TWI818113B - 聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體 - Google Patents
聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體 Download PDFInfo
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- TWI818113B TWI818113B TW108140426A TW108140426A TWI818113B TW I818113 B TWI818113 B TW I818113B TW 108140426 A TW108140426 A TW 108140426A TW 108140426 A TW108140426 A TW 108140426A TW I818113 B TWI818113 B TW I818113B
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- Prior art keywords
- polyolefin
- nucleating agent
- based resin
- film
- tert
- Prior art date
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- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 171
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 120
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 16
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000004429 atom Chemical group 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- -1 amine compounds Chemical class 0.000 claims description 101
- 239000003963 antioxidant agent Substances 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 15
- 239000000806 elastomer Substances 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 239000002530 phenolic antioxidant Substances 0.000 claims description 15
- 239000000975 dye Substances 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 239000002216 antistatic agent Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000011734 sodium Chemical group 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 239000011777 magnesium Chemical group 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000011575 calcium Chemical group 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Chemical group 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- HDVDLQFPDLTOSI-UHFFFAOYSA-L O[AlH]O Chemical group O[AlH]O HDVDLQFPDLTOSI-UHFFFAOYSA-L 0.000 claims description 2
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical group [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 70
- 230000000694 effects Effects 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 235000006708 antioxidants Nutrition 0.000 description 29
- 239000000047 product Substances 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000008188 pellet Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
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- 230000003078 antioxidant effect Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
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- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 229920001567 vinyl ester resin Polymers 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- CKLJMWTZIZZHCS-REOHCLBHSA-N aspartic acid group Chemical group N[C@@H](CC(=O)O)C(=O)O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 8
- 241000208340 Araliaceae Species 0.000 description 7
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 7
- 235000003140 Panax quinquefolius Nutrition 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 235000008434 ginseng Nutrition 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
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- 239000002280 amphoteric surfactant Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
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- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229960003742 phenol Drugs 0.000 description 4
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- 239000010959 steel Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
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- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 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
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 238000003860 storage Methods 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
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- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
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- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 2
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- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 2
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- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
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- CAPOZRICGSDRLP-UHFFFAOYSA-N tris(2,3-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(OP(=O)(OC=2C(=C(C)C=CC=2)C)OC=2C(=C(C)C=CC=2)C)=C1C CAPOZRICGSDRLP-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
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- RSJKGSCJYJTIGS-BJUDXGSMSA-N undecane Chemical compound CCCCCCCCCC[11CH3] RSJKGSCJYJTIGS-BJUDXGSMSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供具有優良之β晶形成作用的聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體。
含有下述通式(1)表示之化合物
(通式(1)中,M表示1~3價之比重為4.0以下之金屬原子等,a表示1或2,b表示1或3,x表示1~3之整數,且滿足ax=2b。Z表示下述通式(2)或(3)表示之基;
(通式(2)及(3)中,*表示與通式(1)之Z連結的位置,Y表示直接鍵結,或碳原子數1~4之伸烷基,R1
~R10
係分別獨立地表示氫原子、羥基、鹵素原子、碳原子數1~10之烷基等))。
Description
本發明係關於聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體(以下亦僅稱為「核劑」、「核劑組成物」、「母料」及「樹脂組成物」),詳而言之,係關於具有優良之β晶形成作用的聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體。
聚烯烴系樹脂,於各種熱可塑性通用樹脂中,尤其在物性、成形加工性、價格等之觀點,係作為應用領域最廣的塑膠材料之一,而使用於廣泛的用途。特別是聚烯烴系樹脂,由於可對成形品賦予優良的耐熱性、透明性、耐衝擊性、剛性、氣體阻斷性等,因此於各種領域之利用受到期待。
聚烯烴系樹脂為結晶性樹脂,除了熱力學上最安定之α晶(單斜晶)以外,亦已知藉由於特定之核劑共存下進行結晶化,會形成β晶(三方晶)。聚烯烴系樹脂之β晶,相較於α晶,具有低熔點、低比重、高耐衝擊性、優良延伸性、優良耐熱性等之特徴。作為使聚烯烴系樹脂優先形成β晶之核劑,於專利文獻1揭示由N,N’-二環己基-2,6-萘二羧醯胺所成之核劑。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開平5-310665號公報
[發明所欲解決之課題]
但是,專利文獻1中提出之核劑,關於β晶形成作用,不一定為充分者,現狀係期望有β晶形成作用優良的新穎核劑。
因而,本發明之目的,為提供具有優良之β晶形成作用的聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體。
[用以解決課題之手段]
本發明者等人,為了解決上述課題而深入探討的結果,發現包含天門冬胺酸結構之特定化合物,對聚烯烴系樹脂顯示優良之β晶形成作用,而完成本發明。
亦即,本發明之聚烯烴系樹脂用核劑,其特徵為含有下述通式(1)
(通式(1)中,M表示1~3價之比重為4.0以下之金屬原子或鍵結有羥基之2~3價之比重為4.0以下之金屬原子,a表示1或2,b表示1或3,x表示1~3之整數,且滿足ax=2b。Z表示下述通式(2)或(3)表示之基。
(通式(2)及(3)中,*表示與通式(1)之Z連結的位置,Y表示直接鍵結,或碳原子數1~4之伸烷基,R1
~R10
係分別獨立地表示氫原子、羥基、鹵素原子、碳原子數1~10之烷基、碳原子數1~10之鹵化烷基、碳原子數1~10之烷氧基或碳原子數2~10之烯基))表示之化合物。
本發明之核劑中,前述M較佳為鋰、鈉、鉀、鎂、鈣、鋇、鋁、羥基鋁,或二羥基鋁。
又,本發明之聚烯烴系樹脂用核劑組成物,其特徵為含有本發明之聚烯烴系樹脂用核劑,與選自由酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、其他抗氧化劑、受阻胺化合物、紫外線吸收劑、與通式(1)表示之化合物不同的核劑、阻燃劑、阻燃助劑、潤滑劑、填充劑、水滑石類、脂肪酸金屬鹽、抗靜電劑、螢光增白劑、顏料及染料所成之群的至少1種添加劑。
進一步地,本發明之聚烯烴系樹脂用母料,其特徵為含有聚烯烴系樹脂,與本發明之聚烯烴系樹脂用核劑。
又進一步地,本發明之聚烯烴系樹脂組成物,其特徵為含有聚烯烴系樹脂與本發明之聚烯烴系樹脂用核劑,且
相對於前述聚烯烴系樹脂100質量份而言,前述聚烯烴系樹脂用核劑之含量為0.001~10質量份。
本發明之樹脂組成物中,前述聚烯烴系樹脂,較佳為聚丙烯系樹脂。又,本發明之樹脂組成物中,前述聚烯烴系樹脂,較佳含有乙烯-丙烯共聚物。進一步地,本發明之樹脂組成物,較佳含有彈性體。又進一步地,本發明之樹脂組成物,較佳含有填充劑。
又,本發明之成形品,其特徵為含有本發明之聚烯烴系樹脂組成物。
本發明之成形品,適合為汽車外裝零件、汽車內裝零件、殼體、容器及配管。
本發明之薄膜,其特徵為含有本發明之聚烯烴系樹脂組成物。
本發明之薄膜,較佳為內包孔隙之多孔質薄膜,適於光反射薄膜或電池隔膜。
又,本發明之多孔質薄膜之製造方法,為包含使聚烯烴系樹脂組成物成形而得到薄膜之成形步驟,與將藉由前述成形步驟所得到之前述薄膜加熱延伸之步驟的多孔質薄膜之製造方法,其特徵為前述聚烯烴系樹脂組成物,為本發明之聚烯烴系樹脂組成物。
進一步地,本發明之包裝體,其特徵為具備本發明之薄膜。
[發明之效果]
依照本發明,可提供具有優良之β晶形成作用的聚烯烴系樹脂用核劑、含有其之聚烯烴系樹脂用核劑組成物、聚烯烴系樹脂用母料、聚烯烴系樹脂組成物、其成形品、其薄膜、多孔質薄膜之製造方法及包裝體。
以下詳細說明本發明之實施形態。首先,說明本發明之聚烯烴系樹脂用核劑。
<聚烯烴系樹脂用核劑>
本發明之聚烯烴系樹脂用核劑,為含有下述通式(1)表示之化合物者,具有優良之β晶形成作用。
此處,通式(1)中,M表示1~3價之比重為4.0以下之金屬原子或鍵結有羥基之2~3價之比重為4.0以下之金屬原子,a表示1或2,b表示1或3,x表示1~3之整數,且滿足ax=2b。又,Z表示下述通式(2)或(3)表示之基。
此處,通式(2)及(3)中,*表示與通式(1)之Z連結的位置,Y表示直接鍵結,或碳原子數1~4之伸烷基,R1
~R10
係分別獨立地表示氫原子、羥基、鹵素原子、碳原子數1~10之烷基、碳原子數1~10之鹵化烷基、碳原子數1~10之烷氧基或碳原子數2~10之烯基。
通式(2)及(3)中之Y表示之碳原子數1~4之伸烷基,例如可列舉亞甲基、伸乙基、伸丙基、伸丁基、伸異丁基。就β晶形成作用優良的觀點,Y較佳為直接鍵結或亞甲基。
通式(2)及(3)中之R1
~R10
表示之鹵素原子,可列舉氟、氯、溴、碘。此等之中特佳為氯。
通式(2)及(3)中之R1
~R10
表示之碳原子數1~10之烷基,例如可列舉直鏈狀或分支狀之烷基,或碳原子數3~10之環烷基等。具體而言,例如可列舉甲基、乙基、n-丙基、異丙基、環丙基、n-丁基、sec-丁基、tert-丁基、異丁基、環丁基、n-戊基、tert-戊基、環戊基、n-己基、環己基、n-庚基、環庚基、n-辛基、異辛基、tert-辛基、2-乙基己基、n-壬基、異壬基、n-癸基等。
通式(2)及(3)中之R1
~R10
表示之碳原子數1~10之鹵化烷基,例如可列舉上述烷基之氫原子的一部分或全部被鹵素原子取代者等,鹵素原子可列舉氟、氯、溴、碘。
通式(2)及(3)中之R1
~R10
表示之碳原子數1~10之烷氧基,例如可列舉直鏈狀或分支狀之烷氧基,或碳原子數5~10之環烷氧基等。具體而言,例如可列舉甲氧基、乙氧基、n-丙氧基、n-丁氧基、n-己氧基、1-甲基乙氧基、2-甲基丙氧基、1-甲基丁氧基、4-甲基戊氧基、環己氧基等。
通式(2)及(3)中之R1
~R10
表示之碳原子數2~10之烯基,例如可列舉乙烯基、丙烯基、丁烯基、己烯基、辛烯基、癸烯基等。雙鍵之位置,可為α-位、可為內部、亦可為ω-位。
通式(2)及(3)之R1
~R10
,較佳為氫原子或鹵素原子、特佳為氫原子。
通式(1)中之M,例如可列舉鋰、鈉、鉀、鎂、鈣、鋇、鋁等之金屬原子。2~3價之金屬原子亦可與羥基鍵結。與羥基鍵結之2~3價之金屬原子,例如,可列舉羥基鋁及二羥基鋁等。進一步地,就得到具有優良之β晶形成作用的核劑之觀點,通式(1)中之M較佳為鋰、鈉、鉀、鎂、鈣、鋇、鋁、羥基鋁或二羥基鋁;更佳為鋰、鈉、鉀、鈣、羥基鋁;特佳為鈉。
通式(1)中之b較佳為1。又,x較佳為1或2。
通式(1)中之Z較佳為通式(3)表示之基。此時,本發明之核劑顯示更優良之β晶形成作用。
通式(1)表示之化合物之具體例子可列舉以下者。惟,本發明之核劑不限定於此等。
通式(1)表示之化合物,例如,可藉由使天門冬胺酸之金屬鹽,與苯甲酸氯化物、環己烷羧酸氯化物等之羧酸氯化物,在鹼之存在下反應之方法等來製造。
<聚烯烴系樹脂用核劑組成物>
接著,說明本發明之聚烯烴系樹脂用核劑組成物之實施形態。本發明之核劑組成物,為含有本發明之核劑,與選自由酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、其他抗氧化劑、受阻胺化合物、紫外線吸收劑、與通式(1)表示之化合物不同的核劑、阻燃劑、阻燃助劑、潤滑劑、填充劑、水滑石類、脂肪酸金屬鹽、抗靜電劑、螢光增白劑、顏料及染料所成之群的至少1種添加劑者,本發明之核劑組成物,顯示優良之β晶形成作用。
酚系抗氧化劑,例如可列舉2,6-二-tert-丁基-4-乙基酚、2-tert-丁基-4,6-二甲基酚、苯乙烯化酚、2,2’-亞甲基雙(4-乙基-6-tert-丁基酚)、2,2’-硫雙-(6-tert-丁基-4-甲基酚)、2,2’-硫二伸乙基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、2-甲基-4,6-雙(辛基氫硫基甲基)酚、2,2’-異亞丁基雙(4,6-二甲基酚)、異辛基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、N,N’-己烷-1,6-二基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙醯胺]、2,2’-草醯胺-雙[乙基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二-tert-丁基-4’-羥基苯基)丙酸酯、2,2’-伸乙基雙(4,6-二-tert-丁基酚)、3,5-二-tert-丁基-4-羥基苯丙酸及C13
-15
烷基之酯、2,5-二-tert-戊基氫醌、受阻酚之聚合物(ADEKA POLYMER ADDITIVES EUROPE SAS公司製商品名「AO.OH.98」)、2,2’-亞甲基雙[6-(1-甲基環己基)-p-甲酚]、丙烯酸2-tert-丁基-6-(3-tert-丁基-2-羥基5-甲基)-4-甲基苯酯、丙烯酸2-[1-(2-羥基-3,5-二-tert-戊基苯基)乙基]-4,6-二-tert-戊基苯酯、6-[3-(3-tert-丁基-4-羥基-5-甲基)丙氧基]-2,4,8,10-四-tert-丁基苯并[d,f][1,3,2]-二氧雜磷雜庚英、六亞甲基雙[3-(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、雙[單乙基(3,5-二-tert-丁基-4-羥基苄基)膦酸酯]鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)-苯并呋喃酮與o-二甲苯之反應生成物、2,6-二-tert-丁基-4-(4,6-雙(辛硫基)-1,3,5-三嗪-2-基胺基)酚、DL-a-生育酚(維生素E)、2,6-雙(α-甲基苄基)-4-甲基酚、雙[3,3-雙-(4’-羥基-3’-tert-丁基-苯基)丁酸]二醇酯、2,6-二-tert-丁基-p-甲酚、2,6-二苯基-4-十八烷氧基酚、硬脂基(3,5-二-tert-丁基-4-羥基苯基)丙酸酯、二硬脂基(3,5-二-tert-丁基-4-羥基苄基)膦酸酯、硫乙酸十三烷基-3,5-tert-丁基-4-羥基苄酯、硫二伸乙基雙[(3,5-二-tert-丁基-4-羥基苯基)丙酸酯]、4,4’-硫雙(6-tert-丁基-m-甲酚)、2-辛硫基-4,6-二(3,5-二-tert-丁基-4-羥基苯氧基)-s-三嗪、2,2’-亞甲基雙(4-甲基-6-tert-丁基酚)、雙[3,3-雙(4-羥基-3-tert-丁基苯基)丁酸]二醇酯、4,4’-亞丁基雙(2,6-二-tert-丁基酚)、4,4’-亞丁基雙(6-tert-丁基-3-甲基酚)、2,2’-亞乙基雙(4,6-二-tert-丁基酚)、1,1,3-參(2-甲基-4-羥基-5-tert-丁基苯基)丁烷、雙[2-tert-丁基-4-甲基-6-(2-羥基-3-tert-丁基-5-甲基苄基)苯基]對苯二甲酸酯、1,3,5-參(2,6-二甲基-3-羥基-4-tert-丁基苄基)異三聚氰酸酯、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-參(3,5-二-tert-丁基-4-羥基苄基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二-tert-丁基-4-羥基苯基)丙醯氧基乙基]異三聚氰酸酯、肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷、2-tert-丁基-4-甲基-6-(2-丙烯醯氧基-3-tert-丁基-5-甲基苄基)酚、3,9-雙[2-(3-tert-丁基-4-羥基-5-甲基氫桂皮醯氧基)-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、三乙二醇雙[β-(3-tert-丁基-4-羥基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、棕櫚基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、肉豆蔻基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺、月桂基-3-(3,5-二-tert-丁基-4-羥基苯基)丙酸醯胺等之3-(3,5-二烷基-4-羥基苯基)丙酸衍生物等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有酚系抗氧化劑時,酚系抗氧化劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,酚系抗氧化劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~5質量份之量即可。
磷系抗氧化劑,例如可列舉亞磷酸三苯酯、亞磷酸二異辛酯、柒(二丙二醇)三亞磷酸酯、亞磷酸三異癸酯、亞磷酸二苯基異辛酯、亞磷酸二異辛基苯酯、亞磷酸二苯基十三烷酯、亞磷酸三異辛酯、亞磷酸三月桂酯、亞磷酸二苯酯、參(二丙二醇)亞磷酸酯、二油基氫亞磷酸酯、三月桂基三硫亞磷酸酯、雙(十三烷基)亞磷酸酯、參(異癸基)亞磷酸酯、參(十三烷基)亞磷酸酯、亞磷酸二苯基癸酯、二壬基苯基雙(壬基苯基)亞磷酸酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙二醇二亞磷酸酯、亞磷酸參壬基苯酯、參(2,4-二-tert-丁基苯基)亞磷酸酯、參(2,4-二-tert-丁基-5-甲基苯基)亞磷酸酯、參[2-tert-丁基-4-(3-tert-丁基-4-羥基-5-甲基苯硫基)-5-甲基苯基]亞磷酸酯、三(癸基)亞磷酸酯、亞磷酸辛基二苯酯、亞磷酸二(癸基)單苯酯、二硬脂基季戊四醇與硬脂酸鈣鹽之混合物、烷基(C10)雙酚A亞磷酸酯、四苯基-四(十三烷基)季戊四醇四亞磷酸酯、亞磷酸雙(2,4-二-tert-丁基-6-甲基苯基)乙酯、四(十三烷基)異亞丙基二酚二亞磷酸酯、四(十三烷基)-4,4’-n-亞丁基雙(2-tert-丁基-5-甲基酚)二亞磷酸酯、六(十三烷基)-1,1,3-參(2-甲基-4-羥基-5-tert-丁基苯基)丁烷三亞磷酸酯、肆(2,4-二-tert-丁基苯基)伸聯苯基二亞膦酸酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、亞磷酸(1-甲基-1-丙烯基-3-亞基)參(1,1-二甲基乙基)-5-甲基-4,1-伸苯基)六-十三烷酯、亞磷酸2,2’-亞甲基雙(4,6-二-tert-丁基苯基)-2-乙基己酯、亞磷酸2,2’-亞甲基雙(4,6-二-tert-丁基苯基)-十八烷酯、2,2’-亞乙基雙(4,6-二-tert-丁基苯基)氟亞磷酸酯、4,4’-亞丁基雙(3-甲基-6-tert-丁基苯基二-十三烷基)亞磷酸酯、參(2-[(2,4,8,10-肆-tert-丁基二苯并[d,f][1,3,2]二氧雜磷雜庚英-6-基)氧基]乙基)胺、3,9-雙(4-壬基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5,5]十一烷、2,4,6-三-tert-丁基苯基-2-丁基-2-乙基-1,3-丙二醇亞磷酸酯、聚4,4’-異亞丙基二酚C12-15醇亞磷酸酯、雙(二異癸基)季戊四醇二亞磷酸酯、雙(十三烷基)季戊四醇二亞磷酸酯、雙(十八烷基)季戊四醇二亞磷酸酯、雙(壬基苯基)季戊四醇二亞磷酸酯、雙(2,4-二-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三-tert-丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-tert-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4-二異丙苯基苯基)季戊四醇二亞磷酸酯等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有磷系抗氧化劑時,磷系抗氧化劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,磷系抗氧化劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~5質量份之量即可。
硫系抗氧化劑,例如可列舉肆[亞甲基-3-(月桂硫基)丙酸酯]甲烷、雙(甲基-4-[3-n-烷基(C12/C14)硫丙醯氧基]5-tert-丁基苯基)硫醚、二-十三烷基-3,3’-硫二丙酸酯、二月桂基-3,3’-硫二丙酸酯、二肉豆蔻基-3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、月桂基/硬脂基硫二丙酸酯、4,4’-硫雙(6-tert-丁基-m-甲酚)、2,2’-硫雙(6-tert-丁基-p-甲酚)、二硬脂基-二硫醚。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有硫系抗氧化劑時,硫系抗氧化劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,硫系抗氧化劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~10質量份之量即可。
其他抗氧化劑,可列舉N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-辛基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十七烷基硝酮等之硝酮化合物;3-芳基苯并呋喃-2(3H)-酮、3-(烷氧基苯基)苯并呋喃-2-酮、3-(醯氧基苯基)苯并呋喃-2(3H)-酮、5,7-二-tert-丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二-tert-丁基-3-(4-羥基苯基)-苯并呋喃-2(3H)-酮、5,7-二-tert-丁基-3-{4-(2-羥基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二-tert-2-側氧基-2,3-二氫苯并呋喃-3-基)苯氧基)乙氧基)-6-側氧基己基-6-((6-羥基己醯基)氧基)己酸酯、5-二-tert-丁基-3-(4-((15-羥基-3,6,9,13-四氧雜十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等之苯并呋喃化合物等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有其他抗氧化劑時,其他抗氧化劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,其他抗氧化劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~20質量份之量即可。
受阻胺化合物,例如可列舉2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、肆(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、雙(2,2,6,6-四甲基-4-哌啶基)・二(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二-tert-丁基-4-羥基苄基)丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-嗎啉基-s-三嗪聚縮合物、1,6-雙(2,2,6,6-四甲基-4-哌啶基胺基)己烷/2,4-二氯-6-tert-辛基胺基-s-三嗪聚縮合物、1,5,8,12-肆[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四氮雜十二烷、1,5,8,12-肆[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基]-1,5,8-12-四氮雜十二烷、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)胺基)-s-三嗪-6-基]胺基十一烷、1,6,11-參[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基)-s-三嗪-6-基]胺基十一烷、雙{4-(1-辛氧基-2,2,6,6-四甲基)哌啶基}癸二酸酯、雙{4-(2,2,6,6-四甲基-1-十一烷基氧基)哌啶基}碳酸酯等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有受阻胺化合物時,受阻胺化合物之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,受阻胺化合物之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~20質量份之量即可。
紫外線吸收劑,例如可列舉2,4-二羥基二苯甲酮、5,5’-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)等之2-羥基二苯甲酮類;2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-tert-辛基苯基)苯并三唑、2-(2-羥基-3,5-二-tert-丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-tert-丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯并三唑、2,2’-亞甲基雙(4-tert-辛基-6-苯并三唑基酚)、2-(2-羥基-3-tert-丁基-5-羧基苯基)苯并三唑之聚乙二醇酯、2-[2-羥基-3-(2-丙烯醯氧基乙基)-5-甲基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-丁基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-辛基苯基]苯并三唑、2-[2-羥基-3-(2-甲基丙烯醯氧基乙基)-5-tert-丁基苯基]-5-氯苯并三唑、2-[2-羥基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-丁基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-戊基-5-(2-甲基丙烯醯氧基乙基)苯基]苯并三唑、2-[2-羥基-3-tert-丁基-5-(3-甲基丙烯醯氧基丙基)苯基]-5-氯苯并三唑、2-[2-羥基-4-(2-甲基丙烯醯氧基甲基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基-2-羥基丙基)苯基]苯并三唑、2-[2-羥基-4-(3-甲基丙烯醯氧基丙基)苯基]苯并三唑等之2-(2-羥基苯基)苯并三唑類;苯基水楊酸酯、間苯二酚單苯甲酸酯、2,4-二-tert-丁基苯基-3,5-二-tert-丁基-4-羥基苯甲酸酯、辛基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十二烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十四烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十六烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、十八烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯、二十二烷基(3,5-二-tert-丁基-4-羥基)苯甲酸酯等之苯甲酸酯類;2-乙基-2’-乙氧基草醯苯胺、2-乙氧基-4’-十二烷基草醯苯胺等之取代草醯苯胺類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(p-甲氧基苯基)丙烯酸酯等之氰基丙烯酸酯類;2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己氧基酚、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、三辛基-2,2’,2”-((1,3,5-三嗪-2,4,6-三基)參(3-羥基苯-4-,1-二基)三丙酸酯)、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己醯基氧基)乙氧基]酚、2,4,6-參(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三嗪、1,12-雙[2-[4-(4,6-二苯基-1,3,5-三嗪-2-基)-3-羥基苯氧基]乙基]十二烷二酸酯等之三嗪類;各種金屬鹽,或金屬鉗合物,特別是鎳、鉻之鹽,或鉗合物類等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有紫外線吸收劑時,紫外線吸收劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,紫外線吸收劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~20質量份之量即可。
與通式(1)表示之化合物不同的其他核劑,例如可列舉鈉-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、鋰-2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯、鋁羥基雙[2,2’-亞甲基雙(4,6-二-tert-丁基苯基)磷酸酯]、苯甲酸鈉、4-tert-丁基苯甲酸鋁鹽、己二酸鈉、2鈉雙環[2.2.1]庚烷-2,3-二羧酸酯、鈣環己烷-1,2-二羧酸酯等之羧酸金屬鹽、二亞苄基山梨醇、雙(甲基亞苄基)山梨醇、雙(3,4-二甲基亞苄基)山梨醇、雙(p-乙基亞苄基)山梨醇,及雙(二甲基亞苄基)山梨醇、1,2,3-三去氧-4,6:5,7-雙-O-((4-丙基苯基)亞甲基)壬糖醇等之多元醇衍生物、N,N’,N”-參[2-甲基環己基]-1,2,3-丙烷三甲醯胺、N,N’,N”-三環己基-1,3,5-苯三甲醯胺、N,N’-二環己基萘二甲醯胺、1,3,5-三(二甲基異丙基胺基)苯等之醯胺化合物等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有與通式(1)表示之化合物不同的其他核劑時,其他核劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,其他核劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~10質量份之量即可。
阻燃劑,例如可列舉磷酸三苯酯、磷酸三甲苯酚酯、磷酸三-二甲苯酯、磷酸甲苯酚基二苯酯、磷酸甲苯酚基-2,6-二-二甲苯酯、間苯二酚雙(二苯基磷酸酯)、(1-甲基亞乙基)-4,1-伸苯基四苯基二磷酸酯、1,3-伸苯基肆(2,6-二甲基苯基)磷酸酯、ADEKA股份有限公司製商品名「Adekastub FP-500」、「Adekastub FP-600」、「Adekastub FP-800」之芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸(1-丁烯酯)等之膦酸酯、二苯基次磷酸苯酯、二苯基次磷酸甲酯、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物衍生物等之次磷酸酯、雙(2-烯丙基苯氧基)膦氮烯、二甲苯酚基膦氮烯等之膦氮烯化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺、多磷酸蜜白胺、多磷酸銨、磷酸哌嗪、焦磷酸哌嗪、多磷酸哌嗪、含有磷之乙烯基苄基化合物及紅磷等之磷系阻燃劑、氫氧化鎂、氫氧化鋁等之金屬氫氧化物、溴化雙酚A型環氧樹脂、溴化酚酚醛清漆型環氧樹脂、六溴苯、五溴甲苯、伸乙基雙(五溴苯基)、伸乙基雙四溴鄰苯二甲醯亞胺、1,2-二溴-4-(1,2-二溴乙基)環己烷、四溴環辛烷、六溴環十二烷、雙(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯及2,4,6-參(三溴苯氧基)-1,3,5-三嗪、三溴苯基馬來醯亞胺、丙烯酸三溴苯酯、甲基丙烯酸三溴苯酯、四溴雙酚A型二甲基丙烯酸酯、丙烯酸五溴苄酯,及溴化苯乙烯等之溴系阻燃劑等。此等阻燃劑較佳與氟樹脂等之滴落防止劑或多元醇、水滑石等之阻燃助劑合併使用。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有阻燃劑時,阻燃劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,阻燃劑之含量,相對於聚烯烴系樹脂100質量份而言,係1~100質量份之量即可。
潤滑劑係以對成形品表面賦予潤滑性,提高損傷防止效果為目的而添加。潤滑劑例如可列舉油酸醯胺、芥子酸醯胺等之不飽和脂肪酸醯胺;二十二酸醯胺、硬脂酸醯胺等之飽和脂肪酸醯胺;硬脂酸丁酯、硬脂醇、硬脂酸單甘油酯、山梨醇酐單棕櫚酸酯、山梨醇酐單硬脂酸酯、甘露醇、硬脂酸、硬化蓖麻油、硬脂酸醯胺、油酸醯胺、伸乙基雙硬脂酸醯胺等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有潤滑劑時,潤滑劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,潤滑劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.01~2質量份之量即可。
填充劑例如可列舉滑石、雲母、碳酸鈣、氧化鈣、氫氧化鈣、碳酸鎂、氫氧化鎂、氧化鎂、硫酸鎂、氫氧化鋁、硫酸鋇、玻璃粉末、玻璃纖維、黏土、白雲石、二氧化矽、氧化鋁、鈦酸鉀鬚晶、矽灰石、纖維狀硫氧鎂(fibrous magnesium oxysulfate)等,可適當選擇粒子徑(纖維狀時係纖維徑或纖維長及長寬比)來使用。此等填充劑之中,由於可對成形品賦予特別優良的剛性,且獲得容易,特佳使用滑石。又,填充劑可使用依需要而經表面處理者。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有填充劑時,填充劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,填充劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.01~80質量份之量即可。
就得到耐熱性或樹脂中之核劑的分散效果之觀點,脂肪酸金屬鹽,較基為下述通式(4)表示之化合物。
此處,通式(4)中,R11
表示直鏈或分支狀之碳原子數12~20之脂肪酸殘基,該脂肪酸殘基亦可經羥基取代,M2
表示1~3價之金屬原子,金屬原子亦可與羥基鍵結,m表示1~3之整數。
本發明之核劑組成物含有脂肪酸金屬鹽時,脂肪酸金屬鹽之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,脂肪酸金屬鹽之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~10質量份之量即可。
通式(4)中,M2
之具體例子,可列舉鈉、鉀、鋰、鈣、鋅、鋇、鎂、羥基鋁等,此等之中尤以鈉、鉀、鋰特佳。
水滑石類為作為天然物或合成物已知的含有鎂、鋁、羥基、碳酸基及任意之結晶水的複合鹽化合物,可列舉鎂或鋁之一部分經鹼金屬或鋅等之其他金屬取代者或羥基、碳酸基經其他陰離子基取代者,具體而言,例如可列舉下述通式(5)表示之水滑石之金屬取代為鹼金屬者。又,Al-Li系之水滑石類,亦可使用下述通式(6)表示之化合物。
此處,通式(5)中,z1及z2分別表示滿足下述式
表示之條件之數,p表示0或正數。
此處,通式(6)中,Aq-
表示q價之陰離子,p表示0或正數。又,水滑石類中之碳酸陰離子,一部分亦可經其他陰離子取代。
水滑石類亦可為結晶水經脫水者,亦可為經硬脂酸等之高級脂肪酸、油酸鹼金屬鹽等之高級脂肪酸金屬鹽、十二烷基苯磺酸鹼金屬鹽等之有機磺酸金屬鹽、高級脂肪酸醯胺、高級脂肪酸酯或蠟等被覆者。
水滑石類可為天然物、又亦可為合成品。水滑石類之合成方法,可列舉日本特公昭46-2280號公報、日本特公昭50-30039號公報、日本特公昭51-29129號公報、日本特公平3-36839號公報、日本特開昭61-174270號公報、日本特開平5-179052號公報等記載之公知方法。又,水滑石類,可不限制於其結晶結構、結晶粒子等地使用。水滑石類可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有水滑石類時,水滑石類之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,水滑石類之含量,相對於聚烯烴系樹脂100質量份而言,係0.001~5質量份之量即可。
抗靜電劑例如可列舉由非離子性、陰離子性、陽離子性或兩性之界面活性劑等所成之低分子型抗靜電劑;由高分子化合物所成之高分子型抗靜電型。非離子性界面活性劑,可列舉高級醇環氧乙烷加成物、脂肪酸環氧乙烷加成物、高級烷基胺環氧乙烷加成物、聚烯烴二醇環氧乙烷加成物等之聚乙二醇型非離子界面活性劑;聚環氧乙烷、甘油之脂肪酸酯、季戊四醇之脂肪酸酯、山梨糖醇或山梨醇酐之脂肪酸酯、多元醇之烷基醚、烷醇胺之脂肪族醯胺等之多元醇型非離子界面活性劑等,陰離子性界面活性劑,例如可列舉高級脂肪酸之鹼金屬鹽等之羧酸鹽;高級醇硫酸酯鹽、高級烷基醚硫酸酯鹽等之硫酸酯鹽;烷基苯磺酸鹽、烷基磺酸鹽、石蠟磺酸鹽等之磺酸鹽;高級醇磷酸酯鹽等之磷酸酯鹽等,陽離子性界面活性劑,可列舉烷基三甲基銨鹽等之4級銨鹽等。兩性界面活性劑,可列舉高級烷基胺基丙酸鹽等之胺基酸型兩性界面活性劑;高級烷基二甲基甜菜鹼、高級烷基二羥基乙基甜菜鹼等之甜菜鹼型兩性界面活性劑等,聚烯烴系樹脂組成物中,較佳為陰離子性界面活性劑,特佳為烷基苯磺酸鹽、烷基磺酸鹽、石蠟磺酸鹽等之磺酸鹽。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有低分子型抗靜電劑時,低分子型抗靜電劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,低分子型抗靜電劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.1~10質量份之量即可。
高分子型抗靜電劑,可列舉離子聚合物或以聚乙二醇為親水部之嵌段聚合物等。離子聚合物可列舉日本特開2010-132927號公報記載之離子聚合物。以聚乙二醇為親水部之聚合物,例如可列舉日本特開平7-10989號公報記載之聚醚酯醯胺、美國專利第6552131號公報記載之由聚烯烴與聚乙二醇所成之聚合物、日本特開2016-023254號公報記載之由聚酯與聚乙二醇所成之聚合物等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有高分子型抗靜電劑時,高分子型抗靜電劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,高分子型抗靜電劑之含量,相對於聚烯烴系樹脂100質量份而言,係3~60質量份之量即可。
螢光增白劑,係指吸收太陽光或人工光之紫外線,藉由將其變為紫~藍色之可見光線而進行輻射之螢光作用,而助長成形體之白色度或藍色度之化合物。螢光增白劑,可列舉苯并噁唑系化合物C.I.Fluorescent Brightner184;香豆素系化合物C.I.Fluorescent Brightner52;二胺基二苯乙烯二磺酸系化合物C.I.Fluorescent Brightner24、85、71等。此等可1種單獨使用、亦可合併使用2種以上。本發明之核劑組成物含有螢光增白劑時,螢光增白劑之含量,當摻合本發明之核劑組成物於聚烯烴系樹脂中時,螢光增白劑之含量,相對於聚烯烴系樹脂100質量份而言,係0.00001~0.1質量份之量即可。
顏料並無特殊限定,亦可使用市售之顏料。顏料之具體例子,例如可列舉顏料紅1、2、3、9、10、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;顏料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;顏料黃1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;顏料綠7、10、36;顏料藍15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、29、56、60、61、62、64;顏料紫1、15、19、23、27、29、30、32、37、40、50等。
染料可列舉偶氮染料、蒽醌染料、靛藍類染料、三芳基甲烷染料、氧雜蒽(xanthene)染料、茜素染料、吖啶染料、二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲達胺染料、噁嗪染料、酞青素染料、花青染料等之染料等,此等可1種單獨使用、亦可合併使用2種以上。
本發明之核劑組成物之製造方法並無特殊限定,例如,只要係將本發明之核劑與其他添加劑混合之方法等即可。又,製造本發明之核劑組成物的其他方法,可列舉將本發明之核劑及其他添加劑與含有高分子化合物或石油樹脂之黏合劑在加熱下混合,於熔解狀態之黏合劑存在下均勻化之後,加工為丸粒形狀之方法等。依照該製造方法,可製造均勻且操作性優良的本發明之核劑組成物。該製造方法中之加工條件並無任何限定。又,該製造方法所使用之加工機器亦無任何限定,只要係擠出機、盤式製粒機(disk pelleter)等眾所週知之一般的加工機器即可。
<聚烯烴系樹脂組成物>
接著,說明本發明之聚烯烴系樹脂組成物。本發明之樹脂組成物,含有聚烯烴系樹脂與通式(1)表示之化合物,相對於聚烯烴系樹脂100質量份而言,本發明之核劑之含量為0.001~10質量份。本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶。
本發明之樹脂組成物中所含有的聚烯烴系樹脂,例如可列舉低密度聚乙烯(LDPE)、直鏈狀低密度聚乙烯(L-LDPE)、高密度聚乙烯(HDPE)、同排聚丙烯、對排聚丙烯、半同排聚丙烯、環烯烴聚合物、立體嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等之α-烯烴聚合物、乙烯/丙烯共聚物、衝擊共聚物聚丙烯、乙烯-甲基丙烯酸甲酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇樹脂(EVOH)等之α-烯烴共聚物,及此等之氯化物等。聚烯烴系樹脂,亦可為此等2種以上經摻合者或經合金化者。
聚烯烴系樹脂,較佳為聚丙烯系樹脂。聚丙烯系樹脂,可列舉丙烯均聚物、乙烯-丙烯共聚物(例如乙烯-丙烯隨機共聚物等)等、乙烯-丙烯-1-丁烯三元共聚物、丙烯與其他α-烯烴(例如1-丁烯、1-己烯、1-辛烯、4-甲基-1-戊烯等)之共聚物、包含乙烯-丙烯共聚物之乙烯-丙烯嵌段共聚物(例如衝擊共聚物聚丙烯、TPO等),及此等之氯化物等。聚丙烯系樹脂,可為此等2種以上經摻合者、可為樹脂經合金化者、亦可為嵌段共聚物。
又,本發明之樹脂組成物所用的聚烯烴系樹脂,更佳包含乙烯-丙烯共聚物。此時,可對成形品賦予特別優之耐衝擊性。如此的聚烯烴系樹脂,例如可列舉上述之乙烯-丙烯共聚物(例如乙烯-丙烯隨機共聚物等)等、乙烯-丙烯嵌段共聚物(例如衝擊共聚物聚丙烯、TPO等)等。
本發明之樹脂組成物中,能夠與聚合觸媒/助觸媒之種類或有無、立體規則性、平均分子量、分子量分布、特定之分子量成分之有無或比率、比重、黏度、對各種溶劑之溶解度、延伸率、衝擊強度、結晶化度、X射線繞射、不飽和羧酸(馬來酸、依康酸、富馬酸等)及其衍生物(馬來酸酐、馬來酸單酯、馬來酸二酯等)或有機過氧化物或能量線之照射及此等處理的組合所為之改質/交聯處理之有無等無關地,來使用聚烯烴系樹脂。
如上所述,本發明之樹脂組成物中,相對於聚烯烴系樹脂100質量份而言,本發明之核劑之含量,為0.001~10質量份。就使β晶形成作用更優良的觀點,相對於聚烯烴系樹脂100質量份而言,本發明之核劑之含量較佳為0.005質量份以上、更佳為0.02質量份以上。又,就抑制起霜(bloom)之產生或核劑之萃取性的觀點,相對於聚烯烴系樹脂100質量份而言,本發明之核劑之含量較佳為1質量份以下、更佳為0.5質量份以下、又更佳為0.3質量份以下。
本發明之樹脂組成物,較佳進一步含有彈性體。此時,可對成形品賦予更加優良的耐衝擊性。
彈性體並無特殊限定,由於與聚烯烴系樹脂之相溶性優良,較佳為乙烯與乙烯以外之單體之共聚物。
上述乙烯以外之單體,可列舉直鏈或具有分支之碳原子數3~20之α-烯烴、碳原子數8~20之芳香族乙烯基化合物、其他乙烯基化合物、共軛二烯、(甲基)丙烯酸烷酯、烷氧基丙烯酸烷酯等。此處(甲基)丙烯酸烷酯,係表示丙烯酸烷酯或甲基丙烯酸烷酯。此等乙烯以外之單體,可為1種、亦可組合2種以上使用。
碳原子數3~20之α-烯烴,例如可列舉丙烯、1-丁烯、3-甲基-1-丁烯、3-乙基-1-丁烯、1-戊烯、3-甲基-1-戊烯、3-乙基-1-戊烯、4,4-二甲基-1-戊烯、1-己烯、4-甲基-1-己烯、4,4-二甲基-1-己烯、4-乙基-1-己烯、3-乙基-1-己烯、1-辛烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯等,較佳可列舉丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯。
碳原子數8~20之芳香族乙烯基化合物,例如可列舉苯乙烯、o-甲基苯乙烯、p-甲基苯乙烯、m-甲基苯乙烯、o-乙基苯乙烯、m-乙基苯乙烯、p-乙基苯乙烯、p-tert-丁基苯乙烯、氯甲基苯乙烯、乙烯基甲苯等,較佳可列舉單或聚烷基苯乙烯。
其他乙烯基化合物,可列舉鹵化烯烴、不飽和胺、不飽和羧酸、乙烯酯、不飽和環氧化合物、乙烯性不飽和矽烷化合物等。
此處,鹵化烯烴,係表示對上述α-烯烴,加成氯、溴、碘等之鹵素原子者。
不飽和胺可列舉烯丙基胺、5-己烯胺、6-庚烯胺等。
不飽和羧酸,例如可列舉(甲基)丙烯酸、3-丁烯酸、4-戊烯酸、5-己烯酸、6-庚烯酸、7-辛烯酸、8-壬烯酸、9-癸烯酸、10-十一烯酸等,亦可為經鹵素原子取代者。
乙烯酯例如可列舉甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、十一酸乙烯酯、月桂酸乙烯酯、肉豆蔻酸乙烯酯、十五酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、叔碳酸(versatic acid)乙烯酯(碳原子數9~11之羧酸混合物)等之脂肪族乙烯酯、苯甲酸乙烯酯等之芳香族乙烯酯等。較佳的乙烯酯,可列舉碳原子數3~20、更佳為碳原子數4~10之乙烯酯,更佳可列舉乙酸乙烯酯。
不飽和環氧化合物,例如可列舉4-環氧基-1-丁烯、5-環氧基-1-戊烯、6-環氧基-1-己烯、7-環氧基-1-庚烯、8-環氧基-1-辛烯、9-環氧基-1-壬烯、10-環氧基-1-癸烯、11-環氧基-1-十一烯等。
乙烯性不飽和矽烷化合物,可列舉乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等。
共軛二烯,例如可列舉1,3-丁二烯、異戊二烯、1,3-戊二烯、2-乙基-1,3-丁二烯、2,3-二甲基丁二烯、2-甲基戊二烯、4-甲基戊二烯、2,4-己二烯、1,3-辛二烯等。
(甲基)丙烯酸烷酯,例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸n-丙酯、(甲基)丙烯酸n-丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸n-戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸n-己酯、(甲基)丙烯酸2-甲基戊酯、(甲基)丙烯酸n-辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸n-癸酯、(甲基)丙烯酸n-十二烷酯、(甲基)丙烯酸n-十八烷酯等。
烷氧基丙烯酸烷酯,可列舉丙烯酸2-甲氧基乙酯、丙烯酸2-乙氧基乙酯、丙烯酸2-(n-丙氧基)乙酯、丙烯酸2-(n-丁氧基)乙酯、丙烯酸3-甲氧基丙酯、丙烯酸3-乙氧基丙酯、丙烯酸2-(n-丙氧基)丙酯、丙烯酸2-(n-丁氧基)丙酯等。
彈性體,可為將此等之單體單獨與乙烯共聚合者、亦可為組合二種以上之單體,而與乙烯共聚合者。
乙烯與乙烯以外之單體之共聚物的彈性體之中,由於與烯烴樹脂之相溶性優良,故較佳為乙烯-α-烯烴共聚物。又,亦佳為乙烯與乙烯酯之共聚物。
乙烯與乙烯以外之單體之共聚物的彈性體之具體例子,可列舉乙烯-丙烯共聚物、乙烯-丁烯共聚物、乙烯-辛烯共聚物等之嵌段或隨機共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、苯乙烯-乙烯-丁烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、乙烯-乙酸乙烯酯共聚物等。
乙烯與乙烯以外之單體之共聚物的彈性體以外之彈性體,例如可列舉熱可塑性聚酯、熱可塑性聚胺基甲酸酯等。
可與分子量、聚合度、密度、軟化點、對溶劑之不溶成分的比例、立體規則性之程度、觸媒殘渣之有無、作為原料的單體之種類或摻合比率、聚合觸媒之種類(例如戚格勒觸媒、二茂金屬觸媒等)等無關地,來使用彈性體。
彈性體之含量,相對於聚烯烴系樹脂100質量份而言,較佳為1~80質量份。此時,本發明之樹脂組成物,成為可對成形品賦予更優良之耐衝擊性者。彈性體之含量,相對於聚烯烴系樹脂100質量份而言,較佳為3質量份以上、特佳為5質量份以上。又,就使成形品於低溫環境下之耐衝擊性成為優良的觀點,彈性體之含量,相對於聚烯烴系樹脂100質量份而言,更佳為50質量份以下、特佳為40質量份以下。
本發明之樹脂組成物,較佳進一步含有填充劑。此時,可對成形品賦予優良之剛性。填充劑可列舉與上述核劑組成物所使用的相同者。填充劑之中,由於可對成形品賦予特別優良之剛性,且容易獲得,特佳為滑石。填充劑之含量,相對於聚烯烴系樹脂100質量份而言,較佳為0.01~80質量份。又,填充劑之摻合量,相對於聚烯烴系樹脂100質量份而言,更佳為1質量份以上。進一步地,填充劑之摻合量,相對於聚烯烴系樹脂100質量份而言,更佳為50質量份以下。
聚烯烴系樹脂組成物中,只要不大幅損及其性能,則亦可進一步於聚烯烴系樹脂摻合一般所用的添加劑,例如酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、其他抗氧化劑、受阻胺化合物、紫外線吸收劑、與通式(1)表示之化合物不同的其他核劑、阻燃劑、阻燃助劑、潤滑劑、水滑石類、脂肪酸金屬鹽、抗靜電劑、螢光增白劑、顏料、染料等。此等之添加劑,可列舉與上述核劑組成物所使用的相同者。此等之添加劑之摻合量並無特殊限定,只要此等之添加劑,係以於聚烯烴系樹脂中以適度之濃度存在的方式摻合即可。
製造本發明之樹脂組成物之方法並無特殊限定,例如可列舉將聚烯烴系樹脂粉末或丸粒,與本發明之核劑及其他添加劑乾摻合之方法、將聚烯烴系樹脂粉末或丸粒,與本發明之核劑及其他添加劑乾摻合並將所得之混合物熔融混練之方法、將本發明之核劑與其他添加劑加工為丸粒形狀,添加至聚烯烴系樹脂之方法等。又,本發明之核劑與其他添加劑,可同時添加至聚烯烴系樹脂、亦可分別添加。進一步地,本發明之樹脂組成物之製造方法,亦可為將本發明之核劑組成物摻合於聚烯烴系樹脂之方法。
<聚烯烴系樹脂用母料>
製造本發明之樹脂組成物的方法之其他方法,可列舉製作本發明之母料,將其摻合於聚烯烴系樹脂之方法。此處,本發明之母料,為含有聚烯烴系樹脂,與上述本發明之核劑者。本發明之母料,可使聚烯烴系樹脂優先形成β晶。本發明之母料,亦可依需要進一步含有其他添加劑。本發明之母料中所含有的聚烯烴系樹脂並無特殊限定,例如可列舉上述之聚烯烴系樹脂等。製造本發明之母料的方法並不受特別限制,例如,可列舉將聚烯烴系樹脂粉末或丸粒,與本發明之核劑及其他添加劑乾摻合,並將所得之混合物熔融混練之方法等。
<成形品>
接著,說明本發明之成形品。本發明之成形品係包含本發明之樹脂組成物。本發明之樹脂組成物可使聚烯烴系樹脂優先形成β晶,因此本發明之成形品,為包含聚烯烴系樹脂之β晶者。
本發明之成形品,例如可列舉射出成形品、纖維、扁平絲紗、二軸延伸薄膜、一軸延伸薄膜、無延伸薄膜、薄片、熱成形品、擠出吹塑成形品、射出吹塑成形品、射出延伸吹塑成形品、異形擠出成形品、旋轉成形品等。更具體而言,本發明之成形品可列舉汽車外裝零件、汽車內裝零件、殼體、容器、配管等。
本發明之成形品之成形方法並無特殊限定,例如可列舉射出成形法、擠出成形法、吹塑成形法、旋轉成形、真空成形法、吹脹成形法、壓延成形法、凝塑成形法、浸漬成形法、熱成形法等之方法。
接著,說明本發明之汽車外裝零件、汽車內裝零件、殼體、容器及配管。
<汽車外裝零件>
本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此包含本發明之樹脂組成物之汽車外裝零件,耐衝擊性優良。汽車外裝零件,例如可列舉保險桿、散熱器格柵、前格柵、前風擋、翼子板、支柱、車柱罩、後視鏡托架罩、窗玻璃導槽、後視鏡外殼、燈具外殼、輪圈蓋、擾流器、空氣擾流器、飾條、窗嵌條、安全帶嵌條、天窗、前端模組、車門模組、後車門模組、外板等。使汽車外裝零件成形之方法,例如可列舉射出成形法、熱成形法、吹塑成形法等之方法。
<汽車內裝零件>
本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此包含本發明之樹脂組成物之汽車內裝零件,耐衝擊性優良。汽車內裝零件,例如可列舉儀錶板、車門飾板、支柱飾條、車門飾條、支柱飾件、置物盤、後側置物盤、手枕箱、空調導管等。使汽車內裝零件成形之方法,例如可列舉射出成形法、熱成形法、吹塑成形法等之方法。
<殼體>
本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此包含本發明之樹脂組成物之殼體,耐衝擊性優良。殼體例如可列舉家電用殼體、大型遊戲機用殼體、家庭用遊戲機用殼體、攜帶型遊戲機用殼體、相機用殼體、行動電話用殼體、智慧型手機用殼體、電子機器用殼體、蓄電池用殼體、安全斷路器用殼體等。使殼體成形之方法,例如可列舉射出成形法、熱成形法、吹塑成形法等之方法。
<容器>
本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此包含本發明之樹脂組成物之容器,耐衝擊性優良。容器例如可列舉餐具、配菜容器、冷凍食品容器、微波爐耐熱容器、冷凍保存容器、殺菌袋容器、杯具、冷凍甜點杯具等之食品用容器;飲料瓶、輸液瓶、醫療用中空瓶等之瓶容器;燒杯、量筒等之理化學試驗用容器;藥品容器、醫療用容器、洗劑容器、化粧品容器、香水容器、碳粉容器等。使容器成形之方法,例如可列舉吹塑成形法、吹脹成形法、熱成形法等之方法。
<配管>
本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此包含本發明之樹脂組成物之配管,耐衝擊性優良。配管例如可列舉水管、輸氣管、基礎設施用管、工廠設施用管、車輛用燃料輸送管、車輛用進氣管等之各種管路(pipe);化粧品/香水噴霧用管、醫療用管、輸液管等之各種管材(tube);水軟管、車輛用空氣導管等之各種軟管(hose)等。使配管成形之方法,例如可列舉射出成形法、擠出成形法、旋轉成形法等之方法。
<薄膜>
接著說明薄膜。本發明之薄膜,包含本發明之樹脂組成物。本發明之樹脂組成物,可使聚烯烴系樹脂優先形成β晶,因此本發明之薄膜延伸性優良。又,聚烯烴系樹脂之β晶,具有較α晶為低之熔點,因此本發明之薄膜熱封性優良。使薄膜成形之方法,例如可列舉擠出成形法、吹脹成形法、流延成形法等。
<多孔質薄膜>
聚烯烴系樹脂之β晶,藉由加熱,而相轉移為α晶。而聚烯烴系樹脂之β晶,較α晶密度低。因此,可藉由包含使本發明之樹脂組成物成形而得到薄膜之成形步驟,與將藉由成形步驟所得之薄膜加熱延伸之步驟的製造方法,來製造本發明之多孔質薄膜,本發明之多孔質薄膜,係內包有微細且均勻之孔隙者。本發明之多孔質薄膜,例如可適合地使用作為光反射薄膜、電池隔膜等。將薄膜加熱延伸時之加熱溫度並無特殊限定,例如80~120℃即可。又,延伸可為一軸延伸亦可為二軸延伸。進一步地,延伸倍率亦無特殊限定,例如1.1~10倍即可。
<光反射薄膜>
本發明之多孔質薄膜係內包有微細且均勻之孔隙者,因此包含本發明之薄膜的本發明之光反射薄膜,光反射性優良。本發明之光反射薄膜,例如適合使用作為組裝於液晶顯示器之背光的板狀材,具體而言係液晶畫面用之端面照光(edge light)的反射板、直下型背光之反射板,及冷陰極射線管之周圍之反射器等。
<電池隔膜>
本發明之多孔質薄膜為內包有微細且均勻之孔隙者,因此包含本發明之多孔質薄膜之本發明之電池隔膜,透過性優良。如此的電池隔膜,例如適合使用於鋰蓄電池、鎳-氫電池、鎳-鎘電池、聚合物電池等。
<包裝體>
接著,說明本發明之包裝體。本發明之包裝體,具備本發明之薄膜。本發明之薄膜,為熱封性優良者,因此本發明之包裝體熱封性優良。本發明之包裝體,可僅由本發明之薄膜所成、亦可為包含將本發明之薄膜層合於基材上而得的層合體者。又,層合體中,本發明之薄膜亦可隔著包含聚烯烴薄膜等之中間層,而層合於基材上。構成層合體之基材,例如可列舉聚烯烴系樹脂、苯乙烯系樹脂、聚酯或聚醯胺之薄膜、此等之延伸薄膜、此等之薄膜與聚醯胺薄膜或乙烯-乙烯醇共聚物薄膜般的具氣體障壁性之樹脂薄膜的層合薄膜、鋁等之金屬箔,或蒸鍍有鋁或二氧化矽等之蒸鍍薄膜或紙等。又,層合體之製造方法,例如可列舉乾層合、共擠出等之方法。本發明之包裝體,例如適合使用於食品或電子材料等之包裝,特別是殺菌袋包裝或自動包裝機之包裝。
[實施例]
以下,列舉實施例,以更具體說明本發明,但本發明不受以下實施例等之任何限制。
[實施例1-1~1-10、比較例1-1~1-4]
對均聚丙烯(230℃、於荷重2.16kg之MFR=8g/10min) 200g,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷) 0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%,及表1記載之聚烯烴系樹脂用核劑0.1質量%,以手混練將此等混練3分鐘後,投入單軸擠出機(裝置:東洋精機製作所股份有限公司製Labo Plastomill Micro),於230℃之熔融溫度造粒。再者,比較例1-1,除了不摻合聚烯烴系樹脂用核劑以外,係以與實施例1-1相同的順序進行造粒。將經造粒之丸粒,於80℃乾燥8小時後,以下述條件評估。表1中,聚烯烴系樹脂用核劑之「立體結構」係表示天門冬胺酸殘基之立體結構,Z表示以下之基。
<結晶化溫度Tc[℃]>
使用所得之丸粒,使用示差掃描熱量測定器(裝置;PerkinElmer公司製Diamond)測定結晶化溫度(Tc)。結晶化溫度,係以50℃/min之速度由室溫昇溫至230℃,保持5分鐘後,以10℃/min之速度冷卻至50℃時,作為於冷卻過程中所觀測到的放熱峰之溫度(℃)而求得。結果示於表1。
<β晶比率>
使用所得之丸粒,藉由示差掃描熱量測定器(裝置;PerkinElmer公司製Diamond)判定β晶之有無,並且測定β晶比率。具體而言,係以50℃/min之速度由室溫昇溫至230℃,保持20分鐘後,以10℃/min之速度冷卻至50℃,進一步保持5分鐘後,以10℃/min之速度昇溫至230℃時,於第2次之昇溫過程中,觀測到於150℃附近具有峰頂之吸熱峰及於165℃附近具有峰頂之吸熱峰時判定為「有」β晶,僅觀測到於165℃附近具有峰頂之吸熱峰時判定為「無」β晶。判定為「有」β晶時,以於150℃附近具有峰頂之吸熱峰的面積為β晶面積、以於165℃附近具有峰頂之吸熱峰的面積為α晶面積,由下述式算出β晶比率。
β晶比率=β晶面積/(α晶面積+β晶面積)×100(%)
結果示於表1。
<著色>
將所得之丸粒於200℃射出成形,對於所得之厚度1mm之試驗片,目視判斷有無著色。結果示於表1。
[實施例2-1~2-10、比較例2-1~2-5]
對均聚丙烯(230℃、於荷重2.16kg之MFR=8g/10min) 200g,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%,及表2記載之化合物0.1質量%,以手混練將此等混練3分鐘後,投入單軸擠出機(裝置:東洋精機製作所股份有限公司製Labo Plastomill Micro),於230℃之熔融溫度造粒。表2中,聚烯烴系樹脂用核劑之「立體結構」係表示天門冬胺酸殘基之立體結構,Z表示上述之基。
將經造粒之丸粒於80℃乾燥8小時後,以與上述實施例1-1相同之順序,評估結晶化溫度Tc[℃]、β晶比率,及著色之有無。結果示於表2。
*喹吖酮由於著色嚴重,故未進行評估Tc及β晶之有無。
[比較例3-1~3-6]
對均聚丙烯(230℃、於荷重2.16kg之MFR=8g/10min) 200g,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%,及以下述通式(7)表示,具有表3記載之Z之比較化合物0.1質量%,以手混練將此等混練3分鐘後,投入單軸擠出機(裝置:東洋精機製作所股份有限公司製Labo Plastomill Micro),於230℃之熔融溫度造粒。表3及通式(7)中,Z表示上述之基。將經造粒之丸粒於80℃乾燥8小時後,以與上述實施例1-1相同之順序,評估結晶化溫度Tc[℃]、β晶比率。結果示於表3。
[實施例4-1~4-9、比較例4-1~4-4]
摻合衝擊共聚物聚丙烯(Prime Polymer公司製Prime Polypro J707G)70質量份、乙烯-辛烯共聚合彈性體(陶氏化學公司製Engage 8842)10質量份、滑石(水分量0.1質量%、以雷射繞射法所得之粒子徑D50
=14.0μm、以JISK5101記載之測定法所得之容積比重0.32g/mL)20質量份,調製樹脂混合物。對該樹脂混合物2kg,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%、表4或表5記載之添加量的表4或表5記載之聚烯烴系樹脂用核劑,以Rocking Mixer(愛知電機公司製)混練30分鐘後,投入二軸擠出機(日本製鋼所公司製TEX-25αIII),於230℃之熔融溫度造粒。再者比較例4-1,除了不摻合聚烯烴系樹脂用核劑以外,係以與實施例4-1相同的順序進行造粒。表4及5中,聚烯烴系樹脂用核劑之「立體結構」係表示天門冬胺酸殘基之立體結構,Z表示上述之基。
[實施例5-1~5-9、比較例5-1~5-4]
摻合衝擊共聚物聚丙烯(Prime Polymer公司製Prime Polypro J707G)60質量份、乙烯-辛烯共聚合彈性體(陶氏化學公司製Engage 8842)20質量份、滑石(水分量0.1質量%、以雷射繞射法所得之粒子徑D50
=14.0μm、以JISK5101記載之測定法所得之容積比重0.32g/mL)20質量份,調製樹脂混合物。對該樹脂混合物2kg,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%、表6或表7記載之添加量的表6或表7記載之聚烯烴系樹脂用核劑,以Rocking Mixer(愛知電機公司製)混練30分鐘後,投入二軸擠出機(日本製鋼所公司製TEX-25αIII),於230℃之熔融溫度造粒。表6及7中,聚烯烴系樹脂用核劑之「立體結構」係表示天門冬胺酸殘基之立體結構,Z表示上述之基。再者比較例5-1,除了不摻合聚烯烴系樹脂用核劑以外,係以與實施例5-1相同的順序進行造粒。
[實施例6-1~6-4、比較例6-1、6-2]
對衝擊共聚物聚丙烯(Prime Polymer公司製Prime Polypro J707G)2kg,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%、表8記載之添加量的表8記載之聚烯烴系樹脂用核劑,以Rocking Mixer(愛知電機公司製)混練30分鐘後,投入二軸擠出機(裝置;日本製鋼所公司製TEX-25αIII),於230℃之熔融溫度造粒。表8中,聚烯烴系樹脂用核劑之「立體結構」係表示天門冬胺酸殘基之立體結構,Z表示上述之基。再者比較例6-1,除了不摻合聚烯烴系樹脂用核劑以外,係以與實施例6-1相同的順序進行造粒。
將如上述般造粒之實施例4-1~4-9、比較例4-1~4-4、實施例5-1~5-9、比較例5-1~5-4、實施例6-1~6-4及比較例6-1~6-2之聚烯烴系樹脂組成物丸粒,於80℃乾燥8小時。使用乾燥後之聚烯烴系樹脂組成物丸粒,以與上述實施例1-1相同之順序評估結晶化溫度,進一步由下述順序評估β晶比率及夏比衝擊強度。結果示於表4~8。
<β晶比率>
使用所得之丸粒,藉由示差掃描熱量測定器(裝置;PerkinElmer公司製Diamond)判定β晶之有無,並且測定β晶比率。具體而言,係以50℃/min之速度由室溫昇溫至230℃,保持20分鐘後,以10℃/min之速度冷卻至50℃,進一步保持5分鐘後,以30℃/min之速度昇溫至230℃時,於第2次之昇溫過程中,觀測到於150℃附近具有峰頂之吸熱峰及於165℃附近具有峰頂之吸熱峰時判定為「有」β晶,僅觀測到於165℃附近具有峰頂之吸熱峰時判定為「無」β晶。判定為「有」β晶時,以於150℃附近具有峰頂之吸熱峰的面積為β晶面積、以於165℃附近具有峰頂之吸熱峰的面積為α晶面積,由下述式算出β晶比率。
β晶比率=β晶面積/(α晶面積+β晶面積)×100(%)
<夏比衝擊強度(Charpy impact strength)>
將所得之丸粒藉由射出成形機(裝置;日精樹脂工業公司製橫型射出成形機NEX80)以樹脂溫度230℃、模具溫度50℃之加工條件成形,製作夏比衝擊強度測定用試驗片(80mm×10mm×4mm)。將所得之試驗片於23℃、濕度60%RH之恆溫恆濕槽內靜置7日後,對試驗片賦予切口。將經賦予切口之試驗片於溫度23℃、濕度60%RH之恆溫恆濕槽內靜置5日後,由恆溫恆濕槽中取出試驗片,根據ISO179-1測定夏比衝擊強度(kJ/m2
)。
[實施例7-1~7-4、比較例7-1~7-3]
對均聚丙烯(230℃、於荷重2.16kg之MFR=3g/10min) 2kg,摻合酚系抗氧化劑(肆[亞甲基-3-(3’,5’-tert-丁基-4’-羥基苯基)丙酸酯]甲烷)0.05質量%、磷系抗氧化劑(參(2,4-二-tert-丁基苯基)亞磷酸酯)0.1質量%、硬脂酸鈣鹽0.05質量%、表9記載之添加量的表9記載之聚烯烴系樹脂用核劑,以手混練將此等混練3分鐘後,投入二軸擠出機(裝置:日本製鋼所公司製TEX-25αIII),於230℃之熔融溫度造粒。表9中聚烯烴系樹脂用核劑之「立體結構」,係表示天門冬胺酸殘基之立體結構,Z表示上述之基。又,比較例7-1,除了不摻合聚烯烴系樹脂用核劑以外,係以與實施例7-1相同的順序進行造粒。將經造粒之丸粒,於80℃乾燥8小時後,投入具備T模及輥的單軸擠出機,以缸體溫度200℃、輥溫度120℃之條件,成形為厚度100μm之薄膜。將如此所得之薄膜以加熱溫度100℃、延伸速度1000mm/分鐘之條件,向MD方向以5倍之倍率加熱延伸。進一步地,將該薄膜於相同條件向TD方向以2倍之倍率加熱延伸,得到延伸薄膜。然後,藉由下述順序評估薄膜之延伸性及所得延伸薄膜之孔隙特性。結果示於表9。
<延伸性>
目視觀察如上述般所得延伸薄膜之表面,藉由以下評估基準評估延伸性。
○:全體均勻地延伸
×:全體未均勻地延伸,延伸狀態存在著不均勻
<孔隙特性>
使用掃描電子顯微鏡,以5000倍之倍率觀察如上述般所得之延伸薄膜之表面,藉由以下評估基準評估孔隙特性。
○:於薄膜全體觀察到微細之孔隙
△:於薄膜之一部分觀察到微細之孔隙
×:未觀察到孔隙
由以上,確認到本發明之聚烯烴系樹脂用核劑,具有優良之β晶形成作用。
Claims (21)
- 如請求項1之聚烯烴系樹脂用核劑,其中前述M,為鋰、鈉、鉀、鎂、鈣、鋇、鋁、羥基鋁,或二羥基鋁。
- 一種聚烯烴系樹脂用核劑組成物,其特徵為含有如請求項1或2之聚烯烴系樹脂用核劑,與選自由酚系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、其他抗氧化劑、受阻胺化合物、紫外線吸收劑、與通式(1)表示之化合物不同的核劑、阻燃劑、阻燃助劑、潤滑劑、填充劑、水滑石類、脂肪酸金屬鹽、抗靜電劑、螢光增白劑、顏料及染料所成之群的至少1種添加劑。
- 一種聚烯烴系樹脂用母料,其特徵為含有聚烯烴系樹脂,與如請求項1或2之聚烯烴系樹脂用核劑。
- 一種聚烯烴系樹脂組成物,其特徵為含有聚烯烴系樹脂,與如請求項1或2之聚烯烴系樹脂用核劑,且相對於前述聚烯烴系樹脂100質量份而言,前述聚烯烴系樹脂用核劑之含量為0.001~10質量份。
- 如請求項5之聚烯烴系樹脂組成物,其中前述聚烯烴系樹脂,為聚丙烯系樹脂。
- 如請求項5或6之聚烯烴系樹脂組成物,其中前述聚烯烴系樹脂,包含乙烯-丙烯共聚物。
- 如請求項5或6之聚烯烴系樹脂組成物,其含有彈性體。
- 如請求項5或6之聚烯烴系樹脂組成物,其含有填充劑。
- 一種成形品,其特徵為包含如請求項5~9中任一項之聚烯烴系樹脂組成物。
- 如請求項10之成形品,其係汽車外裝零件。
- 如請求項10之成形品,其係汽車內裝零件。
- 如請求項10之成形品,其係殼體。
- 如請求項10之成形品,其係容器。
- 如請求項10之成形品,其係配管。
- 一種薄膜,其特徵為包含如請求項5~9中任一項之聚烯烴系樹脂組成物。
- 如請求項16之薄膜,其係內包孔隙之多孔質薄膜。
- 如請求項17之薄膜,其係光反射薄膜。
- 如請求項17之薄膜,其係電池隔膜。
- 一種多孔質薄膜之製造方法,其係包含使聚烯烴系樹脂組成物成形而得到薄膜之成形步驟,與將藉由前述成形步驟所得到之前述薄膜加熱延伸之步驟的多 孔質薄膜之製造方法,其特徵為前述聚烯烴系樹脂組成物,為如請求項5~9中任一項之聚烯烴系樹脂組成物。
- 一種包裝體,其特徵為具備如請求項16之薄膜。
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