JP4260521B2 - Glycolic acid polymer composition - Google Patents
Glycolic acid polymer composition Download PDFInfo
- Publication number
- JP4260521B2 JP4260521B2 JP2003098312A JP2003098312A JP4260521B2 JP 4260521 B2 JP4260521 B2 JP 4260521B2 JP 2003098312 A JP2003098312 A JP 2003098312A JP 2003098312 A JP2003098312 A JP 2003098312A JP 4260521 B2 JP4260521 B2 JP 4260521B2
- Authority
- JP
- Japan
- Prior art keywords
- glycolic acid
- polymer
- acid polymer
- heat
- boron nitride
- 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
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims description 244
- 229920000642 polymer Polymers 0.000 title claims description 159
- 239000000203 mixture Substances 0.000 title claims description 61
- 239000002245 particle Substances 0.000 claims description 56
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 47
- 229910052582 BN Inorganic materials 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 45
- 238000002844 melting Methods 0.000 claims description 36
- 230000008018 melting Effects 0.000 claims description 36
- 238000002425 crystallisation Methods 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 238000012360 testing method Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 26
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000004927 fusion Effects 0.000 claims description 15
- 239000000047 product Substances 0.000 description 57
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
- -1 aliphatic carboxylate Chemical class 0.000 description 24
- 239000000178 monomer Substances 0.000 description 22
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 17
- 239000004014 plasticizer Substances 0.000 description 15
- 239000004310 lactic acid Substances 0.000 description 14
- 235000014655 lactic acid Nutrition 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 9
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- 239000002994 raw material Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 235000014113 dietary fatty acids Nutrition 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
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- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000012773 agricultural material Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 239000002734 clay mineral Substances 0.000 description 2
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- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
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- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
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- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 2
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- XHSVWKJCURCWFU-UHFFFAOYSA-N 19-[3-(19-amino-19-oxononadecyl)phenyl]nonadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCCCCCCCCC(N)=O)=C1 XHSVWKJCURCWFU-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
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- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
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- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、グリコール酸系重合体組成物、及び該組成物を主体とする成形体に関する。更に詳しくは、成形性に優れるグリコール酸系重合体を主体とした組成物、及び該組成物を主体とする耐熱性や透明性に優れる成形体に関するものである。
【０００２】
【従来の技術】
従来から、押出成形や射出成形などにより製造されるプラスチック製品は、加工時や使用時の利便性ゆえに包装用資材、農業用資材、土木建築用資材、機械装置部品など様々な分野で利用されている。しかし、現在の大量消費社会では、その使用量は年々増加の一途をたどっており、同時にプラスチック廃棄物問題は年々深刻化している。プラスチック廃棄物は、多くは焼却や埋め立てにより処分されているが、近年は環境保全の観点から、回収して再びプラスチック製品の原料として用いるマテリアルリサイクルが提唱されている。
【０００３】
食品や医薬品などの包装は、その内容物の輸送や分配の作業を容易にするものであると同時に、品質維持が特に重要な役割である。従って、包装用資材には、品質維持性能の高さが要求される。具体的には、長期保存時に内容物を保護する性能として、衝撃や突き刺しなどの外力に対する機械的強度、内容物の外気酸素による酸化劣化や水分蒸発による乾燥劣化に対するガスバリア性、包装用資材自体が変性や変形しない耐油性や耐熱性などの安定性が挙げられる。また、内容物の認識し易さや、購入者の購買意欲を促すディスプレイ効果によって商品価値を高める為に、包装用資材の要求特性としては透明性も重要な因子である。
【０００４】
しかし、プラスチック製品の包装用資材としての要求性能は多岐にわたり、単一種類のプラスチックのみではこれら全ての要求を満たすことが出来ず、例えば複合化や多層化など、一般に数種類のプラスチックを組み合わせて用いられている。この様な包装材は、各種樹脂への分別が非常に困難であり、コスト面などを考慮するとマテリアルリサイクルは不可能である。
このような状況下、土壌、水中等の自然界で分解する生分解性の樹脂が注目され、研究されている。
【０００５】
下記特許文献１には、土壌や海水中の湿った環境下において分解性を有する脂肪族ポリエステルに脂肪族カルボン酸アミドなどの特定の透明化結晶核剤を添加することにより、透明性／耐熱性／分解性を併有する成形体を得ることが出来ると記載されている。
しかしながら、該特許文献１に記載の脂肪族ポリエステル成形体は、重合体を構成する繰返し単位が乳酸由来である乳酸系重合体からなる組成物を主体とする成形体であり、得られた成形体の耐熱性は不十分であった。なお、該公報には、乳酸系重合体よりも高融点であるために耐熱性がより優れる成形体が得られると予想されるグリコール酸系重合体が脂肪族ポリエステルの一例として記載されているが、本発明者がグリコール酸系重合体に該公報記載の透明化結晶核剤である脂肪族カルボン酸アミドや脂肪族カルボン酸塩を添加したところ得られた成形体の透明性は不十分であった（後述比較例）。
【０００６】
また、特許文献２には、平均粒径と添加量を規定したタルク及び／又は窒化ホウ素からなる無機粒子を含有する乳酸系重合体の組成物が開示され、生分解性があり成形性に優れるものであるとの記載がある。
しかしながら、該特許文献２に記載の組成物は、乳酸系重合体を主体とするために得られた成形体の耐熱性は不十分であった。また、結晶化速度の向上効果から該組成物中含まれる窒化ホウ素の量は０．５重量％以上が必要と記載されており、好ましくは１重量％以上である。なお、実施例では２重量％含有させている。このような組成物を用いて得られる延伸成形体は厚み２０μｍ以下の薄い延伸成形体であっても透明性の点で問題があった。
【０００７】
また、特許文献３には、融点が１５０℃以上、融解熱が２０Ｊ／ｇ以上、無配向結晶化物の密度が１．５０ｇ／ｃｍ３以上であるグリコール酸系重合体を含有する熱可塑性樹脂材料を融点〜２５５℃の温度範囲で溶融押出しすることにより、強靭性やガスバリア性に優れた土中崩壊性を示すシート状成形体が得られると記載されている。
しかしながら、該特許文献３に記載のシート状成形体は、非晶シートを試験片として加熱速度１０℃／分で示差走査熱量測定した場合の融解熱が２０Ｊ／ｇ以上、無配向結晶化物の密度が１．５０ｇ／ｃｍ３以上である結晶性が非常に高いグリコール酸系重合体を含有する熱可塑性樹脂材料から形成されることから、溶融押出し後に急冷し熱固定していない非晶状態のシート状成形体では、耐熱性が劣り長期経時で透明性が悪化する問題点があった。或いは、熱固定したシート状成形体では、透明性が劣り脆いという問題点があった。
【０００８】
更に、該特許文献３に規定されている溶融押出時の加熱温度は２５５℃までの高い温度範囲であるが、これは用いるグリコール酸系重合体の高度な結晶を十分融解させる為に融点よりもかなり高い温度に設定しなければならないからである。グリコール酸系重合体は、熱重量分析による重量減少を測定すると２４０℃から熱分解が始まる（Ｋ．Ｃｈｕｊｏ，ｅｔ ａｌ．，Ｄｉｅ Ｍａｋｒｏｍｏｌｅｋｕｌａｒｅ Ｃｈｅｍｉｅ，Ｎｏ．１００，Ｐ．２６７（１９６７））にも係わらず、該公報に規定される２５５℃までの高い温度範囲の加熱温度で溶融押出する場合には、熱劣化して溶融粘度が著しく低下し溶融押出が困難になったり、褐色に着色して得られるシート状成形体が不衛生な印象を与えるようになるという問題点があった。
【０００９】
【特許文献１】
特開平９−２７８９９１号公報
【特許文献２】
特開平８−３４３２号公報
【特許文献３】
特開平１０−６０１３７号公報
【００１０】
【発明が解決しようとする課題】
本発明の課題は、生分解性を有し、且つ溶融押出や射出成形などの成形性に優れるグリコール酸系重合体を主体とした組成物を提供すること、及び耐熱性や透明性が優れる該グリコール酸系重合体からなる組成物を主体とする成形体を提供することにある。
【００１１】
【課題を解決するための手段】
本発明者は、上記課題を達成する為に鋭意検討した結果、生分解性樹脂のなかでも融点が比較的高いグリコール酸系重合体に特定量の窒化ホウ素系粒子を含有せしめることによって、耐熱性や透明性が優れた生分解性を有する成形体を製造することができることを見出し、本発明に到達した。
即ち、本発明は、
［１］ グリコール酸系重合体と窒化ホウ素系粒子からなる組成物であって、グリコール酸系重合体１００重量部に対し、窒化ホウ素系粒子の含有量が０．００１重量部以上０．３重量部未満であることを特徴とするグリコール酸系重合体組成物、
［２］ グリコール酸系重合体が、該重合体の非晶シートを１５０℃で１００分間熱処理した試験片を用い、加熱速度および冷却速度が１０℃／分で測定した示差走査熱量測定（ＪＩＳ Ｋ７１２１、及びＫ７１２２準拠）において１回目の昇温過程での融点Ｔｍ（℃）、１回目の冷却過程での結晶化熱ΔＨｃ（Ｊ／ｇ）、２回目の昇温過程での融解熱ΔＨｍ（Ｊ／ｇ）が下式（１）〜（３）を満たすグリコール酸系共重合体であることを特徴とする［１］記載のグリコール酸系重合体組成物、
１７５≦Ｔｍ≦２０５ （１）
ΔＨｃ＝０ （２）
０≦ΔＨｍ＜２０ （３）
［３］ グリコール酸系重合体が、対数粘度数０．１５ｍ３／ｋｇ以上であることを特徴とする［１］又は［２］記載のグリコール酸系重合体組成物、
［４］ 窒化ホウ素系粒子の平均粒径が０．０３μｍ以上５μｍ以下であることを特徴とする［１］〜［３］のいずれかに記載のグリコール酸系重合体組成物、
［５］ グリコール酸系重合体と窒化ホウ素系粒子からなる組成物を主体とする成形体であって、グリコール酸系重合体１００重量部に対し、窒化ホウ素系粒子の含有量が０．００１重量部以上０．３重量部未満であることを特徴とするグリコール酸系重合体の成形体、
［６］ グリコール酸系重合体が、該重合体の非晶シートを１５０℃で１００分間熱処理した試験片を用い、加熱速度および冷却速度が１０℃／分で測定した示差走査熱量測定（ＪＩＳ Ｋ７１２１、及びＫ７１２２準拠）において１回目の昇温過程での融点Ｔｍ（℃）、１回目の冷却過程での結晶化熱ΔＨｃ（Ｊ／ｇ）、２回目の昇温過程での融解熱ΔＨｍ（Ｊ／ｇ）が下式（１）〜（３）を満たすグリコール酸系共重合体であることを特徴とする［５］記載のグリコール酸系重合体の成形体、
１７５≦Ｔｍ≦２０５ （１）
ΔＨｃ＝０ （２）
０≦ΔＨｍ＜２０ （３）
［７］ グリコール酸系重合体の対数粘度数が０．１５ｍ３／ｋｇ以上であることを特徴とする［６］又は［７］記載のグリコール酸系重合体の成形体、［８］ 窒化ホウ素系粒子の平均粒径が０．０３μｍ以上５μｍ以下であることを特徴とする［５］〜［７］のいずれかに記載のグリコール酸系重合体の成形体、
である。
【００１２】
【発明の実施の形態】
以下、本発明のグリコール酸系重合体組成物及び成形体について詳細に説明する。本発明のグリコール酸系重合体組成物及び該組成物を主体とする成形体は、生分解性樹脂のなかでも融点が比較的高いグリコール酸系重合体に、窒化ホウ素系粒子を特定量含有せしめることに特徴がある。
従来の技術の欄に記載の特許文献１や、特許文献２において特に好ましい原料として記載されている乳酸系重合体は、該重合体を構成する繰返し単位が不斉炭素を有する乳酸由来であり、光学純度によって該重合体の融点が著しく変化することが一般に知られているが、光学純度１００％のホモポリマーの場合でも融点は１７５℃程度である（辻秀人・筏義人、「ポリ乳酸−医療・製剤・環境のために−」、第１版、高分子刊行会、１９９７年９月２０日、ｐ．３９、図２−２７を参照）。これに対し、グリコール酸系重合体は、ホモポリマーの融点は２２５℃程度である（同書、ｐ．４５参照）ので、耐熱性がより優れる成形体を得ることができる。
【００１３】
本発明の組成物の原料として用いるグリコール酸系重合体とは、主たる繰返し単位がグリコール酸由来の繰返し単位である重合体をいい、単量体にグリコール酸の環状二量体であるグリコリド（１，４−ジオキサ−２，５−ジオン）を用いての開環重合、又はグリコール酸を用いての直接脱水重縮合、例えばグリコール酸メチルなどのグリコール酸エステル類を用いて脱アルコールしながらの重縮合などにより得られる重合体であって、これら単量体のホモポリマー、或いはこれら単量体を主たる単量体とするコポリマーである。該重合体の製造方法は、従来公知の一般的な方法で行われ、例えば主たる単量体にグリコール酸のグリコリドを用い開環重合してグリコール酸系重合体を得るには、Ｇｉｌｄｉｎｇらの方法（Ｐｏｌｙｍｅｒ，ｖｏｌ．２０，Ｄｅｃｅｍｂｅｒ（１９７９））などが挙げられるが、これに限定されるものではない。
【００１４】
共重合で用いられる、上記の主たる単量体であるグリコール酸、グリコリド、及びグリコール酸エステル類と共重合しうる単量体としては、例えば、乳酸、２−ヒドロキシイソ酪酸、２−ヒドロキシ−２，２−ジアルキル酢酸、３−ヒドロキシ酪酸、３−ヒドロキシ吉草酸、３−ヒドロキシヘキサン酸、４−ヒドロキシブタン酸、その他公知の脂肪族ヒドロキシカルボン酸類、これら脂肪族ヒドロキシカルボン酸類のエステル誘導体、これら脂肪族ヒドロキシカルボン酸類の同種、又は異種の環状二量体など、およびβ−ブチロラクトン、β−プロピオラクトン、ピバロラクトン、γ−ブチロラクトン、δ−バレロラクトン、β−メチル−δ−バレロラクトン、ε−カプロラクトンなどのラクトン類等が挙げられ、これらから少なくとも一種が選ばれる。また、これらの他に、等モル量の多価アルコール類と多価カルボン酸類を組み合わせて、上記主たる単量体と共重合させたものでもよく、該多価アルコール類としては、例えば、エチレングリコール、プロピレングリコール、１，２−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、２，２−ジメチル−１，３−プロパンジオール、１，６−ヘキサンジオール、１，３−シクロヘキサノール、１，４−シクロヘキサノール、１，３−シクロヘキサンジメタノール、１，４−シクロヘキサンジメタノールなどの脂肪族ジオール類、或いはこれら脂肪族ジオール類が複数結合した、例えばジエチレングリコール、トリエチレングリコール、テトラエチレングリコールなどが挙げられる。該多価カルボン酸類としては、マロン酸、コハク酸、グルタル酸、２，２−ジメチルグルタル酸、アジピン酸、ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、１，３−シクロペンタンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、ジグリコール酸などの脂肪族ジカルボン酸類、テレフタル酸、イソフタル酸、１，４−ナフタリンジカルボン酸、２，６−ナフタリンジカルボン酸などの芳香族ジカルボン酸類、これら脂肪族ジカルボン酸類や芳香族ジカルボン酸類のエステル誘導体、これら脂肪族ジカルボン酸類の無水物などが挙げられる。
【００１５】
更に、上記の主たる単量体と共重合しうる単量体などが光学活性物質である場合には、Ｌ−体またはＤ−体の何れであってもよいし、Ｄ，Ｌ−体の混合割合が任意の混合組成物、Ｄ，Ｌ−体の共重合割合が任意の共重合体、或いはメソ体の何れであってもよい。
グリコール酸、グリコリド、及びグリコール酸エステル類の上記主たる単量体に、これらの共重合しうる単量体を共重合させる場合、若しくはこれらの共重合しうる単量体を多成分に組み合わせて共重合させる場合は、その配列は特に限定されるものではなく、ランダム共重合体、交互共重合体、ブロック共重合体、グラフト共重合体などの何れでも良いが、生分解性ブラスチックの規格、例えば日本における生分解性プラスチック研究会が定める規格、米国におけるＡＳＴＭ Ｄ−６４００、ドイツにおけるＤＩＮ Ｖ−５４９００などに適合するものとする。
【００１６】
本発明においては、上記に例示した本発明の組成物の原料として用いるグリコール酸系重合体の中で、該重合体の融点と結晶性が特定の範囲にあるグリコール酸系共重合体を用いることが好ましい。該グリコール酸系共重合体を用いた組成物を主体とする成形材料はより優れた成形性を示し、該成形材料から得られる成形体は優れた耐熱性と優れた透明性を同時に併有することが可能となる。即ち、該成形材料を成形加工する際に、熱劣化が起こり難い条件で溶融成形が可能であり、温度変化による著しい溶融粘度変化が起こらない優れた成形性と、乳酸系重合体からなる成形体では不可能であった１７０℃以上の優れた耐熱性と、結晶性が非常に高い場合には必要であった煩雑な急冷操作を経なくても得られる成形体の優れた透明性である。更に、得られた成形体を長期間保管した場合でも、透明性は高いレベルに維持することが可能である。
【００１７】
本発明で用いられる好ましいグリコール酸系重合体は、融点と結晶性が特定の範囲にあるグリコール酸系共重合体であり、該共重合体の非晶シートを１５０℃で１００分間熱処理した試験片を用い、加熱速度および冷却速度が１０℃／分で測定した示差走査熱量測定（ＪＩＳ Ｋ７１２１、及びＫ７１２２準拠）において１回目の昇温過程での融点Ｔｍ（℃）、１回目の冷却過程での結晶化熱ΔＨｃ（Ｊ／ｇ）、２回目の昇温過程での融解熱ΔＨｍ（Ｊ／ｇ）が下式（１）〜（３）を満たすものである。
１７５≦Ｔｍ≦２０５ （１）
ΔＨｃ＝０ （２）
０≦ΔＨｍ＜２０ （３）
【００１８】
上記の好ましいグリコール酸系重合体は、該重合体の非晶シートを１５０℃に設定した熱風循環恒温槽中で１００分間加熱した結晶化物を試験片として、加熱及び冷却速度が１０℃／分の条件で測定した示差走査熱量測定（ＤＳＣ、ＪＩＳＫ７１２１準拠）で１回目の昇温過程での融点Ｔｍが１７５℃以上２０５℃以下の範囲内である。該Ｔｍの値が１７５℃以上であれば、該グリコール酸系重合体の組成物を主体とする成形体は耐熱性が十分なものとなる。一方、該Ｔｍの値が２０５℃以下であれば、溶融成形の際の加工温度と重合体の分解温度の差が広くなり成形性が優れるものとなる。より好ましいグリコール酸系重合体は、該Ｔｍが１８５℃以上２００℃以下の範囲内であり、より優れた耐熱性と成形性を兼備することができる。尚、上記示差操作熱量測定において、結晶融解に起因する吸熱ピークが複数存在する場合は、最も高温の吸熱ピーク温度を融点Ｔｍとする。
【００１９】
本発明でいう重合体の結晶性とは、重合体の結晶化し易さを指しており、結晶化速度や結晶化度を指標として表される。結晶化速度は、過冷却融体から結晶状態に非可逆的に転移するときの速度であり、その目安として熱分析における等速冷却過程での結晶化温度の測定が行われていて、結晶化速度が速い方が結晶化温度は高くなるとされている（日本分析化学会編、新版 高分子分析ハンドブック、ｐ．３３９、紀伊国屋書店（１９９５）参照）。
【００２０】
一方、結晶化度は、高分子固体における結晶領域の重量分率として定義されており、例えば熱分析法などにより測定される。熱分析法では、一般に理論融解熱ΔＨｆに対する試験片の実測融解熱ΔＨｍの比として、結晶化度Ｘｃ（％）＝ΔＨｍ／ΔＨｆ×１００より求められる（日本分析化学会編、新版 高分子分析ハンドブック、ｐ．３３９、紀伊国屋書店（１９９５）参照）。該式において、ΔＨｍは示差走査熱量測定（ＤＳＣ；ＪＩＳ Ｋ７１２２準拠）により測定した値を用い、ΔＨｆはホモポリマーの場合は例えばＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ（ＪＯＨＮ ＷＩＬＥＹ ＆ ＳＯＮＳ）等に記載の値が用いられている。しかし、ΔＨｆは、共重合体の場合は共重合成分やその成分割合が多岐に亘るために文献値が無い場合が多い。結晶化度Ｘｃを求める上記計算式では、試験片の実測融解熱ΔＨｍが大きい方が結晶化度は高くなることを意味していることから、本発明においてはΔＨｍの値によって結晶性を判断する。
【００２１】
上記の好ましいグリコール酸系重合体は、該重合体の非晶シートを１５０℃に設定した熱風循環恒温槽中で１００分間加熱した結晶化物を試験片として、加熱及び冷却速度が１０℃／分の条件で測定した示差走査熱量測定（ＤＳＣ、ＪＩＳＫ７１２２準拠）で１回目の冷却過程での結晶化熱ΔＨｃが０Ｊ／ｇ、２回目の昇温過程での融解熱ΔＨｍが０Ｊ／ｇ以上２０Ｊ／ｇ未満の範囲内である。
示差走査熱量測定（ＤＳＣ）における等速冷却過程で結晶化ピークが現れない場合（結晶化熱ΔＨｃ＝０Ｊ／ｇ）は 、試験片の結晶性は、非晶質であり全く結晶化しないか、或いは結晶化速度が遅いためＤＳＣの測定条件（冷却速度１０℃／分）では結晶化が起こらないかの二通りが考えられる。上記の好ましいグリコール酸系重合体は、前述のとおりＤＳＣにおける１回目の昇温過程での融点Ｔｍが１７５℃以上２０５℃以下であるので、非晶質で全く結晶化しない場合とは異なるものであり、ＤＳＣの測定条件（冷却速度１０℃／分）では結晶化が起こらない結晶化速度を有するものである。該ΔＨｃが０Ｊ／ｇである場合には、該重合体の組成物を主体とする成形材料を用いて溶融成形する際に、急冷操作など特別な非晶化工程は不要となる。
【００２２】
一方、好ましいグリコール酸系重合体の該ΔＨｍの値が０Ｊ／ｇということは、前述の結晶化熱ΔＨｃの場合と同様に、本発明の重合体がＤＳＣにおける１回目の昇温過程での融点Ｔｍが１７５℃以上２０５℃以下であるので非晶質で全く結晶化しない場合とは異なり、ＤＳＣの測定条件（昇温速度１０℃／分）では結晶化が起こらない結晶化速度であることを意味しており、該重合体の組成物を主体とする成形体は、長期間保管した場合でも透明性は高いレベルに維持することが可能になる。該ΔＨｍの値が２０Ｊ／ｇ未満の場合は、該重合体の結晶性が比較的低いために、該重合体の組成物を主体とする成形体は、長期間保管した場合に透明性を高いレベルに維持することができる。より好ましいグリコール酸系重合体は、得られる成形体を長期保管した場合により優れた透明性を維持する為には、該ΔＨｍの値は０Ｊ／ｇ以上１８Ｊ／ｇ以下の範囲内である。
【００２３】
本発明で用いられる好ましいグリコール酸系重合体は、具体的に例示すると、グリコリドとグリコリド以外の単量体を用いて開環重合し得られる共重合体であって、グリコリド以外の単量体としては脂肪族ヒドロキシカルボン酸類の環状二量体、およびラクトン類から少なくとも一種が選ばれる。或いは、グリコール酸とグリコール酸以外の単量体を用いて直接脱水重縮合し得られる共重合体であって、グリコール酸以外の単量体としては乳酸などの脂肪族ヒドロキシカルボン酸類から少なくとも一種が選ばれる。より分子量の高い共重合体を得易いという観点から、グリコリドとラクチド（３，６−ジメチル−１，４−ジオキサ−２，５−ジオン）を用いて開環重合し得られる共重合体が特に好ましい。なお、ラクチドは光学活性物質でありＬ−体、Ｄ−体のいずれであってもよいし、Ｄ，Ｌ−体混合物やメソ体であってもよい。また、グリコリド−Ｌ−ラクチド共重合体とグリコリド−Ｄ−ラクチド共重合体の混合物であってもよい。例えば、単量体単位がグリコリドとラクチドよりなる共重合体である場合には、共重合体中のグリコリド成分割合が７８〜９０ｍｏｌ％とラクチド成分割合が２２〜１０ｍｏｌ％である開環重合により得られたグリコール酸−乳酸共重合体が挙げられる。
【００２４】
本発明で用いるグリコール酸系重合体の分子量は、該重合体からなる組成物を主体とした成形体が十分な機械的特性を有し、且つ溶融押出や射出成形などの成形加工時に温度変化による著しい溶融粘度変化が起こらず優れた成形性を有する為には、対数粘度数で少なくとも０．１５ｍ３／ｋｇ以上が好ましく、０．１８ｍ３／ｋｇ以上であることがより好ましい。一方、該重合体の分子量の上限は、より容易に成形体に成形加工するためには対数粘度数で０．８０ｍ３／ｋｇ以下に留めることが望ましいが、可塑剤などの添加により溶融流動性を調整すれば良く特に限定されるものではない。対数粘度数［η］は、一般に下式（４）により求められる値であり、濃度０．２％以下の希薄溶液では高分子の分子量の指標として用いられる固有粘度に近似できる（化学大辞典 縮刷版、ｐ．７４６、共立出版（１９６３）、及び新版 高分子分析ハンドブック、ｐ．１２０、紀伊国屋書店（１９９５）参照）。
［η］＝｛ｌｎ（ｔ／ｔｏ）｝／ｃ （４）
（式中、ｔは毛管粘度計で測定される高分子溶液の流下時間（秒）を、ｔｏは毛管粘度計で測定される溶媒の流下時間（秒）を、ｃは溶質高分子の濃度（ｋｇ／ｍ３）を示す。）
【００２５】
尚、本発明で用いるグリコール酸系重合体の分子量は、重量平均分子量で表すと５×１０４以上であることが望ましく、より望ましくは１×１０５以上である。分子量の上限は、可塑剤などの添加により溶融流動性を調整すれば良く特に限定されるものではないが、重量平均分子量で表すと８×１０５以下に留めることが望ましい。
透明化結晶核剤としては、金属酸化物、無機金属塩、粘土鉱物類などの無機粒子や、脂肪酸アミド、脂肪酸金属塩、リン酸エステル金属塩などの非相溶型有機系化合物、ソルビトール骨格を有する相溶型有機系化合物など様々な種類のものが知られているが、これら透明化結晶核剤のうち窒化ホウ素系粒子に限ってグリコール酸系重合体の透明性を著しく高めることができることを本発明者は見出した。
【００２６】
本発明の組成物の原料として用いる窒化ホウ素系粒子とは、窒化ホウ素の成分割合が５０ｗｔ％以上の無機粒子をいう。好ましい窒化ホウ素の成分割合は９５ｗｔ％以上であるが、窒化ホウ素の成分割合が高い無機粒子に、希釈やその他の目的で窒化ホウ素以外の無機粒子を混合した粉末パウダーを用いてもよい。また、粒子形状は球状、針状、円盤状、柱状など特に限定されるものではない。窒化ホウ素以外の無機粒子としては、アルミナ、シリカ、酸化チタンなどの金属酸化物、炭酸カルシウム、リン酸カルシウムなどの無機金属塩、タルク、マイカ、カオリンなどの粘土鉱物類の無機粒子が挙げられる。
【００２７】
本発明の組成物を構成する上記窒化ホウ素系粒子の含有量は、グリコール酸系重合体１００重量部に対し、０．００１重量部以上０．３重量部未満であることが必要である。該含有量が０．００１重量部以上であれば、該組成物を用いて得られる成形品は、結晶性の高いグリコール酸系重合体を用いても透明化結晶核剤として有効に作用し、透明性が優れるものとなる。また、該含有量が０．３重量部未満であれば、得られる成形品は、窒化ホウ素系粒子による光散乱が少なく、透明性が優れるものとなる。
【００２８】
上記窒化ホウ素系粒子の平均粒径は、レーザー回折・散乱法により測定した平均粒径が０．０３μｍ以上５μｍ以下であることが好ましい。粉末パウダーの製造や取り扱い性の点から該平均粒径は０．０３μｍ以上が好ましい。一方、窒化ホウ素系粒子による光散乱の量や、得られる成形体の透明性の点から該平均粒径が５μｍ以下であることが好ましい。
該平均粒径は、より容易に粉末パウダーを製造し取り扱う為に、また窒化ホウ素系粒子による光散乱を抑制する為に、０．１μｍ以上１μｍ以下であることが好ましい。該平均粒径が１μｍ以下である場合には、特に結晶性の高いグリコール酸系重合体を用いても透明化結晶核剤としての添加効果が顕著であり、得られる成形体の透明性は非常に優れるものとなる。更に、厚み２０μｍ以下のフィルム状成形体にいては、表面粗れなどの発生を抑制し、透明性が著しく高いものとなる。
【００２９】
本発明のグリコール酸系重合体の成形体は、上述のグリコール酸系重合体組成物を主体とする成形体であり、該成形体の用途によって可塑剤を含有しても良い。グリコール酸系重合体が９５重量％程度より多く、可塑剤が５重量％程度より少ない場合は成形体を硬質な用途で利用することができ、グリコール酸系重合体が９５〜８５重量％程度と可塑剤が５〜１５重量％程度の場合は成形体を半硬質な用途で利用することができ、グリコール酸系重合体が８５〜６０重量％程度と可塑剤が１５〜４０重量％程度の場合は比較的優れた強度を保ちつつ軟質な用途で利用することができる。また、グリコール酸系重合体と窒化ホウ素系粒子からなる組成物に可塑剤を含有せしめることにより、該組成物の結晶化速度をより高めることも可能になる。
【００３０】
本発明で使用される可塑剤の具体例としては、例えばジオクチルフタレートやジエチルフタレートなどのフタル酸エステル類、ラウリン酸エチルやオレイン酸ブチル、リノール酸オクチルなどの脂肪酸エステル類、ジオクチルアジペートやジブチルセバケートなどの脂肪族二塩基酸エステル類、アセチルくえん酸トリブチルやアセチルくえん酸トリエチルなどの脂肪族三塩基酸エステル類、グリセリンジアセテートラウレートやグリセリントリアセテートなどのグリセリン脂肪酸エステル類、ジグリセリンテトラアセテートやテトラグリセリンヘキサアセテートなどのポリグリセリン脂肪酸エステル類、リン酸ジオクチルなどのリン酸エステル類、エポキシ化大豆油やエポキシ化アマニ油などの変性植物油類、ポリブチレンセバケートなどのポリエステル系可塑剤などが挙げられ、これらから一種、または二種以上が選ばれる。安全衛生性の観点からグリセリン脂肪酸エステル類や脂肪族三塩基酸エステル類が望ましく、グリコール酸系重合体との相溶性の観点から溶解性パラメーター値（Ｒ．Ｆ．Ｆｅｄｏｒｓ，Ｐｏｌｙ．Ｅｎｇ．Ｓｃｉ．，Ｖｏｌ．１４，Ｎｏ．２，ｐ．１５２（１９７４））が１０（ｃａｌ／ｃｍ３）０．５以上であるグリセリントリアセテート、ジグリセリンテトラアセテート、アセチルくえん酸トリエチルなどが特に望ましい。これらは、水酸基を持たないため、重合体と可塑剤とのエステル交換反応を起こす可能性が少ない。
【００３１】
本発明のグリコール酸系重合体の組成物は、必要に応じて無機および／または有機化合物よりなる上記以外の添加剤、例えば、滑剤、帯電防止剤、防曇剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、着色剤、難燃剤等が適宜含有されていてもよい。使用される酸化防止剤としては、例えばフェノール系、フェニルアクリレート系、リン系、イオウ系などが挙げられ、これらから一種、又は二種以上を選び、添加量が組成物中に１０重量％未満含有させることができる。
【００３２】
本発明のグリコール酸系重合体の成形体は、グリコール酸系重合体と窒化ホウ素系粒子からなるグリコール酸系重合体組成物を主体とするものであり、その原料である該グリコール酸系重合体を５０重量％以上含有するものである。必須成分である窒化ホウ素系粒子の含有量を含めて５０重量％以下の範囲内で他の生分解性樹脂を混合しても良い。混合し得る生分解性樹脂としては、前述のグリコール酸、グリコリド、及びグリコール酸エステル類の主たる単量体と共重合し得る単量体として例示した、例えば、乳酸などの脂肪族ヒドロキシカルボン酸類の重縮合体、ラクチド（３，６−ジメチル−１，４−ジオキサ−２，５−ジオン）やε−カプロラクトンなどのラクトン類の開環重合体、エチレングリコールとアジピン酸などの多価アルコール類と多価カルボン酸類の重縮合体などの脂肪族ポリエステル類、この他にデンプン系やセルロース系などの天然高分子類、ポリアスパラギン酸などのポリアミノ酸類、酢酸セルロースなどのセルロースエステル類、脂肪族ポリエステルカーボネート類、ポリビニルアルコール類、ポリエチレンオキサイドなどのポリエーテル類、低分子量のポリエチレン、ポリリンゴ酸等が挙げられる。また、、組成物や得られる成形体の生分解性を阻害しない範囲であれば、例えば、ポリオレフィン類、芳香族ポリエステル類、ポリアミド類、エチレン−ビニルアルコール系共重合体類、石油樹脂類やテルペン系樹脂類、その水素添加物、その他公知の熱可塑性樹脂などを混合しても良い。
【００３３】
本発明のグリコール酸系重合体の成形材料は、本発明のグリコール酸系重合体組成物に、必要に応じて、上述の可塑剤、その他の添加剤、その他の熱可塑性樹脂類を含有せしめて得られるものであり、グリコール酸系重合体、窒化ホウ素系粒子、用途によって必要であれば可塑剤、その他の添加剤、その他の熱可塑性樹脂類を、単軸、又は二軸押出機、バンバリーミキサー、ミキシングロール、ニーダー等を使用して溶融混合させて成形材料を作製することが望ましい。
【００３４】
本発明でいう成形体とは、例えば溶融押出法、カレンダー法、溶融プレス成形法などにより作製されるフィルム状やシート状の成形体、及びそれらを延伸加工したり、プラグアシスト成形法やエアークッション成形法などの真空成形加工、圧空成形加工、雄雌型成形加工したものなどが挙げられる。本発明において、フィルムとシートの区別は、単に厚みの違いによって異なる呼称を用いているものであり、通常は厚み２００μｍ未満をフィルム状成形体、厚み０．２ｍｍ以上をシート状成形体と呼んでいる。その他に、射出成形体、射出成形法で得られたプリフォームを加熱しながら気体を吹き込むブロー成形体、発泡成形体なども挙げられる。
【００３５】
本発明の成形体の製造方法は、特に限定されるものではなく従来公知の一般的な方法で行なわれ、具体的に説明すると、例えば溶融押出法では、成形材料を、事前に水分率が２００ｗｔｐｐｍ以下になるまで乾燥させてから押出機に供給して、加熱溶融しながら押出機の先端に接続したダイスから押出し、その後冷却固化させることにより、シート状、若しくはチューブ状の溶融成形物として製造することができる。また、溶融プレス成形法では、前述した成形材料を、事前に水分率が２００ｗｔｐｐｍ以下になるまで乾燥させてから金型に供給して、常圧或いは減圧雰囲気下で加熱溶融させプレスし、その後冷却固化させることにより、シート状の溶融成形物として製造することができる。
【００３６】
また、延伸成形体は、シート状、若しくはチューブ状成形体を加熱しながら少なくとも一軸方向に延伸して得られる成形体である。この延伸方法は、特に限定されるものではなく従来公知の一般的な方法で行われ、具体的には、例えば一軸延伸の場合は、溶融押出法でＴダイより溶融押出し、キャストロールで冷却したシート状成形物を、ロール延伸機でシートの流れ方向に縦一軸延伸したり、該縦延伸倍率を極力抑えてテンターで横一軸延伸して製造する方法、或いは二軸延伸の場合は、溶融押出法でＴダイより溶融押出し、キャストロールで冷却したシート状成形物を、先ずロール延伸機で縦延伸してからテンターで横延伸する逐次二軸延伸や、テンターで縦横両方向に延伸する同時二軸延伸で製造する方法、溶融押出法でサーキュラーダイより溶融押出し、水冷リング等で冷却したチューブ状成形物を、チューブラー延伸して製造する方法などがある。また、溶融プレス法で得られたシート状成形物を、バッチ式延伸装置で一軸或いは二軸延伸する方法などがある。これらの延伸操作は、延伸温度は延伸に供する成形物のガラス転移温度〜（冷結晶化温度＋３０℃）の温度範囲、延伸速度は１０〜２０００００％／分の範囲、延伸倍率は少なくとも一軸方向に面積倍率で２〜５０倍の範囲から適宜選ばれる延伸条件で行なわれることが望ましい。
【００３７】
この様にして得られた延伸成形体は、例えば可塑剤を比較的多量添加し引張弾性率が４．０ＧＰａ未満である軟質から中質の延伸成形体の場合は、ピロー包装、シュリンク包装、ストレッチ包装、ケーシング、家庭用ラップ等の包装材用途に好適である。熱収縮させながら包装するなどのシュリンク包装用途に利用する場合には、そのまま使用しても良いし、或いは熱収縮具合を調整する目的で熱処理やエージング処理を施しても良い。また、電子レンジなどで加熱される耐熱性が要求される包装材に利用する場合には、発熱した内容物からの熱による変形や溶融穿孔を防ぐ目的で熱処理を施すことが望ましい。更に、経時寸法安定性や物性安定性を向上させる目的で、エージング処理などを施すことが望ましい。熱処理は、通常は６０〜１６０℃の温度範囲から適宜選ばれる温度で１秒〜３時間行われることが望ましく、エージング処理は、通常は２５〜６０℃の温度範囲から適宜選ばれる温度で３時間〜１０日間程度行われることが望ましい。
【００３８】
成形体の透明性は、内容物の視認性に優れる透明性を要求される用途に使用される場合には、使用する成形体をサンプルとしてＪＩＳ Ｋ７１０５に準拠して測定したヘーズが１０％以下であることが望ましく、より望ましくは５％以下である。
得られた成形体は、そのまま家庭用ラップ等の包装材などとして使用しても良いが、必要に応じて帯電防止剤や防曇性を向上させる目的でコーティングやコロナ処理等の各種表面処理を施しても良いし、シール適性、防湿性、ガスバリア性、印刷適性などを向上させる目的でラミネート加工やコーティング加工、或いはアルミニウムなどの真空蒸着を施しても良い。更に、二次加工により、用途に応じた形状に成形して使用しても良い。二次加工品としては、例えば延伸フィルムの場合はピロー包装用途やウェルドタイプのケーシング包装用途などの包装材とするシール加工品があり、延伸シートの場合はプラグアシスト成形法やエアークッション成形法などの真空成形加工、圧空成形加工、雄雌型成形加工を施してトレイやカップなどの容器、又はブリスターパッケージングシートなどがある。
【００３９】
また、成形材料に着色剤を適宜混合したり、延伸成形体自体に印刷を施したりして、他シートや発泡体などにラミネートする用途に使用しても良い。この様な用途では、ラミネートした他シートや発泡体を成形して得られるトレイやカップなどの容器のデザイン性を高め、ディスプレイ効果により商品価値を高めることが狙いであるが、ラミネートする延伸成形体の透明性が優れることにより、容器表面のツヤ出しやデザイン印刷が鮮明になるという利点がある。
その他に、ブロー成形法により得られた成形体は、飲料品、或いは洗剤やシャンプーなどの生活衛生用品などのボトルなどに好適である。
【００４０】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。但し、これらの具体例は本発明の範囲を限定するものではない。また、物性測定方法と評価方法を下記に示すが、サンプルは特に断りのない限り測定サンプル作製後に温度（２３±２）℃、相対湿度（５０±５）％の雰囲気下に１〜２日間保管したものを物性測定や評価に供した。
【００４１】
［物性測定方法］
（１）対数粘度数
純溶媒１，１，１，３，３，３−ヘキサフルオロ−２−プロパノール（以下ＨＦＩＰと略記する。）と、グリコール酸系重合体の濃度ｃが１．０ｋｇ／ｍ３となるよう溶解したＨＦＩＰ溶液をサンプルとして、キャピラリーＮｏ．０ａのウベローデ型毛管粘度計（柴山科学器械製作所製毛細管式自動粘度測定装置ＳＳ−１７０−Ｌ１）を使用し２０℃で毛管中を流下する時間を測定し、式（４）により対数粘度数［η］を求めた。
［η］＝｛ｌｎ（ｔ／ｔｏ）｝／ｃ （４）
（式中、ｔは毛管粘度計で測定される高分子溶液の流下時間（秒）、ｔｏは毛管粘度計で測定される溶媒の流下時間（秒）、ｃは溶質高分子の濃度（ｋｇ／ｍ３）を表す。）
【００４２】
（２）示差走査熱量測定（ＤＳＣ）
融点Ｔｍ、結晶化熱ΔＨｃ、融解熱ΔＨｍは、測定装置にセイコー電子工業（株）製ＤＳＣ６２００を使用し、ＪＩＳ Ｋ７１２１、及びＫ７１２２に準拠して測定した。サンプルは、加熱プレス機（テスター産業（株）製 圧縮成形機ＳＡ−３０１）を用いて、原料として用いる重合体の小片をそのまま示差走査熱量測定した際の融解ピーク終了時より約２０℃高い温度に設定し、該重合体を５分間約１２ＭＰａ加圧した後、冷却し厚み約２００μｍの非晶シートを得て、該非晶シートを１５０℃に設定した熱風循環恒温槽中で１００分間加熱結晶化させて作製した。サンプル量は約７．５ｍｇとして、先ず−２０℃で３分間保持した後、加熱速度１０℃／分で２６０℃まで加熱し１回目の昇温過程での融点Ｔｍを測定した。該温度で１分間保持した後、冷却速度１０℃／分で−２０℃まで冷却し、１回目の冷却過程での結晶化熱ΔＨｃを測定した。次いで、−２０℃で１分間保持した後、再び加熱速度１０℃／分で２６０℃まで加熱し２回目の昇温過程での融解熱ΔＨｍを測定した。尚、温度と熱量の校正は、標準物質としてインジウムを用いて行った。尚、本発明でいう非晶シートとは、上記手順で作製したシートをサンプルとして、広角Ｘ線回折法により回折強度曲線を測定し、該回折強度曲線に結晶に起因する回折ピークが存在しないものを指す。
【００４３】
（３）平均粒径
平均粒径は、蒸留水を分散媒体とした濃度１００ｐｐｍの分散液をサンプルとして、測定装置にレーザー回折式粒度分布測定装置（（株）島津製作所製 ＳＡＬＤ−２１００）を使用して測定し、メディアン径として求めた。尚、分散媒体には、必要に応じてステアリン酸マグネシウムなどの分散剤を適宜添加してもよい。
【００４４】
［評価方法］
（１）耐熱性
耐熱性は、厚み１００μｍのシート状成形体をサンプルとして、耐荷重切断試験を行い評価した。耐荷重切断試験は、短冊状試験片に荷重１００ｇをかけた状態で、一定温度に設定した熱風循環恒温槽中で１時間加熱し試験片の切断の有無を調べ、試験片が切断しない最高温度を測定した。サンプルは、加熱プレス機（テスター産業（株）製圧縮成形機ＳＡ−３０１）を用いて、材料として用いる組成物の小片をそのまま示差走査熱量測定した際の融解ピーク終了時より約２０℃高い温度に設定し、該組成物を５分間約１２ＭＰａ加圧した後、冷却し厚み約１００μｍの非晶シートを得て、該非晶シートを１４０℃に設定した熱風循環恒温槽中で１分間熱処理して作製した。サンプルを縦１４０ｍｍ、横３０ｍｍの短冊状に切り出した。短冊状試験片の上下端２０ｍｍづつの部分に固定治具と荷重治具を各々取り付け、一定温度に設定した熱風循環恒温槽中で１時間加熱し試験片の切断の有無を調べた。短冊状試験片が切断しない場合は、新しい試験片で設定温度を５℃上げて前記手順を繰返し試験した。短冊状試験片が切断しない最高温度の測定結果は、この試験を各サンプルにつき５回づつ行い最頻値で示した。
【００４５】
（２）透明性
透明性は、厚み１００μｍのシート状成形体をサンプルとして、ヘーズを測定し評価した。ヘーズの測定は、測定装置に（株）村上色彩技術研究所製ヘーズ計ＨＲ−１００を使用し、ＪＩＳ Ｋ７１０５に準拠して測定した。上記耐熱性の評価方法で作製したシート状成形体を、一辺５０ｍｍの正方形に切り出し、これをホルダーにセットしサンプルのヘーズを測定した。ヘーズの測定結果は、サンプル数５個づつ測定し、その平均値で示した。
【００４６】
【実施例１】
［単量体の精製］
グリコリド１ｋｇを、酢酸エチル３ｋｇに７５℃で溶解させた後、室温にて４８時間放置し析出させた。濾取した析出物を、室温で約３ｋｇの酢酸エチルを用いて洗浄を行った。再度この洗浄操作を繰返した後、洗浄物を真空乾燥機内に入れ、６０℃で２４時間真空乾燥を行った。この乾燥物を、窒素雰囲気下で６〜７ｍｍＨｇに減圧し単蒸留にて１３３〜１３４℃の留出物として蒸留精製グリコリド４８０ｇを得た。
Ｌ−ラクチド１ｋｇを、トルエン３ｋｇに８０℃で溶解させた後、室温にて４８時間放置して析出させた。濾取した析出物を、室温で約３ｋｇのトルエンを用いて洗浄を行った。再度この洗浄操作を繰返した後、洗浄物を真空乾燥機内に入れ６０℃で２４時間真空乾燥を行い、精製Ｌ−ラクチド５６０ｇを得た。
【００４７】
［グリコール酸系重合体の調製］
上記単量体の精製で得られたグリコリド４３０ｇとラクチド２７０ｇ、及び触媒として２−エチルヘキサン酸すず０．２ｇとラウリルアルコール０．０５ｇを、内面をガラスライニングしたジャケット付反応機に仕込み、乾燥窒素を吹き込みながら約１時間室温で乾燥した。次いで、乾燥窒素を吹き込みながら１３０℃に昇温し、４０時間撹拌して重合を行った。重合操作の終了後、ジャケットに冷却水を通水して冷却し、反応機から取り出した塊状ポリマーを約３ｍｍ以下の細粒に粉砕した。この粉砕物を、テトラヒドロフランを用いて６０時間ソックスレー抽出した後、ヘキサフルオロイソプロパノール３ｋｇに５０℃で溶解し、次いで７ｋｇのメタノールで再沈殿させた。この再沈殿物を、１３０℃に設定した真空乾燥機内で６０時間真空乾燥を行い、グリコール酸系重合体５５０ｇを得た。得られた該重合体を樹脂記号Ｐ１とする。
【００４８】
グリコール酸系重合体Ｐ１は、該重合体７０ｍｇをトリフルオロ酢酸−Ｄ１ｍｌに溶解して１Ｈ−ＮＭＲにより共重合成分割合を解析したところ、グリコール酸の成分割合が８０ｍｏｌ％と乳酸の成分割合が２０ｍｏｌ％であった。前述した物性測定方法に従って対数粘度数を測定したところ、該重合体の対数粘度数［η］は０．４２（ｍ３／ｋｇ）であった。前述した物性測定方法に従って示差走査熱量測定を行なったところ、該重合体の１回目の昇温過程での融点Ｔｍは１８８℃、１回目の冷却過程での結晶化熱ΔＨｃは０Ｊ／ｇ、２回目の昇温過程での融解熱ΔＨｍは０Ｊ／ｇであった。
【００４９】
［溶融混合、シート状成形体の作製、及び評価］
窒化ホウ素成分割合が９８％である平均粒径０．８μｍの窒化ホウ素系粒子（電気化学工業（株）製 デンカボロンナイトライドＳＰ−２）を核剤記号Ｎ１とする。該粒子Ｎ１を０．１７ｇ量り取り、４０℃に設定した真空乾燥機中で、含有水分量が２００ｐｐｍ以下になるまで約４８時間放置して乾燥操作を行った。上記重合体の調製で得られたグリコール酸系重合体Ｐ１を１７０ｇ量り取り、１３０℃に設定した熱風循環恒温槽中で、含有水分量が２００ｐｐｍ以下になるまで約２時間放置して乾燥操作を行った。この乾燥させたグリコール酸系重合体Ｐ１と窒化ホウ素系粒子Ｎ１を、２２０℃に設定したニーダー（入江商会社製卓上型ニーダーＰＢＶ−０．３型）に供給し、流量１０Ｌ／分の乾燥窒素を吹き込みながら変速ハンドル目盛りを７に設定（ローター平均回転数３８ｒｐｍ、平均せん断速度約１００／秒）して１５分間溶融混合した。その後、ニーダーから溶融混合物を直ちに取り出し、冷却プレスにて冷却固化させ板状のグリコール酸系重合体の組成物を得た。
【００５０】
該板状物を、４０℃に設定した真空乾燥機中で含有水分量が２００ｐｐｍ以下になるまで約２４時間放置して乾燥操作を行った後、前述の耐熱性評価方法に従って熱処理したシート状成形体を作製した。得られた該成形体をサンプルとして、前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１８０℃、ヘーズは２％であった。
【００５１】
【実施例２】
次いで、窒化ホウ素成分割合が９９％である平均粒径３．５μｍの窒化ホウ素系粒子（電気化学工業(株)製デンカボロンナイトライドＧＰ）を核剤記号Ｎ２とし、窒化ホウ素系粒子Ｎ２を用いることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１８０℃、ヘーズは５％であった（実施例２）。
【００５２】
【比較例１〜３】
ステアリン酸ナトリウム（東京化成工業（株）製）を核剤記号Ｎ３とし、窒化ホウ素系粒子の代わりにＮ３（添加量０．８５ｇ）を用いることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１３０℃、ヘーズは３％であった。該成形体は茶褐色への変色が著しく、Ｎ３はグリコール酸系重合体を分解した（比較例１）。
【００５３】
ｍ−キシリレンビスステアリン酸アミド（日本化成製スリパックスＰＸＳ）を核剤記号Ｎ４とし、窒化ホウ素系粒子の代わりにＮ４（添加量０．８５ｇ）を用いることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１２０℃、ヘーズは２０％であった。該成形体は白濁が著しく、Ｎ４はグリコール酸系重合体との相溶性が著しく悪かった（比較例２）。
【００５４】
窒化ホウ素系粒子Ｎ１の添加量を０．８５ｇとすることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１８０℃、ヘーズは４７％であった（比較例３）。
これら実施例１〜２、及び比較例１〜３の評価結果を表１にまとめる。表１によると、グリコール酸系重合体では、透明化結晶核剤として窒化ホウ素系粒子を用いる場合に限って核剤作用が現れ、得られた成形体の耐熱性と透明性を著しく高めることができる。更に、窒化ホウ素系粒子は、平均粒径が小さいほど光散乱が抑制され透明性を著しく高められた。尚、窒化ホウ素系粒子は、多量に添加すると透明性が悪化した。
【００５５】
【表１】
【実施例３〜５、及び比較例４】
グリコール酸系重合体の調製でラウリルアルコールを０．１ｇ、重合時間を１５時間とすることの他は上記実施例１と同じ実験を繰返し、得られたグリコール酸系重合体を樹脂記号Ｐ２とする。該重合体Ｐ２は、共重合成分割合がグリコール酸成分割合８０ｍｏｌ％と乳酸成分割合２０ｍｏｌ％、対数粘度数［η］が０．１７（ｍ３／ｋｇ）、示差走査熱量測定で融点Ｔｍが１８９℃、結晶化熱ΔＨｃが０Ｊ／ｇ、融解熱ΔＨｍが０Ｊ／ｇであった。該重合体Ｐ２を用いることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１７５℃、ヘーズは２％であった（実施例３）。
【００５７】
グリコール酸系重合体の調製でグリコリドを７００ｇ、ラクチドを使用せず、重合時間を１５時間とすることの他は上記実施例１と同じ実験を繰返し、得られたグリコール酸系重合体を樹脂記号Ｐ３とする。該重合体Ｐ３は、グリコール酸成分のホモポリマーであり、対数粘度数［η］が０．２５（ｍ３／ｋｇ）、示差走査熱量測定で融点Ｔｍが２２３℃、結晶化熱ΔＨｃが−７０Ｊ／ｇ、融解熱ΔＨｍが７０Ｊ／ｇであった。該重合体Ｐ３を用い、ニーダー設定温度を２５０℃とすることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は２１５℃、ヘーズは６％であった（実施例４）。
【００５８】
グリコール酸系重合体の調製でグリコリドを４９０ｇ、ラクチドを２００ｇ、重合時間を３０時間とすることの他は上記実施例１と同じ実験を繰返し、得られたグリコール酸系重合体を樹脂記号Ｐ４とする。該重合体Ｐ４は、共重合成分割合がグリコール酸成分割合８８ｍｏｌ％と乳酸成分割合１２ｍｏｌ％、対数粘度数［η］が０．３９（ｍ３／ｋｇ）、示差走査熱量測定で融点Ｔｍが２０２℃、結晶化熱ΔＨｃが０Ｊ／ｇ、融解熱ΔＨｍが９Ｊ／ｇであった。該重合体Ｐ４を用い、ニーダー設定温度を２３０℃とすることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１９５℃、ヘーズは２％であった（実施例５）。
【００５９】
ポリ乳酸（（株）島津製作所製 ＬＡＣＴＹ９４００）を樹脂記号Ｐ５とし、グリコール酸系重合体の代わりにＰ５を用い、ニーダー設定温度を２００℃とすることの他は上記実施例１と同じ実験を繰返し、得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１６５℃、ヘーズは２％であった。得られたシート状成形体は、融点がより低いポリ乳酸からなるため、耐熱性は劣るものであった（比較例４）。
【００６０】
これら実施例１、３〜５、及び比較例４の評価結果を表２にまとめる。表２によると、グリコール酸系重合体の対数粘度数が大きく、分子量が高い場合には、得られるシート状成形体は機械的特性が優れ、更に、グリコール酸系重合体の融点と結晶性が特定範囲にある場合は、耐熱性と透明性の両特性を兼備し、包装用資材などのプラスチック製品として非常に優れるものである。
【００６１】
【表２】
【実施例６】
実施例１と同様に乾燥させたグリコール酸系重合体Ｐ１（１７０ｇ）と窒化ホウ素系粒子Ｎ１（０．１７ｇ）を２２０℃に設定したニーダーに供給して、乾燥窒素を通気できるバルブ付き密閉蓋で閉じ、混練しながらニーダー槽内を乾燥窒素で十分置換した。可塑剤としてアセチルくえん酸トリエチル（東京化成工業（株）製）を２０ｇ量り取り、ニーダー槽内の乾燥窒素通気を止めた後、バルブからシリンジを用いて可塑剤を注入した。実施例１と同様に、１５分間溶融混合からシート状成形体の作製操作までを行なった。得られたシート状成形体をサンプルとして前述の耐熱性と透明性の評価を行なったところ、試験片が切断しない最高温度は１８０℃、ヘーズは２％であった（実施例６）。
【００６３】
【発明の効果】
本発明によれば、生分解性樹脂のなかでも融点が比較的高いグリコール酸系重合体に窒化ホウ素系粒子を含有せしめることによって、成形性が優れる成形材料組成物を提供することができ、また該組成物を用いることによって、生分解性を有し、且つ耐熱性や透明性が優れた包装用資材、農業用資材、土木建築用資材、機械装置部品など様々な分野、特に包装用資材用途に好適な成形体を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glycolic acid polymer composition and a molded body mainly composed of the composition. More specifically, the present invention relates to a composition mainly composed of a glycolic acid polymer having excellent moldability, and a molded body mainly composed of the composition and excellent in heat resistance and transparency.
[0002]
[Prior art]
Conventionally, plastic products manufactured by extrusion molding or injection molding have been used in various fields such as packaging materials, agricultural materials, civil engineering and building materials, and mechanical equipment parts because of their convenience during processing and use. Yes. However, in the current mass consumer society, the amount of use has been increasing year by year, and at the same time, the plastic waste problem has become more serious every year. Most plastic waste is disposed of by incineration or landfill, but in recent years, from the viewpoint of environmental conservation, material recycling has been proposed for use as a raw material for plastic products.
[0003]
The packaging of food and pharmaceutical products facilitates the work of transporting and distributing the contents, and at the same time maintaining the quality is an especially important role. Therefore, the packaging material is required to have high quality maintenance performance. Specifically, the performance of protecting the contents during long-term storage includes mechanical strength against external forces such as impact and stab, gas barrier properties against oxidative deterioration due to outside oxygen and drying deterioration due to moisture evaporation, and packaging materials themselves. Stability such as oil resistance and heat resistance that does not denature or deform. In addition, transparency is also an important factor for the required characteristics of packaging materials in order to increase the value of products through the ease of recognizing the contents and the display effect that encourages purchasers to purchase.
[0004]
However, the required performance of plastic products as packaging materials is diverse, and only one type of plastic cannot meet all of these requirements. For example, composites and multilayers are generally used in combination with several types of plastics. It has been. Such a packaging material is very difficult to be separated into various resins, and material recycling is impossible in consideration of cost and the like.
Under such circumstances, biodegradable resins that decompose in nature such as soil and water have attracted attention and have been studied.
[0005]
Patent Document 1 below discloses transparency / heat resistance by adding a specific crystallizing crystal nucleating agent such as an aliphatic carboxylic acid amide to an aliphatic polyester that is degradable in a moist environment in soil or seawater. / It is described that a molded product having both degradability can be obtained.
However, the aliphatic polyester molded article described in Patent Document 1 is a molded article mainly composed of a composition comprising a lactic acid-based polymer in which the repeating unit constituting the polymer is derived from lactic acid, and the obtained molded article The heat resistance of was insufficient. In this publication, a glycolic acid polymer, which is expected to obtain a molded product having higher heat resistance because it has a higher melting point than a lactic acid polymer, is described as an example of an aliphatic polyester. When the inventors added an aliphatic carboxylic acid amide or an aliphatic carboxylate which is a crystallizing crystal nucleating agent described in the publication to a glycolic acid polymer, the resulting molded article had insufficient transparency. (Comparative example described later).
[0006]
Patent Document 2 discloses a composition of a lactic acid polymer containing inorganic particles made of talc and / or boron nitride that defines an average particle size and an addition amount, and is biodegradable and excellent in moldability. There is a description that it is.
However, since the composition described in Patent Document 2 is mainly composed of a lactic acid-based polymer, the heat resistance of the molded product obtained is insufficient. Further, it is described that the amount of boron nitride contained in the composition is required to be 0.5% by weight or more, preferably 1% by weight or more from the effect of improving the crystallization rate. In the examples, 2% by weight is contained. Even if the stretch-molded product obtained by using such a composition is a thin stretch-formed product having a thickness of 20 μm or less, there is a problem in terms of transparency.
[0007]
Patent Document 3 discloses that the melting point is 150 ° C. or more, the heat of fusion is 20 J / g or more, and the density of the non-oriented crystallized product is 1.50 g / cm. 3 A thermoplastic resin material containing the glycolic acid polymer as described above is melt-extruded in a temperature range of a melting point to 255 ° C., thereby obtaining a sheet-like molded article exhibiting soil disintegration having excellent toughness and gas barrier properties. It is stated that
However, the sheet-like molded article described in Patent Document 3 has a heat of fusion of 20 J / g or more when the differential scanning calorimetry is performed at a heating rate of 10 ° C./min using an amorphous sheet as a test piece, and the density of the non-oriented crystallized product. 1.50 g / cm 3 Since it is formed from a thermoplastic resin material containing a glycolic acid polymer having a very high crystallinity as described above, a sheet-like molded body in an amorphous state that is rapidly cooled and not heat-set after melt extrusion is heat resistant. However, there was a problem that transparency deteriorates over time. Alternatively, the heat-set sheet-like molded body has a problem that it is inferior in transparency and brittle.
[0008]
Furthermore, although the heating temperature at the time of melt extrusion specified in Patent Document 3 is a high temperature range up to 255 ° C., this is more than the melting point in order to sufficiently melt the advanced crystals of the glycolic acid polymer used. This is because it has to be set to a considerably high temperature. The glycolic acid-based polymer begins to thermally decompose at 240 ° C. when the weight loss by thermogravimetric analysis is measured (K. Chujo, et al., Die Makromolekule Chemie, No. 100, P. 267 (1967)). However, in the case of melt extrusion at a heating temperature in the high temperature range up to 255 ° C. specified in the publication, the melt viscosity is remarkably lowered due to thermal deterioration, making the melt extrusion difficult or coloring in brown. There is a problem that the sheet-like molded product that is produced gives an unsanitary impression.
[0009]
[Patent Document 1]
JP-A-9-278991
[Patent Document 2]
JP-A-8-3432
[Patent Document 3]
Japanese Patent Laid-Open No. 10-60137
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a composition mainly composed of a glycolic acid polymer that has biodegradability and is excellent in moldability such as melt extrusion and injection molding, and is excellent in heat resistance and transparency. An object of the present invention is to provide a molded article mainly composed of a composition comprising a glycolic acid polymer.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventor has included a specific amount of boron nitride-based particles in a glycolic acid-based polymer having a relatively high melting point among biodegradable resins. The present inventors have found that a molded article having excellent biodegradability and excellent transparency can be produced.
That is, the present invention
[1] A composition comprising a glycolic acid polymer and boron nitride particles, wherein the content of the boron nitride particles is 0.001 part by weight or more and 0.3 part by weight with respect to 100 parts by weight of the glycolic acid polymer. Glycolic acid polymer composition, characterized in that it is less than parts,
[2] Differential scanning calorimetry (JIS K7121) in which a glycolic acid polymer was measured at a heating rate and a cooling rate of 10 ° C / min using a test piece obtained by heat-treating an amorphous sheet of the polymer at 150 ° C for 100 minutes. , And K7122), the melting point Tm (° C.) in the first temperature raising process, the heat of crystallization ΔHc (J / g) in the first cooling process, and the heat of fusion ΔHm (J in the second temperature raising process) / G) is a glycolic acid copolymer satisfying the following formulas (1) to (3), the glycolic acid polymer composition according to [1],
175 ≦ Tm ≦ 205 (1)
ΔHc = 0 (2)
0 ≦ ΔHm <20 (3)
[3] Glycolic acid polymer has logarithmic viscosity of 0.15 m 3 / Glycolic acid polymer composition according to [1] or [2], wherein
[4] The glycolic acid polymer composition as described in any one of [1] to [3], wherein the average particle size of the boron nitride particles is 0.03 μm or more and 5 μm or less,
[5] A molded body mainly composed of a composition comprising a glycolic acid-based polymer and boron nitride-based particles, wherein the content of the boron nitride-based particles is 0.001 weight per 100 parts by weight of the glycolic acid-based polymer. More than 0.3 parts by weight and less than 0.3 parts by weight of a glycolic acid polymer molded body,
[6] Differential scanning calorimetry (JIS K7121) in which the glycolic acid polymer was measured at a heating rate and a cooling rate of 10 ° C / min using a test piece obtained by heat-treating an amorphous sheet of the polymer at 150 ° C for 100 minutes. , And K7122), the melting point Tm (° C.) in the first temperature raising process, the heat of crystallization ΔHc (J / g) in the first cooling process, and the heat of fusion ΔHm (J in the second temperature raising process) / G) is a glycolic acid copolymer satisfying the following formulas (1) to (3), a molded article of glycolic acid polymer according to [5],
175 ≦ Tm ≦ 205 (1)
ΔHc = 0 (2)
0 ≦ ΔHm <20 (3)
[7] The logarithmic viscosity number of the glycolic acid polymer is 0.15 m 3 The molded article of glycolic acid polymer according to [6] or [7], wherein the average particle diameter of boron nitride particles is 0.03 μm or more and 5 μm or less. A molded product of the glycolic acid polymer according to any one of [5] to [7],
It is.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the glycolic acid polymer composition and molded article of the present invention will be described in detail. The glycolic acid polymer composition of the present invention and the molded body mainly composed of the composition include a specific amount of boron nitride particles in a glycolic acid polymer having a relatively high melting point among biodegradable resins. There is a special feature.
The lactic acid-based polymer described as a particularly preferable raw material in Patent Document 1 and Patent Document 2 described in the column of conventional technology is derived from lactic acid in which the repeating unit constituting the polymer has an asymmetric carbon, Although it is generally known that the melting point of the polymer varies significantly depending on the optical purity, even in the case of a homopolymer having an optical purity of 100%, the melting point is about 175 ° C. (Hidehito Tsuji, Yoshito Tsuji, “Polylactic acid— For medical treatment / preparation / environment- ”, 1st edition, Polymer publication society, September 20, 1997, p.39, see FIG. 2-27). On the other hand, since the melting point of the homopolymer of the glycolic acid polymer is about 225 ° C. (see the same book, p. 45), it is possible to obtain a molded body having more excellent heat resistance.
[0013]
The glycolic acid polymer used as a raw material of the composition of the present invention refers to a polymer whose main repeating unit is a repeating unit derived from glycolic acid, and glycolide (1) which is a cyclic dimer of glycolic acid as a monomer. , 4-dioxa-2,5-dione), or direct dehydration polycondensation using glycolic acid, for example, polyalcoholation while dealcoholizing with glycolic acid esters such as methyl glycolate. A polymer obtained by condensation or the like, which is a homopolymer of these monomers or a copolymer having these monomers as main monomers. The method for producing the polymer is performed by a conventionally known general method. For example, in order to obtain a glycolic acid polymer by ring-opening polymerization using glycolide of glycolic acid as a main monomer, the method of Gilding et al. (Polymer, vol. 20, December (1979)) and the like, but are not limited thereto.
[0014]
Examples of monomers that can be copolymerized with glycolic acid, glycolide, and glycolic acid esters, which are the main monomers used in copolymerization, include lactic acid, 2-hydroxyisobutyric acid, and 2-hydroxy-2. , 2-dialkylacetic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 4-hydroxybutanoic acid, other known aliphatic hydroxycarboxylic acids, ester derivatives of these aliphatic hydroxycarboxylic acids, these fats The same or different cyclic dimers of aromatic hydroxycarboxylic acids, and β-butyrolactone, β-propiolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone Lactones such as It is. In addition to these, an equimolar amount of a polyhydric alcohol and a polycarboxylic acid may be combined and copolymerized with the main monomer. Examples of the polyhydric alcohol include ethylene glycol. , Propylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexane Diols, 1,3-cyclohexanol, 1,4-cyclohexanol, 1,3-cyclohexanedimethanol, aliphatic diols such as 1,4-cyclohexanedimethanol, or a combination of these aliphatic diols, for example, Examples include diethylene glycol, triethylene glycol, and tetraethylene glycol. Examples of the polyvalent carboxylic acids include malonic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, pimelic acid, peric acid, azelaic acid, sebacic acid, 1,3-cyclopentanedicarboxylic acid, 1 , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid and other aliphatic dicarboxylic acids, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and other aromatics Examples thereof include dicarboxylic acids, ester derivatives of these aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and anhydrides of these aliphatic dicarboxylic acids.
[0015]
Further, when the monomer that can be copolymerized with the main monomer is an optically active substance, it may be either L-form or D-form, or a mixture of D and L-forms. The composition may be any mixture composition, the copolymerization ratio of D, L-forms may be any copolymer, or meso form.
When the above main monomers of glycolic acid, glycolide, and glycolic acid esters are copolymerized with these copolymerizable monomers, or these copolymerizable monomers are combined in a multicomponent combination. In the case of polymerization, the arrangement is not particularly limited, and any of random copolymer, alternating copolymer, block copolymer, graft copolymer, etc. may be used, but the standard of biodegradable plastic, For example, it shall conform to the standards defined by the Biodegradable Plastics Research Society in Japan, ASTM D-6400 in the United States, DIN V-54900 in Germany, and the like.
[0016]
In the present invention, among glycolic acid polymers used as raw materials for the composition of the present invention exemplified above, a glycolic acid copolymer having a melting point and crystallinity within a specific range is used. Is preferred. The molding material mainly composed of the composition using the glycolic acid copolymer exhibits better moldability, and the molding obtained from the molding material has both excellent heat resistance and excellent transparency at the same time. Is possible. That is, when molding the molding material, it can be melt-molded under conditions where thermal degradation does not easily occur, and has excellent moldability that does not cause a significant change in melt viscosity due to a temperature change, and a molded body made of a lactic acid polymer. Thus, excellent heat resistance of 170 ° C. or higher, which was impossible, and excellent transparency of the molded article obtained without the complicated quenching operation required when the crystallinity is very high. Furthermore, even when the obtained molded product is stored for a long period of time, the transparency can be maintained at a high level.
[0017]
A preferred glycolic acid polymer used in the present invention is a glycolic acid copolymer having a melting point and crystallinity within a specific range, and a test piece obtained by heat-treating an amorphous sheet of the copolymer at 150 ° C. for 100 minutes. In the differential scanning calorimetry (based on JIS K7121 and K7122) measured at a heating rate and a cooling rate of 10 ° C./min, the melting point Tm (° C.) in the first heating process and the first cooling process The heat of crystallization ΔHc (J / g) and the heat of fusion ΔHm (J / g) in the second temperature raising process satisfy the following formulas (1) to (3).
175 ≦ Tm ≦ 205 (1)
ΔHc = 0 (2)
0 ≦ ΔHm <20 (3)
[0018]
The preferred glycolic acid-based polymer has a heating and cooling rate of 10 ° C./min using a crystallized product obtained by heating an amorphous sheet of the polymer for 100 minutes in a hot air circulating thermostat set at 150 ° C. In the differential scanning calorimetry (DSC, based on JISK7121) measured under the conditions, the melting point Tm in the first temperature rising process is in the range of 175 ° C. or higher and 205 ° C. or lower. When the value of Tm is 175 ° C. or higher, a molded article mainly composed of the glycolic acid polymer composition has sufficient heat resistance. On the other hand, if the value of Tm is 205 ° C. or less, the difference between the processing temperature during melt molding and the decomposition temperature of the polymer becomes wide, and the moldability becomes excellent. A more preferred glycolic acid polymer has a Tm in the range of 185 ° C. or more and 200 ° C. or less, and can have more excellent heat resistance and moldability. In the differential operation calorimetry, when there are a plurality of endothermic peaks due to crystal melting, the highest endothermic peak temperature is defined as the melting point Tm.
[0019]
The crystallinity of the polymer as used in the present invention refers to the ease of crystallization of the polymer, and is expressed using the crystallization speed and the crystallinity as an index. The crystallization speed is the speed when irreversibly transitioning from the supercooled melt to the crystalline state. As a guideline, the crystallization temperature is measured during the constant cooling process in thermal analysis. It is said that the higher the speed, the higher the crystallization temperature (see Japan Analytical Chemistry Society, New Edition Polymer Analysis Handbook, p.339, Kinokuniya (1995)).
[0020]
On the other hand, the crystallinity is defined as the weight fraction of the crystal region in the polymer solid, and is measured by, for example, thermal analysis. In the thermal analysis method, the ratio of the measured melting heat ΔHm of the test piece to the theoretical melting heat ΔHf is generally obtained from the crystallinity Xc (%) = ΔHm / ΔHf × 100 (Edited by Japan Analytical Society, New Edition Polymer Analysis Handbook) , P.339, Kinokuniya (1995)). In this equation, ΔHm is a value measured by differential scanning calorimetry (DSC; conforming to JIS K7122), and ΔHf is a value described in, for example, POLYMER HANDBOOK (JOHN WILEY & SONS) in the case of a homopolymer. . However, in the case of a copolymer, ΔHf often has no literature value because of a wide variety of copolymer components and component ratios. In the above formula for obtaining the crystallinity Xc, the larger the measured melting heat ΔHm of the test piece means that the crystallinity becomes higher. Therefore, in the present invention, the crystallinity is judged by the value of ΔHm. .
[0021]
The preferred glycolic acid-based polymer has a heating and cooling rate of 10 ° C./min using a crystallized product obtained by heating an amorphous sheet of the polymer for 100 minutes in a hot air circulating thermostat set at 150 ° C. In differential scanning calorimetry (DSC, JISK7122) measured under the conditions, the heat of crystallization ΔHc in the first cooling process is 0 J / g, and the heat of fusion ΔHm in the second temperature raising process is 0 J / g or more and 20 J / g Within the range of less than.
When a crystallization peak does not appear in the constant cooling process in differential scanning calorimetry (DSC) (crystallization heat ΔHc = 0 J / g), the crystallinity of the test piece is amorphous and does not crystallize at all. Alternatively, since the crystallization rate is slow, there are two possible cases where crystallization does not occur under the DSC measurement conditions (cooling rate 10 ° C./min). As described above, the preferred glycolic acid polymer is amorphous and has a melting point Tm of 175 ° C. or higher and 205 ° C. or lower in the first temperature rising process in DSC. There is a crystallization rate at which crystallization does not occur under DSC measurement conditions (cooling rate 10 ° C./min). When the ΔHc is 0 J / g, a special amorphous process such as a rapid cooling operation is not required when melt molding using a molding material mainly composed of the polymer composition.
[0022]
On the other hand, the ΔHm value of the preferred glycolic acid polymer is 0 J / g, as in the case of the above-described crystallization heat ΔHc, the polymer of the present invention has a melting point during the first temperature rising process in DSC. Unlike the case where the Tm is 175 ° C. or higher and 205 ° C. or lower and is not amorphous and does not crystallize at all, the crystallization rate is such that crystallization does not occur under the DSC measurement conditions (temperature increase rate 10 ° C./min). This means that the molded product mainly composed of the polymer composition can maintain a high level of transparency even when stored for a long period of time. When the value of ΔHm is less than 20 J / g, since the crystallinity of the polymer is relatively low, a molded product mainly composed of the polymer composition has high transparency when stored for a long period of time. Can be maintained at a level. A more preferable glycolic acid-based polymer has a value of ΔHm in the range of 0 J / g or more and 18 J / g or less in order to maintain excellent transparency when the obtained molded product is stored for a long time.
[0023]
A preferred glycolic acid polymer used in the present invention is, specifically, a copolymer obtained by ring-opening polymerization using a monomer other than glycolide and glycolide, and as a monomer other than glycolide Is at least one selected from cyclic dimers of aliphatic hydroxycarboxylic acids and lactones. Alternatively, a copolymer obtained by direct dehydration polycondensation using monomers other than glycolic acid and glycolic acid, wherein the monomer other than glycolic acid is at least one kind from aliphatic hydroxycarboxylic acids such as lactic acid To be elected. From the viewpoint of easily obtaining a copolymer having a higher molecular weight, a copolymer obtained by ring-opening polymerization using glycolide and lactide (3,6-dimethyl-1,4-dioxa-2,5-dione) is particularly preferable. preferable. Lactide is an optically active substance and may be either L-form or D-form, or a D, L-form mixture or meso form. Further, it may be a mixture of glycolide-L-lactide copolymer and glycolide-D-lactide copolymer. For example, when the monomer unit is a copolymer composed of glycolide and lactide, it is obtained by ring-opening polymerization in which the glycolide component ratio in the copolymer is 78 to 90 mol% and the lactide component ratio is 22 to 10 mol%. And the resulting glycolic acid-lactic acid copolymer.
[0024]
The molecular weight of the glycolic acid polymer used in the present invention depends on temperature changes during molding such as melt extrusion and injection molding, and the molded body mainly composed of the polymer composition has sufficient mechanical properties. In order to have excellent moldability without significant melt viscosity change, the logarithmic viscosity number is at least 0.15 m. 3 / Kg or more is preferable, 0.18 m 3 / Kg or more is more preferable. On the other hand, the upper limit of the molecular weight of the polymer is 0.80 m in terms of logarithmic viscosity for easier molding into a molded product. 3 / Kg or less is preferable, but it is not particularly limited as long as the melt fluidity is adjusted by adding a plasticizer or the like. The logarithmic viscosity number [η] is generally a value obtained by the following equation (4), and can be approximated to an intrinsic viscosity used as an index of a molecular weight of a polymer in a dilute solution having a concentration of 0.2% or less (Chemical Dictionary Dictionary Reprint) Edition, p.746, Kyoritsu Shuppan (1963), and New Edition Polymer Analysis Handbook, p.120, Kinokuniya (1995)).
[Η] = {ln (t / to)} / c (4)
(Where, t is the flow time (second) of the polymer solution measured with a capillary viscometer, to is the flow time (second) of the solvent measured with a capillary viscometer, and c is the concentration of the solute polymer ( kg / m 3 ). )
[0025]
In addition, the molecular weight of the glycolic acid polymer used in the present invention is 5 × 10 in terms of weight average molecular weight. 4 Or more, more preferably 1 × 10 5 That's it. The upper limit of the molecular weight is not particularly limited as long as the melt fluidity is adjusted by adding a plasticizer or the like. 5 It is desirable to keep it below.
Transparent crystal nucleating agents include inorganic particles such as metal oxides, inorganic metal salts and clay minerals, incompatible organic compounds such as fatty acid amides, fatty acid metal salts and phosphate metal salts, and sorbitol skeletons. Various types of compounds such as compatible organic compounds are known, but the transparency of glycolic acid polymers can be remarkably enhanced only by boron nitride particles among these transparent crystal nucleating agents. The inventor found.
[0026]
The boron nitride-based particles used as a raw material for the composition of the present invention refer to inorganic particles having a boron nitride component ratio of 50 wt% or more. A preferable component ratio of boron nitride is 95 wt% or more. However, powder particles obtained by mixing inorganic particles other than boron nitride with inorganic particles having a high component ratio of boron nitride for dilution or other purposes may be used. The particle shape is not particularly limited, such as a spherical shape, a needle shape, a disk shape, or a column shape. Examples of inorganic particles other than boron nitride include metal oxides such as alumina, silica and titanium oxide, inorganic metal salts such as calcium carbonate and calcium phosphate, and inorganic particles of clay minerals such as talc, mica and kaolin.
[0027]
The content of the boron nitride-based particles constituting the composition of the present invention needs to be 0.001 part by weight or more and less than 0.3 part by weight with respect to 100 parts by weight of the glycolic acid polymer. If the content is 0.001 part by weight or more, a molded product obtained using the composition acts effectively as a transparent crystal nucleating agent even when a highly crystalline glycolic acid polymer is used, Transparency is excellent. Moreover, if this content is less than 0.3 weight part, the molded article obtained will have little light scattering by a boron nitride type particle, and will become excellent in transparency.
[0028]
The average particle diameter of the boron nitride-based particles is preferably 0.03 μm or more and 5 μm or less as measured by a laser diffraction / scattering method. The average particle diameter is preferably 0.03 μm or more from the viewpoint of powder powder production and handleability. On the other hand, the average particle size is preferably 5 μm or less from the viewpoint of the amount of light scattering by the boron nitride-based particles and the transparency of the obtained molded body.
The average particle diameter is preferably 0.1 μm or more and 1 μm or less in order to manufacture and handle powder powder more easily and to suppress light scattering by boron nitride-based particles. When the average particle size is 1 μm or less, the effect of addition as a clearing crystal nucleating agent is particularly remarkable even when a highly crystalline glycolic acid polymer is used, and the resulting molded article has very high transparency. It will be excellent. Furthermore, in a film-like molded body having a thickness of 20 μm or less, the occurrence of surface roughness and the like are suppressed, and the transparency is extremely high.
[0029]
The molded product of the glycolic acid polymer of the present invention is a molded product mainly composed of the glycolic acid polymer composition described above, and may contain a plasticizer depending on the use of the molded product. When the glycolic acid polymer is more than about 95% by weight and the plasticizer is less than about 5% by weight, the molded product can be used for hard applications, and the glycolic acid polymer is about 95 to 85% by weight. When the plasticizer is about 5 to 15% by weight, the molded product can be used for semi-rigid applications, when the glycolic acid polymer is about 85 to 60% by weight and the plasticizer is about 15 to 40% by weight. Can be used in soft applications while maintaining a relatively excellent strength. In addition, by adding a plasticizer to a composition comprising a glycolic acid polymer and boron nitride particles, the crystallization rate of the composition can be further increased.
[0030]
Specific examples of the plasticizer used in the present invention include, for example, phthalates such as dioctyl phthalate and diethyl phthalate, fatty acid esters such as ethyl laurate, butyl oleate, and octyl linoleate, dioctyl adipate and dibutyl sebacate. Aliphatic dibasic esters such as acetyl citrate tributyl and acetyl citrate triethyl, glycerin fatty acid esters such as glycerol diacetate laurate and glycerol triacetate, diglycerol tetraacetate and tetra Polyglycerol fatty acid esters such as glycerol hexaacetate, phosphate esters such as dioctyl phosphate, modified vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and polybutylene sebacate Riesuteru based plasticizer and the like, one or two or more, are selected from these. Glycerin fatty acid esters and aliphatic tribasic acid esters are desirable from the viewpoint of safety and health, and solubility parameter values (R. F. Fedors, Poly. Eng. Sci.) From the viewpoint of compatibility with glycolic acid polymers. , Vol.14, No.2, p.152 (1974)) is 10 (cal / cm 3 ) 0.5 Particularly preferred are glycerol triacetate, diglycerol tetraacetate, and triethyl acetylcitrate. Since these do not have a hydroxyl group, they are less likely to cause a transesterification reaction between the polymer and the plasticizer.
[0031]
The composition of the glycolic acid polymer of the present invention may contain additives other than those described above, if necessary, such as a lubricant, an antistatic agent, an antifogging agent, an antioxidant, and a heat stabilizer. , A light stabilizer, an ultraviolet absorber, a colorant, a flame retardant, and the like may be appropriately contained. Examples of the antioxidant used include phenol, phenyl acrylate, phosphorus, sulfur, etc., and one or two or more of these are selected, and the amount added is less than 10% by weight in the composition. Can be made.
[0032]
The molded product of the glycolic acid polymer of the present invention is mainly composed of a glycolic acid polymer composition comprising a glycolic acid polymer and boron nitride particles, and the glycolic acid polymer as a raw material thereof. Is contained in an amount of 50% by weight or more. You may mix other biodegradable resin within the range of 50 weight% or less including content of the boron nitride type particle which is an essential component. Examples of biodegradable resins that can be mixed are exemplified as monomers that can be copolymerized with the main monomers of glycolic acid, glycolide, and glycolic acid esters described above, for example, aliphatic hydroxycarboxylic acids such as lactic acid. Polycondensates, ring-opening polymers of lactones such as lactide (3,6-dimethyl-1,4-dioxa-2,5-dione) and ε-caprolactone, polyhydric alcohols such as ethylene glycol and adipic acid, Aliphatic polyesters such as polycondensates of polyvalent carboxylic acids, other natural polymers such as starch and cellulose, polyamino acids such as polyaspartic acid, cellulose esters such as cellulose acetate, aliphatic polyesters Polyethers such as carbonates, polyvinyl alcohols, polyethylene oxide, low molecular weight polymers Ethylene, etc. polymalic acid. Moreover, as long as it does not inhibit the biodegradability of the composition and the molded article to be obtained, for example, polyolefins, aromatic polyesters, polyamides, ethylene-vinyl alcohol copolymers, petroleum resins and terpenes. Series resins, hydrogenated products thereof, and other known thermoplastic resins may be mixed.
[0033]
The glycolic acid-based polymer molding material of the present invention contains the above-described plasticizer, other additives, and other thermoplastic resins as necessary in the glycolic acid-based polymer composition of the present invention. Obtained, glycolic acid-based polymer, boron nitride-based particles, plasticizer, other additives, and other thermoplastic resins as required by application, single or twin screw extruder, Banbury mixer It is desirable to produce a molding material by melt mixing using a mixing roll, a kneader or the like.
[0034]
The molded product referred to in the present invention is, for example, a film-like or sheet-like molded product produced by a melt extrusion method, a calender method, a melt press molding method, and the like. Examples include vacuum forming such as a forming method, pressure forming, male and female die forming, and the like. In the present invention, the distinction between a film and a sheet simply uses different names depending on the difference in thickness. Usually, a thickness of less than 200 μm is referred to as a film-shaped molded body, and a thickness of 0.2 mm or more is referred to as a sheet-shaped molded body. Yes. In addition, an injection molded body, a blow molded body in which a gas is blown while heating a preform obtained by an injection molding method, and a foam molded body are also included.
[0035]
The method for producing the molded body of the present invention is not particularly limited, and is performed by a conventionally known general method. Specifically, for example, in the melt extrusion method, a molding material is previously provided with a moisture content of 200 wtppm. It is dried to the following, then supplied to the extruder, extruded from a die connected to the tip of the extruder while being heated and melted, and then cooled and solidified to produce a sheet-like or tube-like melt-formed product. be able to. In the melt press molding method, the above-described molding material is dried in advance until the moisture content becomes 200 wtppm or less, then supplied to the mold, heated and melted under normal pressure or reduced pressure atmosphere, and then cooled. By solidifying, it can be produced as a sheet-like melt-formed product.
[0036]
The stretched molded body is a molded body obtained by stretching a sheet-shaped or tube-shaped molded body in at least a uniaxial direction. This stretching method is not particularly limited and is performed by a conventionally known general method. Specifically, for example, in the case of uniaxial stretching, melt extrusion is performed from a T die by a melt extrusion method, and cooling is performed by a cast roll. A method of producing a sheet-like molded product by longitudinally uniaxially stretching in the flow direction of the sheet with a roll stretching machine, transversely uniaxially stretching with a tenter while suppressing the longitudinal stretching ratio as much as possible, or in the case of biaxial stretching, melt extrusion The sheet-shaped product melt-extruded from the T-die by the method and cooled by the cast roll is first stretched longitudinally with a roll stretcher and then stretched transversely with a tenter, or simultaneously biaxially stretched in both longitudinal and transverse directions with a tenter There are a method of manufacturing by stretching, a method of manufacturing a tubular molded product that is melt-extruded from a circular die by a melt extrusion method and cooled by a water-cooling ring, etc. Moreover, there exists the method of extending | stretching the sheet-like molding obtained by the melt-pressing method uniaxially or biaxially with a batch type extending | stretching apparatus. In these stretching operations, the stretching temperature ranges from the glass transition temperature of the molded article to be stretched to (cold crystallization temperature + 30 ° C.), the stretching speed ranges from 10 to 200,000% / min, and the stretching ratio is at least uniaxial. It is desirable to carry out under the stretching conditions appropriately selected from the range of 2 to 50 times in area magnification.
[0037]
The stretched molded product thus obtained is, for example, a soft-to-medium stretched molded product with a relatively large amount of plasticizer and a tensile elastic modulus of less than 4.0 GPa. Suitable for packaging materials such as packaging, casing and household wrap. When used for shrink wrapping such as packaging while heat shrinking, it may be used as it is, or heat treatment or aging treatment may be performed for the purpose of adjusting the heat shrinkage. Moreover, when using for the packaging material by which the heat resistance heated by a microwave oven etc. is requested | required, it is desirable to heat-process in order to prevent the deformation | transformation by the heat | fever from the heat_generation | fever and the fusion | melting perforation. Furthermore, it is desirable to perform an aging treatment or the like for the purpose of improving dimensional stability over time and physical property stability. The heat treatment is preferably performed at a temperature appropriately selected from a temperature range of 60 to 160 ° C. for 1 second to 3 hours, and the aging treatment is usually performed at a temperature appropriately selected from a temperature range of 25 to 60 ° C. for 3 hours. It is desirable to be performed for about 10 days.
[0038]
The transparency of the molded body is 10% or less when measured in accordance with JIS K7105 using the molded body to be used as a sample when used in applications requiring transparency with excellent visibility of contents. Desirably, it is desirably 5% or less.
The obtained molded product may be used as it is as a packaging material for household wraps, etc., but various surface treatments such as coating and corona treatment are carried out for the purpose of improving antistatic agents and antifogging properties as necessary. For the purpose of improving sealability, moisture resistance, gas barrier properties, printability, etc., lamination processing, coating processing, or vacuum deposition such as aluminum may be performed. Furthermore, you may shape | mold and use it according to a use by the secondary process. Examples of secondary processed products include seal processed products that are used for packaging materials such as pillow packaging and weld-type casing packaging in the case of stretched films, and plug assist molding methods and air cushion molding methods in the case of stretched sheets. There are containers such as trays and cups, blister packaging sheets, etc. by performing vacuum forming processing, pressure forming processing and male / female forming processing.
[0039]
Moreover, you may use for the use which mixes a coloring agent with a shaping | molding material suitably, or performs printing on the extending | stretching molded body itself, and laminates it on another sheet | seat, a foamed body, etc. In such applications, the aim is to increase the design value of containers such as trays and cups obtained by molding other laminated sheets and foams, and to increase the commercial value through display effects. The excellent transparency of the glass has the advantage that the gloss of the container surface and the design printing become clear.
In addition, the molded body obtained by the blow molding method is suitable for beverages or bottles for life hygiene products such as detergents and shampoos.
[0040]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, these specific examples do not limit the scope of the present invention. The physical property measurement method and evaluation method are shown below. Unless otherwise specified, samples are stored for 1 to 2 days in a temperature (23 ± 2) ° C. and relative humidity (50 ± 5)% atmosphere after preparation of the measurement sample. The product was subjected to physical property measurement and evaluation.
[0041]
[Physical property measurement method]
(1) Logarithmic viscosity number
Pure solvent 1,1,1,3,3,3-hexafluoro-2-propanol (hereinafter abbreviated as HFIP) and glycolic acid polymer concentration c is 1.0 kg / m. 3 As a sample, the HFIP solution dissolved so that Using a 0a Ubbelohde capillary viscometer (capillary automatic viscometer SS-170-L1 manufactured by Shibayama Kagaku Seisakusho Co., Ltd.), the time for flowing through the capillary at 20 ° C. is measured, and the logarithmic viscosity number [ η] was determined.
[Η] = {ln (t / to)} / c (4)
(Where, t is the flow time (seconds) of the polymer solution measured with a capillary viscometer, to is the flow time (seconds) of the solvent measured with a capillary viscometer, and c is the concentration of the solute polymer (kg / m 3 ). )
[0042]
(2) Differential scanning calorimetry (DSC)
The melting point Tm, the heat of crystallization ΔHc, and the heat of fusion ΔHm were measured according to JIS K7121 and K7122 using a DSC6200 manufactured by Seiko Denshi Kogyo Co., Ltd. as a measuring device. The temperature of the sample is about 20 ° C. higher than that at the end of the melting peak when the differential scanning calorimetry of the polymer piece used as a raw material is directly performed using a heating press machine (compression molding machine SA-301 manufactured by Tester Sangyo Co., Ltd.). The polymer was pressurized for about 12 MPa for 5 minutes, then cooled to obtain an amorphous sheet having a thickness of about 200 μm, and the amorphous sheet was heated and crystallized for 100 minutes in a hot air circulating thermostat set at 150 ° C. Made. The sample amount was about 7.5 mg. First, the sample was held at −20 ° C. for 3 minutes, then heated to 260 ° C. at a heating rate of 10 ° C./min, and the melting point Tm in the first temperature rising process was measured. After maintaining at this temperature for 1 minute, it was cooled to −20 ° C. at a cooling rate of 10 ° C./min, and the crystallization heat ΔHc in the first cooling process was measured. Next, after maintaining at −20 ° C. for 1 minute, the mixture was again heated to 260 ° C. at a heating rate of 10 ° C./min, and the heat of fusion ΔHm in the second temperature rising process was measured. In addition, the calibration of temperature and heat quantity was performed using indium as a standard substance. The amorphous sheet in the present invention is a sheet prepared by the above procedure as a sample, a diffraction intensity curve is measured by a wide angle X-ray diffraction method, and the diffraction intensity curve does not have a diffraction peak due to the crystal. Point to.
[0043]
(3) Average particle size
The average particle size is measured by using a dispersion of 100 ppm in distilled water as a dispersion medium as a sample and using a laser diffraction particle size distribution measuring device (SALD-2100 manufactured by Shimadzu Corporation) as a measuring device. Obtained as the diameter. In addition, you may add suitably dispersing agents, such as magnesium stearate, to a dispersion medium as needed.
[0044]
[Evaluation methods]
(1) Heat resistance
The heat resistance was evaluated by performing a load-resistant cutting test using a sheet-like molded body having a thickness of 100 μm as a sample. In the load-resistant cutting test, with a load of 100 g applied to a strip-shaped test piece, the test piece is heated for 1 hour in a hot air circulation thermostat set at a constant temperature to check whether the test piece is cut or not. Was measured. The temperature of the sample is about 20 ° C. higher than the end of the melting peak when a differential scanning calorimetry is performed on a small piece of the composition used as a material as it is using a heating press machine (compression molding machine SA-301 manufactured by Tester Sangyo Co., Ltd.). The composition was pressurized for about 12 MPa for 5 minutes, then cooled to obtain an amorphous sheet having a thickness of about 100 μm, and the amorphous sheet was heat-treated in a hot air circulating thermostat set at 140 ° C. for 1 minute. Produced. Samples were cut into strips having a length of 140 mm and a width of 30 mm. A fixing jig and a load jig were respectively attached to the upper and lower ends 20 mm each of the strip-shaped test piece, and heated for 1 hour in a hot-air circulating thermostat set at a constant temperature to examine whether or not the test piece was cut. In the case where the strip-shaped test piece did not cut, the above procedure was repeated by increasing the set temperature by 5 ° C. with a new test piece. The measurement result of the maximum temperature at which the strip-shaped test piece was not cut was indicated by the mode value by performing this test five times for each sample.
[0045]
(2) Transparency
Transparency was evaluated by measuring haze using a sheet-like molded body having a thickness of 100 μm as a sample. The haze was measured according to JIS K7105 using a haze meter HR-100 manufactured by Murakami Color Research Laboratory Co., Ltd. as a measuring device. The sheet-like molded body produced by the above heat resistance evaluation method was cut into a square with a side of 50 mm, this was set in a holder, and the haze of the sample was measured. The measurement result of haze was measured by 5 samples and expressed as an average value.
[0046]
[Example 1]
[Purification of monomer]
1 kg of glycolide was dissolved in 3 kg of ethyl acetate at 75 ° C., and then allowed to stand at room temperature for 48 hours for precipitation. The precipitate collected by filtration was washed with about 3 kg of ethyl acetate at room temperature. After repeating this washing operation again, the washed product was placed in a vacuum dryer and vacuum dried at 60 ° C. for 24 hours. The dried product was decompressed to 6-7 mmHg under a nitrogen atmosphere, and 480 g of distilled and purified glycolide was obtained as a distillate at 133-134 ° C. by simple distillation.
1 kg of L-lactide was dissolved in 3 kg of toluene at 80 ° C. and then left to stand at room temperature for 48 hours to precipitate. The precipitate collected by filtration was washed with about 3 kg of toluene at room temperature. After repeating this washing operation again, the washed product was put in a vacuum dryer and vacuum dried at 60 ° C. for 24 hours to obtain 560 g of purified L-lactide.
[0047]
[Preparation of glycolic acid polymer]
430 g of glycolide and 270 g of lactide obtained by purification of the above monomer and 0.2 g of 2-ethylhexanoic acid tin and 0.05 g of lauryl alcohol as a catalyst were charged into a jacketed reactor whose inner surface was glass-lined, and dried nitrogen For about 1 hour at room temperature. Next, the temperature was raised to 130 ° C. while blowing dry nitrogen, and the mixture was stirred for 40 hours for polymerization. After completion of the polymerization operation, cooling water was passed through the jacket for cooling, and the bulk polymer taken out from the reactor was pulverized into fine particles of about 3 mm or less. This ground product was Soxhlet extracted with tetrahydrofuran for 60 hours, dissolved in 3 kg of hexafluoroisopropanol at 50 ° C., and then reprecipitated with 7 kg of methanol. This re-precipitate was vacuum-dried in a vacuum dryer set at 130 ° C. for 60 hours to obtain 550 g of a glycolic acid polymer. The obtained polymer is designated as resin symbol P1.
[0048]
Glycolic acid polymer P1 was prepared by dissolving 70 mg of the polymer in trifluoroacetic acid-D1 ml. 1 When the copolymerization component ratio was analyzed by H-NMR, the glycolic acid component ratio was 80 mol% and the lactic acid component ratio was 20 mol%. When the logarithmic viscosity number was measured according to the above-described physical property measuring method, the logarithmic viscosity number [η] of the polymer was 0.42 (m 3 / Kg). When differential scanning calorimetry was performed according to the above-described physical property measurement method, the melting point Tm of the polymer during the first heating process was 188 ° C., and the crystallization heat ΔHc during the first cooling process was 0 J / g, 2 The heat of fusion ΔHm in the second temperature raising process was 0 J / g.
[0049]
[Melt-mixing, production of sheet-like molded product, and evaluation]
Boron nitride-based particles having an average particle size of 0.8 μm with a boron nitride component ratio of 98% (DENKABORON NITRIDE SP-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) are designated as nucleating agent symbol N1. 0.17 g of the particles N1 were weighed and dried in a vacuum dryer set at 40 ° C. for about 48 hours until the water content was 200 ppm or less. 170 g of the glycolic acid polymer P1 obtained in the preparation of the above polymer was weighed and left in a hot air circulating thermostat set at 130 ° C. for about 2 hours until the water content was 200 ppm or less, followed by a drying operation. went. The dried glycolic acid polymer P1 and boron nitride particles N1 are supplied to a kneader set at 220 ° C. (desk type kneader PBV-0.3 type manufactured by Irie Trading Co., Ltd.) and dried nitrogen at a flow rate of 10 L / min. The speed change handle scale was set to 7 (rotor average rotation speed 38 rpm, average shear rate about 100 / second) while blowing, and melt mixed for 15 minutes. Thereafter, the molten mixture was immediately taken out from the kneader and solidified by cooling with a cooling press to obtain a plate-like glycolic acid polymer composition.
[0050]
The plate-shaped material was left to dry for about 24 hours in a vacuum dryer set at 40 ° C. until the water content was 200 ppm or less, and then heat-treated in accordance with the heat resistance evaluation method described above. The body was made. When the obtained molded body was used as a sample and the heat resistance and transparency were evaluated as described above, the maximum temperature at which the test piece was not cut was 180 ° C. and haze was 2%.
[0051]
[Example 2]
Next, boron nitride particles having an average particle size of 3.5 μm having a boron nitride component ratio of 99% (DENKABORON NITRIDE GP manufactured by Denki Kagaku Kogyo Co., Ltd.) are used as the nucleating agent symbol N2, and boron nitride particles N2 are used. The same experiment as in Example 1 was repeated, and the heat resistance and transparency were evaluated using the obtained sheet-like molded body as a sample. The maximum temperature at which the test piece was not cut was 180 ° C., haze Was 5% (Example 2).
[0052]
[Comparative Examples 1-3]
Sodium stearate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the nucleating agent symbol N3, and the same experiment as in Example 1 was repeated except that N3 (addition amount 0.85 g) was used instead of boron nitride-based particles. When the obtained sheet-like molded product was used as a sample and the heat resistance and transparency were evaluated, the maximum temperature at which the test piece was not cut was 130 ° C. and haze was 3%. The molded body was remarkably discolored to brown, and N3 decomposed the glycolic acid polymer (Comparative Example 1).
[0053]
The same experiment as in Example 1 except that m-xylylene bis-stearic acid amide (Nihon Kasei Sripax PXS) is used as the nucleating agent symbol N4, and N4 (addition amount 0.85 g) is used instead of boron nitride particles. The above-mentioned evaluation of heat resistance and transparency was performed using the obtained sheet-like molded product as a sample. The maximum temperature at which the test piece was not cut was 120 ° C. and the haze was 20%. The molded product was extremely cloudy, and N4 was extremely poor in compatibility with the glycolic acid polymer (Comparative Example 2).
[0054]
The same experiment as in Example 1 was repeated except that the amount of boron nitride-based particles N1 added was 0.85 g, and the above-described heat resistance and transparency were evaluated using the obtained sheet-like molded body as a sample. However, the maximum temperature at which the test piece was not cut was 180 ° C. and haze was 47% (Comparative Example 3).
Table 1 summarizes the evaluation results of Examples 1 to 2 and Comparative Examples 1 to 3. According to Table 1, in the glycolic acid polymer, the nucleating agent appears only when boron nitride particles are used as the transparent crystal nucleating agent, and the heat resistance and transparency of the obtained molded product are remarkably improved. it can. Furthermore, as the average particle size of the boron nitride particles is smaller, light scattering is suppressed and the transparency is remarkably improved. Note that the transparency of the boron nitride particles deteriorated when added in a large amount.
[0055]
[Table 1]
Examples 3 to 5 and Comparative Example 4
The same experiment as in Example 1 was repeated except that 0.1 g of lauryl alcohol and 15 hours of polymerization time were used in the preparation of the glycolic acid polymer, and the resulting glycolic acid polymer was designated as resin symbol P2. . The polymer P2 has a copolymer component ratio of glycolic acid component ratio of 80 mol% and a lactic acid component ratio of 20 mol%, and a logarithmic viscosity number [η] of 0.17 (m 3 / Kg), the differential scanning calorimetry showed a melting point Tm of 189 ° C., a crystallization heat ΔHc of 0 J / g, and a heat of fusion ΔHm of 0 J / g. The same experiment as in Example 1 was repeated except that the polymer P2 was used, and the above-described evaluation of heat resistance and transparency was performed using the obtained sheet-like molded body as a sample. The temperature was 175 ° C. and the haze was 2% (Example 3).
[0057]
In the preparation of glycolic acid polymer, the same experiment as in Example 1 was repeated except that 700 g of glycolide, no lactide was used, and the polymerization time was 15 hours. The resulting glycolic acid polymer was designated as a resin symbol. Let P3. The polymer P3 is a homopolymer of a glycolic acid component and has a logarithmic viscosity number [η] of 0.25 (m 3 / Kg), the differential scanning calorimetry showed a melting point Tm of 223 ° C., a crystallization heat ΔHc of −70 J / g, and a heat of fusion ΔHm of 70 J / g. Using the polymer P3, the same experiment as in Example 1 was repeated except that the kneader set temperature was 250 ° C., and the above-described heat resistance and transparency were evaluated using the obtained sheet-like molded product as a sample. As a result, the maximum temperature at which the test piece did not cut was 215 ° C., and the haze was 6% (Example 4).
[0058]
The same experiment as in Example 1 was repeated except that 490 g of glycolide, 200 g of lactide, and 30 hours of polymerization time were prepared in the preparation of glycolic acid polymer, and the resulting glycolic acid polymer was designated as resin symbol P4. To do. The polymer P4 has a copolymer component ratio of 88 mol% of glycolic acid component and 12 mol% of lactic acid component, and a logarithmic viscosity number [η] of 0.39 (m 3 / Kg), a differential scanning calorimetry showed a melting point Tm of 202 ° C., a crystallization heat ΔHc of 0 J / g, and a heat of fusion ΔHm of 9 J / g. The same experiment as in Example 1 was repeated except that the polymer P4 was used and the kneader set temperature was set to 230 ° C., and the above-described heat resistance and transparency were evaluated using the obtained sheet-like molded product as a sample. As a result, the maximum temperature at which the test piece was not cut was 195 ° C. and haze was 2% (Example 5).
[0059]
The same experiment as in Example 1 was repeated except that polylactic acid (LACTY 9400, manufactured by Shimadzu Corporation) was made resin symbol P5, P5 was used instead of glycolic acid polymer, and the kneader set temperature was 200 ° C. When the obtained heat resistance and transparency were evaluated using the obtained sheet-like molded product as a sample, the maximum temperature at which the test piece was not cut was 165 ° C. and haze was 2%. Since the obtained sheet-like molded product was made of polylactic acid having a lower melting point, the heat resistance was inferior (Comparative Example 4).
[0060]
The evaluation results of Examples 1 and 3 to 5 and Comparative Example 4 are summarized in Table 2. According to Table 2, when the glycolic acid polymer has a large logarithmic viscosity number and a high molecular weight, the obtained sheet-like molded article has excellent mechanical properties, and the glycolic acid polymer has a melting point and crystallinity. When it is in a specific range, it has both heat resistance and transparency, and is excellent as a plastic product such as packaging material.
[0061]
[Table 2]
[Example 6]
A closed lid with a valve capable of supplying dry nitrogen by supplying glycolic acid polymer P1 (170 g) and boron nitride particles N1 (0.17 g) dried in the same manner as in Example 1 to a kneader set at 220 ° C. The inside of the kneader tank was sufficiently replaced with dry nitrogen while kneading. 20 g of triethyl acetylcitrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was weighed out as a plasticizer, and after aeration of dry nitrogen in the kneader tank was stopped, the plasticizer was injected from the valve using a syringe. In the same manner as in Example 1, the process from melt mixing for 15 minutes to the production operation of the sheet-like molded body was performed. When the obtained heat resistance and transparency were evaluated using the obtained sheet-like molded product as a sample, the maximum temperature at which the test piece was not cut was 180 ° C. and haze was 2% (Example 6).
[0063]
【The invention's effect】
According to the present invention, by incorporating boron nitride particles into a glycolic acid polymer having a relatively high melting point among biodegradable resins, a molding material composition having excellent moldability can be provided. By using the composition, it is biodegradable and has excellent heat resistance and transparency. Various materials such as packaging materials, agricultural materials, civil engineering and building materials, machinery and equipment parts, especially packaging materials It is possible to provide a molded article suitable for the above.
Claims (8)
１７５≦Ｔｍ≦２０５ （１）
ΔＨｃ＝０ （２）
０≦ΔＨｍ＜２０ （３）A differential scanning calorimetry (JIS K7121 and K7122) in which a glycolic acid polymer was measured at a heating rate and a cooling rate of 10 ° C / min using a test piece obtained by heat-treating an amorphous sheet of the polymer at 150 ° C for 100 minutes. The melting point Tm (° C.) in the first temperature raising process, the heat of crystallization ΔHc (J / g) in the first cooling process, and the heat of fusion ΔHm (J / g) in the second temperature raising process. The glycolic acid-based polymer composition according to claim 1, wherein the glycolic acid-based copolymer satisfies the following formulas (1) to (3).
175 ≦ Tm ≦ 205 (1)
ΔHc = 0 (2)
0 ≦ ΔHm <20 (3)
１７５≦Ｔｍ≦２０５ （１）
ΔＨｃ＝０ （２）
０≦ΔＨｍ＜２０ （３）A differential scanning calorimetry (JIS K7121 and K7122) in which a glycolic acid polymer was measured at a heating rate and a cooling rate of 10 ° C / min using a test piece obtained by heat-treating an amorphous sheet of the polymer at 150 ° C for 100 minutes. The melting point Tm (° C.) in the first temperature raising process, the heat of crystallization ΔHc (J / g) in the first cooling process, and the heat of fusion ΔHm (J / g) in the second temperature raising process. 6 is a glycolic acid copolymer satisfying the following formulas (1) to (3), the molded article of glycolic acid polymer according to claim 5.
175 ≦ Tm ≦ 205 (1)
ΔHc = 0 (2)
0 ≦ ΔHm <20 (3)
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