WO2023276857A1 - 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 - Google Patents
塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 Download PDFInfo
- Publication number
- WO2023276857A1 WO2023276857A1 PCT/JP2022/025184 JP2022025184W WO2023276857A1 WO 2023276857 A1 WO2023276857 A1 WO 2023276857A1 JP 2022025184 W JP2022025184 W JP 2022025184W WO 2023276857 A1 WO2023276857 A1 WO 2023276857A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl chloride
- chloride resin
- resin composition
- fatty acid
- mass
- Prior art date
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 421
- 239000011347 resin Substances 0.000 title claims abstract description 213
- 229920005989 resin Polymers 0.000 title claims abstract description 213
- 239000011342 resin composition Substances 0.000 title claims abstract description 209
- 238000000465 moulding Methods 0.000 claims abstract description 133
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 118
- 229930195729 fatty acid Natural products 0.000 claims abstract description 118
- 239000000194 fatty acid Substances 0.000 claims abstract description 118
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 113
- -1 uracil compound Chemical class 0.000 claims abstract description 84
- 150000003839 salts Chemical class 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Natural products O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229940035893 uracil Drugs 0.000 claims abstract description 58
- 239000004014 plasticizer Substances 0.000 claims abstract description 53
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 47
- 239000011701 zinc Substances 0.000 claims abstract description 47
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 29
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- VFGRNTYELNYSKJ-UHFFFAOYSA-N 6-amino-1,3-dimethylpyrimidine-2,4-dione Chemical compound CN1C(N)=CC(=O)N(C)C1=O VFGRNTYELNYSKJ-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 description 37
- 239000002245 particle Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 239000010419 fine particle Substances 0.000 description 16
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- 230000000052 comparative effect Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 125000005591 trimellitate group Chemical group 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- 238000010410 dusting Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012643 polycondensation polymerization Methods 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
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- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- UIYZXYZMGAKDDW-UHFFFAOYSA-N 5-hexyl-1h-pyrimidine-2,4-dione Chemical compound CCCCCCC1=CNC(=O)NC1=O UIYZXYZMGAKDDW-UHFFFAOYSA-N 0.000 description 1
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- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
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- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AKTIAGQCYPCKFX-FDGPNNRMSA-L magnesium;(z)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AKTIAGQCYPCKFX-FDGPNNRMSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- MXHBQKVKHGQWRB-UHFFFAOYSA-N trihexyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC)C(C(=O)OCCCCCC)=C1 MXHBQKVKHGQWRB-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/36—Feeding the material on to the mould, core or other substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded article and a laminate.
- Vinyl chloride resins are generally used in various applications because of their excellent properties such as cold resistance, heat resistance, and oil resistance.
- the skin composed of a vinyl chloride resin molded body or the skin composed of a vinyl chloride resin molded body is lined with a foam such as foamed polyurethane.
- Automobile interior materials such as laminates formed by
- the vinyl chloride resin molded body that constitutes the skin of automobile interior parts such as automobile instrument panels is produced by, for example, powder slush molding a vinyl chloride resin composition containing vinyl chloride resin, a plasticizer, and an additive. is manufactured by molding using the method of powder molding (see, for example, Patent Document 1).
- Patent Document 1 a vinyl chloride resin composition containing vinyl chloride resin particles, a plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and ⁇ -diketones is prepared.
- a hydrotalcite-based stabilizer such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and ⁇ -diketones is prepared.
- the vinyl chloride resin composition when the vinyl chloride resin composition is powder-molded, for example, if there is a temperature distribution in the mold used, the difference in molding temperature may cause variations in the color tone of the vinyl chloride resin composition. When such a change in color tone occurs, unevenness in color tone may occur in the vinyl chloride resin molded article to be formed. Therefore, from the viewpoint of reducing unevenness in color tone of a vinyl chloride resin molded article, it is required to suppress variation in color tone due to differences in molding temperatures in vinyl chloride resin compositions.
- the addition of a uracil compound and zinc acetylacetonate to a vinyl chloride resin composition can suppress variations in color tone due to differences in molding temperatures.
- the vinyl chloride resin composition containing the uracil compound and zinc acetylacetonate has a brownish color that occurs on the surface of the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition. There is room for improvement in terms of reducing the number of spots on the surface.
- the vinyl chloride resin composition containing the uracil compound and zinc acetylacetonate has room for further improvement in terms of suppressing fluctuations in color tone due to differences in molding temperatures.
- a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article with reduced color tone variation due to a difference in molding temperature and with few brown spots.
- Another object of the present invention is to provide a vinyl chloride resin molded article formed using the vinyl chloride resin composition and having few brown spots.
- a further object of the present invention is to provide a laminate comprising the vinyl chloride resin molded article.
- the inventor of the present invention conducted intensive studies with the aim of solving the above problems. Then, the present inventor adds a uracil compound, zinc acetylacetonate, and a predetermined fatty acid metal salt to a vinyl chloride resin composition, and sets the ratio of the content of zinc acetylacetonate to the content of the uracil compound to a predetermined value or more, and If the ratio of the content of a predetermined fatty acid metal salt to the content of zinc acetylacetone is set to a predetermined value or more, the variation in color tone due to the difference in molding temperature is suppressed, and the surface of the formed vinyl chloride resin molded product is brown. The inventors have found that the spots can be reduced, and have completed the present invention.
- an object of the present invention is to advantageously solve the above problems, and the present invention provides [1] a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetone, and zinc other than fatty acid zinc. and a fatty acid metal salt, wherein the content of the zinc acetylacetonate is 0.5 times or more the content of the uracil compound, and the content of the fatty acid metal salt is 1.6 times or more the content of the zinc acetylacetonate. is a vinyl chloride resin composition.
- a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetone, and a fatty acid metal salt other than zinc fatty acid
- the content of zinc acetylacetonate relative to the content of the uracil compound is If the ratio is set to a predetermined value or more, and if the ratio of the content of the fatty acid metal salt other than fatty acid zinc to the content of zinc acetylacetone is set to a predetermined value or more, the variation in color tone due to the difference in the molding temperature of the vinyl chloride resin composition can be suppressed. It is possible to reduce brown spots on the surface of the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition while suppressing it.
- the uracil compound has the following formula (I): [In formula (I), R 1 and R 2 each independently represent a hydrogen atom or an electron donating group, R3 represents a hydrogen atom or an amino group. ] is preferable. If the uracil compound is a compound represented by the given formula above, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the uracil compound preferably contains 6-amino-1,3-dimethyluracil.
- 6-amino-1,3-dimethyluracil as the uracil compound, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the content of the uracil compound is 0.05 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. preferable. If the content of the uracil compound in the vinyl chloride resin composition is at least the predetermined value, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the fatty acid metal salt preferably contains at least one of fatty acid calcium and fatty acid barium. If the vinyl chloride resin composition contains at least one of fatty acid calcium and fatty acid barium as the fatty acid metal salt, it is possible to further suppress color tone fluctuations due to differences in the molding temperature of the vinyl chloride resin composition, and the resulting vinyl chloride resin molding can be further suppressed. It can further reduce brown spots on the surface of the body.
- the fatty acid metal salt preferably contains a metal salt of a fatty acid having 6 or more and 22 or less carbon atoms. If a metal salt of a fatty acid having 6 or more and 22 or less carbon atoms is used as the fatty acid metal salt other than the fatty acid zinc, it is possible to further suppress the color tone fluctuation due to the difference in the molding temperature of the vinyl chloride resin composition, and to form Brown spots on the surface of the vinyl chloride resin molding can be further reduced.
- the vinyl chloride resin composition of any one of [1] to [6] above is preferably used for powder molding.
- the vinyl chloride resin composition for powder molding it is possible to easily obtain a vinyl chloride resin molded article that can be favorably used as an automobile interior material such as an automobile instrument panel skin.
- the vinyl chloride resin composition of any one of [1] to [7] above is preferably used for powder slush molding.
- the vinyl chloride resin composition for powder slush molding it is possible to more easily obtain a vinyl chloride resin molded article that can be favorably used as an automobile interior material such as an automobile instrument panel skin.
- an object of the present invention is to advantageously solve the above problems, and the present invention provides [9] Molding the vinyl chloride resin composition according to any one of [1] to [8] above. It is a vinyl chloride resin molding.
- the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition described above has reduced unevenness in color tone, has few brown spots, and has an excellent appearance, so it is suitable as an automobile interior material. can be used for
- the vinyl chloride resin molded article of [9] is preferably used as an instrument panel skin for automobiles. To manufacture an automobile instrument panel having a skin with reduced unevenness in color tone, few brown spots, and excellent appearance by using the vinyl chloride resin molded article of the present invention for the skin of the automobile instrument panel. can be done.
- an object of the present invention is to advantageously solve the above problems, and the present invention provides a polyurethane foam molded article and a vinyl chloride resin molded article of the above [9] or [10]. It is a laminate having A laminate comprising a foamed polyurethane molded article and the vinyl chloride resin molded article described above has a vinyl chloride resin molded article portion with reduced unevenness in color tone, less brown spots, and excellent appearance.
- the laminate of [11] is preferably for automotive instrument panels. As described above, when the laminate of the present invention is used for an automobile instrument panel, the produced automobile instrument panel has a reduced color unevenness in the outer skin, less brown spots, and a better appearance. be able to.
- the vinyl-chloride resin composition which can form a vinyl-chloride-resin molded object which suppresses the fluctuation
- the vinyl chloride resin composition of the present invention can be used, for example, when forming the vinyl chloride resin molded article of the present invention. Then, the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can be suitably used as an automobile interior material, such as a skin provided for automobile interior parts such as automobile instrument panels and door trims. can be done. Moreover, the vinyl chloride resin molded article of the present invention can be used, for example, when forming the laminate of the present invention. A laminate formed using the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material for manufacturing automobile interior parts such as automobile instrument panels and door trims.
- the vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, (b) a plasticizer, (c) a uracil compound, (d) zinc acetylacetone, and (e) a fatty acid metal salt other than fatty acid zinc. (c) the ratio of the content of (d) zinc acetylacetonate to the content of the uracil compound is a predetermined value or more, and (d) the content of (e) fatty acid metal salt to the content of zinc acetylacetone is It is characterized by being equal to or greater than a predetermined value.
- the term "(e) fatty acid metal salt” refers to fatty acid metal salts other than fatty acid zinc.
- the vinyl chloride resin composition of the present invention may optionally further contain ⁇ -diketones other than zinc acetylacetone (hereinafter sometimes referred to as “(f) other ⁇ -diketones”).
- the vinyl chloride resin composition of the present invention may optionally further contain (g) fatty acid zinc.
- the vinyl chloride resin composition of the present invention includes the above (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetone, (e) fatty acid metal salt, (f) other It may further contain additives other than ⁇ -diketones and (g) fatty acid zinc.
- the vinyl chloride resin composition of the present invention contains at least (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetone, and (e) fatty acid metal salt, (c) the ratio of the content of (d) acetylacetonate metal salt to the content of uracil compound is at least a predetermined value, and the content of (e) fatty acid metal salt to the content of (d) zinc acetylacetonate is a predetermined value; Because of the above, it is possible to suppress variation in color tone due to a difference in molding temperature, and to form a vinyl chloride resin molded article with few brown spots.
- the vinyl chloride resin composition of the present invention is used, unevenness in color tone is reduced, there are few brown spots, and it is used as an automotive interior material such as an automotive instrument panel skin and a door trim skin that has excellent appearance.
- a suitable vinyl chloride resin molding can be obtained.
- the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can suppress changes in color tone such as yellowing even when heated at a high temperature of 270° C. or higher. can be done.
- the vinyl chloride resin composition of the present invention is a powder. It is preferably used for molding, more preferably for powder slush molding.
- the vinyl chloride resin a particulate vinyl chloride resin is usually used.
- the vinyl chloride resin may contain, for example, one or two or more types of vinyl chloride resin particles, and optionally one or two or more types of vinyl chloride resin fine particles. can be done.
- the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
- the vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
- “resin particles” refer to particles having a particle diameter of 30 ⁇ m or more
- “resin fine particles” refer to particles having a particle diameter of less than 30 ⁇ m.
- the (a) vinyl chloride resin may be a homopolymer composed of vinyl chloride monomer units, or vinyl chloride containing vinyl chloride monomer units in an amount of preferably 50% by mass or more, more preferably 70% by mass or more. system copolymers.
- monomers (comonomers) that can be copolymerized with a vinyl chloride monomer that can constitute a vinyl chloride copolymer include, for example, those described in International Publication No. 2016/098344. can use things.
- these components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
- vinyl chloride resin particles usually function as a matrix resin (base material).
- the vinyl chloride resin particles are preferably produced by a suspension polymerization method.
- the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, preferably 5000 or less, and more preferably 3000 or less. It is preferably 2800 or less, and more preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is at least the above lower limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition is sufficiently ensured, for example, tensile This is because properties, particularly tensile elongation, can be improved.
- Vinyl chloride resin moldings with good tensile elongation are used, for example, as skins of automotive instrument panels with excellent ductility that break as designed without scattering fragments when an airbag is inflated and deployed. It can be suitably used as an automobile interior material. Also, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition can be improved.
- the "average degree of polymerization" in the present invention can be measured according to JIS K6720-2.
- the average particle size of the vinyl chloride resin particles is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, preferably 500 ⁇ m or less, and more preferably 200 ⁇ m or less. This is because if the average particle size of the vinyl chloride resin particles is at least the lower limit, the powder flowability of the vinyl chloride resin composition is improved. Further, when the average particle size of the vinyl chloride resin particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition is further improved, and the surface smoothness of the vinyl chloride resin molding formed using the composition is improved. Because it can be improved.
- the "average particle size" can be measured as a volume average particle size by a laser diffraction method in accordance with JIS Z8825.
- the content of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass. It is preferably 90% by mass or less, more preferably 90% by mass or less.
- the content of vinyl chloride resin particles in the vinyl chloride resin is at least the above lower limit, the physical strength of the vinyl chloride resin molding formed using the vinyl chloride resin composition is sufficiently ensured, and the tensile elongation is increased. Because it can be done well. Also, (a) if the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is equal to or less than the above upper limit, the powder fluidity of the vinyl chloride resin composition is improved.
- fine vinyl chloride resin particles usually function as a dusting agent (powder fluidity improver).
- the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, preferably 2600 or less, and more preferably 2400 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles as the dusting agent is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition is improved, and the composition can be obtained using the composition. This is because the tensile elongation of the molded body is improved.
- the meltability of the vinyl chloride resin composition is improved, and the vinyl chloride resin molded article formed using the composition is improved. This is because the surface smoothness is improved.
- the average particle size of the vinyl chloride resin fine particles is usually less than 30 ⁇ m, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, preferably 0.1 ⁇ m or more, and 1 ⁇ m or more. is more preferred. This is because, if the average particle diameter of the vinyl chloride resin fine particles is at least the lower limit, the powder fluidity of the vinyl chloride resin composition is improved without excessively reducing the size of the dusting agent. Further, when the average particle size of the vinyl chloride resin fine particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition is further enhanced, and the surface smoothness of the vinyl chloride resin molded article to be formed can be further improved. is.
- the content of vinyl chloride resin fine particles in the vinyl chloride resin may be 0% by mass, but is preferably 5% by mass or more, more preferably 10% by mass or more, It is preferably 30% by mass or less, more preferably 20% by mass or less. This is because (a) if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is improved. Further, (a) if the content of the vinyl chloride resin fine particles in the vinyl chloride resin is equal to or less than the above upper limit, the physical strength of the vinyl chloride resin molding formed using the vinyl chloride resin composition can be further increased. It is from.
- the vinyl chloride resin composition of the present invention contains (b) a plasticizer.
- a plasticizer in the vinyl chloride resin composition, the vinyl chloride resin molded article formed can exhibit sufficient flexibility, so that it can be suitably used, for example, as an automobile interior material.
- the content of the (b) plasticizer in the vinyl chloride resin composition is preferably 50 parts by mass or more and 60 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin. is more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, preferably 200 parts by mass or less, 180 parts by mass It is more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and even more preferably 120 parts by mass or less. If the content of the (b) plasticizer in the vinyl chloride resin composition is at least the above lower limit with respect to 100 parts by mass of the (a) vinyl chloride resin, the flexibility of the vinyl chloride resin molded article to be formed can be increased.
- the content of the (b) plasticizer in the vinyl chloride resin composition is at least the above lower limit, precipitation (blooming) of the compounded components on the surface of the vinyl chloride resin molding to be formed can be suppressed. That is, the anti-blooming property of the vinyl chloride resin molding can be enhanced.
- the content of the plasticizer (b) in the vinyl chloride resin composition is equal to or less than the above upper limit with respect to 100 parts by mass of the vinyl chloride resin (a), the powder fluidity of the vinyl chloride resin composition is improved. be able to.
- the (b) plasticizer contained in the vinyl chloride resin composition of the present invention is not particularly limited, it is preferable to use (b1) polyester and (b2) trimellitate ester, for example.
- a plasticizer other than (b1) polyester and (b2) trimellitate ester hereinafter sometimes referred to as "(b3) other plasticizer" may be used. good.
- the plasticizer preferably contains (b1) polyester. (b) If the plasticizer contains (b1) polyester, the heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be enhanced.
- the (b1) polyester that can be contained in the plasticizer is not particularly limited. It is possible to use polyesters such as containing polyesters (sebacic acid-based polyesters) and polyesters containing structural units derived from phthalic acid (phthalic acid-based polyesters). In addition, these polyesters may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios.
- the (b1) polyester includes: It is preferable to use a polyester containing a structural unit derived from adipic acid, and it is particularly preferable to use a polyester containing a structural unit derived from adipic acid and a structural unit derived from 3-methyl-1,5-pentanediol.
- the polyester containing structural units derived from adipic acid and structural units derived from 3-methyl-1,5-pentanediol will be referred to as "polyester A".
- the polyester A containing the predetermined structural unit may have a structural unit other than the structural unit derived from adipic acid and the structural unit derived from 3-methyl-1,5-pentanediol.
- the total amount of acid-derived structural units and 3-methyl-1,5-pentanediol-derived structural units is preferably 50% by mass or more, more preferably 80% by mass or more, of all structural units.
- the polyester A containing the predetermined structural unit preferably has only the structural unit derived from adipic acid and the structural unit derived from 3-methyl-1,5-pentanediol as repeating units.
- the polyester A containing the predetermined structural unit is not particularly limited and can be obtained by condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol.
- the condensation polymerization described above can be carried out in the presence of a catalyst.
- the condensation polymerization described above can be carried out using alcohols and/or monoacids as terminal terminating components.
- the condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol, and the termination reaction of the obtained condensation polymer and the above-mentioned terminal terminating component may be carried out collectively or separately. It shall be permitted to do so.
- the product obtained through condensation polymerization and termination reaction may be subjected to post-treatment such as distillation.
- Known conditions can be employed as reaction conditions for condensation polymerization, such as the amounts of the above-mentioned monomers, catalysts and terminal terminating components.
- a commercial product may be used as the polyester A containing the predetermined structural unit.
- the catalyst used for the condensation polymerization reaction is not particularly limited, and examples thereof include dibutyltin oxide and tetraalkyl titanate.
- Alcohols that can be used as terminal terminating components include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, and 2-ethyl.
- monobasic acids that can be used as end-terminating components include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, Capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, benzoic acid and mixtures thereof.
- 2-ethylhexanol is preferable as the terminal terminating component.
- the polyester A containing the predetermined structural unit preferably has a number average molecular weight of 1000 or more, more preferably 2000 or more, preferably 10000 or less, and more preferably 7000 or less. preferable.
- the "number average molecular weight" can be measured by a VPO (vapor pressure osmotic pressure) method.
- the polyester A containing the predetermined structural unit preferably has an acid value of 1 or less.
- it is preferable that the polyester A containing the predetermined structural unit has a hydroxyl value of 30 or less.
- the polyester A containing the predetermined structural unit preferably has a viscosity of 500 mPa s or more, more preferably 1000 mPa s or more, and preferably 8000 mPa s or less, and preferably 5000 mPa s. The following are more preferable. "Viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.
- the content of (b1) polyester in the plasticizer is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and 95% by mass. % or less, more preferably 90 mass % or less. If the content of (b1) polyester in the (b) plasticizer is at least the above lower limit, the heat shrinkage resistance of the resulting vinyl chloride resin molding can be further enhanced. On the other hand, when the content ratio of (b1) polyester in (b) plasticizer is equal to or less than the above upper limit, the resulting vinyl chloride resin molding can maintain good flexibility at low temperatures.
- the content of the (b1) polyester in the vinyl chloride resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, relative to 100 parts by mass of the vinyl chloride resin (a). It is more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, preferably 120 parts by mass or less, and more preferably 110 parts by mass or less.
- the content of (b1) polyester in the vinyl chloride resin composition is at least the above lower limit, the heat shrinkage resistance of the resulting vinyl chloride resin molding can be further enhanced.
- the content of (b1) polyester in the vinyl chloride resin composition is equal to or less than the above upper limit, the powder fluidity of the vinyl chloride resin composition can be improved.
- the plasticizer preferably contains (b2) a trimellitate. If the (b) plasticizer contains (b2) a trimellitate ester, the (b2) trimellitate ester is well absorbed by the (a) vinyl chloride resin, so that the powder flowability of the vinyl chloride resin composition can increase In addition, when the (b) plasticizer contains (b2) a trimellitate ester, the flexibility at low temperatures of the formed vinyl chloride resin molding can be enhanced.
- the (b2) trimellitic acid ester contained in the (b) plasticizer is preferably an ester compound of trimellitic acid and a monohydric alcohol.
- the monohydric alcohol examples include, but are not limited to, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like. of fatty alcohols.
- these monohydric alcohols aliphatic alcohols having 6 to 18 carbon atoms are preferable, and linear aliphatic alcohols having 6 to 18 carbon atoms are more preferable.
- the trimellitic acid ester (b2) is preferably a triesterified product obtained by esterifying substantially all the carboxy groups of trimellitic acid with the above-mentioned monohydric alcohol.
- the alcohol residue moieties in the triester product may be derived from the same alcohol, or may be derived from different alcohols.
- the trimellitate (b2) may consist of a single compound or a mixture of different compounds.
- trimellitate esters include tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, and tri-(2-ethylhexyl trimellitate. ), tri-n-nonyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, trialkyl trimellitate ( Alkyl groups with different numbers of carbon atoms [wherein the number of carbon atoms is 6-18. number is 6 to 18.] in the molecule), mixtures thereof, and the like.
- trimellitate examples include tri-n-octyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, and tri-n-trimellitate.
- decyl, tri-n-alkyl trimellitate ester having two or more alkyl groups with different carbon atoms [wherein the number of carbon atoms is 6 to 18] in the molecule), mixtures thereof, and the like.
- the content of trimellitate (b2) in the plasticizer is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, It is more preferably 45% by mass or less, and even more preferably 40% by mass or less. If the content of (b2) the trimellitate ester in the (b) plasticizer is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is further enhanced, and the low temperature of the vinyl chloride resin molded body to be formed is improved. flexibility can be further enhanced. On the other hand, if the content ratio of (b2) trimellitate ester in (b) plasticizer is equal to or less than the above upper limit, heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be enhanced.
- the content of the (b2) trimellitate ester in the vinyl chloride resin composition is preferably 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). It is preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. If the content of (b2) the trimellitate ester in the vinyl chloride resin composition is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is further enhanced, and the low temperature of the formed vinyl chloride resin molding is maintained. flexibility can be further enhanced. On the other hand, if the content of (b2) the trimellitate ester in the vinyl chloride resin composition is equal to or less than the above upper limit, the heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be enhanced.
- the (b) plasticizer contained in the vinyl chloride resin composition may optionally contain (b3) other plasticizers other than the above-described (b1) polyester and (b2) trimellitate ester.
- plasticizers include, among the plasticizers described in WO 2016/098344, plasticizers other than the above-mentioned (b1) polyester and (b2) trimellitate. be done. Among them, it is preferable to use epoxidized soybean oil from the viewpoint of further increasing the flexibility of the vinyl chloride resin molded article to be formed at low temperatures.
- the content of (b3) other plasticizer in (b) plasticizer is not particularly limited, but is preferably 0% by mass or more and 15% by mass or less. If the content ratio of (b3) other plasticizer in (b) plasticizer is within the above range, the low-temperature tensile elongation after heating of the vinyl chloride resin molding to be formed can be increased.
- the content of the (b3) other plasticizer in the vinyl chloride resin composition is not particularly limited, but is 0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). can do.
- epoxidized vegetable oils such as epoxidized soybean oil are used as (b3) other plasticizers. It is preferable to use 2 parts by mass or more and 7 parts by mass or less based on the mass parts.
- the vinyl chloride resin composition of the present invention contains (c) a uracil compound. Since the vinyl chloride resin composition of the present invention contains (c) a uracil compound, it is possible to suppress variations in color tone due to differences in molding temperature. In addition, in the vinyl chloride resin composition of the present invention, the surface of the vinyl chloride resin molded article formed by using (c) the uracil compound together with (d) zinc acetylacetone and (e) fatty acid metal salt, which will be described later. can reduce brown spots on the skin.
- the (c) uracil compound contained in the vinyl chloride resin composition of the present invention is a compound having a uracil skeleton. From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, (c) the uracil compound has the following formula (I): [In formula (I), R 1 and R 2 each independently represent a hydrogen atom or an electron donating group, R3 represents a hydrogen atom or an amino group. ] is preferably represented by
- R 1 and R 2 are preferably an electron donating group, and R More preferably both 1 and R 2 are electron donating groups.
- the electron donating group is not particularly limited, and examples thereof include an alkyl group, an amino group, and a dialkylamino group. .
- the electron donating group is preferably an alkyl group, more preferably an alkyl group having 6 or less carbon atoms, and a methyl group, from the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- R 1 and R 2 may be the same or different.
- uracil compound represented by the above formula (I) include uracil, 6-amino-1,3-dimethyluracil, 6-amino-1,3-diethyluracil, 6-amino-1 ,3-di-n-propyluracil, 6-amino-1,3-di-n-butyluracil, 6-amino-1,3-di-n-pentyluracil, 6-amino-1,3-di- and n-hexyluracil.
- 6-amino-1,3-dimethyluracil is preferably used as the (c) uracil compound from the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- these (c) uracil compounds may be used singly, or two or more of them may be used by mixing at any ratio.
- the content of the (c) uracil compound in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass, with respect to 100 parts by mass of the (a) vinyl chloride resin. More preferably 0.15 parts by mass or more, still more preferably 0.20 parts by mass or more, even more preferably 0.25 parts by mass or more, and 0.25 parts by mass or more. It is particularly preferably 40 parts by mass or more, preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, further preferably 1.60 parts by mass or less. It is more preferably 0.20 parts by mass or less, and even more preferably 0.80 parts by mass or less.
- the content of (c) the uracil compound in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress color tone fluctuations due to differences in the molding temperature of the vinyl chloride resin composition, and the resulting vinyl chloride resin Brown spots on the surface of the molding can be further reduced.
- the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, the powder flowability of the vinyl chloride resin composition and the blooming resistance of the vinyl chloride resin molding to be formed are improved. can be made
- the vinyl chloride resin composition of the present invention contains (d) zinc acetylacetonate.
- the vinyl chloride resin composition of the present invention can suppress variation in color tone due to a difference in molding temperature.
- the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, and is 0.10 parts by mass or more, relative to 100 parts by mass of the vinyl chloride resin (a). more preferably 0.15 parts by mass or more, still more preferably 0.25 parts by mass or more, even more preferably 0.35 parts by mass or more, and 2.0 parts by mass is preferably 1.5 parts by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.50 parts by mass or less. If the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or less than the above upper limit, brown spots on the surface of the formed vinyl chloride resin molding can be further reduced.
- the content of (d) zinc acetylacetonate in the vinyl chloride resin composition must be at least 0.5 times the content of (c) uracil compound, and 0.6 times is preferably 0.7 times or more, more preferably 0.8 times or more, more preferably 0.8 times or more, preferably 3 times or less, more preferably 2 times or less, It is more preferably 1.5 times or less, still more preferably 1.2 times or less, even more preferably 1.0 times or less, and particularly preferably 0.9 times or less. .
- the vinyl chloride resin composition of the present invention contains (e) a fatty acid metal salt.
- (e) Fatty acid metal salt is a metal salt of a fatty acid other than zinc. Since the vinyl chloride resin composition of the present invention contains (e) fatty acid metal salt other than fatty acid zinc, it is possible to suppress variation in color tone due to differences in molding temperature. Furthermore, the vinyl chloride resin composition of the present invention can reduce brown spots on the surface of the formed vinyl chloride resin molding by containing (e) fatty acid metal salt other than fatty acid zinc.
- the vinyl chloride resin composition of the present invention can reduce brown spots on the surface of the formed vinyl chloride resin molding by including (e) fatty acid metal salt other than fatty acid zinc.
- fatty acid metal salt other than fatty acid zinc reacts with zinc chloride to suppress the occurrence of brown spots due to the zinc burning phenomenon.
- the number of carbon atoms in the fatty acid of the fatty acid metal salt is not particularly limited, but is preferably 6 or more, more preferably 8 or more, more preferably 10 or more, and 22 or less. It is preferably 21 or less, still more preferably 20 or less, and even more preferably 18 or less.
- As the fatty acid metal salt if a metal salt of a fatty acid having a number of carbon atoms within the predetermined range is used, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, and to form Brown spots on the surface of the vinyl chloride resin molding can be further reduced.
- the fatty acid is stearic acid.
- the metal of the fatty acid metal salt is not particularly limited as long as it is other than zinc, but calcium and barium are preferred, and calcium is more preferred.
- the metal of the fatty acid metal salt is not particularly limited as long as it is other than zinc, but calcium and barium are preferred, and calcium is more preferred.
- the (e) fatty acid metal salt one type may be used alone, or two or more types may be mixed and used at an arbitrary ratio.
- the content of (e) fatty acid metal salt in the vinyl chloride resin composition is preferably 0.10 parts by mass or more, and 0.20 parts by mass or more, relative to 100 parts by mass of the vinyl chloride resin (a). more preferably 0.40 parts by mass or more, still more preferably 0.50 parts by mass or more, even more preferably 0.60 parts by mass or more, and 0.70 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and 1.0 It is more preferably not more than 0.86 parts by mass, and particularly preferably not more than 0.86 parts by mass.
- the content of (e) fatty acid metal salt in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variation in color tone due to differences in the molding temperature of the vinyl chloride resin composition, and the resulting vinyl chloride resin Brown spots on the surface of the molding can be further reduced.
- the content of the (e) fatty acid metal salt in the vinyl chloride resin composition is equal to or less than the above upper limit, the blooming resistance of the vinyl chloride resin molded article to be formed can be improved.
- the content of (e) fatty acid metal salt in the vinyl chloride resin composition must be at least 1.6 times the content of (d) zinc acetylacetonate, and is 1.7 times. is preferably 1.8 times or more, more preferably 1.9 times or more, still more preferably 2 times or more, preferably 6 times or less, It is more preferably 5 times or less, still more preferably 4 times or less, even more preferably 3 times or less, even more preferably 2.4 times or less, and 2.3 times or less. is particularly preferred.
- the ratio of the content of (e) fatty acid metal salt to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is at least the above lower limit, the variation in color tone due to the difference in molding temperature of the vinyl chloride resin composition can be prevented. In addition, brown spots on the surface of the formed vinyl chloride resin molding can be reduced.
- the ratio of the content of (e) fatty acid metal salt to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or less than the above upper limit, color tone will be affected by the difference in molding temperature of the vinyl chloride resin composition. The variation can be further suppressed, and the blooming resistance of the vinyl chloride resin molded article to be formed can be improved.
- the vinyl chloride resin composition of the present invention preferably further contains (d) ⁇ -diketones other than zinc acetylacetonate ((f) other ⁇ -diketones).
- ⁇ -diketones other than zinc acetylacetonate
- ⁇ -diketones include, for example, acetylacetone; metal salts of acetylacetone other than zinc, such as calcium acetylacetonate, magnesium acetylacetonate, lithium acetylacetonate, aluminum acetylacetonate and nickel acetylacetonate; and ⁇ -diketone compounds other than acetylacetone and its metal salt; and the like.
- the metal salt of the ⁇ -diketone compound other than acetylacetone is a metal complex formed by binding the conjugate base of the ⁇ -diketone compound other than acetylacetone to a metal ion.
- ⁇ -diketones include benzoyl groups such as dibenzoylmethane, stearoylbenzoylmethane, and palmitoylbenzoylmethane, from the viewpoint of further suppressing variations in color tone due to differences in molding temperature of the vinyl chloride resin composition. and more preferably stearoylbenzoylmethane.
- the content of (f) other ⁇ -diketones in the vinyl chloride resin composition is preferably 0.40 parts by mass or more, preferably 0.50 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (a). parts by mass or more, more preferably 0.60 parts by mass or more, preferably 2.00 parts by mass or less, more preferably 1.50 parts by mass or less, and 1.20 parts by mass or less. It is more preferably not more than parts by mass. If the content of (f) other ⁇ -diketones in the vinyl chloride resin composition is within the above-specified range, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the mass ratio of (f) other ⁇ -diketones to (c) uracil compound ((f) other ⁇ -diketones/(c) uracil compound) in the vinyl chloride resin composition is 2/15 or more. preferably 2/5 or more, more preferably 1/1 or more, still more preferably 4/3 or more, preferably 40/1 or less, 20/ It is more preferably 1 or less, even more preferably 5/1 or less, and even more preferably 3/1 or less.
- the mass ratio of (f) other ⁇ -diketones to (c) uracil compound ((f) other ⁇ -diketones/(c) uracil compound) in the vinyl chloride resin composition is within the above-specified range. If there is, it is possible to further suppress variation in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the mass ratio of (d) zinc acetylacetonate to (f) other ⁇ -diketones ((d) zinc acetylacetone/(f) other ⁇ -diketones) in the vinyl chloride resin composition is 1/10 or more. preferably 1/5 or more, more preferably 3/10 or more, still more preferably 2/5 or more, preferably 3/1 or less, 3/ It is more preferably 2 or less, and even more preferably 3/5 or less.
- the mass ratio of (d) zinc acetylacetonate to (f) other ⁇ -diketones ((d) zinc acetylacetone/(f) other ⁇ -diketones) in the vinyl chloride resin composition is within the above-specified range.
- the mass ratio of (d) zinc acetylacetonate to (f) other ⁇ -diketones in the vinyl chloride resin composition is 1/2. It may be greater than or equal to 1/2 or less.
- the vinyl chloride resin composition of the present invention preferably further contains (g) fatty acid zinc in addition to (e) fatty acid metal salt other than fatty acid zinc.
- the vinyl chloride resin composition of the present invention further contains (g) fatty acid zinc, it is possible to further suppress variation in color tone due to differences in molding temperature.
- the number of carbon atoms in the fatty acid of (g) fatty acid zinc is not particularly limited, but is preferably 6 or more, more preferably 8 or more, more preferably 10 or more, and preferably 22 or less. , 21 or less, and even more preferably 20 or less. If a zinc salt of a fatty acid having a number of carbon atoms within the predetermined range is used as the fatty acid zinc (g), it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, it is particularly preferable to use zinc stearate as (g) fatty acid zinc. In addition, as (g) fatty acid zinc, one type may be used alone, or two or more types may be mixed and used at an arbitrary ratio.
- the content of (g) fatty acid zinc in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, and is preferably 0.10 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin (a). more preferably 0.15 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and 2.0 parts by mass or less and more preferably 1.0 parts by mass or less.
- the content of (g) fatty acid zinc in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.
- the content of (g) fatty acid zinc in the vinyl chloride resin composition is not more than the above upper limit, brown spots on the surface of the formed vinyl chloride resin molding can be further reduced.
- the mass ratio of (e) fatty acid metal salt other than fatty acid zinc to (g) fatty acid zinc ((e) fatty acid metal salt/(g) fatty acid zinc) in the vinyl chloride resin composition is 2/1 or more. is preferably 5/2 or more, more preferably 3/1 or more, even more preferably 4/1 or more, even more preferably 5/1 or more, 20/1 It is preferably 15/1 or less, more preferably 10/1 or less.
- the mass ratio of (e) fatty acid metal salt other than fatty acid zinc and (g) fatty acid zinc ((e) fatty acid metal salt/(g) fatty acid zinc) in the vinyl chloride resin composition is within the predetermined range. It is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, and to further reduce brown spots on the surface of the vinyl chloride resin molded article to be formed.
- the vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above.
- Additives include, but are not limited to, lubricants; stabilizers such as perchloric acid-treated hydrotalcite and zeolite; release agents; dusting agents other than the vinyl chloride resin fine particles; perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); antioxidants; fungicides; flame retardants; antistatic agents; fillers; agent; pigment; and the like.
- the vinyl chloride resin composition of the present invention may contain, for example, those described in International Publication No. 2016/098344 can be used, and the preferred content thereof is also International Publication No. 2016/ It can be the same as described in No. 098344.
- the vinyl chloride resin composition of the present invention may contain silicone oil.
- silicone oil that can be contained in the vinyl chloride resin composition include the silicone oil described in JP-A-2018-35304.
- the content of the silicone oil in the vinyl chloride resin composition is not particularly limited, but is preferably 0.1 parts by mass or more, and 0.2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (a). It is more preferably at least 1 part by mass, preferably at most 1 part by mass, and more preferably at most 0.8 part by mass.
- the vinyl chloride resin composition of the present invention can be prepared by mixing the components described above.
- the above (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetone, and (e) fatty acid metal salt are further blended as necessary (
- the method of mixing f) other ⁇ -diketones, (g) fatty acid zinc and various additives is not particularly limited.
- a method of mixing by blending and then adding and mixing a dusting agent may be used.
- the temperature during dry blending is not particularly limited, and is preferably 50° C. or higher, more preferably 70° C. or higher, and preferably 200° C. or lower.
- the obtained vinyl chloride resin composition can be suitably used for powder molding, and can be suitably used for powder slush molding.
- the vinyl chloride resin molded article of the present invention is characterized by being obtained by molding the vinyl chloride resin composition described above by any method. Since the vinyl chloride resin molded article of the present invention is formed using the vinyl chloride resin composition described above, it usually contains at least (a) a vinyl chloride resin, (b) a plasticizer, and (c) It contains a uracil compound, (d) zinc acetylacetonate, and (e) a fatty acid metal salt other than fatty acid zinc, and the ratio of the content of (d) zinc acetylacetonate to the content of (c) uracil compound is equal to or greater than a predetermined value.
- the vinyl chloride resin molded article of the present invention has reduced unevenness in color tone, has less brown spots, and has an excellent appearance.
- the vinyl chloride resin molded article of the present invention can suppress changes in color tone such as yellowing even when heated at a high temperature of 270° C. or higher, for example. Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material such as an automobile instrument panel skin.
- the mold temperature during powder slush molding is not particularly limited, and is preferably 200° C. or higher, more preferably 220° C. or higher. It is more preferably 300° C. or lower, and more preferably 280° C. or lower.
- the vinyl chloride resin composition of the present invention is used for molding, the vinyl chloride resin molding of the present invention is formed. The unevenness of color tone is reduced on the body.
- the following method for example, can be used without any particular limitation. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold within the above temperature range, left to stand for 5 seconds or more and 30 seconds or less, and then the excess vinyl chloride resin composition is shaken off. , Leave for 30 seconds or more and 3 minutes or less. After that, the mold is cooled to 10° C. or higher and 60° C. or lower, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. Then, a sheet-like molded body having the shape of the mold is obtained.
- the laminate of the present invention comprises a foamed polyurethane molded article and the vinyl chloride resin molded article described above.
- the vinyl chloride resin molding usually constitutes one surface of the laminate.
- the laminate of the present invention is formed, for example, using the vinyl chloride resin composition of the present invention to provide a vinyl chloride resin molded article with reduced unevenness in color tone, less brown spots, and excellent appearance. Therefore, it is suitably used as an automobile interior part, particularly as an automobile interior material forming an automobile instrument panel.
- even when the laminate of the present invention is heated at a high temperature of 270° C. or higher, for example, it is possible to suppress changes in color tone such as yellowing of the vinyl chloride resin molding portion.
- the method for laminating the foamed polyurethane molded article and the vinyl chloride resin molded article is not particularly limited, and for example, the following method can be used. That is, (1) a method in which a foamed polyurethane molded article and a vinyl chloride resin molded article are prepared separately and then bonded together by heat sealing, thermal bonding, or using a known adhesive; (2) vinyl chloride; Isocyanates and polyols, which are the raw materials of the foamed polyurethane molded article, are reacted on the resin molded article to polymerize them, and at the same time, the polyurethane is foamed by a known method to obtain a foamed polyurethane on the vinyl chloride resin molded article.
- the latter method (2) is preferable in that the process is simple and that the vinyl chloride resin molded article and the foamed polyurethane molded article are easily adhered firmly even when laminates of various shapes are obtained. is.
- the vinyl chloride resin composition obtained in each example and comparative example was sprinkled on a textured mold heated to a temperature of 230° C., allowed to stand for an arbitrary time to melt, and then the excess vinyl chloride resin composition was shaken off. Dropped. After that, the textured mold sprinkled with the vinyl chloride resin composition was left to stand in an oven set to a temperature of 200 ° C., and when 60 seconds had passed since the standing, the textured mold was cooled with cooling water. . When the mold temperature was cooled to 40° C., the vinyl chloride resin molded sheet of 150 mm ⁇ 200 mm ⁇ 1 mm as the vinyl chloride resin molded product was removed from the mold.
- Polyesters used in Examples and Comparative Examples were prepared as follows. ⁇ Polyester A> Adipic acid as a polyhydric carboxylic acid, 3-methyl-1,5-pentanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal terminating component) were charged into a reaction vessel, and tetraisopropyl titanate was added as a catalyst. In addition, a solvent was added as appropriate, and the temperature was raised while stirring. By-product water was removed under normal pressure and reduced pressure, and finally the temperature was raised to 220-230° C. to complete the dehydration condensation reaction.
- the resulting product was subjected to thin-film distillation under conditions of a pressure of 4 to 80 Pa and an envelope temperature of 250° C. to obtain a polyester A (viscosity: 3600 mPa s, number average molecular weight: 5300, An acid value of 0.32 and a hydroxyl value of 12.7) were obtained.
- Example 1 ⁇ Preparation of vinyl chloride resin composition> Of the ingredients shown in Table 1, the ingredients excluding the plasticizer (trimellitic acid ester, polyester A, and epoxidized soybean oil) and the vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80° C., all of the plasticizer is added and dried up (the plasticizer is absorbed by the vinyl chloride resin particles, and the mixture becomes smooth. ). Thereafter, when the dried mixture was cooled to a temperature of 70° C. or less, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition. Using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 2 A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the amount of calcium stearate used was changed as shown in Table 1. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 3 A vinyl chloride resin composition was produced in the same manner as in Example 2, except that zinc stearate was not used. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 4 A vinyl chloride resin composition was produced in the same manner as in Example 2, except that barium stearate was used instead of calcium stearate. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 5 A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the amounts of zinc acetylacetonate and calcium stearate used were changed as shown in Table 1. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 6 A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the amounts of 6-amino-1,3-dimethyluracil, zinc acetylacetone and calcium stearate used were changed as shown in Table 1. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 1 A vinyl chloride resin composition was prepared in the same manner as in Example 1, except that none of 6-amino-1,3-dimethyluracil, zinc acetylacetone and calcium stearate was used. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 2 A vinyl chloride resin composition was prepared in the same manner as in Example 1, except that zinc acetylacetone and calcium stearate were not used. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 3-5 A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the amounts of zinc acetylacetonate and/or calcium stearate used were changed as shown in Table 1. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- Example 6 A vinyl chloride resin composition was prepared in the same manner as in Example 2, except that 6-amino-1,3-dimethyluracil was not used. Then, using the obtained vinyl chloride resin composition, the color tone variation due to the difference in molding temperature and the appearance (brown spots) of the vinyl chloride resin molding were evaluated. Table 1 shows the results.
- the vinyl chloride resin composition of Comparative Example 1 which does not contain any of the uracil compound, zinc acetylacetone, and fatty acid metal salt other than zinc fatty acid, cannot sufficiently suppress the variation in color tone due to the difference in molding temperature.
- the vinyl chloride resin composition of Comparative Example 2 which contains a uracil compound but does not contain zinc acetylacetonate and no fatty acid metal salt other than fatty acid zinc, the variation in color tone due to the difference in molding temperature cannot be sufficiently suppressed. I understand.
- vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetonate, and a fatty acid metal salt other than zinc fatty acid are included, but the ratio of the content of zinc acetylacetonate to the content of the uracil compound is less than a predetermined value.
- the uracil compound contains a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetonate, and a fatty acid metal salt other than zinc fatty acid, and the ratio of the content of zinc acetylacetonate to the content of the uracil compound is a predetermined value or more.
- the vinyl-chloride resin composition which can form a vinyl-chloride-resin molded object which suppresses the fluctuation
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Abstract
Description
具体的には、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品の形成には、塩化ビニル樹脂成形体からなる表皮や塩化ビニル樹脂成形体からなる表皮に発泡ポリウレタン等の発泡体を裏打ちしてなる積層体などの自動車内装材が用いられている。
しかしながら、本発明者が更に検討したところ、上記ウラシル化合物とアセチルアセトン亜鉛とを含む塩化ビニル樹脂組成物は、当該塩化ビニル樹脂組成物を成形して得られる塩化ビニル樹脂成形体の表面に発生する茶色の斑点を少なくする点に改善の余地があった。
また、上記ウラシル化合物とアセチルアセトン亜鉛とを含む塩化ビニル樹脂組成物は、成形温度の差による色調の変動を抑制する点にも更なる改善の余地があった。
また、本発明は、当該塩化ビニル樹脂組成物を用いて形成され、茶色の斑点が少ない塩化ビニル樹脂成形体を提供することを目的とする。
さらに、本発明は、当該塩化ビニル樹脂成形体を備える積層体を提供することを目的とする。
このように、塩化ビニル樹脂と、可塑剤と、ウラシル化合物と、アセチルアセトン亜鉛と、脂肪酸亜鉛以外の脂肪酸金属塩とを含む塩化ビニル樹脂組成物において、ウラシル化合物の含有量に対するアセチルアセトン亜鉛の含有量の倍率を所定値以上とし、且つ、アセチルアセトン亜鉛の含有量に対する脂肪酸亜鉛以外の脂肪酸金属塩の含有量の倍率を所定値以上とすれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を抑制しつつ、塩化ビニル樹脂組成物を成形して得られる塩化ビニル樹脂成形体の表面の茶色の斑点を少なくすることができる。
R3は水素原子またはアミノ基を表す。〕で示されることが好ましい。
ウラシル化合物が上記所定の式で示される化合物であれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制することができる。
ウラシル化合物として、6-アミノ-1,3-ジメチルウラシルを用いれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制することができる。
塩化ビニル樹脂組成物中のウラシル化合物の含有量が上記所定値以上であれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制することができる。
塩化ビニル樹脂組成物が脂肪酸金属塩として脂肪酸カルシウムおよび脂肪酸バリウムの少なくとも一方を含めば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制し得ると共に、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を更に少なくすることができる。
脂肪酸亜鉛以外の脂肪酸金属塩として、炭素数が6以上22以下である脂肪酸の金属塩を用いれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制し得ると共に、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を更に少なくすることができる。
塩化ビニル樹脂組成物を粉体成形に用いれば、例えば、自動車インスツルメントパネル用表皮などの自動車内装材として良好に使用し得る塩化ビニル樹脂成形体が容易に得られる。
塩化ビニル樹脂組成物をパウダースラッシュ成形に用いれば、例えば、自動車インスツルメントパネル用表皮などの自動車内装材として良好に使用し得る塩化ビニル樹脂成形体がより容易に得られる。
このように、上述した塩化ビニル樹脂組成物を成形してなる塩化ビニル樹脂成形体は、色調のムラが低減されると共に、茶色の斑点が少なく、外観に優れているため、自動車内装材として良好に使用することができる。
本発明の塩化ビニル樹脂成形体を自動車インスツルメントパネルの表皮に使用すれば、色調のムラが低減され、茶色の斑点が少なく、外観に優れた表皮を有する自動車インスツルメントパネルを製造することができる。
発泡ポリウレタン成形体および上述した塩化ビニル樹脂成形体を有する積層体は、色調のムラが低減され、茶色の斑点が少なく、外観に優れた塩化ビニル樹脂成形体部分を備えている。
このように、本発明の積層体を自動車インスツルメントパネルに用いれば、製造される自動車インスツルメントパネルの表皮における色調のムラを低減すると共に、茶色の斑点を少なくし、外観を良好にすることができる。
また、本発明によれば、当該塩化ビニル樹脂組成物を用いて形成され、茶色の斑点が少ない塩化ビニル樹脂成形体を提供することができる。
さらに、本発明によれば、当該塩化ビニル樹脂成形体を備える積層体を提供することができる。
本発明の塩化ビニル樹脂組成物は、例えば、本発明の塩化ビニル樹脂成形体を形成する際に用いることができる。そして、本発明の塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体は、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品が備える表皮などの、自動車内装材として好適に用いることができる。
また、本発明の塩化ビニル樹脂成形体は、例えば、本発明の積層体を形成する際に用いることができる。そして、本発明の塩化ビニル樹脂成形体を用いて形成した積層体は、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品を製造する際に用いる自動車内装材として好適に用いることができる。
本発明の塩化ビニル樹脂組成物は、(a)塩化ビニル樹脂と、(b)可塑剤と、(c)ウラシル化合物と、(d)アセチルアセトン亜鉛と、脂肪酸亜鉛以外の(e)脂肪酸金属塩とを含み、(c)ウラシル化合物の含有量に対する(d)アセチルアセトン亜鉛の含有量の倍率が所定値以上であり、且つ、(d)アセチルアセトン亜鉛の含有量に対する(e)脂肪酸金属塩の含有量が所定値以上であることを特徴とする。なお、本明細書中において、単に「(e)脂肪酸金属塩」というときは、脂肪酸亜鉛を除く脂肪酸金属塩を指すものとする。
また、本発明の塩化ビニル樹脂組成物は、任意で、(g)脂肪酸亜鉛を更に含み得る。
さらに、本発明の塩化ビニル樹脂組成物は、上記(a)塩化ビニル樹脂、(b)可塑剤、(c)ウラシル化合物、(d)アセチルアセトン亜鉛、(e)脂肪酸金属塩、(f)その他のβ-ジケトン類、および(g)脂肪酸亜鉛以外の添加剤を更に含んでいてもよい。
また、本発明の塩化ビニル樹脂組成物を用いて形成された塩化ビニル樹脂成形体は、例えば、270℃以上の高温で加熱された場合であっても、黄ばみ等の色調の変化を抑制することができる。
(a)塩化ビニル樹脂としては、通常、粒子状の塩化ビニル樹脂を用いる。そして、(a)塩化ビニル樹脂としては、例えば、1種類または2種類以上の塩化ビニル樹脂粒子を含有することができ、任意に、1種類または2種類以上の塩化ビニル樹脂微粒子を更に含有することができる。中でも、(a)塩化ビニル樹脂は、少なくとも塩化ビニル樹脂粒子を含有することが好ましく、塩化ビニル樹脂粒子および塩化ビニル樹脂微粒子を含有することがより好ましい。
そして、(a)塩化ビニル樹脂は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法など、従来から知られているいずれの製造法によっても製造し得る。
なお、本明細書において、「樹脂粒子」とは、粒子径が30μm以上の粒子を指し、「樹脂微粒子」とは、粒子径が30μm未満の粒子を指す。
塩化ビニル樹脂組成物において、塩化ビニル樹脂粒子は、通常、マトリックス樹脂(基材)として機能する。なお、塩化ビニル樹脂粒子は、懸濁重合法により製造することが好ましい。
そして、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度は、800以上であることが好ましく、1000以上であることがより好ましく、5000以下であることが好ましく、3000以下であることがより好ましく、2800以下であることが更に好ましい。塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記下限以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ、例えば、引張特性、特には引張伸びをより良好にできるからである。そして、引張伸びが良好な塩化ビニル樹脂成形体は、例えば、エアバッグが膨張、展開した際に、破片が飛散することなく設計通りに割れる、延性に優れた自動車インスツルメントパネルの表皮などの自動車内装材として好適に用いることができる。また、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性を向上させることができるからである。
なお、本発明において「平均重合度」は、JIS K6720-2に準拠して測定することができる。
また、塩化ビニル樹脂粒子の平均粒子径は、通常30μm以上であり、50μm以上が好ましく、100μm以上がより好ましく、500μm以下が好ましく、200μm以下がより好ましい。塩化ビニル樹脂粒子の平均粒子径が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性が向上するからである。また、塩化ビニル樹脂粒子の平均粒子径が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性がより向上すると共に、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上できるからである。
なお、本発明において、「平均粒子径」は、JIS Z8825に準拠し、レーザー回折法により体積平均粒子径として測定することができる。
そして、(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合は、70質量%以上であることが好ましく、80質量%以上であることがより好ましく、100質量%とすることができ、95質量%以下であることが好ましく、90質量%以下であることがより好ましい。(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が上記下限以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ引張伸びを良好にできるからである。また、(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が上記上限以下であれば、塩化ビニル樹脂組成物の粉体流動性が向上するからである。
塩化ビニル樹脂組成物において、塩化ビニル樹脂微粒子は、通常、ダスティング剤(粉体流動性改良剤)として機能する。なお、塩化ビニル樹脂微粒子は、乳化重合法により製造することが好ましい。
そして、塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度は、500以上が好ましく、700以上がより好ましく、2600以下が好ましく、2400以下がより好ましい。ダスティング剤としての塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性が向上すると共に、当該組成物を用いて得られる成形体の引張伸びがより良好になるからである。また、塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性が向上し、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性が向上するからである。
また、塩化ビニル樹脂微粒子の平均粒子径は、通常30μm未満であり、10μm以下であることが好ましく、5μm以下であることがより好ましく、0.1μm以上であることが好ましく、1μm以上であることがより好ましい。塩化ビニル樹脂微粒子の平均粒子径が上記下限以上であれば、例えばダスティング剤としてのサイズを過度に小さくすることなく、塩化ビニル樹脂組成物の粉体流動性を向上するからである。また、塩化ビニル樹脂微粒子の平均粒子径が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性がより高まり、形成される塩化ビニル樹脂成形体の表面平滑性を更に向上させることができるからである。
そして、(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合は、0質量%であってもよいが、5質量%以上であることが好ましく、10質量%以上であることがより好ましく、30質量%以下であることが好ましく、20質量%以下であることがより好ましい。(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性が向上するからである。また、(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が上記上限以下であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度をより高めることができるからである。
本発明の塩化ビニル樹脂組成物は(b)可塑剤を含む。塩化ビニル樹脂組成物が(b)可塑剤を含むことにより、形成される塩化ビニル樹脂成形体は十分な柔軟性を発揮することができるため、例えば自動車内装材として好適に使用することができる。
(b)可塑剤は、(b1)ポリエステルを含むことが好ましい。(b)可塑剤が(b1)ポリエステルを含めば、形成される塩化ビニル樹脂成形体の耐熱収縮性を高めることができる。
中でも、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制すると共に、形成される塩化ビニル樹脂成形体の加熱後の耐熱収縮性を更に高める観点から、(b1)ポリエステルとしては、アジピン酸由来の構造単位を含有するポリエステルを用いることが好ましく、アジピン酸由来の構造単位と、3-メチル-1,5-ペンタンジオール由来の構造単位とを含有するポリエステルを用いることが特に好ましい。
ここで、上記所定の構造単位を含有するポリエステルAは、アジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位以外の構造単位を有していてもよいが、アジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位の合計が、全構造単位の50質量%以上であることが好ましく、80質量%以上であることがより好ましい。また、上記所定の構造単位を含有するポリエステルAは、繰り返し単位としてアジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位のみを有することが好ましい。
なお、上記所定の構造単位を含有するポリエステルAとしては、市販品を用いてもよい。
更に、末端停止成分として使用し得る一塩基酸としては、例えば、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、ピバル酸、カプロン酸、ヘプタン酸、カプリル酸、2-エチルヘキシル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、安息香酸およびそれらの混合物が挙げられる。
中でも、末端停止成分としては、2-エチルヘキサノールが好ましい。
なお、「数平均分子量」は、VPO(蒸気圧浸透圧)法にて測定することができる。
また、上記所定の構造単位を含有するポリエステルAは、酸価が1以下であることが好ましい。
更に、上記所定の構造単位を含有するポリエステルAは、水酸基価が30以下であることが好ましい。
なお、「粘度」は、JIS Z8803に準拠し、温度23℃で測定することができる。
(b)可塑剤は、(b2)トリメリット酸エステルを含むことが好ましい。(b)可塑剤が(b2)トリメリット酸エステルを含めば、(b2)トリメリット酸エステルは上記(a)塩化ビニル樹脂に良好に吸収されるため、塩化ビニル樹脂組成物の粉体流動性を高めることができる。また、(b)可塑剤が(b2)トリメリット酸エステルを含めば、形成される塩化ビニル樹脂成形体の低温での柔軟性を高めることができる。
上記(b2)トリメリット酸エステルは、単一の化合物からなるものであってもよいし、異なる化合物の混合物であってもよい。
より好ましい(b2)トリメリット酸エステルの具体例は、トリメリット酸トリ-n-オクチル、トリメリット酸トリ-(2-エチルヘキシル)、トリメリット酸トリ-n-ノニル、トリメリット酸トリ-n-デシル、トリメリット酸トリ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~18である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。
塩化ビニル樹脂組成物に含まれる(b)可塑剤は、任意で、上述した(b1)ポリエステル、および(b2)トリメリット酸エステル以外の(b3)その他の可塑剤を含んでいてもよい。
なお、形成される塩化ビニル樹脂成形体の低温での柔軟性を更に高める観点から、(b3)その他の可塑剤として、エポキシ化大豆油などのエポキシ化植物油を、上記(a)塩化ビニル樹脂100質量部に対して2質量部以上7質量部以下用いることが好ましい。
本発明の塩化ビニル樹脂組成物は、(c)ウラシル化合物を含む。本発明の塩化ビニル樹脂組成物は(c)ウラシル化合物を含むことにより、成形温度の差による色調の変動を抑制することができる。また、本発明の塩化ビニル樹脂組成物では、(c)ウラシル化合物と、後述する(d)アセチルアセトン亜鉛および(e)脂肪酸金属塩とを併用することにより、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を少なくすることができる。
そして、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制する観点から、(c)ウラシル化合物は下記式(I):
R3は水素原子またはアミノ基を表す。〕
で示されることが好ましい。
そして、上記式(I)中、R1および/またはR2が電子供与基である場合、電子供与基としては、特に限定されないが、アルキル基、アミノ基、ジアルキルアミノ基等を挙げることができる。中でも、塩化ビニル樹脂組成物の成形温度の差による色調の変動を一層抑制する観点から、電子供与基としては、アルキル基が好ましく、炭素数が6以下であるアルキル基がより好ましく、メチル基が最も好ましい。
なお、上記式(I)中、R1とR2とは、同じであってもよいし、異なっていてもよいものとする。
本発明の塩化ビニル樹脂組成物は、(d)アセチルアセトン亜鉛を含む。本発明の塩化ビニル樹脂組成物は、(d)アセチルアセトン亜鉛を含むことにより、成形温度の差による色調の変動を抑制することができる。
本発明の塩化ビニル樹脂組成物は、(e)脂肪酸金属塩を含む。(e)脂肪酸金属塩は、脂肪酸の亜鉛以外の金属塩である。本発明の塩化ビニル樹脂組成物は、脂肪酸亜鉛以外の(e)脂肪酸金属塩を含むことにより、成形温度の差による色調の変動を抑制することができる。さらに、本発明の塩化ビニル樹脂組成物は、脂肪酸亜鉛以外の(e)脂肪酸金属塩を含むことにより、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を少なくすることができる。
そして、塩化ビニル樹脂組成物の成形温度の差による色調の変動を一層抑制しつつ、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を一層少なくする観点から、(e)脂肪酸金属塩の脂肪酸は、ステアリン酸であることが特に好ましい。
本発明の塩化ビニル樹脂組成物は、上述した(d)アセチルアセトン亜鉛以外のβ-ジケトン類((f)その他のβ-ジケトン類)を更に含むことが好ましい。上述した(d)アセチルアセトン亜鉛に加えて、(f)その他のβ-ジケトン類を更に用いれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制することができる。
本発明の塩化ビニル樹脂組成物は、脂肪酸亜鉛以外の(e)脂肪酸金属塩に加えて、(g)脂肪酸亜鉛を更に含むことが好ましい。本発明の塩化ビニル樹脂組成物が(g)脂肪酸亜鉛を更に含むことにより、成形温度の差による色調の変動を更に抑制することができる。
そして、塩化ビニル樹脂組成物の成形温度の差による色調の変動をより一層抑制する観点から、(g)脂肪酸亜鉛としては、ステアリン酸亜鉛を用いることが特に好ましい。
なお、(g)脂肪酸亜鉛としては、1種を単独で用いてもよいし、2種以上を任意の比率で混合して用いてもよい。
本発明の塩化ビニル樹脂組成物は、上述した成分以外に、各種添加剤を更に含有してもよい。添加剤としては、特に限定されることなく、滑剤;過塩素酸処理ハイドロタルサイト、ゼオライトなどの安定剤;離型剤;上記塩化ビニル樹脂微粒子以外のその他のダスティング剤;耐衝撃性改良剤;過塩素酸処理ハイドロタルサイト以外の過塩素酸化合物(過塩素酸ナトリウム、過塩素酸カリウム等);酸化防止剤;防カビ剤;難燃剤;帯電防止剤;充填剤;光安定剤;発泡剤;顔料;などが挙げられる。
なお、塩化ビニル樹脂組成物が含み得るシリコーンオイルとしては、例えば、特開2018-35304号公報に記載のシリコーンオイルなどが挙げられる。
そして、塩化ビニル樹脂組成物中におけるシリコーンオイルの含有量は、特に限定されないが、上記(a)塩化ビニル樹脂100質量部に対して、0.1質量部以上であることが好ましく、0.2質量部以上であることがより好ましく、1質量部以下であることが好ましく、0.8質量部以下であることがより好ましい。
本発明の塩化ビニル樹脂組成物は、上述した成分を混合して調製することができる。
ここで、上記(a)塩化ビニル樹脂と、(b)可塑剤と、(c)ウラシル化合物と、(d)アセチルアセトン亜鉛と、(e)脂肪酸金属塩と、必要に応じて更に配合される(f)その他のβ-ジケトン類、(g)脂肪酸亜鉛および各種添加剤との混合方法としては、特に限定されることなく、例えば、ダスティング剤(塩化ビニル樹脂微粒子を含む)を除く成分をドライブレンドにより混合し、その後、ダスティング剤を添加、混合する方法が挙げられる。ここで、ドライブレンドには、ヘンシェルミキサーの使用が好ましい。また、ドライブレンド時の温度は、特に制限されることなく、50℃以上が好ましく、70℃以上がより好ましく、200℃以下が好ましい。
そして、得られた塩化ビニル樹脂組成物は、粉体成形に好適に用いることができ、パウダースラッシュ成形により好適に用いることができる。
本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を、任意の方法で成形することにより得られることを特徴とする。そして、本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を用いて形成されているため、通常、少なくとも、(a)塩化ビニル樹脂と、(b)可塑剤と、(c)ウラシル化合物と、(d)アセチルアセトン亜鉛と、脂肪酸亜鉛以外の(e)脂肪酸金属塩とを含み、(c)ウラシル化合物の含有量に対する(d)アセチルアセトン亜鉛の含有量の倍率が所定値以上であり、且つ、(d)アセチルアセトン亜鉛の含有量に対する(e)脂肪酸金属塩の含有量の倍率が所定値以上である。そして、本発明の塩化ビニル樹脂成形体は、色調のムラが低減されると共に、茶色の斑点が少なく、外観に優れている。
また、本発明の塩化ビニル樹脂成形体は、例えば、270℃以上の高温で加熱された場合であっても、黄ばみ等の色調の変化を抑制することができる。
したがって、本発明の塩化ビニル樹脂成形体は、自動車インスツルメントパネルの表皮などの自動車内装材として好適に用いることができる。
ここで、パウダースラッシュ成形により塩化ビニル樹脂成形体を形成する場合、パウダースラッシュ成形時の金型温度は、特に制限されることなく、200℃以上とすることが好ましく、220℃以上とすることがより好ましく、300℃以下とすることが好ましく、280℃以下とすることがより好ましい。
なお、例えばパウダースラッシュ成形時の金型に温度分布が存在する場合であっても、上述した本発明の塩化ビニル樹脂組成物を成形に用いているため、形成される本発明の塩化ビニル樹脂成形体は色調のムラが低減されている。
本発明の積層体は、発泡ポリウレタン成形体と、上述した塩化ビニル樹脂成形体とを有する。なお、塩化ビニル樹脂成形体は、通常、積層体の一方の表面を構成する。
そして、本発明の積層体は、例えば、本発明の塩化ビニル樹脂組成物を用いて形成され、色調のムラが低減されると共に、茶色の斑点が少なく、外観に優れた塩化ビニル樹脂成形体を有しているため、自動車内装部品、特に、自動車インスツルメントパネルを形成する自動車内装材として好適に用いられる。
また、本発明の積層体は、例えば270℃以上の高温で加熱された場合であっても、塩化ビニル樹脂成形体部分の黄ばみ等の色調の変化を抑制することができる。
そして、塩化ビニル樹脂組成物の成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)は、下記の方法で測定および評価した。
各実施例および比較例で得られた塩化ビニル樹脂組成物を、温度230℃に加熱したシボ付き金型に振りかけ、任意の時間放置して溶融させた後、余剰の塩化ビニル樹脂組成物を振り落とした。その後、当該塩化ビニル樹脂組成物を振りかけたシボ付き金型を、温度200℃に設定したオーブン内に静置し、静置から60秒経過した時点で当該シボ付き金型を冷却水で冷却した。金型温度が40℃まで冷却された時点で、塩化ビニル樹脂成形体としての、150mm×200mm×1mmの塩化ビニル樹脂成形シートを金型から脱型した。
また、金型の温度を230℃から270℃に上げたこと以外は上記と同じ操作にて成形を行った。
230℃および270℃の各々の金型温度で成形して得られた塩化ビニル樹脂成形シートの色調を分光測色計(コニカミノルタ製「CM-700d」)により測色した。なお、塩化ビニル樹脂成形シートのシボ付き面を9分割したマスのそれぞれの中央点を合計で9点測色し、b*の値の平均値を求めた。そして、金型温度270℃におけるb*の値の平均値から、金型温度230℃におけるb*の値の平均値を差し引くことにより、Δb*の値を算出した。Δb*の値の値が小さいほど、塩化ビニル樹脂組成物は成形温度の差による色調の変動が抑制されていることを示す。
上述した成形温度の差による色調の変動の評価方法において、塩化ビニル樹脂組成物を金型温度270℃で成形した場合に得られた塩化ビニル樹脂成形シート(塩化ビニル樹脂成形体)のシボ付きの面を目視にて観察し、茶色の斑点の有無を判定した。塩化ビニル樹脂成形体の表面に茶色の斑点が無ければ、当該塩化ビニル樹脂成形体は外観に優れているといえる。
実施例および比較例で使用したポリエステルは、以下のようにして調製した。
<ポリエステルA>
多価カルボン酸としてのアジピン酸、多価アルコールとしての3-メチル-1,5-ペンタンジオール、及びストッパー(末端停止成分)としての2-エチルヘキサノールを反応容器に仕込み、触媒としてテトライソプロピルチタネートを加え、適宜溶剤を添加し、攪拌しながら昇温した。副生する水は常圧および減圧で除去し、最終的に220~230℃まで温度を上げて脱水縮合反応を完結させた。得られた生成物について、圧力4~80Pa、外套温度250℃の条件下で薄膜蒸留を行なうことで、末端が2-エチルヘキソキシ基からなるポリエステルA(粘度:3600mPa・s、数平均分子量:5300、酸価:0.32、水酸基価:12.7)を得た。
<塩化ビニル樹脂組成物の調製>
表1に示す配合成分のうち、可塑剤(トリメリット酸エステル、ポリエステルA、およびエポキシ化大豆油)と、ダスティング剤である塩化ビニル樹脂微粒子とを除く成分をヘンシェルミキサーに入れて混合した。そして、混合物の温度が80℃に上昇した時点で上記可塑剤を全て添加し、ドライアップ(可塑剤が、塩化ビニル樹脂である塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。)させた。その後、ドライアップさせた混合物が温度70℃以下に冷却された時点でダスティング剤である塩化ビニル樹脂微粒子を添加し、塩化ビニル樹脂組成物を調製した。
得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
ステアリン酸カルシウムの使用量を表1に示すように変更したこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
ステアリン酸亜鉛を使用しなかったこと以外は実施例2と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
ステアリン酸カルシウムに代えてステアリン酸バリウムを用いたこと以外は実施例2と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
アセチルアセトン亜鉛およびステアリン酸カルシウムの使用量を表1に示すように変更したこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
6-アミノ-1,3-ジメチルウラシル、アセチルアセトン亜鉛およびステアリン酸カルシウムの使用量を表1に示すように変更したこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
6-アミノ-1,3-ジメチルウラシル、アセチルアセトン亜鉛およびステアリン酸カルシウムをいずれも使用しなかったこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
アセチルアセトン亜鉛およびステアリン酸カルシウムをいずれも使用しなかったこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
アセチルアセトン亜鉛および/またはステアリン酸カルシウムの使用量を表1に示す通りに変更したこと以外は実施例1と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
6-アミノ-1,3-ジメチルウラシルを使用しなかったこと以外は実施例2と同様にして、塩化ビニル樹脂組成物を作製した。そして、得られた塩化ビニル樹脂組成物を用いて、成形温度の差による色調の変動、および、塩化ビニル樹脂成形体の外観(茶色の斑点)を評価した。結果を表1に示す。
2)新第一塩ビ社製、製品名「ZEST PQLTX」(乳化重合法で調製、平均重合度:800、平均粒子径:1.8μm)
3)花王社製、製品名「トリメックスN-08」
4)ADEKA社製、製品名「アデカサイザー O-130S」
5)協和化学工業社製、製品名「アルカマイザー(登録商標)5」
6)水澤化学工業社製、製品名「MIZUKALIZER DS」
7)昭和電工社製、製品名「カレンズDK-1」
8)ADEKA社製、製品名「アデカスタブ LA-63P」
9)堺化学工業社、製品名「SAKAI SZ2000」
10)ADEKA社製、製品名「アデカスタブ LS-12」
11)信越シリコーン社製、製品名「KF-96H-30万cs」(未変性シリコーンオイル(ポリジメチルシロキサン)、粘度:30×104cs)
12)大日精化社製、製品名「DA P-1050ホワイト」
13)大日精化社製、製品名「DA PX-1446イエロー」
一方、ウラシル化合物、アセチルアセトン亜鉛、および、脂肪酸亜鉛以外の脂肪酸金属塩のいずれも含まない比較例1の塩化ビニル樹脂組成物では、成形温度の差による色調の変動を十分に抑制できないことが分かる。
また、ウラシル化合物を含むが、アセチルアセトン亜鉛、および、脂肪酸亜鉛以外の脂肪酸金属塩のいずれも含まない比較例2の塩化ビニル樹脂組成物においても、成形温度の差による色調の変動を十分に抑制できないことが分かる。
さらに、塩化ビニル樹脂と、可塑剤と、ウラシル化合物と、アセチルアセトン亜鉛と、脂肪酸亜鉛以外の脂肪酸金属塩とを含むが、ウラシル化合物の含有量に対するアセチルアセトン亜鉛の含有量の倍率が所定値未満であり、アセチルアセトン亜鉛の含有量に対する所定の脂肪酸金属塩の含有量の倍率も所定値未満である比較例3の塩化ビニル樹脂組成物は、成形温度の差による色調の変動を十分に抑制できず、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を十分に減らすことができないことが分かる。
また、塩化ビニル樹脂と、可塑剤と、ウラシル化合物と、アセチルアセトン亜鉛と、脂肪酸亜鉛以外の脂肪酸金属塩とを含み、ウラシル化合物の含有量に対するアセチルアセトン亜鉛の含有量の倍率が所定値以上であるが、アセチルアセトン亜鉛の含有量に対する所定の脂肪酸金属塩の含有量の倍率が所定値未満である比較例4~5の塩化ビニル樹脂組成物は、少なくとも、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を十分に減らすことができないことが分かる。
さらに、アセチルアセトン亜鉛、および、脂肪酸亜鉛以外の脂肪酸金属塩を含むが、ウラシル化合物を含まない比較例6の塩化ビニル樹脂組成物においては、成形温度の差による色調の変動を十分に抑制できず、形成される塩化ビニル樹脂成形体の表面の茶色の斑点を十分に減らすことができないことが分かる。
また、本発明によれば、当該塩化ビニル樹脂組成物を用いて形成され、茶色い斑点が少ない塩化ビニル樹脂成形体を提供することができる。
さらに、本発明によれば、当該塩化ビニル樹脂成形体を備える積層体を提供することができる。
Claims (12)
- 塩化ビニル樹脂と、
可塑剤と、
ウラシル化合物と、
アセチルアセトン亜鉛と、
脂肪酸亜鉛以外の脂肪酸金属塩と、を含み、
前記アセチルアセトン亜鉛の含有量が前記ウラシル化合物の含有量の0.5倍以上であり、
前記脂肪酸金属塩の含有量が前記アセチルアセトン亜鉛の含有量の1.6倍以上である、塩化ビニル樹脂組成物。 - 前記ウラシル化合物が、6-アミノ-1,3-ジメチルウラシルを含む、請求項1に記載の塩化ビニル樹脂組成物。
- 前記ウラシル化合物の含有量が、前記塩化ビニル樹脂100質量部に対して0.05質量部以上である、請求項1に記載の塩化ビニル樹脂組成物。
- 前記脂肪酸金属塩が、脂肪酸カルシウムおよび脂肪酸バリウムの少なくとも一方を含有する、請求項1に記載の塩化ビニル樹脂組成物。
- 前記脂肪酸金属塩が、炭素数が6以上22以下である脂肪酸の金属塩を含有する、請求項1に記載の塩化ビニル樹脂組成物。
- 粉体成形に用いられる、請求項1に記載の塩化ビニル樹脂組成物。
- パウダースラッシュ成形に用いられる、請求項1に記載の塩化ビニル樹脂組成物。
- 請求項1~8のいずれかに記載の塩化ビニル樹脂組成物を成形してなる、塩化ビニル樹脂成形体。
- 自動車インスツルメントパネル表皮用である、請求項9に記載の塩化ビニル樹脂成形体。
- 発泡ポリウレタン成形体と、請求項9に記載の塩化ビニル樹脂成形体とを有する、積層体。
- 自動車インスツルメントパネル用である、請求項11に記載の積層体。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09125058A (ja) * | 1995-10-13 | 1997-05-13 | Ciba Geigy Ag | 塩素含有ポリマーのための安定剤の組合せ |
JP2004285275A (ja) * | 2003-03-24 | 2004-10-14 | Hirakawa Hewtech Corp | ポリ塩化ビニル樹脂組成物、絶縁電線、ケーブル及びそれらの製造方法 |
JP2009091540A (ja) * | 2007-06-29 | 2009-04-30 | Mitsubishi Rayon Co Ltd | グラフト共重合体、樹脂組成物及びその成形品 |
JP2009132758A (ja) * | 2007-11-28 | 2009-06-18 | Adeka Corp | 塩化ビニル樹脂組成物 |
WO2016098344A1 (ja) | 2014-12-17 | 2016-06-23 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物及びその製造方法、塩化ビニル樹脂成形体及びその製造方法、並びに、積層体 |
JP2018035304A (ja) | 2016-09-02 | 2018-03-08 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体、および積層体 |
WO2019151355A1 (ja) * | 2018-02-02 | 2019-08-08 | 株式会社Adeka | 安定剤組成物、これを含有する塩化ビニル系樹脂組成物、およびその成形体 |
WO2021193165A1 (ja) * | 2020-03-24 | 2021-09-30 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
WO2022138937A1 (ja) * | 2020-12-24 | 2022-06-30 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
-
2022
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09125058A (ja) * | 1995-10-13 | 1997-05-13 | Ciba Geigy Ag | 塩素含有ポリマーのための安定剤の組合せ |
JP2004285275A (ja) * | 2003-03-24 | 2004-10-14 | Hirakawa Hewtech Corp | ポリ塩化ビニル樹脂組成物、絶縁電線、ケーブル及びそれらの製造方法 |
JP2009091540A (ja) * | 2007-06-29 | 2009-04-30 | Mitsubishi Rayon Co Ltd | グラフト共重合体、樹脂組成物及びその成形品 |
JP2009132758A (ja) * | 2007-11-28 | 2009-06-18 | Adeka Corp | 塩化ビニル樹脂組成物 |
WO2016098344A1 (ja) | 2014-12-17 | 2016-06-23 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物及びその製造方法、塩化ビニル樹脂成形体及びその製造方法、並びに、積層体 |
JP2018035304A (ja) | 2016-09-02 | 2018-03-08 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体、および積層体 |
WO2019151355A1 (ja) * | 2018-02-02 | 2019-08-08 | 株式会社Adeka | 安定剤組成物、これを含有する塩化ビニル系樹脂組成物、およびその成形体 |
WO2021193165A1 (ja) * | 2020-03-24 | 2021-09-30 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
WO2022138937A1 (ja) * | 2020-12-24 | 2022-06-30 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
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