KR20220113099A - Vinylchloride resin composition - Google Patents
Vinylchloride resin composition Download PDFInfo
- Publication number
- KR20220113099A KR20220113099A KR1020210016869A KR20210016869A KR20220113099A KR 20220113099 A KR20220113099 A KR 20220113099A KR 1020210016869 A KR1020210016869 A KR 1020210016869A KR 20210016869 A KR20210016869 A KR 20210016869A KR 20220113099 A KR20220113099 A KR 20220113099A
- Authority
- KR
- South Korea
- Prior art keywords
- vinyl chloride
- based resin
- dicarboxylate
- resin composition
- weight
- Prior art date
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 84
- 239000004014 plasticizer Substances 0.000 claims abstract description 70
- 239000000049 pigment Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 125000005591 trimellitate group Chemical group 0.000 claims abstract description 26
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical group OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims abstract description 25
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- HOQGHOMLEVKTBY-UHFFFAOYSA-N bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1CCC(C(=O)OCC(CC)CCCC)CC1 HOQGHOMLEVKTBY-UHFFFAOYSA-N 0.000 claims description 23
- -1 tri-(n-octyl Chemical group 0.000 claims description 22
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- 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 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XFDQLDNQZFOAFK-UHFFFAOYSA-N 2-benzoyloxyethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOC(=O)C1=CC=CC=C1 XFDQLDNQZFOAFK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 3
- 125000001400 nonyl 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])[H] 0.000 claims description 3
- OKGUXCUCCABSEP-UHFFFAOYSA-N 2-propylheptyl benzoate Chemical compound CCCCCC(CCC)COC(=O)C1=CC=CC=C1 OKGUXCUCCABSEP-UHFFFAOYSA-N 0.000 claims description 2
- BBVARVTURNYWGV-UHFFFAOYSA-N 7-methyloctyl benzoate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1 BBVARVTURNYWGV-UHFFFAOYSA-N 0.000 claims description 2
- HNDYULRADYGBDU-UHFFFAOYSA-N 8-methylnonyl benzoate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1 HNDYULRADYGBDU-UHFFFAOYSA-N 0.000 claims description 2
- BFLLYQMTHHKNBS-UHFFFAOYSA-N C(CCC)C1C(CCC(C1)C(=O)O)(C(=O)O)CC(CCCC)CC Chemical compound C(CCC)C1C(CCC(C1)C(=O)O)(C(=O)O)CC(CCCC)CC BFLLYQMTHHKNBS-UHFFFAOYSA-N 0.000 claims description 2
- UMVMVEZHMZTUHD-UHFFFAOYSA-N DL-Propylene glycol dibenzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)COC(=O)C1=CC=CC=C1 UMVMVEZHMZTUHD-UHFFFAOYSA-N 0.000 claims description 2
- DIMOQAGSNHTROK-UHFFFAOYSA-N bis(2-ethylhexyl) cyclohexane-1,2-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1CCCCC1C(=O)OCC(CC)CCCC DIMOQAGSNHTROK-UHFFFAOYSA-N 0.000 claims description 2
- BFNQYORFBJZBBT-UHFFFAOYSA-N bis(2-ethylhexyl) cyclohexane-1,3-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1CCCC(C(=O)OCC(CC)CCCC)C1 BFNQYORFBJZBBT-UHFFFAOYSA-N 0.000 claims description 2
- JZDRRLSAIHHWDY-UHFFFAOYSA-N bis(2-methylpropyl) cyclohexane-1,3-dicarboxylate Chemical compound CC(C)COC(=O)C1CCCC(C(=O)OCC(C)C)C1 JZDRRLSAIHHWDY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- ANSWCYTXKAIJOK-UHFFFAOYSA-N dibutyl cyclohexane-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1CCCCC1C(=O)OCCCC ANSWCYTXKAIJOK-UHFFFAOYSA-N 0.000 claims description 2
- QGUFKMSGOYILME-UHFFFAOYSA-N dibutyl cyclohexane-1,4-dicarboxylate Chemical compound CCCCOC(=O)C1CCC(C(=O)OCCCC)CC1 QGUFKMSGOYILME-UHFFFAOYSA-N 0.000 claims description 2
- SZLIWAKTUJFFNX-UHFFFAOYSA-N dihydrocitronellol benzoate Natural products CC(C)CCCC(C)CCOC(=O)C1=CC=CC=C1 SZLIWAKTUJFFNX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- SYKYENWAGZGAFV-UHFFFAOYSA-N triheptyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC)C(C(=O)OCCCCCCC)=C1 SYKYENWAGZGAFV-UHFFFAOYSA-N 0.000 claims description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims 2
- MJHNUUNSCNRGJE-UHFFFAOYSA-N trimethyl benzene-1,2,4-tricarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 MJHNUUNSCNRGJE-UHFFFAOYSA-N 0.000 claims 2
- 230000005012 migration Effects 0.000 abstract description 21
- 238000013508 migration Methods 0.000 abstract description 21
- 239000000178 monomer Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 229920001944 Plastisol Polymers 0.000 description 11
- 239000004999 plastisol Substances 0.000 description 11
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- CGLQOIMEUPORRI-UHFFFAOYSA-N 2-(1-benzoyloxypropan-2-yloxy)propyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)OC(C)COC(=O)C1=CC=CC=C1 CGLQOIMEUPORRI-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 208000005141 Otitis Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 208000019258 ear infection Diseases 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-L cyclohexane-1,2-dicarboxylate Chemical compound [O-]C(=O)C1CCCCC1C([O-])=O QSAWQNUELGIYBC-UHFFFAOYSA-L 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-L cyclohexane-1,4-dicarboxylate Chemical compound [O-]C(=O)C1CCC(C([O-])=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate 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
- 235000012222 talc Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
본 발명은 겔링 속도 및 가소제 내이행성이 우수하고, 안료 배합 시 내이염성이 우수한 염화비닐계 수지 조성물에 관한 것이다. The present invention relates to a vinyl chloride-based resin composition having excellent geling speed and plasticizer migration resistance, and excellent color migration resistance when mixing pigments.
염화비닐계 수지는 염화비닐의 단독 중합체 및 염화비닐을 50% 이상 함유한 혼성 중합체로서, 현탁중합과 유화 중합으로 제조되는 5대 범용 열가소성 플라스틱 수지 중의 하나이다. Vinyl chloride-based resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of five general-purpose thermoplastic resins manufactured by suspension polymerization and emulsion polymerization.
염화비닐계 수지는 기능성을 부여하기 위하여 가소제, 안정제, 충전제, 발포제 등의 부원료와 혼합하여 사용된다. 가소제는 염화비닐계 수지에 유연성을 부여하여 가공성을 향상시키기 위하여 첨가되는 것으로, 기존에는 DEHP(Di-2-EthylHexyl Phthalate), DINP(Di-IsoNonyl Phthalate), DIDP(Di-Iso-Decyl Phthalate), BBP(Butyl Benzyl Phthalate), DBP(Di-n-butyl phthalate) 등의 프탈레이트계 가소제가 널리 사용되었다. Vinyl chloride-based resins are used by mixing with auxiliary materials such as plasticizers, stabilizers, fillers, and foaming agents in order to impart functionality. Plasticizers are added to improve processability by imparting flexibility to vinyl chloride-based resins. Phthalate-based plasticizers such as BBP (Butyl Benzyl Phthalate) and DBP (Di-n-butyl phthalate) have been widely used.
상기 프탈레이트계 가소제는 가소화 효율은 뛰어나지만 인체에 유해성을 나타내는 바, 최근 국내외에서 사용이 규제되고 있다. 이에, 프탈레이트계 가소제를 대체할 수 있는 물질로서 테레프탈레이트계 가소제, 에폭사이드계 가소제, 식물성 유지계 가소제, 사이클로헥산계 가소제 등이 제안되었다. 대표적인 친환경 가소제로는 디옥틸테레프탈레이트(DOTP)가 있으나, DOTP 가소제는 이행이 잘 되고, 자외선에 대한 내후성이 좋지 않으며, 겔링 및 용융(fusion) 속도가 떨어지는 등의 문제가 있다. 특히, 안료를 포함하는 컬러 염화비닐계 수지 조성물에 DOTP를 사용하는 경우 가소제 이행 과정에서 안료가 함께 이행되어 안료의 이염이 일어나기 쉬운 문제가 있다. The phthalate-based plasticizer has excellent plasticizing efficiency, but is harmful to the human body, and thus its use is regulated at home and abroad. Accordingly, as a material that can replace the phthalate-based plasticizer, a terephthalate-based plasticizer, an epoxide-based plasticizer, a vegetable oil-based plasticizer, a cyclohexane-based plasticizer, and the like have been proposed. A typical eco-friendly plasticizer includes dioctyl terephthalate (DOTP), but the DOTP plasticizer has problems such as good migration, poor weather resistance to UV rays, and low gelling and fusion rates. In particular, when DOTP is used in a color vinyl chloride-based resin composition containing a pigment, there is a problem in that the pigment is migrated together in the plasticizer migration process, so that the pigment migration is easy to occur.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 겔링 속도 및 가소제 내이행성이 우수하고, 안료 배합 시 내이염성이 우수하며, 친환경적인 염화비닐계 수지 조성물을 제공한다.The present invention is to solve the above problems, and provides an environmentally friendly vinyl chloride-based resin composition having excellent geling speed and plasticizer migration resistance, excellent color transfer resistance during pigment mixing, and environment-friendly.
또한, 본 발명은 염화비닐계 수지 조성물을 포함하는 성형품을 제공한다.In addition, the present invention provides a molded article comprising a vinyl chloride-based resin composition.
상기 과제를 해결하기 위하여, 본 발명은 염화비닐계 수지 및 가소제를 포함하는 염화비닐계 수지 조성물로서, 상기 염화비닐계 수지는 페이스트 수지이고, 상기 가소제는 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물을 포함하는 것인, 염화비닐계 수지 조성물을 제공한다.In order to solve the above problems, the present invention provides a vinyl chloride-based resin composition comprising a vinyl chloride-based resin and a plasticizer, wherein the vinyl chloride-based resin is a paste resin, and the plasticizer is a cyclohexane dicarboxylate-based compound, benzoate It provides a vinyl chloride-based resin composition comprising a compound, and a trimellitate-based compound.
또한, 본 발명은 상기 염화비닐계 수지 조성물을 포함하는 성형품을 제공한다.In addition, the present invention provides a molded article comprising the vinyl chloride-based resin composition.
본 발명에 따른 염화비닐계 수지 조성물은 프탈레이트계 화합물을 포함하지 않아 친환경적이면서도, 겔링 속도 및 가소제 내이행성이 우수하며, 안료 배합 시 컬러의 선명도가 우수할 뿐만 아니라 현저히 향상된 내이염성을 나타낸다.The vinyl chloride-based resin composition according to the present invention does not contain a phthalate-based compound, so it is environmentally friendly, and has excellent geling speed and plasticizer migration resistance, and exhibits not only excellent color clarity when blending pigments but also significantly improved color transfer resistance.
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention may have various modifications and various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.
본 발명에 있어서, 용어 "염화비닐계 수지 조성물"은 가열에 의해 성형, 주형 혹은 연속 필름상으로 가공할 수 있도록 수지와 가소제를 섞은 혼합물을 나타내는 "플라스티졸(plastisol)"을 포함하며, 상기 플라스티졸은 예컨대 염화비닐 수지와 가소제를 혼합한 페이스트상을 나타내는 것일 수 있다.In the present invention, the term "vinyl chloride-based resin composition" includes "plastisol", which refers to a mixture of a resin and a plasticizer so that it can be molded, molded, or processed into a continuous film by heating. The plastisol may be in the form of a paste in which, for example, a vinyl chloride resin and a plasticizer are mixed.
이하, 발명의 구체적인 구현예에 따른 염화비닐계 수지 조성물에 대해 보다 상세히 설명하기로 한다.Hereinafter, a vinyl chloride-based resin composition according to a specific embodiment of the present invention will be described in more detail.
염화비닐계 수지vinyl chloride resin
본 발명에서는 염화비닐계 수지로서 유화 중합 또는 미세 현탁 중합에 의하여 제조되는 페이스트 수지를 사용한다. In the present invention, a paste resin prepared by emulsion polymerization or fine suspension polymerization is used as the vinyl chloride-based resin.
상기 페이스트 수지는 평균 입자 크기(D50)가 100 ㎛ 미만, 바람직하게는 0.1 내지 70 ㎛일 수 있다. 상기 염화비닐 수지의 평균 입자 크기(D50)는 광학현미경 관찰법, 광산란 측정법 등의 통상의 입자 크기 분포 측정방법에 따라 측정될 수 있다.The paste resin may have an average particle size (D50) of less than 100 μm, preferably 0.1 to 70 μm. The average particle size (D50) of the vinyl chloride resin may be measured according to a conventional particle size distribution measuring method such as an optical microscope observation method or a light scattering measurement method.
상기 염화비닐계 수지란 염화비닐계 단량체 단독, 또는 염화비닐계 단량체 및 이와 공중합 가능한 공단량체가 공중합된 (공)중합체를 지칭한다. The vinyl chloride-based resin refers to a (co)polymer copolymerized with a vinyl chloride-based monomer alone, or a vinyl chloride-based monomer and a comonomer copolymerizable therewith.
상술한 염화비닐 단량체와 공중합이 가능한 다른 단량체는, 예를 들어, 비닐 아세테이트 단량체, 에틸렌 비닐 아세테이트 단량체 및 프로피온산 비닐 단량체를 포함하는 비닐 에스터계 단량체; 에틸렌, 프로필렌, 이소부틸 비닐에테르, 및 할로겐화 올레핀을 포함하는 올레핀계 단량체; 메타크릴산 알킬에스터를 포함하는 메타크릴산 에스터계 단량체; 무수말레산 단량체; 아크릴로니트릴 단량체; 스티렌 단량체; 및 할로겐화 폴리비닐리덴 등이 있을 수 있으며, 이들을 1종 이상 혼합하여 염화비닐 단량체와의 공중합체를 제조할 수 있다. 그러나 본 발명이 상술한 단량체에 한정되는 것은 아니며, 제조 시, 요구되는 염화비닐계 수지 조성물의 물성이나 용도 등에 따라, 본 발명이 속한 기술분야에서 일반적으로 염화비닐 단량체와 중합반응을 통해 공중합체를 형성하는데 사용되는 단량체는 특별한 제한 없이 사용이 가능하다.Other monomers copolymerizable with the above-mentioned vinyl chloride monomers include, for example, vinyl ester-based monomers including vinyl acetate monomers, ethylene vinyl acetate monomers, and vinyl propionate monomers; olefinic monomers including ethylene, propylene, isobutyl vinyl ether, and halogenated olefins; methacrylic acid ester-based monomers including methacrylic acid alkyl esters; maleic anhydride monomer; acrylonitrile monomer; styrene monomer; and halogenated polyvinylidene, etc., and by mixing one or more of them, a copolymer with a vinyl chloride monomer may be prepared. However, the present invention is not limited to the above-mentioned monomers, and in the technical field to which the present invention belongs, a copolymer is generally prepared through polymerization with a vinyl chloride monomer according to the physical properties or use of the vinyl chloride-based resin composition required during manufacture. The monomer used for the formation may be used without any particular limitation.
바람직한 일 구현예에서, 상기 염화비닐계 수지는 염화비닐 단량체 및 비닐 아세테이트 단량체의 공중합체, 즉, 염화비닐-비닐아세테이트 공중합체일 수 있다. 염화비닐-비닐아세테이트 공중합체는 특히 컬러 플라스티졸 제조 시 색상 선명도를 향상시켜 조색에 도움을 줄 수 있고, 가공이 완료된 상태에서 안료가 이탈하는 현상을 억제하여 이염을 저감시키는 효과가 있다. In a preferred embodiment, the vinyl chloride-based resin may be a copolymer of a vinyl chloride monomer and a vinyl acetate monomer, that is, a vinyl chloride-vinyl acetate copolymer. Vinyl chloride-vinyl acetate copolymer can help toning by improving color clarity, especially when manufacturing color plastisol, and has the effect of reducing color transfer by suppressing the phenomenon of pigment detachment in the state that processing is completed.
이때, 염화비닐계 수지 100 중량% 중의 비닐 아세테이트 함량은 1 중량% 이상 내지 20 중량% 이하가 바람직할 수 있다. 만일 염화비닐계 수지 중 비닐 아세테이트 함량이 20 중량%를 초과하는 경우 시간의 흐름에 따라, 또는 외기 온도에 의해 플라스티졸의 점도가 급상승하는 문제가 있을 수 있고, 1 중량% 미만이면 비닐 아세테이트의 장점인 겔링 및 용융 속도 향상 등의 물성 구현이 어려운 문제가 있으며, 상술한 플라스티졸의 선명도 향상, 이염 저감 효과를 달성하기 어렵다. In this case, the vinyl acetate content in 100 wt% of the vinyl chloride-based resin may be preferably 1 wt% or more to 20 wt% or less. If the content of vinyl acetate in the vinyl chloride-based resin exceeds 20% by weight, there may be a problem in that the viscosity of the plastisol increases rapidly over time or by external temperature, and if it is less than 1% by weight, the amount of vinyl acetate is less than 1% by weight. There is a problem in that it is difficult to implement physical properties such as gelling and melt rate improvement, which are advantages, and it is difficult to achieve the above-described sharpness improvement and color transfer reduction effect of the plastisol.
한편, 상기 염화비닐계 페이스트 수지는 JIS K 6720-2에 따라 측정한 중합도가 500 내지 2,000, 또는 800 내지 1,700인 것을 사용할 수 있다. 중합도가 상기 범위를 만족할 때 적절한 가공성과 기계적 물성을 보이는 효과가 있어 보다 바람직하다.Meanwhile, the vinyl chloride-based paste resin may have a polymerization degree of 500 to 2,000, or 800 to 1,700 measured according to JIS K 6720-2. When the degree of polymerization satisfies the above range, it is more preferable because there is an effect of showing appropriate processability and mechanical properties.
가소제plasticizer
본 발명은 가소제로서 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물의 3종의 화합물을 포함한다. 이러한 특정한 3종의 화합물의 상호 작용으로 인하여 본 발명의 가소제는 우수한 겔링속도, 점도, 및 가소제 내이행성을 나타낸다. The present invention includes three types of compounds: a cyclohexane dicarboxylate-based compound, a benzoate-based compound, and a trimellitate-based compound as a plasticizer. Due to the interaction of these three specific compounds, the plasticizer of the present invention exhibits excellent gelling rate, viscosity, and plasticizer migration resistance.
상기 염화비닐계 수지 조성물 중 가소제의 함량은 목적하는 물성에 따라 적절히 조절할 수 있다. 예를 들어, 상기 가소제는 염화비닐계 수지 100 중량부에 대하여 30 중량부 이상, 바람직하게는 50 중량부 내지 150 중량부, 또는 60 내지 100 중량부로 포함될 수 있다.The content of the plasticizer in the vinyl chloride-based resin composition may be appropriately adjusted according to desired physical properties. For example, the plasticizer may be included in an amount of 30 parts by weight or more, preferably 50 to 150 parts by weight, or 60 to 100 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
상기 사이클로헥산 디카르복실레이트계 화합물은 하기 화학식 1로 표시된다:The cyclohexane dicarboxylate-based compound is represented by the following formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서, In Formula 1,
R1 및 R2는 각각 독립적으로 탄소수 4 내지 12의 직쇄 또는 분지쇄 알킬기이다.R 1 and R 2 are each independently a linear or branched alkyl group having 4 to 12 carbon atoms.
바람직하게는, R1 및 R2는 각각 독립적으로 부틸기, 이소부틸기, 펜틸기, 헥실기, 헵틸기, 2-에틸헥실기, 옥틸기, 노닐기, 이소노닐기, 2-프로필헵틸기, 데실기, 또는 이소데실기이다. 바람직하게는, R1 및 R2는 각각 독립적으로 부틸기, 2-에틸헥실기, 또는 이소노닐기이다.Preferably, R 1 and R 2 are each independently a butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, isononyl group, 2-propylheptyl group , a decyl group, or an isodecyl group. Preferably, R 1 and R 2 are each independently a butyl group, a 2-ethylhexyl group, or an isononyl group.
상기 화학식 1로 표시되는 사이클로헥산 디카르복실레이트계 화합물은 치환기의 상대적 위치에 따라 하기 화학식 1-1 내지 1-3으로 표시될 수 있다.The cyclohexane dicarboxylate-based compound represented by Chemical Formula 1 may be represented by the following Chemical Formulas 1-1 to 1-3 according to the relative positions of the substituents.
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
상기 화학식 1-1 내지 1-3에서 R-1 및 R2는 화학식 1에서 정의한 바와 같다.In Formulas 1-1 to 1-3, R- 1 and R 2 are as defined in Formula 1.
상기 화학식 1-1은 사이클로헥산-1,2-디카르복실레이트계 화합물이고, 상기 화학식 1-2는 사이클로헥산-1,3-디카르복실레이트계 화합물이며, 상기 화학식 1-3은 사이클로헥산-1,4-디카르복실레이트계 화합물이다.Formula 1-1 is a cyclohexane-1,2-dicarboxylate-based compound, Formula 1-2 is a cyclohexane-1,3-dicarboxylate-based compound, and Formula 1-3 is cyclohexane -1,4-dicarboxylate-based compound.
일 구현예에서, 상기 사이클로헥산 디카르복실레이트계 화합물은 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 부틸(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 디부틸사이클로헥산-1,4-디카르복실레이트, 디(2-에틸헥실)사이클로헥산-1,3-디카르복실레이트, 디이소부틸사이클로헥산-1,3-디카르복실레이트, 디부틸사이클로헥산-1,2-디카르복실레이트, 디이소노닐사이클로헥산-1,2-디카르복실레이트, 디(2-에틸헥실)사이클로헥산-1,2-디카르복실레이트, 및 디이소데실사이클로헥산-1,2-디카르복실레이트로 이루어진 군에서 선택되는 1종 이상일 수 있다. In one embodiment, the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate Voxylate, dibutylcyclohexane-1,4-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, diisobutylcyclohexane-1,3-dicarboxylate , dibutylcyclohexane-1,2-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, and It may be at least one selected from the group consisting of diisodecylcyclohexane-1,2-dicarboxylate.
바람직하게는, 상기 사이클로헥산 디카르복실레이트계 화합물은 하기 화학식 1-4로 표시되는 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(di(2-ethylhexyl) cyclohexane-1,4-dicarboxylate, DEHCH)일 수 있다:Preferably, the cyclohexane dicarboxylate-based compound is di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate (di (2-ethylhexyl) cyclohexane-1 represented by Formula 1-4 below) ,4-dicarboxylate, DEHCH):
[화학식 1-4][Formula 1-4]
DEHCH와 같은 사이클로헥산 디카르복실레이트계 화합물은 비프탈레이트계 가소제 중 낮은 점도를 보이며 코팅성이 양호하고, 비교적 겔링 속도가 빠르며 가소화 효율이 우수한 특징이 있다. 특히, 기존 프탈레이트계 가소제에 비하여 휘발성 유기 화합물의 발생을 최소화할 수 있는 장점이 있다. Cyclohexane dicarboxylate-based compounds such as DEHCH show low viscosity among non-phthalate-based plasticizers, have good coating properties, have relatively fast gelling rates, and have excellent plasticization efficiency. In particular, there is an advantage in that the generation of volatile organic compounds can be minimized compared to conventional phthalate-based plasticizers.
단, 사이클로헥산 디카르복실레이트계 화합물을 단독 사용할 경우 프탈레이트계 가소제와 비교하여 가소제 이행성(migration)이 높아 안료 사용 시 이염의 위험이 있고, 두꺼운 코팅에 적용하기에는 겔링 및 용융(Fusion) 속도가 충분하지 않다. 이에, 본 발명에서는 사이클로헥산 디카르복실레이트계 화합물과 더불어 벤조에이트계 화합물 및 트리멜리테이트계 화합물을 함께 사용하여 가소제 이행성 및 이염성을 낮추고 겔링 및 용융(fusion) 속도를 더욱 향상시킨다. However, when cyclohexane dicarboxylate-based compound is used alone, there is a risk of color migration when using pigments due to high plasticizer migration compared to phthalate-based plasticizers. Not full yet. Accordingly, in the present invention, a benzoate-based compound and a trimellitate-based compound are used together with a cyclohexane dicarboxylate-based compound to lower plasticizer transferability and color transfer properties, and to further improve gelling and melting (fusion) rates.
상기 벤조에이트계 화합물은 PhCOO-(이때, Ph는 페닐기를 의미함) 작용기를 포함하는 화합물로서, 구체적으로 소듐 벤조에이트, 이소노닐 벤조에이트, 이소데실 벤조에이트, 2-프로필헵틸 벤조에이트, 디에틸렌글리콜 디벤조에이트, 디프로필렌글리콜 디벤조에이트, 1,2-프로판디올 디벤조에이트, 및 디부틸렌글리콜 디벤조에이트로 이루어지는 군에서 선택되는 1종 이상을 사용할 수 있다. The benzoate-based compound is a compound including a PhCOO- (in this case, Ph means a phenyl group) functional group, specifically sodium benzoate, isononyl benzoate, isodecyl benzoate, 2-propylheptyl benzoate, diethylene At least one selected from the group consisting of glycol dibenzoate, dipropylene glycol dibenzoate, 1,2-propanediol dibenzoate, and dibutylene glycol dibenzoate may be used.
상기 벤조에이트계 화합물은 염화비닐계 페이스트 수지와 배합 시 겔링 및 용융 속도를 빠르게 하는 장점이 있으나, 단독으로 사용할 경우 플라스티졸의 점도를 상승시켜, 염화비닐계 수지 조성물 제조 시 배합 단계에서 플라스티졸이 굳어지는 현상이 발생하는 문제가 있다. The benzoate-based compound has the advantage of speeding up the gelling and melting rate when blended with the vinyl chloride-based paste resin, but when used alone, it increases the viscosity of the plastisol, so that the plastisol in the mixing step when preparing the vinyl chloride-based resin composition There is a problem that the phenomenon of solidification of the sol occurs.
따라서, 벤조에이트계 화합물과 함께 상술한 사이클로헥산 디카르복실레이트계 화합물을 사용하여 점도 특성을 향상시킬 수 있다. 그러나, 사이클로헥산 디카르복실레이트계 화합물 및 벤조에이트계 화합물만을 사용할 경우 가소제 내이행성이 다소 열세하고 이에 따라 안료 배합시 내이염 특성이 부족하게 된다. 이에, 본 발명에서는 트리멜리테이트계 화합물을 포함하여 상기 특성을 보완하였다. Accordingly, the viscosity characteristics may be improved by using the above-described cyclohexane dicarboxylate compound together with the benzoate compound. However, when only the cyclohexane dicarboxylate-based compound and the benzoate-based compound are used, the plasticizer migration resistance is somewhat inferior, and thus the otitis resistance property is insufficient when mixing the pigment. Accordingly, in the present invention, the above characteristics were supplemented by including the trimellitate-based compound.
상기 트리멜리테이트계 화합물은 트리멜리틱산(1,2,4-벤젠트리카르복실산)으로부터 유래한 에스테르 화합물이면 제한이 없으나, 예를 들어 트리-(2-에틸헥실) 트리멜리테이트, 트리메틸 트리멜리테이트, 트리헥실 트리멜리테이트, 트리헵틸 트리멜리테이트, 트리-(n-옥틸,n-데실) 트리멜리테이트, 및 트리-(헵틸,노닐) 트리멜리테이트로 이루어지는 군에서 선택되는 1종 이상을 사용할 수 있다. The trimellitate-based compound is not limited as long as it is an ester compound derived from trimellitic acid (1,2,4-benzenetricarboxylic acid), for example, tri-(2-ethylhexyl) trimellitate, trimethyl tri At least one selected from the group consisting of melitate, trihexyl trimellitate, triheptyl trimellitate, tri-(n-octyl, n-decyl) trimellitate, and tri-(heptyl, nonyl) trimellitate can be used
트리멜리테이트계 화합물은 내이행성이 매우 우수하며, 안료를 포함하는 플라스티졸에 사용되어 이염을 줄이는 효과를 나타내나, 겔링 속도가 느려 가공 시 많은 열량이 필요하므로 열에 약한 기재에 사용 시 기재가 손상되는 문제가 있다. 또한 가공 속도가 느려 생산 효율이 떨어지므로 제한된 영역에서만 사용되어 왔다. 그러나 트리멜리테이트계 화합물을 상기 사이클로헥산 디카르복실레이트계 화합물 및 벤조에이트계 화합물과 함께 사용할 경우 부족한 가공 효율 특성이 보완되면서도 우수한 내이행 특성을 확보할 수 있다. 특히 직물, 섬유 등 열에 약한 기재의 코팅 용도에서 효과가 더욱 향상될 수 있어 바람직하다.The trimellitate-based compound has very good migration resistance and is used in plastisols containing pigments to reduce color migration. There is a problem with damage. In addition, it has been used only in a limited area because of the slow processing speed and poor production efficiency. However, when the trimellitate-based compound is used together with the cyclohexane dicarboxylate-based compound and the benzoate-based compound, it is possible to secure excellent transition resistance while compensating for insufficient processing efficiency characteristics. In particular, it is preferable because the effect can be further improved in the coating use of substrates that are weak to heat, such as fabrics and fibers.
상기 가소제 100 중량부 중 사이클로헥산 디카르복실레이트계 화합물의 함량은 20 중량부 이상, 40 중량부 이상, 또는 60 중량부 이상이면서, 90 중량부 이하, 또는 80 중량부 이하일 수 있다. 사이클로헥산 디카르복실레이트계 화합물의 함량이 20 중량부 미만이면 염화비닐계 수지 조성물의 점도가 상승하여 코팅 및 가공 특성에 문제가 있을 수 있고, 90 중량부를 초과하면 상대적으로 벤조에이트계 화합물 및 트리멜리테이트계 화합물의 함량이 줄어들게 되므로 내이행성, 내이염성, 겔링 및 용융(fusion) 속도 개선이 미미한 문제가 있을 수 있다.The content of the cyclohexane dicarboxylate-based compound in 100 parts by weight of the plasticizer may be 20 parts by weight or more, 40 parts by weight or more, or 60 parts by weight or more, and 90 parts by weight or less, or 80 parts by weight or less. If the content of the cyclohexane dicarboxylate-based compound is less than 20 parts by weight, the viscosity of the vinyl chloride-based resin composition may increase and there may be problems in coating and processing properties, and if it exceeds 90 parts by weight, the benzoate-based compound and tri Since the content of the melitate-based compound is reduced, there may be minor problems in improvement of migration resistance, otitis resistance, gelling and fusion speed.
또, 상기 가소제 100 중량부 중 벤조에이트계 화합물의 함량은 5 중량부 이상, 또는 10 중량부 이상이면서, 40 중량부 이하, 30 중량부 이하, 또는 20 중량부 이하일 수 있다. 벤조에이트계 화합물의 함량이 5 중량부 미만이면 겔링 및 용융 속도가 충분히 향상될 수 없고, 40 중량부를 초과하면 염화비닐계 수지 조성물의 점도가 지나치게 높아 가공성이 저하되는 문제가 있을 수 있다.In addition, the content of the benzoate-based compound in 100 parts by weight of the plasticizer may be 5 parts by weight or more, or 10 parts by weight or more, and 40 parts by weight or less, 30 parts by weight or less, or 20 parts by weight or less. If the content of the benzoate-based compound is less than 5 parts by weight, the gelling and melting rate cannot be sufficiently improved, and if it exceeds 40 parts by weight, the viscosity of the vinyl chloride-based resin composition is too high, so there may be a problem in that processability is deteriorated.
그리고 상기 가소제 100 중량부 중 트리멜리테이트계 화합물의 함량은 5 중량부 이상, 또는 10 중량부 이상이면서, 40 중량부 이하, 30 중량부 이하, 또는 20 중량부 이하일 수 있다. 트리멜리테이트계 화합물의 함량이 5 중량부 미만이면 가소제 내이행성 향상 효과, 나아가 안료 배합시 내이염성 개선 효과를 확보할 수 없고, 40 중량부를 초과하면 겔링 속도가 저하되는 문제가 있을 수 있다.And the content of the trimellitate compound in 100 parts by weight of the plasticizer may be 5 parts by weight or more, or 10 parts by weight or more, and 40 parts by weight or less, 30 parts by weight or less, or 20 parts by weight or less. If the content of the trimellitate-based compound is less than 5 parts by weight, the effect of improving the plasticizer migration resistance and furthermore, the improvement of the dye resistance when mixing the pigment cannot be secured, and when it exceeds 40 parts by weight, there may be a problem in that the gelling rate is lowered.
이에, 본 발명의 바람직한 일 구현예에서, 상기 가소제는 사이클로헥산 디카르복실레이트계 화합물 20 내지 90 중량부, 벤조에이트계 화합물 5 내지 40 중량부, 및 트리멜리테이트계 화합물 5 내지 40 중량부를 포함하는 것일 수 있다. Accordingly, in a preferred embodiment of the present invention, the plasticizer includes 20 to 90 parts by weight of a cyclohexane dicarboxylate-based compound, 5 to 40 parts by weight of a benzoate-based compound, and 5 to 40 parts by weight of a trimellitate-based compound may be doing
또는, 상기 가소제는 사이클로헥산 디카르복실레이트계 화합물 60 내지 80 중량부, 벤조에이트계 화합물 10 내지 20 중량부, 및 트리멜리테이트계 화합물 10 내지 20 중량부를 포함하는 것일 수 있다.Alternatively, the plasticizer may include 60 to 80 parts by weight of a cyclohexane dicarboxylate-based compound, 10 to 20 parts by weight of a benzoate-based compound, and 10 to 20 parts by weight of a trimellitate-based compound.
이때, 상기 사이클로헥산 디카르복실레이트계 화합물은 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트이고, 벤조에이트계 화합물은 디프로필렌글리콜 디벤조에이트이고, 트리멜리테이트계 화합물은 트리-(2-에틸헥실) 트리멜리테이트일 수 있다. 즉, 상기 가소제는 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 60 내지 80 중량부, 디프로필렌글리콜 디벤조에이트 10 내지 20 중량부, 트리-(2-에틸헥실) 트리멜리테이트 10 내지 20 중량부를 포함하는 것일 수 있다.In this case, the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, the benzoate-based compound is dipropylene glycol dibenzoate, and trimellitate-based compound may be tri-(2-ethylhexyl) trimellitate. That is, the plasticizer is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 60 to 80 parts by weight, dipropylene glycol dibenzoate 10 to 20 parts by weight, tri-(2-ethylhexyl) tri It may contain 10 to 20 parts by weight of melitate.
한편, 본 발명의 일 구현예에 따른 가소제는 상술한 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물 외에 다른 가소제를 포함하지 않는 것일 수 있다. 즉, 상기 가소제는 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물로만 이루어진 것일 수 있다. On the other hand, the plasticizer according to an embodiment of the present invention may not include any other plasticizer other than the above-described cyclohexane dicarboxylate-based compound, benzoate-based compound, and trimellitate-based compound. That is, the plasticizer may be composed of only a cyclohexane dicarboxylate-based compound, a benzoate-based compound, and a trimellitate-based compound.
이때, 상기 사이클로헥산 디카르복실레이트계 화합물은 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트이고, 벤조에이트계 화합물은 디프로필렌글리콜 디벤조에이트이고, 트리멜리테이트계 화합물은 트리-(2-에틸헥실) 트리멜리테이트일 수 있다.In this case, the cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, the benzoate-based compound is dipropylene glycol dibenzoate, and trimellitate-based compound may be tri-(2-ethylhexyl) trimellitate.
상기 본 발명의 가소제는 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물의 시너지 효과로 인하여, 각각을 단독으로 사용하거나, 상기 화합물들 중 2종만을 조합 사용하는 경우와 비교하여 우수한 가소화 능력을 나타내면서, 개선된 가소제 내이행성을 나타내며, 안료 배합 시 이염성이 적은 특성을 나타낸다. Due to the synergistic effect of the cyclohexane dicarboxylate-based compound, the benzoate-based compound, and the trimellitate-based compound, the plasticizer of the present invention is used alone or when only two of the compounds are used in combination As compared to , it exhibits excellent plasticizing ability, improved plasticizer migration resistance, and low color transfer properties when blending pigments.
기타 첨가제other additives
상기 염화비닐계 수지 조성물은 첨가제, 예를 들어 안료, 열 안정제, 및 충전제로 구성되는 군으로부터 선택되는 어느 하나 이상을 추가로 포함할 수 있다. 상기 첨가제는 염화비닐계 수지 조성물에서 향상시키고자 하는 물성에 따라 적합하게 선택될 수 있다. The vinyl chloride-based resin composition may further include any one or more selected from the group consisting of additives, for example, pigments, heat stabilizers, and fillers. The additive may be appropriately selected according to the physical properties to be improved in the vinyl chloride-based resin composition.
상기 안료는 염화비닐계 수지 조성물에 색상을 부여하기 위하여 첨가되는 것으로, 퀴나크리돈계 안료, 페릴렌계 안료, 폴리아조축합 안료, 이도인소리논계 안료, 구리프탈로시아닌계 안료, 아조계 안료, 황산바륨계 안료, 탄산칼슘계 안료, 황색산화철계 안료, 크롬계 안료, 카드뮴계안료, 티탄화이트, 및 카본블랙으로 이루어지는 군에서 선택되는 1종 이상일 수 있다. The pigment is added to impart color to the vinyl chloride-based resin composition, and is a quinacridone-based pigment, a perylene-based pigment, a polyazo-condensed pigment, an iidoinsorinone-based pigment, a copper phthalocyanine-based pigment, an azo-based pigment, and a barium sulfate-based pigment. It may be at least one selected from the group consisting of pigments, calcium carbonate-based pigments, yellow iron oxide-based pigments, chromium-based pigments, cadmium-based pigments, titanium white, and carbon black.
상술한 바와 같이 본 발명의 염화비닐계 수지 조성물은 염화비닐 페이스트 수지 및 상기 특정한 3종의 가소제를 포함하여, 안료 배합 시 안료가 이염되는 현상이 현저히 줄어들 수 있다. As described above, the vinyl chloride-based resin composition of the present invention includes the vinyl chloride paste resin and the above-mentioned three specific plasticizers, so that when the pigment is mixed, the pigment transfer phenomenon can be significantly reduced.
상기 안료의 사용량은 색상 구현에 적합하도록 적절히 조절될 수 있으며, 예를 들어 염화비닐계 수지 100 중량부에 대하여 0.1 내지 30 중량부, 또는 1 내지 20 중량부의 함량으로 사용될 수 있다.The amount of the pigment used may be appropriately adjusted to be suitable for color implementation, and for example, may be used in an amount of 0.1 to 30 parts by weight, or 1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride-based resin.
상기 열 안정제는 염화비닐계 수지 조성물의 내열성을 향상시키고 제품의 사용기간 중 물성 변화를 예방하는 목적으로 첨가된다. 본 발명에서 사용될 수 있는 열 안정제의 구체적인 예는 Ca-Zn계 화합물; K-Zn계 화합물; Ba-Zn계 화합물; 머캡티드(Mercaptide)계 화합물, 말레인산계 화합물 또는 카르복실산계 화합물과 같은 유기 Tin계 화합물; Mg-스테아레이트, Ca-스테아레이트, Pb-스테아레이트, Cd-스테아레이트, 또는 Ba-스테아레이트 등과 같은 메탈릭 비누계 화합물; 페놀계 화합물; 인산 에스테르계 화합물; 또는 아인산 에스테르계 화합물 등이다.The heat stabilizer is added for the purpose of improving the heat resistance of the vinyl chloride-based resin composition and preventing a change in physical properties during the period of use of the product. Specific examples of the heat stabilizer that can be used in the present invention include Ca—Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; an organic tin-based compound such as a mercaptide-based compound, a maleic acid-based compound, or a carboxylic acid-based compound; metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; phenolic compounds; phosphoric acid ester compounds; or a phosphorous acid ester compound.
상기 열 안정제는 염화비닐계 수지 100 중량부에 대하여 바람직하게는 0.5 내지 7 중량부, 더욱 바람직하게는 1 내지 4 중량부가 포함된다. 열 안정제의 함량이 0.5 중량부 미만이면, 열안정성이 떨어지는 문제점이 있고, 7 중량부를 초과하면 가공성이 떨어지는 문제가 있다.The heat stabilizer is preferably included in an amount of 0.5 to 7 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the vinyl chloride-based resin. If the content of the heat stabilizer is less than 0.5 parts by weight, there is a problem of poor thermal stability, and if it exceeds 7 parts by weight, there is a problem of poor workability.
본 발명의 충전제는 염화비닐계 수지 조성물의 생산성, 건조 상태의 감촉(Dry touch)감을 향상시키는 목적으로 사용되며, 탄산칼슘, 탈크, 이산화티탄, 카올린, 실리카, 알루미나, 수산화마그네슘 또는 점토로 이루어진 군에서 선택되는 어느 하나 이상인 것을 포함한다.The filler of the present invention is used for the purpose of improving the productivity of the vinyl chloride-based resin composition and the feeling of dry touch, and is composed of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide or clay. Including any one or more selected from.
상기 본 발명에 따른 염화비닐계 수지 조성물에서 상기 충전제는 염화비닐계 수지 100 중량부에 대하여 바람직하게는 10 내지 150 중량부, 더욱 바람직하게는 50 내지 130 중량부로 포함될 수 있다. 충전제가 10 중량부 미만으로 포함된 경우, 치수안정성과 경제성이 낮아지는 문제점이 있고, 130 중량부 초과하여 포함된 경우, 가공성이 저하되는 문제점이 있다.In the vinyl chloride-based resin composition according to the present invention, the filler may be included in an amount of preferably 10 to 150 parts by weight, more preferably 50 to 130 parts by weight, based on 100 parts by weight of the vinyl chloride-based resin. When the filler is included in an amount of less than 10 parts by weight, there is a problem in that dimensional stability and economic efficiency are lowered, and when it is included in an amount exceeding 130 parts by weight, there is a problem in that workability is reduced.
본 발명의 염화비닐계 수지 조성물은 이산화 티타늄(TiO2)을 첨가하여 백색도 및 은폐성을 향상시킬 수 있다. 상기 이산화 티타늄은 염화비닐계 수지 100 중량부에 대하여 바람직하게는 1 내지 20 중량부, 더욱 바람직하게는 3 내지 15 중량부가 포함될 수 있다. 이산화 티타늄이 3 중량부 미만으로 포함된 경우, 백색도 및 은폐성이 떨어져 인쇄 후 색깔이 제대로 나오지 않으며, 15 중량부 초과하여 포함된 경우, 기계적 물성이 저하되는 문제점이 있다.The vinyl chloride-based resin composition of the present invention can improve whiteness and hiding properties by adding titanium dioxide (TiO 2 ). The titanium dioxide may be included in preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the vinyl chloride-based resin. When titanium dioxide is included in less than 3 parts by weight, the color does not come out properly after printing due to poor whiteness and hiding properties, and when it is included in excess of 15 parts by weight, there is a problem in that mechanical properties are lowered.
본 발명에 따른 염화비닐계 수지 조성물은 염화비닐계 수지, 상기 가소제 및 선택적으로 첨가제를 사용하여 당업계에 일반적으로 알려진 방법에 의하여 제조될 수 있으며, 그 방법에 있어서 특별히 한정되지는 않는다.The vinyl chloride-based resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride-based resin, the plasticizer and optionally an additive, and the method is not particularly limited.
상기 염화비닐계 수지 조성물은 겔링 속도가 우수하고 가소제 이행이 저감되며, 안료 배합 시 이염이 잘 일어나지 않는 장점을 나타낸다. 이에, 본 발명의 염화비닐계 수지 조성물은 매트, 바닥재, 의류코팅, 직물코팅, 타포린, 완구류, 벽지, 인조피혁 등 광범위한 분야에 사용될 수 있다. The vinyl chloride-based resin composition exhibits an advantage in that the gelling rate is excellent, the plasticizer migration is reduced, and the color transfer does not occur well when the pigment is mixed. Accordingly, the vinyl chloride-based resin composition of the present invention can be used in a wide range of fields such as mats, flooring, clothing coatings, textile coatings, tarpaulins, toys, wallpaper, and artificial leather.
한편, 본 발명의 다른 일 측면에 따르면, 상기 염화비닐계 수지 조성물을 포함하는 성형품이 제공된다. 상기 성형품은 그 용도에 따라 상기 염화비닐계 수지 조성물에 안정제, 충진제, 및/또는 발포제 등의 첨가제등을 추가로 첨가하여 제조될 수 있다.Meanwhile, according to another aspect of the present invention, there is provided a molded article including the vinyl chloride-based resin composition. The molded article may be manufactured by further adding additives such as a stabilizer, a filler, and/or a foaming agent to the vinyl chloride-based resin composition according to its use.
이하, 하기 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
<실시예><Example>
실시예 1Example 1
디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(DEHCH) 80 중량부, 디프로필렌글리콜 디벤조에이트(이스트만 BenzoflexTM 9-88) 10 중량부 및 트리옥틸트리멜리테이트(TOTM) 10 중량부를 혼합하여 가소제 조성물을 제조하였다. 80 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH), 10 parts by weight of dipropylene glycol dibenzoate (Eastman Benzoflex TM 9-88) and trioctyl trimellitate ( TOTM) 10 parts by weight was mixed to prepare a plasticizer composition.
폴리염화비닐(한화솔루션 KCH-15S, 중합도 1,700, 비닐아세테이트 함량 7.0±1%, D50=2.01㎛) 100 중량부에, 상기 가소제 조성물 100 중량부, Ba-Zn계 열 안정제(우창실업 KBZ-251F) 2 중량부, 및 안료(Pigment Yellow 12) 10 중량부를 혼합하여 염화비닐계 수지 조성물을 제조하였다.100 parts by weight of polyvinyl chloride (Hanwha Solution KCH-15S, polymerization degree 1,700, vinyl acetate content 7.0±1%, D50=2.01㎛), 100 parts by weight of the plasticizer composition, Ba-Zn-based heat stabilizer (Wuchang KBZ-251F) ) 2 parts by weight, and 10 parts by weight of pigment (Pigment Yellow 12) were mixed to prepare a vinyl chloride-based resin composition.
실시예 2Example 2
디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(DEHCH) 60 중량부, 3,3'- 디프로필렌글리콜 디벤조에이트(BenzoflexTM 9-88) 20 중량부 및 트리옥틸트리멜리테이트(TOTM) 20 중량부를 혼합하여 가소제 조성물을 제조하였다. 60 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH), 20 parts by weight of 3,3'-dipropylene glycol dibenzoate (Benzoflex TM 9-88), and trioctilt A plasticizer composition was prepared by mixing 20 parts by weight of limellitate (TOTM).
이후 상기 실시예 1과 동일한 방법으로 염화비닐계 수지 조성물을 제조하였다.Thereafter, a vinyl chloride-based resin composition was prepared in the same manner as in Example 1.
비교예 1Comparative Example 1
가소제로 디옥틸테레프탈레이트(DOTP) 100 중량부를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 염화비닐계 수지 조성물을 제조하였다. A vinyl chloride-based resin composition was prepared in the same manner as in Example 1, except that 100 parts by weight of dioctyl terephthalate (DOTP) was used as a plasticizer.
비교예 2Comparative Example 2
가소제로 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트(DEHCH) 100 중량부를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 염화비닐계 수지 조성물을 제조하였다.A vinyl chloride-based resin composition was prepared in the same manner as in Example 1, except that 100 parts by weight of di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (DEHCH) was used as a plasticizer.
비교예 3Comparative Example 3
가소제로 디프로필렌글리콜 디벤조에이트(BenzoflexTM 9-88) 100 중량부를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 염화비닐계 수지 조성물을 제조하였다.A vinyl chloride-based resin composition was prepared in the same manner as in Example 1, except that 100 parts by weight of dipropylene glycol dibenzoate (Benzoflex TM 9-88) was used as a plasticizer.
비교예 4Comparative Example 4
가소제로 트리옥틸트리멜리테이트(TOTM) 100 중량부를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 염화비닐계 수지 조성물을 제조하였다.A vinyl chloride-based resin composition was prepared in the same manner as in Example 1, except that 100 parts by weight of trioctyl trimellitate (TOTM) was used as a plasticizer.
<실험예><Experimental example>
상기 실시예 및 비교예에서 제조된 염화비닐계 수지 조성물에 대하여, 겔링속도, 점도, 가소제의 이행성, 및 이염성을 하기와 같이 평가하여 표 1에 나타내었다. For the vinyl chloride-based resin compositions prepared in Examples and Comparative Examples, the gelling rate, viscosity, plasticizer transferability, and color transfer properties were evaluated as follows and shown in Table 1.
(1) 점도(1) Viscosity
상기 실시예 및 비교예의 각 접착제 조성물을 25 ℃ 에서 1 시간 안정화시킨 후의 점도를 Brookfield viscometer (#6 spindle, 20 rpm)으로 측정하였다.The viscosity of each adhesive composition of Examples and Comparative Examples after stabilization at 25° C. for 1 hour was measured with a Brookfield viscometer (#6 spindle, 20 rpm).
(2) 겔링속도(2) Gelling rate
제조된 플라스티졸을 SVNC 장비를 이용하여 80 ℃에서 겔링속도를 측정하였다. SVNC 장비에서 겔링이 진행될수록 진폭(amplitude)이 감소하는데 이의 감소 속도를 이용하여 겔링 속도를 비교하고, 이를 점수화하여 하기 표 1에 나타내었다(매우 우수 5>4>3>2>1 매우 열세).The gelling rate of the prepared plastisol was measured at 80 °C using SVNC equipment. As gelling progresses in the SVNC equipment, the amplitude decreases. The gelling rate is compared using the decreasing rate, and the score is shown in Table 1 below (excellent 5>4>3>2>1 very poor) .
(3) 가소제 이행성(3) plasticizer transferability
제조된 플라스티졸을 0.1 mm 두께로 코팅 후 180 ℃에서 1분간 가열하여 Sheet를 제조하였다. 제조된 Sheet를 지름 약 4 cm의 원형 시편으로 절단하였다. ISO 177:1988 시험 규격에 기반하여, 60 ℃, 5 kg 하중 조건에서 7일 후 시트의 무게 변화를 측정하여 점수화하여 이행 특성을 평가하였으며, 그 결과를 하기 표 1에 나타내었다(매우 우수 5>4>3>2>1 매우 열세). After coating the prepared plastisol to a thickness of 0.1 mm, it was heated at 180° C. for 1 minute to prepare a sheet. The prepared sheet was cut into circular specimens with a diameter of about 4 cm. Based on the ISO 177:1988 test standard, the weight change of the sheet was measured and scored after 7 days at 60 ° C. and a load of 5 kg to evaluate the performance characteristics, and the results are shown in Table 1 below (excellent 5> 4>3>2>1 very inferior).
(4) 이염성(4) color transfer
상기 가소제 이행성 평가와 동일한 방식으로 제조된 시편 상부에 백색의 면소재 직물을 올리고, 60 ℃, 5 kg 하중 조건에서 7일 후 백색의 면소재 직물의 Yellow index 변화값(ΔY)을 측정하였으며, 그 결과를 하기 표 1에 나타내었다.A white cotton fabric was placed on the upper part of the specimen prepared in the same manner as in the evaluation of plasticizer transferability, and the yellow index change value (ΔY) of the white cotton fabric was measured after 7 days at 60 ° C. and 5 kg load condition. is shown in Table 1 below.
(중량부)plasticizer composition
(parts by weight)
@25℃(cps)viscosity
@25℃(cps)
상기 표 1을 참조하면, 실시예 1 및 2의 염화비닐계 수지 조성물은 DOTP를 가소제로 사용한 비교예 1에 비하여 점도, 겔링속도, 가소제 내이행성, 내이염성 등의 물성이 모두 우수한 것을 확인할 수 있다. 또한 실시예 1 및 2는 사이클로헥산 디카르복실레이트계 화합물, 또는 트리멜리테이트계 화합물 각각을 가소제로 사용한 비교예 2, 4와 비교하여서도 우수한 물성을 나타내었다. 한편, 가소제로 벤조에이트계 화합물을 단독 사용한 비교예 3의 경우, 제조된 염화비닐계 수지 조성물(플라스티졸)이 제조 직후 굳어져 물성을 측정할 수 없었다. Referring to Table 1, it can be seen that the vinyl chloride-based resin compositions of Examples 1 and 2 are excellent in physical properties such as viscosity, gelling rate, plasticizer migration resistance, and color migration resistance compared to Comparative Example 1 using DOTP as a plasticizer. . In addition, Examples 1 and 2 exhibited excellent physical properties compared to Comparative Examples 2 and 4 in which each of the cyclohexane dicarboxylate-based compound or the trimellitate-based compound was used as a plasticizer. On the other hand, in the case of Comparative Example 3 in which a benzoate-based compound was used alone as a plasticizer, the prepared vinyl chloride-based resin composition (plastisol) was hardened immediately after preparation, and thus physical properties could not be measured.
Claims (11)
상기 염화비닐계 수지는 페이스트 수지이고,
상기 가소제는 사이클로헥산 디카르복실레이트계 화합물, 벤조에이트계 화합물, 및 트리멜리테이트계 화합물을 포함하는 것인, 염화비닐계 수지 조성물.
A vinyl chloride-based resin composition comprising a vinyl chloride-based resin and a plasticizer, comprising:
The vinyl chloride-based resin is a paste resin,
The plasticizer is a vinyl chloride-based resin composition comprising a cyclohexane dicarboxylate-based compound, a benzoate-based compound, and a trimellitate-based compound.
상기 염화비닐계 수지는 염화비닐-비닐아세테이트 공중합체인, 염화비닐계 수지 조성물.
According to claim 1,
The vinyl chloride-based resin is a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-based resin composition.
상기 염화비닐계 수지는 중합도가 500 내지 2,000인, 염화비닐계 수지 조성물.
According to claim 1,
The vinyl chloride-based resin has a polymerization degree of 500 to 2,000, the vinyl chloride-based resin composition.
상기 가소제는 염화비닐계 수지 100 중량부에 대하여 50 내지 150 중량부로 포함되는, 염화비닐계 수지 조성물.
According to claim 1,
The plasticizer is included in an amount of 50 to 150 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, the vinyl chloride-based resin composition.
상기 가소제는,
사이클로헥산 디카르복실레이트계 화합물 20 내지 90 중량부,
벤조에이트계 화합물 5 내지 40 중량부, 및
트리멜리테이트계 화합물 5 내지 40 중량부를 포함하는, 염화비닐계 수지 조성물.
According to claim 1,
The plasticizer is
20 to 90 parts by weight of a cyclohexane dicarboxylate-based compound,
5 to 40 parts by weight of a benzoate-based compound, and
A vinyl chloride-based resin composition comprising 5 to 40 parts by weight of a trimellitate-based compound.
상기 사이클로헥산 디카르복실레이트계 화합물은 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 부틸(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 디부틸사이클로헥산-1,4-디카르복실레이트, 디(2-에틸헥실)사이클로헥산-1,3-디카르복실레이트, 디이소부틸사이클로헥산-1,3-디카르복실레이트, 디부틸사이클로헥산-1,2-디카르복실레이트, 디이소노닐사이클로헥산-1,2-디카르복실레이트, 디(2-에틸헥실)사이클로헥산-1,2-디카르복실레이트, 및 디이소데실사이클로헥산-1,2-디카르복실레이트로 이루어지는 군에서 선택되는 1종 이상인, 염화비닐계 수지 조성물.
According to claim 1,
The cyclohexane dicarboxylate-based compound is di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, butyl(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, dibutyl Cyclohexane-1,4-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,3-dicarboxylate, diisobutylcyclohexane-1,3-dicarboxylate, dibutylcyclohexane -1,2-dicarboxylate, diisononylcyclohexane-1,2-dicarboxylate, di(2-ethylhexyl)cyclohexane-1,2-dicarboxylate, and diisodecylcyclohexane - At least one selected from the group consisting of 1,2-dicarboxylate, a vinyl chloride-based resin composition.
상기 벤조에이트계 화합물은 소듐 벤조에이트, 이소노닐 벤조에이트, 이소데실 벤조에이트, 2-프로필헵틸 벤조에이트, 디에틸렌글리콜 디벤조에이트, 디프로필렌글리콜 디벤조에이트, 1,2-프로판디올 디벤조에이트, 및 디부틸렌글리콜 디벤조에이트로 이루어지는 군에서 선택되는 1종 이상인, 염화비닐계 수지 조성물.
According to claim 1,
The benzoate-based compound is sodium benzoate, isononyl benzoate, isodecyl benzoate, 2-propylheptyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, 1,2-propanediol dibenzoate , And at least one selected from the group consisting of dibutylene glycol dibenzoate, a vinyl chloride-based resin composition.
상기 트리멜리테이트계 화합물은 트리-(2-에틸헥실) 트리멜리테이트, 트리메틸 트리멜리테이트, 트리헥실 트리멜리테이트, 트리헵틸 트리멜리테이트, 트리-(n-옥틸,n-데실) 트리멜리테이트, 및 트리-(헵틸,노닐) 트리멜리테이트로 이루어지는 군에서 선택되는 1종 이상인, 염화비닐계 수지 조성물.
According to claim 1,
The trimellitate-based compound is tri-(2-ethylhexyl) trimellitate, trimethyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, tri-(n-octyl, n-decyl) trimellitate. , And tri- (heptyl, nonyl) at least one selected from the group consisting of trimellitate, a vinyl chloride-based resin composition.
상기 가소제는 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트, 3 디프로필렌글리콜 디벤조에이트, 및 트리-(2-에틸헥실) 트리멜리테이트를 포함하는 것인, 염화비닐계 수지 조성물
According to claim 1,
Wherein the plasticizer comprises di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate, 3 dipropylene glycol dibenzoate, and tri- (2-ethylhexyl) trimellitate, vinyl chloride based resin composition
열 안정제 및 안료를 더 포함하는, 염화비닐계 수지 조성물.
According to claim 1,
Further comprising a heat stabilizer and a pigment, a vinyl chloride-based resin composition.
A molded article comprising the vinyl chloride-based resin composition of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210016869A KR20220113099A (en) | 2021-02-05 | 2021-02-05 | Vinylchloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210016869A KR20220113099A (en) | 2021-02-05 | 2021-02-05 | Vinylchloride resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20220113099A true KR20220113099A (en) | 2022-08-12 |
Family
ID=82803945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210016869A KR20220113099A (en) | 2021-02-05 | 2021-02-05 | Vinylchloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20220113099A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220259401A1 (en) * | 2021-02-18 | 2022-08-18 | Hanwha Solutions Corporation | Plasticizer Composition, and Sealant/adhesive Compositions including the Same |
-
2021
- 2021-02-05 KR KR1020210016869A patent/KR20220113099A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220259401A1 (en) * | 2021-02-18 | 2022-08-18 | Hanwha Solutions Corporation | Plasticizer Composition, and Sealant/adhesive Compositions including the Same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9388293B2 (en) | Polyvinyl chloride compositions | |
| KR101833175B1 (en) | Plasticizer, resin composition and method for preparing them | |
| CN106604963A (en) | Stabilizer composition for vinyl chloride resin, vinyl chloride resin composition using said stabilizer composition, and molded article obtained from said resin composition | |
| TWI609904B (en) | Plasticizer composition | |
| KR20220113099A (en) | Vinylchloride resin composition | |
| CA2047335A1 (en) | Barrier pvc resins, compounds and articles derived therefrom | |
| KR102496350B1 (en) | Plasticizer composition and vinylchloride resin composition comprising the same | |
| KR102546139B1 (en) | Vinylchloride resin composition | |
| KR102658860B1 (en) | Vinylchloride resin composition | |
| KR100838474B1 (en) | Chlorinated vinyl resin composition for transparent and soft sheet | |
| US20230365798A1 (en) | Vinylchloride resin composition | |
| KR102506279B1 (en) | Plasticizer composition and vinylchloride resin composition comprising the same | |
| KR102640280B1 (en) | Vinylchloride resin composition for gloves | |
| KR102462258B1 (en) | Composite plasticizer and resin composition comprising same | |
| KR20220094805A (en) | Plasticizer composition | |
| WO2023085815A1 (en) | Plasticizer composition, and vinylchloride resin composition comprising same | |
| KR20190026377A (en) | Stabilizer and polyvinyl chloride sheet prepared using the same | |
| KR20220094806A (en) | Plasticizer composition | |
| WO2021033399A1 (en) | Chlorine-containing resin composition and molded product thereof | |
| KR20220113098A (en) | Plasticizer composition and vinylchloride resin composition comprising the same | |
| JPH10219058A (en) | Vinyl chloride resin composition | |
| KR20220124429A (en) | Plasticizer composition | |
| KR20230085664A (en) | Plasticizer composition and Polyvinyl chloride based resin composition comprising the same | |
| KR20230068032A (en) | Plasticizer composition and vinylchloride resin composition comprising the same | |
| JP2024501336A (en) | plasticizer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal |