CN1263798C - Vinyl chloride series resin paste for hollow forming and formed article therefrom - Google Patents
Vinyl chloride series resin paste for hollow forming and formed article therefrom Download PDFInfo
- Publication number
- CN1263798C CN1263798C CNB031076556A CN03107655A CN1263798C CN 1263798 C CN1263798 C CN 1263798C CN B031076556 A CNB031076556 A CN B031076556A CN 03107655 A CN03107655 A CN 03107655A CN 1263798 C CN1263798 C CN 1263798C
- Authority
- CN
- China
- Prior art keywords
- vinyl chloride
- paste
- based resin
- slush molding
- tetrahydrobenzene
- 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 - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 130
- 239000011347 resin Substances 0.000 title claims abstract description 130
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000465 moulding Methods 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- NMEZJSDUZQOPFE-UHFFFAOYSA-N Cyclohex-1-enecarboxylic acid Chemical compound OC(=O)C1=CCCCC1 NMEZJSDUZQOPFE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000004902 Softening Agent Substances 0.000 description 47
- -1 2-ethylhexyl Chemical group 0.000 description 46
- 239000000203 mixture Substances 0.000 description 31
- 239000002253 acid Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001879 gelation Methods 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 230000002322 anti-exudative effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 208000034189 Sclerosis Diseases 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- OZJAWXWQIPFNKT-UHFFFAOYSA-N cyclohex-4-ene-1,2,3-tricarboxylic acid Chemical compound C1(C(C(CC=C1)C(=O)O)C(=O)O)C(=O)O OZJAWXWQIPFNKT-UHFFFAOYSA-N 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 6
- 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 5
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004439 Isononyl alcohol Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- 239000000126 substance Substances 0.000 description 4
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- IGVGCQGTEINVOH-UHFFFAOYSA-N 2-methyloctan-1-ol Chemical compound CCCCCCC(C)CO IGVGCQGTEINVOH-UHFFFAOYSA-N 0.000 description 3
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000004440 Isodecyl alcohol Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001149 thermolysis Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 2
- ZVHAANQOQZVVFD-UHFFFAOYSA-N 5-methylhexan-1-ol Chemical compound CC(C)CCCCO ZVHAANQOQZVVFD-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 239000001836 Dioctyl sodium sulphosuccinate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- UGCLRTASPKBMRY-UHFFFAOYSA-N cyclohex-5-ene-1,2,3,4-tetracarboxylic acid Chemical compound C1(C(C(C(C=C1)C(=O)O)C(=O)O)C(=O)O)C(=O)O UGCLRTASPKBMRY-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000000892 gravimetry Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229940057402 undecyl alcohol Drugs 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- RBPAPQWTNWGCGO-UHFFFAOYSA-N 2,3,4-tri(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=C(O)C(CCCCCCCCC)=C1CCCCCCCCC RBPAPQWTNWGCGO-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229910007572 Zn-K Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 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
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- FEXXLIKDYGCVGJ-UHFFFAOYSA-N butyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OCCCC FEXXLIKDYGCVGJ-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- YOQGAGHVQDTPKB-UHFFFAOYSA-N chloroethene;ethenyl octadecanoate Chemical compound ClC=C.CCCCCCCCCCCCCCCCCC(=O)OC=C YOQGAGHVQDTPKB-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YVWBQGFBSVLPIK-UHFFFAOYSA-N cyclohex-2-ene-1-carboxylic acid Chemical compound OC(=O)C1CCCC=C1 YVWBQGFBSVLPIK-UHFFFAOYSA-N 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229960002366 magnesium silicate Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G08—SIGNALLING
- G08B—SIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
- G08B3/00—Audible signalling systems; Audible personal calling systems
- G08B3/10—Audible signalling systems; Audible personal calling systems using electric transmission; using electromagnetic transmission
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种中空成型用氯乙烯系树脂糊，即使反复使用中空成型工序中受热的剩余部分中空成型用氯乙烯系树脂糊，也不损害该中空成型用氯乙烯系树脂糊的溶胶粘度特性和所得成型物的特性等。此外，本发明还提供了一种用上述氯乙烯系树脂糊形成的成型物。中空成型用氯乙烯系树脂糊含有糊用氯乙烯系树脂和作为增塑剂的环己烯羧酸酯。利用中空成型法将上述氯乙烯系树脂糊成型而制得成型物。The present invention provides a vinyl chloride resin paste for hollow molding that does not impair the sol viscosity of the vinyl chloride resin paste for hollow molding even if the remaining portion of the vinyl chloride resin paste heated in the hollow molding process is repeatedly used characteristics and the characteristics of the resulting molded products, etc. In addition, the present invention also provides a molded article formed using the above-mentioned vinyl chloride-based resin paste. The vinyl chloride-based resin paste for hollow molding contains a vinyl chloride-based resin for paste and cyclohexene carboxylate as a plasticizer. The above-mentioned vinyl chloride-based resin paste was molded by a hollow molding method to obtain a molded article.
Description
Technical field
The present invention relates to that a kind of slush molding is stuck with paste with vinyl chloride-based resin and with the forming composition of its formation.
The dissolved adhesiveness that excellent heat stability when more particularly, the present invention relates to a kind of slush molding, slush molding are stuck with paste with vinyl chloride-based resin is low excellent and vinyl chloride-based resin anti-exudative excellence is stuck with paste and with the forming composition of its formation to desired non-migratings for acrylonitrile-butadiene-styrene resin (ABS resin) or polystyrene resin etc. such as suitable practical level and forming composition toys.
Said slush molding is stuck with paste with vinyl chloride-based resin and is generally known as paste glue between personage in the field of business among the present invention.
Background technology
So far, to stick with paste be that cooperation is made use as the aromatic carboxylic acid esters of softening agent in sticking with paste with vinyl chloride-based resin to vinyl chloride-based resin always.In employed aromatic carboxylic acid esters, phthalate plasticizers, phthalic acid two (2-ethylhexyl) ester (hereinafter referred to as DOP) particularly, have the various rerum naturas of comparison isostatic, be suitable for forming methods such as dip forming, coated and molded, rotoforming, slush molding, injection molding, be widely used in dwelling house interior finish fields such as toy, gloves, wallpaper, bed material, automotive fields such as back boxing, seal gum, various uses such as steel plate coating, canvas coating.
But, in above-mentioned phthalate plasticizers, exist suspection and might upset the internal secretion effect, to Wildlife, human reproduction, the material (so-called environmental hormone) that growth exerts an influence, as the development trend of industrial community, wish to develop the softening agent that substitutes phthalate plasticizers such as DOP with excellent properties always.
For this reason, for example, softening agent has as an alternative obtained application as tributyl acetylcitrate (ATBC) of citrate plasticizer etc. in certain fields, but, therefore exist the problem that the softening agent acid number rises under hot conditions because the heat-resisting decomposability of softening agent self is poor.
Especially, as a large amount of forming methods that adopt in toy etc., the slush molding method is slush molding to be stuck with paste with vinyl chloride-based resin be injected in the mould, heating then, the slush molding that remains not gelation is stuck with paste discharge so that reuse with vinyl chloride-based resin, at this moment, because the temperature that the slush molding of discharging is stuck with paste with vinyl chloride-based resin rises to 40～100 ℃ usually, therefore require it to have and to withstand the thermostability of using repeatedly.
But, in the past any plasticizer can withstand aspect this thermostability of using repeatedly all undesirable.It is generally acknowledged that one of its reason is, heating makes moieties oxygenolysis in the plasticizer molecule, so the acid number of softening agent rises.
The viscosity characteristics that the acid number of softening agent is stuck with paste with vinyl chloride-based resin slush molding has a significant impact, and therefore considers from processibility (sagging during fusion, thickness inhomogeneous etc.) aspect, requires it to have satisfactory stability.
Therefore, proposed to use technology as the diisononyl adipate (DINA) of adipate plasticizers, according to this technology,, exist heat-resisting decomposability, non-migrating (p-poly-phenyl ethenoid resin etc.), the anti-unfavorable problem in aspect such as exudative though initial stage viscosity can reduce.
In order to address the above problem, various solutions have been proposed.
For example, proposed the technology (for example, with reference to patent documentation 1) of cyclohexane carboxylate as softening agent.But, though this technology anti-exudative, non-migrating aspects such as (to ABS resin, p-poly-phenyl ethenoid resins etc.) is good, but owing to be wanting in heat-resisting decomposability, therefore softening agent acid number in heat-processed rises, and thermostability (dissolved adhesiveness, the thixotropy etc.) aspect that slush molding is stuck with paste with vinyl chloride-based resin during moulding exists problem.
[patent documentation 1] spy opens 2001-207002 communique (page 2, paragraph " 0005 "～page 3, paragraph " 0011 ")
Summary of the invention
The object of the present invention is to provide a kind of slush molding to stick with paste with vinyl chloride-based resin and with the forming composition of its formation, the characteristics that this slush molding is stuck with paste with vinyl chloride-based resin are, even use the slush molding of the remaining component of in the slush molding operation, being heated to stick with paste repeatedly, do not damage the dissolved adhesiveness characteristic that this slush molding sticks with paste with vinyl chloride-based resin, the characteristic of prepared forming composition etc. with vinyl chloride-based resin yet.
The present inventor has carried out repeatedly with keen determination research in order to solve above-mentioned problem, it found that, by the cyclohexene carboxylate ester is used for sticking with paste with vinyl chloride-based resin (as necessary composition) as softening agent, even use repeatedly in the slush molding operation remainder not the slush molding of gelation stick with paste with vinyl chloride-based resin, do not occur in the rough sledding that is subjected in the thermal process caused dissolved adhesiveness deterioration in characteristics because the softening agent acid number rises yet, heat-resisting decomposability is improved, thereby finished the present invention.
That is, the invention provides a kind of slush molding and stick with paste, it is characterized in that: contain and stick with paste with vinyl chloride-based resin with as the cyclohexene carboxylate ester of softening agent with vinyl chloride-based resin.
In addition, the invention provides a kind of forming composition, it is characterized in that: make by with the slush molding method vinyl chloride-based resin being stuck with paste moulding, wherein, vinyl chloride-based resin is stuck with paste to contain and is stuck with paste with vinyl chloride-based resin with as the cyclohexene carboxylate ester of softening agent.
Below further the present invention is described in detail.
Slush molding involved in the present invention is stuck with paste to contain with vinyl chloride-based resin and is stuck with paste with vinyl chloride-based resin with as the cyclohexene carboxylate ester of softening agent, and the state of its existence is: this paste is scattered in the softening agent with vinyl chloride-based resin.
Be used for paste vinyl chloride-based resin of the present invention, it is the vinyl chloride-based resin that can be used in resin paste, and this resin paste can be used for the slush molding method.As this paste vinyl chloride-based resin, it comprises for example polyvinyl chloride resin, the vinyl chloride-vinyl acetate copolymer resins, vinylchlorid-stearic acid vinyl ester copolymer resins, the vinyl chloride-ethylene copolymer resins, vinylchlorid-copolymerization of propylene resin, vinylchlorid-iso-butylene copolymer resins, vinylchlorid-methacrylic ester copolymer resins, the known monomers that vinylchlorid-IVE copolymer resins is such and the polyvinyl chloride copolymer resins of vinylchlorid, and be resin etc. with the chlorinated polyvinyl chloride that hydrogen atom in polyvinyl chloride resin or the polyvinyl chloride copolymer resins is substituted by the chlorine atom, its form for example is spherical.These polymkeric substance can use a kind of or use two or more mixtures.
Here said slush molding is meant a kind of with the working method of resin paste moulding slush molding thing, and the back will be described in detail it.
Be used for paste of the present invention with below the preferred a few μ m of median size of vinyl chloride-based resin, more preferably in the scope of 0.02～2 μ m.
This paste can carry out drying by suspension liquid of monomer mixtures such as vinylchlorid being carried out emulsion that letex polymerization obtains or obtaining with microsuspension etc. with vinyl chloride-based resin and prepare.
The above-mentioned emulsion polymerization uses the monomer mixture of chloride vinyl monomer such as vinylchlorid etc. usually, as emulsifying agents such as the sodium lauryl sulphate of anion surfactant, dioctyl sodium sulphosuccinate, and water-soluble catalysts such as ammonium persulphate, Potassium Persulphate, in water medium, carry out.In addition, also can in monomer, import hydrophilic radical, not use emulsifier-free (soap-free) letex polymerization of emulsifying agent.
In addition, microsuspension uses the monomer mixture of chloride vinyl monomer such as vinylchlorid etc. usually, as emulsifying agents such as the sodium lauryl sulphate of anion surfactant, dioctyl sodium sulphosuccinate, dispersing auxiliary, and oil-soluble catalysts such as dodecanoyl superoxide, two-2-ethylhexyl superoxide, in water medium, make it be separated into oil droplet with homogenizer etc. by mechanical shearing and react.
As the drying means of above-mentioned emulsion, suspension liquid etc., it comprises for example spraying drying etc.
In slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin, use cyclohexene carboxylate ester as softening agent, also can and use cyclohexene carboxylate ester softening agent in addition.
In this case, in employed whole softening agent the content of cyclohexene carboxylate ester preferably in the scope of 50～100 weight %, the scope of preferred especially 70～100 weight %, most preferably, the content of cyclohexene carboxylate ester is 100 weight %.If the content of cyclohexene carboxylate ester is in the scope of 50～100 weight %, then softening agent has excellent heat-resisting decomposability, and has excellent dissolved adhesiveness, dissolved adhesiveness stability, anti-exudative, non-migrating, nonvolatile harmony.
As being used for cyclohexene carboxylate ester of the present invention, it comprises for example tetrahydrobenzene monocarboxylic ester, tetrahydrobenzene dicarboxylic diester, tetrahydrobenzene tricarboxylic acid three esters, tetrahydrobenzene tetracarboxylic acid four esters etc.
In these cyclohexene carboxylate esters, from considering preferred tetrahydrobenzene dicarboxylic diester, tetrahydrobenzene tricarboxylic acid three esters with the consistency and the non-volatile aspect of sticking with paste with vinyl chloride-based resin.
As the tetrahydrobenzene dicarboxylic diester, it comprises for example 4-tetrahydrobenzene-1,2-dicarboxylic acid two (2-ethylhexyl) ester, 4-tetrahydrobenzene-1,2-dicarboxylic acid dinonyl, 4-tetrahydrobenzene-1,2-dicarboxylic acid two isodecyl esters, 2-tetrahydrobenzene-1,4-dicarboxylic acid dinonyl etc.
In addition, as tetrahydrobenzene tricarboxylic acid three esters, it comprises for example 4-tetrahydrobenzene-1,2,3-tricarboxylic acid three (2-ethylhexyl) ester, 5-tetrahydrobenzene-1,2,4-tricarboxylic acid three ester in the different ninth of the ten Heavenly Stems etc.
In addition, consider that from anti-exudative aspect the acid number of cyclohexene carboxylate ester used in the present invention is preferred below 0.2.
Here said acid number, the milligram number of the sour necessary potassium hydroxide that contains in being meant and in the 1g sample.
Be used for cyclohexene carboxylate ester of the present invention, it can for example make cyclohexene carboxylate and monohydroxy-alcohol carry out condensation reaction with known method commonly used and make.For example, can be in nitrogen gas stream, carry out under the condition of stirring at raw material regulation, additional reflux exchanger, superfluous monohydroxy-alcohol is refluxed to be reached below 0.5 until acid number, preferably, on one side under 130～250 ℃ temperature continuously heating continuously the water that generates is removed, subsequently, preferably, under 230～180 ℃ temperature, below 10hPa, more preferably, under the reduced pressure below the 4hPa, unreacted alcohol is removed, neutralized in case of necessity thereafter, filter the softening agent that obtains having the regulation proterties then.
As the cyclohexene carboxylate that can use, enumerate tetrahydrobenzene monocarboxylic acid, tetrahydrobenzene dicarboxylic acid, tetrahydrobenzene tricarboxylic acid, tetrahydrobenzene tetracarboxylic acid etc. here.In these cyclohexene carboxylates, consider preferred tetrahydrobenzene dicarboxylic acid, tetrahydrobenzene tricarboxylic acid from its carboxylate and the consistency and the non-volatile aspect of sticking with paste with vinyl chloride-based resin.
As above-mentioned tetrahydrobenzene dicarboxylic acid, it comprises for example 1-tetrahydrobenzene-1,2-dicarboxylic acid, 2-tetrahydrobenzene-1,2-dicarboxylic acid, 3-tetrahydrobenzene-1,2-dicarboxylic acid, 4-tetrahydrobenzene-1,2-dicarboxylic acid, 4-methyl-4-tetrahydrobenzene-1,2-dicarboxylic acid, 1-tetrahydrobenzene-1,3-dicarboxylic acid, 3-tetrahydrobenzene-1,3-dicarboxylic acid, 4-tetrahydrobenzene-1,3-dicarboxylic acid, 1-tetrahydrobenzene-1,4-dicarboxylic acid, 2-tetrahydrobenzene-1,4-dicarboxylic acid etc.
As above-mentioned tetrahydrobenzene tricarboxylic acid, it comprises for example 1-tetrahydrobenzene-1,2,3-tricarboxylic acid, 3-tetrahydrobenzene-1,2,3-tricarboxylic acid, 4-tetrahydrobenzene-1,2,3-tricarboxylic acid, 1-tetrahydrobenzene-1,2,4-tricarboxylic acid, 2-tetrahydrobenzene-1,2,4-tricarboxylic acid, 3-tetrahydrobenzene-1,2,4-tricarboxylic acid, 4-tetrahydrobenzene-1,2,4-tricarboxylic acid, 5-tetrahydrobenzene-1,2,4-tricarboxylic acid, 6-tetrahydrobenzene-1,2,4-tricarboxylic acid, 1-tetrahydrobenzene-1,3,5-tricarboxylic acid etc.
Except above-mentioned cyclohexene carboxylate, replace cyclohexene carboxylate, can use esters such as their acid anhydrides or their acyl chlorides formation property derivative.In addition, also can use the alkyl ester compound of these cyclohexene carboxylates.In employed alkyl ester compound, can under the mitigation condition, consider preferred lower alkyl ester compound, wherein special preferable methyl ester cpds from the dealcoholization operation.
These materials can use separately, also can two or more mixing use.
As be used for the operable monohydroxy-alcohol of cyclohexene carboxylate ester of the present invention in manufacturing, it comprises for example butanols, isopropylcarbinol, hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol, isooctyl alcohol, 2-Ethylhexyl Alcohol, nonyl alcohol, isononyl alcohol, 2-methyl octanol, decyl alcohol, isodecyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol etc.
These monohydroxy-alcohols can use separately, also can two or more mixing use.
In the cyclohexene carboxylate ester that obtains carrying out condensation reaction with above-mentioned cyclohexene carboxylate, these alcohol have constituted pure unit.
As above-mentioned alcohol, preferably have the monohydroxy-alcohol of the alkyl of carbon number in 6～11 scopes.If the carbon number of monohydroxy-alcohol alkyl is in 6～11 scope, then prepared cyclohexene carboxylate ester has the non-volatile of excellence, and has excellent consistency with paste with vinyl chloride-based resin.
As the employed monohydroxy-alcohol that has carbon number alkyl in 6～11 scopes, it comprises for example hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol, isooctyl alcohol, 2-Ethylhexyl Alcohol, nonyl alcohol, isononyl alcohol, 2-methyl octanol, decyl alcohol, isodecyl alcohol, undecyl alcohol etc.
In addition, in the monohydroxy-alcohol of the alkyl of 6～11 scopes, preferred especially hydroxyl value is at the monohydroxy-alcohol of 370～420 scopes at the above-mentioned carbon number that has.As the carbon number of alkyl in 6～11 scopes and hydroxyl value at the monohydroxy-alcohol of 370～420 scopes, in above-mentioned monohydroxy-alcohol, enumerate nonyl alcohol, isononyl alcohol, 2-methyl octanol etc.If use the cyclohexene carboxylate ester that satisfies the monohydroxy-alcohol of alkyl carbon number and hydroxyl value scope simultaneously and obtain, then it has excellent non-volatile reaching and the consistency of sticking with paste with vinyl chloride-based resin.
Here said hydroxyl value is meant method according to the rules, with neutralize under specified temperature and the time milligram number of the required potassium hydroxide of the acetate that generates when making the 1g specimen reaction of acetylizing agent.
When being used for the condensation reaction of the synthetic employed cyclohexene carboxylate ester of the present invention,, preferably use catalyzer in order to promote the carrying out of condensation reaction.As employed catalyzer, it comprises for example metal catalysts such as acid catalyst such as tosic acid, phosphoric acid, titanium isopropylate, tetrabutyl titanate, dibutyl tin oxide, dioctyltin oxide, zinc chloride etc.
In addition, preferred 100～250 ℃ of the temperature during this condensation reaction, more preferably 130～250 ℃.
In slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin, except the cyclohexene carboxylate ester, can also use known softening agent.It comprises for example phthalate, adipic acid ester class, sebacic acid ester, trimellitate class, pyromellitic ester class, epoxy soybean wet goods epoxy ester series, clorafin class, phosphoric acid ester, polyester, cyclohexane carboxylate etc.
For the paste vinyl chloride-based resin of 100 weight parts, preferred 10～300 weight parts of usage quantity of softening agent were preferably 20～200 weight parts especially during slush molding involved in the present invention was stuck with paste with vinyl chloride-based resin.If the usage quantity of above-mentioned softening agent was in above-mentioned scope during slush molding was stuck with paste with vinyl chloride-based resin, then processing viscosity is adjusted easily in the slush molding operation, does not produce and oozes out.
Slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin, when this vinyl chloride-based resin of slush molding is stuck with paste, in order to suppress to be used thermo-stabilizer usually owing to heating the paste that the causes desalination acid-respons of vinyl chloride-based resin.
As above-mentioned thermo-stabilizer, it comprises various thermo-stabilizers such as for example plumbous system, tin system, Ba-Zn system, Ca-Zn system, Zn-K system, Zn-Na system.The use level of the thermo-stabilizer that uses, for the paste vinyl chloride-based resin of 100 weight parts, it is preferably in 0.1～10 weight part scope.
In the scope of not damaging the object of the invention, slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin can further cooperate various additives.As employed additive, it comprises for example oxidation inhibitor, UV light absorber, weighting agent, thinner, whipping agent, stabilization aid etc.
As above-mentioned oxidation inhibitor, it for example comprises 2, phenol such as 6-di-t-butyl-p-cresol are that hindered phenols such as oxidation inhibitor, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester are that thioethers such as oxidation inhibitor, Tyox B are that oxidation inhibitor, TNP trinonylphenol phosphite ester phosphoric acid such as (Off オ ス Off ア イ ト) are oxidation inhibitor etc.The use level of the oxidation inhibitor that uses is used vinyl chloride-based resin for 100 weight parts paste, and it is preferably in 0.1～10 weight part scope.
As above-mentioned UV light absorber, it comprises for example benzotriazole based compound, 2-ethylhexyls-2-cyano group-3 such as benzophenone based compounds such as salicylate based compound, 2-hydroxyl-4-methoxy benzophenone, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole such as salol, cyanoacrylate based compounds, two (2 such as 3 '-diphenylacrylate ester, 2,6,6-tetramethyl--4-piperazine base) hindered amine compound such as sebate etc.For 100 weight parts paste vinyl chloride-based resin, the scope of preferred 0.1～10 weight part of the use level of employed UV light absorber.
As above-mentioned weighting agent, it comprises for example lime carbonate, clay, talcum, silicon-dioxide, aluminium hydroxide, magnesium oxide, magnesiumcarbonate, Magnesium Silicate q-agent, Calucium Silicate powder etc.For the paste vinyl chloride-based resin of 100 weight parts, the use level of employed weighting agent is preferably in the scope of 1～120 weight part.
As above-mentioned thinner, it for example comprises 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate, normal alkane etc.For the paste vinyl chloride-based resin of 100 weight parts, the use level of employed thinner is preferably in the scope of 1～50 weight part.
As above-mentioned whipping agent, it for example comprises that with azoformamide, p, p '-oxybis-benzenesulfonyl hydrazide is the organic blowing agent of representative, is inorganic foaming agent of representative etc. with the sodium bicarbonate.For the paste vinyl chloride-based resin of 100 weight parts, the use level of the whipping agent that uses is preferably in the scope of 0.1～30 weight part.
In addition, as the aforementioned stable auxiliary agent, it comprises for example epoxy compoundss such as epoxidised soybean oil, epoxidation linseed oil, butyl epoxy stearate etc.
For the paste vinyl chloride-based resin of 100 weight parts, the use level of aforementioned stable auxiliary agent is preferably in the scope of 0.5～50 weight part.
The paste that obtains is like this mixed, stirs with vinyl chloride-based resin with as the cyclohexene carboxylate ester of softening agent and various additives etc., by make this paste with vinyl chloride-based resin and various additives that use in case of necessity etc. be scattered in this softening agent, can prepare by this softening agent and in this softening agent dispersive stick with paste the slush molding involved in the present invention that constitutes with vinyl chloride-based resin and stick with paste with vinyl chloride-based resin.
As the device that can use when mixing, stir, disperseing to constitute each composition that above-mentioned slush molding sticks with paste with vinyl chloride-based resin, it comprises for example kneader, butterfly mixing tank, planetary-type mixer, Henschel mixer, pulverizer etc.
So-called slush molding is that a kind of utilization will be stuck with paste with vinyl chloride-based resin and is scattered in equably in the softening agent and the slush molding that forms is composed with shape with the flowability of vinyl chloride-based resin paste, makes its gelation fusion make the method for forming of forming composition by heating.
The paste vinyl chloride-based resin that is used for slush molding, be about general vinyl chloride-based resin about 100 μ m for size, because sticking with paste with vinyl chloride-based resin is the minute spherical particle of particle diameter below a few μ m, therefore slush molding is stuck with paste with vinyl chloride-based resin and can be kept stable solid-liquid dispersion state, can only make the forming composition of homogeneous with heat energy.
Forming composition involved in the present invention can make by the slush molding that obtains is like this carried out slush molding with the vinyl chloride-based resin paste.
Slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin, because it contains the cyclohexene carboxylate ester as softening agent, therefore being subjected in the thermal process of heating repeatedly, the acid number that produces owing to this softening agent thermolysis rises few, therefore heat-resisting decomposability excellence can be used for slush molding especially effectively.
Said among the present invention " slush molding " typically refers to and passes through following operation (1) in turn to each operation of operation (4) and make the forming method of forming composition.
Operation (1): slush molding is injected into the mould from sticking with paste groove with the vinyl chloride-based resin paste, heats this mould, make this slush molding that contacts with this mould inner wall face stick with paste gelation, form the gelation layer with vinyl chloride-based resin.
Operation (2): stop heating, the slush molding of the not gelation of the remainder beyond the gelation layer is stuck with paste with vinyl chloride-based resin discharged, be recovered to and stick with paste in the groove.
Operation (3): heating mould once more, thus make the fusion of gelation layer that gelation is carried out thoroughly.
Operation (4): make mold cools down, take out forming composition.
Pass through above-mentioned each operation in turn, can make hollow form forming composition as the object of the invention.
In addition, the mould that uses in above-mentioned operation has the husk that jog grades as inner-wall surface, and this jog has required layout.
As the heating means of mould in the operation (1), so long as the method that can heat mould there is no special qualification.It comprises the method for for example using oil bath, the method for using air-heating furnace etc.In addition, Heating temperature is generally and can makes the temperature of slush molding with the gelation of vinyl chloride-based resin paste, preferred 120～200 ℃ scope.
In addition, since the gelation layer of operation (1) in time prolongation and therefore thickening can be adjusted the bed thickness of forming composition by the termination of setting suitable heating according to the kind of forming composition period.
Being recovered to the slush molding of sticking with paste the not gelation in the groove in the operation (2) sticks with paste with vinyl chloride-based resin, its operation at slush molding is used in (1) once more, this moment, the slush molding of gelation was not recycled in the paste groove with the vinyl chloride-based resin paste, this operation is carried out repeatedly repeatedly later on, thereby it is used repeatedly.
The method of cooling of mould is not particularly limited in the operation (4), for example can cool off with water-cooled.
Forming composition involved in the present invention is owing to used slush molding to stick with paste with vinyl chloride-based resin, and this slush molding has used the softening agent that contains the related essential composition of cyclohexene carboxylate ester conduct of the invention described above with the vinyl chloride-based resin paste, even therefore use this slush molding to stick with paste repeatedly with vinyl chloride-based resin, in being subjected to thermal process, rise also seldom, usually can make the harmonious excellent forming composition of non-exudative (consistency of softening agent), non-migrating, all characteristics such as non-volatile owing to thermolysis produces the softening agent acid number.
As forming composition involved in the present invention, it comprises for example toy, gloves, trolley part etc.
As forming composition involved in the present invention, from requiring to have the angle of extra high aesthetic property, preferred toy in above-mentioned forming composition.
As prepared toy among the present invention, it for example comprises and to be the doll of soft plastics toy, digital commodities, children's play commodity, phantom etc.
Because these toys are on the formation of commodity, usually contact or be used in combination with ABS resin or polystyrene resin etc., therefore require slush molding in these resins that are in contact with it or are used in combination, not move (promptly with the softening agent in the vinyl chloride-based resin paste, has non-migrating), as the toy of forming composition of the present invention, excellent performance in this respect.
Embodiment
Below in conjunction with embodiment the present invention is more specifically illustrated.Powder in the literary composition " all be to be benchmark with weight.
" embodiment 1～4 " and " comparative example 1～5 "
Press the cooperation shown in table 1 and the table 2 and form, modulation contains to stick with paste sticks with paste with vinyl chloride-based resin with the slush molding of vinyl chloride-based resin, softening agent and additive, makes sheet material with it.With the heat-resisting decomposability of vinyl chloride-based resin paste, softening agent and forming composition, dissolved adhesiveness, anti-exudative, non-migrating and non-volatile the evaluation, it the results are shown in table 1 and table 2 to these slush moldings.
Modulation and evaluation method that this slush molding is stuck with paste with vinyl chloride-based resin are as described below.
[modulation that slush molding is stuck with paste with vinyl chloride-based resin]
According to the cooperation ratio shown in table 1 and the table 2, with mixing and blending machine [Tokyo physics and chemistry apparatus (strain) system, ケ ミ ス one ラ one B-100], stirring revolution is to mix stirring under 1100rpm, 4 minutes the condition, under reduced pressure implement 30 minutes standing and defoaming then, modulate to be dispersed with to stick with paste and stick with paste with vinyl chloride-based resin with the slush molding of vinyl chloride-based resin.
[sheet baking condition]
The slush molding that obtains in embodiment and the comparative example is pasted into test film with vinyl chloride-based resin, with ワ one Na one マ チ ス baking oven (ワ one Na one マ チ ス AG system, LTF-ST), after coating 1mm on the sheet glass was thick, baking was 10 minutes under 190 ℃ temperature, makes flakiness.
[measuring method of the heat-resisting decomposability of softening agent and metewand]
The softening agent that uses in 100g embodiment and the comparative example is packed in the sample bottle of 250cc, under the situation of placing of uncapping, 100 ℃ drying machine internal heating 14 days.After the off-test, measure the acid number of softening agent, compare, estimate according to following benchmark with the initial stage acid number.
Zero: acid number is less than 2
*: acid number is more than 2
[measuring method of dissolved adhesiveness stability and metewand]
The mensuration of＜initial stage dissolved adhesiveness 〉
With BM type viscometer, according to ロ one one No.3 at 6rpm, to measure temperature be under 25 ℃ the condition, resulting slush molding in embodiment and the comparative example is stuck with paste with vinyl chloride-based resin is measured.
The mensuration of＜dissolved adhesiveness stability 〉
Under 25 ℃ condition, above-mentioned slush molding is left standstill preservation 7 days with the vinyl chloride-based resin paste, under the condition identical, with BM type viscometer determining dissolved adhesiveness with the initial stage dissolved adhesiveness.
Calculate the dissolved adhesiveness after 7 days and the ratio (dissolved adhesiveness after 7 days/initial stage dissolved adhesiveness) of initial stage dissolved adhesiveness, estimate according to following metewand.
Zero: less than 1.5 times
*: more than 1.5 times
[anti-exudative measuring method and metewand]
The above-mentioned thin slice that makes is cut into 5cm * 5cm size,, under 70 ℃, the condition of relative humidity 95%, place the state of thin slice after 10 days, 20 days, 30 days and 40 days, estimate according to following metewand with visual observation used as test film.
Zero: do not ooze out.
△: do not ooze out, but the adhesion sense on surface increases.
*: ooze out
Sclerosis: do not ooze out, but the softening agent volatilization, the test film sclerosis.
[measuring method of non-migrating and metewand]
The above-mentioned thin slice that makes is cut into 2.5mm * 2.5mm size, used as test film, with ABS resin plate [Asahi Chemical Industry's industry (strain) system, ス イ ラ Star Network 121] and HIPS resin (high-impact polystyrene resin) plate [A﹠amp; M vinylbenzene (strain) system, AGI02], respectively test film is clamped in the middle one-tenth of two resin boards " sandwich " shape, at 10g/cm
2Load under, under 40 ℃ of temperature, keep after 24 hours, visual observation owing to softening agent to the erosion state that the migration of ABS resin plate and HIPS resin board produces, estimate according to following judgement criteria.
Zero: do not have to find owing to migration of plasticizer produces erosion to resin board.
△: do not have owing to migration of plasticizer produces erosion to resin board, but find to have vestige slightly.
*: find to have owing to migration of plasticizer produces erosion to resin board.
* *: obviously found to have owing to migration of plasticizer produces erosion to resin board.
[nonvolatile measuring method]
The above-mentioned thin slice that makes is cut into 5cm * 5cm size, and used as test film, behind the gravimetry (a), in the drying machine of packing into, drying is 120 hours under 100 ℃ of temperature in advance.Take out thin slice subsequently, gravimetry (b) is once more tried to achieve weight decrement (%) according to following calculating formula thereafter.
Weight decrement (%)=(a-b)/a * 100
[table 1]
| Table 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Vinyl chloride-based resin *1)(part) | 100 | 100 | 100 | 100 | 100 | 100 |
| Tetrahydrobenzene is that A (part) tetrahydrobenzene is that B (part) tetrahydrobenzene is C (part) | 50 ? ? | ? 50 ? | ? ? 50 | |||
| DOP (part) DINA (part) ATBC (part) | 50 ? ? | ? 50 ? | ? ? 50 | |||
| Epoxidised soybean oil *2(part) Ca/Zn is a stablizer *3(part) | 5 3 | 5 3 | 5 3 | 5 3 | 5 3 | 5 3 |
| Heat-resisting decomposability acid number heat-resisting decomposability evaluation after 14 days (mgKOH/g) initial stages of softening agent | ? ? 0.11 0.71 ○ | ? ? 0.03 0.50 ○ | ? ? 0.15 0.85 ○ | ? ? 0.03 3.15 × | ? ? 0.08 10.15 × | ? ? 0.10 3.75 × |
| The dissolved adhesiveness initial stage (25 ℃, mPa.s) viscosity stability evaluation after 7 days | 5540 5730 ○ | 6020 6230 ○ | 6660 6720 ○ | 6150 9840 × | 2430 5120 × | 4150 7310 × |
| After anti-exudative 10 days after 20 days after 30 days after 40 days | ○ ○ ○ ○ | ○ ○ ○ ○ | ○ ○ ○ △ | ○ ○ ○ ○ | ○ △ × × | Sclerosis sclerosis sclerosis sclerosis |
| Non-migrating ABS resin plate HIPS resin board | ○ △ | ○ △ | ○ △ | ○ △ | ○ ×× | ×× ×× |
| Non-volatile weight decrement (%) | ? 7.9 | ? 4.7 | ? 3.1 | ? 7.2 | ? 8.8 | ? 19.3 |
[table 2]
In embodiment 4 and comparative example 5, carry out the assessment item that table 2 is put down in writing with the softening agent of heat-resisting decomposability after 14 days on-tests.
[explanation and the note of the softening agent of table 1 and table 2 record]
Tetrahydrobenzene is A: by 4-tetrahydrobenzene-1, and the 4-tetrahydrobenzene-1 that 2-dicarboxylic acid and 2-Ethylhexyl Alcohol (hydroxyl value 432) constitute, 2-dicarboxylic acid two (2-ethylhexyl) ester.Viscosity is 37mPa.s (25 ℃).
Tetrahydrobenzene is B: by 4-tetrahydrobenzene-1, and 2-dicarboxylic acid and isononyl alcohol (consonance fermentation (strain) system, trade(brand)name; オ キ ソ コ one Le 900, hydroxyl value 390) the 4-tetrahydrobenzene-1 that constitutes, 2-dicarboxylic acid dinonyl.Viscosity 48mPa.s (25 ℃).
Tetrahydrobenzene is C: by 4-tetrahydrobenzene-1, and the 4-tetrahydrobenzene-1 that 2-dicarboxylic acid and isodecyl alcohol (hydroxyl value 355) constitute, 2-dicarboxylic acid two isodecyl esters.Viscosity 67mPa.s (25 ℃).
DOP: phthalic acid two (2-ethylhexyl) ester.
DINA: diisononyl adipate.
ATBC: tributyl acetylcitrate.
The hexamethylene methane series: with hexanaphthene-1,2-dicarboxylic acid and isononyl alcohol (consonance fermentation (strain) system, trade(brand)name; オ キ ソ コ one Le 900) carries out condensation reaction and the hexanaphthene-1 that obtains, 2-dicarboxylic acid dinonyl.Viscosity 42mPa.s (25 ℃).
*1) sticks with paste with polyvinyl chloride resin (polymerization degree 1650)
*2) stabilization aid, big Japanese ink chemical industry (strain) system, W-100-EL
*3) thermo-stabilizer, big Japanese ink chemical industry (strain) system, ゲ レ Star Network ML-610A
Result according to table 1 and table 2 can see, slush molding involved in the present invention is stuck with paste at dissolved adhesiveness, anti-exudative, non-migrating, aspect such as non-volatile and DOP with vinyl chloride-based resin and is equal to, owing to the cyclohexene carboxylate ester that in slush molding is stuck with paste with vinyl chloride-based resin, contains as softening agent, therefore has excellent heat-resistant stability and dissolved adhesiveness stability in addition.
Wherein, the pure unitary hydroxyl value that constitutes the cyclohexene carboxylate ester is 390 embodiment 2, and its dissolved adhesiveness, anti-exudative, non-migrating, nonvolatile harmony are very good.
Slush molding involved in the present invention is stuck with paste with vinyl chloride-based resin, owing to contain cyclohexene carboxylate ester as softening agent as neccessary composition, therefore stick with paste with vinyl chloride-based resin with known slush molding in the past and compare, even it is heating use repeatedly in the slush molding operation, be subjected to the moieties of softening agent in the thermal process also to be difficult for taking place thermolysis, therefore heat-resisting decomposability excellence, and viscosity stability, non-migrating, anti-exudative, non-volatile excellence extremely are applicable to slush molding.Can be widely used in mainly and be undertaken in the slush molding things such as toy of moulding by the slush molding method.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP085606/2002 | 2002-03-26 | ||
| JP2002085606 | 2002-03-26 |
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| CN1263798C true CN1263798C (en) | 2006-07-12 |
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| CN (1) | CN1263798C (en) |
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| TWI686187B (en) * | 2018-11-30 | 2020-03-01 | 業峰企業有限公司 | Multi-layer hollow massage device and manufacturing method thereof |
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| CN105061951A (en) * | 2015-09-24 | 2015-11-18 | 江南大学 | Foamed sealant for metal packaging barrel covers and preparation method thereof |
| CN106905640A (en) * | 2017-04-07 | 2017-06-30 | 深圳市索呢雅科技有限公司 | A kind of cartoon product polyvinyl chloride resin paste and its moulding process |
| EP3875526B1 (en) * | 2018-10-29 | 2022-10-19 | Lg Chem, Ltd. | Cyclohexane triester-based plasticizer composition, and resin composition comprising the same |
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| JPH06279642A (en) * | 1993-03-26 | 1994-10-04 | Shin Etsu Chem Co Ltd | Vinyl chloride-based resin composition for powder slash molding |
| JP4314711B2 (en) * | 2000-01-27 | 2009-08-19 | 新日本理化株式会社 | Cyclohexanedicarboxylic acid diester plasticizer, vinyl chloride resin composition, and vinyl chloride resin molded article using the same |
| JP2003147142A (en) * | 2001-11-16 | 2003-05-21 | C I Kasei Co Ltd | Heat-shrinkable polyvinyl chloride resin film |
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2003
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| TWI686187B (en) * | 2018-11-30 | 2020-03-01 | 業峰企業有限公司 | Multi-layer hollow massage device and manufacturing method thereof |
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| CN1446846A (en) | 2003-10-08 |
| TW200304925A (en) | 2003-10-16 |
| HK1058372A1 (en) | 2004-05-14 |
| TWI303643B (en) | 2008-12-01 |
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