JP2019044009A - Method for producing polyvinyl chloride resin molding - Google Patents
Method for producing polyvinyl chloride resin molding Download PDFInfo
- Publication number
- JP2019044009A JP2019044009A JP2017165847A JP2017165847A JP2019044009A JP 2019044009 A JP2019044009 A JP 2019044009A JP 2017165847 A JP2017165847 A JP 2017165847A JP 2017165847 A JP2017165847 A JP 2017165847A JP 2019044009 A JP2019044009 A JP 2019044009A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- mass
- parts
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 193
- 239000011347 resin Substances 0.000 title claims abstract description 193
- 238000000465 moulding Methods 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000004800 polyvinyl chloride Substances 0.000 title abstract description 47
- 229920000915 polyvinyl chloride Polymers 0.000 title abstract description 46
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 174
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 15
- 239000000194 fatty acid Substances 0.000 description 15
- 229930195729 fatty acid Natural products 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 13
- -1 coalesced Chemical compound 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 239000004609 Impact Modifier Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 239000003549 soybean oil Chemical class 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 241000251468 Actinopterygii Species 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 150000005846 sugar alcohols Chemical class 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001279 adipic acids Chemical class 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 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 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical class OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229960002969 oleic acid Drugs 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BEEPXSBZGLKIOT-UHFFFAOYSA-N 1-(4-fluorophenyl)-1,3,8-triazaspiro[4.5]decan-4-one Chemical compound C1=CC(F)=CC=C1N1C2(CCNCC2)C(=O)NC1 BEEPXSBZGLKIOT-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
- VRHUZZLSVQTROS-UHFFFAOYSA-N 2-butoxycarbonylcyclohexane-1-carboxylic acid Chemical compound CCCCOC(=O)C1CCCCC1C(O)=O VRHUZZLSVQTROS-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QNFATTZINRAXTI-UHFFFAOYSA-N C(C)C(COP(=O)(OCC(CCCC)CC)OCC(CCCC)CC)CCCC.P(=O)(O)(O)O Chemical class C(C)C(COP(=O)(OCC(CCCC)CC)OCC(CCCC)CC)CCCC.P(=O)(O)(O)O QNFATTZINRAXTI-UHFFFAOYSA-N 0.000 description 1
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019074 Mg-Sn Inorganic materials 0.000 description 1
- 229910019382 Mg—Sn Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229910020220 Pb—Sn Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- ZTUZDYWYNQDJKR-UHFFFAOYSA-N diethyl cyclohexane-1,2-dicarboxylate Chemical compound CCOC(=O)C1CCCCC1C(=O)OCC ZTUZDYWYNQDJKR-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、摩擦抵抗が小さく、艶消しの表面を有する成形物を得ることができる、ポリ塩化ビニル系樹脂成形物の製造方法に関する。 The present invention relates to a method for producing a polyvinyl chloride resin molded article, which can obtain a molded article having a low frictional resistance and a matte surface.
ポリ塩化ビニル（ＰＶＣ）を用いた樹脂成形物は、耐薬品性・耐候性・難燃性・電気絶縁性などの優れた化学的・物理的性質を有し、かつ安価であることから、利用価値の高い汎用樹脂材料として広く用いられている。ＰＶＣ樹脂は、可塑剤の添加により容易に柔軟性を付与したり軟質化できることから、被覆材、床材や防水シート、テープ類や袋類、ホース等、多岐に亘る用途に使用されている。 Resin moldings made of polyvinyl chloride (PVC) are used because they have excellent chemical and physical properties such as chemical resistance, weather resistance, flame retardancy, and electrical insulation, and are inexpensive. It is widely used as a high-value general purpose resin material. PVC resin is used in a wide variety of applications such as covering materials, floorings, waterproof sheets, tapes and bags, hoses, etc. because it can be easily imparted with flexibility or softened by the addition of a plasticizer.
従来の一般的なＰＶＣからなる樹脂成形物は、手や脚などの肌で触れた際の感触が好ましくなく、べたつきや肌への張り付き感を感じることもあった。また、合成樹脂特有の光沢があることから、特に高級感を求められるような場面においては、外観上好ましいとは必ずしもいえなかった。例えば、軟質ＰＶＣを用いた散水用ホースは、平滑で滑らかな表面形態を有するものの、その一方で、ホース表面の粘着性や摩擦抵抗性が高いため、リールに巻き取るとホース同士が密着して巻き取りや引き出しがスムーズにできない等の問題があった。 The conventional resin molded product made of PVC has an undesirable feel when touched with skin such as hands and legs, and sometimes feels stickiness or sticking to the skin. In addition, because of the luster unique to synthetic resins, it was not always preferable in terms of appearance particularly in situations where a high-class feeling is required. For example, although a hose for watering using soft PVC has a smooth and smooth surface form, the adhesion and friction resistance of the hose surface are high, so the hoses adhere to each other when wound up on a reel There were problems such as being unable to take up and pull out smoothly.
そのため、ＰＶＣ樹脂成形物の表面形態を改善することが行われている。例えば、ポリ塩化ビニル系樹脂に部分架橋樹脂および表面改質剤を添加することが提案されている（特許文献１）。特許文献１によれば、部分架橋樹脂を添加した塩化ビニル樹脂組成物を押出成形することで低摩擦性面が形成され、樹脂成形物表面の摩擦抵抗を低減できるとされている。また、特許文献１のような部分架橋樹脂を使用せずに塩化ビニル樹脂製ホース表面のベタつきを改善することも提案されている（特許文献２）。特許文献２によれば、分子量の異なる複数の合成樹脂を混合し、低分子量樹脂の溶融温度よりも高く、かつ高分子量樹脂の溶融温度よりも低い温度で加熱成形を行うことにより、成形物の外表面に微細な凹凸（フィッシュアイ）が形成され、摩擦抵抗を低減した合成樹脂ホースが得られるとされている。 Therefore, improving the surface form of a PVC resin molding is performed. For example, it has been proposed to add a partially crosslinked resin and a surface modifier to a polyvinyl chloride resin (Patent Document 1). According to Patent Document 1, by extruding a vinyl chloride resin composition to which a partially crosslinked resin is added, a low friction surface is formed, and it is said that the frictional resistance on the surface of a resin molded product can be reduced. Further, it has also been proposed to improve the stickiness of the surface of a vinyl chloride resin hose without using a partially crosslinked resin as in Patent Document 1 (Patent Document 2). According to Patent Document 2, a plurality of synthetic resins having different molecular weights are mixed, and heat molding is performed at a temperature higher than the melting temperature of the low molecular weight resin and lower than the melting temperature of the high molecular weight resin. Fine irregularities (fish eyes) are formed on the outer surface, and it is believed that a synthetic resin hose with reduced frictional resistance can be obtained.
しかしながら、特許文献２に記載の成形物においては、フィッシュアイを形成するためには、ベースとして用いられるＰＶＣ樹脂の溶融温度よりも実質的に高い溶融温度で成形を行う必要があるため、通常のＰＶＣ樹脂を用いた成形物製造ラインの押出成形機を用いてフィッシュアイを形成するには、押出成形機の温度条件を変更する必要がある。そのため、同じ製造ラインの押出成形機を用いて、通常のＰＶＣ樹脂成形物と、フィッシュアイを形成したＰＶＣ樹脂成形物とを交互に製造するような場合には、その都度、押出成形機の温度調整を行う必要があるため、煩雑である。また、通常のＰＶＣ樹脂に加えて高分子量のＰＶＣ樹脂を使用するため、成形加工時の安定性が損なわれる場合もあった。 However, in the molding described in Patent Document 2, in order to form a fish-eye, it is necessary to carry out molding at a melting temperature substantially higher than the melting temperature of the PVC resin used as a base. In order to form a fish eye using an extruder of a molding production line using a PVC resin, it is necessary to change the temperature condition of the extruder. Therefore, when using an extrusion molding machine of the same production line to alternately produce a normal PVC resin molding and a PVC resin molding having a fish eye formed thereon, the temperature of the extrusion molding machine each time It is complicated because it is necessary to make adjustments. Moreover, in addition to the normal PVC resin, in order to use a high molecular weight PVC resin, the stability at the time of a shaping | molding process might be impaired.
したがって、本発明は、押出成形機の温度等の成形加工条件を変更することなく、表面の摩擦抵抗が低減され、艶消しの表面を有する成形物を得ることができる、ポリ塩化ビニル系樹脂成形物の製造方法を提供することである。また、本発明の別の目的は、表面の摩擦抵抗が低減され、艶消しの表面を有するポリ塩化ビニル系樹脂成形物を提供することである。 Therefore, according to the present invention, polyvinyl chloride resin molding in which the frictional resistance of the surface is reduced and a molded article having a matte surface can be obtained without changing molding processing conditions such as the temperature of the extruder. It is providing the manufacturing method of goods. In addition, another object of the present invention is to provide a polyvinyl chloride resin molded article having a matte surface and reduced surface frictional resistance.
本発明者は、鋭意研究した結果、ポリ塩化ビニル系樹脂に可塑剤を配合したコンパウンドを用いてポリ塩化ビニル系樹脂成形物を製造する際に、コンパウンドとともにポリ塩化ビニル系樹脂を添加して押出成形を行うことで、上記課題を達成できることを見出した。本発明は係る知見によるものである。 As a result of intensive researches, the present inventor adds polyvinyl chloride resin together with a compound and extrudes it when manufacturing a polyvinyl chloride resin molded article using a compound in which a plasticizer is mixed with polyvinyl chloride resin. It has been found that the above problems can be achieved by molding. The present invention is based on such findings.
すなわち、本発明によるポリ塩化ビニル系樹脂成形物の製造方法は、
（Ａ）成分（ａ）第１の塩化ビニル系樹脂 １００質量部と、
成分（ｂ）可塑剤 ４０質量部以上、１００質量部以下と、
を混練した塩化ビニル系樹脂コンパウンドを準備する工程、および
（Ｂ）前記塩化ビニル系樹脂コンパウンドに、第２の塩化ビニル系樹脂を添加して、溶融成形を行う工程、
を含み、
前記第２の塩化ビニル系樹脂の平均重合度Ｐ２が、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１の０．５倍以上、１．９倍以下であり、
前記第２の塩化ビニル系樹脂の配合量が、前記塩化ビニル系樹脂コンパウンド１００質量部に対して１質量部以上、８質量部以下である、ことを特徴とする。
That is, the method for producing a polyvinyl chloride resin molded article according to the present invention is
(A) Component (a) 100 parts by mass of a first vinyl chloride resin,
Component (b) plasticizer 40 to 100 parts by mass,
Preparing a vinyl chloride resin compound obtained by kneading, and (B) adding a second vinyl chloride resin to the vinyl chloride resin compound and performing melt molding,
Including
The average polymerization degree P2 of the second vinyl chloride resin is 0.5 times or more and 1.9 times or less the average polymerization degree P1 of the first vinyl chloride resin,
The compounding amount of the second vinyl chloride resin is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin compound.
第２の発明は、前記溶融成形が、前記塩化ビニル系樹脂コンパウンドの溶融成形温度にて行われる、第１の発明に記載の製造方法である。 A second invention is the manufacturing method according to the first invention, wherein the melt molding is performed at a melt molding temperature of the vinyl chloride resin compound.
第３の発明は、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１が、５００以上、３，０００以下である、第１または第２の発明に記載の製造方法である。 A third invention is the production method according to the first or second invention, wherein the average degree of polymerization P1 of the first vinyl chloride resin is 500 or more and 3,000 or less.
第４の発明は、前記塩化ビニル系樹脂コンパウンドは、安定剤をさらに含む、第１〜第３の発明のいずれかに記載の製造方法である。 A fourth invention is the process according to any one of the first to third inventions, wherein the vinyl chloride resin compound further contains a stabilizer.
第５の発明は、前記第２の塩化ビニル系樹脂の平均重合度Ｐ２が、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．０倍以下である、第１〜第４の発明のいずれかに記載の製造方法である。 The fifth invention is the first to fourth inventions, wherein the average polymerization degree P2 of the second vinyl chloride resin is 1.0 times or less the average polymerization degree P1 of the first vinyl chloride resin. It is a manufacturing method as described in any of.
第６の発明の塩化ビニル系樹脂成形物は、
（Ａ）成分（ａ）第１の塩化ビニル系樹脂 １００質量部と、
成分（ｂ）可塑剤 ４０質量部以上、１００質量部以下と、
を混練した塩化ビニル系樹脂コンパウンド、および
（Ｂ）第２の塩化ビニル系樹脂、
を含む、塩化ビニル系樹脂成形物であって、
前記前記第２の塩化ビニル系樹脂の平均重合度Ｐ２が、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．０倍以下であり、
前記第２の塩化ビニル系樹脂の配合量が、前記塩化ビニル系樹脂コンパウンド１００質量部に対して１質量部以上、８質量部以下である、ことを特徴とする。
The vinyl chloride resin molded article of the sixth invention is
(A) Component (a) 100 parts by mass of a first vinyl chloride resin,
Component (b) plasticizer 40 to 100 parts by mass,
Vinyl chloride resin compound obtained by kneading and (B) second vinyl chloride resin,
A vinyl chloride resin molded product containing
The average polymerization degree P2 of the second vinyl chloride resin is 1.0 times or less of the average polymerization degree P1 of the first vinyl chloride resin,
The compounding amount of the second vinyl chloride resin is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin compound.
第７の発明は、表面に、前記第２の塩化ビニル系樹脂の未ゲル物が分散されてなる、第６の発明に記載の塩化ビニル系樹脂成形物である。 A seventh invention is the molded vinyl chloride resin article according to the sixth invention, wherein the ungelled product of the second vinyl chloride resin is dispersed on the surface.
本発明によれば、第１の塩化ビニル系樹脂を含む塩化ビニル系樹脂コンパウンドに、所定の重合度を有する第２の塩化ビニル系樹脂を添加して、溶融成形を行うことにより、押出成形機の温度等の成形加工条件を変更することなく、表面の摩擦抵抗性が低減され、摺動性があり、艶消しの（マット感のある）外観を有する塩化ビニル系樹脂成形物を製造することができる。 According to the present invention, an extrusion molding machine is obtained by adding a second vinyl chloride resin having a predetermined degree of polymerization to a first vinyl chloride resin compound containing a vinyl chloride resin and performing melt molding. Manufacturing a vinyl chloride resin molded article having a sliding property and having a matte (matt) appearance, with the surface being reduced in frictional resistance and without changing molding processing conditions such as the temperature of Can.
＜塩化ビニル系樹脂成形物の製造方法＞
本発明による塩化ビニル系樹脂成形物の製造方法は、所定の塩化ビニル系樹脂コンパウンドを準備する工程と、準備した塩化ビニル系樹脂コンパウンドに第２の塩化ビニル系樹脂を添加して溶融成形を行う工程を含むものである。以下、各工程について説明する。
<Method for producing vinyl chloride resin molded product>
The method for producing a vinyl chloride resin molded article according to the present invention comprises the steps of preparing a predetermined vinyl chloride resin compound, and performing melt molding by adding a second vinyl chloride resin to the prepared vinyl chloride resin compound. Including the steps. Each step will be described below.
塩化ビニル系樹脂コンパウンド準備工程：
本発明による塩化ビニル系樹脂成形物の製造方法においては、塩化ビニル系樹脂コンパウンドが使用される。塩化ビニル系樹脂コンパウンドとは、塩化ビニル系樹脂に可塑剤や安定剤等の添加剤を予め添加し、混練して得られた樹脂組成物を意味する。所定量の可塑剤を配合した塩化ビニル系樹脂コンパウンドとすることにより、得られる成形物は軟質塩化ビニル系樹脂成形物となる。
Preparation process of vinyl chloride resin compound:
In the method for producing a vinyl chloride resin molded article according to the present invention, a vinyl chloride resin compound is used. The vinyl chloride-based resin compound means a resin composition obtained by adding, in advance, additives such as a plasticizer and a stabilizer to a vinyl chloride-based resin and kneading them. By forming a vinyl chloride resin compound containing a predetermined amount of a plasticizer, the resulting molded product becomes a soft vinyl chloride resin molded product.
塩化ビニル系樹脂コンパウンドの調製時に使用する成分（ａ）第１の塩化ビニル系樹脂とは、−ＣＨ２−ＣＨＣｌ−で表される基を有する重合体を意味し、塩化ビニルの単独重合体だけでなく、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニルと塩化ビニルと共重合可能な他のモノマーとの共重合体；後塩素化ビニル共重合体等の塩化ビニル単独重合体や塩化ビニル系共重合体を改質したもの；更には塩素化ポリエチレン等の構造上塩化ビニル樹脂と類似の塩素化ポリオレフィンを包含する。これらの塩化ビニル樹脂は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Component (a) The first vinyl chloride-based resin used in preparation of the vinyl chloride-based resin compound means a polymer having a group represented by -CH 2 -CHCl-, and it is only a homopolymer of vinyl chloride Not, but vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / methyl (meth) acrylate copolymer, vinyl chloride / ethyl (meth) acrylate copolymer, Vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer , Vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene Polymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate ternary copolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymer Copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride, such as coalesced, etc .; Post-modified vinyl chloride homopolymers and vinyl chloride-based copolymers such as chlorinated vinyl copolymers; Include chlorinated polyolefins structurally similar to vinyl chloride resins such as chlorinated polyethylene. These vinyl chloride resins may be used alone or in combination of two or more.
成分（ａ）第１の塩化ビニル系樹脂の平均重合度Ｐ１は、３００以上、５，０００以下の範囲にあることが好ましく、５００以上、３，０００以下のものがより好ましく、７００以上、１，３００以下のものがさらに好ましい。平均重合度Ｐ１を３００以上とすることで、得られる成形体の機械特性が良好となる。また、平均重合度を５，０００以下とすることで、ゲル化特性が良好となる。なお、平均重合度とは、塩化ビニル系樹脂をテトラヒドロフラン（ＴＨＦ）に溶解させ、ろ過により不溶成分を除去した後、ろ液中のＴＨＦを乾燥除去して得られた樹脂を試料として、ＪＩＳ Ｋ６７２１「塩化ビニル樹脂試験方法」に準拠して測定された値を意味する。 Component (a) The average degree of polymerization P1 of the first vinyl chloride resin is preferably in the range of 300 or more and 5,000 or less, more preferably 500 or more and 3,000 or less, 700 or more, 1 , 300 or less is more preferable. By setting the average degree of polymerization P1 to 300 or more, the mechanical properties of the obtained molded article become good. In addition, by setting the average degree of polymerization to 5,000 or less, the gelling property becomes good. The average degree of polymerization is determined by dissolving a vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and then drying and removing THF in the filtrate as a sample according to JIS K6721. It means the value measured in accordance with the "vinyl chloride resin test method".
本発明に用いる成分（ａ）第１の塩化ビニル系樹脂の製造方法は特に制限はなく、乳化重合法、懸濁重合法、塊状重合法等の種々の重合法で製造したものを使用することができる。 There is no particular limitation on the method for producing the first vinyl chloride-based resin used in the component (a) of the present invention, and it is possible to use those produced by various polymerization methods such as emulsion polymerization, suspension polymerization and bulk polymerization. Can.
塩化ビニル系樹脂コンパウンドを調製する際に用いられる成分（ｂ）可塑性としては、本発明の目的に反しない限度において、任意の適切な可塑剤を用いることができる。このような可塑剤としては、例えば、フタル酸エステル可塑剤、や非フタル酸系の可塑剤を用いることができる。フタル酸エステル可塑剤としては、フタル酸ジオクチル（ＤＯＰ）を用いることが特に好ましい。 As the component (b) plasticity used in preparing the vinyl chloride resin compound, any suitable plasticizer can be used as long as the object of the present invention is not violated. As such a plasticizer, for example, a phthalate ester plasticizer or a non-phthalic acid plasticizer can be used. It is particularly preferable to use dioctyl phthalate (DOP) as a phthalate ester plasticizer.
また、非フタル酸系の可塑剤を併用してもよい。非フタル酸系の可塑剤としては、トリメリット酸系化合物、リン酸系化合物、アジピン酸系化合物、クエン酸系化合物、エーテル系化合物、ポリエステル系化合物、大豆油系化合物、シクロヘキサンジカルボキシレート系化合物、テレフタル酸系化合物から選ばれる少なくとも１種であることが好ましく、例えば、トリメリット酸トリス（２−エチルヘキシル）、トリメリット酸トリイソノニル等のトリメリット酸エステル類；リン酸トリ（２−エチルヘキシル）、リン酸トリクレジル、リン酸トリキシレニル等のリン酸エステル類；アジピン酸（２−エチルヘキシル）、アジピン酸ジイソノニル等のアジピン酸エステル類；アセチルクエン酸トリブチル等のクエン酸エステル；ポリプロピレングリコール等のエーテル系化合物；ポリエステル系化合物；エポキシ化大豆油等の大豆油系化合物；ジメチルシクロヘキサン−１，２−ジカルボキシレート、ジエチルシクロヘキサン−１，２−ジカルボキシレート、ジｎ−ブチルシクロヘキサン−１，２−ジカルボキシレート、ジ−２−エチルヘキシルシクロヘキサン−１，２−ジカルボキシレート、ジイソノニルシクロヘキサン−１，２−ジカルボキシレート、ジイソデシルシクロヘキサン−１，２−ジカルボキシレートなどのシクロヘキサンジカルボキシレート系化合物；ジテレフタル酸ジ−２−エチルヘキシルなどのテレフタル酸系化合物を挙げることができる。中でも、ジイソノニルシクロヘキサン−１，２−ジカルボキシレート、テレフタル酸ジ−２−エチルヘキシルが人体への安全性の面で好ましい。これらは、１種を単独で用いることもできるし、また、２種以上を組合せて併用することもできる。 In addition, non-phthalic acid plasticizers may be used in combination. Non-phthalic acid plasticizers include trimellitic acid compounds, phosphoric acid compounds, adipic acid compounds, citric acid compounds, ether compounds, polyester compounds, soybean oil compounds, cyclohexane dicarboxylate compounds And at least one selected from terephthalic acid compounds, for example, trimellitic esters such as tris (2-ethylhexyl) trimellitate and triisononyl trimellitate; tri (2-ethylhexyl) phosphate Phosphoric acid esters such as tricresyl phosphate and trixylyl phosphate; adipic acid esters such as adipic acid (2-ethylhexyl) and diisononyl adipate; citric acid esters such as tributyl acetyl citrate; ether compounds such as polypropylene glycol; Polyeste Compound; soybean oil compound such as epoxidized soybean oil; dimethylcyclohexane-1,2-dicarboxylate, diethylcyclohexane-1,2-dicarboxylate, di n-butylcyclohexane-1,2-dicarboxylate, Cyclohexane dicarboxylate compounds such as di-2-ethylhexyl cyclohexane-1,2-dicarboxylate, diisononyl cyclohexane-1,2-dicarboxylate, diisodecyl cyclohexane-1,2-dicarboxylate; diterephthalic acid di-2 -Terephthalic acid compounds such as ethylhexyl can be mentioned. Among them, diisononylcyclohexane-1,2-dicarboxylate and di-2-ethylhexyl terephthalate are preferable in terms of safety to the human body. One of these may be used alone, or two or more of these may be used in combination.
塩化ビニル系樹脂コンパウンドを調製する際の成分（ｂ）可塑剤の配合量を、成形物の使用用途に応じて調整することにより、例えば、カーテンレール、散水用や材料送達用などの可撓性ホース、自動車内装材料、被覆電線・床材・防水シートをはじめとしたシート類、テープ・農業用をはじめとしたフィルム類など、様々な用途で用いることができる。 By adjusting the compounding amount of the component (b) plasticizer at the time of preparing a vinyl chloride resin compound according to the use application of a molding, for example, flexibility for curtain rails, for water sprinkling, for material delivery, etc. It can be used in various applications such as hoses, automotive interior materials, sheets such as coated electric wires / floors and waterproof sheets, and films such as tapes and agricultural products.
成分（ｂ）可塑性の配合量としては、目的とする成形物の用途にもよるが、本発明においては、第１の塩化ビニル系樹脂１００質量部に対して、４０質量部以上、１００質量部以下の割合で配合する。可塑剤の配合量が上記範囲であれば、柔軟性が良好ないわゆる軟質塩化ビニル系樹脂成形物を得ることがきるとともに、成形加工時のベタつきを抑制することができる。可塑剤の好ましい配合量は、第１の塩化ビニル系樹脂１００質量部に対して、４５質量部以上、９０質量部以下であり、より好ましくは５０質量部以上、８０質量部以下である。 Although the compounding amount of the component (b) plasticity depends on the intended use of the molded product, in the present invention, 40 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the first vinyl chloride resin. Blend in the following proportions. If the compounding quantity of a plasticizer is the said range, while being able to obtain what is called a soft vinyl chloride resin molded article with a favorable softness | flexibility, the stickiness at the time of shaping | molding processing can be suppressed. The preferable blending amount of the plasticizer is 45 parts by mass or more and 90 parts by mass or less, more preferably 50 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the first vinyl chloride resin.
塩化ビニル系樹脂コンパウンドを調製する際、上記した成分（ａ）および成分（ｂ）以外の成分が含まれていてもよい。本発明においては、本発明の効果を損なわない限りにおいて、その目的に応じて、慣用の安定剤、充填材、難燃剤、滑剤、耐衝撃性改質剤等の各種添加剤を必要に応じて添加することができる。 When preparing a vinyl chloride resin compound, components other than the above-mentioned component (a) and component (b) may be contained. In the present invention, various additives such as conventional stabilizers, fillers, flame retardants, lubricants, impact modifiers and the like may be used according to the purpose, as long as the effects of the present invention are not impaired. It can be added.
安定剤としては、例えば三塩基性硫酸鉛、二塩基性亜リン酸鉛、塩基性亜硫酸鉛、ケイ酸鉛等の鉛系安定剤、カリウム、マグネシウム、バリウム、亜鉛、カドミウム、鉛等の金属と２‐エチルヘキサン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、オレイン酸、リシノール酸、リノール酸、ベヘニン酸等の脂肪酸から誘導される金属石けん系安定剤；アルキル基、エステル基、脂肪酸基、マレイン酸基、含硫化物基等を有してなる有機スズ系安定剤；Ｂａ−Ｚｎ系、Ｃａ−Ｚｎ系、Ｂａ−Ｃａ−Ｓｎ系、Ｃａ−Ｍｇ−Ｓｎ系、Ｃａ−Ｚｎ−Ｓｎ系、Ｐｂ−Ｓｎ系、Ｐｂ−Ｂａ−Ｃａ系等の複合金属石けん系安定剤；バリウム、亜鉛等の金属基と２−エチルヘキサン酸、イソデカン酸、トリアルキル酢酸等の分岐脂肪酸、オレイン酸、リシノール酸、リノール酸等の不飽和脂肪酸、ナフテン酸等の脂環族酸、石炭酸、安息香酸、サリチル酸、それらの置換誘導体等の芳香族酸といった有機酸の通常２種以上から誘導される金属塩系安定剤；これら安定剤を石油系炭化水素、アルコール、グリセリン誘導体等の有機溶剤に溶解し、さらに亜リン酸エステル、エポキシ化合物、発色防止剤、透明性改良剤、光安定剤、酸化防止剤、ブリードアウト防止剤、滑剤等の安定化助剤を配合してなる金属塩液状安定剤等といった金属系安定剤のほか、エポキシ樹脂、エポキシ化脂肪酸アルキルエステル等のエポキシ化合物、有機亜リン酸エステル等の非金属系安定剤が挙げられ、これらは１種または２種以上組み合わせて用いられる。 Examples of stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate, and metals such as potassium, magnesium, barium, zinc, cadmium and lead Metal soap stabilizers derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid; Group, ester group, fatty acid group, maleic acid group, sulfur-containing group and the like; organotin-based stabilizer; Ba-Zn-based, Ca-Zn-based, Ba-Ca-Sn-based, Ca-Mg-Sn Complex metal soap stabilizers such as Ca-Zn-Sn, Pb-Sn and Pb-Ba-Ca systems; metal groups such as barium and zinc and 2-ethylhexanoic acid, isodeca Branched fatty acids such as trialkylacetic acid etc., unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and their substituted derivatives Metal salt stabilizers derived usually from two or more of organic acids; these stabilizers are dissolved in an organic solvent such as petroleum hydrocarbon, alcohol, glycerin derivative, etc., and phosphite, epoxy compound, color forming inhibitor In addition to metal-based stabilizers such as metal salt liquid stabilizers, etc., which are made by blending stabilizing agents such as transparency improvers, light stabilizers, antioxidants, anti-bleedout agents, lubricants, etc., epoxy resins, epoxidation Epoxy compounds such as fatty acid alkyl esters, non-metallic stabilizers such as organic phosphorous esters, etc. may be mentioned, and these may be used alone or in combination of two or more.
安定剤の添加量については特に制限されないが、成分（ａ）第１の塩化ビニル系樹脂１００質量部に対して、１〜１５質量部が好ましく、１〜８質量部がより好ましい。１質量部以上とすることで、加工時の熱分解を抑制することができ、１５質量部以下とすることで、成形体の機械物性の低下を防ぐことができる。 The addition amount of the stabilizer is not particularly limited, but it is preferably 1 to 15 parts by mass, and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the component (a) first vinyl chloride resin. By setting it as 1 mass part or more, the thermal decomposition at the time of processing can be suppressed, and the fall of the mechanical property of a molded object can be prevented by setting it as 15 mass parts or less.
充填材としては、タルク、重質炭酸カルシウム、沈降性炭酸カルシウム、膠質炭酸カルシウム等の炭酸塩、水酸化アルミニウム、水酸化マグネシウム、酸化チタン、クレー、マイカ、ウォラストナイト、ゼオライト、シリカ、酸化亜鉛、酸化マグネシウム、カーボンブラック、グラファイト、ガラスビーズ、ガラス繊維、炭素繊維、金属繊維等の無機質系のもののほか、ポリアミド等のような有機繊維も使用でき、これらは１種または２種以上組み合わせて用いることができる。 As the filler, talc, heavy calcium carbonate, precipitated calcium carbonate, carbonates such as colloidal calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, clay, mica, wollastonite, zeolite, silica, zinc oxide Besides inorganic materials such as magnesium oxide, carbon black, graphite, glass beads, glass fibers, carbon fibers and metal fibers, organic fibers such as polyamide can also be used, and these are used in combination of one or more kinds be able to.
充填材の添加量については特に制限されないが、塩化ビニル系樹脂１００質量部に対して、１〜１５０質量部が好ましく、１０〜１００質量部がより好ましい。１質量部以上とすることで、成形体に適度な剛性を付与することができ、１５０質量部以下とすることで、成形体の柔軟性の低下を防ぐことができる。 The addition amount of the filler is not particularly limited, but it is preferably 1 to 150 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. By setting it as 1 mass part or more, moderate rigidity can be provided to a molded object, and the fall of the softness | flexibility of a molded object can be prevented by setting it as 150 mass parts or less.
難燃剤としては、例えば金属水酸化物、臭素系化合物、トリアジン環含有化合物、亜鉛化合物、リン系化合物、ハロゲン系難燃剤、シリコーン系難燃剤、イントメッセント系難燃剤、酸化アンチモン等が使用できる。これらは１種または２種以上組み合わせて用いることができる。 As the flame retardant, for example, metal hydroxide, bromine based compound, triazine ring containing compound, zinc compound, phosphorus based compound, halogen based flame retardant, silicone based flame retardant, intomescent based flame retardant, antimony oxide and the like can be used . These can be used alone or in combination of two or more.
難燃剤の添加量については特に制限されないが、塩化ビニル系樹脂１００質量部に対して、１〜１５０質量部が好ましく、１０〜１００質量部がより好ましい。１質量部以上とすることで、成形体の難燃性を向上することができ、１５０質量部以下とすることで、成形体の柔軟性の低下を防ぐことができる。 The addition amount of the flame retardant is not particularly limited, but is preferably 1 to 150 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. By setting it as 1 mass part or more, the flame retardance of a molded object can be improved, and the fall of the softness | flexibility of a molded object can be prevented by setting it as 150 mass parts or less.
滑剤としては、例えば流動パラフィン、天然パラフィン、マイクロワックス、合成パラフィン、低分子量ポリエチレン等の純炭化水素系滑剤、ハロゲン化炭化水素系滑剤、高級脂肪酸、オキシ脂肪酸等の脂肪酸系滑剤、脂肪酸アミド、ビス脂肪酸アミド等の脂肪酸アミド系滑剤、脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸の多価アルコールエステル、脂肪酸のポリグリコールエステル、脂肪酸の脂肪アルコールエステル（エステルワックス）等のエステル系滑剤のほか、金属石けん、脂肪アルコール、多価アルコール、ポリグリコール、ポリグリセロール、脂肪酸と多価アルコールの部分エステル、脂肪酸とポリグリコール、ポリグリセロールの部分エステル等が挙げられ、これらは１種あるいは２種以上組み合わせて使用することができる。 Examples of lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin and low molecular weight polyethylene, halogenated hydrocarbon lubricants, fatty acid lubricants such as higher fatty acids and oxy fatty acids, fatty acid amide, bis Fatty acid amide-based lubricants such as fatty acid amides, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, ester-based lubricants such as fatty alcohol esters of fatty acids (ester wax) And fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, partial esters of polyglycerols, etc. These may be used alone or in combination of two or more. It is possible.
滑剤の添加量については特に制限されないが、塩化ビニル系樹脂１００質量部に対して、０．１〜１５質量部が好ましく、０．１〜５質量部がより好ましい。０．１質量部以上とすることで、樹脂組成物の成形機への付着を低減することができ、１５質量部以下とすることで、加工性の低下を防ぐことができる。 The addition amount of the lubricant is not particularly limited, but is preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. By setting it as 0.1 mass part or more, adhesion to the molding machine of a resin composition can be reduced, and the fall of workability can be prevented by setting it as 15 mass parts or less.
耐衝撃性改質剤を配合する場合には、例えば塩素化ポリエチレン、ポリブタジエン、ポリイソプレン、ポリクロロプレン、フッ素ゴム、スチレン‐ブタジエン共重合体ゴム、アクリロニトリル‐スチレン‐ブタジエン共重合体ゴム、メタクリル酸メチル‐スチレン‐ブタジエン共重合体ゴム、アクリル酸エステル‐メタクリル酸エステル共重合体等のアクリル系コアシェル型ゴム、シリコーン‐アクリル酸エステル‐メタクリル酸エステル共重合体、シリコーン‐アクリル酸エステル‐アクリロニトリル‐スチレン共重合体等のシリコーン系コアシェル型ゴム等が挙げられる。これらの耐衝撃性改質剤は１種または２種以上組み合わせて用いることができる。 In the case of incorporating an impact modifier, for example, chlorinated polyethylene, polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, methyl methacrylate Acrylic core-shell rubbers such as styrene-butadiene copolymer rubber, acrylic ester-methacrylic acid ester copolymer, silicone-acrylic acid ester-methacrylic acid ester copolymer, silicone-acrylic acid ester-acrylonitrile-styrene copolymer Examples thereof include silicone-based core-shell rubbers such as polymers. These impact modifiers can be used alone or in combination of two or more.
耐衝撃性改質剤の添加量については特に制限されないが、塩化ビニル系樹脂１００質量部に対して、１〜２０質量部が好ましく、１〜１５質量部がより好ましい。１質量部以上とすることで、成形体の衝撃強度を向上することができ、２０質量部以下とすることで、成形外観の低下を防ぐことができる。 The addition amount of the impact modifier is not particularly limited, but is preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. By setting it as 1 mass part or more, the impact strength of a molded object can be improved, and the fall of shaping | molding external appearance can be prevented by setting it as 20 mass parts or less.
その他、離型剤、流動性改良剤、着色剤、帯電防止剤、界面活性剤、防曇剤、抗菌剤、発泡剤等も、本発明の効果を損なわない限りにおいて、目的に応じて任意に配合することができる。 In addition, mold release agents, fluidity improvers, colorants, antistatic agents, surfactants, antifogging agents, antibacterial agents, foaming agents, etc. may be optionally selected according to the purpose as long as the effects of the present invention are not impaired. It can be blended.
塩化ビニル系樹脂コンパウンドは、上記した各成分をヘンシェルミキサー、Ｖ型ミキサー、リボンブレンダー等の装置を用いてブレンドし、バンバリーミキサー、単軸押出機、二軸押出機、ロール、ニーダー等の装置を用いて１４０〜１８０℃の温度で混練することにより得ることができる。得られた塩化ビニル系樹脂コンパウンドは、適宜ペレット製造装置等を用いてペレット化することが好ましい。 The vinyl chloride resin compound is prepared by blending the above-mentioned components using an apparatus such as a Henschel mixer, a V-type mixer, a ribbon blender, etc., and an apparatus such as a Banbury mixer, a single screw extruder, a twin screw extruder, a roll, a kneader, etc. It can be obtained by using and kneading at a temperature of 140 to 180 ° C. It is preferable to pelletize the obtained vinyl chloride resin compound using a pellet manufacturing apparatus etc. suitably.
溶融成形工程：
本発明による塩化ビニル系樹脂成形物の製造方法においては、上記のようにして準備した塩化ビニル系樹脂コンパウンドに第２の塩化ビニル系樹脂を添加して、溶融成形を行うことで成形物を得る。上記した特許第４１８７１１２号公報等に記載の方法では、異なる分子量を有する塩化ビニル樹脂を混合して溶融成形を行うのに対して、本発明では、塩化ビニル系樹脂コンパウンド（即ち、可塑剤等が既に配合された樹脂組成物）に第２の塩化ビニル系樹脂を添加して溶融成形を行う点が特徴といえる。
Melt forming process:
In the method for producing a vinyl chloride resin molded article according to the present invention, a second vinyl chloride resin is added to the vinyl chloride resin compound prepared as described above, and a molded article is obtained by melt molding. . In the method described in the above-mentioned Japanese Patent No. 4187112 and the like, vinyl chloride resins having different molecular weights are mixed and melt-molded, whereas in the present invention, a vinyl chloride resin compound (that is, a plasticizer etc.) is used. It can be said that the second embodiment is characterized in that the second vinyl chloride resin is added to the already blended resin composition to perform melt molding.
第１の塩化ビニル系樹脂を含む塩化ビニル系樹脂コンパウンドは、所定量の可塑剤が配合されているため、塩化ビニル系樹脂の一部が擬似架橋したような状態となっている。本発明においては、塩化ビニル系樹脂コンパウンドに第２の塩化ビニル系樹脂を添加して溶融形成を行うと、塩化ビニル系樹脂コンパウンドと第２の塩化ビニル系樹脂とが溶融混練された場合であっても、第２の塩化ビニル系樹脂は未溶融のまま成形されるため、成形物表面に未ゲル物として第２の塩化ビニル系樹脂が粒状に出現する。その結果、表面の摩擦抵抗が低減され、艶消しの表面を有する成形物が得られる。即ち、高分子量のＰＶＣ樹脂を未溶融物として表面に析出させた特許文献２に記載の手法とは全く異なる概念である。 The vinyl chloride-based resin compound containing the first vinyl chloride-based resin contains a predetermined amount of plasticizer, so that part of the vinyl chloride-based resin is in a state of being pseudo-crosslinked. In the present invention, when the second vinyl chloride resin is added to the vinyl chloride resin compound for melt formation, the vinyl chloride resin compound and the second vinyl chloride resin are melt-kneaded. However, since the second vinyl chloride resin is molded without being melted, the second vinyl chloride resin appears as particles on the surface of the molded product as an ungelled product. As a result, the frictional resistance of the surface is reduced, and a molding having a matte surface is obtained. That is, it is a concept completely different from the method described in Patent Document 2 in which a high molecular weight PVC resin is precipitated on the surface as an unmelted substance.
塩化ビニル系樹脂コンパウンドに添加する第２の塩化ビニル系樹脂としては、成分（ａ）第１の塩化ビニル系樹脂の欄で列挙した種々のものを使用することができる。また、第２の塩化ビニル系樹脂は、成分（ａ）第１の塩化ビニル系樹脂と同じものであってもよく、また異なるものであってもよい。但し、本発明においては、第２の塩化ビニル系樹脂の平均重合度Ｐ２が、第１の塩化ビニル系樹脂の平均重合度Ｐ１の０．５倍以上、１．９倍以下とする必要がある。第２の塩化ビニル系樹脂の平均重合度Ｐ２が、第１の塩化ビニル系樹脂の平均重合度Ｐ１の０．５倍未満では、成形物の表面に第２の塩化ビニル系樹脂の未ゲル物を出現させるのが難しくなり、摩擦抵抗が低減され、艶消しの表面を有する成形物が得られ難くなる。一方、第２の塩化ビニル系樹脂の平均重合度Ｐ２が、第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．９倍を超えると成形性が悪化して、安定的に成形物を得ることが困難となる場合がある。第２の塩化ビニル系樹脂の好ましい平均重合度Ｐ２は、第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．０倍以下である。 As the second vinyl chloride resin to be added to the vinyl chloride resin compound, various ones listed in the column of component (a) first vinyl chloride resin can be used. The second vinyl chloride resin may be the same as or different from the component (a) first vinyl chloride resin. However, in the present invention, the average degree of polymerization P2 of the second vinyl chloride resin needs to be 0.5 times or more and 1.9 times or less the average degree of polymerization P1 of the first vinyl chloride resin. . When the average degree of polymerization P2 of the second vinyl chloride resin is less than 0.5 times the average degree of polymerization P1 of the first vinyl chloride resin, the ungelled product of the second vinyl chloride resin is formed on the surface of the molding. Is difficult to produce, the friction resistance is reduced, and it is difficult to obtain a molded product having a matte surface. On the other hand, when the average degree of polymerization P2 of the second vinyl chloride resin exceeds 1.9 times the average degree of polymerization P1 of the first vinyl chloride resin, the moldability deteriorates and a molded article is stably obtained. May be difficult. The preferred average degree of polymerization P2 of the second vinyl chloride resin is not more than 1.0 times the average degree P1 of the first vinyl chloride resin.
塩化ビニル系樹脂コンパウンドに添加する第２の塩化ビニル系樹脂の添加量は、塩化ビニル系樹脂コンパウンド１００質量部に対して１質量部以上、８質量部以下とする。第２の塩化ビニル系樹脂の添加量が塩化ビニル系樹脂コンパウンド１００質量部に対して１質量未満であると、成形物表面に粒状に出現する未ゲル物の量が少なく、摩擦抵抗の低減や艶消し効果が不十分となる。一方、第２の塩化ビニル系樹脂の添加量が塩化ビニル系樹脂コンパウンド１００質量部に対して８質量部を超えると、成形性が悪化して、安定的に成形物を得ることが困難となる場合がある。好ましい第２の塩化ビニル系樹脂の添加量は、塩化ビニル系樹脂コンパウンド１００質量部に対して２質量部以上、７質量部以下であり、より好ましくは３質量部以上、６質量部以下である。 The addition amount of the second vinyl chloride resin added to the vinyl chloride resin compound is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin compound. When the amount of the second vinyl chloride-based resin added is less than 1 mass with respect to 100 parts by mass of the vinyl chloride-based resin compound, the amount of ungelled matter appearing in the form of particles on the surface of the molded article is small. The matting effect is insufficient. On the other hand, when the addition amount of the second vinyl chloride resin exceeds 8 parts by mass with respect to 100 parts by mass of the vinyl chloride resin compound, the formability deteriorates and it becomes difficult to stably obtain a molded article There is a case. The preferable addition amount of the second vinyl chloride resin is 2 parts by mass or more and 7 parts by mass or less, more preferably 3 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin compound .
塩化ビニル系樹脂コンパウンドと塩化ビニル系樹脂コンパウンドとを溶融成形するには、従来公知の成形機を用いることができる。成形物の使用用途に応じて、射出成形、押出成形、インフレーション成形、カレンダー成形、ブロー成形等の成形方法を適宜選択することができる。成形加工を行う際には、塩化ビニル系樹脂コンパウンドおよび塩化ビニル系樹脂コンパウンドに加えて、適宜、上記した可塑剤等の添加剤を添加してもよい。 In order to melt-mold the vinyl chloride resin compound and the vinyl chloride resin compound, a conventionally known molding machine can be used. A molding method such as injection molding, extrusion molding, inflation molding, calendar molding, blow molding and the like can be appropriately selected according to the use application of the molding. When molding processing is performed, in addition to the vinyl chloride resin compound and the vinyl chloride resin compound, additives such as the above-described plasticizer may be added as appropriate.
成形加工する際の温度（成形加工温度）は、塩化ビニル系樹脂コンパウンドの溶融成形温度とすることが好ましい。例えば、上記したように、平均重合度が１３００程度のＰＶＣと所定量の可塑剤を配合した塩化ビニル系樹脂コンパウンドでは、成形温度は１４０〜１６０℃程度であり、当該塩化ビニル系樹脂コンパウンドに第２の塩化ビニル系樹脂を添加して溶融成形を行う際も、１４０〜１６０℃程度の温度で溶融成形を行うことが好ましい。そのため、本発明においては、押出成形機の温度等の成形加工条件を変更することなく、表面の摩擦抵抗性が低減され、摺動性があり、艶消しの外観を有する塩化ビニル系樹脂成形物を製造することができる。 It is preferable that the temperature (molding processing temperature) at the time of molding processing be the melt molding temperature of the vinyl chloride resin compound. For example, as described above, in a vinyl chloride resin compound in which PVC having an average polymerization degree of about 1300 and a predetermined amount of plasticizer are blended, the molding temperature is about 140 to 160 ° C. Also when performing melt molding by adding the vinyl chloride resin of 2, it is preferable to carry out melt molding at a temperature of about 140 to 160 ° C. Therefore, in the present invention, a vinyl chloride resin molded article having reduced surface friction resistance, slidability, and a matte appearance without changing molding processing conditions such as the temperature of the extruder. Can be manufactured.
＜塩化ビニル系樹脂成形物＞
上記のようにして得られる塩化ビニル系樹脂成形物は、第２の塩化ビニル系樹脂の未ゲル物が粒状に出現して、表面に分散した形態を有している。そのため、摩擦抵抗性が低減され、摺動性があり、艶消しの外観を有する成形物を実現することができる。
<Polyvinyl chloride resin molding>
The vinyl chloride resin molded product obtained as described above has a form in which the ungelled product of the second vinyl chloride resin appears in the form of particles and is dispersed on the surface. Therefore, it is possible to realize a molded article having reduced friction resistance, slidability, and a matte appearance.
特に、成分（ａ）第１の塩化ビニル系樹脂 １００質量部と成分（ｂ）可塑剤 ４０質量部以上、１００質量部以下とを混練して得られた塩化ビニル系樹脂コンパウンドに、平均重合度Ｐ２が、第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．０倍以下の第２の塩化ビニル系樹脂を添加して溶融成形した塩化ビニル系樹脂成形物は、表面の摩擦抵抗性が低減され、摺動性があり、艶消しの外観を有するとともに、成形性にも優れている。 In particular, an average degree of polymerization of the vinyl chloride resin compound obtained by kneading 100 parts by mass of the component (a) first vinyl chloride resin and 40 parts by mass or more and 100 parts by mass or less of the component (b) plasticizer The polyvinyl chloride-based resin molded product obtained by melt-molding a second vinyl chloride-based resin in which P2 is not more than 1.0 times the average polymerization degree P1 of the first vinyl chloride-based resin has a surface friction resistance It is reduced, slidable, has a matte appearance, and is excellent in formability.
本発明の塩化ビニル系樹脂成形物は、カーテンレール、散水用や材料送達用などの可撓性ホース、自動車内装材料、被覆電線・床材・防水シートをはじめとしたシート類、テープ・農業用をはじめとしたフィルム類など、様々な用途に使用することができる。 The vinyl chloride resin molded article of the present invention includes curtain rails, flexible hoses for water sprinkling and material delivery, automotive interior materials, sheets such as coated electric wires, floors, and waterproof sheets, tapes and agricultural products It can be used for various applications such as films including
以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
評価方法：
（１）成形物の表面荒れ性
後記する押出成形条件により成形した各シートについて、対照として用いた比較例１および比較例２との対比により目視で評価した。表面荒れ性の評価基準は以下のとおりとした。
○：比較例１と同等の表面形態である
△：比較例１と比較例２との中間の表面形態である
×：比較例２と同等の表面形態である
Evaluation method:
(1) Surface Roughness of Molded Product Each sheet molded under the extrusion molding conditions described later was visually evaluated by comparison with Comparative Example 1 and Comparative Example 2 used as a control. The evaluation criteria of surface roughness were as follows.
○: surface morphology equivalent to Comparative Example 1 Δ: surface morphology intermediate to Comparative Examples 1 and 2 ×: surface morphology equivalent to Comparative Example 2
（２）成形性
押出成形条件によりシートを作製し、得られた各シートを目視で評価した。成形性の評価基準は、以下のとおりとした。
○：シートの端が切れていない
△：シートの端が若干切れている
×：シートが断続的に切れている
(2) Moldability Sheets were produced under extrusion molding conditions, and each sheet obtained was evaluated visually. The evaluation criteria for formability were as follows.
○: The end of the sheet is not cut △: The end of the sheet is slightly cut ×: The sheet is cut intermittently
押出成形条件：
押出成形機：ＬＳＥ−２０（Ｌ／Ｄ＝２０）
スクリュー：フルフライトスクリュー
スクリュー回転速度：４０ｒｐｍ
プレート：メッシュ付ブレーカープレート
成形温度：Ｃ１温度１４０℃、Ｃ２温度１５０℃、Ｃ３温度１６０℃、ダイ温度１６０℃
Extrusion molding conditions:
Extrusion molding machine: LSE-20 (L / D = 20)
Screw: Full flight screw Screw rotational speed: 40 rpm
Plate: Breaker plate with mesh Molding temperature: C1 temperature 140 ° C, C2 temperature 150 ° C, C3 temperature 160 ° C, die temperature 160 ° C
使用した原料：
・塩化ビニル系樹脂
Ｐ−４００（平均重合度４００、ポリ塩化ビニル、積水化学工業株式会社製）
Ｐ−７００（平均重合度７００、ポリ塩化ビニル、信越化学工業株式会社製）
Ｐ−８００（平均重合度８００、ポリ塩化ビニル、信越化学工業株式会社製）
Ｐ−１０５０（平均重合度１０５０、ポリ塩化ビニル、信越化学工業株式会社製）
Ｐ−１３００（平均重合度１３００、ポリ塩化ビニル、信越化学工業株式会社製）
Ｐ−１７００（平均重合度１７００、ポリ塩化ビニル、信越化学工業株式会社製）
Ｐ−２５００（平均重合度２５００、ポリ塩化ビニル、信越化学工業株式会社製）
・部分架橋塩化ビニル系樹脂
Ｋ１３Ｍ（平均重合度１１００、ゲル分率５７％、株式会社カネカ製）
・可塑剤
ＤＯＰ（フタル酸ジオクチル）
Ｏ−１３０Ｓ（エポキシ化大豆油、株式会社ＡＤＥＫＡ製）
・安定剤
ＳＰ−２０１５（Ｃａ−Ｚｎ系安定剤、株式会社ＡＤＥＫＡ製）
Raw materials used:
・ Vinyl chloride resin P-400 (average polymerization degree 400, polyvinyl chloride, manufactured by Sekisui Chemical Co., Ltd.)
P-700 (average degree of polymerization 700, polyvinyl chloride, manufactured by Shin-Etsu Chemical Co., Ltd.)
P-800 (average degree of polymerization 800, polyvinyl chloride, Shin-Etsu Chemical Co., Ltd.)
P-1050 (average polymerization degree 1050, polyvinyl chloride, manufactured by Shin-Etsu Chemical Co., Ltd.)
P-1300 (average polymerization degree 1300, polyvinyl chloride, manufactured by Shin-Etsu Chemical Co., Ltd.)
P-1700 (average degree of polymerization 1700, polyvinyl chloride, manufactured by Shin-Etsu Chemical Co., Ltd.)
P-2500 (average degree of polymerization 2500, polyvinyl chloride, Shin-Etsu Chemical Co., Ltd.)
Partially cross-linked vinyl chloride resin K13 M (average polymerization degree 1100, gel fraction 57%, Kaneka Co., Ltd.)
・ Plasticizer DOP (dioctyl phthalate)
O-130S (epoxidized soybean oil, manufactured by ADEKA Corporation)
・ Stabilizer SP-2015 (Ca-Zn stabilizer, manufactured by ADEKA Corporation)
比較例１および比較例２
下表１に示す組成に従って各成分を、混練機（バンバリーミキサー）により１６０℃で混練してコンパウンドを調製した。なお、表中の数値は質量部を表す。得られた各コンパウンドを用いて、上記押出成形条件にてシートを作製した。
Comparative Example 1 and Comparative Example 2
Each component was kneaded at 160 ° C. by a kneader (Banbury mixer) according to the composition shown in Table 1 below to prepare a compound. The numerical values in the table represent parts by mass. A sheet was produced under the above extrusion molding conditions using each of the obtained compounds.
比較例１は架橋ＰＶＣを含むため、成形物の表面には粒状の凹凸が形成されており、表面摩擦性が小さく、艶消しの表面を有している。一方、比較例２は架橋ＰＶＣを含まないため、成形物の表面は光沢があり、表面荒れ性は不良である。 Since Comparative Example 1 contains crosslinked PVC, granular irregularities are formed on the surface of the molded product, the surface friction is small, and it has a matte surface. On the other hand, Comparative Example 2 does not contain cross-linked PVC, so the surface of the molded product is glossy and the surface roughness is poor.
実施例１〜５、比較例３および４
比較例２で用いたコンパウンドに、表２に示す組成に従って各重合度のＰＶＣ樹脂（Ｐ−４００、Ｐ−７００、Ｐ−８００、Ｐ−１０５０、Ｐ−１３００、Ｐ−１７００、およびＰ−２５００）を添加して、上記と同様の押出成形条件にて成形することによりシートを作製した。得られた各シートについて、表面荒れ性および成形性の評価を行った。結果は下記表２に示されるとおりであった。
Examples 1 to 5, Comparative Examples 3 and 4
According to the composition shown in Table 2, the compound used in Comparative Example 2 was a PVC resin of each polymerization degree (P-400, P-700, P-800, P-1050, P-1300, P-1700, and P-2500). ) Was added and molded under the same extrusion molding conditions as described above to prepare a sheet. The surface roughness and the formability were evaluated for each of the obtained sheets. The results were as shown in Table 2 below.
実施例１〜５は、比較例１および２と比較して、表面荒れ性および成形性のいずれも良好であった。驚くべきことに、コンパウンドに含まれるＰＶＣ樹脂よりも重合度の高いＰＶＣ樹脂を加えた実施例５のみならず、それと同等、またはそれよりも重合度の低いＰＶＣ樹脂を加えた実施例１、実施例２、実施例３、および実施例４においても、表面荒れ性および成形性のいずれも良好であった。一方、コンパウンドに含まれるＰＶＣ樹脂よりも平均重合度が１．９倍以上大きいＰＶＣ樹脂を添加した比較例３では、表面荒れ性は良好であるものの、成形性が不良であった。また、コンパウンドに含まれるＰＶＣ樹脂よりも平均重合度が０．５倍未満であるＰＶＣ樹脂を添加した比較例４では、成形性は良好であるものの、表面荒れ性が不十分であった。 Both Examples 1 to 5 had better surface roughness and moldability as compared to Comparative Examples 1 and 2. Surprisingly, not only Example 5 where a PVC resin having a higher degree of polymerization than the PVC resin contained in the compound is added, but also Example 1, where a PVC resin having an equivalent degree or a lower degree of polymerization is added, is carried out Also in each of Example 2, Example 3, and Example 4, both of the surface roughness and the formability were good. On the other hand, in Comparative Example 3 in which a PVC resin having an average degree of polymerization of at least 1.9 times that of the PVC resin contained in the compound was added, although the surface roughness was good, the moldability was poor. In addition, in Comparative Example 4 in which a PVC resin having an average degree of polymerization of less than 0.5 times the PVC resin contained in the compound was added, although the formability was good, the surface roughness was insufficient.
実施例６〜７および比較例５
比較例２で用いたコンパウンドに、ＰＶＣ樹脂（Ｐ−１０５０）を、それぞれ１重量部、８重量部および１０重量部添加して、上記と同様の押出成形条件にて成形することによりシートを作製した。得られた各シートについて、表面荒れ性および成形性の評価を行った。結果は下記表３に示されるとおりであった。
Examples 6 to 7 and Comparative Example 5
1 part by weight, 8 parts by weight and 10 parts by weight of a PVC resin (P-1050) were added to the compound used in Comparative Example 2, and a sheet was produced by molding under the same extrusion molding conditions as described above. did. The surface roughness and the formability were evaluated for each of the obtained sheets. The results were as shown in Table 3 below.
実施例６は、コンパウンドに添加するＰＶＣ樹脂の添加量が少ないため、実施例３と比べて表面荒れ性がやや劣っており、実施例７は、コンパウンドに添加するＰＶＣ樹脂の添加量が多いため、実施例３と比べて成形性がやや劣っている一方、ＰＶＣ樹脂の添加量を１０質量部とした比較例５は、表面荒れ性は良好であるが、成形性が不良であった。 In Example 6, the surface roughness is slightly inferior to that in Example 3 because the amount of PVC resin added to the compound is small, and in Example 7, the amount of PVC resin added to the compound is large, While the moldability was slightly inferior to that of Example 3, Comparative Example 5 in which the addition amount of the PVC resin was 10 parts by mass was good in surface roughness, but poor in moldability.
Claims (7)
成分（ｂ）可塑剤 ４０質量部以上、１００質量部以下と、
を混練した塩化ビニル系樹脂コンパウンドを準備する工程、および
（Ｂ）前記塩化ビニル系樹脂コンパウンドに、第２の塩化ビニル系樹脂を添加して、溶融成形を行う工程、
を含み、
前記第２の塩化ビニル系樹脂の平均重合度Ｐ２が、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１の０．５倍以上、１．９倍以下であり、
前記第２の塩化ビニル系樹脂の配合量が、前記塩化ビニル系樹脂コンパウンド１００質量部に対して１質量部以上、８質量部以下である、ことを特徴とする塩化ビニル系樹脂成形物の製造方法。 (A) Component (a) 100 parts by mass of a first vinyl chloride resin,
Component (b) plasticizer 40 to 100 parts by mass,
Preparing a vinyl chloride resin compound obtained by kneading, and (B) adding a second vinyl chloride resin to the vinyl chloride resin compound and performing melt molding,
Including
The average polymerization degree P2 of the second vinyl chloride resin is 0.5 times or more and 1.9 times or less the average polymerization degree P1 of the first vinyl chloride resin,
The compounding amount of the second vinyl chloride-based resin is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the vinyl chloride-based resin compound. Production of a vinyl chloride-based resin molded article Method.
成分（ｂ）可塑剤 ４０質量部以上、１００質量部以下と、
を混練した塩化ビニル系樹脂コンパウンド、および
（Ｂ）第２の塩化ビニル系樹脂、
を含む、塩化ビニル系樹脂成形物であって、
前記前記第２の塩化ビニル系樹脂の平均重合度Ｐ２が、前記第１の塩化ビニル系樹脂の平均重合度Ｐ１の１．０倍以下であり、
前記第２の塩化ビニル系樹脂の配合量が、前記塩化ビニル系樹脂コンパウンド１００質量部に対して１質量部以上、８質量部以下である、ことを特徴とする塩化ビニル系樹脂成形物。 (A) Component (a) 100 parts by mass of a first vinyl chloride resin,
Component (b) plasticizer 40 to 100 parts by mass,
Vinyl chloride resin compound obtained by kneading and (B) second vinyl chloride resin,
A vinyl chloride resin molded product containing
The average polymerization degree P2 of the second vinyl chloride resin is 1.0 times or less of the average polymerization degree P1 of the first vinyl chloride resin,
The compounded quantity of said 2nd vinyl chloride resin is 1 mass part or more and 8 mass parts or less with respect to 100 mass parts of said vinyl chloride resin compound, The vinyl chloride resin molded article characterized by the above-mentioned.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111856880A (en) * | 2020-08-05 | 2020-10-30 | 李有伟 | High-performance photosensitive film for LDI (laser direct immersion) and preparation method thereof |
| JP2021116815A (en) * | 2020-01-22 | 2021-08-10 | タイガースポリマー株式会社 | Flexible hose |
| JP2021162720A (en) * | 2020-03-31 | 2021-10-11 | 日本カーバイド工業株式会社 | Light diffusion film, and method for producing light diffusion film |
| DE112020001207T5 (en) | 2019-03-11 | 2021-11-25 | Livedo Corporation | Absorbent article |
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|---|---|---|---|---|
| JP2003311812A (en) * | 2002-04-26 | 2003-11-06 | Shin Etsu Polymer Co Ltd | Extrusion molded product using vinyl chloride resin pellets |
| JP2009529083A (en) * | 2006-03-08 | 2009-08-13 | アルケマ フランス | Thermoplastic resin composition for production of single layer or composite skin having spotted pattern for vehicle passenger compartment parts, and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003311812A (en) * | 2002-04-26 | 2003-11-06 | Shin Etsu Polymer Co Ltd | Extrusion molded product using vinyl chloride resin pellets |
| JP2009529083A (en) * | 2006-03-08 | 2009-08-13 | アルケマ フランス | Thermoplastic resin composition for production of single layer or composite skin having spotted pattern for vehicle passenger compartment parts, and method for producing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112020001207T5 (en) | 2019-03-11 | 2021-11-25 | Livedo Corporation | Absorbent article |
| JP2021116815A (en) * | 2020-01-22 | 2021-08-10 | タイガースポリマー株式会社 | Flexible hose |
| JP7360773B2 (en) | 2020-01-22 | 2023-10-13 | タイガースポリマー株式会社 | Use of flexible hoses |
| JP2021162720A (en) * | 2020-03-31 | 2021-10-11 | 日本カーバイド工業株式会社 | Light diffusion film, and method for producing light diffusion film |
| CN111856880A (en) * | 2020-08-05 | 2020-10-30 | 李有伟 | High-performance photosensitive film for LDI (laser direct immersion) and preparation method thereof |
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