JP2008115372A - 生分解性樹脂組成物 - Google Patents
生分解性樹脂組成物 Download PDFInfo
- Publication number
- JP2008115372A JP2008115372A JP2007263342A JP2007263342A JP2008115372A JP 2008115372 A JP2008115372 A JP 2008115372A JP 2007263342 A JP2007263342 A JP 2007263342A JP 2007263342 A JP2007263342 A JP 2007263342A JP 2008115372 A JP2008115372 A JP 2008115372A
- Authority
- JP
- Japan
- Prior art keywords
- nucleating agent
- biodegradable resin
- crystal nucleating
- acid
- resin composition
- 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.)
- Granted
Links
- 229920006167 biodegradable resin Polymers 0.000 title claims abstract description 106
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 78
- 239000004014 plasticizer Substances 0.000 claims abstract description 47
- 150000002148 esters Chemical class 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 125000004185 ester group Chemical group 0.000 claims abstract description 22
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 125000003368 amide group Chemical group 0.000 claims abstract description 7
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 235000013877 carbamide Nutrition 0.000 claims abstract description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims abstract description 4
- 150000007974 melamines Chemical class 0.000 claims abstract description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003672 ureas Chemical class 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 20
- 239000004626 polylactic acid Substances 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000001384 succinic acid Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 150000008431 aliphatic amides Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- -1 aromatic sulfonates Chemical class 0.000 abstract description 40
- 238000002425 crystallisation Methods 0.000 abstract description 19
- 230000008025 crystallization Effects 0.000 abstract description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229930182843 D-Lactic acid Natural products 0.000 description 5
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 5
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229940022769 d- lactic acid Drugs 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- WQJURGLUMGXTAR-UHFFFAOYSA-N phenylphosphonic acid;zinc Chemical compound [Zn].OP(O)(=O)C1=CC=CC=C1 WQJURGLUMGXTAR-UHFFFAOYSA-N 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000011701 zinc Chemical class 0.000 description 3
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 3
- RJRRZABNCURWAM-UHFFFAOYSA-N (2-butylphenyl)phosphonic acid Chemical compound CCCCC1=CC=CC=C1P(O)(O)=O RJRRZABNCURWAM-UHFFFAOYSA-N 0.000 description 2
- YXTSJMYYIRPSDF-UHFFFAOYSA-N (2-methylphenyl)phosphonic acid Chemical compound CC1=CC=CC=C1P(O)(O)=O YXTSJMYYIRPSDF-UHFFFAOYSA-N 0.000 description 2
- GDKNDQBTIVRVAV-UHFFFAOYSA-N (2-propylphenyl)phosphonic acid Chemical compound CCCC1=CC=CC=C1P(O)(O)=O GDKNDQBTIVRVAV-UHFFFAOYSA-N 0.000 description 2
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 2
- MBEBPYJMHLBHDJ-UHFFFAOYSA-N 1,4-dimethyl-2,5-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C)=C(C(C)C)C=C1C MBEBPYJMHLBHDJ-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 2
- SHVCSCWHWMSGTE-UHFFFAOYSA-N 6-methyluracil Chemical compound CC1=CC(=O)NC(=O)N1 SHVCSCWHWMSGTE-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- CDSMQIKSBQLILH-UHFFFAOYSA-N [2,3-bis(ethoxycarbonyl)phenyl]phosphonic acid Chemical compound CCOC(=O)C1=CC=CC(P(O)(O)=O)=C1C(=O)OCC CDSMQIKSBQLILH-UHFFFAOYSA-N 0.000 description 2
- VONVWUIMYVDDGL-UHFFFAOYSA-N [2,3-bis(methoxycarbonyl)phenyl]phosphonic acid Chemical compound COC(=O)C1=CC=CC(P(O)(O)=O)=C1C(=O)OC VONVWUIMYVDDGL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 230000003078 antioxidant effect Effects 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
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- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical class OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】 生分解性樹脂、可塑剤及び結晶核剤を含有する生分解性樹脂組成物であって、可塑剤が分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物であり、結晶核剤が、分子中に水酸基とアミド基を有する化合物から選ばれる結晶核剤(1)と、フェニルホスホン酸金属塩、リン酸エステルの金属塩、芳香族スルホン酸ジアルキルエステルの金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、ロジン酸アミド、カルボヒドラジド類、N−置換尿素類、メラミン化合物の塩及びウラシル類から選ばれる結晶核剤(2)の混合物である生分解性樹脂組成物。
【選択図】 なし
Description
結晶核剤(2):フェニルホスホン酸金属塩、リン酸エステルの金属塩、芳香族スルホン酸ジアルキルエステルの金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、ロジン酸アミド、カルボヒドラジド類、N−置換尿素類、メラミン化合物の塩及びウラシル類からなる群から選ばれる少なくとも1種
本発明で使用される生分解性樹脂としては、JIS K6953(ISO14855)「制御された好気的コンポスト条件の好気的かつ究極的な生分解度及び崩壊度試験」に基づいた生分解性を有するポリエステル樹脂が好ましい。
尚、生分解性樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)を用い、溶媒にクロロホルム、カラムに東ソー(株)製高温SECカラム(GMHHR−Hシリーズ)、流量1.0mL/min、カラム温度40℃、検出器に示差屈折率検出器(RI)、リファレンスとして既知の分子量を有するスチレンを用いて換算して求めることができる。
本発明に用いられる可塑剤は、可塑化効率の観点から、分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物であり、分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物が好ましく、分子中に2個以上のエステル基を有する多価アルコールエステル又は多価カルボン酸エーテルエステルで、エステルを構成するアルコール成分の水酸基1個当たりエチレンオキサイドを平均0.5〜5モル付加した化合物がより好ましい。エステルを構成するアルコール成分は、生分解性樹脂との相溶性と可塑化効率、耐揮発性の観点から、好ましくは炭素数2〜3のアルキレンオキサイドを平均1〜4モル、さらに好ましくは2〜3モル付加した化合物である。また、可塑化効率の観点からアルキレンオキサイドはエチレンオキサイドが好ましい。可塑剤に含まれるアルキル基、アルキレン基等の炭化水素基の炭素数、例えばエステル化合物を構成する多価アルコールや多価カルボン酸の炭化水素基の炭素数は、相溶性の観点から1〜8が好ましく、1〜6がより好ましく、1〜4がさらに好ましい。また可塑剤のエステル化合物を構成するモノカルボン酸、モノアルコールの炭素数は、相溶性の観点から1〜8が好ましく、1〜6がより好ましく、1〜4がさらに好ましく、1〜2がさらにより好ましい。
平均分子量=56108×(エステル基の数)/鹸化価
本発明の結晶核剤は、前記結晶核剤(1)と前記結晶核剤(2)の混合物である。本発明において結晶核剤(1)としては、結晶化速度及び生分解性樹脂との相溶性を向上させる観点から、水酸基を有する脂肪族アミドが好ましく、分子中に水酸基を2つ以上有し、アミド基を2つ以上有する脂肪族アミドがより好ましい。また、結晶核剤(1)の融点は、混練時の結晶核剤の分散性を向上させ、また結晶化速度を向上させる観点から、65℃以上が好ましく、70〜220℃がより好ましく、80〜190℃が更に好ましい。
本発明の生分解性樹脂組成物は、生分解性樹脂、分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物、好ましくは分子中に2個以上のエステル基を有する多価アルコールエステル又は多価カルボン酸エーテルエステルで、エステルを構成するアルコール成分の水酸基1個当たりエチレンオキサイドを平均0.5〜5モル付加した化合物、より好ましくは分子中に2個以上のエステル基を有し、エチレンオキサイドの平均付加モル数が3〜9の化合物からなる可塑剤、および上記結晶核剤(1)と結晶核剤(2)好ましくはフェニルホスホン酸金属塩との混合物からなる結晶核剤を含有するものである。本発明の生分解性樹脂組成物における生分解性樹脂、可塑剤、結晶核剤の特に好ましい組合せとしては、生分解性樹脂がポリ乳酸樹脂、可塑剤がコハク酸とトリエチレングリコールモノメチルエーテルとのエステル、結晶核剤がエチレンビス12−ヒドロキシステアリン酸アミドとフェニルホスホン酸亜鉛塩との混合物である。
生分解性樹脂組成物として、表1に示す本発明品(A〜I)及び表2に示す比較品(a〜i)を、ニーダー((株)森山製作所製 DS3-20MWB-E)にて180℃、10分間溶融混練し、その後直ちに80℃の8インチロール(日本ロール製造(株)製)で約5mmの厚さに引き延ばし、縦×横=8cm×8cm程度の大きさに裁断した後、40℃以下で粉砕機(ダイコー精機(株)製 S-20)にて粉砕し、生分解性樹脂組成物の粉砕品を得た。
*2:コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル(合成品)
*3:エチレンビス12−ヒドロキシステアリン酸アミド(日本化成(株)製、スリパックス H)
*4:無置換のフェニルホスホン酸亜鉛塩(日産化学工業(株)製 PPA−Zn)
*5:カルボジライトLA−1(日清紡績(株)製)
*6:デカメチレンジカルボニルジベンゾイルヒドラジド((株)アデカ製T−1287)
*7:5−スルホイソフタル酸ジメチル二バリウム(合成品)
*8:1,3,5−ベンゼントリカルボン酸トリシクロヘキシルアミド(合成品)
*9:リン酸エステルの金属塩((株)アデカ製 アデカスタブNA−21)
*10:6−メチルウラシル(和工純薬工業(株)製、試薬)
*11:メラミンシアヌレート(日産化学工業(株)製 MC−6000)
*12:ロジン酸金属塩(荒川化学(株)製、パインクリスタルKM−1500)
表3及び表4に示す金型温度において、各テストピースの変形がなく、取り出しが容易と判断されるまでに有する時間を、離型に必要な金型保持時間とした。金型保持時間が240秒以上必要とされる場合、離型不可と評価した。
尚、金型内部及びランナー部分でテストピースの溶融結晶化速度が速いほど、離型に必要な金型保持時間は短くなる。
生分解性樹脂組成物として前記表1に示す本発明品(A〜B)及び前記表2に示す比較品(a〜b)を用い、実施例1と同様にして生分解性樹脂組成物の粉砕品を得た。
○:非常に離れ易い(テストピースの変形がなく、取り出しが容易。)
△:若干離れ難い(テストピースの変形が若干あり、取り出しが困難。)
×:離れない(テストピースの変形が大きく、ランナー部から離れない。)
尚、金型離型性は、金型内部及びランナー部分でテストピースの溶融結晶化速度が速いほど成形性が良好となる。
角柱状試験片(125mm×12mm×6mm)について、JIS-K7191に基づいて、熱変形温度測定機(東洋精機製作所製 B-32)を使用して、荷重0.45MPaにおいて0.025mmたわむときの温度を測定した。この温度が高い方が耐熱性に優れていることを示す。
射出成形後の平板(70mm×40mm×3mm)について、テストピースを広角X線回折測定装置(理学電機製 RINT2500VPC,光源CuKα,管電圧40kV,管電流120mA)を使用し、2θ=5〜30°の範囲の非晶及び結晶のピーク面積を解析して結晶化度を求めた。
結晶核剤(2):フェニルホスホン酸金属塩から選ばれる少なくとも1種
本発明の生分解性樹脂組成物は、生分解性樹脂、分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物、好ましくは分子中に2個以上のエステル基を有する多価アルコールエステル又は多価カルボン酸エーテルエステルで、エステルを構成するアルコール成分の水酸基1個当たりエチレンオキサイドを平均0.5〜5モル付加した化合物、より好ましくは分子中に2個以上のエステル基を有し、エチレンオキサイドの平均付加モル数が3〜9の化合物からなる可塑剤、および上記結晶核剤(1)と結晶核剤(2)との混合物からなる結晶核剤を含有するものである。本発明の生分解性樹脂組成物における生分解性樹脂、可塑剤、結晶核剤の特に好ましい組合せとしては、生分解性樹脂がポリ乳酸樹脂、可塑剤がコハク酸とトリエチレングリコールモノメチルエーテルとのエステル、結晶核剤がエチレンビス12−ヒドロキシステアリン酸アミドとフェニルホスホン酸亜鉛塩との混合物である。
生分解性樹脂組成物として、表1に示す本発明品(A〜B)及び表2に示す比較品(a〜b)を、ニーダー((株)森山製作所製 DS3-20MWB-E)にて180℃、10分間溶融混練し、その後直ちに80℃の8インチロール(日本ロール製造(株)製)で約5mmの厚さに引き延ばし、縦×横=8cm×8cm程度の大きさに裁断した後、40℃以下で粉砕機(ダイコー精機(株)製 S-20)にて粉砕し、生分解性樹脂組成物の粉砕品を得た。
*2:コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル(合成品)
*3:エチレンビス12−ヒドロキシステアリン酸アミド(日本化成(株)製、スリパックス H)
*4:無置換のフェニルホスホン酸亜鉛塩(日産化学工業(株)製 PPA−Zn)
*5:カルボジライトLA−1(日清紡績(株)製)
生分解性樹脂組成物として前記表1に示す本発明品(A〜B)及び前記表2に示す比較品(a〜b)を用い、実施例1と同様にして生分解性樹脂組成物の粉砕品を得た。
Claims (7)
- 生分解性樹脂、可塑剤及び結晶核剤を含有する生分解性樹脂組成物であって、可塑剤が分子中に2個以上のエステル基を有し、エステルを構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜5モル付加した化合物であり、結晶核剤が、次の結晶核剤(1)と結晶核剤(2)の混合物である生分解性樹脂組成物。
結晶核剤(1):分子中に水酸基とアミド基を有する化合物から選ばれる少なくとも1種
結晶核剤(2):フェニルホスホン酸金属塩、リン酸エステルの金属塩、芳香族スルホン酸ジアルキルエステルの金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、ロジン酸アミド、カルボヒドラジド類、N−置換尿素類、メラミン化合物の塩及びウラシル類からなる群から選ばれる少なくとも1種 - 結晶核剤(1)と結晶核剤(2)との割合が、結晶核剤(1)/結晶核剤(2)(重量比)=20/80〜80/20である、請求項1記載の生分解性樹脂組成物。
- 結晶核剤(1)が、水酸基を有する脂肪族アミドである請求項1又は2記載の生分解性樹脂組成物。
- 結晶核剤(2)が、フェニルホスホン酸金属塩である請求項1〜3いずれかに記載の生分解性樹脂組成物。
- 可塑剤が、コハク酸又はアジピン酸とポリエチレングリコールモノメチルエーテルとのエステル、及び酢酸とグリセリン又はエチレングリコールのエチレンオキサイド付加物とのエステルからなる群より選ばれる少なくとも1種である請求項1〜4いずれかに記載の生分解性樹脂組成物。
- 生分解性樹脂100重量部に対し、可塑剤の含有量が5〜30重量部、結晶核剤(1)の含有量が0.1〜3重量部、結晶核剤(2)の含有量が0.1〜3重量部である、請求項1〜5いずれかに記載の生分解性樹脂組成物。
- 生分解性樹脂が、ポリ乳酸樹脂である請求項1〜6いずれかに記載の生分解性樹脂組成物。
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