place of the liquid acrylic polymer, there was no change in the erasure rate, but almost the same result was obtained, but there was an improvement effect on the migration amount and folding resistance. I couldn't.
（実施例７〜１０、比較例４〜５）
表３に示す配合割合（数字は質量部）で配合した組成物を減圧下にて攪拌した後、１２０〜１４０℃で成形して、字消しを作成した。各字消しについて消字率及び移行性を上記方法で測定した結果を表３に示す。
(Examples 7 to 10, Comparative Examples 4 to 5)
After stirring the composition mix | blended by the compounding ratio (a number is a mass part) shown in Table 3 under reduced pressure, it shape | molded at 120-140 degreeC, and created the eraser. Table 3 shows the results of measuring the erasure rate and transferability of each erasure by the above method.
表３より、鉛筆で作成した画線に対する消字率に関して、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単独で用いた場合とほぼ同等の結果が得られ、ポリエステル系可塑剤単体で配合した場合よりも若干優れていた。 From Table 3, with regard to the erasure rate for the image line created with a pencil, the result is almost the same as when cyclohexane-1,2-dicarboxylic acid diisononyl ester is used alone, and when blended with a polyester plasticizer alone Was slightly better.
可塑剤の移行量に関しては、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単独で用いるよりも、アジピン酸系ポリエステルを併用することによって減少した。 The amount of plasticizer transferred was decreased by using adipic acid-based polyester in combination rather than using cyclohexane-1,2-dicarboxylic acid diisononyl ester alone.
また、アジピン酸系ポリエステルとシクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを併用することにより、それぞれを単体で配合した場合に比べて耐折れ性が向上し、相乗効果が認められた。 Further, by using adipic acid polyester and cyclohexane-1,2-dicarboxylic acid diisononyl ester in combination, the folding resistance was improved as compared with the case where each was blended alone, and a synergistic effect was recognized.
以上の結果より、本発明の字消しは、シクロヘキサン−１，２−ジカルボン酸ジイソノニルエステルを単独で配合した字消しよりも、可塑剤の耐移行性ならびに耐折れ性に関して性能向上が見られ、安全性においても人体及び環境に対する負荷が少ない安全な字消しを作成できた。 From the above results, the eraser of the present invention has improved performance with respect to the migration resistance and folding resistance of the plasticizer, compared to the eraser in which cyclohexane-1,2-dicarboxylic acid diisononyl ester is blended alone, and is safer. In terms of gender, we were able to create a safe erasure with less impact on the human body and the environment.
Claims (4)
［式中、Ｒ１、Ｒ２は互いに独立して、炭素数１〜２０のアルキル基を表す。］ At least 1 chosen from the plasticizer (A) which consists of cyclohexane dicarboxylic acid ester represented by General formula (1), a liquid transition polymer whose glass transition point (Tg) is 0 degrees C or less, and a polyester plasticizer for base resin. An eraser characterized by blending with a plasticizer (B) of a kind.
[In formula, R < 1 >, R < 2 > represents a C1-C20 alkyl group mutually independently. ]
The polyester plasticizer condenses at least one kind of aliphatic dicarboxylic acid having 4 to 12 carbon atoms, at least one kind of polyhydric alcohol, and at least one kind selected from monohydric alcohol or monovalent carboxylic acid. The eraser according to any one of claims 1 to 3, wherein the eraser is a polyester-based plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012177420A JP6066615B2 (en) | 2012-08-09 | 2012-08-09 | Erasure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012177420A JP6066615B2 (en) | 2012-08-09 | 2012-08-09 | Erasure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014034169A true JP2014034169A (en) | 2014-02-24 |
| JP6066615B2 JP6066615B2 (en) | 2017-01-25 |
Family
ID=50283453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012177420A Active JP6066615B2 (en) | 2012-08-09 | 2012-08-09 | Erasure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6066615B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016026835A1 (en) * | 2014-08-19 | 2016-02-25 | Basf Se | Plasticizer composition, containing polymeric dicarboxylic acid esters and 1,2-cyclohexanedicarboxylic acid esters |
| CN110168440A (en) * | 2017-06-16 | 2019-08-23 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
| WO2021190968A1 (en) * | 2020-03-25 | 2021-09-30 | Basf Se | Cyclohexanol-capped compounds and their use as plasticizers |
| EP3356457B2 (en) † | 2015-09-30 | 2022-12-21 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and 1,2-cyclohexane dicarboxylic acid esters |
| US11732107B2 (en) | 2017-01-04 | 2023-08-22 | Lg Chem, Ltd. | Plasticizer composition including cyclohexane 1,4-diester-based compound and resin composition including the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285156A (en) * | 2003-03-20 | 2004-10-14 | Mitsubishi Rayon Co Ltd | Composition for transparent articles, article, and laminate |
| JP2009196119A (en) * | 2008-02-19 | 2009-09-03 | Tombow Pencil Co Ltd | Eraser |
| JP2010090178A (en) * | 2008-09-10 | 2010-04-22 | Mitsubishi Rayon Co Ltd | Manufacturing method for latex, and acrylic sol composition |
-
2012
- 2012-08-09 JP JP2012177420A patent/JP6066615B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285156A (en) * | 2003-03-20 | 2004-10-14 | Mitsubishi Rayon Co Ltd | Composition for transparent articles, article, and laminate |
| JP2009196119A (en) * | 2008-02-19 | 2009-09-03 | Tombow Pencil Co Ltd | Eraser |
| JP2010090178A (en) * | 2008-09-10 | 2010-04-22 | Mitsubishi Rayon Co Ltd | Manufacturing method for latex, and acrylic sol composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016026835A1 (en) * | 2014-08-19 | 2016-02-25 | Basf Se | Plasticizer composition, containing polymeric dicarboxylic acid esters and 1,2-cyclohexanedicarboxylic acid esters |
| EP3356457B2 (en) † | 2015-09-30 | 2022-12-21 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and 1,2-cyclohexane dicarboxylic acid esters |
| US11732107B2 (en) | 2017-01-04 | 2023-08-22 | Lg Chem, Ltd. | Plasticizer composition including cyclohexane 1,4-diester-based compound and resin composition including the same |
| CN110168440A (en) * | 2017-06-16 | 2019-08-23 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
| WO2021190968A1 (en) * | 2020-03-25 | 2021-09-30 | Basf Se | Cyclohexanol-capped compounds and their use as plasticizers |
| CN115003741A (en) * | 2020-03-25 | 2022-09-02 | 巴斯夫欧洲公司 | Cyclohexanol end-capping compounds and their use as plasticizers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6066615B2 (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6066615B2 (en) | Erasure | |
| JP5777901B2 (en) | Plastic eraser | |
| CA2851637C (en) | Plasticizers derived from renewable feedstock | |
| TWI351355B (en) | ||
| JP6954509B1 (en) | Plasticizer for vinyl chloride resin, vinyl chloride resin composition and its molded products | |
| JP2012031220A (en) | Plasticizer for vinyl chloride resin, vinyl chloride resin composition using the same and molded product of the composition | |
| Langer et al. | Plasticizers derived from post-consumer PET: Research trends and potential applications | |
| JP2010053187A (en) | Vinyl chloride based resin composition, vinyl chloride based resin composition for food packaging and film obtained by using the same | |
| JP6659740B2 (en) | Plasticizer composition | |
| WO2013084707A1 (en) | Resin composition, and packaging film and method for producing same | |
| JP2013119624A (en) | Vinyl chloride-based flexible resin composition and plastic wrap | |
| JP6082549B2 (en) | Erasure | |
| JP6326974B2 (en) | Vinyl chloride food packaging film | |
| JP6218301B2 (en) | Plastic eraser | |
| TWI778152B (en) | Plasticizer for vinyl chloride resin, vinyl chloride resin composition, electric wire, and vehicle interior material | |
| CA3176757A1 (en) | Cyclohexanol-capped compounds and their use as plasticizers | |
| JP7394447B2 (en) | Eraser | |
| JP2018184556A (en) | Vinyl chloride resin composition in which coloring is suppressed during high-temperature use | |
| JP2013181148A (en) | Vinyl chloride-based soft resin composition, and lap film | |
| DE10116812A1 (en) | A mixture containing at least one cyclohexane polycarboxylic acid or derivative and a core hydrated phthalic plasticizer useful for electric stoves, computer housings, telephones, wire coverings and having low volatility and toxicity | |
| EP4368669A1 (en) | Plasticizer composition for vinyl chloride resin, plastisol and coating thereof | |
| JP2007021768A (en) | Plastic eraser | |
| US20110301267A1 (en) | Plastisols containing glycerol esters as plasticizers | |
| JP2022049644A (en) | Eraser | |
| Weisfeld | Plasticizers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150710 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160809 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160812 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161014 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161206 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161220 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161220 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6066615 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |