JP5261006B2 - Polylactic acid resin composition - Google Patents
Polylactic acid resin composition Download PDFInfo
- Publication number
- JP5261006B2 JP5261006B2 JP2008100023A JP2008100023A JP5261006B2 JP 5261006 B2 JP5261006 B2 JP 5261006B2 JP 2008100023 A JP2008100023 A JP 2008100023A JP 2008100023 A JP2008100023 A JP 2008100023A JP 5261006 B2 JP5261006 B2 JP 5261006B2
- Authority
- JP
- Japan
- Prior art keywords
- polylactic acid
- acid resin
- coupling agent
- resin composition
- isocyanate
- 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.)
- Expired - Fee Related
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 109
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 109
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 50
- 239000012948 isocyanate Substances 0.000 claims abstract description 36
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 36
- 238000000465 moulding Methods 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 239000003484 crystal nucleating agent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 9
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 2
- -1 aromatic carbodiimide Chemical class 0.000 description 19
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 12
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 125000003368 amide group Chemical group 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 7
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229930182843 D-Lactic acid Natural products 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 229940022769 d- lactic acid Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 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
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- YSARBTHSZMNCIB-UHFFFAOYSA-N hexane-1,3,6-tricarboxylic acid Chemical compound OC(=O)CCCC(C(O)=O)CCC(O)=O YSARBTHSZMNCIB-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 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
- 229940114069 12-hydroxystearate Drugs 0.000 description 2
- 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 2
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 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
- 239000005995 Aluminium silicate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Chemical class 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Chemical class 0.000 description 2
- RJRRZABNCURWAM-UHFFFAOYSA-N (2-butylphenyl)phosphonic acid Chemical compound CCCCC1=CC=CC=C1P(O)(O)=O RJRRZABNCURWAM-UHFFFAOYSA-N 0.000 description 1
- YXTSJMYYIRPSDF-UHFFFAOYSA-N (2-methylphenyl)phosphonic acid Chemical compound CC1=CC=CC=C1P(O)(O)=O YXTSJMYYIRPSDF-UHFFFAOYSA-N 0.000 description 1
- GDKNDQBTIVRVAV-UHFFFAOYSA-N (2-propylphenyl)phosphonic acid Chemical compound CCCC1=CC=CC=C1P(O)(O)=O GDKNDQBTIVRVAV-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FOMSGFMDVIDZMI-QEMDMZNVSA-N OC(C(=O)O)CCCCCCCCCCCCCCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O Chemical compound OC(C(=O)O)CCCCCCCCCCCCCCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O FOMSGFMDVIDZMI-QEMDMZNVSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- FQOUHJLOCJLNOH-UHFFFAOYSA-N [SiH4].N#CO Chemical compound [SiH4].N#CO FQOUHJLOCJLNOH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical class 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 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- CJRXKDVOJJXMMR-UHFFFAOYSA-N n,n'-bis(2,3-dimethylphenyl)methanediimine Chemical compound CC1=CC=CC(N=C=NC=2C(=C(C)C=CC=2)C)=C1C CJRXKDVOJJXMMR-UHFFFAOYSA-N 0.000 description 1
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- GPZRJTOZLDJPBA-UHFFFAOYSA-N n,n'-bis[2,3-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(N=C=NC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C GPZRJTOZLDJPBA-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012860 organic pigment Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 description 1
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- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
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- 239000011734 sodium Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 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 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
本発明は、ポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体に関する。 The present invention relates to a polylactic acid resin composition and a polylactic acid resin molded article.
生分解性樹脂の中でポリ乳酸樹脂は、トウモロコシ、芋などからとれる糖分から、発酵法によりＬ−乳酸が大量に製造され安価になってきたこと、原料が自然農作物なので二酸化炭素排出量を増加させにくい、また得られた樹脂の性能として剛性が強く透明性が良いという特徴があるので、現在その利用が期待されている。しかしポリ乳酸樹脂の場合、脆く、硬く、可撓性に欠ける特性のために包装材や日用品のような消費材としての実用化例は多数あるが、射出成形によって得られる家電部品や自動車部品のような耐久材として高度な要求特性が求められる分野には、使用実績はほとんどない。射出成形体などに成形した場合は、可撓性、耐衝撃性のような機械的強度が不足したり、折り曲げたときに白化したり、ヒンジ特性が劣るなどの問題があり、使用されていないのが現状である。 Among the biodegradable resins, polylactic acid resin is produced by mass production of L-lactic acid from sugars obtained from corn, straw, etc., and has become cheap, and carbon dioxide emissions are increased because the raw material is a natural crop. This resin is characterized by its high rigidity and good transparency as a performance of the obtained resin. However, in the case of polylactic acid resin, there are many practical applications as consumer materials such as packaging materials and daily necessities because of its brittle, hard and inflexible properties. There is almost no record of use in fields where high demands are required for such durable materials. When molded into an injection-molded body, etc., it is not used due to problems such as insufficient mechanical strength such as flexibility and impact resistance, whitening when bent, and poor hinge characteristics. is the current situation.
また、ポリ乳酸樹脂は結晶化速度が遅く、延伸などの機械的工程を行わない限り成形後は非晶状態である。しかし、ポリ乳酸樹脂のガラス転移温度（Ｔｇ）は６０℃と低く耐熱性に劣るため、温度が５５℃以上となる環境下では使用できない問題があった。 In addition, the polylactic acid resin has a slow crystallization rate and is in an amorphous state after molding unless a mechanical process such as stretching is performed. However, since the glass transition temperature (Tg) of polylactic acid resin is as low as 60 ° C. and poor in heat resistance, there is a problem that it cannot be used in an environment where the temperature is 55 ° C. or higher.
更に家電部品や自動車部品のような耐久材としての利用には、耐熱性と耐衝撃性を備えた上で、ある程度の可撓性を有することが求められる。 Furthermore, utilization as a durable material such as home appliance parts and automobile parts is required to have a certain degree of flexibility in addition to heat resistance and impact resistance.
特許文献１には、乳酸系樹脂に、シランカップリング剤により表面処理された金属水酸化物と、芳香族カルボジイミドを含有する、難燃性と耐久性を兼ね備えた難燃性射出成形体が開示されており、シランカップリング剤としてはエポキシシランが好ましいと記載され、エポキシシランカップリング剤を用いた実施例だけが記載されている。しかし、エポキシシランカップリング剤により表面処理された金属水酸化物を用いた場合、その効果は不十分であり、更なる、耐熱性、耐衝撃性、可撓性が良好なポリ乳酸樹脂組成物の開発が求められている。
本発明の課題は、優れた耐熱性、耐衝撃性、更に可撓性を有するポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体を提供することにある。 An object of the present invention is to provide a polylactic acid resin composition and a polylactic acid resin molded article having excellent heat resistance, impact resistance, and flexibility.
本発明は、ポリ乳酸樹脂と、イソシアネート系シランカップリング剤によって表面処理された金属水和物とを含有するポリ乳酸樹脂組成物、更に可塑剤を含有するポリ乳酸樹脂組成物、更に有機結晶核剤を含有するポリ乳酸樹脂組成物、並びにこのポリ乳酸樹脂組成物を成形してなるポリ乳酸樹脂成形体を提供する。 The present invention relates to a polylactic acid resin composition containing a polylactic acid resin and a metal hydrate surface-treated with an isocyanate-based silane coupling agent, a polylactic acid resin composition further containing a plasticizer, and an organic crystal nucleus A polylactic acid resin composition containing an agent, and a polylactic acid resin molded article formed by molding the polylactic acid resin composition are provided.
本発明のポリ乳酸樹脂組成物は、優れた耐熱性、耐衝撃性、更に可撓性を示す。 The polylactic acid resin composition of the present invention exhibits excellent heat resistance, impact resistance, and flexibility.
［ポリ乳酸樹脂］
本発明に用いられるポリ乳酸樹脂は、ポリ乳酸、又は乳酸とヒドロキシカルボン酸とのコポリマーである。ヒドロキシカルボン酸としては、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシペンタン酸、ヒドロキシカプロン酸、ヒドロキシヘプタン酸等が挙げられ、グリコール酸、ヒドロキシカプロン酸が好ましい。好ましいポリ乳酸の分子構造は、例えばＬ−乳酸又はＤ−乳酸いずれかの単位２０〜１００モル％とそれぞれの対掌体の乳酸単位０〜８０モル％からなるものである。
[Polylactic acid resin]
The polylactic acid resin used in the present invention is polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxyheptanoic acid and the like, and glycolic acid and hydroxycaproic acid are preferable. The molecular structure of polylactic acid is preferably composed of, for example, 20 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 80 mol% of each enantiomer.
また、本発明におけるポリ乳酸樹脂としては、Ｌ−乳酸単位９０〜１００モル％と、Ｄ−乳酸等の単位０〜１０モル％とにより構成されるポリ乳酸単位（Ａ）と、Ｄ−乳酸単位９０〜１００モル％と、Ｌ−乳酸等の単位０〜１０モル％とにより構成されるポリ乳酸単位（Ｂ）との混合物からなり、（Ａ）／（Ｂ）（質量比）が１０／９０〜９０／１０である、ステレオコンプレックスポリ乳酸を用いることもできる。これらのステレオコンプレックスポリ乳酸を構成する各ポリ乳酸単位（Ａ）及び（Ｂ）に使用される乳酸以外の共重合成分単位は、２個以上のエステル結合を形成可能な官能基を持つジカルボン酸、多価アルコール、ヒドロキシカルボン酸、ラクトン等及びこれら種々の構成成分からなり、未反応の前記官能基を分子内に２つ以上有するポリエステル、ポリエーテル、ポリカーボネート等が挙げられる。 Moreover, as a polylactic acid resin in this invention, the polylactic acid unit (A) comprised by 90-100 mol% of L-lactic acid units, and 0-10 mol% of units, such as D-lactic acid, and D-lactic acid unit It consists of a mixture of 90 to 100 mol% and polylactic acid units (B) composed of 0 to 10 mol% of units such as L-lactic acid, and (A) / (B) (mass ratio) is 10/90. Stereocomplex polylactic acid that is ˜90 / 10 can also be used. The copolymer component unit other than lactic acid used in each of the polylactic acid units (A) and (B) constituting these stereocomplex polylactic acid is a dicarboxylic acid having a functional group capable of forming two or more ester bonds, Examples include polyesters, polyethers, polycarbonates, and the like, which are composed of polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like and various kinds of these structural components and have two or more unreacted functional groups in the molecule.
また、乳酸とヒドロキシカルボン酸とのコポリマーは、例えばＬ−乳酸又はＤ−乳酸いずれかの単位８５〜１００モル％とヒドロキシカルボン酸単位０〜１５モル％からなるものである。これらのポリ乳酸樹脂は、Ｌ−乳酸、Ｄ−乳酸及びヒドロキシカルボン酸の中から必要とする構造のものを選んで原料とし、脱水重縮合することにより得ることができる。好ましくは、乳酸の環状二量体であるラクチド、グリコール酸の環状二量体であるグリコリド及びカプロラクトン等から必要とする構造のものを選んで開環重合することにより得ることができる。ラクチドにはＬ−乳酸の環状二量体であるＬ−ラクチド、Ｄ−乳酸の環状二量体であるＤ−ラクチド、Ｄ−乳酸とＬ−乳酸とが環状二量化したメソ−ラクチド及びＤ−ラクチドとＬ−ラクチドとのラセミ混合物であるＤＬ−ラクチドがある。本発明ではいずれのラクチドも用いることができる。但し、主原料は、Ｄ−ラクチド又はＬ−ラクチドが好ましい。 The copolymer of lactic acid and hydroxycarboxylic acid is composed of, for example, 85 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 15 mol% of hydroxycarboxylic acid units. These polylactic acid resins can be obtained by dehydrating polycondensation using L-lactic acid, D-lactic acid and hydroxycarboxylic acid as a raw material by selecting those having the required structure. Preferably, it can be obtained by ring-opening polymerization by selecting a desired structure from lactide, which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, and caprolactone. Lactide includes L-lactide which is a cyclic dimer of L-lactic acid, D-lactide which is a cyclic dimer of D-lactic acid, meso-lactide obtained by cyclic dimerization of D-lactic acid and L-lactic acid, and D-lactide. There is DL-lactide, which is a racemic mixture of lactide and L-lactide. Any lactide can be used in the present invention. However, the main raw material is preferably D-lactide or L-lactide.
ポリ乳酸樹脂の中で好ましいものとしては、耐熱性の観点から、光学純度９０％以上の結晶性ポリ乳酸と光学純度９０％未満のポリ乳酸の割合が質量比で、光学純度９０％以上の結晶性ポリ乳酸／光学純度９０％未満のポリ乳酸＝１００／０〜１０／９０、好ましくは１００／０〜２５／７５、より好ましくは１００／０〜５０／５０、更に好ましくは１００／０〜９０／１０のポリ乳酸樹脂が挙げられる。 Among the polylactic acid resins, from the viewpoint of heat resistance, a crystal ratio of crystalline polylactic acid having an optical purity of 90% or more and polylactic acid having an optical purity of less than 90% is a mass ratio, and crystals having an optical purity of 90% or more. Polylactic acid / polylactic acid with an optical purity of less than 90% = 100/0 to 10/90, preferably 100/0 to 25/75, more preferably 100/0 to 50/50, still more preferably 100/0 to 90 / 10 polylactic acid resin.
市販されているポリ乳酸樹脂としては、例えば、三井化学（株）製、商品名レイシア；ネイチャーワークス社製、商品名Ｎａｔｕｒｅ Ｗｏｒｋｓ；トヨタ自動車（株）製、商品名エコプラスチックＵ’ｚ等が挙げられる。 Examples of commercially available polylactic acid resins include Mitsui Chemicals, Inc., trade name Lacia; Nature Works, trade name Nature Works; Toyota Motor Corporation, trade name Eco Plastic U'z, and the like. It is done.
これらの中では、三井化学（株）製、商品名レイシアＨ−１００，Ｈ−２８０，Ｈ−４００，Ｈ−４４０；ネイチャーワークス社製、商品名Ｎａｔｕｒｅ Ｗｏｒｋｓ；トヨタ自動車（株）製、商品名エコプラスチックＵ’ｚが好ましい。 Among these, Mitsui Chemicals, Inc., trade names Lacia H-100, H-280, H-400, H-440; Nature Works, trade names Nature Works; Toyota Motor Corporation, trade names Eco plastic U'z is preferred.
耐熱性の観点では、Ｌ−乳酸純度が高い結晶性ポリ乳酸樹脂が好ましく、延伸により配向結晶化させることが好ましい。結晶性ポリ乳酸樹脂としては、三井化学（株）製、レイシアＨ−１００、Ｈ−４００、Ｈ−４４０、トヨタ自動車（株）製、エコプラスチックＵ’ｚ Ｓ−０９、Ｓ−１２、Ｓ−１７等が挙げられる。 From the viewpoint of heat resistance, a crystalline polylactic acid resin having a high L-lactic acid purity is preferable, and orientation crystallization is preferably performed by stretching. As crystalline polylactic acid resin, Mitsui Chemicals, Laissia H-100, H-400, H-440, Toyota Motor Corporation, Eco-Plastic U'z S-09, S-12, S- 17 etc. are mentioned.
［イソシアネート系シランカップリング剤によって表面処理された金属水和物］
本発明に用いられるイソシアネート系シランカップリング剤によって表面処理された金属水和物としては、イソシアネート系シランカップリング剤と金属水和物とを、イソシアネート系シランカップリング剤／金属水和物（質量比）＝０．１／９９．９〜５／９５の割合で処理したものが、本発明の効果を得る観点から好ましく、０．３／９９．７〜３／９７の割合で処理したものがより好ましく、０．５／９９．５〜２／９８の割合で処理したものが更に好ましい。
[Metal hydrate surface-treated with isocyanate-based silane coupling agent]
As the metal hydrate surface-treated with the isocyanate-based silane coupling agent used in the present invention, an isocyanate-based silane coupling agent and a metal hydrate are combined with an isocyanate-based silane coupling agent / metal hydrate (mass). Ratio) = 0.1 / 99.9 to 5/95 is preferably processed from the viewpoint of obtaining the effects of the present invention, and is processed at a ratio of 0.3 / 99.7 to 3/97. More preferably, it is more preferably treated at a ratio of 0.5 / 99.5 to 2/98.
イソシアネート系シランカップリング剤としては、３−イソシアネートプロピルトリメトキシシラン及び３−イソシアネートプロピルトリエトキシシランから選ばれる少なくとも１種が挙げられる。 Examples of the isocyanate-based silane coupling agent include at least one selected from 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.
本発明に用いられる金属水和物は、平均粒径１０μｍ以下の粒状体からなるものが好ましく、０．１〜５μｍの粒状体からなるものがより好ましい。 The metal hydrate used in the present invention is preferably composed of granules having an average particle diameter of 10 μm or less, more preferably composed of granules having a size of 0.1 to 5 μm.
尚、金属水和物の平均粒径は、回折・散乱法によって体積基準のメジアン径を測定することにより求めることができる。例えば市販の装置としてはコールター社製レーザー回折・光散乱法粒度測定装置ＬＳ２３０等が挙げられる。 The average particle diameter of the metal hydrate can be determined by measuring the volume-based median diameter by a diffraction / scattering method. For example, as a commercially available apparatus, a laser diffraction / light scattering particle size measuring apparatus LS230 manufactured by Coulter, Inc. can be mentioned.
本発明に用いられる金属水和物としては、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、ドーソナイト、アルミン酸カルシウム、水和石膏、ホウ酸亜鉛、メタホウ酸バリウム、ホウ砂、カオリンクレー、炭酸カルシウム等が挙げられ、水酸化マグネシウム、水酸化アルミニウム及び水酸化カルシウムから選ばれる少なくとも１種が好ましい。 Examples of the metal hydrate used in the present invention include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, dosonite, calcium aluminate, hydrated gypsum, zinc borate, barium metaborate, borax, kaolin clay, calcium carbonate And at least one selected from magnesium hydroxide, aluminum hydroxide and calcium hydroxide is preferable.
イソシアネート系シランカップリング剤によって表面処理された金属水和物を得る方法は特に限定されず、例えば、イソシアネート系シランカップリング剤を、アセトン、酢酸エチル、トルエン等の溶媒に溶解させた溶液を、金属水和物の表面に噴霧又は塗工した後、乾燥して溶媒を除去する方法等が挙げられる。 A method for obtaining a metal hydrate surface-treated with an isocyanate-based silane coupling agent is not particularly limited. For example, a solution obtained by dissolving an isocyanate-based silane coupling agent in a solvent such as acetone, ethyl acetate, toluene, Examples include a method of spraying or coating the surface of the metal hydrate and then drying to remove the solvent.
［可塑剤］
本発明のポリ乳酸樹脂組成物は更に可塑剤を含有することが好ましい。
[Plasticizer]
The polylactic acid resin composition of the present invention preferably further contains a plasticizer.
本発明に用いられる可塑剤としては特に限定されないが、マロン酸、コハク酸、グルタル酸、アジピン酸、１，３，６−ヘキサントリカルボン酸等の多塩基酸と、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、テトラエチレングリコールモノメチルエーテル等のポリエチレングリコールモノアルキルエーテルとのエステル；グリセリン、エチレングリコール、ジグリセリン、１，４−ブタンジオール等の多価アルコールに、エチレンオキサイド及び／又はプロピレンオキサイドを付加させた付加物のアセチル化物；ヒドロキシ安息香酸２−エチルヘキシル等のヒドロキシ安息香酸エステル；フタル酸ジ−２−エチルヘキシル等のフタル酸エステル；アジピン酸ジオクチル等のアジピン酸エステル；マレイン酸ジ−ｎ−ブチル等のマレイン酸エステル；アセチルクエン酸トリブチル等のクエン酸エステル；リン酸トリクレジル等のアルキルリン酸エステル；トリメリット酸トリオクチル等のトリカルボン酸エステル；アセチル化ポリオキシエチレンヘキシルエーテル等のアセチル化ポリオキシエチレンアルキル（アルキル基の炭素数２〜１５）エーテル等が挙げられる。ポリ乳酸樹脂の柔軟性、透明性、結晶化速度に優れる観点から、コハク酸、アジピン酸又は１，３，６−ヘキサントリカルボン酸とポリエチレングリコール（エチレンオキサイドの平均付加モル数０．５〜５）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（エチレンオキサイドの平均付加モル数３〜２０）とのエステルからなる群より選ばれる少なくとも１種が好ましい。 The plasticizer used in the present invention is not particularly limited, but polybasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, 1,3,6-hexanetricarboxylic acid, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Esters with polyethylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and tetraethylene glycol monomethyl ether; polyhydric alcohols such as glycerin, ethylene glycol, diglycerin and 1,4-butanediol Acetylated products of adducts obtained by adding ethylene oxide and / or propylene oxide; hydroxybenzoic acid esters such as 2-ethylhexyl hydroxybenzoate; di-2 phthalate Phthalates such as ethylhexyl; adipates such as dioctyl adipate; maleates such as di-n-butyl maleate; citrates such as tributyl acetylcitrate; alkyl phosphates such as tricresyl phosphate; Examples thereof include tricarboxylic acid esters such as trioctyl merit acid; acetylated polyoxyethylene alkyl (alkyl group having 2 to 15 carbon atoms) ether such as acetylated polyoxyethylene hexyl ether. From the viewpoint of excellent flexibility, transparency and crystallization speed of polylactic acid resin, succinic acid, adipic acid or 1,3,6-hexanetricarboxylic acid and polyethylene glycol (average added mole number of ethylene oxide 0.5 to 5) At least one selected from the group consisting of an ester with monomethyl ether and an ester with acetic acid and an ethylene oxide adduct of glycerin or ethylene glycol (average added mole number of ethylene oxide of 3 to 20) is preferred.
［有機結晶核剤］
本発明のポリ乳酸樹脂組成物は更に有機結晶核剤を含有することが好ましい。
[Organic crystal nucleating agent]
The polylactic acid resin composition of the present invention preferably further contains an organic crystal nucleating agent.
有機結晶核剤としては、脂肪酸モノアミド、脂肪酸ビスアミド、芳香族カルボン酸アミド、ロジン酸アミド等のアミド類；ヒドロキシ脂肪酸エステル類；芳香族スルホン酸ジアルキルエステルの金属塩、フェニルホスホン酸金属塩、リン酸エステルの金属塩、ロジン酸類金属塩等の金属塩類；カルボヒドラジド類、Ｎ−置換尿素類、有機顔料類等が挙げられるが、成形性、耐熱性、耐衝撃性及び有機結晶核剤の耐ブルーム性の観点から、分子中に水酸基とアミド基とを有する化合物及びヒドロキシ脂肪酸エステルからなる群から選ばれる少なくとも１種が好ましく、更にこれらの少なくとも１種と、フェニルホスホン酸金属塩を併用することがより好ましく、分子中に水酸基とアミド基とを有する化合物とフェニルホスホン酸金属塩を併用することが更に好ましい。 Organic crystal nucleating agents include fatty acid monoamides, fatty acid bisamides, aromatic carboxylic acid amides, rosinic acid amides and the like; hydroxy fatty acid esters; aromatic sulfonic acid dialkyl ester metal salts, phenylphosphonic acid metal salts, phosphoric acid Metal salts such as metal salts of esters and rosin acid salts; carbohydrazides, N-substituted ureas, organic pigments, etc., including moldability, heat resistance, impact resistance, and bloom resistance of organic crystal nucleating agents From the viewpoint of properties, at least one selected from the group consisting of a compound having a hydroxyl group and an amide group in the molecule and a hydroxy fatty acid ester is preferable, and at least one of these may be used in combination with a metal salt of phenylphosphonic acid. More preferably, a compound having a hydroxyl group and an amide group in the molecule and a phenylphosphonic acid metal salt are used in combination. It is more preferable.
分子中に水酸基とアミド基とを有する化合物としては、ポリ乳酸樹脂との相溶性を向上させる観点から、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好ましい。また、分子中に水酸基とアミド基とを有する化合物の融点は、混練時の有機結晶核剤の分散性を向上させ、またポリ乳酸樹脂組成物の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。 The compound having a hydroxyl group and an amide group in the molecule is preferably an aliphatic amide having two or more hydroxyl groups and two or more amide groups from the viewpoint of improving compatibility with the polylactic acid resin. The melting point of the compound having a hydroxyl group and an amide group in the molecule is 65 ° C. or higher from the viewpoint of improving the dispersibility of the organic crystal nucleating agent during kneading and improving the crystallization rate of the polylactic acid resin composition. Is preferable, 70-220 degreeC is more preferable, and 80-190 degreeC is still more preferable.
分子中に水酸基とアミド基とを有する化合物の具体例としては、１２−ヒドロキシステアリン酸モノエタノールアミド等のヒドロキシ脂肪酸モノアミド、メチレンビス１２−ヒドロキシステアリン酸アミド、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミド等のヒドロキシ脂肪酸ビスアミド等が挙げられる。ポリ乳酸樹脂組成物の成形性、耐熱性、耐衝撃性及び耐ブルーム性の観点から、メチレンビス１２−ヒドロキシステアリン酸アミド、エチレンビス１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス１２−ヒドロキシステアリン酸アミド等のアルキレンビスヒドロキシステアリン酸アミドが好ましく、エチレンビス１２−ヒドロキシステアリン酸アミドがより好ましい。 Specific examples of the compound having a hydroxyl group and an amide group in the molecule include hydroxy fatty acid monoamides such as 12-hydroxystearic acid monoethanolamide, methylene bis 12-hydroxystearic acid amide, ethylene bis 12-hydroxystearic acid amide, and hexamethylene. And hydroxy fatty acid bisamides such as bis-12-hydroxystearic acid amide. From the viewpoint of moldability, heat resistance, impact resistance and bloom resistance of the polylactic acid resin composition, methylene bis 12-hydroxystearic acid amide, ethylene bis 12-hydroxystearic acid amide, hexamethylene bis 12-hydroxystearic acid amide, etc. The alkylene bishydroxystearic acid amide is preferable, and ethylene bis 12-hydroxystearic acid amide is more preferable.
ヒドロキシ脂肪酸エステルの具体例としては、１２−ヒドロキシステアリン酸トリグリセライド、１２−ヒドロキシステアリン酸ジグリセライド、１２−ヒドロキシステアリン酸モノグリセライド、ペンタエリスリトール−モノ−１２−ヒドロキシステアレート、ペンタエリスリトール−ジ−１２−ヒドロキシステアレート、ペンタエリスリトール−トリ−１２−ヒドロキシステアレート等のヒドロキシ脂肪酸エステルが挙げられる。ポリ乳酸樹脂成形体の成形性、耐熱性、耐衝撃性及び有機結晶核剤の耐ブルーム性の観点から、１２−ヒドロキシステアリン酸トリグリセライドが好ましい。 Specific examples of the hydroxy fatty acid ester include 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid diglyceride, 12-hydroxystearic acid monoglyceride, pentaerythritol mono-12-hydroxystearate, pentaerythritol di-12-hydroxystearate. And hydroxy fatty acid esters such as pentaerythritol-tri-12-hydroxystearate. From the viewpoint of moldability of the polylactic acid resin molded article, heat resistance, impact resistance, and bloom resistance of the organic crystal nucleating agent, 12-hydroxystearic acid triglyceride is preferable.
本発明に用いられるフェニルホスホン酸金属塩は、置換基を有しても良いフェニル基とホスホン基（−ＰＯ（ＯＨ）2）を有するフェニルホスホン酸の金属塩であり、フェニル基の置換基としては、炭素数１〜１０のアルキル基、アルコキシ基の炭素数が１〜１０のアルコキシカルボニル基等が挙げられる。フェニルホスホン酸の具体例としては、無置換のフェニルホスホン酸、メチルフェニルホスホン酸、エチルフェニルホスホン酸、プロピルフェニルホスホン酸、ブチルフェニルホスホン酸、ジメトキシカルボニルフェニルホスホン酸、ジエトキシカルボニルフェニルホスホン酸等が挙げられ、無置換のフェニルホスホン酸が好ましい。 The phenylphosphonic acid metal salt used in the present invention is a phenylphosphonic acid metal salt having a phenyl group which may have a substituent and a phosphonic group (—PO (OH) 2 ). Includes an alkyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms in an alkoxy group, and the like. Specific examples of phenylphosphonic acid include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, and diethoxycarbonylphenylphosphonic acid. And unsubstituted phenylphosphonic acid is preferred.
フェニルホスホン酸の金属塩としては、リチウム、ナトリウム、マグネシウム、アルミニウム、カリウム、カルシウム、バリウム、銅、亜鉛、鉄、コバルト、ニッケル等の塩が挙げられ、亜鉛塩が好ましい。 Examples of the metal salt of phenylphosphonic acid include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.
本発明において有機結晶核剤として、分子中に水酸基とアミド基とを有する化合物及びヒドロキシ脂肪酸エステルからなる群から選ばれる少なくとも１種と、フェニルホスホン酸金属塩とを併用する場合、これらの割合は、本発明の効果を発現する観点から、分子中に水酸基とアミド基とを有する化合物及びヒドロキシ脂肪酸エステルからなる群から選ばれる少なくとも１種／フェニルホスホン酸金属塩（質量比）＝２０／８０〜８０／２０が好ましく、３０／７０〜７０／３０がより好ましく、４０／６０〜６０／４０が更に好ましい。 In the present invention, when an organic crystal nucleating agent is used in combination with a phenylphosphonic acid metal salt and at least one selected from the group consisting of a compound having a hydroxyl group and an amide group in the molecule and a hydroxy fatty acid ester, these ratios are: From the viewpoint of expressing the effect of the present invention, at least one selected from the group consisting of a compound having a hydroxyl group and an amide group in the molecule and a hydroxy fatty acid ester / metal salt of phenylphosphonic acid (mass ratio) = 20/80 to 80/20 is preferable, 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is still more preferable.
［ポリ乳酸樹脂組成物］
本発明のポリ乳酸樹脂組成物は、ポリ乳酸樹脂と、イソシアネート系シランカップリング剤によって表面処理された金属水和物とを含有するものであり、更に、可塑剤や有機結晶核剤を含有することが好ましい。
[Polylactic acid resin composition]
The polylactic acid resin composition of the present invention contains a polylactic acid resin and a metal hydrate surface-treated with an isocyanate-based silane coupling agent, and further contains a plasticizer and an organic crystal nucleating agent. It is preferable.
本発明のポリ乳酸樹脂組成物は、上記のようなポリ乳酸樹脂と、イソシアネート系シランカップリング剤によって表面処理された金属水和物を含有することにより、格別顕著な耐熱性、耐衝撃性、可撓性の効果が奏される。このような顕著な効果が発現される理由は定かではないが、金属水和物に表面処理されたシランカップリング剤のイソシアネート基が、ポリ乳酸樹脂が有する水酸基に対して反応する等の作用によってもたらされているものと考えられる。 The polylactic acid resin composition of the present invention contains a polylactic acid resin as described above and a metal hydrate surface-treated with an isocyanate-based silane coupling agent. A flexible effect is exhibited. The reason why such a remarkable effect is manifested is not clear, but the action of the isocyanate group of the silane coupling agent surface-treated with metal hydrate reacts with the hydroxyl group of the polylactic acid resin. It is thought to have been brought.
本発明のポリ乳酸樹脂組成物中の、ポリ乳酸樹脂の含有量は、本発明の目的を達成する観点から、好ましくは３０質量％以上であり、より好ましくは４０質量％以上である。 The content of the polylactic acid resin in the polylactic acid resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of achieving the object of the present invention.
本発明のポリ乳酸樹脂組成物中の、ポリ乳酸樹脂とイソシアネート系シランカップリング剤によって表面処理された金属水和物の割合は、本発明の目的を達成する観点から、ポリ乳酸樹脂／イソシアネート系シランカップリング剤によって表面処理された金属水和物（質量比）＝３０／７０〜７０／３０が好ましく、４０／６０〜６０／４０がより好ましい。 In the polylactic acid resin composition of the present invention, the ratio of the metal hydrate surface-treated with the polylactic acid resin and the isocyanate-based silane coupling agent is selected from the viewpoint of achieving the object of the present invention. Metal hydrate (mass ratio) surface-treated with a silane coupling agent is preferably 30/70 to 70/30, more preferably 40/60 to 60/40.
本発明のポリ乳酸樹脂組成物において、可塑剤の含有量は、本発明の目的を達成する観点から、ポリ乳酸樹脂１００質量部に対し、５〜５０質量部が好ましく、７〜３０質量部がより好ましく、８〜３０質量部が更に好ましい。 In the polylactic acid resin composition of the present invention, the content of the plasticizer is preferably 5 to 50 parts by mass, and 7 to 30 parts by mass with respect to 100 parts by mass of the polylactic acid resin, from the viewpoint of achieving the object of the present invention. More preferably, 8-30 mass parts is still more preferable.
本発明のポリ乳酸樹脂組成物において、有機結晶核剤の含有量は、十分な耐衝撃性、及び可撓性を得る観点から、ポリ乳酸樹脂１００質量部に対し、０．０５〜５質量部が好ましく、０．１〜３質量部がより好ましく、０．２〜２質量部が更に好ましい。 In the polylactic acid resin composition of the present invention, the content of the organic crystal nucleating agent is 0.05 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin from the viewpoint of obtaining sufficient impact resistance and flexibility. Is preferable, 0.1-3 mass parts is more preferable, 0.2-2 mass parts is still more preferable.
本発明の組成物は、更に無機充填剤を含有することができる。無機充填剤としては、タルク、スメクタイト、カオリン、マイカ、モンモリロナイト等のケイ酸塩、シリカ、酸化マグネシウム、酸化チタン、炭酸カルシウム等の無機化合物や、ガラス繊維、炭素繊維、グラファイト繊維、ワラスナイト、チタン酸カリウムウィスカー、珪素系ウィスカー等の繊維状無機充填剤等が挙げられる。無機充填剤の平均粒径は、良好な分散性を得る観点から、０．１〜２０μｍが好ましく、０．１〜１０μｍがより好ましい。また、繊維状の無機充填剤のアスペクト比は、剛性向上の観点から５以上が好ましく、１０以上がより好ましく、２０以上が更に好ましい。無機充填剤の中でも、ポリ乳酸樹脂成形体の成形性及び耐熱性の観点からケイ酸塩が好ましく、タルク又はマイカがより好ましく、タルクが特に好ましい。また、ポリ乳酸樹脂成形体の成形性及び透明性の観点からは、シリカが好ましい。 The composition of the present invention can further contain an inorganic filler. Examples of inorganic fillers include silicates such as talc, smectite, kaolin, mica, and montmorillonite; inorganic compounds such as silica, magnesium oxide, titanium oxide, and calcium carbonate; glass fiber, carbon fiber, graphite fiber, wollastonite, and titanic acid. Examples thereof include fibrous inorganic fillers such as potassium whiskers and silicon-based whiskers. The average particle size of the inorganic filler is preferably from 0.1 to 20 μm, more preferably from 0.1 to 10 μm, from the viewpoint of obtaining good dispersibility. Further, the aspect ratio of the fibrous inorganic filler is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more, from the viewpoint of improving rigidity. Among the inorganic fillers, silicates are preferable, talc or mica is more preferable, and talc is particularly preferable from the viewpoint of moldability and heat resistance of the polylactic acid resin molded body. Silica is preferable from the viewpoint of moldability and transparency of the polylactic acid resin molded body.
尚、無機充填剤の平均粒径は、回折・散乱法によって体積基準のメジアン径を測定することにより求めることができる。例えば市販の装置としてはコールター社製レーザー回折・光散乱法粒度測定装置ＬＳ２３０等が挙げられる。 The average particle diameter of the inorganic filler can be obtained by measuring the volume-based median diameter by the diffraction / scattering method. For example, as a commercially available apparatus, a laser diffraction / light scattering particle size measuring apparatus LS230 manufactured by Coulter, Inc. can be mentioned.
本発明のポリ乳酸樹脂組成物において、無機充填剤の含有量は、十分な耐熱性及び耐衝撃性を得る観点から、ポリ乳酸樹脂１００質量部に対し、１〜２００質量部が好ましく、３〜５０質量部がより好ましく、５〜４０質量部が更に好ましい。 In the polylactic acid resin composition of the present invention, the content of the inorganic filler is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the polylactic acid resin from the viewpoint of obtaining sufficient heat resistance and impact resistance. 50 mass parts is more preferable, and 5-40 mass parts is still more preferable.
本発明のポリ乳酸樹脂組成物は、更に、加水分解抑制剤を含有することができる。加水分解抑制剤としては、ポリカルボジイミド化合物やモノカルボジイミド化合物等のカルボジイミド化合物が挙げられ、ポリ乳酸樹脂成形体の成形性の観点からポリカルボジイミド化合物が好ましく、ポリ乳酸樹脂成形体の耐熱性、耐衝撃性及び有機結晶核剤の耐ブルーム性の観点から、モノカルボジイミド化合物が好ましく、また、ポリ乳酸樹脂成形体の耐久性の観点から、モノカルボジイミド化合物とポリカルボジイミド化合物の併用が好ましい。 The polylactic acid resin composition of the present invention can further contain a hydrolysis inhibitor. Examples of the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds, and polycarbodiimide compounds are preferred from the viewpoint of moldability of polylactic acid resin molded products, and heat resistance and impact resistance of polylactic acid resin molded products. From the viewpoint of the property and the bloom resistance of the organic crystal nucleating agent, a monocarbodiimide compound is preferable, and from the viewpoint of the durability of the polylactic acid resin molded article, the combined use of the monocarbodiimide compound and the polycarbodiimide compound is preferable.
ポリカルボジイミド化合物としては、ポリ（４，４’−ジフェニルメタンカルボジイミド）、ポリ（４，４’−ジシクロヘキシルメタンカルボジイミド）、ポリ（１，３，５−トリイソプロピルベンゼン）ポリカルボジイミド、ポリ（１，３，５−トリイソプロピルベンゼン及び１，５−ジイソプロピルベンゼン）ポリカルボジイミド等が挙げられ、モノカルボジイミド化合物としては、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジフェニルカルボジイミド、ビス(メチルフェニル)カルボジイミド、ビス（メトキシフェニル）カルボジイミド、ビス（ニトロフェニル）カルボジイミド、ビス（ジメチルフェニル）カルボジイミド、ビス(ジイソプロピルフェニル)カルボジイミド、ビス（ジーｔ−ブチル）カルボジイミド、Ｎ−エチル−Ｎ‘−（３−ジメチルアミノプロピル）カルボジイミド、ビス（トリフェニルシリル）カルボジイミド、Ｎ，Ｎ’−ジ−２，６−ジイソプロピルフェニルカルボジイミド等が挙げられる。 Examples of the polycarbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide and the like, and monocarbodiimide compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, diphenylcarbodiimide, bis (methylphenyl) carbodiimide, bis (methoxyphenyl) carbodiimide, bis (Nitrophenyl) carbodiimide, bis (dimethylphenyl) carbodiimide, bis (diisopropylphenyl) carbodiimide, bis (di-t-butyl) carbodiimi And N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide, bis (triphenylsilyl) carbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide and the like.
上記カルボジイミド化合物は、ポリ乳酸樹脂成形体の成形性、耐熱性、耐衝撃性及び有機結晶核剤の耐ブルーム性を満たすために、単独又は２種以上組み合わせて用いてもよい。また、ポリ（４，４’−ジシクロヘキシルメタンカルボジイミド）はカルボジライトＬＡ−１（日清紡績（株）製）を、ポリ（１，３，５−トリイソプロピルベンゼン）ポリカルボジイミド及びポリ（１，３，５−トリイソプロピルベンゼン及び１，５−ジイソプロピルベンゼン）ポリカルボジイミドはスタバクゾールＰ及びスタバクゾールＰ−１００（Rhein Chemie社製）を、Ｎ，Ｎ’−ジ−２，６−ジイソプロピルフェニルカルボジイミドはスタバクゾール１、スタバクゾール１−ＬＦ（Rhein Chemie社製）をそれぞれ購入して使用することができる。 The above carbodiimide compounds may be used alone or in combination of two or more in order to satisfy the moldability, heat resistance, impact resistance and bloom resistance of the organic crystal nucleating agent of the polylactic acid resin molding. Poly (4,4′-dicyclohexylmethanecarbodiimide) is obtained from carbodilite LA-1 (Nisshinbo Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5). -Triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide is stabuxol P and stabuxol P-100 (manufactured by Rhein Chemie), N, N'-di-2,6-diisopropylphenylcarbodiimide is stabuxol 1 and stabuxol 1 -LF (manufactured by Rhein Chemie) can be purchased and used.
本発明のポリ乳酸樹脂組成物において、加水分解抑制剤の含有量は、ポリ乳酸樹脂成形体の成形性の観点から、ポリ乳酸樹脂１００質量部に対し、０．０５〜３質量部が好ましく、０．１〜２質量部が更に好ましい。 In the polylactic acid resin composition of the present invention, the content of the hydrolysis inhibitor is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polylactic acid resin, from the viewpoint of moldability of the polylactic acid resin molded body. 0.1-2 mass parts is still more preferable.
本発明のポリ乳酸樹脂組成物は、上記以外に、更にヒンダードフェノール又はフォスファイト系の酸化防止剤、又は炭化水素系ワックス類やアニオン型界面活性剤である滑剤等の他の成分を含有することができる。酸化防止剤、滑剤のそれぞれの含有量は、ポリ乳酸樹脂１００質量部に対し、０．０５〜３質量部が好ましく、０．１〜２質量部が更に好ましい。 In addition to the above, the polylactic acid resin composition of the present invention further contains other components such as a hindered phenol or a phosphite antioxidant, or a hydrocarbon wax or a lubricant that is an anionic surfactant. be able to. The content of each of the antioxidant and the lubricant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polylactic acid resin.
本発明のポリ乳酸樹脂組成物は、上記以外の他の成分として、帯電防止剤、防曇剤、光安定剤、紫外線吸収剤、顔料、防カビ剤、抗菌剤、発泡剤等を、本発明の目的達成を妨げない範囲で含有することができる。 The polylactic acid resin composition of the present invention includes an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, an antifungal agent, an antibacterial agent, a foaming agent and the like as components other than the above. It can contain in the range which does not prevent achievement of the objective.
本発明のポリ乳酸樹脂組成物は、加工性が良好で、例えば２００℃以下の低温で加工することができ、フィルムやシートに成形して、各種用途に用いることができる。 The polylactic acid resin composition of the present invention has good processability, can be processed at a low temperature of, for example, 200 ° C. or lower, and can be formed into a film or sheet and used for various applications.
［ポリ乳酸樹脂成形体及びその製造法］
本発明のポリ乳酸樹脂成形体は、本発明のポリ乳酸樹脂組成物を成形することにより得られる。具体的には、例えば、押出し機等を用いてポリ乳酸樹脂を溶融させながら、イソシアネート系シランカップリング剤によって表面処理された金属水和物、必要により可塑剤、有機結晶核剤等を混合し、次に得られた溶融物を射出成形機等により金型に充填して成形する。金型温度は、特に限定されないが、作業性を向上させる観点から、１１０℃以下が好ましく、９０℃以下がより好ましく、８０℃以下が更に好ましい。またポリ乳酸樹脂組成物の結晶化速度を向上させる観点から、３０℃以上が好ましく、４０℃以上がより好ましく、６０℃以上が更に好ましい。かかる観点から、金型温度は３０〜１１０℃が好ましく、４０〜９０℃がより好ましく、６０〜８０℃が更に好ましい。
[Polylactic acid resin molded article and its production method]
The polylactic acid resin molded product of the present invention can be obtained by molding the polylactic acid resin composition of the present invention. Specifically, for example, while melting polylactic acid resin using an extruder or the like, a metal hydrate surface-treated with an isocyanate-based silane coupling agent, and if necessary, a plasticizer, an organic crystal nucleating agent, etc. are mixed. Then, the obtained melt is filled into a mold by an injection molding machine or the like and molded. The mold temperature is not particularly limited, but is preferably 110 ° C. or less, more preferably 90 ° C. or less, and still more preferably 80 ° C. or less from the viewpoint of improving workability. Moreover, from a viewpoint of improving the crystallization rate of a polylactic acid resin composition, 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 60 degreeC or more is still more preferable. From this viewpoint, the mold temperature is preferably 30 to 110 ° C, more preferably 40 to 90 ° C, and still more preferably 60 to 80 ° C.
本発明のポリ乳酸樹脂成形体の好ましい製造方法は、ポリ乳酸樹脂、及びイソシアネート系シランカップリング剤によって表面処理された金属水和物を含有するポリ乳酸樹脂組成物を溶融混練する工程（以下工程（１）という）と、工程（１）で得られた溶融物を１１０℃以下の金型内に充填して成形する工程（以下工程（２）という）を含む方法である。 A preferred method for producing the polylactic acid resin molded article of the present invention is a step of melt-kneading a polylactic acid resin and a polylactic acid resin composition containing a metal hydrate surface-treated with an isocyanate-based silane coupling agent (following steps) (1)) and a step of filling the melt obtained in step (1) into a mold of 110 ° C. or lower and molding (hereinafter referred to as step (2)).
本発明においては、工程（１）を経た後、冷却して非晶状態（すなわち高角Ｘ線回折法で測定される結晶化度が１％以下となる条件）とした後、工程（２）を行う方法や、工程（１）を経た後、冷却して直ちに工程（２）を行う方法が好ましく、本発明の結晶化速度の向上効果が発現する観点から、工程（１）を経た後、冷却して直ちに工程（２）を行う方法がより好ましい。 In the present invention, after the step (1), after cooling to an amorphous state (that is, the condition that the degree of crystallinity measured by high angle X-ray diffraction is 1% or less), the step (2) is performed. The method of performing and the method of performing the step (2) immediately after cooling after the step (1) is preferable. From the viewpoint of the effect of improving the crystallization speed of the present invention, the cooling is performed after the step (1). Thus, a method in which step (2) is performed immediately is more preferable.
本発明の成形体の製造法における、工程（２）の具体例としては、例えば、射出成形機等によりポリ乳酸樹脂組成物を１１０℃以下の金型内に充填し、成形する方法等が挙げられる。工程（２）における金型温度は、結晶化速度向上及び作業性向上の観点から、１１０℃以下であり、９０℃以下が好ましく、８０℃以下がより好ましい。また３０℃以上が好ましく、４０℃以上がより好ましく、６０℃以上が更に好ましい。かかる観点から、金型温度は３０〜１１０℃が好ましく、４０〜９０℃がより好ましく、６０〜８０℃が更に好ましい。 As a specific example of the step (2) in the method for producing a molded article of the present invention, for example, a method of filling a polylactic acid resin composition in a mold of 110 ° C. or less with an injection molding machine or the like and molding the same. It is done. The mold temperature in the step (2) is 110 ° C. or lower, preferably 90 ° C. or lower, more preferably 80 ° C. or lower, from the viewpoint of improving the crystallization speed and improving workability. Moreover, 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 60 degreeC or more is still more preferable. From this viewpoint, the mold temperature is preferably 30 to 110 ° C, more preferably 40 to 90 ° C, and still more preferably 60 to 80 ° C.
本発明の工程（２）における金型内での保持時間は、相対結晶化度６０％以上を達成し、かつ生産性向上の観点から、５〜６０秒が好ましく、８〜５０秒がより好ましく、１０〜４５秒が更に好ましい。 The holding time in the mold in the step (2) of the present invention is preferably 5 to 60 seconds, more preferably 8 to 50 seconds from the viewpoint of achieving a relative crystallinity of 60% or more and improving productivity. 10 to 45 seconds is more preferable.
実施例１〜１１、比較例１〜３
ポリ乳酸樹脂組成物として、表１に示す本発明品（Ａ〜Ｋ）及び比較品（ａ〜ｃ）を、２軸押出機（（株）池貝製 PCM-45）にて１９０℃で溶融混練し、ストランドカットを行い、ポリ乳酸樹脂組成物のペレットを得た。
得られたペレットは、７０℃減圧下で１日乾燥し、水分量を５００ppm以下とした。
Examples 1-11, Comparative Examples 1-3
As the polylactic acid resin composition, the products of the present invention (AK) and comparative products (ac) shown in Table 1 are melt-kneaded at 190 ° C. with a twin-screw extruder (PCM-45 manufactured by Ikegai Co., Ltd.). Then, strand cutting was performed to obtain pellets of the polylactic acid resin composition.
The obtained pellets were dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.
表１において、＊１〜＊１４は以下の意味を示す。
＊１：ポリ乳酸樹脂（三井化学（株）製、ＬＡＣＥＡ Ｈ−４００）
＊２：イソシアネート系シランカップリング剤（３−イソシアネートプロピルトリエトキシシラン、信越化学（株）製、ＫＢＥ−９００７）／水酸化アルミニウム（巴工業（株）製、B-303、平均粒径３．８μｍ、アルカリ金属系物質の含有量０．２５質量％）（質量比）＝１／９９の割合で処理したイソシアネート系シランカップリング剤処理水酸化アルミニウム
＊３：イソシアネート系シランカップリング剤（３−イソシアネートプロピルトリエトキシシラン、信越化学（株）製、ＫＢＥ−９００７）／水酸化アルミニウム（巴工業（株）製、B-303、平均粒径３．８μｍ、アルカリ金属系物質の含有量０．２５質量％）（質量比）＝１．５／９８．５の割合で処理したイソシアネート系シランカップリング剤処理水酸化アルミニウム
＊４：イソシアネート系シランカップリング剤（３−イソシアネートプロピルトリエトキシシラン、信越化学（株）製、ＫＢＥ−９００７）／水酸化アルミニウム（昭和電工（株）製、H-42M、平均粒径１．１μｍ、アルカリ金属系物質の含有量０．３３質量％）（質量比）＝１／９９の割合で処理したイソシアネート系シランカップリング剤処理水酸化アルミニウム
＊５：イソシアネート系シランカップリング剤（３−イソシアネートプロピルトリエトキシシラン、信越化学（株）製、ＫＢＥ−９００７）／水酸化アルミニウム（昭和電工（株）製、HM-43M、平均粒径０．７５μｍ、アルカリ金属系物質の含有量０．３４質量％）（質量比）＝１／９９の割合で処理したイソシアネート系シランカップリング剤処理水酸化アルミニウム
＊６：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
＊７：１，３，６−ヘキサントリカルボン酸とトリエチレングリコールモノメチルエーテルとのトリエステル
＊８：グリセリンにエチレンオキサイドを６モル付加させたトリアセテート
＊９：アジピン酸ジエステル（大八化学（株）製、DAIFATTY-101）
＊１０：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）
＊１１：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）
＊１２：水酸化アルミニウム（巴工業（株）製、B-303、平均粒径３．８μｍ、アルカリ金属系物質の含有量０．２５質量％）
＊１３：エポキシ系シランカップリング剤（３−グリシドキシプロピルトリメトキシシラン、信越化学（株）製、ＫＢＭ−４０３）／水酸化アルミニウム（巴工業（株）製、B-303、平均粒径３．８μｍ、アルカリ金属系物質の含有量０．２５質量％）（質量比）＝１／９９の割合で処理したエポキシ系シランカップリング剤処理水酸化アルミニウム
＊１４：ビニル系シランカップリング剤（ビニルトリメトキシシラン、信越化学（株）製、ＫＢＭ１００３）／水酸化アルミニウム（巴工業（株）製、B-303、平均粒径３．８μｍ、アルカリ金属系物質の含有量０．２５質量％）（質量比）＝１／９９の割合で処理したビニル系シランカップリング剤処理水酸化アルミニウム。
In Table 1, * 1 to * 14 indicate the following meanings.
* 1: Polylactic acid resin (manufactured by Mitsui Chemicals, LACEA H-400)
* 2: Isocyanate-based silane coupling agent (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) / aluminum hydroxide (manufactured by Sakai Kogyo Co., Ltd., B-303, average particle size 3. 8 μm, content of alkali metal material 0.25 mass%) (mass ratio) = 1/99 isocyanate-treated silane coupling agent treated aluminum hydroxide * 3: isocyanate-based silane coupling agent (3- Isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) / aluminum hydroxide (manufactured by Sakai Kogyo Co., Ltd., B-303, average particle size 3.8 μm, content of alkali metal substance 0.25 (Mass%) (mass ratio) = 1.5 / 98.5 treated with isocyanate-based silane coupling agent treated aluminum hydroxide * 4: Cyanate silane coupling agent (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) / aluminum hydroxide (manufactured by Showa Denko KK, H-42M, average particle size 1.1 μm, alkali Isocyanate-based silane coupling agent-treated aluminum hydroxide treated at a ratio of metal-based substance content of 0.33% by mass) (mass ratio) = 1/99 * 5: isocyanate-based silane coupling agent (3-isocyanatepropyltri Ethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) / aluminum hydroxide (manufactured by Showa Denko KK, HM-43M, average particle size of 0.75 μm, content of alkali metal substance 0.34% by mass) (Mass ratio) = isocyanate-based silane coupling agent treated aluminum hydroxide treated at a ratio of 1/99 * 6: succinic acid and tri Diester with ethylene glycol monomethyl ether * 7: Triester of 1,3,6-hexanetricarboxylic acid and triethylene glycol monomethyl ether * 8: Triacetate obtained by adding 6 mol of ethylene oxide to glycerin * 9: Adipic acid diester ( Daihachi Chemical Co., Ltd., DAIFATTY-101)
* 10: Ethylene bis 12-hydroxystearic acid amide (Nihon Kasei Co., Ltd., SLIPAX H)
* 11: Unsubstituted zinc phenylphosphonic acid salt (manufactured by Nissan Chemical Industries, PPA-Zn)
* 12: Aluminum hydroxide (manufactured by Sakai Kogyo Co., Ltd., B-303, average particle size 3.8 μm, content of alkali metal substance 0.25% by mass)
* 13: Epoxy silane coupling agent (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) / aluminum hydroxide (manufactured by Sakai Kogyo Co., Ltd., B-303, average particle size) Epoxy silane coupling agent treated aluminum hydroxide treated at a ratio of 3.8 μm, alkali metal content 0.25% by mass) (mass ratio) = 1/99 * 14: vinyl silane coupling agent ( Vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM1003) / aluminum hydroxide (manufactured by Sakai Kogyo Co., Ltd., B-303, average particle size 3.8 μm, content of alkali metal substance 0.25% by mass) (Mass ratio) = vinyl silane coupling agent treated aluminum hydroxide treated at a ratio of 1/99.
尚、上記において、金属水和物にシランカップリング剤を表面処理する方法は、有機溶剤（アセトン）２００ｇにシランカップリング剤５ｇを溶解させ、そこに金属水和物５００ｇを入れ、ミキサーで攪拌し、その後有機溶剤を除去し、乾燥する方法で行った。 In the above method, the surface treatment of the silane coupling agent to the metal hydrate is performed by dissolving 5 g of the silane coupling agent in 200 g of an organic solvent (acetone), putting 500 g of the metal hydrate therein, and stirring with a mixer. Then, the organic solvent was removed and the drying was performed.
次に、このようにして得られたペレットを、シリンダー温度を２００℃とした射出成形機（日本製鋼所製 J75E-D）を用いて射出成形し、金型温度８０℃、成形時間１０分でテストピース〔角柱状試験片（１２５mm×１２mm×６mm）〕を成形し、物性を下記の方法で評価した。これらの結果を表２に示す。 Next, the pellets thus obtained were injection-molded using an injection molding machine (J75E-D manufactured by Nippon Steel Works) with a cylinder temperature of 200 ° C., with a mold temperature of 80 ° C. and a molding time of 10 minutes. A test piece [a prismatic test piece (125 mm × 12 mm × 6 mm)] was molded, and the physical properties were evaluated by the following methods. These results are shown in Table 2.
＜曲げ試験＞
角柱状試験片（１２５mm×１２mm×６mm）について、ＪＩＳ Ｋ７２０３に基づいて、テンシロン（オリエンテック製テンシロン万能試験機ＲＴＣ−１２１０Ａ）を用いて曲げ試験を行い、曲げ破断歪みを求めた。クロスヘッド速度は３ｍｍ／ｍｉｎ。
この曲げ破断歪みが高い方が可撓性に優れていることを示す。
<Bending test>
The prismatic test piece (125 mm × 12 mm × 6 mm) was subjected to a bending test using Tensilon (Orientec Tensilon Universal Testing Machine RTC-1210A) based on JIS K7203 to determine the bending fracture strain. Crosshead speed is 3 mm / min.
A higher bending fracture strain indicates superior flexibility.
＜耐衝撃性＞
角柱状試験片（６３mm×１２mm×５mm）について、ＪＩＳ-Ｋ７１１０に基づいて、衝撃試験機（株式会社上島製作所製 863型）を使用して、Izod衝撃強度を測定した。
この強度が高い方が耐衝撃性に優れていることを示す。
<Impact resistance>
The Izod impact strength of a prismatic test piece (63 mm × 12 mm × 5 mm) was measured using an impact tester (type 863 manufactured by Ueshima Seisakusho Co., Ltd.) based on JIS-K7110.
The higher the strength, the better the impact resistance.
＜熱変形温度＞
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1.81MPaにおいて0.25mm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。
<Heat deformation temperature>
For a prismatic test piece (125 mm x 12 mm x 6 mm), the temperature at which it deflects 0.25 mm at a load of 1.81 MPa using a thermal deformation temperature measuring machine (B-32 manufactured by Toyo Seiki Seisakusho) based on JIS-K7191. It was measured. The higher this temperature, the better the heat resistance.
表２の結果から、イソシアネート系シランカップリング剤で処理した金属水和物を含有した本発明のポリ乳酸樹脂組成物（実施例１〜１１）は、曲げ破断歪み、耐衝撃性、および熱変形温度を向上させることが可能であった。 From the results of Table 2, the polylactic acid resin compositions (Examples 1 to 11) of the present invention containing metal hydrates treated with an isocyanate-based silane coupling agent were found to have bending fracture strain, impact resistance, and thermal deformation. It was possible to improve the temperature.
一方、シランカップリング剤による処理が施されていない、もしくはイソシアネート系以外のシランカップリング剤で処理した金属水和物を含有したポリ乳酸樹脂組成物（比較例１〜３）は、曲げ破断歪み、耐衝撃性、および熱変形温度を向上させることができなかった。 On the other hand, the polylactic acid resin composition (Comparative Examples 1 to 3) containing a metal hydrate not treated with a silane coupling agent or treated with a silane coupling agent other than an isocyanate-based compound has a bending fracture strain. , Impact resistance, and heat distortion temperature could not be improved.
イソシアネート系シランカップリング剤で処理した金属水和物を含有し、更に可塑剤、結晶核剤を併用した本発明のポリ乳酸樹脂組成物（実施例７〜１１）は、さらに曲げ破断歪み、耐衝撃性、および熱変形温度を向上させることができた。 The polylactic acid resin compositions (Examples 7 to 11) of the present invention containing a metal hydrate treated with an isocyanate-based silane coupling agent and further using a plasticizer and a crystal nucleating agent were further subjected to bending strain and resistance. The impact property and heat distortion temperature could be improved.
以上の結果から、ポリ乳酸樹脂と金属水和物、もしくはイソシアネート系以外のシランカップリング剤で処理した金属水和物だけの組成物では、ポリ乳酸樹脂と金属水和物の界面が弱く、界面強化の効果を十分に発現できなかったが、イソシアネート系シランカップリング剤で処理した金属水和物を用いることでポリ乳酸樹脂と金属水和物の界面が強化され、物性が向上したものと考えられる。 From the above results, in the composition only of polylactic acid resin and metal hydrate, or metal hydrate treated with a silane coupling agent other than isocyanate, the interface between polylactic acid resin and metal hydrate is weak. Although the effect of strengthening could not be fully expressed, it was thought that the interface between polylactic acid resin and metal hydrate was strengthened by using metal hydrate treated with isocyanate-based silane coupling agent, and physical properties were improved. It is done.
Claims (6)
イソシアネート系シランカップリング剤によって表面処理された金属水和物が、イソシアネート系シランカップリング剤と金属水和物とを、イソシアネート系シランカップリング剤／金属水和物（質量比）＝０．１／９９．９〜５／９５の割合で処理したものであり、
ポリ乳酸樹脂と、イソシアネート系シランカップリング剤によって表面処理された金属水和物との質量比が、ポリ乳酸樹脂／イソシアネート系シランカップリング剤によって表面処理された金属水和物＝３０／７０〜７０／３０であり、
イソシアネート系シランカップリング剤が、３−イソシアネートプロピルトリメトキシシラン及び３−イソシアネートプロピルトリエトキシシランから選ばれる少なくとも１種である、ポリ乳酸樹脂組成物。 A polylactic acid resin composition comprising a polylactic acid resin and a metal hydrate surface-treated with an isocyanate-based silane coupling agent ,
The metal hydrate surface-treated with the isocyanate-based silane coupling agent is converted into an isocyanate-based silane coupling agent and a metal hydrate by an isocyanate-based silane coupling agent / metal hydrate (mass ratio) = 0.1. /99.9 to 5/95 ratio,
Mass ratio of polylactic acid resin and metal hydrate surface-treated with isocyanate-based silane coupling agent is polylactic acid resin / metal hydrate surface-treated with isocyanate-based silane coupling agent = 30 / 70- 70/30,
A polylactic acid resin composition, wherein the isocyanate-based silane coupling agent is at least one selected from 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane .
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