JPS6354302B2 - - Google Patents
Info
- Publication number
- JPS6354302B2 JPS6354302B2 JP58153463A JP15346383A JPS6354302B2 JP S6354302 B2 JPS6354302 B2 JP S6354302B2 JP 58153463 A JP58153463 A JP 58153463A JP 15346383 A JP15346383 A JP 15346383A JP S6354302 B2 JPS6354302 B2 JP S6354302B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- parts
- weight
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000004014 plasticizer Substances 0.000 claims description 27
- 239000011342 resin composition Substances 0.000 claims description 23
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 22
- 239000003381 stabilizer Substances 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical group [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 5
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001944 Plastisol Polymers 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 239000004999 plastisol Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 description 24
- -1 polyoxyethylene units Polymers 0.000 description 18
- 238000002845 discoloration Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 150000008051 alkyl sulfates Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000010557 suspension polymerization reaction Methods 0.000 description 7
- 239000000805 composite resin Substances 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- LVAGMBHLXLZJKZ-UHFFFAOYSA-N 2-o-decyl 1-o-octyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC LVAGMBHLXLZJKZ-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-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
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000000740 bleeding effect Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- HCQHIEGYGGJLJU-UHFFFAOYSA-N didecyl hexanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCC HCQHIEGYGGJLJU-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Description
本発明は、自動車の内装材、オートバイの座
席、一般家庭の内装材、家具表装材等の成形品の
成形に用いて、特にウレタン樹脂との複合体とな
る成形品の成形に好適な塩化ビニル樹脂組成物に
係る。
従来、自動車の内装材、例えばクラツシユパツ
ド、アームレスト、ヘツドレスト、天井、ドア、
グローブボツクスリツド、リヤーパーセル等に軟
質、半硬質の塩化ビニル樹脂が多用されている。
特に軟質塩化ビニル樹脂成形品は、安全性と柔軟
性を増すために、内部を発泡軟質ウレタンにした
ウレタン樹脂との複合体にして用いられる。この
ウレタン樹脂が塩化ビニル樹脂に接触した状態に
おいてはウレタン樹脂が接触していない場合と比
較して、塩化ビニル樹脂の熱劣化、光劣化が促進
される現象が起き、使用中に亀裂変色等が生じ、
内装材として充分な性能を発揮しているとは伝い
難い。
特許出願人は、先に特願昭57―19287号（特開
昭58―136645号公報参照）にて、フオギング性の
改良、ウレタン樹脂複合体としたときの耐熱性、
耐光性の改良を目的として、アニオン界面活性剤
及び過酸化水素触媒の存在下に水性乳化重合また
は微細懸濁重合したペースト用塩化ビニル系重合
体にポリオキシエチレンユニツトを有するノニオ
ン界面活性剤及びエポキシレジンを含有せしめた
内装材用ゾル組成物に関する発明を提案したが、
本発明者らは、通常の重合法によつて製造された
塩化ビニル系樹脂に可塑剤、安定剤等を配合して
塩化ビニル系樹脂組成物を調製する際に、上述の
ノニオン界面活性剤を添加することなく、単にア
ルキル硫酸またはその塩を添加することによつ
て、自動車等内装材の低フオギング性を損なうこ
となく、ウレタン樹脂との複合体における耐熱性
及び耐光性を改良しうることを見いだし、本発明
を完成するに到つた。
すなわち、本発明の目的は、ノニオン界面活性
剤の添加がなくても低フオギング性が保たれかつ
ウレタン樹脂と接触しても熱劣化、光劣化が促進
されず、使用中に亀裂、変色等が生じない塩化ビ
ニル樹脂組成物を提供するにある。
しかして、本発明の要旨は、ウレタン樹脂との
複合体にされる塩化ビニル系樹脂を主体とした組
成物であつて、塩化ビニル系樹脂100重量部当り
ラウリル硫酸またはその塩0.04〜６重量部、非錫
系金属安定剤0.1〜10重量部及びエポキシ系可塑
剤0.5〜20重量部を含有してなる塩化ビニル樹脂
組成物に存する。
本発明を詳細に説明する。
本発明の塩化ビニル樹脂組成物に用いられる塩
化ビニル系樹脂は、塩化ビニルまたは塩化ビニル
とそれに共重合可能なコモノマーの混合物を懸濁
重合法、塊状重合法、微細懸濁重合法または乳化
重合法等通常の方法によつて製造されたものすべ
てが用いられ、懸濁重合法または塊状重合法によ
つて製造されたものは、可塑剤、安定剤等をホツ
トドライブレンドした塩化ビニル樹脂組成物にし
て、または上述のホツトドライブレンドした組成
物に流動性改良剤を添加して粉体成形用塩化ビニ
ル樹脂組成物にして、また乳化重合または微細懸
濁重合法によつて製造されたものは、可塑剤、安
定剤等を均一に混合したプラスチゾルまたはオル
ガノゾルにして使用される。しかして、塩化ビニ
ルに共重合可能なコモノマーとしては、例えば酢
酸ビニル、プロピオン酸ビニル、ラウリン酸ビニ
ル等のビニルエステル類、メチルアクリレート、
エチルアクリレート、ブチルアクリレート等のア
クリル酸エステル類、メチルメタクリレート、エ
チルメタクリレート等のメタクリル酸エステル
類、ジブチルマレエート、ジエチルマレエート等
のマレイン酸エステル類、ジブチルフマレート、
ジエチルフマレート等のフマール酸エステル類、
ビニルメチルエーテル、ビニルブチルエーテル、
ビニルオクチルエーテル等のビニルエーテル類、
アクリロニトリル、メタクリロニトリル等のシア
ン化ビニル類、エチレン、プロピレン、スチレン
等のα―オレフイン類、塩化ビニリデン、臭化ビ
ニル等の塩化ビニル以外のハロゲン化ビニリデン
またはハロゲン化ビニル類が挙げられ、これらコ
モノマーは、塩化ビニル系樹脂の構成成分中30重
量％以下、好ましくは20重量％以下の範囲で用い
られる。勿論、コモノマーは、上述のものに限定
されるものではない。
塩化ビニル系樹脂を主体とした組成物には、通
常塩化ビニル樹脂に使用される添加剤、例えば可
塑剤、安定剤、酸化防止剤、紫外線吸収剤、充填
材、着色剤、離型剤等が併用されることが多い。
可塑剤は、例えばフタル酸ジ―ｎ―ブチル、フ
タル酸ジ―ｎ―オクチル、フタル酸ジ―２―エチ
ルヘキシル、フタル酸ジイソオクチル、フタル酸
オクチルデシル、フタル酸ジイソデシル、フタル
酸ブチルベンジル、イソフタル酸ジ―２―エチル
ヘキシル、または炭素原子数11〜13程度の高級ア
ルコールのフタル酸エステル等のフタル酸系可塑
剤、トリメリツト酸ｎ―オクチル―ｎ―デシル、
トリメリツト酸トリー２―エチルヘキシル、トリ
メリツト酸トリイソデシル、トリメリツト酸トリ
―ｎ―オクチル等のトリメリツト酸系可塑剤、ア
ジピン酸ジ―２―エチルヘキシル、アジピン酸ジ
―ｎ―デシル、アジピン酸ジイソデシル、アゼラ
イン酸ジ―２―エチルヘキシル、セバシン酸ジブ
チル、セバシン酸ジ―２―エチルヘキシル等の脂
肪酸エステル系可塑剤、リン酸トリブチル、リン
酸トリ―２―エチルヘキシル、リン酸―２―エチ
ルヘキシルジフエニル、リン酸トリクレジル等の
リン酸エステル系可塑剤、エポキシ化大豆油、エ
ポキシ化アマニ油、エポキシ化トール油脂肪酸―
２―エチルヘキシル等のエポキシ系可塑剤または
液状のエポキシレジン等があげられ、これら一種
または二種以上を混合して使用する。本発明の組
成物では揮発性の低いトリメリツト酸系可塑剤ま
たは高級アルコールとフタル酸とのエステル可塑
剤が好ましい。
上述の液状のエポキシレジンは、エポキシ化大
豆油などの二次可塑剤とは若干異なるが、エポキ
シ化大豆油等のエポキシ系可塑剤と同様に熱安定
性に寄与し、かつ液状であるので、本発明の組成
物においてはエポキシ系可塑剤の範疇に含めるも
のとした。
そして、エポキシレジンとしては、例えば分子
内に２個のエポキシ基を有する樹脂でビスフエノ
ールＡ型のもの、環状脂肪族のもの、ポリブタジ
エンから誘導されるもの、あるいは１分子当り７
個以上のエポキシ基を有するエポキシノボラツク
樹脂が用いられる。エポキシ当量は、普通エポキ
シ化大豆油よりも高く、一般に100〜1500、好ま
しくは150〜700程度のものが使用される。
しかして、可塑剤の使用量は、組成物の成形
性、加工性、作業性、成形品の用途などによつて
適宜選択されるが一般に塩化ビニル系樹脂100重
量部に対して30〜400重量部、好ましくは50〜200
重量部の範囲である。また、本発明の組成物は、
上述の可塑剤の一部をエポキシ化大豆油、エポキ
シ化アマニ油、またはエポキシレジンなどのエポ
キシ系可塑剤、特にエポキシ化アマニ油またはエ
ポキシレジン0.5〜20重量部、好ましくは１〜５
重量部の範囲で置換することにより、フオギング
性能を劣化させることなく、ウレタン樹脂複合体
としたときの塩化ビニル樹脂組成物の耐熱性、耐
光性に大きく寄与する。エポキシ系可塑剤の添加
量が0.5重量部より少ないときは、耐熱性、耐光
性の充分満足しうる効果が得られ難く、一方20重
量部より多いとエポキシ系可塑剤がブリードし易
く、成形品に粘着性を生ずるという不都合が生
じ、また組成物がゾルの場合ゾルの粘度が高くな
つて加工性が低下する。
ゾル組成物の場合、可塑剤の一部をテキサノー
ルイソブチレート、ドデシルベンゼン、ケロシン
等の稀釈剤、あるいはトルエン、キシレン等の塩
化ビニル系樹脂を膨潤させる有機溶剤に換えるこ
とができ、オルガノゾルの形態にして用いてもよ
い。稀釈剤、有機溶剤の添加量は、用途により適
宜決定される。
安定剤は、錫脂肪酸塩、錫メルカプタイド等錫
系のものを使用するよりも、バリウム―亜鉛
（Ba―Zn）系、カルシウム―亜鉛（Ca―Zn）系、
マグネシウム―亜鉛（Mg―Zn）系等の非錫系金
属安定剤を使用した方が、ウレタン樹脂と接触し
た状態での熱及び光による硬化、ブリード、ブル
ーム等の現象が押えられる。安定剤の使用量は、
塩化ビニル系樹脂100重量部当り0.1〜10重量部、
好ましくは１〜５重量部の範囲であるのが好まし
い。
塩化ビニル系樹脂を主体とした組成物に配合せ
しめるアルキル硫酸またはその塩は、ラウリル硫
酸またはその塩が挙げられる。アルキル硫酸は粘
稠な液体であり、酸性を呈し、使用時には塩基と
併用してアルキル硫酸塩として用いることが多
い。この場合水が生成し、組成物の中に含まれる
可能性があり、組成物の成形法に工夫する必要が
あるので、むしろアルキル硫酸塩として使用する
のが望ましい。アルキル硫酸塩は、ナトリウム
塩、カリウム塩、リチウム塩等が挙げられ、入手
の容易さ、経済性の点からナトリウム塩の形で用
いるのが好ましい。アルキル硫酸塩は、常温で固
体であり、市販品としては粉末状、顆粒状、溶液
状のものがある。溶液状のものはゾル組成物への
分散は容易であるが、ゾル組成物中に水分あるい
は成分不明の溶剤が混入することになるので粉末
状または顆粒状のアルキル硫酸塩を使用するのが
望ましい。勿論、アルキル硫酸またはその塩の使
用は、ラウリル硫酸またはその塩に他のアルキル
硫酸またはその塩を二種類以上を混合して用いて
もよい。
しかして、アルキル硫酸またはその塩の使用量
は、塩化ビニル系樹脂100重量部当り0.04〜６重
量部配合せしめる必要があり、好ましくは0.1〜
３重量部の範囲が適当である。含有量が0.04重量
部より少ないと塩化ビニル樹脂組成物の成形品が
ウレタン樹脂と複合されたとき、成形品の耐熱性
及び耐光性を充分に発揮することができず、また
６重量部より多くなるとウレタン樹脂接触時の耐
熱性、耐光性は良好であるが、成形品からアルキ
ル硫酸またはその塩がブリードし易くなる。
本発明の塩化ビニル樹脂組成物は、上述の必須
成分または必要に応じて他の添加剤を添加して高
速ミキサー、ニーダー、リボンブレタンダー、ロ
ール、バンバリーミキサー、押出機等の混合撹拌
機または混練機等を用いて均一に配合する。
例えば、懸濁重合または塊状重合によつて得ら
れた塩化ビニル系重合体から塩化ビニル樹脂組成
物を製造するには、塩化ビニル系樹脂及びアルキ
ル硫酸またはその塩等の必須成分、安定剤及び可
塑剤等のほかの添加剤を添加して、リボンブレン
ダー、高速撹拌機で均一に混合、ドライアツプ
し、更に必要ならばロール、バンバリーミキサ
ー、押出機等の混練機で加熱溶融してペレツト状
としても差支えない、そして該樹脂組成物は、一
般に射出成形法、ブロー成形法によつて成形品に
される。
また、粉体成形用の樹脂組成物を製造するに
は、粒径50〜150μm程度の塩化ビニル系樹脂をア
ルキル硫酸またはその塩とともに、可塑剤を均一
に混合してホツトドライブレンドした後、50〜70
℃に冷却し、該温度で粒径0.001〜10μの範囲にあ
る無機化合物粉末や粉末状熱可塑性樹脂等からな
る流動性改良剤を添加し、ホツトドライブレンド
した塩化ビニル系樹脂の表面に均一に被覆して製
造する方法が採用される。流動性改良剤として
は、乳化重合または微細懸濁重合で製造された塩
化ビニル系樹脂、ポリメチルメタクリレート、ス
チレンーアクリロニトリル共重合体、微粒子酸化
ケイ素等が挙げられ、その使用量は、粉体成形方
法、成形性、加工性、作業性等によつて適宜選択
されるが、一般に塩化ビニル系重合体100重量部
に対して50重量部以下、好ましくは５〜30重量部
の範囲である。勿論、粉体成形用の組成物は、単
に塩化ビニル系樹脂、アルキル硫酸塩、安定剤及
び可塑剤等をホツトドライブレンドしただけのも
のでも使用可能であり、流動性改良剤の添加は必
ずしも必要としない。このようにして製造された
組成物は、エンゲルプロセス、ハイスラープロセ
ス、ハヤシプロセス、流動浸漬塗装、静電粉末塗
装、回転成形法等に使用される。
本発明の塩化ビニル樹脂組成物がゾル組成物の
場合、乳化重合または微細懸濁重合によつて製造
された塩化ビニル系樹脂に単にアルキル硫酸塩、
安定剤、可塑剤等を添加して高速ミキサー、ニー
ダー等の混合撹拌機で均一に混合することによつ
て製造される該ゾル組成物は、回転成形、スラツ
シユ成形等に使用され、具体的には例えば次の様
にして成形される。目的とする表装材成形金型に
ゾル組成物を所定量流し込み、溶融温度、例えば
125〜250℃で約５〜20分間加熱し溶融させ、次い
で冷却して表装材を金型から取り出す。更にこの
表装材をウレタン樹脂加工用型に固定し、裏面に
ウレタン樹脂を接合させた複合体とする。
本発明の塩化ビニル樹脂組成物から得られた成
形品は強靭で、それを自動車等の部品として用い
た場合、著しくフオギング現象が少なく、ウレタ
ン樹脂との複合体として用いても、イソシアネー
ト、アミンまたはウレタンの発泡剤として用いた
発泡ガスの影響を受けることがなく、また、性熱
性、耐光性に優れた性能を示し、長期間にわたつ
て使用しても亀裂、変色等の現象は生じない、し
たがつて、本発明の塩化ビニル樹脂組成物は、車
輌の天井材、壁材、グローブボツクスリツド、リ
ヤーパーセル、アームレスト、ヘツドレスト、ク
ラツシユパツド等に、一般家庭の壁材、天井材、
床材等に、家具の表装材等として極めて有効に利
用しうる。
次に、本発明を実施例にて詳述するが、本発明
はその要旨を超えない限り、以下の実施例に限定
されるものではない。
なお、実施例中「部」とあるは「重量部」を示
す。
また、実施例におけるフオギング性、耐熱性及
び耐光性の試験は次のように行つた。
＜フオギング性＞
内装材50mm×100mm×１mmを広口ビンに入れ、
透明ガラス板で広口ビンの開口部を覆つた。これ
を80℃のオイルバス中に20時間保ち、透明ガラス
板の曇り具合を積分球型光度計で測定した。（日
本自動車規格）。
＜耐熱性＞
ウレタン樹脂複合後の試験片を110℃のギヤー
オーブン中に入れ、変色するに到るまでの時間を
測定し、かつ、劣化後の状態を観察した。また
400時間後の変色の程度を５段級に評価した。
５級：変色なし、４級：変色ほとんどなし、
（以上合格）、３級：若干変色、２級：変色著し
い、１級：黒変
＜耐光性＞
ウレタン樹脂複合後の試験片（ウレタン樹脂厚
み10mm）をサンシヤインウエザロメーター（スガ
試験機(株)製）中に入れ、ブラツクパネル温度を83
℃とし、変色するに到るまでの時間を測定し、か
つ劣化後の状態を観察した。
実施例 １
塩化ビニル樹脂（懸濁重合品平均重合度1300）
100部
トリメリツト酸トリ―２―エチルヘキシル 65
Ba―Zn系安定剤 ４
エポキシ化大豆油 ４
炭化カルシウム 15
顔料 2.5
ラウリル硫酸ソーダ 所定量
ラウリル硫酸ソーダーの添加量を変えた上記配
合組成物をスーパーミキサーでホツトドライブレ
ンドし、これをロールを用いてシート化して、ペ
レタイザーでペレツト化し塩化ビニル樹脂組成物
を得た。該組成物を射出成形によりアームレスト
用表装材を成形した後、この中にウレタン樹脂を
注入発泡（ポリオール、ポリイソシアネートを炭
酸ガス発泡、触媒アミン使用）して複合体とし
た。アームレスト用表装材のフオギング性及び複
合体の耐熱性、耐光性を測定し、第１表に示し
た。
The present invention is a polyvinyl chloride material that can be used in the molding of molded products such as automobile interior materials, motorcycle seats, general household interior materials, furniture surface materials, etc., and is particularly suitable for molding molded products that are composites with urethane resins. It relates to a resin composition. Traditionally, automotive interior materials such as crash pads, armrests, headrests, ceilings, doors,
Soft and semi-hard vinyl chloride resins are often used for glove box slides, rear parcels, etc.
In particular, soft vinyl chloride resin molded products are used in the form of a composite with a urethane resin that has a soft urethane foam inside to increase safety and flexibility. When the urethane resin is in contact with the vinyl chloride resin, thermal deterioration and photodeterioration of the vinyl chloride resin are accelerated compared to when the urethane resin is not in contact with the resin, causing cracks and discoloration during use. arise,
It is difficult to say that it is demonstrating sufficient performance as an interior material. The patent applicant had previously proposed improvements in fogging properties, heat resistance when made into a urethane resin composite,
For the purpose of improving light resistance, nonionic surfactants and epoxy resins containing polyoxyethylene units are added to vinyl chloride polymers for pastes that are subjected to aqueous emulsion polymerization or fine suspension polymerization in the presence of anionic surfactants and hydrogen peroxide catalysts. They proposed an invention related to a sol composition for interior materials containing resin,
The present inventors added the above-mentioned nonionic surfactant when preparing a vinyl chloride resin composition by blending plasticizers, stabilizers, etc. with vinyl chloride resin produced by a normal polymerization method. It has been shown that by simply adding alkyl sulfuric acid or its salt, the heat resistance and light resistance of a composite with urethane resin can be improved without impairing the low fogging properties of interior materials for automobiles, etc. This discovery led to the completion of the present invention. That is, the object of the present invention is to maintain low fogging properties even without the addition of nonionic surfactants, to prevent thermal deterioration and photodeterioration from being accelerated even when it comes into contact with urethane resin, and to prevent cracking, discoloration, etc. during use. To provide a vinyl chloride resin composition that does not generate Therefore, the gist of the present invention is a composition mainly consisting of a vinyl chloride resin which is made into a composite with a urethane resin, the composition comprising 0.04 to 6 parts by weight of lauryl sulfate or a salt thereof per 100 parts by weight of the vinyl chloride resin. , a vinyl chloride resin composition containing 0.1 to 10 parts by weight of a non-tin metal stabilizer and 0.5 to 20 parts by weight of an epoxy plasticizer. The present invention will be explained in detail. The vinyl chloride resin used in the vinyl chloride resin composition of the present invention is produced by a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, or an emulsion polymerization method. All products manufactured by normal methods such as suspension polymerization or bulk polymerization are used, and those manufactured by suspension polymerization or bulk polymerization are made into vinyl chloride resin compositions with hot dry blends of plasticizers, stabilizers, etc. or by adding a fluidity improver to the above-mentioned hot dry blended composition to make a vinyl chloride resin composition for powder molding, and produced by emulsion polymerization or fine suspension polymerization method: It is used in the form of plastisol or organosol, which is a uniform mixture of plasticizers, stabilizers, etc. Therefore, examples of comonomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; methyl acrylate;
Acrylic esters such as ethyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, maleic esters such as dibutyl maleate and diethyl maleate, dibutyl fumarate,
Fumaric acid esters such as diethyl fumarate,
vinyl methyl ether, vinyl butyl ether,
Vinyl ethers such as vinyl octyl ether,
Examples include vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene, propylene, and styrene, and vinylidene halides other than vinyl chloride or vinyl halides such as vinylidene chloride and vinyl bromide. is used in an amount of 30% by weight or less, preferably 20% by weight or less in the constituent components of the vinyl chloride resin. Of course, the comonomers are not limited to those mentioned above. Compositions based on vinyl chloride resins contain additives normally used in vinyl chloride resins, such as plasticizers, stabilizers, antioxidants, ultraviolet absorbers, fillers, colorants, and mold release agents. Often used together. Plasticizers include, for example, di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, octyldecyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, and diisophthalate. Phthalic acid plasticizers such as -2-ethylhexyl or phthalate esters of higher alcohols having about 11 to 13 carbon atoms, n-octyl-n-decyl trimellistate,
Trimellitic acid plasticizers such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, tri-n-octyl trimellitate, di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, di-azelaate Fatty acid ester plasticizers such as 2-ethylhexyl, dibutyl sebacate, di-2-ethylhexyl sebacate, phosphorus such as tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, etc. Acid ester plasticizer, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid
Examples include epoxy plasticizers such as 2-ethylhexyl, liquid epoxy resins, etc., and these may be used alone or in combination of two or more. In the composition of the present invention, a trimellitic acid plasticizer with low volatility or an ester plasticizer of higher alcohol and phthalic acid is preferred. The above-mentioned liquid epoxy resin is slightly different from secondary plasticizers such as epoxidized soybean oil, but it contributes to thermal stability in the same way as epoxy plasticizers such as epoxidized soybean oil, and is liquid. In the composition of the present invention, it is included in the category of epoxy plasticizers. Epoxy resins include, for example, bisphenol A type resins having two epoxy groups in the molecule, cycloaliphatic resins, those derived from polybutadiene, or resins with 7 epoxy groups per molecule.
Epoxy novolac resins having more than 1 epoxy groups are used. The epoxy equivalent weight is generally higher than that of epoxidized soybean oil, and is generally about 100 to 1500, preferably about 150 to 700. The amount of plasticizer to be used is appropriately selected depending on the moldability, processability, workability of the composition, the purpose of the molded product, etc., but it is generally 30 to 400 parts by weight per 100 parts by weight of the vinyl chloride resin. parts, preferably 50-200
Parts by weight range. Moreover, the composition of the present invention has
A portion of the above-mentioned plasticizers may be epoxidized soybean oil, epoxidized linseed oil or epoxy resin, in particular 0.5 to 20 parts by weight, preferably 1 to 5 parts by weight of epoxidized linseed oil or epoxy resin.
Substitution within the range of parts by weight greatly contributes to the heat resistance and light resistance of the vinyl chloride resin composition when made into a urethane resin composite without deteriorating the fogging performance. When the amount of the epoxy plasticizer added is less than 0.5 parts by weight, it is difficult to obtain sufficiently satisfactory effects on heat resistance and light resistance.On the other hand, when the amount is more than 20 parts by weight, the epoxy plasticizer tends to bleed, resulting in molded products. However, when the composition is a sol, the viscosity of the sol becomes high and processability is reduced. In the case of a sol composition, part of the plasticizer can be replaced with a diluent such as texanol isobutyrate, dodecylbenzene, or kerosene, or an organic solvent that swells the vinyl chloride resin such as toluene or xylene. It may also be used in the form of The amount of the diluent and organic solvent to be added is appropriately determined depending on the application. Rather than using tin-based stabilizers such as tin fatty acid salts and tin mercaptide, stabilizers based on barium-zinc (Ba-Zn), calcium-zinc (Ca-Zn), etc.
The use of a non-tin metal stabilizer such as magnesium-zinc (Mg-Zn) suppresses phenomena such as curing, bleeding, and blooming due to heat and light when in contact with the urethane resin. The amount of stabilizer used is
0.1 to 10 parts by weight per 100 parts by weight of vinyl chloride resin,
It is preferably in the range of 1 to 5 parts by weight. Examples of the alkyl sulfuric acid or its salt to be incorporated into the composition mainly composed of vinyl chloride resin include lauryl sulfuric acid or its salt. Alkyl sulfuric acid is a viscous liquid and exhibits acidity, and is often used in combination with a base to form an alkyl sulfate. In this case, water is generated and may be contained in the composition, and it is necessary to devise a method for molding the composition, so it is preferable to use the alkyl sulfate as an alkyl sulfate. Examples of the alkyl sulfate include sodium salts, potassium salts, lithium salts, etc., and it is preferable to use the sodium salt form from the viewpoint of easy availability and economical efficiency. Alkyl sulfates are solid at room temperature, and commercially available products include powders, granules, and solutions. A solution form is easy to disperse into a sol composition, but since water or an unknown solvent may be mixed into the sol composition, it is preferable to use a powder or granular alkyl sulfate. . Of course, when using the alkyl sulfuric acid or its salt, lauryl sulfuric acid or its salt may be mixed with two or more other alkyl sulfuric acid or its salt. Therefore, the amount of alkyl sulfuric acid or its salt used must be 0.04 to 6 parts by weight, preferably 0.1 to 6 parts by weight, per 100 parts by weight of vinyl chloride resin.
A range of 3 parts by weight is suitable. If the content is less than 0.04 parts by weight, when a molded product of the vinyl chloride resin composition is composited with a urethane resin, the molded product will not be able to fully exhibit its heat resistance and light resistance, and if the content is more than 6 parts by weight. In this case, the heat resistance and light resistance when in contact with the urethane resin are good, but the alkyl sulfuric acid or its salt tends to bleed from the molded product. The vinyl chloride resin composition of the present invention can be kneaded using a mixing agitator such as a high-speed mixer, kneader, ribbon blender, roll, Banbury mixer, or extruder by adding the above-mentioned essential components or other additives as necessary. Mix evenly using a machine etc. For example, to produce a vinyl chloride resin composition from a vinyl chloride polymer obtained by suspension polymerization or bulk polymerization, a vinyl chloride resin, essential components such as alkyl sulfuric acid or its salt, a stabilizer, and a plasticizer are required. Add other additives such as additives, mix uniformly with a ribbon blender or high-speed stirrer, dry-up, and if necessary, heat and melt with a kneading machine such as a roll, Banbury mixer, or extruder to form pellets. There is no problem, and the resin composition is generally made into a molded article by injection molding or blow molding. In addition, to produce a resin composition for powder molding, vinyl chloride resin with a particle size of about 50 to 150 μm is homogeneously mixed with an alkyl sulfuric acid or its salt, a plasticizer, and then hot dry blended. ~70
℃, add a fluidity improver consisting of an inorganic compound powder or a powdered thermoplastic resin with a particle size in the range of 0.001 to 10μ at that temperature, and apply it uniformly to the surface of the hot dry blended vinyl chloride resin. A method of manufacturing by coating is adopted. Examples of fluidity improvers include vinyl chloride resins produced by emulsion polymerization or fine suspension polymerization, polymethyl methacrylate, styrene-acrylonitrile copolymers, and finely divided silicon oxide. Although it is appropriately selected depending on the method, moldability, processability, workability, etc., the amount is generally 50 parts by weight or less, preferably 5 to 30 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. Of course, the composition for powder molding can be simply a hot dry blend of a vinyl chloride resin, an alkyl sulfate, a stabilizer, a plasticizer, etc., and the addition of a fluidity improver is not necessarily necessary. I don't. The composition thus produced is used in the Engel process, Heisler process, Hayashi process, fluidized dip coating, electrostatic powder coating, rotational molding, and the like. When the vinyl chloride resin composition of the present invention is a sol composition, simply adding an alkyl sulfate to the vinyl chloride resin produced by emulsion polymerization or fine suspension polymerization.
The sol composition, which is produced by adding stabilizers, plasticizers, etc. and uniformly mixing it with a mixing agitator such as a high-speed mixer or kneader, is used for rotary molding, slush molding, etc. For example, it is molded as follows. A predetermined amount of the sol composition is poured into a mold for molding the desired surface material, and the melting temperature is adjusted to the desired temperature, e.g.
The material is heated at 125 to 250°C for about 5 to 20 minutes to melt it, then cooled and the facing material is removed from the mold. Further, this facing material is fixed to a urethane resin processing mold, and a urethane resin is bonded to the back side to form a composite. Molded products obtained from the vinyl chloride resin composition of the present invention are strong, and when used as parts for automobiles, there is significantly less fogging phenomenon, and even when used as a composite with urethane resin, isocyanate, amine or It is not affected by the foaming gas used as a foaming agent for urethane, has excellent heat resistance and light resistance, and does not cause cracks or discoloration even after long-term use. Therefore, the vinyl chloride resin composition of the present invention can be used as ceiling materials, wall materials, glove box slides, rear parcels, armrests, headrests, crash pads, etc. of vehicles, wall materials, ceiling materials,
It can be used extremely effectively as flooring material, furniture covering material, etc. Next, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "parts" in the examples indicate "parts by weight." Further, tests for fogging property, heat resistance, and light resistance in Examples were conducted as follows. <Fogging property> Place the interior material 50mm x 100mm x 1mm in a wide mouth bottle,
The opening of the wide-mouth bottle was covered with a transparent glass plate. This was kept in an oil bath at 80°C for 20 hours, and the degree of cloudiness of the transparent glass plate was measured using an integrating sphere photometer. (Japanese Automobile Standards). <Heat resistance> The test piece after the urethane resin composite was placed in a gear oven at 110°C, the time until it changed color was measured, and the state after deterioration was observed. Also
The degree of discoloration after 400 hours was evaluated on a 5-grade scale. Grade 5: No discoloration, Grade 4: Almost no discoloration,
(passed), Grade 3: Slight discoloration, Grade 2: Significant discoloration, Grade 1: Black discoloration <light resistance> Test specimens after urethane resin composite (urethane resin thickness 10 mm) were measured using Sunshine Weatherometer (Suga Test Instruments). Co., Ltd.) and set the black panel temperature to 83.
℃, the time until discoloration was measured, and the state after deterioration was observed. Example 1 Vinyl chloride resin (suspension polymerization product average degree of polymerization 1300)
100 parts Tri-2-ethylhexyl trimellitate 65 Ba-Zn stabilizer 4 Epoxidized soybean oil 4 Calcium carbide 15 Pigment 2.5 Sodium lauryl sulfate Predetermined amount The above blended compositions with varying amounts of sodium lauryl sulfate were heated in a super mixer. The mixture was dry blended, formed into a sheet using a roll, and pelletized using a pelletizer to obtain a vinyl chloride resin composition. After molding the composition into an armrest covering material by injection molding, a urethane resin was injected into the material and foamed (polyol and polyisocyanate were foamed with carbon dioxide gas, using a catalyst amine) to form a composite. The fogging properties of the armrest covering material and the heat resistance and light resistance of the composite were measured and are shown in Table 1.
【表】
実施例 ２
実施例１において塩化ビニル樹脂をペースト用
塩化ビニル樹脂（重合度1500）に変えたほかは同
一配合にてプラスゾル組成物を得た。該ゾル組成
物を自動車のメーターフード用金型に流し込み、
250℃で約５分間加熱回転成形し、次いで冷却し
て成形品を取り出し、メーターフード内装材を得
た。これを実施例１と同様にウレタン樹脂複合体
とし、実施例１と同様の試験を行つた。
その結果、ラウリル硫酸ソーダ０部、0.5部及
び１部用いた場合のそれぞれが実施例１と同じ値
となつた。
実施例 ３
実施例１において塩化ビニル樹脂を重合度700
のものに換えたほかは実施例１と同様にしてホツ
トドライブレンドし、50℃に冷却したところで、
流動性改良剤として乳化重合したペースト用塩化
ビニル樹脂15部を添加し、均一に撹拌貼着した後
42メツシユのタイラー標準篩で篩て大粒子径のも
のを除き粉体成形用塩化ビニル樹脂組成物を得
た。該組成物でクラツシユパツド内装材を成形
し、実施例１と同様にウレタン樹脂複合体とし、
実施例１と同様に試験した。その結果を第２表に
示す。[Table] Example 2 A plus sol composition was obtained using the same formulation as in Example 1 except that the vinyl chloride resin for paste was changed to vinyl chloride resin for paste (degree of polymerization: 1500). Pour the sol composition into a mold for an automobile meter hood,
The molded product was heated and rotary molded at 250° C. for about 5 minutes, then cooled and the molded product was taken out to obtain a meter hood interior material. This was made into a urethane resin composite in the same manner as in Example 1, and the same tests as in Example 1 were conducted. As a result, the values were the same as in Example 1 when using 0 part, 0.5 part, and 1 part of sodium lauryl sulfate. Example 3 In Example 1, the vinyl chloride resin had a polymerization degree of 700.
Hot dry blending was carried out in the same manner as in Example 1 except that the mixture was changed to
After adding 15 parts of emulsion-polymerized vinyl chloride resin for paste as a fluidity improver and uniformly stirring and pasting.
The particles were sieved through a 42 mesh Tyler standard sieve to remove particles with large particle sizes to obtain a vinyl chloride resin composition for powder molding. A crush pad interior material is molded from the composition to form a urethane resin composite in the same manner as in Example 1,
The test was conducted in the same manner as in Example 1. The results are shown in Table 2.
【表】
実施例 ４
実施例２において、ラウリル硫酸ソーダー１
部、錫系安定剤４部にしたほかは実施例２と同様
に成形して、試験を行い、錫（Sn）系安定剤と
Ba―Zn系安定剤を比較し、第３表に示した。[Table] Example 4 In Example 2, sodium lauryl sulfate 1
The molding was carried out in the same manner as in Example 2 except that 4 parts of the tin-based stabilizer and the tin-based stabilizer were used.
A comparison of Ba-Zn stabilizers is shown in Table 3.
【表】
実施例 ５
実施例１において、ラウリル硫酸ソーダを１部
にし、エポキシ系可塑剤を各種変更してフオギン
グ性、耐熱性及び耐光性の評価を行つた。その結
果を第４表に記した。[Table] Example 5 In Example 1, one part of sodium lauryl sulfate was used, and various changes were made to the epoxy plasticizer to evaluate the fogging property, heat resistance, and light resistance. The results are shown in Table 4.
Claims (1)
系樹脂を主体とした組成物であつて、塩化ビニル
系樹脂100重量部当りラウリル硫酸またはその塩
0.04〜６重量部、非錫系金属安定剤0.1〜10重量
部及びエポキシ系可塑剤0.5〜20重量部を含有し
てなる塩化ビニル樹脂組成物。 ２ 塩化ビニル系樹脂を主体とした組成物がプラ
スチゾルまたはオルガノゾルである特許請求の範
囲第１項記載の塩化ビニル樹脂組成物。 ３ 塩化ビニル系樹脂を主体とした組成物が粉体
成形用樹脂組成物である特許請求の範囲第１項記
載の塩化ビニル樹脂組成物。 ４ 非錫系金属安定剤がバリウム―亜鉛系安定
剤、カルシウム―亜鉛系安定剤またはマグネシウ
ム―亜鉛系安定剤である特許請求の範囲第１項、
第２項または第３項記載の塩化ビニル樹脂組成
物。[Scope of Claims] 1. A composition mainly consisting of a vinyl chloride resin which is made into a composite with a urethane resin, wherein lauryl sulfate or its salt is contained per 100 parts by weight of the vinyl chloride resin.
A vinyl chloride resin composition comprising 0.04 to 6 parts by weight, 0.1 to 10 parts by weight of a non-tin metal stabilizer, and 0.5 to 20 parts by weight of an epoxy plasticizer. 2. The vinyl chloride resin composition according to claim 1, wherein the composition mainly composed of vinyl chloride resin is plastisol or organosol. 3. The vinyl chloride resin composition according to claim 1, wherein the composition mainly consisting of a vinyl chloride resin is a resin composition for powder molding. 4. Claim 1, wherein the non-tin metal stabilizer is a barium-zinc stabilizer, a calcium-zinc stabilizer, or a magnesium-zinc stabilizer,
The vinyl chloride resin composition according to item 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15346383A JPS6047046A (en) | 1983-08-23 | 1983-08-23 | Vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15346383A JPS6047046A (en) | 1983-08-23 | 1983-08-23 | Vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6047046A JPS6047046A (en) | 1985-03-14 |
| JPS6354302B2 true JPS6354302B2 (en) | 1988-10-27 |
Family
ID=15563109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15346383A Granted JPS6047046A (en) | 1983-08-23 | 1983-08-23 | Vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6047046A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62256872A (en) * | 1986-04-30 | 1987-11-09 | Mitsubishi Kasei Vinyl Co | Primer |
| WO2016143343A1 (en) * | 2015-03-10 | 2016-09-15 | 日本ゼオン株式会社 | Vinyl chloride resin composition for powder molding, vinyl chloride resin molded article and laminate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113229A (en) * | 1981-12-28 | 1983-07-06 | Mitsubishi Monsanto Chem Co | Manufacture of open-cell foam |
-
1983
- 1983-08-23 JP JP15346383A patent/JPS6047046A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113229A (en) * | 1981-12-28 | 1983-07-06 | Mitsubishi Monsanto Chem Co | Manufacture of open-cell foam |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6047046A (en) | 1985-03-14 |
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