WO2019230949A1 - Rigid vinyl chloride-based resin tube - Google Patents
Rigid vinyl chloride-based resin tube Download PDFInfo
- Publication number
- WO2019230949A1 WO2019230949A1 PCT/JP2019/021714 JP2019021714W WO2019230949A1 WO 2019230949 A1 WO2019230949 A1 WO 2019230949A1 JP 2019021714 W JP2019021714 W JP 2019021714W WO 2019230949 A1 WO2019230949 A1 WO 2019230949A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- parts
- polyvinyl chloride
- chloride resin
- resin tube
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 133
- 239000011347 resin Substances 0.000 title claims abstract description 133
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title abstract description 35
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 107
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 107
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 70
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000012860 organic pigment Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 238000000465 moulding Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000295 complement effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004605 External Lubricant Substances 0.000 description 3
- 239000004610 Internal Lubricant Substances 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- FUIBVSHMELLXFV-UHFFFAOYSA-K S[Sn](CCCC)CCCC.S[Sn](CCCCCCCC)CCCCCCCC.S[Sn](CCCC)CCCC.C[Sn]C Chemical compound S[Sn](CCCC)CCCC.S[Sn](CCCCCCCC)CCCCCCCC.S[Sn](CCCC)CCCC.C[Sn]C FUIBVSHMELLXFV-UHFFFAOYSA-K 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910009202 Y—Mn Inorganic materials 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- MGFRKBRDZIMZGO-UHFFFAOYSA-N barium cadmium Chemical compound [Cd].[Ba] MGFRKBRDZIMZGO-UHFFFAOYSA-N 0.000 description 1
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- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- MXMZCLLIUQEKSN-UHFFFAOYSA-N benzimidazoline Chemical compound C1=CC=C2NCNC2=C1 MXMZCLLIUQEKSN-UHFFFAOYSA-N 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
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 235000013539 calcium stearate Nutrition 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
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- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
Definitions
- the present invention relates to a hard vinyl chloride resin pipe having excellent heat shielding properties and color tone stability.
- Hard vinyl chloride resin pipes are widely used for transporting general fluids such as water pipes and drain pipes, and are colored gray in JIS standards. Conventionally, carbon black is often used as a coloring pigment as a means for coloring a hard vinyl chloride resin tube gray.
- the solar panel has a low solar reflectance due to the high endothermic properties of carbon black, and outdoor sunlight is irradiated onto the hard vinyl chloride resin tube.
- Patent Document 1 describes that an organic pigment having excellent infrared transmittance is used as a coloring pigment without using carbon black.
- the molding process of the hard vinyl chloride resin tube is performed by heating and melting the material in an extruder to knead it into a fluidized state and continuously extrude it from a die. Since the kneaded material has a high viscosity and receives a temperature difference generated due to a temperature setting of the apparatus through which the kneaded raw material passes, a difference in shape, and the like, there is a problem that the heat history is inevitably non-uniform.
- the present inventor has studied various types of hard vinyl chloride resin tubes using colored pigments. When an organic pigment is used as a colored pigment as in Patent Document 1, the organic pigment is affected by heat and deteriorated.
- the characteristic that is easy to perform and the non-uniformity of the thermal history as described above cause a variation in the color tone of the hard vinyl chloride resin tube that is a molded product, and the variation in the color tone is a hard vinyl chloride type
- the present invention faced a particularly significant problem when it was colored in a bright color tone with a whiteness of 50 or more.
- an object of the present invention is to provide a hard vinyl chloride resin tube having excellent heat shielding properties (high solar reflectance) and color tone stability.
- the present inventor has achieved excellent thermal insulation (high solar reflectance) and color tone stability of the hard vinyl chloride resin tube by using two or more kinds of metal-based inorganic pigments as color pigments. Found to get.
- the present invention has been completed by further studies based on this finding.
- Item 1 A rigid polyvinyl chloride resin tube comprising a polyvinyl chloride resin and two or more metal inorganic pigments and having a whiteness of 50 or more.
- Item 2. Item 2. The rigid polyvinyl chloride resin tube according to Item 1, wherein the total content of the two or more metal inorganic pigments is 0.050 part by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- Item 3. Item 3.
- Item 4 The rigid polyvinyl chloride resin tube according to any one of Items 1 to 3, wherein the two or more metal inorganic pigments are a mixture of a metal inorganic pigment exhibiting a color and a metal inorganic pigment exhibiting a white color.
- Item 5. The rigid polyvinyl chloride according to any one of Items 1 to 4, further comprising a stearate, wherein the content of the stearate is 10 to 54 parts by weight per part by weight of the metallic inorganic pigment exhibiting a color. Resin tube.
- Item 6. Item 6.
- Item 7. The rigid polyvinyl chloride according to any one of Items 1 to 6, wherein the content of the metallic inorganic pigment exhibiting a color is 0.025 to 0.06 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
- Item 9. Item 9.
- Item 10. Item 10. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 9, further comprising an organic pigment.
- Item 11. Item 11. The rigid polyvinyl chloride resin tube according to Item 10, wherein the organic pigment is a phthalocyanine pigment.
- Item 12. Item 12. The rigid polyvinyl chloride resin tube according to Item 10 or 11, wherein the content of the organic pigment is 0.0001 to 0.004% by weight per 100 parts by weight of the polyvinyl chloride resin.
- a hard vinyl chloride resin tube having excellent heat shielding properties (high solar reflectance) and color tone stability is provided.
- the rigid polyvinyl chloride resin tube of the present invention includes a polyvinyl chloride resin and two or more kinds of metal inorganic pigments, and has a whiteness of 50 or more.
- the rigid polyvinyl chloride resin pipe of the present invention will be described in detail.
- Polyvinyl chloride resin examples include a polyvinyl chloride homopolymer and a composite polyvinyl chloride resin mainly composed of vinyl chloride. These may be used alone or in combination of two or more.
- the average degree of polymerization of the polyvinyl chloride resin is 600 to 3000, and preferably 800 to 2000.
- An average polymerization degree of 600 or more is preferable from the viewpoint of obtaining good mechanical strength, and an average polymerization degree of 3000 or less is preferable from the viewpoint of ease of molding.
- the average degree of polymerization is obtained by dissolving a vinyl chloride homopolymer or a composite vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and drying and removing THF in the filtrate. This means the average degree of polymerization measured using a resin as a sample in accordance with the “vinyl chloride resin test method” of Japanese Industrial Standard JIS K-6721.
- Examples of the composite polyvinyl chloride resin mainly composed of vinyl chloride include a vinyl chloride monomer and a copolymer of a monomer or a polymer copolymerizable with the vinyl chloride monomer.
- Examples of monomers copolymerizable with vinyl chloride monomer include ⁇ -olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl propionate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; methyl (meth) acrylate. , (Meth) acrylates such as butyl (meth) acrylate and hydroxyethyl (meth) acrylate; aromatic vinyls such as styrene and ⁇ -methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide Etc. These copolymerizable monomers may be used alone or in combination of two or more.
- Examples of the polymer copolymerizable with the vinyl chloride monomer include acrylic copolymers composed of alkyl (meth) acrylate monomers and the like. These copolymerizable polymers may be used alone or in combination of two or more.
- (meth) acrylate means acrylate or methacrylate.
- the amount of the copolymerizable monomer or polymer used may be appropriately determined according to the performance and purpose of the obtained rigid vinyl chloride tube. There is no particular limitation.
- a conventionally known method may be used, and examples thereof include a suspension polymerization method.
- the rigid polyvinyl chloride resin tube of the present invention contains two or more metal inorganic pigments as pigments. By including two or more kinds of metal-based inorganic pigments, it is possible to achieve both excellent heat shielding properties (high solar reflectance) and color tone stability.
- any metal-based inorganic pigment can be used as long as it can be adjusted to a color tone having a whiteness of 50 or more.
- a mixed pigment of a metallic inorganic pigment exhibiting color (non-white) and a metallic inorganic pigment exhibiting white is used. More preferably, a mixed pigment mixed so as to be adjusted to a gray color tone defined in “Hard Polyvinyl Chloride Tube” defined in JIS K6741.
- one (single salt) or a plurality of metals selected from the group consisting of chromium, iron, cobalt, copper, manganese, magnesium, bismuth, yttrium, aluminum, and vanadium are used.
- Examples include compounds containing seeds (double salts).
- the compounds containing these metals may be used alone or in combination of two or more.
- Specific examples of the double salt include Fe—Co—Cr, Cu—Cr, Fe—Cr, Fe—Mn, Cu—Mn, Cu—Mg, Cu—Bi, Mn—Bi,
- the salt include Y—Mn, Co—Al, and Fe—Co—Al—Mg.
- a chromium-containing compound preferably a Fe—Cr system, is preferable because it has high infrared absorption suppression and excellent heat shielding properties.
- examples of the metal-based inorganic pigment include oxides, hydroxides, sulfides, silicates, and ferrocyanide salts of the above-described metals. These compounds may be used alone or in combination of two or more. Among these, an oxide is preferable in terms of excellent color tone stability.
- the metallic inorganic pigment exhibiting a color is preferably a pigment exhibiting a black color by combining one or a plurality of pigments from the above-described metallic inorganic pigment exhibiting a color.
- pigments exhibiting black mixed pigments of two or more pigments exhibiting complementary colors or colors close to complementary colors; metals constituting each of two or more pigments exhibiting colors complementary or complementary to each other And double salt pigments containing a plurality of ions; and mixtures thereof.
- a metallic inorganic pigment exhibiting a color, preferably, green chromium oxide (Cr 2 O 3 ) and a red pigment (for example, a complementary color thereof) Iron oxide) in combination as a mixed pigment, and a black-toned pigment; a composite oxide containing chromium oxide and iron oxide; and a mixture thereof, more preferably, chromium oxide and iron oxide.
- the composite oxide containing is mentioned.
- the content of the metallic inorganic pigment exhibiting color in the rigid polyvinyl chloride resin tube of the present invention is 100 wt% of polyvinyl chloride resin from the viewpoint of preferably suppressing non-uniformity in color tone due to non-uniform dispersion of the pigment.
- the rigid polyvinyl chloride resin tube of the present invention contains an organic pigment, 0.025 per 100 parts by weight of the polyvinyl chloride resin from the viewpoint of improving the color tone stability by concealing the color tone instability due to the organic pigment. It is preferable that it is at least parts by weight.
- the content of the metallic inorganic pigment exhibiting a color is, for example, 0.09 parts by weight or less, preferably 0. 0 parts by weight per 100 parts by weight of the polyvinyl chloride resin, in consideration of suppression of contamination of equipment in extrusion molding. 08 parts by weight or less, more preferably 0.07 parts by weight or less, and still more preferably 0.06 parts by weight or less.
- the specific range of the content of the colored metallic inorganic pigment in the rigid polyvinyl chloride resin tube of the present invention is 0.013 to 0.09 parts by weight per 100 parts by weight of the polyvinyl chloride resin, 0 .013 to 0.08 parts by weight, 0.013 to 0.07 parts by weight, 0.013 to 0.06 parts by weight, 0.25 to 0.09 parts by weight, 0.25 to 0.08 parts by weight, 0 .25 to 0.07 parts by weight, 0.25 to 0.06 parts by weight.
- white metallic inorganic pigments examples include metal oxides such as titanium dioxide, aluminum oxide, and zinc oxide.
- metal oxides such as titanium dioxide, aluminum oxide, and zinc oxide.
- titanium dioxide is preferable because it has a high refractive index and high whiteness.
- the content of the metallic inorganic pigment exhibiting white color in the rigid polyvinyl chloride resin tube of the present invention is, for example, 0.03 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin from the viewpoint of obtaining good heat shielding properties. , Preferably 0.06 parts by weight or more, more preferably 0.07 parts by weight or more, and from the viewpoint of preferable gray coloring, for example, 0.2 parts by weight or less, preferably 0.15 parts by weight or less. .
- the specific range of the content of the white metallic inorganic pigment in the rigid polyvinyl chloride resin tube of the present invention is 0.03 to 0.2 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Examples include 03 to 0.15 parts by weight, 0.06 to 0.2 parts by weight, 0.06 to 0.15 parts by weight, 0.07 to 0.2 parts by weight, and 0.07 to 0.15 parts by weight. .
- the ratio of the metallic inorganic pigment exhibiting color to the metallic inorganic pigment exhibiting white is not particularly limited as long as the whiteness is 50 or more.
- the total of two or more metallic inorganic pigments is 100.
- the content ratio of the metallic inorganic pigment exhibiting color is 18 to 58% by weight, preferably 18 to 45% by weight.
- the total content of the two or more types of metal-based inorganic pigments in the rigid polyvinyl chloride resin tube of the present invention preferably suppresses color tone non-uniformity due to pigment dispersion non-uniformity and / or color tone stability.
- From the viewpoint of obtaining good light shielding properties for example, 0.050 parts by weight or more, preferably 0.085 parts by weight or more, more preferably 0.087 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- the total content of the two or more kinds of metal-based inorganic pigments is, for example, 0.500 parts by weight or less, preferably 0.280 parts by weight or less, more preferably, considering the suppression of contamination to equipment in extrusion molding.
- 0.230 weight part or less More preferably, 0.210 weight part or less is mentioned.
- Specific ranges of the total content of two or more kinds of metal inorganic pigments in the rigid polyvinyl chloride resin tube of the present invention are 0.050 to 0.500 parts by weight, 0.050 to 0.280 parts by weight. , 0.050 to 0.230 parts by weight, 0.050 to 0.210 parts by weight, 0.085 to 0.500 parts by weight, 0.085 to 0.280 parts by weight, 0.085 to 0.230 parts by weight 0.085 to 0.210 parts by weight, 0.087 to 0.500 parts by weight, 0.087 to 0.280 parts by weight, 0.087 to 0.230 parts by weight, 0.087 to 0.210 parts by weight Is mentioned.
- the rigid polyvinyl chloride resin tube of the present invention is provided with an organic pigment, a stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, and a filler as necessary. Etc. may also be included. Among these additives, a stabilizer and a filler are preferable.
- organic pigments have excellent dispersion characteristics, hard polyvinyl chloride resin tubes can be colored more uniformly when combined with inorganic pigments.
- the organic pigment is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments (such as phthalocyanine copper), selenium pigments, and dye lake pigments. These may be used alone or in combination of two or more.
- a phthalocyanine pigment is preferable, and phthalocyanine copper is more preferable, from the viewpoint of obtaining excellent color tone stability of the hard vinyl chloride resin tube.
- the content of the organic pigment is 100% by weight of the total content of the two or more metal inorganic pigments from the viewpoint of not impairing the color stability. 15 parts by weight or less per part, preferably 10 parts by weight or less, more preferably 6 parts by weight or less, more preferably 3 parts by weight or less. Moreover, as content of an organic pigment, 0.004 weight part or less is mentioned per 100 weight part of polyvinyl chloride-type resin from a viewpoint which does not impair color tone stability.
- the content of the organic pigment is 0.0001 parts by weight or more, preferably 0.00015 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin, from the viewpoint of more preferably suppressing unevenness in color tone.
- the specific range of the organic pigment content is 0.0001 to 15 parts by weight, 0.0001 to 10 parts by weight, 0.0001 to 6 parts by weight, 0.0001 per 100 parts by weight of the polyvinyl chloride resin. -3 parts by weight, 0.0001-0.004 parts by weight, 0.00015-15 parts by weight, 0.00015-10 parts by weight, 0.00015-6 parts by weight, 0.00015-3 parts by weight, 0.00015 Up to 0.004 parts by weight.
- the stabilizer is not particularly limited.
- the blending amount of the stabilizer is, for example, 0.8 to 2 parts by weight, preferably 1 to 1.4 parts by weight per 100 parts by weight of the polyvinyl chloride resin.
- stearates (stearic acid stabilizers) are preferable, and lead stearate is more preferable.
- the upper limit of the content of stearate is colored from the viewpoint of obtaining even better color tone stability of the hard vinyl chloride resin tube.
- Per 1 part by weight of the metal-based inorganic pigment exhibiting the following: 54 parts by weight or less, preferably 53 parts by weight or less, more preferably 52 parts by weight or less.
- the lower limit is 10 parts by weight per 1 part by weight of the metal-based inorganic pigment exhibiting color. Part by weight or more, preferably 15 parts by weight or more, more preferably 20 parts by weight or more.
- the specific range of the stearate content is 10 to 54 parts by weight, 10 to 53 parts by weight, 10 to 52 parts by weight, 15 to 54 parts by weight, based on 1 part by weight of the colored metallic inorganic pigment. Examples thereof include 15 to 53 parts by weight, 15 to 52 parts by weight, 20 to 54 parts by weight, 20 to 53 parts by weight, and 20 to 52 parts by weight.
- the stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester. These may be used alone or in combination of two or more.
- the lubricant examples include an internal lubricant and an external lubricant.
- the internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation.
- the internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl stearate, epoxidized soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more.
- the external lubricant is used for the purpose of increasing the sliding effect between the molten resin and the metal surface during the molding process.
- the external lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyolefin wax, and ester wax. These may be used alone or in combination of two or more.
- the processing aid is not particularly limited, and examples thereof include acrylic processing aids that are alkyl acrylate / alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000. Specific examples include n-butyl acrylate / Examples thereof include a methyl methacrylate copolymer and a 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer. These may be used alone or in combination of two or more.
- the antioxidant is not particularly limited, and examples thereof include phenolic antioxidants. These may be used alone or in combination of two or more.
- the filler is not particularly limited, and examples thereof include calcium carbonate and talc. These may be used alone or in combination of two or more. Among these fillers, calcium carbonate is preferably used from the viewpoint of obtaining better color tone stability of the hard vinyl chloride resin tube and / or obtaining better heat shielding properties. In addition, when calcium carbonate is included in the hard polyvinyl chloride resin tube of the present invention, the content of calcium carbonate is polyvinyl chloride from the viewpoint of obtaining even better color tone stability of the hard vinyl chloride resin tube. 3 parts by weight or more per 100 parts by weight of the resin.
- the content thereof is particularly a metal system exhibiting white. It is suitable when the inorganic pigment is 0.06 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- the upper limit of the content of calcium carbonate is not particularly limited, but is, for example, 10 parts by weight or less, preferably 9 parts by weight or less, more preferably 8 parts by weight or less, and further preferably 7 parts by weight per 100 parts by weight of the polyvinyl chloride resin. The following are listed.
- the specific range of the calcium carbonate content is 3 to 10 parts by weight, 3 to 9 parts by weight, 3 to 8 parts by weight, 3 to 7 parts by weight, and 5 to 10 parts per 100 parts by weight of the polyvinyl chloride resin. 5 parts by weight, 5-9 parts by weight, 5-8 parts by weight, 5-7 parts by weight, 6-10 parts by weight, 6-9 parts by weight, 6-8 parts by weight, 6-7 parts by weight.
- the amount of the filler relative to 1 part by weight of the white metallic inorganic pigment is used to obtain better color stability of the hard vinyl chloride resin tube.
- the lower limit is 30 parts by weight or more
- the white metallic inorganic pigment is 0.06 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- 55 parts by weight or more is preferable.
- 93 weight part or less is mentioned as an upper limit of the quantity of the filler with respect to 1 weight part of metallic inorganic pigments which exhibit white. Specific ranges of the amount of the filler relative to 1 part by weight of the metallic inorganic pigment exhibiting white include 30 to 93 parts by weight and 55 to 93 parts by weight.
- the rigid polyvinyl chloride resin tube of the present invention has a color tone with a whiteness of 50 or more. This makes it possible to obtain excellent heat shielding properties of the hard polyvinyl chloride resin tube. In addition, when a relatively bright color tone having a whiteness of 50 or more is colored, inherent variations in color tone (color tone instability) tend to occur. However, in the rigid polyvinyl chloride resin tube of the present invention, the above-described two types are used. By using the above metallic inorganic pigment as a color pigment, excellent color tone stability can be achieved.
- the upper limit of the whiteness range is not particularly limited, but is 70 or less, preferably 60 from the viewpoint of adapting to the gray color tone defined in “Hard Polyvinyl Chloride Tube” defined in JIS K6741. The following are mentioned. Since the rigid polyvinyl chloride resin pipe of the present invention is excellent in heat shielding properties, even if the whiteness is gray of less than 60, excellent heat shielding properties can be obtained. From such a viewpoint, a suitable example of whiteness of the rigid polyvinyl chloride resin tube of the present invention is 56 or less, preferably 54 or less. Specific ranges of whiteness of the rigid polyvinyl chloride resin tube of the present invention include 50 to 70, 50 to 60, 50 to 56, and 50 to 54.
- the whiteness can be adjusted by adjusting the content of the metallic inorganic pigment exhibiting a color and / or the content of the metallic inorganic pigment exhibiting a white color in the above-described two or more metallic inorganic pigments.
- Whiteness refers to an L * value measured under a D65 light source based on the CIE 1976 L * a * b * colorimetric system.
- the hard polyvinyl chloride resin pipe of the present invention has excellent heat shielding properties, it is possible to achieve a high solar reflectance of, for example, more than 28.5%. From the viewpoint of obtaining better heat shielding properties, the solar reflectance is preferably more than 29.5%, more preferably more than 30.5%, still more preferably more than 31.5%, particularly preferably more than 32.5%. Can be mentioned. Although the upper limit of solar reflectance is not particularly limited, it is 70% or less, preferably 65% or less in consideration of the above-described whiteness.
- Specific ranges of the solar reflectance of the rigid polyvinyl chloride resin tube of the present invention include 28.5 to 70%, 28.5 to 65%, 29.5 to 70%, 29.5 to 65%, 30.5-70%, 30.5-65%, 31.5-70%, 31.5-65%, 32.5-70%, 32.5-65%.
- the solar reflectance is adjusted by adjusting the content of the above-described two or more kinds of metal-based inorganic pigments, adjusting the content of the organic pigment in the case of blending the organic pigment, and / or adjusting the above-described whiteness. be able to.
- the solar reflectance is a value measured according to JIS R3106-1998.
- the method for producing a rigid polyvinyl chloride resin tube of the present invention comprises mixing the above-mentioned polyvinyl chloride resin and two or more kinds of metal inorganic pigments, and other components blended as required, to produce a polyvinyl chloride resin.
- molds a polyvinyl chloride-type resin compound are included.
- a polyvinyl chloride resin compound is prepared by mixing polyvinyl chloride resin with two or more metal inorganic pigments and other components blended as required.
- the mixing method include a hot blend method and a cold blend method.
- the compound in the case of using an organic pigment in the cold blending method, the compound is prepared under conditions where energy (heat, shearing force), which is an element necessary for the color development of the organic pigment, is not sufficiently applied.
- energy heat, shearing force
- the cold blend method is a mixing method that inherently tends to be unstable in color tone.
- the rigid polyvinyl chloride resin tube of the present invention has excellent color tone stability, even when a compound is prepared by a cold blend method, which tends to be inherently unstable in color tone, the color tone is effectively stabilized. The effect can be demonstrated.
- a polyvinyl chloride resin compound preferably a cold blend compound of polyvinyl chloride resin
- a conventionally known method is used as the molding method, and for example, an extrusion molding method is preferably used.
- polyvinyl chloride resin compound The resin, pigment, and additive shown in Table 1 are stirred and mixed by a cold blending method using a super mixer (100 L, manufactured by Kawata) to obtain a polyvinyl chloride resin compound (a cold blend compound of a polyvinyl chloride resin). It was. Details of each component are as follows.
- Polyvinyl chloride resin Polyvinyl chloride homopolymer (trade name “TS-1000R”, manufactured by Tokuyama Sekisui Industry Co., Ltd.)
- Lead stearate trade name “SAK-NSBN”, manufactured by San Ace
- -Calcium carbonate trade name "Whiteon 305S”, manufactured by Shiraishi Calcium Co., Ltd.
- -Pigment composition A Inorganic pigment composition (including titanium oxide, chromium compound, copper phthalocyanine, dispersant.
- Pigment composition B Carbon pigment composition (including titanium oxide, carbon black, copper phthalocyanine, and dispersant)
- Pigment composition C Organic pigment three-color composition (including titanium oxide, diketopyrrolopyrrole, monoazo yellow, copper phthalocyanine, and dispersant)
- Pigment composition D Organic pigment two-color composition (including titanium oxide, copper phthalocyanine, benzimidazoline, and dispersant)
- the polyvinyl chloride resin composition obtained above was supplied to a biaxial counter-rotating extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm, and an outer diameter of 60 mm and a wall thickness of 4.
- a vinyl chloride resin tube having a length of 5 mm and a length of 1 m was obtained.
- the obtained hard polyvinyl chloride resin composition was molded by a hot press with two heated rolls to obtain a plate-shaped molded body having a thickness of 1.5 mm. The following measurements and evaluations were performed on the obtained tube or plate-shaped molded body.
- the solar reflectance was measured in accordance with JIS R3106-1998. Specifically, the reflectance of the near-infrared wavelength region (300 to 2100 nm) of the plate-like molded body was measured, and the solar reflectance (%) was obtained based on the formula defined in JIS R3106-1998. The obtained solar reflectance was classified based on the following criteria. -: 28.5% or less +: 28.5% or more 29.5% or less ++: 29.5% or more 30.5% or less ++++: 30.5% or more 31.5% or less ++++: 31.5% or less 32.5% or less +++++: More than 32.5%
- Mixing condition (1) The mixture was put into a 200 mL capacity cup and manually mixed at a speed of about 20 rotations per minute using a spatula.
- Mixing condition (2) It put into the 200 mL capacity
- Example 5 The heat shielding property was impaired (Comparative Example 5).
- the color pigments (Examples 1 to 5)
- high solar reflectance is achieved when the color is adjusted so that the whiteness is 50 or more.
- the color stability was excellent.
- the vinyl chloride resin tube of Example 1 was irradiated with infrared rays (780 to 3000 nm) for 30 minutes with an infrared lamp (IR100 / 110V / 250WRH manufactured by Iwasaki Electric Co., Ltd.) in a 23 ° C. environment.
- Example 1 when the content of stearate per 1 part by weight of a colored metallic inorganic pigment (that is, chromium compound) is 10 to 54 parts by weight (Examples 2 to 5), the color tone It was observed that the stability was further significantly improved. Further, in Examples 2 to 5, when the content of calcium carbonate per 100 parts by weight of the polyvinyl chloride resin is 5 parts by weight or more (Examples 3 to 5), the solar reflectance is further remarkably improved. It was recognized that
- Examples 2 to 5 all have excellent color stability as shown in Table 1.
- specific values of ⁇ E (amount to be used as an evaluation criterion for color tone stability) in Examples 2, 3, 4, and 5 are 0.43, 0.35, 0.54, and 0.64, respectively. there were. That is, when compared in Examples 2 to 5, it was confirmed that the color tone stability tends to decrease as the amount of the pigment composition A increases with the peak at Example 3. And in order to obtain color tone stability at the most preferable level (that is, “ ⁇ ” evaluation), it was confirmed that the amount used in Example 5 should be the upper limit as the addition amount of the pigment composition A. .
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Abstract
The objective of the present invention is to provide a rigid vinyl chloride-based resin tube having excellent heat-shielding properties and color tone stability. This rigid polyvinyl chloride-based resin tube contains a polyvinyl chloride-based resin, and two or more kinds of metallic inorganic pigments, has a whiteness of 50 or more and a solar reflectance of 20% or more, and has excellent heat-shielding properties and color tone stability. Preferably, the rigid polyvinyl chloride-based resin tube further includes a stearic acid salt, wherein the content of the stearic acid salt is 10-54 parts by weight per 1 part by weight of the metallic inorganic pigments exhibiting the color. More preferably, the rigid polyvinyl chloride-based resin tube further includes a calcium carbonate, wherein the content of the calcium carbonate is 5 parts by weight or more per 100 parts by weight of the polyvinyl chloride-based resin.
Description
本発明は、優れた遮熱性と色調安定性とを有する硬質塩化ビニル系樹脂管に関する。
The present invention relates to a hard vinyl chloride resin pipe having excellent heat shielding properties and color tone stability.
硬質塩化ビニル系樹脂管は、水道管や排水管といった一般流体輸送用に広く使用され、ＪＩＳ規格において灰色に着色が施されている。硬質塩化ビニル系樹脂管を灰色に着色する手段として、従来より、カーボンブラックを着色顔料に用いることが多い。
Hard vinyl chloride resin pipes are widely used for transporting general fluids such as water pipes and drain pipes, and are colored gray in JIS standards. Conventionally, carbon black is often used as a coloring pigment as a means for coloring a hard vinyl chloride resin tube gray.
しかしながら、着色顔料として、カーボンブラックを使用した場合、カーボンブラックが有する高い吸熱特性のため、硬質塩化ビニル系樹脂管の日射反射率が低く、硬質塩化ビニル系樹脂管を屋外の太陽光が照射される状況下で保管した場合、特に太陽光に暴露されている面で著しい温度上昇が生じる。このような温度上昇が起こると、硬質塩化ビニル系樹脂管の太陽光が暴露された面とそうでない面とにおいて表面温度に大きな差が生じ、熱変形により管自体に湾曲や反りが生じる問題を招来する。
However, when carbon black is used as the color pigment, the solar panel has a low solar reflectance due to the high endothermic properties of carbon black, and outdoor sunlight is irradiated onto the hard vinyl chloride resin tube. When stored under certain conditions, the temperature rises particularly when exposed to sunlight. When such a temperature rise occurs, there is a large difference in the surface temperature between the surface exposed to sunlight and the surface not exposed to the surface of the hard vinyl chloride resin tube, and the tube itself is bent or warped due to thermal deformation. Invite you.
このような熱変形の問題を解消する技術として、特許文献１に、着色顔料としてカーボンブラックを使用せず、優れた赤外線透過率を有する有機系顔料を使用することが記載されている。
As a technique for solving such a problem of thermal deformation, Patent Document 1 describes that an organic pigment having excellent infrared transmittance is used as a coloring pigment without using carbon black.
硬質塩化ビニル系樹脂管の成形加工は、材料を押出機中で加熱溶融して流動状態にして混錬し、ダイから連続的に押し出すことによって行う。混錬材料は粘度が高く、且つ、混錬原料が通過する装置の温度設定、形状の違い等によって発生する温度差を受けるため、不可避的に熱履歴が不均一となる課題を有する。本発明者は、着色顔料を用いた硬質塩化ビニル樹脂管を種々検討したところ、特許文献１のように着色顔料として有機系顔料を使用した場合において、有機系顔料が熱の影響を受けて変質しやすい特性と、上述のような熱履歴の不均一性とが相まって、成形物である硬質塩化ビニル系樹脂管の色調のばらつきを招来すること、及び、その色調のばらつきが、硬質塩化ビニル系樹脂管の遮熱性を向上させようとして白色度が５０以上となる明るい色調に着色した場合において特に顕著となる課題に直面した。
The molding process of the hard vinyl chloride resin tube is performed by heating and melting the material in an extruder to knead it into a fluidized state and continuously extrude it from a die. Since the kneaded material has a high viscosity and receives a temperature difference generated due to a temperature setting of the apparatus through which the kneaded raw material passes, a difference in shape, and the like, there is a problem that the heat history is inevitably non-uniform. The present inventor has studied various types of hard vinyl chloride resin tubes using colored pigments. When an organic pigment is used as a colored pigment as in Patent Document 1, the organic pigment is affected by heat and deteriorated. The characteristic that is easy to perform and the non-uniformity of the thermal history as described above cause a variation in the color tone of the hard vinyl chloride resin tube that is a molded product, and the variation in the color tone is a hard vinyl chloride type In order to improve the heat shielding property of the resin tube, the present invention faced a particularly significant problem when it was colored in a bright color tone with a whiteness of 50 or more.
そこで本発明の目的は、優れた遮熱性（高い日射反射率）と色調安定性とを有する硬質塩化ビニル系樹脂管を提供することにある。
Therefore, an object of the present invention is to provide a hard vinyl chloride resin tube having excellent heat shielding properties (high solar reflectance) and color tone stability.
本発明者は鋭意検討の結果、２種以上の金属系無機顔料を着色顔料として用いることによって、硬質塩化ビニル系樹脂管の優れた遮熱性（高い日射反射率）と色調安定性とが両立し得ることを見出した。本発明は、この知見に基づいてさらに検討を重ねることにより完成したものである。
As a result of intensive studies, the present inventor has achieved excellent thermal insulation (high solar reflectance) and color tone stability of the hard vinyl chloride resin tube by using two or more kinds of metal-based inorganic pigments as color pigments. Found to get. The present invention has been completed by further studies based on this finding.
即ち、本発明は、下記に掲げる態様の発明を提供する。
項１． ポリ塩化ビニル系樹脂と、２種以上の金属系無機顔料とを含み、白色度が５０以上である、硬質ポリ塩化ビニル系樹脂管。
項２． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０重量部以上である、項１に記載の硬質ポリ塩化ビニル系樹脂管。
項３． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０～０．５００重量部である、項１又は２に記載の硬質ポリ塩化ビニル系樹脂管。
項４． 前記２種以上の金属系無機顔料が、有色を呈する金属系無機顔料と白色を呈する金属系無機顔料との混合物である、項１～３のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項５． ステアリン酸塩を更に含み、前記有色を呈する金属系無機顔料１重量部当たり、前記ステアリン酸塩の含有量が１０～５４重量部である、項１～４のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項６． 炭酸カルシウムを更に含み、前記ポリ塩化ビニル系樹脂１００重量部当たり、前記炭酸カルシウムの含有量が５重量部以上である、項１～５のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項７． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有色を呈する金属系無機顔料の含有量が、０．０２５～０．０６重量部である、項１～６のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項８． 前記有色を呈する金属系無機顔料がクロム含有化合物を含む、項１～７のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項９． 前記白色を呈する金属系無機顔料が酸化チタンである、項１～８のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項１０． 有機顔料を更に含む、項１～９のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項１１． 前記有機顔料がフタロシアニン系顔料である、項１０に記載の硬質ポリ塩化ビニル系樹脂管。
項１２． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有機顔料の含有量が、０．０００１～０．００４重量％重量部である、項１０又は１１に記載の硬質ポリ塩化ビニル系樹脂管。 That is, this invention provides the invention of the aspect hung up below.
Item 1. A rigid polyvinyl chloride resin tube comprising a polyvinyl chloride resin and two or more metal inorganic pigments and having a whiteness of 50 or more.
Item 2. Item 2. The rigid polyvinyl chloride resin tube according to Item 1, wherein the total content of the two or more metal inorganic pigments is 0.050 part by weight or more per 100 parts by weight of the polyvinyl chloride resin.
Item 3. Item 3. The hard polyvinyl chloride system according to Item 1 or 2, wherein the total content of the two or more metal inorganic pigments is 0.050 to 0.500 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
Item 4. Item 4. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 3, wherein the two or more metal inorganic pigments are a mixture of a metal inorganic pigment exhibiting a color and a metal inorganic pigment exhibiting a white color.
Item 5. Item 5. The rigid polyvinyl chloride according to any one of Items 1 to 4, further comprising a stearate, wherein the content of the stearate is 10 to 54 parts by weight per part by weight of the metallic inorganic pigment exhibiting a color. Resin tube.
Item 6. Item 6. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 5, further comprising calcium carbonate, wherein the content of the calcium carbonate is 5 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
Item 7. Item 7. The rigid polyvinyl chloride according to any one of Items 1 to 6, wherein the content of the metallic inorganic pigment exhibiting a color is 0.025 to 0.06 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
Item 8. Item 8. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 7, wherein the colored metal-based inorganic pigment contains a chromium-containing compound.
Item 9. Item 9. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 8, wherein the white metallic inorganic pigment is titanium oxide.
Item 10. Item 10. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 9, further comprising an organic pigment.
Item 11. Item 11. The rigid polyvinyl chloride resin tube according to Item 10, wherein the organic pigment is a phthalocyanine pigment.
Item 12. Item 12. The rigid polyvinyl chloride resin tube according to Item 10 or 11, wherein the content of the organic pigment is 0.0001 to 0.004% by weight per 100 parts by weight of the polyvinyl chloride resin.
項１． ポリ塩化ビニル系樹脂と、２種以上の金属系無機顔料とを含み、白色度が５０以上である、硬質ポリ塩化ビニル系樹脂管。
項２． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０重量部以上である、項１に記載の硬質ポリ塩化ビニル系樹脂管。
項３． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０～０．５００重量部である、項１又は２に記載の硬質ポリ塩化ビニル系樹脂管。
項４． 前記２種以上の金属系無機顔料が、有色を呈する金属系無機顔料と白色を呈する金属系無機顔料との混合物である、項１～３のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項５． ステアリン酸塩を更に含み、前記有色を呈する金属系無機顔料１重量部当たり、前記ステアリン酸塩の含有量が１０～５４重量部である、項１～４のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項６． 炭酸カルシウムを更に含み、前記ポリ塩化ビニル系樹脂１００重量部当たり、前記炭酸カルシウムの含有量が５重量部以上である、項１～５のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項７． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有色を呈する金属系無機顔料の含有量が、０．０２５～０．０６重量部である、項１～６のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項８． 前記有色を呈する金属系無機顔料がクロム含有化合物を含む、項１～７のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項９． 前記白色を呈する金属系無機顔料が酸化チタンである、項１～８のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項１０． 有機顔料を更に含む、項１～９のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。
項１１． 前記有機顔料がフタロシアニン系顔料である、項１０に記載の硬質ポリ塩化ビニル系樹脂管。
項１２． 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有機顔料の含有量が、０．０００１～０．００４重量％重量部である、項１０又は１１に記載の硬質ポリ塩化ビニル系樹脂管。 That is, this invention provides the invention of the aspect hung up below.
Item 1. A rigid polyvinyl chloride resin tube comprising a polyvinyl chloride resin and two or more metal inorganic pigments and having a whiteness of 50 or more.
Item 2. Item 2. The rigid polyvinyl chloride resin tube according to Item 1, wherein the total content of the two or more metal inorganic pigments is 0.050 part by weight or more per 100 parts by weight of the polyvinyl chloride resin.
Item 3. Item 3. The hard polyvinyl chloride system according to Item 1 or 2, wherein the total content of the two or more metal inorganic pigments is 0.050 to 0.500 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
Item 4. Item 4. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 3, wherein the two or more metal inorganic pigments are a mixture of a metal inorganic pigment exhibiting a color and a metal inorganic pigment exhibiting a white color.
Item 5. Item 5. The rigid polyvinyl chloride according to any one of Items 1 to 4, further comprising a stearate, wherein the content of the stearate is 10 to 54 parts by weight per part by weight of the metallic inorganic pigment exhibiting a color. Resin tube.
Item 6. Item 6. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 5, further comprising calcium carbonate, wherein the content of the calcium carbonate is 5 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
Item 7. Item 7. The rigid polyvinyl chloride according to any one of Items 1 to 6, wherein the content of the metallic inorganic pigment exhibiting a color is 0.025 to 0.06 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
Item 8. Item 8. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 7, wherein the colored metal-based inorganic pigment contains a chromium-containing compound.
Item 9. Item 9. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 8, wherein the white metallic inorganic pigment is titanium oxide.
Item 10. Item 10. The rigid polyvinyl chloride resin tube according to any one of Items 1 to 9, further comprising an organic pigment.
Item 11. Item 11. The rigid polyvinyl chloride resin tube according to Item 10, wherein the organic pigment is a phthalocyanine pigment.
Item 12. Item 12. The rigid polyvinyl chloride resin tube according to Item 10 or 11, wherein the content of the organic pigment is 0.0001 to 0.004% by weight per 100 parts by weight of the polyvinyl chloride resin.
本発明によれば、優れた遮熱性（高い日射反射率）と色調安定性とを有する硬質塩化ビニル系樹脂管が提供される。
According to the present invention, a hard vinyl chloride resin tube having excellent heat shielding properties (high solar reflectance) and color tone stability is provided.
本発明の硬質ポリ塩化ビニル系樹脂管は、ポリ塩化ビニル系樹脂と、２種以上の金属系無機顔料とを含み、白色度が５０以上であることを特徴とする。以下、本発明の硬質ポリ塩化ビニル系樹脂管について詳述する。
The rigid polyvinyl chloride resin tube of the present invention includes a polyvinyl chloride resin and two or more kinds of metal inorganic pigments, and has a whiteness of 50 or more. Hereinafter, the rigid polyvinyl chloride resin pipe of the present invention will be described in detail.
［ポリ塩化ビニル系樹脂］
ポリ塩化ビニル系樹脂としては、ポリ塩化ビニル単独重合体及び塩化ビニルを主成分とする複合ポリ塩化ビニル系樹脂が挙げられる。これらは単独で用いられてもよいし、２種類以上が併用されてもよい。 [Polyvinyl chloride resin]
Examples of the polyvinyl chloride resin include a polyvinyl chloride homopolymer and a composite polyvinyl chloride resin mainly composed of vinyl chloride. These may be used alone or in combination of two or more.
ポリ塩化ビニル系樹脂としては、ポリ塩化ビニル単独重合体及び塩化ビニルを主成分とする複合ポリ塩化ビニル系樹脂が挙げられる。これらは単独で用いられてもよいし、２種類以上が併用されてもよい。 [Polyvinyl chloride resin]
Examples of the polyvinyl chloride resin include a polyvinyl chloride homopolymer and a composite polyvinyl chloride resin mainly composed of vinyl chloride. These may be used alone or in combination of two or more.
ポリ塩化ビニル系樹脂の平均重合度としては６００～３０００が挙げられ、好ましくは８００～２０００が挙げられる。平均重合度が６００以上であることは機械的強度を良好に得る点で好ましく、平均重合度が３０００以下であることは成形容易性の点で好ましい。なお、上記の平均重合度とは、塩化ビニル単独重合体や複合塩化ビニル系樹脂をテトラヒドロフラン（ＴＨＦ）に溶解させ、ろ過により不溶成分を除去した後、濾液中のＴＨＦを乾燥除去して得た樹脂を試料とし、日本工業規格ＪＩＳ Ｋ－６７２１の「塩化ビニル樹脂試験法」に準拠して測定される平均重合度を意味する。
The average degree of polymerization of the polyvinyl chloride resin is 600 to 3000, and preferably 800 to 2000. An average polymerization degree of 600 or more is preferable from the viewpoint of obtaining good mechanical strength, and an average polymerization degree of 3000 or less is preferable from the viewpoint of ease of molding. The average degree of polymerization is obtained by dissolving a vinyl chloride homopolymer or a composite vinyl chloride resin in tetrahydrofuran (THF), removing insoluble components by filtration, and drying and removing THF in the filtrate. This means the average degree of polymerization measured using a resin as a sample in accordance with the “vinyl chloride resin test method” of Japanese Industrial Standard JIS K-6721.
塩化ビニルを主成分とする複合ポリ塩化ビニル系樹脂としては、塩化ビニルモノマーと、塩化ビニルモノマーと共重合可能なモノマーや重合体との共重合体等が挙げられる。
Examples of the composite polyvinyl chloride resin mainly composed of vinyl chloride include a vinyl chloride monomer and a copolymer of a monomer or a polymer copolymerizable with the vinyl chloride monomer.
塩化ビニルモノマーと共重合可能なモノマーとしては、例えば、エチレン、プロピレン、ブチレン等のα―オレフィン類；プロピオン酸ビニル等のビニルエステル類；エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類；メチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート等の（メタ）アクリレート類；スチレン、α－メチルスチレン等の芳香族ビニル類；Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－置換マレイミド類等が挙げられる。これらの共重合性モノマーは、単独で用いられてもよいし、２種類以上が併用されてもよい。
Examples of monomers copolymerizable with vinyl chloride monomer include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl propionate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; methyl (meth) acrylate. , (Meth) acrylates such as butyl (meth) acrylate and hydroxyethyl (meth) acrylate; aromatic vinyls such as styrene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide Etc. These copolymerizable monomers may be used alone or in combination of two or more.
塩化ビニルモノマーと共重合可能な重合体としては、例えば、アルキル（メタ）アクリレートモノマーなどからなるアクリル系共重合体等が挙げられる。これらの共重合性重合体は、単独で用いられてもよいし、２種類以上が併用されてもよい。なお、ここでいう（メタ）アクリレートとはアクリレートまたはメタクリレートを意味する。
Examples of the polymer copolymerizable with the vinyl chloride monomer include acrylic copolymers composed of alkyl (meth) acrylate monomers and the like. These copolymerizable polymers may be used alone or in combination of two or more. Here, (meth) acrylate means acrylate or methacrylate.
塩化ビニルモノマーと、上記の共重合性モノマーや重合体とを併用する場合、共重合性モノマーや重合体の使用量は、得られる硬質塩化ビニル管の性能や目的に応じて適宜されればよく、特に限定されるものではない。
When the vinyl chloride monomer is used in combination with the above copolymerizable monomer or polymer, the amount of the copolymerizable monomer or polymer used may be appropriately determined according to the performance and purpose of the obtained rigid vinyl chloride tube. There is no particular limitation.
ポリ塩化ビニル単独重合体や塩化ビニルを主成分とする複合ポリ塩化ビニル系樹脂の重合方法としては従来公知の方法でよく、例えば、懸濁重合法等が挙げられる。
As a polymerization method of a polyvinyl chloride homopolymer or a composite polyvinyl chloride resin mainly composed of vinyl chloride, a conventionally known method may be used, and examples thereof include a suspension polymerization method.
［顔料］
本発明の硬質ポリ塩化ビニル系樹脂管は、顔料として２種以上の金属系無機顔料を含む。２種以上の金属系無機顔料を含むことにより、優れた遮熱性（高い日射反射率）と、色調安定性とを両立することができる。 [Pigment]
The rigid polyvinyl chloride resin tube of the present invention contains two or more metal inorganic pigments as pigments. By including two or more kinds of metal-based inorganic pigments, it is possible to achieve both excellent heat shielding properties (high solar reflectance) and color tone stability.
本発明の硬質ポリ塩化ビニル系樹脂管は、顔料として２種以上の金属系無機顔料を含む。２種以上の金属系無機顔料を含むことにより、優れた遮熱性（高い日射反射率）と、色調安定性とを両立することができる。 [Pigment]
The rigid polyvinyl chloride resin tube of the present invention contains two or more metal inorganic pigments as pigments. By including two or more kinds of metal-based inorganic pigments, it is possible to achieve both excellent heat shielding properties (high solar reflectance) and color tone stability.
２種以上の金属系無機顔料としては、白色度５０以上の色調に調色可能な限度において、任意の金属系無機顔料を用いることができる。好ましくは、有色（非白色）を呈する金属系無機顔料と白色を呈する金属系無機顔料との混合顔料が挙げられる。より好ましくは、ＪＩＳ Ｋ６７４１に規定される「硬質ポリ塩化ビニル管」に規定する灰色の色調に調色されるように混合された混合顔料が挙げられる。
As the two or more kinds of metal-based inorganic pigments, any metal-based inorganic pigment can be used as long as it can be adjusted to a color tone having a whiteness of 50 or more. Preferably, a mixed pigment of a metallic inorganic pigment exhibiting color (non-white) and a metallic inorganic pigment exhibiting white is used. More preferably, a mixed pigment mixed so as to be adjusted to a gray color tone defined in “Hard Polyvinyl Chloride Tube” defined in JIS K6741.
有色（非白色）を呈する金属系無機顔料としては、クロム、鉄、コバルト、銅、マンガン、マグネシウム、ビスマス、イットリウム、アルミニウム、バナジウムからなる群より選択される金属を１種（単塩）又は複数種（複塩）含有する化合物が挙げられる。これらの金属を含有する化合物は、単独で用いられてもよいし、２種類以上が併用されてもよい。複塩の具体例としては、Ｆｅ－Ｃｏ－Ｃｒ系、Ｃｕ－Ｃｒ系、Ｆｅ－Ｃｒ系、Ｆｅ－Ｍｎ系、Ｃｕ－Ｍｎ系、Ｃｕ－Ｍｇ系、Ｃｕ－Ｂｉ系、Ｍｎ－Ｂｉ系、Ｙ－Ｍｎ系、Ｃｏ－Ａｌ系、Ｆｅ－Ｃｏ－Ａｌ－Ｍｇ系等の塩が挙げられる。これらの中でも、赤外線の吸収抑制性が高く遮熱性に優れる点で、好ましくはクロム含有化合物、好ましくはＦｅ－Ｃｒ系が挙げられる。
As a metallic inorganic pigment exhibiting a color (non-white), one (single salt) or a plurality of metals selected from the group consisting of chromium, iron, cobalt, copper, manganese, magnesium, bismuth, yttrium, aluminum, and vanadium are used. Examples include compounds containing seeds (double salts). The compounds containing these metals may be used alone or in combination of two or more. Specific examples of the double salt include Fe—Co—Cr, Cu—Cr, Fe—Cr, Fe—Mn, Cu—Mn, Cu—Mg, Cu—Bi, Mn—Bi, Examples of the salt include Y—Mn, Co—Al, and Fe—Co—Al—Mg. Among these, a chromium-containing compound, preferably a Fe—Cr system, is preferable because it has high infrared absorption suppression and excellent heat shielding properties.
また、上述の金属系無機顔料としては、上述の金属の、酸化物、水酸化物、硫化物、ケイ酸塩、フェロシアン化塩等が挙げられる。これらの化合物は、単独で用いられてもよいし、２種類以上が併用されてもよい。これらの中でも、色調安定性に優れる点で、好ましくは酸化物が挙げられる。
Also, examples of the metal-based inorganic pigment include oxides, hydroxides, sulfides, silicates, and ferrocyanide salts of the above-described metals. These compounds may be used alone or in combination of two or more. Among these, an oxide is preferable in terms of excellent color tone stability.
より具体的には、有色を呈する金属系無機顔料としては、上述の有色を呈する金属系無機顔料から１種又は複数種の顔料の組み合わせによって、黒色を呈する顔料であることが好ましい。黒色を呈する顔料としては、互いに補色の関係又は補色の関係に近い色を呈する２種以上の顔料の混合顔料；互いに補色又は補色の関係に近い色を呈する２種以上の顔料それぞれを構成する金属イオンを複数含む複塩顔料；及びそれらの混合物が挙げられる。高い日射反射率と色調安定性とをより良好に得る観点から、有色を呈する金属系無機顔料として、好ましくは、緑色の酸化クロム（Ｃｒ2Ｏ3）と、その補色となる赤色の顔料（例えば酸化鉄）とを、混合顔料として組み合わせて黒色に調色された顔料；酸化クロムと酸化鉄とを含む複合酸化物；及びそれらの混合物が挙げられ、より好ましくは、酸化クロムと酸化鉄とを含む複合酸化物が挙げられる。
More specifically, the metallic inorganic pigment exhibiting a color is preferably a pigment exhibiting a black color by combining one or a plurality of pigments from the above-described metallic inorganic pigment exhibiting a color. As pigments exhibiting black, mixed pigments of two or more pigments exhibiting complementary colors or colors close to complementary colors; metals constituting each of two or more pigments exhibiting colors complementary or complementary to each other And double salt pigments containing a plurality of ions; and mixtures thereof. From the viewpoint of better obtaining high solar reflectance and color tone stability, as a metallic inorganic pigment exhibiting a color, preferably, green chromium oxide (Cr 2 O 3 ) and a red pigment (for example, a complementary color thereof) Iron oxide) in combination as a mixed pigment, and a black-toned pigment; a composite oxide containing chromium oxide and iron oxide; and a mixture thereof, more preferably, chromium oxide and iron oxide. The composite oxide containing is mentioned.
本発明の硬質ポリ塩化ビニル系樹脂管における有色を呈する金属系無機顔料の含有量としては、顔料の分散不均一性による色調の不均一性を好ましく抑制する観点から、ポリ塩化ビニル系樹脂１００重量部当たり、例えば０．０１３重量部以上、好ましくは０．０２５重量部以上が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管が有機顔料を含む場合は、有機顔料による色調不安定性を隠蔽して色調安定性を向上させる観点から、ポリ塩化ビニル系樹脂１００重量部当たり、０．０２５重量部以上であることが好ましい。また、有色を呈する金属系無機顔料の含有量としては、さらに押出成形における機器への汚染抑制を考慮すると、ポリ塩化ビニル系樹脂１００重量部当たり、例えば０．０９重量部以下、好ましくは０．０８重量部以下、より好ましくは０．０７重量部以下、さらに好ましくは０．０６重量部以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管における有色を呈する金属系無機顔料の含有量の具体的な範囲としては、ポリ塩化ビニル系樹脂１００重量部当たり、０．０１３～０．０９重量部、０．０１３～０．０８重量部、０．０１３～０．０７重量部、０．０１３～０．０６重量部、０．２５～０．０９重量部、０．２５～０．０８重量部、０．２５～０．０７重量部、０．２５～０．０６重量部が挙げられる。
The content of the metallic inorganic pigment exhibiting color in the rigid polyvinyl chloride resin tube of the present invention is 100 wt% of polyvinyl chloride resin from the viewpoint of preferably suppressing non-uniformity in color tone due to non-uniform dispersion of the pigment. For example, 0.013 parts by weight or more, and preferably 0.025 parts by weight or more per part. When the rigid polyvinyl chloride resin tube of the present invention contains an organic pigment, 0.025 per 100 parts by weight of the polyvinyl chloride resin from the viewpoint of improving the color tone stability by concealing the color tone instability due to the organic pigment. It is preferable that it is at least parts by weight. The content of the metallic inorganic pigment exhibiting a color is, for example, 0.09 parts by weight or less, preferably 0. 0 parts by weight per 100 parts by weight of the polyvinyl chloride resin, in consideration of suppression of contamination of equipment in extrusion molding. 08 parts by weight or less, more preferably 0.07 parts by weight or less, and still more preferably 0.06 parts by weight or less. The specific range of the content of the colored metallic inorganic pigment in the rigid polyvinyl chloride resin tube of the present invention is 0.013 to 0.09 parts by weight per 100 parts by weight of the polyvinyl chloride resin, 0 .013 to 0.08 parts by weight, 0.013 to 0.07 parts by weight, 0.013 to 0.06 parts by weight, 0.25 to 0.09 parts by weight, 0.25 to 0.08 parts by weight, 0 .25 to 0.07 parts by weight, 0.25 to 0.06 parts by weight.
白色を呈する金属系無機顔料としては、二酸化チタン、酸化アルミニウム、酸化亜鉛などの金属酸化物が挙げられる。これらの中でも、高屈折率且つ高白色度である点で、好ましくは二酸化チタンが挙げられる。
Examples of white metallic inorganic pigments include metal oxides such as titanium dioxide, aluminum oxide, and zinc oxide. Among these, titanium dioxide is preferable because it has a high refractive index and high whiteness.
本発明の硬質ポリ塩化ビニル系樹脂管における白色を呈する金属系無機顔料の含有量としては、遮熱性を良好に得る観点から、ポリ塩化ビニル系樹脂１００重量部当たり、例えば０．０３重量部以上、好ましくは０．０６重量部以上、より好ましくは０．０７重量部以上が挙げられ、好ましい灰色に着色する観点から、例えば０．２重量部以下、好ましくは０．１５重量部以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管における白色を呈する金属系無機顔料の含有量の具体的な範囲としてはポリ塩化ビニル系樹脂１００重量部当たり、０．０３～０．２重量部、０．０３～０．１５重量部、０．０６～０．２重量部、０．０６～０．１５重量部、０．０７～０．２重量部、０．０７～０．１５重量部が挙げられる。
The content of the metallic inorganic pigment exhibiting white color in the rigid polyvinyl chloride resin tube of the present invention is, for example, 0.03 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin from the viewpoint of obtaining good heat shielding properties. , Preferably 0.06 parts by weight or more, more preferably 0.07 parts by weight or more, and from the viewpoint of preferable gray coloring, for example, 0.2 parts by weight or less, preferably 0.15 parts by weight or less. . The specific range of the content of the white metallic inorganic pigment in the rigid polyvinyl chloride resin tube of the present invention is 0.03 to 0.2 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Examples include 03 to 0.15 parts by weight, 0.06 to 0.2 parts by weight, 0.06 to 0.15 parts by weight, 0.07 to 0.2 parts by weight, and 0.07 to 0.15 parts by weight. .
有色を呈する金属系無機顔料と、白色を呈する金属系無機顔料との比率としては、白色度５０以上となることを限度として特に限定されないが、例えば、２種以上の金属系無機顔料全体を１００重量％とした場合、有色を呈する金属系無機顔料の含有比率として、１８～５８重量％、好ましくは１８～４５重量％が挙げられる。
The ratio of the metallic inorganic pigment exhibiting color to the metallic inorganic pigment exhibiting white is not particularly limited as long as the whiteness is 50 or more. For example, the total of two or more metallic inorganic pigments is 100. In the case of weight%, the content ratio of the metallic inorganic pigment exhibiting color is 18 to 58% by weight, preferably 18 to 45% by weight.
本発明の硬質ポリ塩化ビニル系樹脂管における２種以上の金属系無機顔料の総含有量としては、顔料の分散不均一性による色調の不均一性を好ましく抑制する、及び／又は、色調安定性と遮光性を良好に得る等観点から、ポリ塩化ビニル系樹脂１００重量部当たり、例えば０．０５０重量部以上、好ましくは０．０８５重量部以上、より好ましくは０．０８７重量部以上が挙げられる。また、２種以上の金属系無機顔料の総含有量としては、さらに押出成形における機器への汚染抑制を考慮すると、例えば０．５００重量部以下、好ましくは０．２８０重量部以下、より好ましくは０．２３０重量部以下、更に好ましくは０．２１０重量部以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管における２種以上の金属系無機顔料の総含有量の具体的な範囲としては、０．０５０～０．５００重量部、０．０５０～０．２８０重量部、０．０５０～０．２３０重量部、０．０５０～０．２１０重量部、０．０８５～０．５００重量部、０．０８５～０．２８０重量部、０．０８５～０．２３０重量部、０．０８５～０．２１０重量部、０．０８７～０．５００重量部、０．０８７～０．２８０重量部、０．０８７～０．２３０重量部、０．０８７～０．２１０重量部が挙げられる。
The total content of the two or more types of metal-based inorganic pigments in the rigid polyvinyl chloride resin tube of the present invention preferably suppresses color tone non-uniformity due to pigment dispersion non-uniformity and / or color tone stability. From the viewpoint of obtaining good light shielding properties, for example, 0.050 parts by weight or more, preferably 0.085 parts by weight or more, more preferably 0.087 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin. . In addition, the total content of the two or more kinds of metal-based inorganic pigments is, for example, 0.500 parts by weight or less, preferably 0.280 parts by weight or less, more preferably, considering the suppression of contamination to equipment in extrusion molding. 0.230 weight part or less, More preferably, 0.210 weight part or less is mentioned. Specific ranges of the total content of two or more kinds of metal inorganic pigments in the rigid polyvinyl chloride resin tube of the present invention are 0.050 to 0.500 parts by weight, 0.050 to 0.280 parts by weight. , 0.050 to 0.230 parts by weight, 0.050 to 0.210 parts by weight, 0.085 to 0.500 parts by weight, 0.085 to 0.280 parts by weight, 0.085 to 0.230 parts by weight 0.085 to 0.210 parts by weight, 0.087 to 0.500 parts by weight, 0.087 to 0.280 parts by weight, 0.087 to 0.230 parts by weight, 0.087 to 0.210 parts by weight Is mentioned.
［添加剤］
本発明の硬質ポリ塩化ビニル系樹脂管は、本発明の効果を損なわない限り、必要に応じて、有機顔料、安定化剤、安定化助剤、滑剤、加工助剤、酸化防止剤、充填剤等の添加剤を含んでもよい。これらの添加物の中でも、好ましくは、安定化剤及び充填剤が挙げられる。 [Additive]
As long as the effects of the present invention are not impaired, the rigid polyvinyl chloride resin tube of the present invention is provided with an organic pigment, a stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, and a filler as necessary. Etc. may also be included. Among these additives, a stabilizer and a filler are preferable.
本発明の硬質ポリ塩化ビニル系樹脂管は、本発明の効果を損なわない限り、必要に応じて、有機顔料、安定化剤、安定化助剤、滑剤、加工助剤、酸化防止剤、充填剤等の添加剤を含んでもよい。これらの添加物の中でも、好ましくは、安定化剤及び充填剤が挙げられる。 [Additive]
As long as the effects of the present invention are not impaired, the rigid polyvinyl chloride resin tube of the present invention is provided with an organic pigment, a stabilizer, a stabilizing aid, a lubricant, a processing aid, an antioxidant, and a filler as necessary. Etc. may also be included. Among these additives, a stabilizer and a filler are preferable.
有機顔料は分散特性が優れているため、無機顔料と組み合わせることで、より均一に硬質ポリ塩化ビニル系樹脂管を着色することができる。有機顔料としては特に限定されず、例えば、アゾ系顔料、フタロシアニン系顔料（フタロシアニン銅等）、スレン系顔料、染料レーキ系顔料等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの有機顔料の中でも、硬質塩化ビニル系樹脂管の優れた色調安定性を得る観点から、好ましくは、フタロシアニン系顔料が挙げられ、より好ましくはフタロシアニン銅が挙げられる。
Since organic pigments have excellent dispersion characteristics, hard polyvinyl chloride resin tubes can be colored more uniformly when combined with inorganic pigments. The organic pigment is not particularly limited, and examples thereof include azo pigments, phthalocyanine pigments (such as phthalocyanine copper), selenium pigments, and dye lake pigments. These may be used alone or in combination of two or more. Among these organic pigments, a phthalocyanine pigment is preferable, and phthalocyanine copper is more preferable, from the viewpoint of obtaining excellent color tone stability of the hard vinyl chloride resin tube.
本発明の硬質ポリ塩化ビニル系樹脂管に有機顔料を含ませる場合、有機顔料の含有量としては、色調安定性を損なわない観点から、前記２種以上の金属系無機顔料の総含有量１００重量部当たり１５重量部以下、好ましくは１０重量部以下、より好ましくは６重量部以下、より好ましくは３重量部以下が挙げられる。また、有機顔料の含有量としては、色調安定性を損なわない観点からポリ塩化ビニル系樹脂１００重量部当たり０．００４重量部以下が挙げられる。また、有機顔料の含有量としては、色調の不均一性をより一層好ましく抑制する観点からポリ塩化ビニル系樹脂１００重量部当たり０．０００１重量部以上、好ましくは０．０００１５重量部以上が挙げられる。有機顔料の含有量の具体的な範囲としては、ポリ塩化ビニル系樹脂１００重量部当たり、０．０００１～１５重量部、０．０００１～１０重量部、０．０００１～６重量部、０．０００１～３重量部、０．０００１～０．００４重量部、０．０００１５～１５重量部、０．０００１５～１０重量部、０．０００１５～６重量部、０．０００１５～３重量部、０．０００１５～０．００４重量部が挙げられる。
When the organic pigment is included in the rigid polyvinyl chloride resin tube of the present invention, the content of the organic pigment is 100% by weight of the total content of the two or more metal inorganic pigments from the viewpoint of not impairing the color stability. 15 parts by weight or less per part, preferably 10 parts by weight or less, more preferably 6 parts by weight or less, more preferably 3 parts by weight or less. Moreover, as content of an organic pigment, 0.004 weight part or less is mentioned per 100 weight part of polyvinyl chloride-type resin from a viewpoint which does not impair color tone stability. In addition, the content of the organic pigment is 0.0001 parts by weight or more, preferably 0.00015 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin, from the viewpoint of more preferably suppressing unevenness in color tone. . The specific range of the organic pigment content is 0.0001 to 15 parts by weight, 0.0001 to 10 parts by weight, 0.0001 to 6 parts by weight, 0.0001 per 100 parts by weight of the polyvinyl chloride resin. -3 parts by weight, 0.0001-0.004 parts by weight, 0.00015-15 parts by weight, 0.00015-10 parts by weight, 0.00015-6 parts by weight, 0.00015-3 parts by weight, 0.00015 Up to 0.004 parts by weight.
安定化剤としては特に限定されず、例えば、ジメチル錫メルカプト、ジブチル錫メルカプト、ジオクチル錫メルカプト、ジブチル錫マレート、ジブチル錫マレートポリマー、ジオクチル錫マレート、ジオクチル錫マレートポリマー、ジブチル錫ラウレート、ジブチル錫ラウレートポリマー等の有機錫安定剤；ステアリン酸鉛、二塩基性亜リン酸鉛、三塩基性硫酸鉛等の鉛系安定剤、カルシウム－亜鉛系安定剤、バリウム－亜鉛系安定剤、バリウム－カドミウム系安定剤；ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸バリウム、ステアリン酸鉛等のステアリン酸塩系安定剤；サリチル酸エステル系、べンゾフェノン系、べンゾトリアゾール系、シアノアクリレート系等の紫外線吸収剤；ヒンダードアミン系の光安定剤等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
The stabilizer is not particularly limited. For example, dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, dibutyltin malate polymer, dioctyltin malate, dioctyltin malate polymer, dibutyltin laurate, dibutyltin Organotin stabilizers such as laurate polymers; lead stabilizers such as lead stearate, dibasic lead phosphite, tribasic lead sulfate, calcium-zinc stabilizers, barium-zinc stabilizers, barium- Cadmium stabilizers; stearate stabilizers such as calcium stearate, zinc stearate, barium stearate and lead stearate; UV absorbers such as salicylic acid ester, benzophenone, benzotriazole and cyanoacrylate ; Hindered amine light stabilizers It is. These may be used alone or in combination of two or more.
安定化剤の配合量としては、ポリ塩化ビニル系樹脂１００重量部当たり例えば０．８～２重量部、好ましくは１～１．４重量部が挙げられる。
The blending amount of the stabilizer is, for example, 0.8 to 2 parts by weight, preferably 1 to 1.4 parts by weight per 100 parts by weight of the polyvinyl chloride resin.
これらの安定化剤の中でも、好ましくはステアリン酸塩（ステアリン酸系安定剤）が挙げられ、より好ましくはステアリン酸鉛が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管にステアリン酸塩を含ませる場合、ステアリン酸塩の含有量の上限としては、硬質塩化ビニル系樹脂管のより一層優れた色調安定性を得る観点から、有色を呈する金属系無機顔料１重量部当たり、５４重量部以下好ましくは５３重量部以下、より好ましくは５２重量部以下が挙げられ、下限としては、有色を呈する金属系無機顔料１重量部当たり、１０重量部以上、好ましくは１５重量部以上、より好ましくは２０重量部以上が挙げられる。ステアリン酸塩の含有量の具体的な範囲としては、有色を呈する金属系無機顔料１重量部当たり、１０～５４重量部、１０～５３重量部、１０～５２重量部、１５～５４重量部、１５～５３重量部、１５～５２重量部、２０～５４重量部、２０～５３重量部、２０～５２重量部が挙げられる。
Among these stabilizers, stearates (stearic acid stabilizers) are preferable, and lead stearate is more preferable. When stearate is included in the hard polyvinyl chloride resin tube of the present invention, the upper limit of the content of stearate is colored from the viewpoint of obtaining even better color tone stability of the hard vinyl chloride resin tube. Per 1 part by weight of the metal-based inorganic pigment exhibiting the following: 54 parts by weight or less, preferably 53 parts by weight or less, more preferably 52 parts by weight or less. The lower limit is 10 parts by weight per 1 part by weight of the metal-based inorganic pigment exhibiting color. Part by weight or more, preferably 15 parts by weight or more, more preferably 20 parts by weight or more. The specific range of the stearate content is 10 to 54 parts by weight, 10 to 53 parts by weight, 10 to 52 parts by weight, 15 to 54 parts by weight, based on 1 part by weight of the colored metallic inorganic pigment. Examples thereof include 15 to 53 parts by weight, 15 to 52 parts by weight, 20 to 54 parts by weight, 20 to 53 parts by weight, and 20 to 52 parts by weight.
安定化助剤としては特に限定されず、例えば、エポキシ化大豆油、エポキシ化アマニ豆油、エポキシ化テトラヒドロフタレート、エポキシ化ポリブタジエン、リン酸エステル等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
The stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester. These may be used alone or in combination of two or more.
滑剤としては、内部滑剤、外部滑剤等が挙げられる。内部滑剤は、成形加工時の溶融樹脂の流動粘度を下げ、摩擦発熱を防止する目的で使用される。上記の内部滑剤としては特に限定されず、例えば、ブチルステアレート、ラウリルアルコール、ステアリルステアレート、エポキシ化大豆油、グリセリンモノステアレート、ステアリン酸、ビスアミド等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。外部滑剤は、成形加工時の溶融樹脂と金属面との滑り効果を上げる目的で使用される。上記の外部滑剤としては特に限定されず、例えば、モンタン酸ワックス、パラフィンワックス、ポリオレフインワックス、エステルワックス等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
Examples of the lubricant include an internal lubricant and an external lubricant. The internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation. The internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl stearate, epoxidized soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more. The external lubricant is used for the purpose of increasing the sliding effect between the molten resin and the metal surface during the molding process. The external lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyolefin wax, and ester wax. These may be used alone or in combination of two or more.
加工助剤としては特に限定されず、例えば、重量平均分子１０万～２００万のアルキルアクリレート／アルキルメタクリレート共重合体であるアクリル系加工助剤が挙げられ、具体例としては、n－ブチルアクリレート／メチルメタクリレート共重合体、２－エチルヘキシルアクリレート／メチルメタクリレート／ブチルメタクリレート共重合体等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
The processing aid is not particularly limited, and examples thereof include acrylic processing aids that are alkyl acrylate / alkyl methacrylate copolymers having a weight average molecular weight of 100,000 to 2,000,000. Specific examples include n-butyl acrylate / Examples thereof include a methyl methacrylate copolymer and a 2-ethylhexyl acrylate / methyl methacrylate / butyl methacrylate copolymer. These may be used alone or in combination of two or more.
酸化防止剤としては特に限定されず、例えば、フェノール系抗酸化剤等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants. These may be used alone or in combination of two or more.
充填剤としては特に限定されず、例えば、炭酸カルシウム、タルク等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの充填剤の中でも、硬質塩化ビニル系樹脂管のより優れた色調安定性を得る観点、及び／又は、より優れた遮熱性を得る観点から、好ましくは炭酸カルシウムが挙げられる。また、本発明の硬質ポリ塩化ビニル系樹脂管に炭酸カルシウムを含ませる場合、炭酸カルシウムの含有量としては、硬質塩化ビニル系樹脂管のより一層優れた色調安定性を得る観点から、ポリ塩化ビニル系樹脂１００重量部当たり、３重量部以上が挙げられる。また、硬質塩化ビニル系樹脂のより一層優れた遮熱性を得る観点から、好ましくは５重量部以上、より好ましくは６重量部以上が挙げられ、これらの含有量は、特に、白色を呈する金属系無機顔料がポリ塩化ビニル系樹脂１００重量部当たり０．０６重量部以上である場合に好適である。炭酸カルシウムの含有量の上限としては特に限定されないが、ポリ塩化ビニル系樹脂１００重量部当たり、例えば１０重量部以下、好ましくは９重量部以下、より好ましくは８重量部以下、さらに好ましくは７重量部以下が挙げられる。炭酸カルシウムの含有量の具体的な範囲としては、ポリ塩化ビニル系樹脂１００重量部当たり、３～１０重量部、３～９重量部、３～８重量部、３～７重量部、５～１０重量部、５～９重量部、５～８重量部、５～７重量部、６～１０重量部、６～９重量部、６～８重量部、６～７重量部が挙げられる。
The filler is not particularly limited, and examples thereof include calcium carbonate and talc. These may be used alone or in combination of two or more. Among these fillers, calcium carbonate is preferably used from the viewpoint of obtaining better color tone stability of the hard vinyl chloride resin tube and / or obtaining better heat shielding properties. In addition, when calcium carbonate is included in the hard polyvinyl chloride resin tube of the present invention, the content of calcium carbonate is polyvinyl chloride from the viewpoint of obtaining even better color tone stability of the hard vinyl chloride resin tube. 3 parts by weight or more per 100 parts by weight of the resin. Further, from the viewpoint of obtaining a further excellent heat shielding property of the hard vinyl chloride resin, preferably 5 parts by weight or more, more preferably 6 parts by weight or more, and the content thereof is particularly a metal system exhibiting white. It is suitable when the inorganic pigment is 0.06 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin. The upper limit of the content of calcium carbonate is not particularly limited, but is, for example, 10 parts by weight or less, preferably 9 parts by weight or less, more preferably 8 parts by weight or less, and further preferably 7 parts by weight per 100 parts by weight of the polyvinyl chloride resin. The following are listed. The specific range of the calcium carbonate content is 3 to 10 parts by weight, 3 to 9 parts by weight, 3 to 8 parts by weight, 3 to 7 parts by weight, and 5 to 10 parts per 100 parts by weight of the polyvinyl chloride resin. 5 parts by weight, 5-9 parts by weight, 5-8 parts by weight, 5-7 parts by weight, 6-10 parts by weight, 6-9 parts by weight, 6-8 parts by weight, 6-7 parts by weight.
また、充填剤と白色を呈する金属系無機顔料との比率としては、白色を呈する金属系無機顔料１重量部に対する充填剤の量として、硬質塩化ビニル系樹脂管のより優れた色調安定性を得る観点、及び／又は、より優れた遮熱性を得る観点から、下限が、３０重量部以上が挙げられ、白色を呈する金属系無機顔料がポリ塩化ビニル系樹脂１００重量部当たり０．０６重量部以上である場合には、より一層優れた遮熱性を得る観点から、好ましくは５５重量部以上が挙げられる。また、白色を呈する金属系無機顔料１重量部に対する充填剤の量の上限としては、９３重量部以下が挙げられる。白色を呈する金属系無機顔料１重量部に対する充填剤の量の具体的な範囲としては、３０～９３重量部、５５～９３重量部が挙げられる。
In addition, as a ratio of the filler to the white metallic inorganic pigment, the amount of the filler relative to 1 part by weight of the white metallic inorganic pigment is used to obtain better color stability of the hard vinyl chloride resin tube. From the viewpoint and / or from the viewpoint of obtaining better heat-shielding properties, the lower limit is 30 parts by weight or more, and the white metallic inorganic pigment is 0.06 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin. When it is, from the viewpoint of obtaining a further excellent heat shielding property, 55 parts by weight or more is preferable. Moreover, 93 weight part or less is mentioned as an upper limit of the quantity of the filler with respect to 1 weight part of metallic inorganic pigments which exhibit white. Specific ranges of the amount of the filler relative to 1 part by weight of the metallic inorganic pigment exhibiting white include 30 to 93 parts by weight and 55 to 93 parts by weight.
［白色度］
本発明の硬質ポリ塩化ビニル系樹脂管は、白色度５０以上の色調を有する。これによって、硬質ポリ塩化ビニル系樹脂管の優れた遮熱性を得ることができる。また、白色度が５０以上となる比較的明るい色調に着色した場合、本来的に色調のばらつき（色調不安定性）が生じやすいが、本発明の硬質ポリ塩化ビニル系樹脂管では、上述の２種以上の金属系無機顔料を着色顔料として用いることにより、優れた色調安定性も兼備することができる。白色度の範囲の上限値は特に限定されるものではないが、ＪＩＳ Ｋ６７４１に規定される「硬質ポリ塩化ビニル管」に規定する灰色の色調に適合させる等の観点で、７０以下、好ましくは６０以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管は遮熱性に優れているため、白色度が６０未満の灰色であっても効果的に優れた遮熱性を得ることができる。このような観点から、本発明の硬質ポリ塩化ビニル系樹脂管の白色度の好適な例としては、５６以下、好ましくは５４以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管の白色度の具体的な範囲としては、５０～７０、５０～６０、５０～５６、５０～５４が挙げられる。白色度の調整は、上述の２種以上の金属系無機顔料において、有色を呈する金属系無機顔料の含有量及び／又は白色を呈する金属系無機顔料の含有量を調整することで行うことができる。なお、白色度は、ＣＩＥ１９７６Ｌ*ａ*ｂ*比色系に基づきＤ６５光源下で測定されるＬ*値を指す。 [Whiteness]
The rigid polyvinyl chloride resin tube of the present invention has a color tone with a whiteness of 50 or more. This makes it possible to obtain excellent heat shielding properties of the hard polyvinyl chloride resin tube. In addition, when a relatively bright color tone having a whiteness of 50 or more is colored, inherent variations in color tone (color tone instability) tend to occur. However, in the rigid polyvinyl chloride resin tube of the present invention, the above-described two types are used. By using the above metallic inorganic pigment as a color pigment, excellent color tone stability can be achieved. The upper limit of the whiteness range is not particularly limited, but is 70 or less, preferably 60 from the viewpoint of adapting to the gray color tone defined in “Hard Polyvinyl Chloride Tube” defined in JIS K6741. The following are mentioned. Since the rigid polyvinyl chloride resin pipe of the present invention is excellent in heat shielding properties, even if the whiteness is gray of less than 60, excellent heat shielding properties can be obtained. From such a viewpoint, a suitable example of whiteness of the rigid polyvinyl chloride resin tube of the present invention is 56 or less, preferably 54 or less. Specific ranges of whiteness of the rigid polyvinyl chloride resin tube of the present invention include 50 to 70, 50 to 60, 50 to 56, and 50 to 54. The whiteness can be adjusted by adjusting the content of the metallic inorganic pigment exhibiting a color and / or the content of the metallic inorganic pigment exhibiting a white color in the above-described two or more metallic inorganic pigments. . Whiteness refers to an L * value measured under a D65 light source based on the CIE 1976 L * a * b * colorimetric system.
本発明の硬質ポリ塩化ビニル系樹脂管は、白色度５０以上の色調を有する。これによって、硬質ポリ塩化ビニル系樹脂管の優れた遮熱性を得ることができる。また、白色度が５０以上となる比較的明るい色調に着色した場合、本来的に色調のばらつき（色調不安定性）が生じやすいが、本発明の硬質ポリ塩化ビニル系樹脂管では、上述の２種以上の金属系無機顔料を着色顔料として用いることにより、優れた色調安定性も兼備することができる。白色度の範囲の上限値は特に限定されるものではないが、ＪＩＳ Ｋ６７４１に規定される「硬質ポリ塩化ビニル管」に規定する灰色の色調に適合させる等の観点で、７０以下、好ましくは６０以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管は遮熱性に優れているため、白色度が６０未満の灰色であっても効果的に優れた遮熱性を得ることができる。このような観点から、本発明の硬質ポリ塩化ビニル系樹脂管の白色度の好適な例としては、５６以下、好ましくは５４以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管の白色度の具体的な範囲としては、５０～７０、５０～６０、５０～５６、５０～５４が挙げられる。白色度の調整は、上述の２種以上の金属系無機顔料において、有色を呈する金属系無機顔料の含有量及び／又は白色を呈する金属系無機顔料の含有量を調整することで行うことができる。なお、白色度は、ＣＩＥ１９７６Ｌ*ａ*ｂ*比色系に基づきＤ６５光源下で測定されるＬ*値を指す。 [Whiteness]
The rigid polyvinyl chloride resin tube of the present invention has a color tone with a whiteness of 50 or more. This makes it possible to obtain excellent heat shielding properties of the hard polyvinyl chloride resin tube. In addition, when a relatively bright color tone having a whiteness of 50 or more is colored, inherent variations in color tone (color tone instability) tend to occur. However, in the rigid polyvinyl chloride resin tube of the present invention, the above-described two types are used. By using the above metallic inorganic pigment as a color pigment, excellent color tone stability can be achieved. The upper limit of the whiteness range is not particularly limited, but is 70 or less, preferably 60 from the viewpoint of adapting to the gray color tone defined in “Hard Polyvinyl Chloride Tube” defined in JIS K6741. The following are mentioned. Since the rigid polyvinyl chloride resin pipe of the present invention is excellent in heat shielding properties, even if the whiteness is gray of less than 60, excellent heat shielding properties can be obtained. From such a viewpoint, a suitable example of whiteness of the rigid polyvinyl chloride resin tube of the present invention is 56 or less, preferably 54 or less. Specific ranges of whiteness of the rigid polyvinyl chloride resin tube of the present invention include 50 to 70, 50 to 60, 50 to 56, and 50 to 54. The whiteness can be adjusted by adjusting the content of the metallic inorganic pigment exhibiting a color and / or the content of the metallic inorganic pigment exhibiting a white color in the above-described two or more metallic inorganic pigments. . Whiteness refers to an L * value measured under a D65 light source based on the CIE 1976 L * a * b * colorimetric system.
［日射反射率］
本発明の硬質ポリ塩化ビニル系樹脂管は優れた遮熱性を有しているため、例えば２８．５％超という高い日射反射率を達成することができる。より優れた遮熱性を得る観点から、日射反射率としては好ましくは２９．５％超、より好ましくは３０．５％超、さらに好ましくは３１．５％超、特に好ましくは３２．５％超が挙げられる。日射反射率の上限値は特に限定されるものではないが、上述の白色度を考慮すると、７０％以下、好ましくは６５％以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管の日射反射率の具体的な範囲としては、２８．５～７０％、２８．５～６５％、２９．５～７０％、２９．５～６５％、３０．５～７０％、３０．５～６５％、３１．５～７０％、３１．５～６５％、３２．５～７０％、３２．５～６５％が挙げられる。日射反射率の調整は、上述の２種以上の金属系無機顔料の含有量の調整、有機顔料を配合する場合においては有機顔料の含有量の調整、及び／又は上述の白色度の調整により行うことができる。なお、日射反射率は、ＪＩＳ Ｒ３１０６－１９９８に準拠して測定される値である。 [Solar reflectance]
Since the hard polyvinyl chloride resin pipe of the present invention has excellent heat shielding properties, it is possible to achieve a high solar reflectance of, for example, more than 28.5%. From the viewpoint of obtaining better heat shielding properties, the solar reflectance is preferably more than 29.5%, more preferably more than 30.5%, still more preferably more than 31.5%, particularly preferably more than 32.5%. Can be mentioned. Although the upper limit of solar reflectance is not particularly limited, it is 70% or less, preferably 65% or less in consideration of the above-described whiteness. Specific ranges of the solar reflectance of the rigid polyvinyl chloride resin tube of the present invention include 28.5 to 70%, 28.5 to 65%, 29.5 to 70%, 29.5 to 65%, 30.5-70%, 30.5-65%, 31.5-70%, 31.5-65%, 32.5-70%, 32.5-65%. The solar reflectance is adjusted by adjusting the content of the above-described two or more kinds of metal-based inorganic pigments, adjusting the content of the organic pigment in the case of blending the organic pigment, and / or adjusting the above-described whiteness. be able to. The solar reflectance is a value measured according to JIS R3106-1998.
本発明の硬質ポリ塩化ビニル系樹脂管は優れた遮熱性を有しているため、例えば２８．５％超という高い日射反射率を達成することができる。より優れた遮熱性を得る観点から、日射反射率としては好ましくは２９．５％超、より好ましくは３０．５％超、さらに好ましくは３１．５％超、特に好ましくは３２．５％超が挙げられる。日射反射率の上限値は特に限定されるものではないが、上述の白色度を考慮すると、７０％以下、好ましくは６５％以下が挙げられる。本発明の硬質ポリ塩化ビニル系樹脂管の日射反射率の具体的な範囲としては、２８．５～７０％、２８．５～６５％、２９．５～７０％、２９．５～６５％、３０．５～７０％、３０．５～６５％、３１．５～７０％、３１．５～６５％、３２．５～７０％、３２．５～６５％が挙げられる。日射反射率の調整は、上述の２種以上の金属系無機顔料の含有量の調整、有機顔料を配合する場合においては有機顔料の含有量の調整、及び／又は上述の白色度の調整により行うことができる。なお、日射反射率は、ＪＩＳ Ｒ３１０６－１９９８に準拠して測定される値である。 [Solar reflectance]
Since the hard polyvinyl chloride resin pipe of the present invention has excellent heat shielding properties, it is possible to achieve a high solar reflectance of, for example, more than 28.5%. From the viewpoint of obtaining better heat shielding properties, the solar reflectance is preferably more than 29.5%, more preferably more than 30.5%, still more preferably more than 31.5%, particularly preferably more than 32.5%. Can be mentioned. Although the upper limit of solar reflectance is not particularly limited, it is 70% or less, preferably 65% or less in consideration of the above-described whiteness. Specific ranges of the solar reflectance of the rigid polyvinyl chloride resin tube of the present invention include 28.5 to 70%, 28.5 to 65%, 29.5 to 70%, 29.5 to 65%, 30.5-70%, 30.5-65%, 31.5-70%, 31.5-65%, 32.5-70%, 32.5-65%. The solar reflectance is adjusted by adjusting the content of the above-described two or more kinds of metal-based inorganic pigments, adjusting the content of the organic pigment in the case of blending the organic pigment, and / or adjusting the above-described whiteness. be able to. The solar reflectance is a value measured according to JIS R3106-1998.
［製造方法］
本発明の硬質ポリ塩化ビニル系樹脂管の製造方法は、上述のポリ塩化ビニル系樹脂及び２種以上の金属系無機顔料、並びに必要に応じて配合される他の成分を混合しポリ塩化ビニル系樹脂コンパウンドを調製する工程１、及びポリ塩化ビニル系樹脂コンパウンドを成形する工程２を含む。 [Production method]
The method for producing a rigid polyvinyl chloride resin tube of the present invention comprises mixing the above-mentioned polyvinyl chloride resin and two or more kinds of metal inorganic pigments, and other components blended as required, to produce a polyvinyl chloride resin. The process 1 which prepares a resin compound, and the process 2 which shape | molds a polyvinyl chloride-type resin compound are included.
本発明の硬質ポリ塩化ビニル系樹脂管の製造方法は、上述のポリ塩化ビニル系樹脂及び２種以上の金属系無機顔料、並びに必要に応じて配合される他の成分を混合しポリ塩化ビニル系樹脂コンパウンドを調製する工程１、及びポリ塩化ビニル系樹脂コンパウンドを成形する工程２を含む。 [Production method]
The method for producing a rigid polyvinyl chloride resin tube of the present invention comprises mixing the above-mentioned polyvinyl chloride resin and two or more kinds of metal inorganic pigments, and other components blended as required, to produce a polyvinyl chloride resin. The process 1 which prepares a resin compound, and the process 2 which shape | molds a polyvinyl chloride-type resin compound are included.
工程１においては、ポリ塩化ビニル系樹脂に、２種以上の金属系無機顔料、並びに必要に応じて配合される他の成分を混合し、ポリ塩化ビニル系樹脂コンパウンドを調製する。混合方法としては、ホットブレンド法及びコールドブレンド法が挙げられる。これらの混合方法の中でも、コールドブレンド法では、有機顔料を用いた場合、有機顔料の発色に必要な要素であるエネルギー（熱、剪断力）が十分に与えられない条件でコンパウンドが調製されるため、引き続く成形工程において、成形条件（成形温度、滞留時間、剪断力）の不均一性の影響による発色の不均一性が顕著となる。つまり、コールドブレンド法は、本来的に色調不安定となりやすい混合方法である。しかしながら、本発明の硬質ポリ塩化ビニル系樹脂管は、優れた色調安定性を有するため、本来的に色調不安定となりやすいコールドブレンド法によりコンパウンドを調製した場合であっても、効果的に色調安定効果を発揮することができる。
In step 1, a polyvinyl chloride resin compound is prepared by mixing polyvinyl chloride resin with two or more metal inorganic pigments and other components blended as required. Examples of the mixing method include a hot blend method and a cold blend method. Among these mixing methods, in the case of using an organic pigment in the cold blending method, the compound is prepared under conditions where energy (heat, shearing force), which is an element necessary for the color development of the organic pigment, is not sufficiently applied. In the subsequent molding step, color unevenness due to the influence of unevenness of molding conditions (molding temperature, residence time, shearing force) becomes remarkable. In other words, the cold blend method is a mixing method that inherently tends to be unstable in color tone. However, since the rigid polyvinyl chloride resin tube of the present invention has excellent color tone stability, even when a compound is prepared by a cold blend method, which tends to be inherently unstable in color tone, the color tone is effectively stabilized. The effect can be demonstrated.
工程２においては、ポリ塩化ビニル系樹脂コンパウンド、好ましくはポリ塩化ビニル系樹脂のコールドブレンドコンパウンドを成形する。成形方法としては従来公知の方法が用いられ、例えば押出成形方法が好適に用いられる。
In step 2, a polyvinyl chloride resin compound, preferably a cold blend compound of polyvinyl chloride resin, is formed. A conventionally known method is used as the molding method, and for example, an extrusion molding method is preferably used.
以下に実施例を示して本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
［ポリ塩化ビニル系樹脂コンパウンドの作製］
表１に示す樹脂、顔料、及び添加剤をスーパーミキサー（１００Ｌ、カワタ社製）にてコールドブレンド法で攪拌混合し、ポリ塩化ビニル系樹脂コンパウンド（ポリ塩化ビニル系樹脂のコールドブレンドコンパウンド）を得た。それぞれの成分の詳細は以下の通りである。 [Production of polyvinyl chloride resin compound]
The resin, pigment, and additive shown in Table 1 are stirred and mixed by a cold blending method using a super mixer (100 L, manufactured by Kawata) to obtain a polyvinyl chloride resin compound (a cold blend compound of a polyvinyl chloride resin). It was. Details of each component are as follows.
表１に示す樹脂、顔料、及び添加剤をスーパーミキサー（１００Ｌ、カワタ社製）にてコールドブレンド法で攪拌混合し、ポリ塩化ビニル系樹脂コンパウンド（ポリ塩化ビニル系樹脂のコールドブレンドコンパウンド）を得た。それぞれの成分の詳細は以下の通りである。 [Production of polyvinyl chloride resin compound]
The resin, pigment, and additive shown in Table 1 are stirred and mixed by a cold blending method using a super mixer (100 L, manufactured by Kawata) to obtain a polyvinyl chloride resin compound (a cold blend compound of a polyvinyl chloride resin). It was. Details of each component are as follows.
・ポリ塩化ビニル系樹脂：ポリ塩化ビニル単独重合体（商品名「ＴＳ－１０００Ｒ」、徳山積水工業社製）
・ステアリン酸鉛：商品名「ＳＡＫ－ＮＳＢＮ」、サンエース社製、
・炭酸カルシウム：商品名「ホワイトン３０５Ｓ」、白石カルシウム社製
・顔料組成物Ａ：無機顔料組成物（酸化チタン、クロム化合物、銅フタロシアニン、分散剤を含む。なお、クロム化合物は、酸化クロムと酸化鉄との複合酸化物である。）
・顔料組成物Ｂ：カーボン顔料組成物（酸化チタン、カーボンブラック、銅フタロシアニン、分散剤を含む。）
・顔料組成物Ｃ：有機顔料３色組成物（酸化チタン、ジケトピロロピロール、モノアゾイエロー、銅フタロシアニン、分散剤を含む。）
・顔料組成物Ｄ：有機顔料２色組成物（酸化チタン、銅フタロシアニン、ベンズイミダゾリン、分散剤を含む。） ・ Polyvinyl chloride resin: Polyvinyl chloride homopolymer (trade name “TS-1000R”, manufactured by Tokuyama Sekisui Industry Co., Ltd.)
Lead stearate: trade name “SAK-NSBN”, manufactured by San Ace,
-Calcium carbonate: trade name "Whiteon 305S", manufactured by Shiraishi Calcium Co., Ltd.-Pigment composition A: Inorganic pigment composition (including titanium oxide, chromium compound, copper phthalocyanine, dispersant. (This is a complex oxide with iron oxide.)
Pigment composition B: Carbon pigment composition (including titanium oxide, carbon black, copper phthalocyanine, and dispersant)
Pigment composition C: Organic pigment three-color composition (including titanium oxide, diketopyrrolopyrrole, monoazo yellow, copper phthalocyanine, and dispersant)
Pigment composition D: Organic pigment two-color composition (including titanium oxide, copper phthalocyanine, benzimidazoline, and dispersant)
・ステアリン酸鉛：商品名「ＳＡＫ－ＮＳＢＮ」、サンエース社製、
・炭酸カルシウム：商品名「ホワイトン３０５Ｓ」、白石カルシウム社製
・顔料組成物Ａ：無機顔料組成物（酸化チタン、クロム化合物、銅フタロシアニン、分散剤を含む。なお、クロム化合物は、酸化クロムと酸化鉄との複合酸化物である。）
・顔料組成物Ｂ：カーボン顔料組成物（酸化チタン、カーボンブラック、銅フタロシアニン、分散剤を含む。）
・顔料組成物Ｃ：有機顔料３色組成物（酸化チタン、ジケトピロロピロール、モノアゾイエロー、銅フタロシアニン、分散剤を含む。）
・顔料組成物Ｄ：有機顔料２色組成物（酸化チタン、銅フタロシアニン、ベンズイミダゾリン、分散剤を含む。） ・ Polyvinyl chloride resin: Polyvinyl chloride homopolymer (trade name “TS-1000R”, manufactured by Tokuyama Sekisui Industry Co., Ltd.)
Lead stearate: trade name “SAK-NSBN”, manufactured by San Ace,
-Calcium carbonate: trade name "Whiteon 305S", manufactured by Shiraishi Calcium Co., Ltd.-Pigment composition A: Inorganic pigment composition (including titanium oxide, chromium compound, copper phthalocyanine, dispersant. (This is a complex oxide with iron oxide.)
Pigment composition B: Carbon pigment composition (including titanium oxide, carbon black, copper phthalocyanine, and dispersant)
Pigment composition C: Organic pigment three-color composition (including titanium oxide, diketopyrrolopyrrole, monoazo yellow, copper phthalocyanine, and dispersant)
Pigment composition D: Organic pigment two-color composition (including titanium oxide, copper phthalocyanine, benzimidazoline, and dispersant)
［硬質ポリ塩化ビニル系樹脂成形体の作製］
上記で得られたポリ塩化ビニル系樹脂組成物を、直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ－５０」、長田製作所社製）に供給し、外径６０ｍｍ、肉厚４．５ｍｍ、長さ１ｍの塩化ビニル系樹脂管を得た。或いは、得られた硬質ポリ塩化ビニル系樹脂組成物を加熱２本ロールにより加熱プレスで成形し、肉厚１．５ｍｍの板状成形体を得た。得られた管又は板状成形体について、以下の測定及び評価を行った。 [Production of rigid polyvinyl chloride resin moldings]
The polyvinyl chloride resin composition obtained above was supplied to a biaxial counter-rotating extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm, and an outer diameter of 60 mm and a wall thickness of 4. A vinyl chloride resin tube having a length of 5 mm and a length of 1 m was obtained. Alternatively, the obtained hard polyvinyl chloride resin composition was molded by a hot press with two heated rolls to obtain a plate-shaped molded body having a thickness of 1.5 mm. The following measurements and evaluations were performed on the obtained tube or plate-shaped molded body.
上記で得られたポリ塩化ビニル系樹脂組成物を、直径５０ｍｍの２軸異方向回転押出機（商品名「ＳＬＭ－５０」、長田製作所社製）に供給し、外径６０ｍｍ、肉厚４．５ｍｍ、長さ１ｍの塩化ビニル系樹脂管を得た。或いは、得られた硬質ポリ塩化ビニル系樹脂組成物を加熱２本ロールにより加熱プレスで成形し、肉厚１．５ｍｍの板状成形体を得た。得られた管又は板状成形体について、以下の測定及び評価を行った。 [Production of rigid polyvinyl chloride resin moldings]
The polyvinyl chloride resin composition obtained above was supplied to a biaxial counter-rotating extruder (trade name “SLM-50”, manufactured by Nagata Seisakusho Co., Ltd.) having a diameter of 50 mm, and an outer diameter of 60 mm and a wall thickness of 4. A vinyl chloride resin tube having a length of 5 mm and a length of 1 m was obtained. Alternatively, the obtained hard polyvinyl chloride resin composition was molded by a hot press with two heated rolls to obtain a plate-shaped molded body having a thickness of 1.5 mm. The following measurements and evaluations were performed on the obtained tube or plate-shaped molded body.
［白色度の測定］
SPECTRO PHTO METER CM3600d装置（コニカミノルタ社製）を用い、管の白色度を、ＣＩＥ１９７６Ｌ*ａ*ｂ*比色系に基づくＬ*値として測定した。 [Measurement of whiteness]
Using a SPECTRO PHTO METER CM3600d apparatus (manufactured by Konica Minolta), the whiteness of the tube was measured as an L * value based on the CIE 1976 L * a * b * colorimetric system.
SPECTRO PHTO METER CM3600d装置（コニカミノルタ社製）を用い、管の白色度を、ＣＩＥ１９７６Ｌ*ａ*ｂ*比色系に基づくＬ*値として測定した。 [Measurement of whiteness]
Using a SPECTRO PHTO METER CM3600d apparatus (manufactured by Konica Minolta), the whiteness of the tube was measured as an L * value based on the CIE 1976 L * a * b * colorimetric system.
［遮熱性の評価（日射反射率の測定）］
ＪＩＳ Ｒ３１０６－１９９８に準拠して、日射反射率を測定した。具体的には、板状成形体について、近赤外の波長域（３００～２１００ｎｍ）の反射率を測定し、ＪＩＳ Ｒ３１０６－１９９８に定められる式に基づき日射反射率（％）を得た。得られた日射反射率を、以下の基準に基づいて分類した。
－：２８．５％以下
＋：２８．５％超２９．５％以下
＋＋：２９．５％超３０．５％以下
＋＋＋：３０．５％超３１．５％以下
＋＋＋＋：３１．５％超３２．５％以下
＋＋＋＋＋：３２．５％超 [Evaluation of thermal insulation (measurement of solar reflectance)]
The solar reflectance was measured in accordance with JIS R3106-1998. Specifically, the reflectance of the near-infrared wavelength region (300 to 2100 nm) of the plate-like molded body was measured, and the solar reflectance (%) was obtained based on the formula defined in JIS R3106-1998. The obtained solar reflectance was classified based on the following criteria.
-: 28.5% or less +: 28.5% or more 29.5% or less ++: 29.5% or more 30.5% or less ++++: 30.5% or more 31.5% or less ++++: 31.5% or less 32.5% or less +++++: More than 32.5%
ＪＩＳ Ｒ３１０６－１９９８に準拠して、日射反射率を測定した。具体的には、板状成形体について、近赤外の波長域（３００～２１００ｎｍ）の反射率を測定し、ＪＩＳ Ｒ３１０６－１９９８に定められる式に基づき日射反射率（％）を得た。得られた日射反射率を、以下の基準に基づいて分類した。
－：２８．５％以下
＋：２８．５％超２９．５％以下
＋＋：２９．５％超３０．５％以下
＋＋＋：３０．５％超３１．５％以下
＋＋＋＋：３１．５％超３２．５％以下
＋＋＋＋＋：３２．５％超 [Evaluation of thermal insulation (measurement of solar reflectance)]
The solar reflectance was measured in accordance with JIS R3106-1998. Specifically, the reflectance of the near-infrared wavelength region (300 to 2100 nm) of the plate-like molded body was measured, and the solar reflectance (%) was obtained based on the formula defined in JIS R3106-1998. The obtained solar reflectance was classified based on the following criteria.
-: 28.5% or less +: 28.5% or more 29.5% or less ++: 29.5% or more 30.5% or less ++++: 30.5% or more 31.5% or less ++++: 31.5% or less 32.5% or less +++++: More than 32.5%
［色調安定性の評価］
同一の組成を有するポリ塩化ビニル系樹脂組成物（１０６．３７ｇ）それぞれから、混合条件が異なる２種の硬質ポリ塩化ビニル系樹脂の板状成形体を得た。２種の混合条件は、以下の通りである。これら２種の混合条件の違いにより、混合条件（２）で得られる樹脂組成物が、混合条件（１）で得られる樹脂組成物よりも熱履歴の蓄積の度合いが大きくなるように調製した。 [Evaluation of color stability]
From each of the polyvinyl chloride resin compositions (106.37 g) having the same composition, plate-like molded bodies of two kinds of hard polyvinyl chloride resins having different mixing conditions were obtained. The two mixing conditions are as follows. Due to the difference between these two kinds of mixing conditions, the resin composition obtained under the mixing condition (2) was prepared such that the degree of accumulation of thermal history was larger than that of the resin composition obtained under the mixing condition (1).
同一の組成を有するポリ塩化ビニル系樹脂組成物（１０６．３７ｇ）それぞれから、混合条件が異なる２種の硬質ポリ塩化ビニル系樹脂の板状成形体を得た。２種の混合条件は、以下の通りである。これら２種の混合条件の違いにより、混合条件（２）で得られる樹脂組成物が、混合条件（１）で得られる樹脂組成物よりも熱履歴の蓄積の度合いが大きくなるように調製した。 [Evaluation of color stability]
From each of the polyvinyl chloride resin compositions (106.37 g) having the same composition, plate-like molded bodies of two kinds of hard polyvinyl chloride resins having different mixing conditions were obtained. The two mixing conditions are as follows. Due to the difference between these two kinds of mixing conditions, the resin composition obtained under the mixing condition (2) was prepared such that the degree of accumulation of thermal history was larger than that of the resin composition obtained under the mixing condition (1).
混合条件（１）：２００ｍＬ容量のカップに入れ、スパチュラを用い、手動で１分間に約２０回転の速さで混合した。
混合条件（２）：２００ｍＬ容量のカップに入れ、家庭用クッキングミル（１０，０００ｒｐｍ）で４０秒撹拌した。 Mixing condition (1): The mixture was put into a 200 mL capacity cup and manually mixed at a speed of about 20 rotations per minute using a spatula.
Mixing condition (2): It put into the 200 mL capacity | capacitance cup, and stirred for 40 seconds with a household cooking mill (10,000 rpm).
混合条件（２）：２００ｍＬ容量のカップに入れ、家庭用クッキングミル（１０，０００ｒｐｍ）で４０秒撹拌した。 Mixing condition (1): The mixture was put into a 200 mL capacity cup and manually mixed at a speed of about 20 rotations per minute using a spatula.
Mixing condition (2): It put into the 200 mL capacity | capacitance cup, and stirred for 40 seconds with a household cooking mill (10,000 rpm).
混合条件（１）及び（２）それぞれによる板状成形体について、SPECTRO PHTO METER CM3600d（コニカミノルタ社製）を用い、ＣＩＥ１９７６Ｌ*ａ*ｂ*比色系に基づくＬ*値、ａ*値、及びｂ*値を測定した。Ｌ*値、ａ*値、及びｂ*値は、いずれも、ｎ＝１当たり５箇所測定した場合の平均値とした。混合条件（１）による板状成形体のＬａｂ値を基準として、混合条件（２）による板状成形体のＬａｂ値の変化量から、色差ΔＥを導出した。ΔＥから、以下の基準に基づいて、色調安定性の程度を評価した。
◎： ΔＥ＜０．６５
○：０．６５≦ΔＥ＜１．６０
△：１．６０≦ΔＥ＜２．５５
×：２．５５≦ΔＥ About the plate-shaped molded products according to the mixing conditions (1) and (2), using SPECTRO PHTO METER CM3600d (manufactured by Konica Minolta), L * value based on CIE1976L * a * b * colorimetric system, a * value, and b * values were measured. The L * value, the a * value, and the b * value were all average values when 5 points were measured per n = 1. The color difference ΔE was derived from the amount of change in the Lab value of the plate-like molded product according to the mixing condition (2), based on the Lab value of the plate-shaped molded product according to the mixing condition (1). From ΔE, the degree of color stability was evaluated based on the following criteria.
A: ΔE <0.65
○: 0.65 ≦ ΔE <1.60
Δ: 1.60 ≦ ΔE <2.55
×: 2.55 ≦ ΔE
◎： ΔＥ＜０．６５
○：０．６５≦ΔＥ＜１．６０
△：１．６０≦ΔＥ＜２．５５
×：２．５５≦ΔＥ About the plate-shaped molded products according to the mixing conditions (1) and (2), using SPECTRO PHTO METER CM3600d (manufactured by Konica Minolta), L * value based on CIE1976L * a * b * colorimetric system, a * value, and b * values were measured. The L * value, the a * value, and the b * value were all average values when 5 points were measured per n = 1. The color difference ΔE was derived from the amount of change in the Lab value of the plate-like molded product according to the mixing condition (2), based on the Lab value of the plate-shaped molded product according to the mixing condition (1). From ΔE, the degree of color stability was evaluated based on the following criteria.
A: ΔE <0.65
○: 0.65 ≦ ΔE <1.60
Δ: 1.60 ≦ ΔE <2.55
×: 2.55 ≦ ΔE
結果を表１に示す。着色顔料として２種以上の金属系無機顔料を含まない場合（比較例１）は、白色度を５０以上に調色したとしても日射反射率はわずか１．５％であり、遮熱性が極めて悪かった。一方、着色顔料として有機顔料を用いた場合（比較例２～４）は、白色度を５０以上に調色すると日射反射率が良好で、遮熱性には問題なかったが、色調安定性が極めて悪かった。着色顔料として有機顔料を用いた場合に色調安定性を向上させようとすると、白色度が５０を大きく下回る色調まで調色しなければならず、今度は日射反射率は１６．４％に下がり、遮熱性が損なわれた（比較例５）。これに対し、着色顔料として２種以上の金属系無機顔料を含む場合（実施例１～５）は、白色度が５０以上となるように調色した場合に、高い日射反射率が達成されるとともに、且つ色調安定性にも優れていた。例えば、実施例１の塩化ビニル系樹脂管を、２３℃環境において、得られた管に対し、赤外ランプ（岩崎電機社製ＩＲ１００／１１０Ｖ／２５０ＷＲＨ）で赤外線（７８０～３０００ｎｍ）を３０分間照射し（積算光量２７０００００ｍＪ／ｃｍ2）、３０分間照射完了時の管の表面（照射面）温度を測定する遮熱性試験を行うと、５８．２℃であった。この遮熱性試験は、６０℃未満であれば遮熱性が良好であると評価することができるため、実際に、実施例１～５の塩化ビニル系樹脂成形体の遮熱性が良好であることが認められた。
The results are shown in Table 1. When two or more kinds of metallic inorganic pigments are not included as the color pigment (Comparative Example 1), even if the whiteness is adjusted to 50 or more, the solar reflectance is only 1.5%, and the heat shielding property is extremely poor. It was. On the other hand, when an organic pigment was used as the coloring pigment (Comparative Examples 2 to 4), when the whiteness was adjusted to 50 or more, the solar reflectance was good and there was no problem with the heat shielding property, but the color tone stability was extremely high It was bad. If an organic pigment is used as the coloring pigment, if it is attempted to improve the color tone stability, the whiteness must be adjusted to a color tone greatly below 50, and the solar reflectance is reduced to 16.4%. The heat shielding property was impaired (Comparative Example 5). On the other hand, when two or more kinds of metallic inorganic pigments are included as the color pigments (Examples 1 to 5), high solar reflectance is achieved when the color is adjusted so that the whiteness is 50 or more. In addition, the color stability was excellent. For example, the vinyl chloride resin tube of Example 1 was irradiated with infrared rays (780 to 3000 nm) for 30 minutes with an infrared lamp (IR100 / 110V / 250WRH manufactured by Iwasaki Electric Co., Ltd.) in a 23 ° C. environment. (Accumulated light amount 2700000 mJ / cm 2 ), a heat shielding test for measuring the surface (irradiated surface) temperature of the tube after completion of irradiation for 30 minutes was 58.2 ° C. In this heat insulation test, since it can be evaluated that the heat insulation property is good if it is less than 60 ° C., the heat insulation properties of the vinyl chloride resin molded bodies of Examples 1 to 5 are actually good. Admitted.
実施例１～５の中でも、有色を呈する金属系無機顔料（つまりクロム化合物）１重量部当たりのステアリン酸塩の含有量が１０～５４重量部である場合（実施例２～５）は、色調安定性が更に顕著に向上したことが認められた。また、実施例２～５の中でも、ポリ塩化ビニル系樹脂１００重量部当たりの炭酸カルシウムの含有量が５重量部以上である場合（実施例３～５）は、日射反射率が更に顕著に向上したことが認められた。
Among Examples 1 to 5, when the content of stearate per 1 part by weight of a colored metallic inorganic pigment (that is, chromium compound) is 10 to 54 parts by weight (Examples 2 to 5), the color tone It was observed that the stability was further significantly improved. Further, in Examples 2 to 5, when the content of calcium carbonate per 100 parts by weight of the polyvinyl chloride resin is 5 parts by weight or more (Examples 3 to 5), the solar reflectance is further remarkably improved. It was recognized that
実施例２～５は、表１に示されているとおりいずれも優れた色調安定性を有する。ここで、実施例２、３、４及び５の具体的なΔＥ（色調安定性の評価基準となる量）の値は、それぞれ、０．４３、０．３５、０．５４、０．６４であった。つまり、実施例２～５の中で比較すると、色調安定性は、実施例３をピークとして、顔料組成物Ａの添加量が多くなるほど低下する傾向が確認された。そして、色調安定性を最も好ましいレベル（つまり「◎」評価）で得るためには、顔料組成物Ａの添加量として実施例５で用いられた量を上限とすべきであることが確認された。
Examples 2 to 5 all have excellent color stability as shown in Table 1. Here, specific values of ΔE (amount to be used as an evaluation criterion for color tone stability) in Examples 2, 3, 4, and 5 are 0.43, 0.35, 0.54, and 0.64, respectively. there were. That is, when compared in Examples 2 to 5, it was confirmed that the color tone stability tends to decrease as the amount of the pigment composition A increases with the peak at Example 3. And in order to obtain color tone stability at the most preferable level (that is, “◎” evaluation), it was confirmed that the amount used in Example 5 should be the upper limit as the addition amount of the pigment composition A. .
Claims (12)
- ポリ塩化ビニル系樹脂と、２種以上の金属系無機顔料とを含み、白色度が５０以上である、硬質ポリ塩化ビニル系樹脂管。 A rigid polyvinyl chloride resin tube containing a polyvinyl chloride resin and two or more metal inorganic pigments and having a whiteness of 50 or more.
- 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０重量部以上である、請求項１に記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to claim 1, wherein the total content of the two or more metal inorganic pigments is 0.050 part by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記２種以上の金属系無機顔料の総含有量が、０．０５０～０．５００重量部である、請求項１又は２に記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride according to claim 1 or 2, wherein the total content of the two or more metallic inorganic pigments is 0.050 to 0.500 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Resin tube.
- 前記２種以上の金属系無機顔料が、有色を呈する金属系無機顔料と白色を呈する金属系無機顔料との混合物である、請求項１～３のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to any one of claims 1 to 3, wherein the two or more metal inorganic pigments are a mixture of a metal inorganic pigment exhibiting a color and a metal inorganic pigment exhibiting a white color. .
- ステアリン酸塩を更に含み、前記有色を呈する金属系無機顔料１重量部当たり、前記ステアリン酸塩の含有量が１０～５４重量部である、請求項１～４のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The hard polychlorinated product according to any one of claims 1 to 4, further comprising a stearate, wherein the content of the stearate is 10 to 54 parts by weight per part by weight of the metallic inorganic pigment exhibiting a color. Vinyl resin tube.
- 炭酸カルシウムを更に含み、前記ポリ塩化ビニル系樹脂１００重量部当たり、前記炭酸カルシウムの含有量が５重量部以上である、請求項１～５のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to any one of claims 1 to 5, further comprising calcium carbonate, wherein the content of the calcium carbonate is 5 parts by weight or more per 100 parts by weight of the polyvinyl chloride resin.
- 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有色を呈する金属系無機顔料の含有量が、０．０２５～０．０６重量部である、請求項１～６のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The hard polychlorinated product according to any one of claims 1 to 6, wherein the content of the colored metallic inorganic pigment is 0.025 to 0.06 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Vinyl resin tube.
- 前記有色を呈する金属系無機顔料がクロム含有化合物を含む、請求項１～７のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to any one of claims 1 to 7, wherein the colored inorganic inorganic pigment contains a chromium-containing compound.
- 前記白色を呈する金属系無機顔料が酸化チタンである、請求項１～８のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to any one of claims 1 to 8, wherein the white metallic inorganic pigment is titanium oxide.
- 有機顔料を更に含む、請求項１～９のいずれかに記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to any one of claims 1 to 9, further comprising an organic pigment.
- 前記有機顔料がフタロシアニン系顔料である、請求項１０に記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to claim 10, wherein the organic pigment is a phthalocyanine pigment.
- 前記ポリ塩化ビニル系樹脂１００重量部当たり、前記有機顔料の含有量が、０．０００１～０．００４重量％重量部である、請求項１０又は１１に記載の硬質ポリ塩化ビニル系樹脂管。 The rigid polyvinyl chloride resin tube according to claim 10 or 11, wherein the content of the organic pigment is 0.0001 to 0.004% by weight per 100 parts by weight of the polyvinyl chloride resin.
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| JP2002053726A (en) * | 2000-08-10 | 2002-02-19 | Mitsubishi Plastics Ind Ltd | Flame-retardant vinyl chloride resin composition, flame- retardant vinyl chloride resin molding, and production method for flame-retardant vinyl chloride resin composition |
| WO2008012982A1 (en) * | 2006-07-26 | 2008-01-31 | Adeka Corporation | Vinyl chloride resin composition |
| JP2013159774A (en) * | 2012-02-09 | 2013-08-19 | Sekisui Chem Co Ltd | Hard vinyl chloride resin pipe |
| JP2019108411A (en) * | 2017-12-15 | 2019-07-04 | アロン化成株式会社 | Hard vinyl chloride-based resin molded body |
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| JPH09263667A (en) * | 1996-03-28 | 1997-10-07 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
| JP3608702B2 (en) * | 1996-09-30 | 2005-01-12 | ゼオン化成株式会社 | Vinyl chloride resin composition and vinyl chloride resin molded product |
| JP3475076B2 (en) * | 1998-04-30 | 2003-12-08 | 大日精化工業株式会社 | Chalking-resistant vinyl chloride resin molded article and chalking-resistant vinyl chloride resin composition |
| JP3590297B2 (en) * | 1999-04-30 | 2004-11-17 | タキロン株式会社 | Flame retardant vinyl chloride resin molding |
| JP3949538B2 (en) * | 2002-08-20 | 2007-07-25 | 株式会社トクヤマ | Polyvinyl chloride resin extrusion |
| DE102005040582A1 (en) * | 2005-08-22 | 2007-03-01 | Itn Nanovation Gmbh | High temperature stable ceramic layers and moldings |
| CN103339209B (en) * | 2011-02-07 | 2016-09-07 | F顾问株式会社 | Coating material, coating material layers and laminated layer structures |
| JP2017043063A (en) * | 2015-08-28 | 2017-03-02 | 積水化学工業株式会社 | Vinyl chloride-based waterproof sheet |
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| JP2002053726A (en) * | 2000-08-10 | 2002-02-19 | Mitsubishi Plastics Ind Ltd | Flame-retardant vinyl chloride resin composition, flame- retardant vinyl chloride resin molding, and production method for flame-retardant vinyl chloride resin composition |
| WO2008012982A1 (en) * | 2006-07-26 | 2008-01-31 | Adeka Corporation | Vinyl chloride resin composition |
| JP2013159774A (en) * | 2012-02-09 | 2013-08-19 | Sekisui Chem Co Ltd | Hard vinyl chloride resin pipe |
| JP2019108411A (en) * | 2017-12-15 | 2019-07-04 | アロン化成株式会社 | Hard vinyl chloride-based resin molded body |
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