JP4967149B2 - Polylactic acid resin composition - Google Patents
Polylactic acid resin composition Download PDFInfo
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- JP4967149B2 JP4967149B2 JP2006227830A JP2006227830A JP4967149B2 JP 4967149 B2 JP4967149 B2 JP 4967149B2 JP 2006227830 A JP2006227830 A JP 2006227830A JP 2006227830 A JP2006227830 A JP 2006227830A JP 4967149 B2 JP4967149 B2 JP 4967149B2
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- polylactic acid
- resin composition
- acid resin
- inositol
- nucleating agent
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 37
- 239000004626 polylactic acid Substances 0.000 title claims description 37
- 239000011342 resin composition Substances 0.000 title claims description 25
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 19
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 19
- 229960000367 inositol Drugs 0.000 claims description 18
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002667 nucleating agent Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- -1 carbodiimide compound Chemical class 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001432 poly(L-lactide) Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004001 inositols Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CDAISMWEOUEBRE-CDRYSYESSA-N scyllo-inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O CDAISMWEOUEBRE-CDRYSYESSA-N 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
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- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリ乳酸樹脂組成物に関する。 The present invention relates to a polylactic acid resin composition.
ポリ乳酸は、生分解性を有し、環境に優しい樹脂として昨今いろいろな成形品への用途が開発されている。
しかし、ポリ乳酸は、結晶性の高分子であるものの、結晶化が遅いという欠点を有しているために、成形加工を行う際には、造核剤を添加しなければならない。
Polylactic acid has biodegradability and has been developed as an environmentally friendly resin for various molded products.
However, although polylactic acid is a crystalline polymer, it has a drawback of slow crystallization, and therefore, a nucleating agent must be added when performing molding.
造核剤としては、脂肪族カルボン酸アミドを用いる方法（特許文献１）がすでに提案されている。 As a nucleating agent, a method using an aliphatic carboxylic acid amide (Patent Document 1) has already been proposed.
ところで、上記のような従来の造核剤を配合したポリ乳酸樹脂組成物を得ようとした場合、混練の際の樹脂の劣化を抑止するために、造核剤だけでなく、カルボジイミド化合物等の劣化防止剤をさらに加える必要があった。
しかし、ポリ乳酸だけでなく樹脂材料へ添加する添加剤の種類が多くなると、それだけ管理が煩雑になるとともに、材料コストがかかるという問題があり、さらに、添加剤同士が予期せぬ副作用を招く虞もある。
By the way, when trying to obtain a polylactic acid resin composition containing the conventional nucleating agent as described above, not only the nucleating agent but also a carbodiimide compound or the like in order to suppress the deterioration of the resin during kneading. It was necessary to add further deterioration inhibitors.
However, if the types of additives to be added to the resin material as well as polylactic acid are increased, there is a problem that the management becomes complicated and the material cost is increased, and the additives may cause unexpected side effects. There is also.
本発明は、上記事情に鑑みて、結晶化速度が速く、しかも、造核剤とともに劣化防止剤を添加する必要がないポリ乳酸樹脂組成物を提供することを目的としている。 In view of the above circumstances, an object of the present invention is to provide a polylactic acid resin composition that has a high crystallization rate and does not require the addition of a deterioration inhibitor together with a nucleating agent.
上記目的を達成するために、本発明にかかるポリ乳酸樹脂組成物は、ポリ乳酸と、添加剤とを含むポリ乳酸樹脂組成物であって、前記添加剤として、少なくとも下式（１）で示されポリ乳酸の造核剤として機能するイノシトールを含むことを特徴としている。
本発明のポリ乳酸樹脂組成物において、イノシトールとしては、myo-、epi-、allo-、myo-、muco-、chiro-、scyllo-の各イノシトールを用いることができる。 In the polylactic acid resin composition of the present invention, as inositol, myo-, epi-, allo-, myo-, muco-, chiro-, scyllo- inositol can be used.
イノシトールの添加量は、ポリ乳酸に対して0.01〜10重量％が好ましい。
すなわち、イノシトールの添加量がポリ乳酸の0.01重量％未満であると、その効果があまり期待できず、イノシトールまたはイノシトール誘導体の添加量がポリ乳酸の10重量％を超えると、ブリードアウトの現象が顕著になり、脆い成型品となり不具合となる虞がある。
The amount of inositol added is preferably 0.01 to 10% by weight with respect to polylactic acid.
That is, when the amount of inositol added is less than 0.01% by weight of polylactic acid, the effect cannot be expected so much, and when the amount of inositol or inositol derivative added exceeds 10% by weight of polylactic acid, the phenomenon of bleed out is remarkable. It becomes a fragile molded product and may cause a problem.
本発明において、ポリ乳酸とは、Ｌ−乳酸及び／またはＤ−乳酸を主たる構成成分とするポリマーである。 In the present invention, polylactic acid is a polymer mainly composed of L-lactic acid and / or D-lactic acid.
本発明のポリ乳酸樹脂組成物には、イノシトール以外の添加剤を必要に応じて添加しても構わない。
このような添加剤としては、特に限定されないが、たとえば、アロイ化樹脂、増粘剤、可塑剤、結晶核剤、難燃剤、充填剤、安定剤、滑剤等が挙げられる。
You may add additives other than inositol to the polylactic acid resin composition of this invention as needed.
Examples of such additives include, but are not limited to, alloyed resins, thickeners, plasticizers, crystal nucleating agents, flame retardants, fillers, stabilizers, lubricants, and the like.
上記アロイ化樹脂としては、特に限定されないが、たとえば、ポリエチレン、ポリプロピレン、ポリスチレン、塩化ビニル、セルロース、フェノール樹脂、ポリエチレングリコールテレフタレート、ポリブチレングリコールテレフタレート、ポリエチレングリコールナフタレート、ポリブチレングリコールナフタレート、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリル酸エステル、ポリ酢酸ビニル、ポリオキシメチレン、ナイロン-6、ナイロン-6.6、ナイロン-6.12、ナイロン-4,6、天然ゴム、ポリブタジエン、ＡＢＳ樹脂、等が挙げられる。また、2つ以上のアロイ化樹脂を添加することもある。 The alloyed resin is not particularly limited. For example, polyethylene, polypropylene, polystyrene, vinyl chloride, cellulose, phenol resin, polyethylene glycol terephthalate, polybutylene glycol terephthalate, polyethylene glycol naphthalate, polybutylene glycol naphthalate, polycarbonate, Polyacrylic acid ester, polymethacrylic acid ester, polyvinyl acetate, polyoxymethylene, nylon-6, nylon-6.6, nylon-6.12, nylon-4,6, natural rubber, polybutadiene, ABS resin, and the like. Two or more alloyed resins may be added.
上記増粘剤としては、特に限定されないが、たとえば、酸化マグネシウム、水酸化マグネシウム、酸化カルシウム、酸化カリウム、 水酸化カリウム、酸化亜鉛等が挙げられる。
上記可塑剤としては、特に限定されないが、たとえば、フタル酸エステルなどの多価カルボン酸系可塑剤、ポリビニルアルコール等のポリアルキレングリコール系可塑剤、ポリエステル系可塑剤、グリセリン系可塑剤、エポキシ系可塑剤、等が挙げられる。
Although it does not specifically limit as said thickener, For example, magnesium oxide, magnesium hydroxide, calcium oxide, potassium oxide, potassium hydroxide, zinc oxide etc. are mentioned.
The plasticizer is not particularly limited. For example, a polycarboxylic acid plasticizer such as phthalate ester, a polyalkylene glycol plasticizer such as polyvinyl alcohol, a polyester plasticizer, a glycerin plasticizer, and an epoxy plasticizer. Agents and the like.
上記結晶核剤としては、特に限定されないが、たとえば、タルクなどの無機核剤、安息香酸ナトリウムなどの有機カルボン酸金属塩、リン酸エステル金属塩、ベンジリデンソルビトール、カルボン酸アミドなどの有機核剤、等が挙げられる。
上記難燃剤としては、特に限定されないが、たとえば、臭素系難燃剤、塩素系難燃剤、リン系難燃剤、窒素化合物系難燃剤、シリコーン系難燃剤、金属水酸化物系難燃剤、等が挙げられる。
The crystal nucleating agent is not particularly limited. For example, an inorganic nucleating agent such as talc, an organic carboxylic acid metal salt such as sodium benzoate, a phosphoric acid ester metal salt, benzylidene sorbitol, an organic nucleating agent such as carboxylic acid amide, Etc.
The flame retardant is not particularly limited, and examples thereof include brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, metal hydroxide flame retardants, and the like. It is done.
上記充填剤としては、特に限定されないが、たとえば、炭酸カルシウム、マイカ、クレー、チタン酸カリウム、珪酸カルシウム、酸化亜鉛、酸化チタン、水酸化アルミニウム、ホウ酸アルミニウム、モンモリロナイト、ガラス繊維、炭素繊維、またケナフ繊維などの植物系繊維、等が挙げられる。 The filler is not particularly limited. For example, calcium carbonate, mica, clay, potassium titanate, calcium silicate, zinc oxide, titanium oxide, aluminum hydroxide, aluminum borate, montmorillonite, glass fiber, carbon fiber, Plant fiber such as kenaf fiber, etc. can be mentioned.
上記安定剤としては、特に限定されないが、たとえば、ヒンダードフェノール系、ホスファイト系、チオエーテル系、ビタミン系、ホスフェート系、ベンゾフェノン系、ベンゾトリアゾール系、芳香族ベンゾエート系、多価アミン系、シュウ酸アニリド系、シアノアクリレート系、ヒンダードアミン系、トリアジン系、ヒドラジン誘導体系化合物、等が挙げられる。
上記滑剤としては、特に限定されないが、たとえば、ステリン酸等の脂肪酸、ステアリン酸ナトリウム等の脂肪酸金属塩、脂肪酸エステル、パラフィン、低分子量ポリオレフィン、等が挙げられる。
The stabilizer is not particularly limited. For example, hindered phenols, phosphites, thioethers, vitamins, phosphates, benzophenones, benzotriazoles, aromatic benzoates, polyamines, oxalic acid Examples include anilide, cyanoacrylate, hindered amine, triazine, and hydrazine derivative compounds.
The lubricant is not particularly limited, and examples thereof include fatty acids such as steric acid, fatty acid metal salts such as sodium stearate, fatty acid esters, paraffin, and low molecular weight polyolefin.
本発明にかかるポリ乳酸樹脂組成物は、以上のように、添加剤としてイノシトールを用いるようにしたので、イノシトールがポリ乳酸の造核剤として機能し、結晶化を促進させると共に、イノシトールが劣化防止剤としても働き、別に劣化防止剤を添加することが不要となる。したがって、材料管理や製造管理が簡略化できるとともに、材料コストの低減を図ることができる。しかも、添加剤の種類が少なくなり、副作用の問題も低減できる。 As described above, in the polylactic acid resin composition according to the present invention, inositol is used as an additive, so that inositol functions as a nucleating agent for polylactic acid, promotes crystallization, and prevents inositol from deteriorating. It also works as an agent, and it becomes unnecessary to add a separate deterioration preventing agent. Therefore, material management and manufacturing management can be simplified, and material costs can be reduced. In addition, the types of additives are reduced, and the problem of side effects can be reduced.
以下に、本発明を、その実施例を参照しつつ参照しつつ詳しく説明する。なお、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples thereof. The present invention is not limited to the following examples.
（実施例１）
ポリ-Ｌ-乳酸（三井化学社製商品名Lacea H-100）に対し、１０重量％のmyo-イノシトール（和光純薬社製）をドライブレンドするとともに、二軸混練押出機を用いて混練し、ポリ乳酸樹脂組成物を得た。
Example 1
10% by weight of myo-inositol (manufactured by Wako Pure Chemical Industries, Ltd.) is dry blended with poly-L-lactic acid (trade name Lacea H-100, manufactured by Mitsui Chemicals) and kneaded using a twin-screw kneading extruder. A polylactic acid resin composition was obtained.
（実施例２）
myo-イノシトールの配合量を１重量％とした以外は、実施例１と同様にしてポリ乳酸樹脂組成物を得た。
(Example 2)
A polylactic acid resin composition was obtained in the same manner as in Example 1 except that the amount of myo-inositol was 1% by weight.
（実施例３）
myo-イノシトールの配合量を０．１重量％とした以外は、実施例１と同様にしてポリ乳酸樹脂組成物を得た。
(Example 3)
A polylactic acid resin composition was obtained in the same manner as in Example 1 except that the amount of myo-inositol was changed to 0.1% by weight.
（実施例４）
myo-イノシトールの配合量を０．０１重量％とした以外は、実施例１と同様にしてポリ乳酸樹脂組成物を得た。
Example 4
A polylactic acid resin composition was obtained in the same manner as in Example 1 except that the amount of myo-inositol was 0.01% by weight.
上記実施例１〜４で得られたポリ乳酸樹脂組成物と、比較例１としてのポリ-Ｌ-乳酸（三井化学社製商品名Lacea H-100）および比較例２としての二軸混練押出機を用いて混練したポリ-Ｌ-乳酸（三井化学社製商品名Lacea H-100）のそれぞれについて
結晶化ピーク温度、多分散度、数平均分子量を測定し、その結果を表１に示した。
Polylactic acid resin compositions obtained in Examples 1 to 4 above, poly-L-lactic acid as Comparative Example 1 (trade name Racea H-100 manufactured by Mitsui Chemicals), and twin-screw kneading extruder as Comparative Example 2 The crystallization peak temperature, polydispersity, and number average molecular weight of each of poly-L-lactic acid (trade name Lacea H-100, manufactured by Mitsui Chemicals, Inc.) that were kneaded using the above were measured, and the results are shown in Table 1.
なお、結晶化ピーク温度は、得られたポリ乳酸樹脂組成物の結晶化温度を熱示差走査測定装置で測定した。数平均分子量は、得られたポリ乳酸樹脂組成物の１％クロロホルム溶液を調整し、その分子量、多分散度をＧＰＣ（クロロホルム溶媒、ポリスチレン標準）で測定した。 In addition, the crystallization peak temperature measured the crystallization temperature of the obtained polylactic acid resin composition with the thermal differential scanning measuring apparatus. For the number average molecular weight, a 1% chloroform solution of the obtained polylactic acid resin composition was prepared, and the molecular weight and polydispersity thereof were measured by GPC (chloroform solvent, polystyrene standard).
上記表１から、イノシトールを添加することにより分子量の低下(樹脂の劣化)を防ぐことができるとともに、結晶化ピークが観測され、結晶化促進効果が発現することがよくわかる。 From Table 1 above, it can be seen that the addition of inositol can prevent a decrease in molecular weight (deterioration of the resin), a crystallization peak is observed, and a crystallization promoting effect is exhibited.
また、実施例１で得られたポリ乳酸樹脂組成物を１２０℃、１時間で結晶化させた後、透過型電子顕微鏡写真を、図１に示した。
図１で示すように、イノシトールを中心とした球晶成長が観測され、イノシトールが造核剤としての有効に働いていることが分かる。
Further, after the polylactic acid resin composition obtained in Example 1 was crystallized at 120 ° C. for 1 hour, a transmission electron micrograph was shown in FIG.
As shown in FIG. 1, spherulite growth centering on inositol is observed, indicating that inositol works effectively as a nucleating agent.
また、実施例２、比較例１，２で得られたポリ乳酸樹脂組成物について、シャルピー衝撃強度、曲げ弾性率、引張弾性率を測定し、その結果を表２に示した。 The polylactic acid resin compositions obtained in Example 2 and Comparative Examples 1 and 2 were measured for Charpy impact strength, bending elastic modulus, and tensile elastic modulus, and the results are shown in Table 2.
なお、シャルピー衝撃強度の測定は、東洋精機製作所製シャルピー衝撃試験機B-121203601を用い、ハンマー４Ｊ、ノッチ無しの条件で行った。 The Charpy impact strength was measured using a Charpy impact tester B-121203601 manufactured by Toyo Seiki Seisakusho under the conditions of hammer 4J and no notch.
曲げ弾性率の測定は、インストロン社製材料試験機5569を用い、3点曲げ、支点間距離64mm、試験速度5mm/min、曲げ試験片（2個,80mmx10mmx4mm）の条件で行った。 The flexural modulus was measured using an Instron material testing machine 5569 under the conditions of three-point bending, a fulcrum distance of 64 mm, a test speed of 5 mm / min, and a bending test piece (two pieces, 80 mm × 10 mm × 4 mm).
引張弾性率の測定は、インストロン社製材料試験機5569を用い、チャック間距離115mm、試験速度50mm/min、ダンベル型引張試験片(1個,160mmx10mmx4mm)の条件で行った。 The tensile elastic modulus was measured using a material testing machine 5569 manufactured by Instron under the conditions of a distance between chucks of 115 mm, a test speed of 50 mm / min, and a dumbbell-type tensile test piece (one piece, 160 mm × 10 mm × 4 mm).
また、シャルピー衝撃強度、曲げ弾性率、引張弾性率の測定に用いた試験片は、各ポリ乳酸樹脂組成物を射出成形機（日精樹脂工業製、型締力35kN、スクリュー径30mm）を用いて射出成形することによって得た。 The test pieces used for measurement of Charpy impact strength, flexural modulus, and tensile modulus were obtained by using each polylactic acid resin composition with an injection molding machine (manufactured by Nissei Plastic Industries, mold clamping force 35 kN, screw diameter 30 mm). Obtained by injection molding.
上記表２から、比較例１と比較例２とを比較することにより、ポリ乳酸樹脂組成物は押出成形による熱履歴が加わることにより樹脂の劣化が起こり、力学的な物性が低下することが分かる。 From Table 2 above, by comparing Comparative Example 1 and Comparative Example 2, it can be seen that the polylactic acid resin composition is deteriorated in resin due to the addition of the heat history by extrusion molding, and the mechanical properties are lowered. .
一方、イノシトールを添加することにより、力学的物性の低下が抑制されるだけではなく、イノシトールが核剤として働き物性が向上することが分かる。 On the other hand, it can be seen that the addition of inositol not only suppresses the decrease in mechanical properties, but also acts as a nucleating agent to improve the physical properties.
本発明にかかるポリ乳酸樹脂組成物は、たとえば、例えば繊維、フィルム、シート、チューブ、肉厚成型品、食器、電化製品の筐体等の種々の成形物を得るのに有用である。 The polylactic acid resin composition according to the present invention is useful for obtaining various molded articles such as, for example, fibers, films, sheets, tubes, thick molded articles, tableware, and housings for electrical appliances.
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