JP7397310B2 - Crystal nucleating agent for polyolefin resin with improved dispersibility in resin, and polyolefin resin composition containing the crystal nucleating agent - Google Patents
Crystal nucleating agent for polyolefin resin with improved dispersibility in resin, and polyolefin resin composition containing the crystal nucleating agent Download PDFInfo
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- JP7397310B2 JP7397310B2 JP2020040389A JP2020040389A JP7397310B2 JP 7397310 B2 JP7397310 B2 JP 7397310B2 JP 2020040389 A JP2020040389 A JP 2020040389A JP 2020040389 A JP2020040389 A JP 2020040389A JP 7397310 B2 JP7397310 B2 JP 7397310B2
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- JP
- Japan
- Prior art keywords
- polyolefin resin
- dicarboxylic acid
- nucleating agent
- crystal nucleating
- salt
- 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 205
- 239000003484 crystal nucleating agent Substances 0.000 title claims description 97
- 239000011342 resin composition Substances 0.000 title claims description 97
- 229920005989 resin Polymers 0.000 title claims description 35
- 239000011347 resin Substances 0.000 title claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 101
- 239000002184 metal Substances 0.000 claims description 101
- 150000003839 salts Chemical class 0.000 claims description 98
- 238000002425 crystallisation Methods 0.000 claims description 82
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 76
- 125000002723 alicyclic group Chemical group 0.000 claims description 71
- 230000008025 crystallization Effects 0.000 claims description 56
- -1 hydroxyaluminum ion Chemical class 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims description 18
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 8
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 150000004682 monohydrates Chemical class 0.000 claims description 3
- 238000005481 NMR spectroscopy Methods 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 description 56
- 238000012360 testing method Methods 0.000 description 52
- 238000000034 method Methods 0.000 description 38
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical class [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 33
- 230000000694 effects Effects 0.000 description 31
- ACTKQYFQQDFDAM-UHFFFAOYSA-N 4-methylcyclohexane-1,1-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)(C(O)=O)CC1 ACTKQYFQQDFDAM-UHFFFAOYSA-N 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 22
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 20
- 238000000465 moulding Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 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
- 239000002253 acid Substances 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 8
- OGTDIVCVFKBYJD-UHFFFAOYSA-N 4-tert-butylcyclohexane-1,1-dicarboxylic acid Chemical compound CC(C)(C)C1CCC(C(O)=O)(C(O)=O)CC1 OGTDIVCVFKBYJD-UHFFFAOYSA-N 0.000 description 8
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- RUSTYNDGQSCBHW-UHFFFAOYSA-N cyclohex-3-ene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC=CC1 RUSTYNDGQSCBHW-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 229940125898 compound 5 Drugs 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 4
- WXYTXCXWNITTLN-UHFFFAOYSA-N 3-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCCC(C(O)=O)C1C(O)=O WXYTXCXWNITTLN-UHFFFAOYSA-N 0.000 description 4
- OJSHXMUNQKNYGS-UHFFFAOYSA-N 4-propylcyclohexane-1,2-dicarboxylic acid Chemical compound CCCC1CCC(C(O)=O)C(C(O)=O)C1 OJSHXMUNQKNYGS-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- UFDHBDMSHIXOKF-UHFFFAOYSA-N cyclohexene-1,2-dicarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 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
- 239000002667 nucleating agent Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- BRYYPPIMRHLVMD-UHFFFAOYSA-N 3-(2-methylpropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound CC(CC1C(C(C(=O)O)CCC1)C(=O)O)C BRYYPPIMRHLVMD-UHFFFAOYSA-N 0.000 description 3
- ZPRXNOLDOXHXIQ-UHFFFAOYSA-N 3-methylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CC1C=CCC(C(O)=O)C1C(O)=O ZPRXNOLDOXHXIQ-UHFFFAOYSA-N 0.000 description 3
- TUOHHYUIUYSMPB-UHFFFAOYSA-N 3-propan-2-ylcyclohexane-1,2-dicarboxylic acid Chemical compound CC(C)C1CCCC(C(O)=O)C1C(O)=O TUOHHYUIUYSMPB-UHFFFAOYSA-N 0.000 description 3
- LUTGRVASPNHYTG-UHFFFAOYSA-N 3-propylcyclohexane-1,2-dicarboxylic acid Chemical compound CCCC1CCCC(C(O)=O)C1C(O)=O LUTGRVASPNHYTG-UHFFFAOYSA-N 0.000 description 3
- MXMNQVNQRNLVTQ-UHFFFAOYSA-N 4-butylcyclohexane-1,2-dicarboxylic acid Chemical compound CCCCC1CCC(C(O)=O)C(C(O)=O)C1 MXMNQVNQRNLVTQ-UHFFFAOYSA-N 0.000 description 3
- IODOHPXRYMDKQF-UHFFFAOYSA-N 4-ethylcyclohexane-1,2-dicarboxylic acid Chemical compound CCC1CCC(C(O)=O)C(C(O)=O)C1 IODOHPXRYMDKQF-UHFFFAOYSA-N 0.000 description 3
- YWVFNWVZBAWOOY-UHFFFAOYSA-N 4-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1 YWVFNWVZBAWOOY-UHFFFAOYSA-N 0.000 description 3
- DKUPVPAQXKDDEV-UHFFFAOYSA-N 4-propylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CCCC1=CCC(C(O)=O)C(C(O)=O)C1 DKUPVPAQXKDDEV-UHFFFAOYSA-N 0.000 description 3
- ISOYJNMPVHWZMJ-UHFFFAOYSA-N 4-tert-butylcyclohexane-1,2-dicarboxylic acid Chemical compound C(C)(C)(C)C1CC(C(CC1)C(=O)O)C(=O)O ISOYJNMPVHWZMJ-UHFFFAOYSA-N 0.000 description 3
- HBKPBJGXEHHTBJ-UHFFFAOYSA-N CC(C)(C)C1CCCC(C(O)=O)C1C(O)=O Chemical compound CC(C)(C)C1CCCC(C(O)=O)C1C(O)=O HBKPBJGXEHHTBJ-UHFFFAOYSA-N 0.000 description 3
- COMJBAOFCGKXRE-UHFFFAOYSA-N CC(C)CC(C1C(O)=O)C=CCC1C(O)=O Chemical class CC(C)CC(C1C(O)=O)C=CCC1C(O)=O COMJBAOFCGKXRE-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 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
- 230000002776 aggregation Effects 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KMMAWEBXBXUIFM-UHFFFAOYSA-N 1-butylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CCCCC1(C(O)=O)CC=CCC1C(O)=O KMMAWEBXBXUIFM-UHFFFAOYSA-N 0.000 description 2
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- GMLGUFKRCQRQLR-UHFFFAOYSA-N 3-butylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CCCCC(C1C(O)=O)C=CCC1C(O)=O GMLGUFKRCQRQLR-UHFFFAOYSA-N 0.000 description 2
- DKKCYEVGEXEXAS-UHFFFAOYSA-N 3-butylcyclohexane-1,2-dicarboxylic acid Chemical compound CCCCC1CCCC(C(O)=O)C1C(O)=O DKKCYEVGEXEXAS-UHFFFAOYSA-N 0.000 description 2
- KCQIAPVAICXOFL-UHFFFAOYSA-N 3-ethylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CCC1C=CCC(C(O)=O)C1C(O)=O KCQIAPVAICXOFL-UHFFFAOYSA-N 0.000 description 2
- GLVRUIAMYISNHU-UHFFFAOYSA-N 3-ethylcyclohexane-1,2-dicarboxylic acid Chemical compound CCC1CCCC(C(O)=O)C1C(O)=O GLVRUIAMYISNHU-UHFFFAOYSA-N 0.000 description 2
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- OAKIBDGEEQFWHU-UHFFFAOYSA-N 4-propan-2-ylcyclohex-4-ene-1,2-dicarboxylic acid Chemical compound CC(C)C1=CCC(C(O)=O)C(C(O)=O)C1 OAKIBDGEEQFWHU-UHFFFAOYSA-N 0.000 description 2
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- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 2
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- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical class OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical class OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、樹脂中での分散性の改良されたポリオレフィン系樹脂用の結晶核剤としての本質的な性能である結晶性の改善効果に非常に優れたポリオレフィン系樹脂用の結晶核剤に関するものであり、詳しくは、結晶性の改善効果に優れた特定の構造からなる脂環式ジカルボン酸の金属塩を含み、更に該脂環式ジカルボン酸の金属塩中の水和物の割合が特定の範囲であり、更に特定の割合の結晶水を含むことにより、ポリオレフィン系樹脂中での分散性が大きく向上し、成形加工条件に影響されることなく、安定して上記結晶核剤としての性能をより一層発揮させることのできるポリオレフィン系樹脂用の結晶核剤、更には該結晶核剤を含んでなる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 crystal nucleating agent for polyolefin resins that has an excellent effect of improving crystallinity, which is the essential performance as a crystal nucleating agent for polyolefin resins with improved dispersibility in the resin. Specifically, it contains a metal salt of an alicyclic dicarboxylic acid having a specific structure that has an excellent effect of improving crystallinity, and furthermore, the proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid has a specific structure. By containing a specific proportion of crystallization water, the dispersibility in the polyolefin resin is greatly improved, and the performance as the crystal nucleating agent is stably maintained without being affected by molding conditions. The present invention relates to a crystal nucleating agent for polyolefin resins that can exhibit even greater performance, a polyolefin resin composition comprising the crystal nucleating agent, and a polyolefin resin molded article using the resin composition as a raw material.
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で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.
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、添加剤を配合する方法が、簡易でより実用的な方法として広く用いられている。結晶核剤は、樹脂の結晶性を改良することのできる代表的な添加剤であり、これまでも様々な検討がなされ、タルク等の無機化合物、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有機化合物などの結晶核剤が様々な結晶性の樹脂で検討され、実用化されている。 As a method to improve the crystallinity of resins, methods of controlling the structure and composition of resins have been widely studied and have actually been put into practical use, but the method of blending additives is a simpler and more practical method. This method is widely used. Crystal nucleating agents are typical additives that can improve the crystallinity of resins, and various studies have been conducted to date. Crystal nucleating agents such as organic compounds such as metal salts of sulfonic acids and sulfonic acid have been investigated and put into practical use with various crystalline resins.
上記結晶核剤のなかでも、カルボン酸の金属塩が優れた核剤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 crystal nucleating agents mentioned above, it has long been known that metal salts of carboxylic acids have excellent nucleating agent effects, and typical examples include sodium salt of benzoic acid and p-tert-butylbenzoic acid. and hydroxyaluminum salts, which have been widely used in various applications (Patent Documents 1 and 2, Non-Patent Documents 1 and 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核剤として優れた効果を有することは報告されている（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 crystal nucleating agents 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が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核剤による結晶性の改善では、成形加工性の改善や機械的特性の改善の面で必ずしも十分とは言えず、更なる結晶性の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 improvement of crystallinity using the known crystal nucleating agents is not necessarily sufficient in terms of improving moldability and mechanical properties. First, further improvement in crystallinity is 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特性が必要であり、ポリオレフィン系樹脂単独で十分な機械的特性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特性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、結晶核剤は、ポリオレフィン系樹脂の成形加工性や機械的特性を向上することが可能であり、上記の機械的特性等の性能低下を結晶核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、従来の結晶核剤の多くは、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核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 properties such as rigidity and strength, and it is difficult to obtain sufficient mechanical properties with polyolefin resin alone, and 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 properties inevitably deteriorates, and improvement thereof has been a major issue. As mentioned above, crystal nucleating agents can improve the moldability and mechanical properties of polyolefin resins, and it is being considered to compensate for the above-mentioned performance decline in mechanical properties by adding crystal nucleating agents. , is actually used. However, it is difficult for many conventional crystal nucleating agents to exhibit sufficient effects when used in combination with fillers, making it difficult to meet the demands for weight reduction that have become increasingly strict in recent years. . Therefore, there is a strong desire to develop a crystal nucleating agent that exhibits excellent effects when used in combination with fillers such as talc.
一方、上記カルボン酸の金属塩やリン酸エステルの金属塩などの金属塩系の結晶核剤の多くは、樹脂で溶解せず、分散状態で使われる所謂分散タイプの核剤であり、樹脂中での分散性が、結晶核剤としての性能に大きく影響することが知られている。一般的に樹脂中での分散性は結晶核剤の粒子が小さいほど、良好であると言われているが、上記結晶核剤の多くは二次凝集性を有しており、粒子が小さくなると二次凝集し易くなるため、粒子形状だけでは十分に樹脂中での分散性を改良することが困難であった。 On the other hand, many of the metal salt-based crystal nucleating agents, such as metal salts of carboxylic acids and metal salts of phosphoric acid esters, are so-called dispersion-type nucleating agents that do not dissolve in the resin and are used in a dispersed state. It is known that the dispersibility of crystals greatly affects their performance as crystal nucleating agents. It is generally said that the smaller the particles of the crystal nucleating agent, the better the dispersibility in the resin, but many of the above crystal nucleating agents have secondary agglomeration, and the smaller the particles Since secondary agglomeration is likely to occur, it has been difficult to sufficiently improve the dispersibility in the resin based on the particle shape alone.
また、樹脂中での分散性の改良方法として、他の添加剤を併用する方法もこれまで多く検討されてきたが、結晶核剤としての本来の性能を損なう懸念があり、更に、用途によっては使うことのできる添加剤に制限があり、できれば添加剤を使わずに樹脂中での分散性を改良する方法が望まれている。 In addition, as a method of improving dispersibility in resin, methods of using other additives in combination have been studied many times, but there is a concern that the original performance as a crystal nucleating agent will be impaired, and furthermore, depending on the application, There are restrictions on the additives that can be used, and if possible, a method of improving dispersibility in the resin without using additives is desired.
本発明は、樹脂中での分散性を改良することにより、ポリオレフィン系樹脂中での分散性が大きく向上し、成形加工条件に影響されることなく、安定して上記結晶核剤としての性能をより一層発揮させることのできるポリオレフィン系樹脂用の結晶核剤、及び該結晶核剤を含んでなる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。 By improving the dispersibility in the resin, the present invention greatly improves the dispersibility in the polyolefin resin, and stably maintains the performance as the crystal nucleating agent without being affected by molding conditions. The purpose of the present invention is to provide a crystal nucleating agent for a polyolefin resin that can exhibit even greater performance, a polyolefin resin composition comprising the crystal nucleating agent, and a polyolefin resin molded article using the resin composition as a raw material. shall be.
本発明者らは、上述の状況に鑑み、これまでにポリオレフィン系樹脂用の結晶核剤としての本質的な性能である結晶性の改善効果に非常に優れた結晶核剤の開発を続けてきた。その結果、特定の構造の脂環式ジカルボン酸の金属塩が、脂環式ジカルボン酸の金属塩を含めた従来公知の結晶核剤に比べて、結晶性の改善効果、特に結晶化速度の向上に非常に優れた効果を示すことを確認し、報告した（特願２０１８－１４９６５７、特願２０１９－１６５２８８）。 In view of the above-mentioned circumstances, the present inventors have continued to develop crystal nucleating agents that are extremely effective in improving crystallinity, which is the essential performance as a crystal nucleating agent for polyolefin resins. . As a result, the metal salt of an alicyclic dicarboxylic acid with a specific structure has an effect of improving crystallinity, especially an improvement in the crystallization rate, compared to conventionally known crystal nucleating agents including metal salts of an alicyclic dicarboxylic acid. It was confirmed and reported that it has very excellent effects on (Japanese Patent Application No. 2018-149657, Patent Application No. 2019-165288).
本発明者らは、上記結果に満足することなく、更に上記課題を解決すべく、鋭意検討した結果、上記脂環式ジカルボン酸の金属塩中の水和物の割合を特定の範囲に制御し、更に特定の割合の結晶水を含ませることにより、ポリオレフィン系樹脂中での分散性が大きく向上し、結晶性の改善効果が更に向上するだけでなく、成形加工条件に影響されることなく、安定して上記結晶核剤としての性能を発揮させることができることを見出し、本発明を完成するに至った。 The present inventors were not satisfied with the above results, and as a result of intensive studies to further solve the above problems, the inventors of the present invention controlled the proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid within a specific range. Furthermore, by including a specific proportion of water of crystallization, the dispersibility in the polyolefin resin is greatly improved, and the effect of improving crystallinity is not only further improved, but also unaffected by molding processing conditions. It was discovered that the above-mentioned performance as a crystal nucleating agent can be stably exhibited, and the present invention was completed.
即ち、本発明は以下に示す樹脂中での分散性の改良されたポリオレフィン系樹脂用の結晶核剤としての本質的な性能である結晶性の改善効果に非常に優れたポリオレフィン系樹脂用の結晶核剤、及び該結晶核剤を含んでなる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 provides the following crystals for polyolefin resins which have excellent dispersibility in resins and which are extremely effective in improving crystallinity, which is the essential performance as a crystal nucleating agent for polyolefin resins. The present invention provides a nucleating agent, a polyolefin resin composition comprising the crystal nucleating agent, and a polyolefin resin molded article using the resin composition as a raw material.
［項１］ 樹脂中での分散性の改良されたポリオレフィン系樹脂用の結晶核剤であって、
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み、且つ、
前記脂環式ジカルボン酸の金属塩の全量又は一部が結晶水を有する水和物であることを特徴とするポリオレフィン系樹脂用の結晶核剤。
Contains a metal salt of an alicyclic dicarboxylic acid represented by the following general formula (1) or general formula (2), and
A crystal nucleating agent for a polyolefin resin, wherein all or a part of the metal salt of the alicyclic dicarboxylic acid is a hydrate having water of crystallization.
［項２］ 前記脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して１０質量％以上であり、更に、
前記脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、０．５質量％以上である、［項１］に記載のポリオレフィン系樹脂用の結晶核剤。
[Item 2] The proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid is 10% by mass or more based on the entire metal salt of the alicyclic dicarboxylic acid, and further,
The crystal nucleating agent for a polyolefin resin according to item 1, wherein the proportion of crystal water contained in the metal salt of the alicyclic dicarboxylic acid is 0.5% by mass or more.
［項３］ 脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して３０質量％以上であり、且つ、脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、１．５質量％以上である、［項１］又は［項２］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 3] The proportion of hydrate in the metal salt of alicyclic dicarboxylic acid is 30% by mass or more based on the entire metal salt of alicyclic dicarboxylic acid, and the metal salt of alicyclic dicarboxylic acid The crystal nucleating agent for a polyolefin resin according to [Item 1] or [Item 2], wherein the proportion of crystal water contained in the salt is 1.5% by mass or more.
［項４］ 脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して５０質量％以上であり、且つ、脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、２．５質量％以上である、［項２］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 4] The proportion of hydrate in the metal salt of alicyclic dicarboxylic acid is 50% by mass or more based on the entire metal salt of alicyclic dicarboxylic acid, and the metal salt of alicyclic dicarboxylic acid The crystal nucleating agent for polyolefin resin according to item 2, wherein the proportion of crystal water contained in the salt is 2.5% by mass or more.
［項５］ 脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して７０質量％以上であり、且つ、脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、３．５質量以上である、［項２］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 5] The proportion of hydrate in the metal salt of alicyclic dicarboxylic acid is 70% by mass or more based on the entire metal salt of alicyclic dicarboxylic acid, and the metal salt of alicyclic dicarboxylic acid The crystal nucleating agent for polyolefin resin according to item 2, wherein the proportion of crystal water contained in the salt is 3.5 mass or more.
［項６］ 脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して９０質量％以上であり、且つ、脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、４．５質量％以上である、［項２］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 6] The proportion of hydrate in the metal salt of alicyclic dicarboxylic acid is 90% by mass or more based on the entire metal salt of alicyclic dicarboxylic acid, and the metal salt of alicyclic dicarboxylic acid The crystal nucleating agent for polyolefin resin according to item 2, wherein the proportion of crystal water contained in the salt is 4.5% by mass or more.
［項７］ 前記水和物が、一水和物である、［項１］～［項６］の何れかに記載のポリオレフィン系樹脂用の結晶核剤。 [Item 7] The crystal nucleating agent for a polyolefin resin according to any one of [Item 1] to [Item 6], wherein the hydrate is a monohydrate.
［項８］ 脂環式ジカルボン酸の金属塩が、下記一般式（１）で示される脂環式ジカルボン酸の金属塩である、［項１］～［項７］の何れかに記載のポリオレフィン系樹脂用の結晶核剤。
［項９］ 前項における一般式（１）中のＲ１が、メチル基又はｔｅｒｔ－ブチル基であり、ａが１又は２であり、更に、その置換位置が３位又は４位である、［項８］に記載の結晶核剤組成物。 [Item 9] R 1 in the general formula (1) in the preceding paragraph is a methyl group or a tert-butyl group, a is 1 or 2, and the substitution position is the 3rd or 4th position, [ Item 8].
［項１０］ 核磁気共鳴分光分析で測定したシクロヘキサン環を介したＲ１基と金属塩を構成するオキシカルボニル基の立体異性体中、シス異性体の比率（モル比）が、７０％以上である［項９］又は［項１０］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 10] Among the stereoisomers of the R1 group via the cyclohexane ring and the oxycarbonyl group constituting the metal salt, the ratio (molar ratio) of the cis isomer is 70% or more, as measured by nuclear magnetic resonance spectroscopy. A crystal nucleating agent for a polyolefin resin according to [Item 9] or [Item 10].
［項１１］ 脂環式ジカルボン酸の金属塩が、下記一般式（２）で示される脂環式ジカルボン酸の金属塩である、［項１］～［項７］の何れかに記載のポリオレフィン系樹脂用の結晶核剤。
［項１２］ 前項における一般式（２）中の２つのオキシカルボニル基が、シス配置である、［項１１］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 12] The crystal nucleating agent for a polyolefin resin according to [Item 11], wherein the two oxycarbonyl groups in the general formula (2) in the preceding item have a cis configuration.
［項１３］ Ｍ２がヒドロキシアルミニウムイオンである、［項１１］又は［項１２］に記載のポリオレフィン系樹脂用の結晶核剤。 [Item 13] The crystal nucleating agent for a polyolefin resin according to [Item 11] or [Item 12], wherein M 2 is a hydroxyaluminum ion.
［項１４］ ［項１］～［項１３］の何れかに記載されたポリオレフィン系樹脂用の結晶核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 14] A polyolefin resin composition comprising a crystal nucleating agent for polyolefin resin according to any one of [Item 1] to [Item 13].
［項１５］ ポリオレフィン系樹脂用の結晶核剤の含有量が、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１４］に記載のポリオレフィン系樹脂組成物。 [Item 15] The polyolefin resin composition according to [Item 14], wherein the content of the crystal nucleating agent for polyolefin resin is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin resin.
［項１６］ ［項１］～［項１３］の何れかに記載されたポリオレフィン系樹脂用の結晶核剤と、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とを含んでなり、前記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形成する金属種が、リチウム、マグネシウム、アルミニウム又は亜鉛であるポリオレフィン系樹脂用の結晶核剤組成物。 [Item 16] The crystal nucleating agent for polyolefin resins described in any one of [Item 1] to [Item 13] and a carbon number of 12 to 22 which may have at least one hydroxyl group in the molecule. A metal species that forms a metal salt of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, which may have at least one hydroxyl group in the molecule. is lithium, magnesium, aluminum or zinc. A crystal nucleating agent composition for a polyolefin resin.
［項１７］ 前項におけるポリオレフィン系樹脂用の結晶核剤と脂肪酸の金属塩との比率が、結晶核剤/脂肪酸の金属塩＝５／１～１／４の範囲である、［項１６］に記載のポリオレフィン系樹脂用の結晶核剤組成物。 [Item 17] According to [Item 16], the ratio of the crystal nucleating agent for polyolefin resin and the metal salt of fatty acid in the preceding item is in the range of crystal nucleating agent/metal salt of fatty acid = 5/1 to 1/4. A crystal nucleating agent composition for the polyolefin resin described above.
［項１８］ ［項１６］又は［項１７］に記載されたポリオレフィン系樹脂用の結晶核剤組成物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 18] A polyolefin resin composition comprising the crystal nucleating agent composition for polyolefin resin described in [Item 16] or [Item 17].
［項１９］ ポリオレフィン系樹脂用の結晶核剤組成物の含有量が、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１８］に記載のポリオレフィン系樹脂組成物。 [Item 19] The polyolefin resin composition according to [Item 18], wherein the content of the crystal nucleating agent composition for polyolefin resin is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin resin. .
［項２０］ ［項１４］、［項１５］、［項１８］又は［項１９］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 20] A polyolefin resin molded article made from the polyolefin resin composition described in [Item 14], [Item 15], [Item 18], or [Item 19].
［項２１］ 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核剤の樹脂中での分散性の改良方法であって、前記脂環式ジカルボン酸の金属塩中に占める水和物の割合が、脂環式ジカルボン酸の金属塩全体に対して１０質量％以上であり、且つ、前記脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、０．５質量％以上であることを特徴とする樹脂中での分散性の改良方法。
本発明の結晶核剤又は結晶核剤組成物をポリオレフィン系樹脂に配合することにより、成形加工条件等に影響されることなく、安定して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、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、本発明の結晶核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。特に、本発明の結晶核剤又は結晶核剤組成物は、上述の通り成形加工条件等の影響はなく、安定して目的の性能が容易に得られるようになり、今後これまで以上に様々な用途での開発が期待される。 By blending the crystal nucleating agent or the crystal nucleating agent composition of the present invention into a polyolefin resin, the crystallization rate, that is, the crystallization temperature, of the polyolefin resin can be stably and significantly increased without being affected by molding processing conditions, etc. can be improved. As a result, the molding cycle, especially for large parts, is greatly shortened, which is very 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. Furthermore, the crystal nucleating agent of the present invention can exhibit excellent effects even when used in combination with fillers such as talc without reducing its effects. In particular, the crystal nucleating agent or crystal nucleating agent composition of the present invention is not affected by molding processing conditions, etc. as described above, and the desired performance can be easily obtained stably. It is expected that it will be developed for other applications.
＜ポリオレフィン系樹脂用結晶核剤＞
本発明のポリオレフィン系樹脂用結晶核剤は、特定の構造の脂環式ジカルボン酸の金属塩を含み、且つ、前記脂環式ジカルボン酸の金属塩の全量又は一部が水和物であり、且つ、前記脂環式ジカルボン酸が結晶水を含むことを特徴とし、好ましくは前記脂環式ジカルボン酸の金属塩中に占める水和物の割合、及び前記脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、特定の範囲であることを特徴とする。
<Crystal nucleating agent for polyolefin resin>
The crystal nucleating agent for polyolefin resins of the present invention contains a metal salt of an alicyclic dicarboxylic acid having a specific structure, and the whole or a part of the metal salt of the alicyclic dicarboxylic acid is a hydrate, The alicyclic dicarboxylic acid is characterized in that it contains water of crystallization, and preferably the proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid and the proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid are It is characterized in that the proportion of crystal water contained is within a specific range.
脂環式ジカルボン酸の金属塩
本発明の脂環式ジカルボン酸の金属塩は、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であることを特徴とする。
上記一般式（１）で示される脂環式ジカルボン酸の金属塩は、下記一般式（３）で示される脂環式ジカルボン酸又はその無水物と金属酸化物、金属水酸化物、又は金属塩化物などを水系で反応させることにより、容易に製造することができる。
一般式（３）におけるＲ１は、炭素数１～４の直鎖又は分岐鎖状のアルキル基であり、具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。中でも、メチル基やｔｅｒｔ－ブチル基が、結晶化の改善効果の観点等より、特に推奨される。 R 1 in the general formula (3) is a linear or branched alkyl group having 1 to 4 carbon atoms, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. group, isobutyl group, sec-butyl group, tert-butyl group, etc. Among these, a methyl group and a tert-butyl group are particularly recommended from the viewpoint of improving crystallization.
一般式（３）におけるＲ１の置換位置は、３位又は４位であることが好ましく、どちらの位置に置換されていても良いが、特に好ましい置換位置は、置換されているアルキル基と金属塩を形成する金属種の種類により、適宜選択される。 The substitution position of R 1 in general formula (3) is preferably the 3rd or 4th position, and it may be substituted at either position, but particularly preferred substitution positions are between the substituted alkyl group and the metal It is appropriately selected depending on the type of metal species forming the salt.
上記一般式（１）で示される脂環式ジカルボン酸の金属塩を形成する金属種は、カルシウム、アルミニウム、ナトリウム及びリチウムからなる群より選ばれた一種であり、中でも、結晶性改善効果の観点より、カルシウム又はナトリウムであることがより好ましい。 The metal species forming the metal salt of the alicyclic dicarboxylic acid represented by the above general formula (1) is one selected from the group consisting of calcium, aluminum, sodium, and lithium, and among them, from the viewpoint of crystallinity improvement effect. More preferably, it is calcium or sodium.
上記一般式（１）で示される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、３－メチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－メチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－メチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－メチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－エチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－エチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－エチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－エチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－イソプロピルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－イソプロピルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－イソプロピルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－イソプロピルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウムの塩、３－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、３－イソブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、３－イソブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、３－イソブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－イソブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－メチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－メチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－メチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－メチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－エチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－エチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－エチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－エチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｎ－プロピルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－イソプロピルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－イソプロピルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－イソプロピルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－イソプロピルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｎ－ブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩、４－イソブチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－イソブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－イソブチルシクロヘキサン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－イソブチルシクロヘキサン－１，２－ジカルボン酸の二リチウム塩などが例示され、中でも好ましい態様としては、３－メチルシクロヘキサン－１，２－ジカルボン酸の二ナトリウム塩、４－メチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩、４－ｔｅｒｔ－ブチルシクロヘキサン－１，２－ジカルボン酸のカルシウム塩などが挙げられる。 Specific embodiments of the metal salt of the alicyclic dicarboxylic acid represented by the above general formula (1) include, for example, disodium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, 3-methylcyclohexane-1, Calcium salt of 2-dicarboxylic acid, hydroxyaluminum salt of 3-methylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, 3-ethylcyclohexane-1,2-dicarboxylic acid disodium salt of acid, calcium salt of 3-ethylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-ethylcyclohexane-1,2-dicarboxylic acid, dicarboxylic acid of 3-ethylcyclohexane-1,2-dicarboxylic acid Lithium salt, disodium salt of 3-n-propylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-n-propylcyclohexane-1,2-dicarboxylic acid, 3-n-propylcyclohexane-1,2-dicarboxylic acid hydroxyaluminum salt of acid, dilithium salt of 3-n-propylcyclohexane-1,2-dicarboxylic acid, disodium salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, 3-isopropylcyclohexane-1,2-dicarboxylic acid Calcium salt of acid, hydroxyaluminum salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, 3-n-butylcyclohexane-1,2-dicarboxylic acid disodium salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, 3-n-butylcyclohexane-1,2-dicarboxylic acid - dilithium salt of dicarboxylic acid, disodium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, 3-tert-butylcyclohexane Hydroxyaluminum salt of -1,2-dicarboxylic acid, dilithium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, 3-isobutylcyclohexane Calcium salt of -1,2-dicarboxylic acid, hydroxyaluminum salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1, Disodium salt of 2-dicarboxylic acid, calcium salt of 4-methylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-methylcyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid Dilithium salt of acid, disodium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, hydroxyl of 4-ethylcyclohexane-1,2-dicarboxylic acid Aluminum salt, dilithium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, 4-n-propylcyclohexane-1,2-dicarboxylic acid calcium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, 4-isopropylcyclohexane-1,2-dicarboxylic acid disodium salt of acid, calcium salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, dicarboxylic acid of 4-isopropylcyclohexane-1,2-dicarboxylic acid Lithium salt, disodium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, 4-n-butylcyclohexane-1,2-dicarboxylic acid hydroxyaluminum salt of acid, dilithium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, 4-tert-butylcyclohexane-1 , calcium salt of 2-dicarboxylic acid, hydroxyaluminum salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, 4-isobutylcyclohexane- Disodium salt of 1,2-dicarboxylic acid, calcium salt of 4-isobutylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-isobutylcyclohexane-1,2-dicarboxylic acid, 4-isobutylcyclohexane-1,2 Examples include dilithium salts of -dicarboxylic acids, among which preferred embodiments include disodium salts of 3-methylcyclohexane-1,2-dicarboxylic acids, calcium salts of 4-methylcyclohexane-1,2-dicarboxylic acids, Examples include calcium salt of -tert-butylcyclohexane-1,2-dicarboxylic acid.
上記一般式（１）で示される脂環式ジカルボン酸の金属塩には、シクロヘキサン環を介したアルキル置換基と金属塩を構成するオキシカルボニル基が同方向を向いているシス異性体とそれ以外の立体異性体が存在するが、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いが、結晶性改善の効果の観点より、シス異性体がリッチであることが望ましく、例えば、上記立体異性体中、シス異性体の比率（モル比）が、７０％以上、好ましくは８０％以上、より好ましくは９０％以上、更に好ましくは９５％以上であることが推奨される。 The metal salt of the alicyclic dicarboxylic acid represented by the above general formula (1) includes a cis isomer in which the alkyl substituent via the cyclohexane ring and the oxycarbonyl group constituting the metal salt are oriented in the same direction, and other types. Although the present invention does not depend on the structure of the isomer as long as the effect of the present invention is achieved, from the viewpoint of the effect of improving crystallinity, it is preferable that the cis isomer is rich. For example, the ratio (molar ratio) of cis isomers among the stereoisomers is 70% or more, preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. is recommended.
また、上記一般式（１）で示される脂環式ジカルボン酸の金属塩には、金属塩を構成する２つのオキシカルボニル基が同方向を向いているシス異性体と異方向を向いているトランス異性体の２種類の立体異性体が存在するが、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、シス異性体、トランス異性体及びその混合物の何れであっても良いが、結晶性改善の効果の観点より、シス異性体がリッチであることが望ましく、例えば、上記立体異性体中、シス異性体の比率（モル比）が、７０％以上、好ましくは８０％以上、より好ましくは９０％以上、更に好ましくは９５％以上であることが推奨される。 In addition, in the metal salt of the alicyclic dicarboxylic acid represented by the above general formula (1), there are cis isomers in which the two oxycarbonyl groups constituting the metal salt are oriented in the same direction, and trans isomers in which the two oxycarbonyl groups composing the metal salt are oriented in the same direction. Although there are two types of stereoisomers, the present invention does not depend on the structure of the isomer, as long as the effect of the present invention is achieved, and the present invention does not depend on the structure of the isomer, but may include cis isomers, trans isomers, and mixtures thereof. Any of these may be used, but from the viewpoint of the effect of improving crystallinity, it is desirable that the cis isomer is rich.For example, the ratio (molar ratio) of the cis isomer among the above stereoisomers is 70% or more. , preferably 80% or more, more preferably 90% or more, even more preferably 95% or more.
上記一般式（２）で示される脂環式ジカルボン酸の金属塩は、下記一般式（４）で示される脂環式ジカルボン酸又はその無水物と金属酸化物、金属水酸化物、又は金属塩化物などを水系で反応させることにより、容易に製造することができる。
上記一般式（４）で示される脂環式ジカルボン酸としては、置換基のないシクロヘキセン－１，２－ジカルボン酸が実用面や性能面で好ましいが、シクロヘキセン環上に１個以上の炭素数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てもよく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等のアルキル基が置換されたシクロヘキセン－１，２－ジカルボン酸などが例示される。 As the alicyclic dicarboxylic acid represented by the above general formula (4), cyclohexene-1,2-dicarboxylic acid without a substituent is preferable from a practical and performance standpoint; ~4 linear or branched alkyl groups may be substituted, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include cyclohexene-1,2-dicarboxylic acid substituted with an alkyl group such as tert-butyl group.
また、上記一般式（４）で示される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 represented by the above general formula (4) has two 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. However, 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. From the viewpoint of the oxidation-promoting effect, the cis configuration is desirable.
上記一般式（２）で示される脂環式ジカルボン酸の金属塩を形成する金属種は、ヒドロキシアルミニウム、ナトリウム及びリチウムからなる群より選ばれた１種又は２種以上の金属種であり、中でも、結晶性改善効果の観点より、ヒドロキシアルミニウムであることが最も好ましい。 The metal species forming the metal salt of the alicyclic dicarboxylic acid represented by the above general formula (2) is one or more metal species selected from the group consisting of hydroxyaluminum, sodium, and lithium, and among them, From the viewpoint of improving crystallinity, hydroxyaluminum is most preferable.
上記一般式（２）で示される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、４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－エチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、３－エチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－エチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、３－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、３－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、３－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウムの塩、３－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウムの塩、３－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－メチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－メチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－メチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－エチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－エチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－エチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｎ－プロピル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－イソプロピル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｎ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－ｔｅｒｔ－ブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、４－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸の二ナトリウム塩、４－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－イソブチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩などが例示され、中でも好ましい態様としては、４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩、３－メチル－４－シクロヘキセン－１，２－ジカルボン酸の二リチウム塩などが挙げられ、特に４－シクロヘキセン－１，２－ジカルボン酸のヒドロキシアルミニウム塩が最も推奨される。 Specific embodiments of the metal salt of the alicyclic dicarboxylic acid represented by the above general formula (2) include, for example, hydroxyaluminum salt of 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2- Disodium salt of dicarboxylic acid, dilithium salt of 4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1 , hydroxyaluminum salt of 2-dicarboxylic acid, dilithium salt of 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 3-ethyl-4-cyclohexene-1,2-dicarboxylic acid, 3- Hydroxyaluminum salt of ethyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 3-ethyl-4-cyclohexene-1,2-dicarboxylic acid, 3-n-propyl-4-cyclohexene-1,2- Disodium salt of dicarboxylic acid, hydroxyaluminum salt of 3-n-propyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 3-n-propyl-4-cyclohexene-1,2-dicarboxylic acid, 3 -Disodium salt of isopropyl-4-cyclohexene-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-isopropyl-4-cyclohexene-1,2-dicarboxylic acid, 3-isopropyl-4-cyclohexene-1,2-dicarboxylic acid Dilithium salt of acid, disodium salt of 3-n-butyl-4-cyclohexene-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-n-butyl-4-cyclohexene-1,2-dicarboxylic acid, 3- Dilithium salt of n-butyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 3-tert-butyl-4-cyclohexene-1,2-dicarboxylic acid, 3-tert-butyl-4-cyclohexene Hydroxyaluminum salt of -1,2-dicarboxylic acid, dilithium salt of 3-tert-butyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 3-isobutyl-4-cyclohexene-1,2-dicarboxylic acid salt, hydroxyaluminum salt of 3-isobutyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 3-isobutyl-4-cyclohexene-1,2-dicarboxylic acid, 4-methyl-4-cyclohexene-1 , 2-dicarboxylic acid disodium salt, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid hydroxyaluminum salt, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid dilithium salt, 4- Disodium salt of ethyl-4-cyclohexene-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-ethyl-4-cyclohexene-1,2-dicarboxylic acid, 4-ethyl-4-cyclohexene-1,2-dicarboxylic acid dilithium salt of 4-n-propyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 4-n-propyl-4-cyclohexene-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-n-propyl-4-cyclohexene-1,2-dicarboxylic acid, 4-n -Dilithium salt of propyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 4-isopropyl-4-cyclohexene-1,2-dicarboxylic acid, 4-isopropyl-4-cyclohexene-1,2-dicarboxylic acid hydroxyaluminum salt of acid, dilithium salt of 4-isopropyl-4-cyclohexene-1,2-dicarboxylic acid, disodium salt of 4-n-butyl-4-cyclohexene-1,2-dicarboxylic acid, 4-n- hydroxyaluminum salt of butyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 4-n-butyl-4-cyclohexene-1,2-dicarboxylic acid, 4-tert-butyl-4-cyclohexene-1, Disodium salt of 2-dicarboxylic acid, hydroxyaluminum salt of 4-tert-butyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 4-tert-butyl-4-cyclohexene-1,2-dicarboxylic acid , 4-isobutyl-4-cyclohexene-1,2-dicarboxylic acid disodium salt, 4-isobutyl-4-cyclohexene-1,2-dicarboxylic acid hydroxyaluminum salt, 4-isobutyl-4-cyclohexene-1,2 Examples include dilithium salts of -dicarboxylic acids, among which preferred embodiments include hydroxyaluminum salts of 4-cyclohexene-1,2-dicarboxylic acids, dilithium salts of 4-cyclohexene-1,2-dicarboxylic acids, and 3-dicarboxylic acid dilithium salts. Examples include hydroxyaluminum salt of methyl-4-cyclohexene-1,2-dicarboxylic acid, dilithium salt of 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, and especially 4-cyclohexene-1,2-dicarboxylic acid. The hydroxyaluminum salt of the acid is most recommended.
上記一般式（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、上記脂環式ジカルボン酸の金属塩が、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、より優れた結晶核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以下、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 metal salt of the alicyclic dicarboxylic acid represented by the above general formula (1) or general formula (2) is not particularly limited as long as the effect of the present invention is achieved. When the salt is a dispersion type, the smaller the particle size is to the extent that the dispersibility in the resin is not deteriorated due to secondary aggregation, the wider the contact surface with the resin, and the smaller the amount, the better the crystal nucleus. It may be possible to demonstrate its performance as an agent. Therefore, from the viewpoint of crystallization promotion performance, it is recommended that the average value of the 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. be done. 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.
前記脂環式ジカルボン酸の金属塩中に占める水和物の割合
上記の通り、本発明のポリオレフィン系樹脂用の結晶核剤は、該結晶核剤に含まれる脂環式ジカルボン酸の金属塩の全量又は一部が水和物であることを特徴とし、その脂環式ジカルボン酸の金属塩中に占める水和物の割合は、本発明の効果を奏する限り特に限定されないが、好ましくは１０質量％以上、より好ましくは３０質量％以上、更に好ましくは５０質量％以上、特に好ましくは７０質量％以上、最も好ましくは９０質量％以上であることを大きな特徴とする。上記水和物の割合を上記範囲にすることにより、本発明の最大の特徴である樹脂中での分散性をより一層改善することが可能となる。
The proportion of hydrate in the metal salt of alicyclic dicarboxylic acid As mentioned above , the crystal nucleating agent for polyolefin resin of the present invention has a proportion of hydrate in the metal salt of alicyclic dicarboxylic acid contained in the crystal nucleating agent. It is characterized in that the whole amount or a part thereof is a hydrate, and the proportion of the hydrate in the metal salt of the alicyclic dicarboxylic acid is not particularly limited as long as the effect of the present invention is achieved, but it is preferably 10 mass. % or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably 70% by mass or more, and most preferably 90% by mass or more. By setting the proportion of the hydrate within the above range, it becomes possible to further improve the dispersibility in the resin, which is the most important feature of the present invention.
本発明における水和物とは、結晶水を持つ金属塩を意味し、結晶水の数により一水和物、二水和物などが存在する。また、本発明の場合、上述の通り、水または水分を含んだ溶媒から結晶化が行われるため、結晶格子の中に水を取り込まれた状態で存在するものと推測される。また、本発明の水和物も、一般的な水和物と同様に１００℃以上の温度をかけることにより徐々に消失されるものである。 The hydrate in the present invention means a metal salt having water of crystallization, and there are monohydrates, dihydrates, etc. depending on the number of water of crystallization. Furthermore, in the case of the present invention, as described above, since crystallization is performed from water or a solvent containing water, it is presumed that water is present in a state in which water is incorporated into the crystal lattice. Further, the hydrate of the present invention is also gradually eliminated by applying a temperature of 100° C. or higher, as is the case with general hydrates.
前記脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合
本発明のポリオレフィン系樹脂用の結晶核剤は、該結晶核剤中に含まれる脂環式ジカルボン酸の金属塩中に結晶水を含むことを特徴とし、その脂環式ジカルボン酸中に含まれる結晶水の割合は、本発明の効果を奏する限り特に限定されないが、好ましくは０．５質量％以上、より好ましくは１．５質量％以上、更に好ましくは２．５質量％以上、特に好ましくは３．５質量％以上、最も好ましくは４．５質量％以上であることをもう一つの大きな特徴とする。上記結晶水の割合を上記範囲にすることにより、本発明の最大の特徴である樹脂中での分散性をより一層改善することが可能となる。
Proportion of crystal water contained in the metal salt of the alicyclic dicarboxylic acid The crystal nucleating agent for polyolefin resins of the present invention contains crystal water in the metal salt of the alicyclic dicarboxylic acid contained in the crystal nucleating agent. The proportion of water of crystallization contained in the alicyclic dicarboxylic acid is not particularly limited as long as the effects of the present invention are achieved, but is preferably 0.5% by mass or more, more preferably 1.5% by mass. Another major feature is that the content is at least 2.5% by mass, more preferably at least 2.5% by mass, particularly preferably at least 3.5% by mass, and most preferably at least 4.5% by mass. By setting the proportion of the crystal water within the above range, it becomes possible to further improve the dispersibility in the resin, which is the most important feature of the present invention.
本発明のポリオレフィン系樹脂用の結晶核剤に中に含まれる脂環式ジカルボン酸の金属塩の全量又は一部が水和物であり、且つ結晶水を含むことにより樹脂中での分散性が著しく改善されるメカニズムは定かではないが、顕微鏡観察等より上記範囲の水和物及び結晶水を含むものは、ポリオレフィン系樹脂の加工温度まで加熱することにより結晶核剤を形成する脂環式ジカルボン酸の金属塩の結晶中に内包されていた結晶水に揮発しようとする強い力が働き、結果溶融樹脂中で上記脂環式ジカルボン酸の金属塩が破砕されて微細化し、樹脂中に分散される結果、結晶核剤の樹脂中での分散性が著しく改善されたものと推測されている。 All or part of the metal salt of alicyclic dicarboxylic acid contained in the crystal nucleating agent for polyolefin resin of the present invention is a hydrate, and the dispersibility in the resin is improved by containing crystal water. Although the mechanism by which this remarkable improvement occurs is not clear, microscopic observations indicate that those containing hydrates and water of crystallization in the above range are alicyclic dicarbonates that form crystal nucleating agents when heated to the processing temperature of polyolefin resins. A strong force acts on the crystal water contained in the crystals of the metal salt of the acid, and as a result, the metal salt of the alicyclic dicarboxylic acid is crushed in the molten resin, becomes fine, and dispersed in the resin. It is presumed that as a result of this, the dispersibility of the crystal nucleating agent in the resin was significantly improved.
また、上記脂環式ジカルボン酸中に含まれる水和物及び結晶水の割合は、例えば、水系で金属塩を合成し、得られた湿結を乾燥する工程で、温度と圧力を適宜調整することにより容易に制御することが可能である。即ち、水系で脂環式ジカルボン酸の金属塩を合成することによりその湿結中に含まれる脂環式ジカルボン酸の金属塩は１００％水和物となることが確認されており、湿結中に含まれる前記水和物中の結晶水は加熱することにより容易に蒸散して無水の脂環式ジカルボン酸の金属塩に変化することが確認されており、乾燥時に温度と圧力を適宜調整することにより目標の水和物及び結晶水の割合になるように制御することができる。 In addition, the proportion of hydrate and crystal water contained in the alicyclic dicarboxylic acid is determined by adjusting the temperature and pressure as appropriate, for example, in the process of synthesizing a metal salt in an aqueous system and drying the resulting wet product. This allows easy control. That is, it has been confirmed that by synthesizing a metal salt of an alicyclic dicarboxylic acid in an aqueous system, the metal salt of an alicyclic dicarboxylic acid contained in the wetting becomes 100% hydrate; It has been confirmed that the water of crystallization contained in the hydrate is easily evaporated by heating and converted into a metal salt of anhydrous alicyclic dicarboxylic acid, and the temperature and pressure should be adjusted appropriately during drying. By this, it is possible to control the ratio of hydrate and water of crystallization to the target.
＜ポリオレフィン系樹脂用の結晶核剤組成物＞
本発明のポリオレフィン系樹脂用の結晶核剤組成物は、本発明に係る上記ポリオレフィン系樹脂用の結晶核剤と、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とを含んでなることを特徴とする。
<Crystal nucleating agent composition for polyolefin resin>
The crystal nucleating agent composition for polyolefin resins of the present invention includes the crystal nucleating agent for polyolefin resins according to the present invention, and a carbon number of 12 to 22 which may have at least one hydroxyl group in the molecule. and a metal salt of a saturated or unsaturated fatty acid.
脂肪酸の金属塩
上記の結晶核剤組成物に用いられる脂肪酸の金属塩としては、上記分散性の改善効果等の観点より、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であることが推奨される。
Metal Salt of Fatty Acid The metal salt of a fatty acid used in the crystal nucleating agent composition described above is preferably a metal salt of a fatty acid having a carbon number of 12 and which may have at least one hydroxyl group in the molecule, from the viewpoint of improving the dispersibility. ~22 metal salts of saturated or unsaturated fatty acids are recommended.
上記ポリオレフィン系樹脂用の結晶核剤と、上記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とを含んでなるポリオレフィン系樹脂用の結晶核剤組成物もまた、本発明の一態様である。 For polyolefin resins comprising the crystal nucleating agent for polyolefin resins and the metal salt of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, which may have at least one hydroxyl group in the molecule. The crystal nucleating agent composition is also an aspect of the present invention.
上記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構成する脂肪酸としては、具体的には、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、エルカ酸等が挙げられる。これらの中でもラウリン酸、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又はベヘン酸が推奨され、特にステアリン酸又は１２－ヒドロキシステアリン酸が最も推奨される。 Specifically, the fatty acids constituting the metal salt of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms which may have at least one hydroxyl group in the molecule include lauric acid, myristic acid, and pentadecyl acid. , palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, 12-hydroxystearic acid, behenic acid, erucic acid and the like. Among these, lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid or behenic acid are recommended, with stearic acid or 12-hydroxystearic acid being the most recommended.
また、上記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、亜鉛等が挙げられる。これらの中でもリチウム、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、亜鉛が最も推奨される。 Further, the metal species forming the metal salt of the saturated or unsaturated fatty acid having 12 to 22 carbon atoms which may have at least one hydroxyl group in the molecule include lithium, magnesium, barium, Examples include sodium, aluminum, potassium, strontium, and zinc. Among these, lithium, magnesium, aluminum, and zinc are recommended, with lithium and zinc being the most 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、本発明に係る上記ポリオレフィン系樹脂用の結晶核剤又は結晶核剤組成物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。
<Polyolefin resin composition>
The polyolefin resin composition of the present invention comprises the crystal nucleating agent or crystal nucleating agent composition for polyolefin resins according to the present invention and a polyolefin resin, with other additives for polyolefin resins added as necessary. It can be easily obtained by dry blending 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核剤組成物の含有量は、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好ましい。 The content of the crystal nucleating agent composition for polyolefin resin according to the present invention in the polyolefin resin is not particularly limited as long as it is effective as a crystal nucleating agent, but with respect to 100 parts by mass of the polyolefin resin, The amount is preferably 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質量％以上、好ましくは７０質量％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質量％以上、好ましくは７０質量％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質量％以上、好ましくは７０質量％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質量％以上、好ましくは７０質量％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 mass or more, preferably 70% by mass or more, propylene homopolymers, propylene 50% by mass or more, preferably 70% by mass % 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% by weight 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（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.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliphatic hydrocarbons, higher fatty acids with 8 to 22 carbon atoms, higher fatty acid metal (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 fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.), fillers (talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agents, foaming aids, polymer additives, plasticizers (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants , 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.
＜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用いて、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 can be obtained by molding the polyolefin resin composition of the present invention 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。また、本発明のポリオレフィン系樹脂組成物を用いることにより、結晶性が大きく改善され、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、本発明の結晶核剤及び結晶核剤組成物は、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り、また、成形加工条件等の影響はなく、安定して目的の性能が容易に得られるものであり、今後これまで以上に様々な用途での応用が期待される。 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 In addition, by using the polyolefin resin composition of the present invention, crystallinity is greatly improved, and as a result, the resulting molded product has improved 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, the crystal nucleating agent and the crystal nucleating agent composition of the present invention can exhibit excellent effects even when used in combination with fillers such as talc without reducing their effects, and can be easily molded and processed. It is unaffected by conditions, and the desired performance can be easily obtained stably, so it is expected that it will be used in a wider range of applications than ever before.
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、実施例中の化合物の略号、及び各特性の測定方法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 abbreviations of the compounds in the examples and the measurement methods of each property are as follows.
［ポリオレフィン系樹脂成形体の評価方法］
（１）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]
(1) 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).
（２）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。
(2) 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.
（３）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。
(3) 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.
（４）曲げ弾性率
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を測定した。なお、試験温度は２５℃、試験速度は１０ｍｍ／分とした。
(4) Flexural Modulus Flexural modulus was measured using a universal material testing machine (manufactured by Instron) in accordance with JIS K7171 (2016). Note that the test temperature was 25° C. and the test speed was 10 mm/min.
実施例又は比較例で用いた脂環式ジカルボン酸の金属塩
化合物１：４－メチルシクロヘキサンジカルボン酸のカルシウム塩（ＭＨ－Ｃａ）、水和物の割合；１００質量％、結晶水の含有量；７．４４質量％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率９５％
化合物２：４－メチルシクロヘキサンジカルボン酸のカルシウム塩（ＭＨ－Ｃａ）、水和物の割合；７５質量％、結晶水の含有量；５．５８質量％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率９５％
化合物３：４-メチルシクロヘキサンジカルボン酸のカルシウム塩（ＭＨ－Ｃａ）、水和物の割合；５０質量％、結晶水の含有量；３．７２質量％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率９５％
化合物４：４－メチルシクロヘキサンジカルボン酸のカルシウム塩（ＭＨ－Ｃａ）、水和物の割合；１２．５質量％、結晶水の含有量；０．９３質量％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率９５％
化合物５：４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩（ｔＢｕＨ－Ｃａ）、水和物の割合；１００質量％、結晶水の含有量；６．３４質量％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率１００％
化合物６：シクロヘキサンジカルボン酸のカルシウム塩（ＨＨ－Ｃａ）、水和物の割合；１００質量％、結晶水の含有量；７．８９質量％、
化合物７：４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩（ＴＨ－ＡｌＯＨ）、水和物の割合；１００質量％、結晶水の含有量；７．８３質量％、２つのオキシカルボニル基の立体構造；シス体比率１００％
化合物８：４－メチルシクロヘキサンジカルボン酸のカルシウム塩（ＭＨ－Ｃａ）、水和物の割合；０％、結晶水の含有量；０％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率９５％
化合物９：４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩（ｔＢｕＨ－Ｃａ）、水和物の割合；０％、結晶水の含有量；０％、アルキル置換基とオキシカルボニル基の立体構造；シス体比率１００％
化合物１０：シクロヘキサンジカルボン酸のカルシウム塩（ＨＨ－Ｃａ）、水和物の割合；０％、結晶水の含有量；０％、
化合物１１：４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩（ＴＨ－ＡｌＯＨ）、水和物の割合；０％、結晶水の含有量；０％、２つのオキシカルボニル基の立体構造；シス体比率１００％
Metal salt of alicyclic dicarboxylic acid used in Examples or Comparative Examples Compound 1: Calcium salt of 4-methylcyclohexanedicarboxylic acid (MH-Ca), proportion of hydrate: 100% by mass, water of crystallization Content: 7.44% by mass, steric structure of alkyl substituent and oxycarbonyl group: cis form ratio 95%
Compound 2: Calcium salt of 4-methylcyclohexanedicarboxylic acid (MH-Ca), hydrate ratio: 75% by mass, crystal water content: 5.58% by mass, steric structure of alkyl substituent and oxycarbonyl group ;cis ratio 95%
Compound 3: Calcium salt of 4-methylcyclohexanedicarboxylic acid (MH-Ca), hydrate ratio: 50% by mass, crystal water content: 3.72% by mass, steric structure of alkyl substituent and oxycarbonyl group ;cis ratio 95%
Compound 4: Calcium salt of 4-methylcyclohexanedicarboxylic acid (MH-Ca), hydrate ratio: 12.5% by mass, crystal water content: 0.93% by mass, alkyl substituent and oxycarbonyl group Stereostructure; cis ratio 95%
Compound 5: Calcium salt of 4-t-butylcyclohexanedicarboxylic acid (tBuH-Ca), hydrate ratio: 100% by mass, crystal water content: 6.34% by mass, alkyl substituent and oxycarbonyl group Stereostructure: cis form ratio 100%
Compound 6: Calcium salt of cyclohexanedicarboxylic acid (HH-Ca), hydrate ratio: 100% by mass, crystal water content: 7.89% by mass,
Compound 7: hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid (TH-AlOH), hydrate ratio: 100% by mass, crystal water content: 7.83% by mass, three-dimensional structure of two oxycarbonyl groups; cis Body ratio 100%
Compound 8: Calcium salt of 4-methylcyclohexanedicarboxylic acid (MH-Ca), hydrate ratio: 0%, crystal water content: 0%, steric structure of alkyl substituent and oxycarbonyl group; cis form ratio 95%
Compound 9: Calcium salt of 4-t-butylcyclohexanedicarboxylic acid (tBuH-Ca), hydrate ratio: 0%, crystal water content: 0%, steric structure of alkyl substituent and oxycarbonyl group; cis Body ratio 100%
Compound 10: Calcium salt of cyclohexanedicarboxylic acid (HH-Ca), hydrate ratio: 0%, crystal water content: 0%,
Compound 11: hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid (TH-AlOH), hydrate ratio: 0%, crystal water content: 0%, three-dimensional structure of two oxycarbonyl groups; cis form ratio: 100%
［実施例１］
ポリプロピレンホモポリマー（ＭＦＲ＝９ｇ/１０分（荷重２１６０ｇ、温度２３０℃））１００質量部に、結晶核剤として化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩０．２質量部及びその他の添加剤としてステアリン酸カルシウム（日東化成工業（株）製）０．０５質量部、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質量部を加えて、ドライブレンドした。得られた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]
To 100 parts by mass of polypropylene homopolymer (MFR = 9 g / 10 minutes (load 2160 g, temperature 230 ° C.)), 0.2 parts by mass of the calcium salt of 4-methylcyclohexanedicarboxylic acid of compound 1 as a crystal nucleating agent and other additives. 0.05 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), and tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (manufactured by BASF Japan Co., Ltd.). , trade name "IRGANOX1010") and 0.05 part by mass of tetrakis(2,4-di-tert-butylphenyl) phosphite (manufactured by BASF Japan Co., Ltd., trade name "IRGAFOS168"). , dry blended. The obtained 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 then extruded into strands. was cooled and cut 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 Resin Industries Co., Ltd.). A polyolefin resin molded article (test piece) of the present invention was obtained by molding under the following conditions. 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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物２の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Example 2]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 2 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 1.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物３の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Example 3]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 3 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 1.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物４の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Example 4]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of compound 4 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 1.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物５の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Example 5]
A polyolefin resin composition was prepared in the same manner as in Example 1 except that the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 5 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 1. 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.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物６のシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Example 6]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that Compound 6, a calcium salt of cyclohexanedicarboxylic acid, was used instead of Compound 1, a calcium salt of 4-methylcyclohexanedicarboxylic acid. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 1.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物７の４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩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。
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。
[Example 7]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid of Compound 7 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 1.
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４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物８の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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。
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。
[Comparative example 1]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 8 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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.
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５の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物９の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩を用いた以外は実施例５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。
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５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。
[Comparative example 2]
A polyolefin resin composition was prepared in the same manner as in Example 5, except that the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 9 was used instead of the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 5. 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 2.
Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 5 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６のシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物１０のシクロヘキサンジカルボン酸のカルシウム塩を用いた以外は実施例６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。
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６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。
[Comparative example 3]
A polyolefin resin composition was prepared in the same manner as in Example 6, except that Compound 10, a calcium salt of cyclohexanedicarboxylic acid, was used instead of Compound 6, a calcium salt of cyclohexanedicarboxylic acid. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
Subsequently, the obtained polyolefin resin composition was used in the same manner as in Example 6 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７の４－シクロヘキセンジカルボン酸のヒドロキアルミニウム塩の代わりに化合物１１の４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩を用いた以外は実施例７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。
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７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。
[Comparative example 4]
A polyolefin resin composition was prepared in the same manner as in Example 7 except that the hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid of compound 11 was used instead of the hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid of compound 7. . The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 2.
Subsequently, the obtained polyolefin resin composition was used in the same manner as in Example 7 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］
結晶核剤を用いない以外は実施例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。
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。
[Comparative example 5]
A polyolefin resin composition was prepared in the same manner as in Example 1 except that a crystal nucleating agent was not 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.
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］
一軸押出機（（株）テクノベル社製、Ｌ／Ｄ＝２８、スクリュー径２５ｍｍ、ダイス径４ｍｍ）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３に示した。
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３に示した。
[Example 8]
A polyolefin resin composition was prepared in the same manner as in Example 1, except that a single screw extruder (manufactured by Technovel Co., Ltd., L/D = 28, screw diameter 25 mm, die diameter 4 mm) 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 3.
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 3.
［実施例９］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物２の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 9]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 2 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１０］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物３の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 10]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of compound 3 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１１］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物４の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 11]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of compound 4 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１２］
更に、１２ヒドロキシステアリン酸の亜鉛塩０．２質量部を加えた以外は実施例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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 12]
Furthermore, a polyolefin resin composition was prepared in the same manner as in Example 8, except that 0.2 parts by mass of zinc salt of 12-hydroxystearic acid was added. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１３］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物５の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 13]
A polyolefin resin composition was prepared in the same manner as in Example 8 except that the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 5 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 1. Prepared. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１４］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物６のシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 14]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that Compound 6, a calcium salt of cyclohexanedicarboxylic acid, was used instead of Compound 1, a calcium salt of 4-methylcyclohexanedicarboxylic acid. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［実施例１５］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物７の４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表３に示した。
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３に示した。
[Example 15]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the hydroxyaluminum salt of 4-cyclohexanedicarboxylic acid of compound 7 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 3.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 3.
［比較例６］
化合物１の４－メチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物８の４－メチルシクロヘキサンジカルボン酸のカルシウム塩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及び半結晶化時間を測定し、得られた結果を合わせて表４に示した。
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４に示した。
[Comparative example 6]
A polyolefin resin composition was prepared in the same manner as in Example 8, except that the calcium salt of 4-methylcyclohexanedicarboxylic acid of Compound 8 was used instead of the calcium salt of 4-methylcyclohexanedicarboxylic acid 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 4.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 4.
［比較例７］
化合物５の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物９の４－ｔ－ブチルシクロヘキサンジカルボン酸のカルシウム塩を用いた以外は実施例１３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４に示した。
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１３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４に示した。
[Comparative Example 7]
A polyolefin resin composition was prepared in the same manner as in Example 13, except that the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 9 was used instead of the calcium salt of 4-t-butylcyclohexanedicarboxylic acid of Compound 5. 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 4.
Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 13 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 4.
［比較例８］
化合物６のシクロヘキサンジカルボン酸のカルシウム塩の代わりに化合物１０のシクロヘキサンジカルボン酸のカルシウム塩を用いた以外は実施例１４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４に示した。
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１４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４に示した。
[Comparative example 8]
A polyolefin resin composition was prepared in the same manner as in Example 14, except that Compound 10, a calcium salt of cyclohexanedicarboxylic acid, was used instead of Compound 6, a calcium salt of cyclohexanedicarboxylic acid. The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 4.
Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 14 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 4.
［比較例９］
化合物７の４－シクロヘキセンジカルボン酸のヒドロキアルミニウム塩の代わりに化合物１１の４－シクロヘキセンジカルボン酸のヒドロキシアルミニウム塩を用いた以外は実施例１５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４に示した。
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１５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４に示した。
[Comparative Example 9]
A polyolefin resin composition was prepared in the same manner as in Example 15, except that the hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid of compound 11 was used instead of the hydroxyaluminum salt of 4-cyclohexenedicarboxylic acid of compound 7. . The crystallization temperature and half-crystallization time of the obtained polyolefin resin composition were measured, and the obtained results are shown in Table 4.
Subsequently, using the obtained polyolefin resin composition, the same procedure as in Example 15 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 4.
［比較例１０］
結晶核剤を用いない以外は実施例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及び半結晶化時間を測定し、得られた結果を合わせて表４に示した。
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４に示した。
[Comparative Example 10]
A polyolefin resin composition was prepared in the same manner as in Example 8 except that no crystal nucleating agent 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 4.
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 flexural modulus and haze value of the obtained test piece were measured, and the obtained results are shown in Table 4.
表１中の実施例の結果と表２中の比較例結果の比較より、水和物並びに結晶水の存在により樹脂中での分散性が大きく改善され、その結果、結晶化促進効果だけでなく、得られた成形品の透明性や剛性との性能もより一層改善されていることがわかる。また、表３中の実施例の結果と表４中の比較例の比較より、上記効果は練り効果の少ない加工条件下でより一層発揮され、成形加工条件に影響されることなく、安定して優れた性能を得られることを示している。 Comparison of the results of the examples in Table 1 and the results of comparative examples in Table 2 shows that the presence of hydrates and water of crystallization greatly improves the dispersibility in the resin, and as a result, not only the effect of promoting crystallization but also the It can be seen that the performance of the obtained molded product in terms of transparency and rigidity is further improved. In addition, from the comparison between the results of the examples in Table 3 and the comparative examples in Table 4, the above effects are exhibited even more under processing conditions with little kneading effect, and are stable and unaffected by the forming processing conditions. This shows that excellent performance can be obtained.
本発明の結晶核剤及び結晶核剤組成物は、ポリオレフィン系樹脂に配合することにより成形加工条件等に影響されることなく、安定的に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、本発明の結晶核剤は、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、本発明の結晶核剤は、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。 By blending the crystal nucleating agent and the crystal nucleating agent composition of the present invention into a polyolefin resin, the crystallization rate, that is, the crystallization temperature, of the polyolefin resin can be stably and significantly increased without being affected by molding processing conditions. For example, the molding cycle for large parts etc. can be shortened by about half, and as a result, it can greatly contribute to cost reduction and trouble prevention during processing. In addition, the crystal nucleating agent of the present invention can improve crystallinity, and as a result, the resulting molded product can be improved in mechanical performance such as rigidity, optical performance such as transparency, and thermal performance such as heat resistance. This not only improves mechanical 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, by taking advantage of the above characteristics, the crystal nucleating agent of the present invention can be widely used in various applications such as automobile parts, electrical parts, mechanical parts, daily necessities, cases for clothing, containers for food, etc. I can do it.
Claims (10)
下記一般式（１）で示される脂環式ジカルボン酸の金属塩を含み、且つ、
前記脂環式ジカルボン酸の金属塩の全量又は一部が結晶水を有する水和物であることを特徴とするポリオレフィン系樹脂用の結晶核剤。
Contains a metal salt of an alicyclic dicarboxylic acid represented by the following general formula (1), and
A crystal nucleating agent for a polyolefin resin, wherein all or a part of the metal salt of the alicyclic dicarboxylic acid is a hydrate having water of crystallization.
前記脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、０．５質量％以上である、請求項１に記載のポリオレフィン系樹脂用の結晶核剤。 The proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid is 10% by mass or more based on the entire metal salt of the alicyclic dicarboxylic acid, and further,
The crystal nucleating agent for a polyolefin resin according to claim 1, wherein the proportion of crystal water contained in the metal salt of the alicyclic dicarboxylic acid is 0.5% by mass or more.
脂環式ジカルボン酸の金属塩中に含まれる結晶水の割合が、１．５質量％以上である、請求項２又は３に記載のポリオレフィン系樹脂用の結晶核剤。 The proportion of hydrate in the metal salt of the alicyclic dicarboxylic acid is 30% by mass or more based on the entire metal salt of the alicyclic dicarboxylic acid, and
The crystal nucleating agent for polyolefin resin according to claim 2 or 3, wherein the proportion of crystal water contained in the metal salt of the alicyclic dicarboxylic acid is 1.5% by mass or more.
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| CN102181092A (en) | 2011-03-31 | 2011-09-14 | 广州呈和科技有限公司 | Application of carboxylic acid metal salt of tetrahydrophthalic anhydride as nucleating agent for polypropylene beta crystal form |
| US20140364553A1 (en) | 2011-12-31 | 2014-12-11 | Gch Technology Co., Ltd. | B-crystal form nucleating agent composition for polypropylene and use thereof |
| WO2020023384A1 (en) | 2018-07-24 | 2020-01-30 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
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| CN102181092A (en) | 2011-03-31 | 2011-09-14 | 广州呈和科技有限公司 | Application of carboxylic acid metal salt of tetrahydrophthalic anhydride as nucleating agent for polypropylene beta crystal form |
| US20140364553A1 (en) | 2011-12-31 | 2014-12-11 | Gch Technology Co., Ltd. | B-crystal form nucleating agent composition for polypropylene and use thereof |
| WO2020023384A1 (en) | 2018-07-24 | 2020-01-30 | Milliken & Company | Additive composition and method for producing a polymer composition using the same |
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