JP7368705B2 - Crystallization promoter for polyolefin resin, and polyolefin resin composition containing the crystallization promoter - Google Patents
Crystallization promoter for polyolefin resin, and polyolefin resin composition containing the crystallization promoter Download PDFInfo
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- JP7368705B2 JP7368705B2 JP2019167928A JP2019167928A JP7368705B2 JP 7368705 B2 JP7368705 B2 JP 7368705B2 JP 2019167928 A JP2019167928 A JP 2019167928A JP 2019167928 A JP2019167928 A JP 2019167928A JP 7368705 B2 JP7368705 B2 JP 7368705B2
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- Prior art keywords
- polyolefin resin
- crystallization
- resin composition
- dicarboxylic acid
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005672 polyolefin resin Polymers 0.000 title claims description 145
- 238000002425 crystallisation Methods 0.000 title claims description 111
- 230000008025 crystallization Effects 0.000 title claims description 97
- 239000011342 resin composition Substances 0.000 title claims description 71
- -1 hydroxyaluminum ions Chemical class 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 125000002723 alicyclic group Chemical group 0.000 claims description 17
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 20
- 239000000654 additive Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 12
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 11
- 159000000007 calcium salts Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009616 inductively coupled plasma Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 230000001737 promoting effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 6
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical class [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- QYJGMAIQZRWXSD-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1(C)C(C(O)=O)C2C(O)=O QYJGMAIQZRWXSD-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- NRIMHVFWRMABGJ-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylic acid Chemical compound C1C2C(C(=O)O)=C(C(O)=O)C1C=C2 NRIMHVFWRMABGJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000002354 daily effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 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 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- ORACIQIJMCYPHQ-UHFFFAOYSA-N 2-[4-[2-[4-(1,3-benzoxazol-2-yl)phenyl]ethenyl]phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=CC=3C=CC(=CC=3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ORACIQIJMCYPHQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- NBAHYAAOJLJZTI-UHFFFAOYSA-N 5-(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C(C)(C)(C)C1=C(OC2OPOCC23COPOC3)C(=CC(=C1)C)C(C)(C)C NBAHYAAOJLJZTI-UHFFFAOYSA-N 0.000 description 1
- MXJGWNPVKBVVTM-UHFFFAOYSA-N 5-tert-butyl-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC=NC2=C1 MXJGWNPVKBVVTM-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリオレフィン系樹脂の結晶化促進効果に非常に優れた新規な結晶化促進剤に関するものであり、詳しくは、特定の構造の多環脂環式構造を基本骨格とする特定の構造の脂環式ジカルボン酸の金属塩を含むことを特徴とする結晶化促進剤、及び該結晶化促進剤を含む結晶性に優れたポリオレフィン系樹脂組成物並びに該樹脂組成物を原料とするポリオレフィン系樹脂成形体に関する。 The present invention relates to a novel crystallization promoter that has an extremely excellent effect of promoting crystallization of polyolefin resins. A crystallization promoter characterized by containing a metal salt of an alicyclic dicarboxylic acid, a polyolefin resin composition containing the crystallization promoter with excellent crystallinity, and a polyolefin resin using the resin composition as a raw material Regarding molded objects.
ポリエチレンやポリプロピレン等のポリオレフィン系樹脂は、安価でバランスの良い性能を有し、汎用のプラスチックとして様々な用途で使用されている。また、一般的に結晶性の樹脂の場合、その結晶性を改良することにより、例えば、成形加工性を改善することや得られた成形品の機械的特性や熱的特性、光学的特性を向上することが可能あることが広く知られており、ポリオレフィン系樹脂の場合も同様である。 Polyolefin resins such as polyethylene and polypropylene are inexpensive and have well-balanced performance, and are used as general-purpose plastics for various purposes. In addition, in the case of crystalline resins, improving the crystallinity can, for example, improve molding processability and improve the mechanical, thermal, and optical properties of the resulting molded product. It is widely known that it is possible to do this, and the same is true for polyolefin resins.
ポリオレフィン系樹脂等の結晶性樹脂の結晶性を改良する方法には、樹脂の構造・組成を制御する方法も広く検討されており、実際に実用化されているが、結晶化促進剤等の添加剤を配合することにより結晶化を促進する方法が、簡易でより実用的な方法として広く用いられている。上記結晶化促進剤は、結晶核の生成速度や生成した結晶核からの成長速度を高める効果を有しており、その結果、成形加工時間の短縮が可能であり、更には得られた成形品の機械的特性、熱的特性、更には光学的特性を改善する効果を有する。その様な結晶化促進剤としては、これまでタルク等の無機化合物、エチレンビスステアリン酸アミド等のアミド化合物、ジアセタール化合物、リン酸エステルの金属塩、カルボン酸やスルホン酸の金属塩等の有機化合物などが良く知られており、実際に広く実用化されている。 As a method for improving the crystallinity of crystalline resins such as polyolefin resins, methods of controlling the structure and composition of the resin have been widely studied and have been put into practical use, but the addition of crystallization accelerators, etc. A method of promoting crystallization by blending an agent is widely used as a simple and more practical method. The above-mentioned crystallization promoter has the effect of increasing the rate of crystal nucleus generation and the growth rate from the generated crystal nuclei, and as a result, it is possible to shorten the molding time, and furthermore, the molded product obtained can be It has the effect of improving mechanical properties, thermal properties, and even optical properties. Such crystallization promoters have so far been inorganic compounds such as talc, amide compounds such as ethylene bisstearamide, diacetal compounds, metal salts of phosphoric acid esters, and organic compounds such as metal salts of carboxylic acids and sulfonic acids. are well known and have been widely put into practical use.
上記結晶促進剤のなかでも、ステアリン酸等の脂肪酸、安息香酸等の芳香族カルボン酸、ヘキサヒドロフタル酸等の脂環式カルボン酸など、様々なカルボン酸の金属塩が優れた結晶化促進効果を有することが古くから知られており、代表的なものとしては、安息香酸のナトリウム塩やｐ－ｔｅｒｔ－ブチル安息香酸のヒドロキシアルミニウム塩などが挙げられ、様々な用途で広く使われてきた（特許文献１、２、非特許文献１、２）。 Among the crystallization promoters mentioned above, metal salts of various carboxylic acids, such as fatty acids such as stearic acid, aromatic carboxylic acids such as benzoic acid, and alicyclic carboxylic acids such as hexahydrophthalic acid, have excellent crystallization promoting effects. It has been known for a long time that it possesses Patent Documents 1, 2, Non-Patent Documents 1, 2).
また、最近では、ヘキサヒドロフタル酸や水添ナジック酸のカルシウム塩やナトリウム塩などの脂環式カルボン酸の金属塩が、熱可塑性樹脂の結晶化促進剤として優れた効果を有することが報告されている（特許文献３～７） In addition, it has recently been reported that metal salts of alicyclic carboxylic acids, such as calcium and sodium salts of hexahydrophthalic acid and hydrogenated nadic acid, have excellent effects as crystallization promoters for thermoplastic resins. (Patent Documents 3 to 7)
近年、様々な用途で、コスト削減や軽量化等の目的でプラスチックへの切り替えが進んでおり、なかでもポリオレフィン系樹脂は安価でかつ軽量であることより最も有用な材料として注目されている。その中でも、自動車用途は、最近の環境問題より低燃費化の要求が強く、最もポリオレフィン系樹脂の使用が進んでいる分野であり、最近では小型部材にとどまらず、大型部材にもポリオレフィン系樹脂を使われるようになっており、その様な分野では、これまでに知られている結晶化促進剤では必ずしも満足されておらず、更なる改善が望まれている。 In recent years, there has been a shift to plastics for various purposes in order to reduce cost and weight, and polyolefin resins are attracting attention as the most useful materials because they are inexpensive and lightweight. Among these, automotive applications are the field where the use of polyolefin resins is the most advanced due to the strong demand for lower fuel consumption due to recent environmental issues.Recently, polyolefin resins are being used not only for small parts but also for large parts. In such fields, the crystallization promoters known so far are not necessarily satisfactory, and further improvements are desired.
また、上記自動車部材の中でもバンパー等の安全性に係る部材では、優れた剛性や強度等の機械的性能が必要であり、ポリオレフィン系樹脂単独では十分な機械的性能を得ることが難しく、タルク等の充填剤を配合する処方が一般的である。近年、上述の様に軽量化の要求が強く、充填剤の配合量を可能な限り少なくする傾向が一般的となってきている。しかし、充填剤の配合量を少なくすると機械的性能等の性能低下は避けられず、その改善が大きな課題であった。上述の通り、結晶化促進剤を用いることにより、ポリオレフィン系樹脂の結晶性や機械的強度を向上することが可能であり、上記の機械的性能等の性能低下を結晶化促進剤の配合で補うことが検討され、実際に使われている。しかし、従来の結晶化促進剤の多くは、充填剤との併用系では十分な効果を発揮することが難しく、近年益々厳しくなってきている軽量化の要求に対応することが難しいのが現状である。従って、タルク等の充填剤との併用系で優れた効果を発揮する結晶化促進剤の開発が強く望まれている。 Furthermore, among the above automobile parts, safety-related parts such as bumpers require excellent mechanical performance such as rigidity and strength, and it is difficult to obtain sufficient mechanical performance with polyolefin resin alone, so talc etc. It is common for formulations to include fillers. In recent years, as mentioned above, there has been a strong demand for weight reduction, and there has been a general trend to reduce the amount of filler blended as much as possible. However, when the amount of filler blended is reduced, performance such as mechanical performance inevitably deteriorates, and improvement thereof has been a major issue. As mentioned above, by using a crystallization promoter, it is possible to improve the crystallinity and mechanical strength of polyolefin resin, and the above-mentioned decrease in mechanical performance can be compensated for by adding a crystallization promoter. This has been considered and is actually being used. However, it is difficult for many conventional crystallization promoters to exhibit sufficient effects when used in combination with fillers, making it difficult to meet the demands for weight reduction that have become increasingly severe in recent years. be. Therefore, there is a strong desire to develop a crystallization promoter that exhibits excellent effects when used in combination with fillers such as talc.
また、ポリオレフィン系樹脂等では、結晶化促進剤を配合することにより透明性が大きく向上することが知られており、日用雑貨品や食品包装材料等の用途において、広く使われている。従って、特にポリオレフィン系樹脂等においては透明性の改善効果も非常に重要であり、且つ必須な性能である。 Furthermore, it is known that the transparency of polyolefin resins and the like can be greatly improved by adding a crystallization accelerator, and they are widely used in applications such as daily necessities and food packaging materials. Therefore, especially in polyolefin resins, the effect of improving transparency is also very important and is an essential performance.
本発明は、ポリオレフィン系樹脂の結晶化促進効果に非常に優れた、即ち、ポリオレフィン系樹脂に配合することによりポリオレフィン系樹脂の結晶化速度、即ち結晶化温度を著しく向上することのできる結晶化促進剤、及び該結晶化促進剤を含むポリオレフィン系樹脂組成物並びに該樹脂組成物を原料とするポリオレフィン系樹脂成形体を提供することを目的とする。 The present invention has an extremely excellent crystallization promoting effect on polyolefin resins, that is, crystallization promoters that can significantly improve the crystallization rate, that is, the crystallization temperature, of polyolefin resins by blending them into polyolefin resins. An object of the present invention is to provide a polyolefin resin composition containing a crystallization promoter, and a polyolefin resin molded article using the resin composition as a raw material.
本発明者らは、上述の状況に鑑み、上記課題を解決すべく、鋭意検討した結果、特定の構造の脂環式ジカルボン酸の金属塩が、ポリオレフィン系樹脂に配合することによりポリオレフィン系樹脂の結晶化速度、即ち結晶化温度を著しく向上することのできることを見出し、本発明を完成するに至った。 In view of the above-mentioned situation, the present inventors have made extensive studies to solve the above problems, and have found that by blending a metal salt of an alicyclic dicarboxylic acid with a specific structure into a polyolefin resin, It was discovered that the crystallization rate, that is, the crystallization temperature, can be significantly improved, and the present invention was completed.
即ち、本発明は以下に示す新規な脂環式ジカルボン酸の金属塩を含有してなるポリオレフィン系樹脂用の結晶化促進剤、及び該結晶化促進剤を含むポリオレフィン系樹脂組成物並びに該樹脂組成物を原料とするポリオレフィン系樹脂成形体を提供するものである。 That is, the present invention relates to a crystallization accelerator for polyolefin resin containing the following novel metal salt of alicyclic dicarboxylic acid, a polyolefin resin composition containing the crystallization accelerator, and the resin composition. The object of the present invention is to provide a polyolefin resin molded article made from a polyolefin resin.
［項１］ 下記一般式（１）又は一般式（２）で示される脂環式ジカルボン酸の金属塩を含んでなるポリオレフィン系樹脂用の結晶化促進剤。
［項２］ 前記金属イオンが、カルシウムイオン、ナトリウムイオン、リチウムイオン、ヒドロキシアルミニウムイオン及び亜鉛イオンからなる群より選ばれた１種である［項１］に記載の結晶化促進剤。 [Item 2] The crystallization promoter according to [Item 1], wherein the metal ion is one selected from the group consisting of calcium ions, sodium ions, lithium ions, hydroxyaluminum ions, and zinc ions.
［項３］ 前記脂環式ジカルボン酸中の２つのオキシカルボニル基が、シス配置である［項１］又は［項２］に記載の結晶化促進剤。 [Item 3] The crystallization promoter according to [Item 1] or [Item 2], wherein the two oxycarbonyl groups in the alicyclic dicarboxylic acid have a cis configuration.
［項４］ ［項１］～［項３］の何れかに記載の結晶化促進剤を含むことを特徴とするポリオレフィン系樹脂組成物。 [Item 4] A polyolefin resin composition comprising the crystallization promoter according to any one of [Item 1] to [Item 3].
［項５］ 結晶化促進剤の含有量が、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部である［項４］に記載のポリオレフィン系樹脂組成物。 [Item 5] The polyolefin resin composition according to [Item 4], wherein the content of the crystallization promoter is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin resin.
［項６］ 結晶化促進剤の含有量が、ポリオレフィン系樹脂１００質量部に対して、０．０１～５質量部である［項５］に記載のポリオレフィン系樹脂組成物。 [Item 6] The polyolefin resin composition according to [Item 5], wherein the content of the crystallization promoter is 0.01 to 5 parts by mass based on 100 parts by mass of the polyolefin resin.
［項７］ ［項４］～［項６］の何れかに記載されたポリオレフィン系樹脂組成物を原料とするポリオレフィン系樹脂成形体。 [Item 7] A polyolefin resin molded article made from the polyolefin resin composition described in any one of [Item 4] to [Item 6].
本発明の結晶化促進剤をポリオレフィン系樹脂に配合することによりポリオレフィン系樹脂の結晶化速度、即ち結晶化温度を著しく向上することができる。その結果、特に大型部材等における成形サイクルが大幅に短縮され、コストダウンや加工時のトラブル防止等に非常に有効である。更に、結晶性を改善することにより、えられた成形品の剛性等の機械的性能、透明性等の光学的性能、耐熱性等の熱的性能が向上するだけでなく、ひけやそりが少なくなり、複雑な形状の成形品も安定して製造可能となる。また、本発明の結晶化促進剤は、タルク等の充填剤との併用系でもその効果が低減することなく、優れた効果を発揮することが可能である。 By blending the crystallization promoter of the present invention into a polyolefin resin, the crystallization rate, that is, the crystallization temperature, of the polyolefin resin can be significantly improved. As a result, the molding cycle, especially for large parts, is significantly shortened, which is extremely effective in reducing costs and preventing trouble during processing. Furthermore, by improving crystallinity, the resulting molded product not only improves mechanical performance such as rigidity, optical performance such as transparency, and thermal performance such as heat resistance, but also reduces sink marks and warpage. This makes it possible to stably manufacture molded products with complex shapes. Moreover, the crystallization accelerator of the present invention can exhibit excellent effects without reducing its effects even when used in combination with fillers such as talc.
＜ポリオレフィン系樹脂用の結晶化促進剤＞
本発明のポリオレフィン系樹脂用の結晶化促進剤は、以下に示す特定の構造の脂環式ジカルボン酸の金属塩を含有してなることを特徴とする。なお、該結晶化促進剤には、本発明の効果を損なわない範囲で、本発明の結晶化促進剤以外のその他の結晶化促進剤や一般的にポリオレフィン系樹脂に使われている各種添加剤を含有していても良い。その場合、結晶化促進剤中に占める本発明の結晶化促進剤の含有量は、結晶化促進剤全体を１００質量％とした場合に、７０質量％以上、好ましくは８０質量％以上、より好ましくは９０質量％以上、特に好ましくは９５質量％以上であることが推奨される。
<Crystallization promoter for polyolefin resin>
The crystallization promoter for polyolefin resins of the present invention is characterized by containing a metal salt of an alicyclic dicarboxylic acid having the specific structure shown below. The crystallization promoter may include other crystallization promoters other than the crystallization promoter of the present invention and various additives generally used in polyolefin resins, to the extent that the effects of the present invention are not impaired. It may contain. In that case, the content of the crystallization promoter of the present invention in the crystallization promoter is 70% by mass or more, preferably 80% by mass or more, more preferably is recommended to be 90% by mass or more, particularly preferably 95% by mass or more.
［脂環式ジカルボン酸］
本発明の脂環式ジカルボン酸は、下記一般式（３）又は一般式（４）で示される多環構造の脂環式ジカルボン酸である。
The alicyclic dicarboxylic acid of the present invention is an alicyclic dicarboxylic acid having a polycyclic structure represented by the following general formula (3) or general formula (4).
上記脂環式ジカルボン酸は、工業的にはシクロ環上に置換基のない構造が好ましいか、本発明の効果を奏するものであれば、シクロ環上に、例えば、炭素数１～４の直鎖状又は分岐鎖状のアルキル基が置換されているものを用いることもできる。 The above-mentioned alicyclic dicarboxylic acid preferably has a structure without a substituent on the cyclo ring, or has a structure in which there is no substituent on the cyclo ring, for example, if it has the effect of the present invention. Those in which a chain or branched alkyl group is substituted can also be used.
また、本発明の脂環式ジカルボン酸には、２つのオキシカルボニル基が同方向を向いているシス配置と異方向を向いているトランス配置の２種類の立体異性体が存在する場合があるが、本発明においては、本発明の効果を奏する限り、その異性体の構造に依存するものではなく、シス配置、トランス配置及びその混合物の何れであっても良いが、結晶化促進効果の観点より、シス配置であることが望ましい。 Furthermore, the alicyclic dicarboxylic acid of the present invention may exist in two types of stereoisomers: a cis configuration in which the two oxycarbonyl groups face in the same direction, and a trans configuration in which the two oxycarbonyl groups face in different directions. In the present invention, it does not depend on the structure of the isomer as long as the effect of the present invention is achieved, and any of the cis configuration, trans configuration, and a mixture thereof may be used, but from the viewpoint of crystallization promoting effect. , preferably in the cis configuration.
［金属イオン］
本発明の金属塩を形成する金属イオンは、本発明の効果を奏するものであれば、特に限定されることなく、一価又は二価の金属イオンを用いることができるが、結晶化促進効果の観点より、カルシウムイオン、ナトリウムイオン、リチウムイオン、ヒドロキシアルミニウムイオン及び亜鉛イオンからなる群より選ばれた１種であることが好ましい。
[Metal ions]
The metal ion forming the metal salt of the present invention is not particularly limited, and any monovalent or divalent metal ion can be used as long as it achieves the effects of the present invention. From this point of view, one type selected from the group consisting of calcium ions, sodium ions, lithium ions, hydroxyaluminum ions, and zinc ions is preferable.
本発明の脂環式ジカルボン酸の金属塩の具体的な態様としては、例えば、５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩、５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩、５－ノルボルネン－２，３－ジカルボン酸のカルシウム塩、５－ノルボルネン－２，３－ジカルボン酸のヒドロキシアルミニウム塩、５－ノルボルネン－２，３－ジカルボン酸の亜鉛塩、メチル－５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩、メチル－５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩、メチル－５－ノルボルネン－２，３－ジカルボン酸のカルシウム塩、メチル－５－ノルボルネン－２，３－ジカルボン酸のヒドロキシアルミニウム塩、メチル－５－ノルボルネン－２，３－ジカルボン酸の亜鉛塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二リチウム塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸のカルシウム塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸のヒドロキシアルミニウム塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の亜鉛塩などが挙げられ、中でも、５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩、５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩、５－ノルボルネン－２，３－ジカルボン酸の亜鉛塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩などが好ましく、５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩などが特に推奨される。 Specific embodiments of the metal salt of alicyclic dicarboxylic acid of the present invention include, for example, disodium salt of 5-norbornene-2,3-dicarboxylic acid, dilithium salt of 5-norbornene-2,3-dicarboxylic acid, , calcium salt of 5-norbornene-2,3-dicarboxylic acid, hydroxyaluminum salt of 5-norbornene-2,3-dicarboxylic acid, zinc salt of 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene- Disodium salt of 2,3-dicarboxylic acid, dilithium salt of methyl-5-norbornene-2,3-dicarboxylic acid, calcium salt of methyl-5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene- Hydroxyaluminum salt of 2,3-dicarboxylic acid, zinc salt of methyl-5-norbornene-2,3-dicarboxylic acid, disodium 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid salt, dilithium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid, calcium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid , hydroxyaluminum salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid, zinc salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid, etc. Among them, disodium salt of 5-norbornene-2,3-dicarboxylic acid, dilithium salt of 5-norbornene-2,3-dicarboxylic acid, zinc salt of 5-norbornene-2,3-dicarboxylic acid, Disodium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid is preferred, and disodium salt of 5-norbornene-2,3-dicarboxylic acid, 1,4:5,8 -Dimethanodecahydronaphthalene-2,3-dicarboxylic acid disodium salt and the like are particularly recommended.
＜脂環式ジカルボン酸の金属塩の製造方法＞
本発明の脂環式ジカルボン酸の製造方法は、本発明の効果を奏する限り、特に制限されないが、例えば、共役ジエン化合物と無水マレイン酸とのディールス・アルダー反応により、脂環式ジカルボン酸無水物を得て、続いて、得られた脂環式ジカルボン酸無水物と水と金属酸化物、金属水酸化物、又は金属塩化物とを反応させて、金属塩とする方法などで容易に製造することができる。
<Method for producing metal salt of alicyclic dicarboxylic acid>
The method for producing an alicyclic dicarboxylic acid of the present invention is not particularly limited as long as the effects of the present invention are achieved. and then reacting the obtained alicyclic dicarboxylic acid anhydride with water and a metal oxide, metal hydroxide, or metal chloride to obtain a metal salt. be able to.
本発明のポリオレフィン系樹脂用の結晶化促進剤の粒子形状は、本発明の効果を奏する限り、特に制限はないが、本発明の結晶化促進剤が、分散タイプである場合、二次凝集により樹脂中での分散性が悪化しない程度に粒子の大きさが小さいほど、樹脂との接触面が広くなり、より少量で、より優れた結晶化促進剤としての性能を発揮できる可能性がある。従って、結晶化促進性能の観点より、レーザー回折式粒度分布測定により求めた粒径の平均値が、１００μｍ以下、好ましくは５０μｍ、より好ましくは２０μｍ以下、特に好ましくは１０μｍ以下であることが推奨される。また、分散性の観点より、上述の通り、レーザー回折式粒度分布測定により求めた粒径の平均値が、０．０１μｍ以上、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上であることが推奨される。 The particle shape of the crystallization accelerator for polyolefin resins of the present invention is not particularly limited as long as the effects of the present invention are achieved. The smaller the particle size is to the extent that the dispersibility in the resin is not deteriorated, the wider the contact surface with the resin, and it is possible to exhibit better performance as a crystallization promoter with a smaller amount. Therefore, from the viewpoint of crystallization promotion performance, it is recommended that the average particle size determined by laser diffraction particle size distribution measurement is 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, particularly preferably 10 μm or less. Ru. In addition, from the viewpoint of dispersibility, as mentioned above, the average value of the particle size determined by laser diffraction particle size distribution measurement is 0.01 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more. is recommended.
＜ポリオレフィン系樹脂組成物＞
本発明のポリオレフィン系樹脂組成物は、上記特定の構造の脂環式ジカルボン酸の金属塩を含有してなるポリオレフィン系樹脂用の結晶化促進剤を含んでなることを最大の特徴とする。
<Polyolefin resin composition>
The main feature of the polyolefin resin composition of the present invention is that it contains a crystallization accelerator for polyolefin resins containing a metal salt of an alicyclic dicarboxylic acid having the above-described specific structure.
本発明のポリオレフィン系樹脂組成物は、上記ポリオレフィン系樹脂用の結晶化促進剤とポリオレフィン系樹脂とを、必要に応じてその他のポリオレフィン系樹脂用添加剤を加えて、室温にてドライブレンド後、所定の条件にて溶融混合することにより、容易に得ることができる。 The polyolefin resin composition of the present invention is prepared by dry blending the crystallization accelerator for polyolefin resin and the polyolefin resin at room temperature, adding other additives for polyolefin resin as necessary. It can be easily obtained by melt-mixing under predetermined conditions.
また、上記ポリオレフィン系樹脂用の結晶化促進剤に、必要に応じてその他のポリオレフィン系樹脂用の添加剤を配合して、ポリオレフィン系樹脂用の添加剤組成物を調製して、該組成物とポリオレフィン系樹脂とを、室温にてドライブレンド後、所定の条件にて溶融混合することによって、得ることもできる。 In addition, an additive composition for polyolefin resins is prepared by blending other additives for polyolefin resins with the crystallization accelerator for polyolefin resins as necessary. It can also be obtained by dry blending with a polyolefin resin at room temperature and then melt-mixing under predetermined conditions.
ポリオレフィン系樹脂中の本発明に係るポリオレフィン系樹脂用の結晶化促進剤の含有量は、結晶核剤としての効果を奏する限り、特に制約はないが、ポリオレフィン系樹脂１００質量部に対して、好ましくは０．００１～１０質量部、より好ましくは０．０１～５質量部であることが推奨される。 The content of the crystallization accelerator for polyolefin resin according to the present invention in the polyolefin resin is not particularly limited as long as it has an effect as a crystal nucleating agent, but it is preferably based on 100 parts by mass of the polyolefin resin. is recommended to be 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight.
［ポリオレフィン系樹脂］
上記ポリオレフィン系樹脂としては、本発明の効果を奏する限り特に限定されることなく、従来公知のポリオレフィン系樹脂が使用可能であり、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブテン系樹脂、ポリメチルペンテン系樹脂、ポリブタジエン系樹脂などが例示される。より具体的には、高密度ポリエチレン、中密度ポリエチレン、直鎖状ポリエチレン、エチレン含量５０重量％以上、好ましくは７０重量％以上のエチレンコポリマー、プロピレンホモポリマー、プロピレン５０重量％以上、好ましくは７０重量％以上のプロピレンコポリマー、ブテンホモポリマー、ブテン含量５０重量％以上、好ましくは７０重量％以上のブテンコポリマー、メチルペンテンホモポリマー、メチルペンテン含量５０重量％以上、好ましくは７０重量％以上のメチルペンテンコポリマー、ポリブタジエン等が例示される。また、上記コポリマーはランダムコポリマーであってもよく、ブロックコポリマーであってもよい。更に、これらの樹脂の立体規則性がある場合は、アイソタクチックでもシンジオタクチックでもよい。上記コポリマーを構成し得るコモノマーとして、具体的にはエチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、ウンデセン、ドデセン等の炭素数２～１２のα－オレフィン、１，４－エンドメチレンシクロヘキセン等のビシクロ型モノマー、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等の（メタ）アクリル酸エステル、酢酸ビニル等が例示される。
[Polyolefin resin]
The above-mentioned polyolefin resin is not particularly limited as long as it achieves the effects of the present invention, and conventionally known polyolefin resins can be used, such as polyethylene resins, polypropylene resins, polybutene resins, and polymethylpentene resins. Examples include polybutadiene-based resins and polybutadiene-based resins. More specifically, high-density polyethylene, medium-density polyethylene, linear polyethylene, ethylene copolymers with an ethylene content of 50% by weight or more, preferably 70% by weight or more, propylene homopolymers, propylene 50% by weight or more, preferably 70% by weight % or more propylene copolymers, butene homopolymers, butene copolymers with a butene content of 50% by weight or more, preferably 70% by weight or more, methylpentene homopolymers, methylpentene copolymers with a methylpentene content of 50% or more, preferably 70% by weight or more. , polybutadiene, etc. Further, the above copolymer may be a random copolymer or a block copolymer. Furthermore, if these resins have stereoregularity, they may be isotactic or syndiotactic. Examples of comonomers that can constitute the above-mentioned copolymer include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene; Examples include bicyclo-type monomers such as endomethylenecyclohexene, (meth)acrylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate, and vinyl acetate.
かかる重合体を製造するために適用される触媒としては、一般に使用されているチーグラー・ナッタ型触媒はもちろん、遷移金属化合物（例えば、三塩化チタン、四塩化チタン等のチタンのハロゲン化物）を塩化マグネシウム等のハロゲン化マグネシウムを主成分とする担体に担持してなる触媒と、アルキルアルミニウム化合物（トリエチルアルミニウム、ジエチルアルミニウムクロリド等）とを組み合わせてなる触媒系、メタロセン触媒等も使用できる。 Catalysts that can be applied to produce such polymers include commonly used Ziegler-Natta type catalysts, as well as transition metal compounds (for example, titanium halides such as titanium trichloride and titanium tetrachloride). Catalyst systems comprising a combination of a catalyst supported on a carrier containing a magnesium halide such as magnesium as a main component and an alkyl aluminum compound (triethyl aluminum, diethylaluminum chloride, etc.), metallocene catalysts, etc. can also be used.
本発明に係るポリオレフィン系樹脂のメルトフローレート（以下「ＭＦＲ」と略記する。ＪＩＳ Ｋ ７２１０－１９９９）は、その適用する成形方法により適宜選択されるが、通常０．０１～２００ｇ／１０分程度、好ましくは０．０５～１００ｇ／１０分程度が推奨される。 The melt flow rate (hereinafter abbreviated as "MFR", JIS K 7210-1999) of the polyolefin resin according to the present invention is appropriately selected depending on the molding method to be applied, but is usually about 0.01 to 200 g/10 minutes. , preferably about 0.05 to 100 g/10 minutes.
［その他の添加剤］
また、上述の通り、本発明のポリオレフィン系樹脂組成物には、その使用目的やその用途に応じて、本発明の効果を損なわない範囲でその他のポリオレフィン系樹脂用添加剤が含まれていてもよい。
[Other additives]
In addition, as mentioned above, the polyolefin resin composition of the present invention may contain other additives for polyolefin resins depending on the purpose and use thereof, as long as the effects of the present invention are not impaired. good.
上記ポリオレフィン系樹脂用添加剤としては、例えば、ポリオレフィン等衛生協議会編「ポジティブリストの添加剤要覧」（２００４年９月）に記載されている各種添加剤が挙げられる。具体的には、蛍光増白剤（２，５－チオフェンジイル（５－ｔ－ブチル－１，３－ベンゾオキサゾール）、４，４’－ビス（ベンゾオキサゾール－２－イル）スチルベン等）、酸化防止剤、安定剤（金属化合物、エポキシ化合物、窒素化合物、燐化合物、硫黄化合物等）、紫外線吸収剤（ベンゾフェノン系化合物、ベンゾトリアゾール系化合物等）、界面活性剤、滑剤（パラフィン、ワックス等の脂肪族炭化水素、炭素数８～２２の高級脂肪酸、炭素数８～２２の高級脂肪酸金属（Ａｌ、Ｃａ等）塩、炭素数８～２２の高級脂肪族アルコール、ポリグリコール、炭素数４～２２の高級脂肪酸と炭素数４～１８の脂肪族１価アルコールとのエステル、炭素数８～２２の高級脂肪酸アマイド、シリコーン油、ロジン誘導体等）、充填剤（タルク、ハイドロタルサイト、マイカ、ゼオライト、パーライト、珪藻土、炭酸カルシウム、ガラス繊維等）、発泡剤、発泡助剤、ポリマー添加剤、可塑剤（ジアルキルフタレート、ジアルキルヘキサヒドロフタレート等）、架橋剤、架橋促進剤、帯電防止剤、難燃剤、分散剤、有機無機の顔料（インディゴ化合物、フタロシアニン系化合物、アントラキノン系化合物、ウルトラマリン化合物、アルミン酸コバルト化合物等）、加工助剤、他の核剤等の各種添加剤が例示される。 Examples of the above-mentioned additives for polyolefin resins include various additives listed in "Positive List Additive Directory" (September 2004) edited by the Polyolefin Hygiene Council. Specifically, fluorescent brighteners (2,5-thiophenediyl(5-t-butyl-1,3-benzoxazole), 4,4'-bis(benzoxazol-2-yl)stilbene, etc.), oxidized Inhibitors, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (fats such as paraffin and wax) Group hydrocarbons, higher fatty acids with 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca, etc.) salts with 8 to 22 carbon atoms, higher aliphatic alcohols with 8 to 22 carbon atoms, polyglycols, higher fatty acids with 4 to 22 carbon atoms Esters of higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oil, rosin derivatives, etc.), fillers (talc, hydrotalcite, mica, zeolite, perlite) , diatomaceous earth, calcium carbonate, glass fiber, etc.), blowing agents, foaming aids, polymer additives, plasticizers (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersion Examples include various additives such as additives, organic and inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents.
これらの添加剤を使用する場合、その使用量は、本発明の効果を阻害しない限り、通常使用されている範囲で使用すればよいが、例えば、ポリオレフィン系樹脂１００質量部に対して、好ましくは０．０００１～１００質量部程度、より好ましくは０．００１～５０質量部程度で使用されるのが一般的である。 When using these additives, the amount used may be within the range normally used as long as it does not impede the effects of the present invention. It is generally used in an amount of about 0.0001 to 100 parts by mass, more preferably about 0.001 to 50 parts by mass.
上記酸化防止剤としては、フェノール系酸化防止剤、亜リン酸エステル系酸化防止剤、イオウ系酸化防止剤等が例示され、具体的な酸化防止剤としては、２，６－ジ－ｔｅｒｔ－ブチルフェノール、テトラキス［メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、２－ヒドロキシ－４－メトキシベンゾフェノンなどのフェノール系酸化防止剤、アルキルジスルフィド、チオジプロピオン酸エステル、ベンゾチアゾールなどの硫黄系酸化防止剤、トリスノニルフェニルホスファイト、ジフェニルイソデシルホスファイト、トリフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカンなどの亜リン酸エステル系酸化防止剤等が例示される。中でも、フェノール系酸化防止剤であるテトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、亜リン酸エステル系の酸化防止剤であるトリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスファスピロ［５，５］ウンデカンなどが特に推奨される。 Examples of the above-mentioned antioxidants include phenolic antioxidants, phosphite-based antioxidants, sulfur-based antioxidants, etc. Specific antioxidants include 2,6-di-tert-butylphenol. , tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, phenolic antioxidants such as 2-hydroxy-4-methoxybenzophenone, alkyl disulfides, thiodipropionic acid Sulfur-based antioxidants such as esters and benzothiazole, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, 3,9-bis Phosphite ester antioxidants such as (2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, etc. Illustrated. Among them, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, which is a phenolic antioxidant, and tris(2, 4-di-tert-butylphenyl) phosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[ 5,5] Undecane etc. are particularly recommended.
また、本発明のポリオレフィン系樹脂用の結晶化促進剤のポリオレフィン系樹脂中での分散性等の観点より、その他の添加剤として分子中に少なくとも１個の水酸基を有していても良い炭素数１２～２２の飽和又は不飽和脂肪酸の金属塩を配合する処方が推奨される。 In addition, from the viewpoint of dispersibility in the polyolefin resin of the crystallization accelerator for polyolefin resin of the present invention, other additives may have at least one hydroxyl group in the molecule. A formulation containing 12 to 22 metal salts of saturated or unsaturated fatty acids is recommended.
上記金属塩における脂肪酸としては、具体的に、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、パルミトレイン酸、マルガリン酸、ステアリン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、１２－ヒドロキシステアリン酸、ベヘン酸、エルカ酸などが挙げられ、中でもラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、１２－ヒドロキシステアリン酸、ベヘン酸が推奨され、特にステアリン酸、１２－ヒドロキステアリン酸が最も推奨される。 Specifically, the fatty acids in the metal salt include lauric acid, myristic acid, pentadecyl acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, and 12-hydroxystearic acid. , behenic acid, erucic acid, etc. Among them, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, and behenic acid are recommended, and especially stearic acid and 12-hydroxystearic acid are the most recommended. .
また、上記金属塩を形成する金属種としては、具体的に、リチウム、マグネシウム、バリウム、ナトリウム、アルミニウム、カリウム、ストロンチウム、亜鉛などが挙げられ、中でもリチウム、マグネシウム、アルミニウム、亜鉛が推奨され、特にリチウム、亜鉛が推奨される。 Further, specific examples of the metal species forming the metal salt include lithium, magnesium, barium, sodium, aluminum, potassium, strontium, zinc, etc. Among them, lithium, magnesium, aluminum, and zinc are recommended, and especially Lithium and zinc are recommended.
＜ポリオレフィン系樹脂成形体＞
本発明のポリオレフィン系樹脂成形体は、上記本発明のポリオレフィン系樹脂組成物を原料とし、慣用されている成形方法に従って成形することにより得られる。前記成形方法としては、本発明の効果を奏する限り、特に制約はなく、射出成形、押出成形、ブロー成形、圧空成形、回転成形、フィルム成形等の従来公知の成形方法のいずれも採用できる。
<Polyolefin resin molded body>
The polyolefin resin molded article of the present invention is obtained by using the polyolefin resin composition of the present invention as a raw material and molding it according to a commonly used molding method. The molding method is not particularly limited as long as it achieves the effects of the present invention, and any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotational molding, and film molding can be employed.
かくして得られたポリオレフィン系樹脂成形体は、結晶化温度が高く、即ち結晶化速度が速く、その結果、特に大型部材等における成形サイクルが大きく短縮され、コストダウンや加工時のトラブル防止等に非常に有効である。更に、結晶性を改善することにより、えられた成形品の剛性等の機械的性能、透明性等の光学的性能、耐熱性等の熱的性能が向上するだけでなく、ひけやそりが少なくなり、複雑な形状の成形品も安定して製造可能となり、成形品やシート、フィルムとして、自動車部材、電気部材、機械部品、日常雑貨など様々な用途で、非常に有用である。 The polyolefin resin molded product obtained in this way has a high crystallization temperature, that is, a fast crystallization speed, and as a result, the molding cycle, especially for large parts, can be greatly shortened, which is extremely useful for reducing costs and preventing trouble during processing. It is effective for Furthermore, by improving crystallinity, the resulting molded product not only improves mechanical performance such as rigidity, optical performance such as transparency, and thermal performance such as heat resistance, but also reduces sink marks and warpage. This makes it possible to stably produce molded products with complex shapes, making them extremely useful as molded products, sheets, and films for a variety of applications such as automobile parts, electrical parts, mechanical parts, and everyday miscellaneous goods.
以下に実施例を示し、本発明を更に詳しく説明するが、本発明はこれらの実施例によって制限されるものではない。尚、各特性の測定は以下の通りである。 EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, the measurement of each characteristic is as follows.
［得られた化合物の分析方法］ [Method of analyzing the obtained compound]
（１）赤外線分光分析（ＩＲ分析）
ＦＴ－ＩＲ装置：商品名「Ｓｐｅｃｔｒｕｍ Ｏｎｅ」、パーキンエルマー社製、測定範囲：６５０～４０００ｃｍ－１、測定方法：ＡＴＲ法、積算回数：３回、分解能：４．００ｃｍ－１
なお、測定はサンプルを装置のセル上に押し付けて分析を行った。
(1) Infrared spectroscopy (IR analysis)
FT-IR device: Product name "Spectrum One", manufactured by PerkinElmer, measurement range: 650 to 4000 cm -1 , measurement method: ATR method, number of integrations: 3 times, resolution: 4.00 cm -1
Note that the measurement was performed by pressing the sample onto the cell of the device.
（２）核磁気共鳴分光分析（ＮＭＲ分析）
ＮＭＲ分析装置：商品名「ＤＲＸ－５００」、Ｂｒｕｋｅｒ社製
溶媒：重ジメチルスルホキシド（ＤＭＳＯ－ｄ６）
内部標準物質：テトラメチルシラン（ＴＭＳ）
試料管：５ｍｍ
１Ｈ－ＮＭＲ・・・共鳴周波数：５００．１ＭＨｚ、積算回数４回
１３Ｃ－ＮＭＲ・・・共鳴周波数：１２５．８ＭＨｚ、積算回数２３回
なお、測定試料は、３０ｍｇの試料を０．８ｍｌの溶媒で希釈して調製した。
(2) Nuclear magnetic resonance spectroscopy (NMR analysis)
NMR analyzer: Trade name “DRX-500”, manufactured by Bruker Solvent: Heavy dimethyl sulfoxide (DMSO-d6)
Internal standard substance: Tetramethylsilane (TMS)
Sample tube: 5mm
1 H-NMR...Resonance frequency: 500.1MHz, integration number of 4 times
13 C-NMR: Resonance frequency: 125.8 MHz, 23 integrations The measurement sample was prepared by diluting 30 mg of sample with 0.8 ml of solvent.
（３）誘導結合プラズマ分析（ＩＣＰ分析）
ＩＣＰ装置：商品名「ｉＣＡＰ ６５００Ｄｕｏ」Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ ＳＣＩＥＮＴＩＦＩＣ社製、
スプレイチャンバ：サイクロン噴霧器
プラズマ条件：プラズマ／補助／キャリアー＝１５／１．０／０．６
プラズマ観測方向：アキシャル方向３回
なお、測定はマイクロウェーブ分解法による前処理を行い測定用試料とした。
マイクロウェーブ装置：Ａｎｔｏｎ Ｐａａｒ社製Ｍｕｌｔｉｗａｖｅ ＰＲＯ
分解条件：試料 約０．０５ｇと硝酸（特級）６ｍＬを分解後、蒸留水で希釈して調製した。
(3) Inductively coupled plasma analysis (ICP analysis)
ICP device: Product name “iCAP 6500Duo” manufactured by Thermo Fisher SCIENTIFIC,
Spray chamber: Cyclone atomizer Plasma conditions: Plasma/auxiliary/carrier = 15/1.0/0.6
Plasma observation direction: axial direction 3 times In addition, the measurement was pretreated by microwave decomposition method and used as a measurement sample.
Microwave device: Multiwave PRO manufactured by Anton Paar
Decomposition conditions: About 0.05 g of sample and 6 mL of nitric acid (special grade) were decomposed and then diluted with distilled water to prepare.
［ポリオレフィン系樹脂成形体の評価方法］
（４）結晶化温度
示差走査熱量分析装置（パーキンエルマー社製、ＤＳＣ８５００）を用い、ＪＩＳＫ７１２１（１９８７）に従って測定した。評価用試料には、各実施例・比較例のポリオレフィン樹脂組成物約６ｍｇを使用した。その試料を装置にセットし、２００℃で３分間保持した後、１０℃／分の冷却速度で冷却し、吸熱ピークの頂点を結晶化温度（℃）とした。
[Evaluation method of polyolefin resin molded product]
(4) Crystallization temperature Measured according to JIS K7121 (1987) using a differential scanning calorimeter (DSC8500, manufactured by PerkinElmer). Approximately 6 mg of the polyolefin resin composition of each Example and Comparative Example was used as the evaluation sample. The sample was set in the apparatus, held at 200°C for 3 minutes, and then cooled at a cooling rate of 10°C/min, and the apex of the endothermic peak was taken as the crystallization temperature (°C).
（５）半結晶化時間（Ｔ１／２）
示差走査熱量分析装置（同社製）を用い、ＪＩＳＫ７１２１（１９８７）に従って測定した。評価用試料には、各実施例・比較例のポリオレフィン樹脂組成物約６ｍｇを使用した。その試料を装置にセットし、２００℃で３分間保持した後、７５０℃/分の冷却速度で１４０℃まで冷却し、その温度において等温結晶化を行った。等温結晶化工程開始から、時間と熱量との関係図において認められる結晶化に基づく発熱ピークの面積の １／２ に到達するまでの所要時間を半結晶化時間（Ｔ１／２、秒）とした。
(5) Half crystallization time (T 1/2 )
Measurement was performed using a differential scanning calorimeter (manufactured by the same company) in accordance with JIS K7121 (1987). Approximately 6 mg of the polyolefin resin composition of each Example and Comparative Example was used as the evaluation sample. The sample was set in the apparatus and held at 200°C for 3 minutes, then cooled to 140°C at a cooling rate of 750°C/min, and isothermal crystallization was performed at that temperature. The time required from the start of the isothermal crystallization process to reach 1/2 of the area of the exothermic peak due to crystallization observed in the relationship diagram between time and heat amount is called the half-crystallization time (T 1/2 , seconds). did.
（６）曇り度（ヘイズ値）
日本電色工業（株）のヘイズメータ（ＮＤＨ ７０００）を用いて、ＪＩＳＫ７１３６（２０００）に準じた方法でヘイズ値（％）を測定した。評価試料には、０．５ｍｍ厚み射出成形品のオレフィン系樹脂成形体を使用した。得られたヘイズ値の数値が小さい程、透明性に優れていることを示す。
(6) Cloudiness (haze value)
The haze value (%) was measured using a haze meter (NDH 7000) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7136 (2000). An olefin-based resin molded article having a thickness of 0.5 mm was used as an evaluation sample. The smaller the obtained haze value, the better the transparency.
（７）曲げ弾性率及び 応力
万能材料試験機（インストロン社製）を用い、ＪＩＳＫ７１７１（２０１６）に準じた方法で曲げ弾性率及び 応力を測定した。なお、試験温度は２５℃、試験速度は１０ｍｍ／分とした。
(7) Flexural modulus and stress Using a universal material testing machine (manufactured by Instron), the flexural modulus and stress were measured in accordance with JIS K7171 (2016). Note that the test temperature was 25° C. and the test speed was 10 mm/min.
［製造例１］
攪拌装置と温度計を備えた４つ口フラスコに、市販の５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）６４ｇ（０．３９モル）と、水３００ｍｌ、水酸化ナトリウム３２ｇ（０．８モル）を仕込み、室温下で反応系が均一になるまで攪拌した（攪拌中、僅かに発熱）。得られた均一溶液をアセトン（６Ｌ）中へ注ぎ、析出した白色固体を濾別後、１４０℃で減圧乾燥して、５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩６６ｇ（化合物１）を得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物１の構造が目的の化合物の構造であることを確認した。
[Manufacture example 1]
In a four-necked flask equipped with a stirrer and a thermometer, 64 g (0.39 mol) of commercially available 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) and 300 ml of water were added. , 32 g (0.8 mol) of sodium hydroxide were charged, and the mixture was stirred at room temperature until the reaction system became homogeneous (slight heat generation occurred during stirring). The obtained homogeneous solution was poured into acetone (6 L), the precipitated white solid was filtered off, and then dried under reduced pressure at 140°C to obtain 66 g of disodium salt of 5-norbornene-2,3-dicarboxylic acid (compound 1). I got it. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 1 was the structure of the target compound.
［製造例２］
攪拌装置と温度計を備えた４つ口フラスコに、市販の５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）６４ｇ（０．３９モル）と、水３００ｍｌ、水酸化リチウム１９．２ｇ（０．８モル）を仕込み、室温下で反応系が均一になるまで攪拌した（攪拌中、僅かに発熱）。得られた均一溶液をアセトン（６Ｌ）中へ注ぎ、析出した白色固体を濾別後、１４０℃で減圧乾燥して、５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩６０ｇ（化合物２）を得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物２の構造が目的の化合物の構造であることを確認した。
[Manufacture example 2]
In a four-necked flask equipped with a stirrer and a thermometer, 64 g (0.39 mol) of commercially available 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) and 300 ml of water were added. , 19.2 g (0.8 mol) of lithium hydroxide was charged, and the mixture was stirred at room temperature until the reaction system became homogeneous (slight heat generation occurred during stirring). The obtained homogeneous solution was poured into acetone (6 L), the precipitated white solid was filtered off, and then dried under reduced pressure at 140°C to obtain 60 g of dilithium salt of 5-norbornene-2,3-dicarboxylic acid (compound 2). I got it. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 2 was the structure of the target compound.
［製造例３］
攪拌装置と温度計を備えた４つ口フラスコに、水５００ｍｌと水酸化カルシウム６１ｇ（０．８１モル）を仕込み、室温下で攪拌してスラリー化した。得られたスラリーに市販の５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）１３３ｇ（０．８１モル）を加えて、５０℃に加熱して、５時間攪拌し、反応を行った。反応終了後、スラリーを濾別し、更に十分な量の水で洗浄後、１４０℃で一晩減圧乾燥して、５－ノルボルネン－２，３－ジカルボン酸のカルシウム塩（化合物３）１６８ｇを得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物３の構造が目的の化合物の構造であることを確認した。
[Manufacture example 3]
A four-necked flask equipped with a stirrer and a thermometer was charged with 500 ml of water and 61 g (0.81 mol) of calcium hydroxide, and stirred at room temperature to form a slurry. 133 g (0.81 mol) of commercially available 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) was added to the obtained slurry, and the mixture was heated to 50°C for 5 hours. The mixture was stirred and the reaction was carried out. After the reaction was completed, the slurry was filtered, washed with a sufficient amount of water, and dried under reduced pressure at 140°C overnight to obtain 168 g of calcium salt of 5-norbornene-2,3-dicarboxylic acid (compound 3). Ta. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 3 was the structure of the target compound.
［製造例４］
攪拌装置と温度計を備えた４つ口フラスコに、水５００ｍｌと酸化亜鉛６６ｇ（０．８１モル）を仕込み、室温下で攪拌してスラリー化した。得られたスラリーに市販の５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）１３３ｇ（０．８１モル）を加えて、５０℃に加熱して、５時間攪拌し、反応を行った。反応終了後、スラリーを濾別し、更に十分な量の水で洗浄後、１４０℃で一晩減圧乾燥して、５－ノルボルネン－２，３－ジカルボン酸の亜鉛塩（化合物４）１６０ｇを得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物の構造が目的の化合物４の構造であることを確認した。
[Manufacture example 4]
A four-neck flask equipped with a stirrer and a thermometer was charged with 500 ml of water and 66 g (0.81 mol) of zinc oxide, and stirred at room temperature to form a slurry. 133 g (0.81 mol) of commercially available 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) was added to the obtained slurry, and the mixture was heated to 50°C for 5 hours. The mixture was stirred and the reaction was carried out. After the reaction, the slurry was filtered, washed with a sufficient amount of water, and dried under reduced pressure at 140°C overnight to obtain 160 g of zinc salt of 5-norbornene-2,3-dicarboxylic acid (compound 4). Ta. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound was that of the target compound 4.
［製造例５］
攪拌装置と温度計を備えた４つ口フラスコに、水５００ｍｌと水酸化アルミニウム３０．４ｇ（０．３９モル）を仕込み、室温下で攪拌してスラリー化した。５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）６４ｇ（０．３９モル）を加えて、５０℃に加熱して、５時間攪拌し、反応を行った。反応終了後、スラリーを濾別し、更に十分な量の水で洗浄後、１４０℃で一晩減圧乾燥して、５－ノルボルネン－２，３－ジカルボン酸のヒドロキシアルミニウム塩（化合物５）７０ｇを得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物５の構造が目的の化合物の構造であることを確認した。
[Manufacture example 5]
A four-necked flask equipped with a stirrer and a thermometer was charged with 500 ml of water and 30.4 g (0.39 mol) of aluminum hydroxide, and stirred at room temperature to form a slurry. 64 g (0.39 mol) of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent) was added, heated to 50°C, and stirred for 5 hours to perform a reaction. . After the reaction, the slurry was filtered, washed with a sufficient amount of water, and dried under reduced pressure at 140°C overnight to obtain 70 g of hydroxyaluminum salt of 5-norbornene-2,3-dicarboxylic acid (compound 5). Obtained. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 5 was the structure of the target compound.
［製造例６］
耐圧オートクレーブ中に、市販の５－ノルボルネン－２，３－ジカルボン酸無水物（東京化成工業（株）製、試薬）１１５ｇ（０．６９モル）、ジシクロペンタジエン４６ｇ（０．７モル）、トルエン１６０ｇを仕込み、撹拌下、１９０℃まで昇温し、３時間保持した後、反応器を２５℃まで冷却した。
次に、上記反応液３２０ｇに対して、トルエン６４５ｇをガラス容器に仕込み、撹拌下、室温にて、５重量％水酸化ナトリウム水溶液４２０ｇを２時間かけて滴下した。滴下終了後、更に２０分間撹拌した後攪拌を停止し、１０分間静置後、水層を除去した。更に、上記水洗操作を３回実施した。上記で得られたトルエン溶液を、ロータリーエバポレーターにてトルエンの存在量が５０重量％になるまで濃縮した。
[Manufacture example 6]
In a pressure-resistant autoclave, 115 g (0.69 mol) of commercially available 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), 46 g (0.7 mol) of dicyclopentadiene, and toluene. After 160 g of the reactor was charged, the temperature was raised to 190°C with stirring and held for 3 hours, and then the reactor was cooled to 25°C.
Next, 645 g of toluene was charged into a glass container with respect to 320 g of the above reaction liquid, and 420 g of a 5% by weight aqueous sodium hydroxide solution was added dropwise over 2 hours at room temperature while stirring. After the dropwise addition was completed, the mixture was stirred for an additional 20 minutes, then the stirring was stopped, and after being allowed to stand for 10 minutes, the aqueous layer was removed. Furthermore, the above water washing operation was performed three times. The toluene solution obtained above was concentrated using a rotary evaporator until the amount of toluene present was 50% by weight.
続いて、ガラスの撹拌槽に、ヘプタン３３２ｇを仕込み、２５℃にて上記で得られた濃縮液１７３ｇを滴下した。撹拌下、反応器の温度を５℃まで冷却し、更に２時間撹拌下で保持した後、得られたスラリーを濾過後、更に新たなヘプタンで洗浄した。最後に、得られた固体を減圧乾燥させ１，２，３，４，４ａ，５，８ａ－オクタヒドロ－１，４：５，８－ジメタノナフタレン－２，３－ジカルボン酸無水物（白色の固体）６６ｇを得た。 Subsequently, 332 g of heptane was charged into a glass stirring tank, and 173 g of the concentrate obtained above was added dropwise at 25°C. After cooling the temperature of the reactor to 5° C. under stirring and keeping it under stirring for an additional 2 hours, the resulting slurry was filtered and washed with additional heptane. Finally, the obtained solid was dried under reduced pressure to produce 1,2,3,4,4a,5,8a-octahydro-1,4:5,8-dimethanonaphthalene-2,3-dicarboxylic anhydride (white Solid) 66g was obtained.
続いて、上記で得られた１，２，３，４，４ａ，５，８ａ－オクタヒドロ－１，４：５，８－ジメタノナフタレン－２，３－ジカルボン酸無水物５０ｇ、トルエン１００ｇとパラジウム触媒（パラジウム５％／アルミナ９５％）０．５ｇを耐圧オートクレーブ中に仕込み、水素圧１ＭＰａ、温度８０℃で、攪拌下に４時間水素化反応した。反応終了後、反応物を遠心分離法で触媒と分離して、トルエン溶液１５０ｇを得た。ロータリーエバポレーターにてトルエンを濃縮し、白色の固体３２ｇを得た。ＩＲ分析及びＮＭＲ分析により、得られた白色固体が１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸無水物であることを確認した。 Subsequently, 50 g of 1,2,3,4,4a,5,8a-octahydro-1,4:5,8-dimethanonaphthalene-2,3-dicarboxylic acid anhydride obtained above, 100 g of toluene and palladium 0.5 g of a catalyst (5% palladium/95% alumina) was charged into a pressure autoclave, and a hydrogenation reaction was carried out at a hydrogen pressure of 1 MPa and a temperature of 80° C. for 4 hours with stirring. After the reaction was completed, the reaction product was separated from the catalyst by centrifugation to obtain 150 g of toluene solution. Toluene was concentrated using a rotary evaporator to obtain 32 g of a white solid. IR analysis and NMR analysis confirmed that the obtained white solid was 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid anhydride.
続いて、攪拌装置と温度計を備えた４つ口フラスコに、上記で得られた１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸無水物１１．６ｇ（０．０５モル）と、水５０ｍｌ、水酸化ナトリウム４ｇ（０．１モル）を仕込み、室温下で反応系が均一になるまで攪拌した（攪拌中、僅かに発熱）。得られた均一溶液をアセトン（６Ｌ）中へ注ぎ、析出した白色固体を濾別後、１４０℃で減圧乾燥して、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩１２ｇ（化合物６）を得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物６の構造が目的の化合物の構造であることを確認した。 Subsequently, 11.6 g (0.0 g) of the 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic anhydride obtained above was placed in a four-necked flask equipped with a stirrer and a thermometer. 05 mol), 50 ml of water, and 4 g (0.1 mol) of sodium hydroxide were added, and the mixture was stirred at room temperature until the reaction system became homogeneous (slight heat generation occurred during stirring). The obtained homogeneous solution was poured into acetone (6 L), and the precipitated white solid was filtered off and dried under reduced pressure at 140°C to obtain 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarbonate. 12 g of the disodium salt of the acid (compound 6) was obtained. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 6 was the structure of the target compound.
［製造例７］
攪拌装置と温度計を備えた４つ口フラスコに、水５０ｍｌと水酸化カルシウム３．８ｇ（０．０５モル）を仕込み、室温下で攪拌してスラリー化した。得られたスラリーに製造例６で得られた１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸無水物１１．６ｇ（０．０５モル）を加えて、５０℃に加熱して、５時間攪拌し、反応を行った。反応終了後、スラリーを濾別し、更に十分な量の水で洗浄後、１４０℃で一晩減圧乾燥して、１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸無水物のカルシウム塩（化合物７）１０ｇを得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物７の構造が目的の化合物の構造であることを確認した。
[Manufacture example 7]
A four-necked flask equipped with a stirrer and a thermometer was charged with 50 ml of water and 3.8 g (0.05 mol) of calcium hydroxide, and stirred at room temperature to form a slurry. 11.6 g (0.05 mol) of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid anhydride obtained in Production Example 6 was added to the obtained slurry, and the mixture was heated to 50°C. The reaction was carried out by heating and stirring for 5 hours. After the reaction, the slurry was filtered, washed with a sufficient amount of water, and dried under reduced pressure at 140°C overnight to obtain 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid. 10 g of anhydrous calcium salt (compound 7) was obtained. It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 7 was the structure of the target compound.
［製造例８］
攪拌装置と温度計を備えた４つ口フラスコに、水５００ｍｌと水酸化カルシウム６１ｇ（０．８１モル）を仕込み、室温下で攪拌してスラリー化した。得られたスラリーにシクロヘキサン－１，２－ジカルボン酸無水物（新日本理化（株）製、リカシッドＨＨ）１２５ｇ（０．８１モル）を加えて、５０℃に加熱して、５時間攪拌し、反応を行った。反応終了後、スラリーを濾別し、更に十分な量の水で洗浄後、１４０℃で一晩減圧乾燥して、シクロヘキサン－１，２－ジカルボン酸のカルシウム塩（化合物８）１６８ｇを得た。ＩＲ分析、ＩＣＰ分析より、得られた化合物８の構造が目的の化合物の構造であることを確認した。
[Manufacture example 8]
A four-necked flask equipped with a stirrer and a thermometer was charged with 500 ml of water and 61 g (0.81 mol) of calcium hydroxide, and stirred at room temperature to form a slurry. 125 g (0.81 mol) of cyclohexane-1,2-dicarboxylic anhydride (Rikacid HH, manufactured by Shin Nippon Chemical Co., Ltd.) was added to the obtained slurry, heated to 50 ° C., and stirred for 5 hours. The reaction was carried out. After the reaction was completed, the slurry was filtered, washed with a sufficient amount of water, and dried under reduced pressure at 140° C. overnight to obtain 168 g of calcium salt of cyclohexane-1,2-dicarboxylic acid (Compound 8). It was confirmed by IR analysis and ICP analysis that the structure of the obtained compound 8 was the structure of the target compound.
［実施例１］
ポリオレフィン系樹脂としてポリプロピレンホモポリマー（ＭＦＲ＝９ｇ/１０分（荷重２１６０ｇ、温度２３０℃））１００質量部、結晶化促進剤として上記製造例１で得られた５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩（化合物１）０.２質量部、及びその他の添加剤としてテトラキス［メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン（株）製、商品名「ＩＲＧＡＮＯＸ１０１０」）０．０５質量部、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト（ＢＡＳＦジャパン（株）製、商品名「ＩＲＧＡＦＯＳ１６８」）０．０５質量部をドライブレンドした。そのドライブレンド物を二軸押出機（（株）テクノベル社製 Ｌ/Ｄ=４５、スクリュー径１５ｍｍ、ダイス径５ｍｍ）を用いてバレル温度２００℃にて溶融混合後、押し出されたストランドを冷却し、ペレタイザーでカッティングして、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 1]
100 parts by mass of polypropylene homopolymer (MFR = 9 g/10 min (load 2160 g, temperature 230°C)) as a polyolefin resin, and 5-norbornene-2,3-dicarboxylic acid obtained in Production Example 1 as a crystallization promoter. 0.2 parts by mass of the disodium salt (Compound 1), and other additives such as tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (BASF Japan Ltd. 0.05 parts by mass of Tetrakis(2,4-di-tert-butylphenyl)phosphite (manufactured by BASF Japan Co., Ltd., trade name "IRGAFOS168"), 0.05 parts by mass of Dry blended. The dry blend was melt-mixed using a twin-screw extruder (manufactured by Technovel Co., Ltd., L/D=45, screw diameter 15 mm, die diameter 5 mm) at a barrel temperature of 200°C, and the extruded strands were cooled. and cutting with a pelletizer to prepare a polyolefin resin composition. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、射出成形機（日精樹脂工業（株）製ＮＳ４０－５Ａ）にて射出成形温度（加熱温度）２００℃、金型温度（冷却温度）４０℃の条件下で成形して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the injection molding temperature (heating temperature) was 200°C and the mold temperature (cooling temperature) was 40°C using an injection molding machine (NS40-5A manufactured by Nissei Jushi Kogyo Co., Ltd.). The polyolefin resin molded article (test piece) of the present invention was obtained by molding under the conditions of .degree. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例２］
化合物１の代わりに製造例２で得られた５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩（化合物２）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 2]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the dilithium salt of 5-norbornene-2,3-dicarboxylic acid (Compound 2) obtained in Production Example 2 was used instead of Compound 1. I prepared something. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例３］
化合物１の代わりに製造例３で得られた５－ノルボルネン－２，３－ジカルボン酸のカルシウム塩（化合物３）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 3]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of 5-norbornene-2,3-dicarboxylic acid (Compound 3) obtained in Production Example 3 was used instead of Compound 1. was prepared. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例４］
化合物１の代わりに製造例４で得られた５－ノルボルネン－２，３－ジカルボン酸の亜鉛塩（化合物４）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１示した。
[Example 4]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the zinc salt of 5-norbornene-2,3-dicarboxylic acid (Compound 4) obtained in Production Example 4 was used instead of Compound 1. was prepared. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例５］
化合物１の代わりに製造例５で得られた５－ノルボルネン－２，３－ジカルボン酸のヒドロキシアルミニウム塩（化合物５）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 5]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the hydroxyaluminum salt of 5-norbornene-2,3-dicarboxylic acid (Compound 5) obtained in Production Example 5 was used instead of Compound 1. I prepared something. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例６］
化合物１の代わりに製造例６で得られた１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩（化合物６）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 6]
Example 1 except that the disodium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid (Compound 6) obtained in Production Example 6 was used instead of Compound 1. A polyolefin resin composition was prepared in the same manner. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［実施例７］
化合物１の代わりに製造例７で得られた１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸のカルシウム塩（化合物７）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表１に示した。
[Example 7]
Same as Example 1 except that the calcium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid (Compound 7) obtained in Production Example 7 was used instead of Compound 1. A polyolefin resin composition was prepared. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表１に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 1.
［比較例１］
化合物１の代わりに製造例８で得られたシクロヘキサン－１，２－ジカルボン酸のカルシウム塩（化合物８）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表２に示した。
[Comparative example 1]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of cyclohexane-1,2-dicarboxylic acid (Compound 8) obtained in Production Example 8 was used instead of Compound 1. did. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表２に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 2.
［比較例２］
化合物１の代わりに市販の２，２‘－メチレンビス－（４，６－ジ－ｔｅｒｔ－ブチルフェニル)リン酸ナトリウム塩（（株）ＡＤＥＫＡ製、アデカスタブ ＮＡ－１１、以下ＮＡ－１１と略記する）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表２に示した。
[Comparative example 2]
Instead of Compound 1, commercially available 2,2'-methylenebis-(4,6-di-tert-butylphenyl) phosphate sodium salt (ADEKA Co., Ltd., ADEKA STAB NA-11, hereinafter abbreviated as NA-11) A polyolefin resin composition was prepared in the same manner as in Example 1 except that the following was used. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表２に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 2.
［比較例３］
化合物１の代わりに市販のｐ－ｔｅｒｔ－ブチル安息香酸のヒドロキシアルミニウム塩（以下ＡＬ－ＰＴＢＢＡと略記する）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表２に示した。
[Comparative example 3]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that a commercially available hydroxyaluminum salt of p-tert-butylbenzoic acid (hereinafter abbreviated as AL-PTBBA) was used instead of Compound 1. did. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表２に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 2.
［比較例４］
化合物１の代わりに市販の安息香酸のナトリウム塩（以下ＢＡ－Ｎａと略記する）を用いた以外は、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表２に示した。
[Comparative example 4]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that a commercially available sodium salt of benzoic acid (hereinafter abbreviated as BA-Na) was used instead of Compound 1. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表２に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 2.
［比較例５］
結晶化促進剤を配合しないで、実施例１と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度及び半結晶化時間を測定し、得られた結果を合わせて表２に示した。
[Comparative example 5]
A polyolefin resin composition was prepared in the same manner as in Example 1 without adding a crystallization promoter. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例１と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片の曲げ弾性率及びヘイズ値を測定し、得られた結果を合わせて表２に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 1 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 2.
［実施例８］
ポリオレフィン系樹脂としてリニア低密度ポリエチレン（ＭＦＲ＝２０ｇ/１０分（荷重２１６０ｇ、温度１９０℃））１００重量部、結晶化促進剤として上記製造例１で得られた５－ノルボルネン－２，３－ジカルボン酸の二ナトリウム塩（化合物１）０.２重量部、及びその他の添加剤としてテトラキス［メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン（株）製、商品名「ＩＲＧＡＮＯＸ１０１０」）０．０５重量部、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト（ＢＡＳＦジャパン（株）製、商品名「ＩＲＧＡＦＯＳ１６８」）０．０５重量部をドライブレンドした。そのドライブレンド物を二軸押出機（（株）テクノベル社製 Ｌ/Ｄ=４５、スクリュー径１５ｍｍ、ダイス径５ｍｍ）を用いてバレル温度２００℃にて溶融混合後、押し出されたストランドを冷却し、ペレタイザーでカッティングして、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度を測定し、得られた結果を表３に示した。
[Example 8]
100 parts by weight of linear low density polyethylene (MFR = 20 g/10 min (load 2160 g, temperature 190°C)) as a polyolefin resin, 5-norbornene-2,3-dicarbonate obtained in Production Example 1 as a crystallization promoter 0.2 parts by weight of disodium salt of acid (compound 1) and other additives such as tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (BASF Japan ( 0.05 parts by weight of tetrakis(2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Japan Ltd., brand name "IRGAFOS168") 0.05 parts by weight was dry blended. The dry blend was melt-mixed using a twin-screw extruder (manufactured by Technovel Co., Ltd., L/D=45, screw diameter 15 mm, die diameter 5 mm) at a barrel temperature of 200°C, and the extruded strands were cooled. and cutting with a pelletizer to prepare a polyolefin resin composition. The crystallization temperature of the obtained polyolefin resin composition was measured, and the obtained results are shown in Table 3.
続いて、得られたポリオレフィン系樹脂組成物を用いて、射出成形機（日精樹脂工業株式会社製ＮＳ４０－５Ａ）にて射出成形温度（加熱温度）２００℃、金型温度（冷却温度）４０℃の条件下で成形して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片のヘイズ値を測定し、得られた結果を表３に示した。 Subsequently, using the obtained polyolefin resin composition, the injection molding temperature (heating temperature) was 200°C and the mold temperature (cooling temperature) was 40°C using an injection molding machine (NS40-5A manufactured by Nissei Resin Industries Co., Ltd.). A polyolefin resin molded article (test piece) of the present invention was obtained by molding under the following conditions. The haze value of the obtained test piece was measured, and the obtained results are shown in Table 3.
［実施例９］
化合物１の変わりに製造例２で得られた５－ノルボルネン－２，３－ジカルボン酸の二リチウム塩（化合物２）を用いた以外は、実施例８と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度を測定し、得られた結果を表３に示した。
[Example 9]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the dilithium salt of 5-norbornene-2,3-dicarboxylic acid (Compound 2) obtained in Production Example 2 was used instead of Compound 1. I prepared something. The crystallization temperature of the obtained polyolefin resin composition was measured, and the obtained results are shown in Table 3.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例８と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片のヘイズ値を測定し、得られた結果を表３に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 8 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The haze value of the obtained test piece was measured, and the obtained results are shown in Table 3.
［実施例１０］
化合物１の代わりに製造例６で得られた１，４：５，８－ジメタノデカヒドロナフタレン－２，３－ジカルボン酸の二ナトリウム塩（化合物６）を用いた以外は、実施例８と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度を測定し、得られた結果を合わせて表３に示した。
[Example 10]
Example 8 except that the disodium salt of 1,4:5,8-dimethanodecahydronaphthalene-2,3-dicarboxylic acid (Compound 6) obtained in Production Example 6 was used instead of Compound 1. A polyolefin resin composition was prepared in the same manner. The crystallization temperature of the obtained polyolefin resin composition was measured, and the obtained results are shown in Table 3.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例８と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片のヘイズ値を測定し、得られた結果を表３に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 8 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The haze value of the obtained test piece was measured, and the obtained results are shown in Table 3.
［比較例６］
化合物１の代わりにＮＡ－１１を用いた以外は、実施例８と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度を測定し、得られた結果を表３に示した。
[Comparative example 6]
A polyolefin resin composition was prepared in the same manner as in Example 8 except that NA-11 was used instead of Compound 1. The crystallization temperature of the obtained polyolefin resin composition was measured, and the obtained results are shown in Table 3.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例８と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片のヘイズ値を測定し、得られた結果を表３に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 8 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The haze value of the obtained test piece was measured, and the obtained results are shown in Table 3.
［比較例７］
結晶化促進剤を配合しないで、実施例８と同様に実施して、ポリオレフィン系樹脂組成物を調製した。得られたポリオレフィン系樹脂組成物の結晶化温度を測定し、得られた結果を表３に示した。
[Comparative Example 7]
A polyolefin resin composition was prepared in the same manner as in Example 8 without adding a crystallization promoter. The crystallization temperature of the obtained polyolefin resin composition was measured, and the obtained results are shown in Table 3.
続いて、得られたポリオレフィン系樹脂組成物を用いて、実施例８と同様に実施して、本発明のポリオレフィン系樹脂成形体（試験片）を得た。得られた試験片のヘイズ値を測定し、得られた結果を表３に示した。 Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 8 was carried out to obtain a polyolefin resin molded article (test piece) of the present invention. The haze value of the obtained test piece was measured, and the obtained results are shown in Table 3.
表１の実施例１～７と表２の比較例５の結晶化温度及び半結晶化時間の比較より、本発明の結晶化促進剤が非常に優れた結晶化促進効果を有することがわかる。また、ヘイズ値及び曲げ弾性率の比較より、本発明の結晶化促進剤が、結晶化が促進すると同時に、透明性や剛性の改善にも非常に効果があることがわかる。また、表２の比較例２～４の従来公知の結晶化促進剤と比べても、その効果が非常に優れていることが明確に示されている。 A comparison of the crystallization temperature and half-crystallization time of Examples 1 to 7 in Table 1 and Comparative Example 5 in Table 2 shows that the crystallization promoter of the present invention has an extremely excellent crystallization promoting effect. Further, from a comparison of haze value and flexural modulus, it can be seen that the crystallization promoter of the present invention is very effective in promoting crystallization and improving transparency and rigidity. Furthermore, even when compared with the conventionally known crystallization promoters of Comparative Examples 2 to 4 in Table 2, it is clearly shown that the effect is very excellent.
本発明の結晶化促進剤は、ポリオレフィン系樹脂に配合することによりポリオレフィン系樹脂の結晶化速度、即ち結晶化温度を著しく向上することが可能であり、例えば、大型部材等における成形サイクルが約半分に短縮され、その結果、コストダウンや加工時のトラブル防止等に大きく貢献することができる。また、本発明の結晶化促進剤は、結晶性を改善することが可能であり、その結果、得られた成形品の剛性等の機械的性能、透明性等の光学的性能、耐熱性等の熱的性能が向上するだけでなく、ひけやそりが少なくなり、複雑な形状の成形品も安定して製造可能となる。更に、タルク等の充填剤との併用系でも、優れた効果を示すことが可能であり、剛性や強度等の要求される用途でも有効に使用することが可能である。従って、本発明の結晶化促進剤は、上記の様な特徴を活かして、自動車部材、電気部材、機械部品、日用雑貨、衣装等のケース、食品等の容器など、様々な用途で広く使うことができる。 The crystallization accelerator of the present invention can significantly improve the crystallization rate, that is, the crystallization temperature, of the polyolefin resin by blending it with the polyolefin resin, for example, the molding cycle for large parts etc. can be reduced by about half. As a result, it can greatly contribute to cost reduction and trouble prevention during processing. In addition, the crystallization accelerator of the present invention can improve crystallinity, and as a result, the resulting molded product can improve mechanical performance such as rigidity, optical performance such as transparency, and heat resistance. This not only improves thermal performance, but also reduces sink marks and warpage, making it possible to stably manufacture molded products with complex shapes. Furthermore, even when used in combination with a filler such as talc, excellent effects can be exhibited, and it can be effectively used in applications that require rigidity, strength, and the like. Therefore, the crystallization accelerator of the present invention takes advantage of the above-mentioned characteristics and can be widely used in various applications such as automobile parts, electrical parts, mechanical parts, daily goods, cases for clothing, containers for food, etc. be able to.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001507395A (en) | 1996-12-27 | 2001-06-05 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Modifier for polyolefin |
| JP2006225576A (en) | 2005-02-21 | 2006-08-31 | Dainichiseika Color & Chem Mfg Co Ltd | Resin composition |
| JP2009149724A (en) | 2007-12-19 | 2009-07-09 | Japan Polypropylene Corp | Propylene-ethylene-based resin composition and container consisting of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001507395A (en) | 1996-12-27 | 2001-06-05 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Modifier for polyolefin |
| JP2006225576A (en) | 2005-02-21 | 2006-08-31 | Dainichiseika Color & Chem Mfg Co Ltd | Resin composition |
| JP2009149724A (en) | 2007-12-19 | 2009-07-09 | Japan Polypropylene Corp | Propylene-ethylene-based resin composition and container consisting of the same |
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