JP3647989B2 - Poly (γ-glutamic acid) salt complex and method for producing the same - Google Patents
Poly (γ-glutamic acid) salt complex and method for producing the same Download PDFInfo
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- JP3647989B2 JP3647989B2 JP24887896A JP24887896A JP3647989B2 JP 3647989 B2 JP3647989 B2 JP 3647989B2 JP 24887896 A JP24887896 A JP 24887896A JP 24887896 A JP24887896 A JP 24887896A JP 3647989 B2 JP3647989 B2 JP 3647989B2
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- 108700022290 poly(gamma-glutamic acid) Proteins 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 carboxy anion Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 150000001340 alkali metals Chemical group 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000012779 reinforcing material Substances 0.000 claims description 8
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 5
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 5
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 5
- 235000018553 tannin Nutrition 0.000 claims description 5
- 229920001864 tannin Polymers 0.000 claims description 5
- 239000001648 tannin Substances 0.000 claims description 5
- 229940045136 urea Drugs 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920002643 polyglutamic acid Polymers 0.000 description 49
- 238000000034 method Methods 0.000 description 13
- 229920001661 Chitosan Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000465 moulding Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 108010020346 Polyglutamic Acid Proteins 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000004108 freeze drying Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
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Landscapes
- Medicinal Preparation (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、機能性ポリマーの分野に属し、詳細には、ポリ（γ−グルタミン酸）をベースとする新規な複合材料とその製造方法に関する。
【０００２】
【従来の技術とその課題】
ポリグルタミン酸系ポリマーは、繊維、食品、化粧品、医薬、農業等の諸分野において機能性材料として期待されている。本発明者らは、既にグルタミン酸のγ位のカルボキシル基とα位のアミノ基がアミド結合により結合している化合物、ポリ（γ−グルタミン酸）（以下、γ−ＰＧＡと略記することがある）の高度重合体を微生物を用いて有利に製造する方法を開発し（特開平７−１３５９９１号）、また、２価以上の金属イオン（例えばアルカリ土類金属イオン、繊維金属イオン等）を添加することによって成形物（以下、γ−ＰＧＡ改質物と略記することがある）を得ることに成功している（特開平７−１３８３６４号）。
【０００３】
これらのγ−ＰＧＡ改質物は、従来のポリマーの生分解性を改良したものであるが、反面、吸湿性が高く、柔軟性がないという性質のため、例えば安定なフィルムや膜を形成することができず、このことが広範な用途開発の障害となっていた。
【０００４】
【問題点を解決するための手段】
本発明者らは、上述したようなγ−ＰＧＡ改質物における欠点をなくしたポリグルタミン酸系材料について研究を重ねた結果、特定構造のポリ（γ−グルタミン酸）の塩と、該塩と結合し得る第二の化合物とから構成され、吸湿性もなく柔軟で取扱いが容易であり安定な成形物を供し得る新しいタイプの複合材料の開発に成功した。
【０００５】
かくして、本発明は、下記の繰り返し単位（Ａ）を有するポリ（γ−グルタミン酸）塩と、該ポリ（γ−グルタミン酸）塩のカルボキシアニオンに水素結合可能な部位を有する化合物とから形成されるポリ（γ−グルタミン酸）塩複合体を提供するものである。
【０００６】
【化５】
このような本発明に従うポリ（γ−グルタミン酸）塩複合体において諸特性が向上する理由は完全には判らないが、次のように理解される。すなわち、従来のγ−ＰＧＡ系材料において吸湿性が高いという性質の原因の一つとして、γ−ＰＧＡを構成するグルタミン酸のγ位のカルボキシル基とα位のアミノ基の水素結合によるということが考えられるが、本発明の複合体においてはγ−グルタミン酸塩のカルボキシアニオン（ＣＯＯ- ）に第２の化合物が水素結合することによりそのような現象が回避または減少されるものと推測される。
【０００７】
【発明の実施の形態】
本発明の複合体は、ポリ（γ−グルタミン酸）を前記繰り返し単位（Ａ）を有する塩にしたものと、水素結合性化合物（カルボキシアニオンに水素結合可能な部位を有する化合物）とから形成される。
繰り返し単位（Ａ）におけるＸとしては、ナトリウム、カリウム、リチウムなどのアルカリ金属、マグネシウム、カルシウム、バリウムなどのアルカリ土類金属、およびアンモニウムが例示される。
【０００８】
より具体的には、繰り返し単位（Ａ）として、次のものが例示できるが、これらの例示は本発明を限定するものではない。
１．Ｘが、アルカリ金属である場合。
【化６】
【化７】
【化８】
なお、本発明のポリ（γ−グルタミン酸）塩においては、繰り返し単位（Ａ）が２種類以上含まれていてもよい。また、本発明におけるポリ（γ−グルタミン酸）塩は、通常、４００，０００〜４，４００，０００（ｇ／ｍｏｌ）の平均分子量を有するものである。分子量がこれより低いと所望の特性を有する複合体が得られず、他方、分子量があまり高いものは製造も困難であり実用的でない。
【００１０】
本発明のポリ（γ−グルタミン酸）塩複合体を形成するための水素結合可能な部位を有する化合物としては、水溶液または水性溶液中でポリ（γ−グルタミン酸）塩のカルボキシアニオン（ＣＯＯ- ）の少なくとも一部に水素結合を介して結合し得るものであれば、任意の化合物が使用可能である。そのような化合物として特に好ましいのは、下記の繰り返し単位（Ｂ）を有するキトサンアミンである。
【化９】
【００１１】
このようにすることによって、該キトサンアミンから成るポリカチオンと、ポリ（γ−グルタミン酸）塩から得られるポリアニオンのと間にポリマーイオンコンプレックスが形成される。この場合、繰り返し単位（Ａ）が繰り返し単位（Ｂ）に対して１０モル％以上、または繰り返し単位（Ｂ）が繰り返し単位（Ａ）に対して１０モル％以上になるようにする。繰り返し単位（Ａ）と繰り返し単位（Ｂ）のうち、いずれか一方が他方に比べて少な過ぎると充分なポリマーイオンコンプレックスが生成されないからである。
【００１２】
ポリマーイオンコンプレックスの生成の確認は、反応の追跡に当たり、赤外スペクトル（ＩＲ）を測定することによって行うことができる。すなわち、キトサンとγ−ＰＧＡに由来する１６００ｃｍ-1付近のピークに加えて、ポリマーイオンコンプレックスが生成すると１６３０ｃｍ-1付近に架橋結合の形成による特性吸収を有しているため、この特性吸収の出現よりポリマーイオンコンプレックスの生成が確認できる。
この態様は、バイオマスとして大量に存在するキトサンを利用できる点において有利である。
【００１３】
本発明の別の好ましい態様においては、水素結合可能な部位を有する化合物として、尿素、グアニジン塩酸塩、グアニジン硫酸塩、グアニジン硝酸塩、タンニンなどを用いることができる。特に好ましいのは、タンパク質の変性効果が大きいという理由から尿素である。これらの化合物の濃度は、ポリ（γ−グルタミン酸）塩に対して、モル比で０．１〜５、好ましくは０．１〜２とすることにより、ポリ（γ−グルタミン酸）塩のカルボキシアニオンに当該化合物が水素結合を介して結合した所望の複合体が得られる。
【００１４】
さらに、本発明の別の好ましい態様においては、尿素等の化合物とともに、繊維補強材（繊維質補強材）が添加される。繊維補強材としては、天然繊維、例えば絹、綿等が挙げられる。繊維補強材濃度は、通常０．１〜５ｗｔ％、好ましくは０．１〜２ｗｔ％である。このように繊維補強材を添加すると、吸湿性や強伸度に向上がみられるという利点がある。
【００１５】
本発明者は、以上のようなポリ（γ−グルタミン酸）塩複合体を簡便で大量に得ることができる方法を確立した。したがって、本発明は、別の視点として、ポリ（γ−グルタミン酸）塩複合体の製造方法を提供するものであり、本発明の方法は、ポリ（γ−グルタミン酸）を水または水と親水性溶媒の混合溶媒に溶解させた溶液にアルカリ金属、アルカリ土類金属またアンモニウムイオンの水溶性塩を添加することによって得られた前述の繰り返し単位（Ａ）を有するポリ（γ−グルタミン酸）塩の水性溶液に、該ポリ（γ−グルタミン酸）塩のカルボキシアニオンに水素結合可能な部位を有する化合物を添加し混合してポリ（γ−グルタミン酸）塩複合体を形成させることから成る。
【００１６】
このような製造方法を実施するには、まずγ−ＰＧＡ〔ポリ（γ−グルタミン酸）〕を用意する必要があるが、γ−ＰＧＡは周知の物質であり、例えば化学合成法、発酵法、半化学合成法等の種々の方法により得ることができる。但し、γ−ＰＧＡを効率良く入手するには、発酵法による方法が好ましい。なお、この方法の詳細については、例えば特開平７−１３５９９１に記載されている。
【００１７】
次に得られたγ−ＰＧＡをγ−ＰＧＡ塩にする。これはγ−ＰＧＡのγ位のカルボン酸が塩になったものである。ここでいうγ−ＰＧＡ塩とは、特に限定されないが、アルカリ金属塩では例えば、γ−ＰＧＡナトリウム塩、γ−ＰＧＡカリウム塩、γ−ＰＧＡリチウム塩等、アルカリ土類金属塩では例えば、γ−ＰＧＡマグネシウム塩、γ−ＰＧＡカルシウム塩、γ−ＰＧＡバリウム塩等、γ−ＰＧＡアンモニウム塩等が挙げられる。但し、これらの例示は、本発明を限定するものではない。
【００１８】
γ−ＰＧＡをγ−ＰＧＡ塩にする際には、予めγ−ＰＧＡを水または水と親水性有機溶媒の混合溶媒に溶解させた後、水溶性塩類を添加し、完全に溶液にした水性溶液を得る。
本発明で用いられる親水性有機溶媒としては、例えばメタノール、エタノール、アセトン、イソプロパノール等が挙げられる。水溶性塩類としては、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カルシウム、塩化カルシウム、酢酸アンモニウム等である。また、γ−ＰＧＡアンモニウム塩は、アンモニア水を添加することによってもできる。
【００１９】
本発明の方法においては、次に、このようにして得られた前述の繰り返し単位（Ａ）を有するγ−ＰＧＡの水性溶液に、水素結合性化合物（γ−ＰＧＡ塩のカルボキシアニオンに水素結合可能な部位を有する化合物）を添加する。
なお、アルカリ金属、アルカリ土類金属またはアンモニウムの水溶性塩類を添加して得られたγ−ＰＧＡ塩含有水性溶液は、そのまま、水素結合性化合物が直接添加されてもよいが、通常は、該水性溶液を凍結乾燥する（凍結乾燥の前に透析を行うことが好ましい）ことによりγ−ＰＧＡ塩を粉末とし、水素結合性の添加に際してγ−ＰＧＡ塩粉末を上述したような水または水と親水性溶媒の混合溶媒（例えば、水、水およびメタノール混合溶媒、水およびエタノール混合溶媒、水およびアセトン混合溶媒、水およびイソプロパノール混合溶媒等）に溶解して水性溶液を調製し、これに水素結合性化合物を添加する。水性溶液の溶液濃度は１〜２０ｗｔ％、好ましくは５〜１０ｗｔ％である。
【００２０】
本発明の方法に従い、γ−ＰＧＡ塩から成るポリアニオンとキトサン誘導体から成るポリカチオンとから形成されるポリマーイオンコンプレックスを製造するには、キトサンを有機酸に溶解することにより前述の繰り返し単位（Ｂ）を有するキトサン第４級アミンを形成させ、これを水素結合性化合物としてγ−ＰＧＡ塩含有水性溶液に添加する。キトサンを第４級アミン塩にするには、キトサンを少量の希有機酸に溶解すればよい。一般に、キトサン１に対して有機酸１０〜１００当量の割合で用いる。本発明で用いられる希有機酸は、例えばギ酸、酢酸、メタンスルホン酸等挙げられる。
【００２１】
次にアミノ基を希有機酸で第４級アミン塩になったキトサン溶液にポリ（γ−グルタミン酸）塩含有水性溶液を混合する。このとき、繰り返し単位（Ａ）と繰り返し単位（Ｂ）のモル比を、１：９から９：１まで設定して所望のポリマーイオンコンプレックスを製造することができる。
【００２２】
このようにして得られたポリマーイオンコンプレックス溶液は、そのまま、膜または繊維を形成するための原料として有用なものである。本発明によるポリマーイオンコンプレックスの好ましい応用例は、このようなポリマーイオンコンプレックス溶液の溶媒を蒸散させることにより（フィルムキャスト法）、フィルムや膜に成形できることである。また、溶融成形法によって紡糸することもできる。溶液または溶融物からの製膜および紡糸は、従来より慣用されているところに従って行うことができる。膜および繊維は、延伸したものであってもよい。
【００２３】
水素結合性化合物として、尿素、グアニジン塩酸塩、グアニジン硫酸塩、グアニジン硝酸塩、タンニン等を用いる場合には、上述したようなγ−ＰＧＡ塩の水性溶液にそれらの化合物をそのまま添加し、さらに必要に応じて、繊維補強材を添加して、混合することにより、所望のポリ（γ−グルタミン酸）塩複合体を製造することができる。既述のように、尿素等の濃度は、γ−ＰＧＡ塩に対してモル比で０．１〜５、好ましくは、０．１〜２であり、また補強材濃度は、０．１〜５ｗｔ％、好ましくは０．１〜２ｗｔ％である。このようにして得られたポリ（γ−グルタミン酸）塩複合体の成形は、乾式法および湿式法により行うことはできる。
【００２４】
【実施例】
以下、本発明の特徴をさらに明らかにするために実施例を示すが、本発明は、これらの実施例の記載によって限定されるものではない。
実施例１：ポリマーイオンコンプレックスの製造と成形
〔γ−ＰＧＡ塩の調製〕
原料となるγ−ＰＧＡは、例えば特開平７−１３５９９１号公報に記載の方法により製造されたものを使用した。γ−ＰＧＡ（１．３ｇ）を水（５０ｍｌ）に溶解後、室温下（２５℃）にて炭酸水素ナトリウム（０．８４ｇ）を添加した。添加後６０分攪拌後、凍結乾燥によってγ−ＰＧＡ塩（ナトリウム塩）の粉末を得た。なお、このγ−ＰＧＡ塩の分子量をゲル濾過クロマトグラフィで測定したところ、ピーク分子量が６５０，０００であった。
【００２５】
〔キトサン第４級アミンの調製〕
キトサン（０．１６ｇ）〔九州片山化学（株）製〕を６０％に希釈したギ酸溶液（１０ｍｌ）に溶解させることによって第４級アミン塩を得た。
【００２６】
〔ポリマーイオンコンプレックスの調製〕
上述のようにして得られたγ−ＰＧＡ塩（ナトリウム塩）粉末を
溶媒に溶解させたγ−ＰＧＡ水性溶液を、上述のようにして得たキトサンの第４級アミン塩の溶液に室温下（２５℃）において攪拌しながら、γ−ＰＧＡ塩とキトサンアミンのモル比を以下の表に示すように変化させて、混合し、全体で２％濃度の溶液になるように調製した。
【００２７】
【表１】
サンプル１〜サンプル５については、ＩＲ（赤外吸収スペクトル）で、１６
０ｃｍ-1における特性吸収ピークが認められ、ポリマーイオンコンプレックスの形成が確認されたが、サンプル６および７についてはこの特性吸収ピークが観測されなかった。
【００２９】
〔ポリマーイオンコンプレックスの成形〕
得られたポリマーイオンコンプレックス溶液（サンプル１〜サンプル５）をフィルムキャスト法により溶媒を室温下（２５℃）にて４８時間、蒸発させることにより、膜（厚さ２０〜６０μｍ）を得ることができた。得られた膜は、従来のγ−ＰＧＡ系材料製の膜におけるような吸湿性による劣化は認められず、１週間経過しても安定な形状を保持していた。
【００３０】
実施例２：尿素を用いる複合体の製造と成形
γ−ＰＧＡ５ｇを蒸留水１００ｍｌに加え、水酸化ナトリウム水溶液をγ−ＰＧＡが溶解するまで加え均一溶液とした。これに尿素２．３ｇを添加し攪拌混合することによりγ−ＰＧＡ複合体溶液とした。これをテフロンシート上に展開し、乾燥器中６０℃６時間乾燥することによりフィルム（厚さ５０〜１００μｍ）を得た。得られたフィルムは１週間経過後も安定であった。
【００３１】
実施例３：尿素＋繊維強化材を用いる複合体の製造と成形
γ−ＰＧＡ１０ｇを蒸留水１００ｍｌに加え、水酸化ナトリウム水溶液をγ−ＰＧＡが溶解するまで加え均一溶液とした。これに尿素２．３ｇ及び絹糸１ｇを添加し攪拌混合することによりγ−ＰＧＡ複合体溶液とした。これをテフロンシート上に展開し、室温下２４時間放置乾燥することによりフィルム（厚さ８０〜１５０μｍ）を得た。得られたフィルムは１週間経過しても安定であった。
【００３２】
【発明の効果】
本発明のポリ（γ−グルタミン酸）塩複合体は、吸湿性がなく柔軟であり、長期間安定なフィルムや膜などに容易に成形できる。その製造方法も簡単である。[0001]
BACKGROUND OF THE INVENTION
The present invention belongs to the field of functional polymers, and particularly relates to a novel composite material based on poly (γ-glutamic acid) and a method for producing the same.
[0002]
[Prior art and its problems]
A polyglutamic acid-based polymer is expected as a functional material in various fields such as fiber, food, cosmetics, medicine and agriculture. The present inventors have already disclosed a compound, poly (γ-glutamic acid) (hereinafter sometimes abbreviated as γ-PGA), in which a carboxyl group at the γ-position and an amino group at the α-position of glutamic acid are bonded by an amide bond. Development of a method for producing a high polymer advantageously using microorganisms (Japanese Patent Laid-Open No. 7-135991), and addition of bivalent or higher metal ions (for example, alkaline earth metal ions, fiber metal ions, etc.) Has succeeded in obtaining a molded product (hereinafter sometimes abbreviated as γ-PGA modified product) (JP-A-7-138364).
[0003]
These γ-PGA modified products are improved biodegradability of conventional polymers, but on the other hand, they are highly hygroscopic and not flexible so that, for example, stable films and membranes are formed. This has been an obstacle to the development of a wide range of applications.
[0004]
[Means for solving problems]
As a result of repeated studies on a polyglutamic acid-based material that eliminates the drawbacks of the above-described modified γ-PGA, the present inventors can bind a salt of poly (γ-glutamic acid) having a specific structure and the salt. We have succeeded in developing a new type of composite material that is composed of the second compound, has no hygroscopicity, is flexible, easy to handle, and can provide a stable molding.
[0005]
Thus, the present invention provides a poly (γ-glutamic acid) salt having the following repeating unit (A) and a compound formed from a compound having a site capable of hydrogen bonding to the carboxy anion of the poly (γ-glutamic acid) salt. A (γ-glutamic acid) salt complex is provided.
[0006]
[Chemical formula 5]
The reason why various properties are improved in such a poly (γ-glutamic acid) salt complex according to the present invention is not completely understood, but is understood as follows. That is, it is considered that one of the causes of the high hygroscopic property in the conventional γ-PGA materials is due to hydrogen bonding between the carboxyl group at the γ-position and the amino group at the α-position of glutamic acid constituting γ-PGA. However, in the complex of the present invention, it is speculated that such a phenomenon is avoided or reduced by hydrogen bonding of the second compound to the carboxy anion (COO − ) of γ-glutamate.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The complex of the present invention is formed from a poly (γ-glutamic acid) salt having the repeating unit (A) and a hydrogen bonding compound (a compound having a site capable of hydrogen bonding to a carboxy anion). .
Examples of X in the repeating unit (A) include alkali metals such as sodium, potassium and lithium, alkaline earth metals such as magnesium, calcium and barium, and ammonium.
[0008]
More specifically, examples of the repeating unit (A) include the following, but these examples do not limit the present invention.
1. When X is an alkali metal.
[Chemical 6]
[Chemical 7]
[Chemical 8]
In addition, in the poly ((gamma) -glutamic acid) salt of this invention, 2 or more types of repeating units (A) may be contained. The poly (γ-glutamic acid) salt in the present invention usually has an average molecular weight of 400,000 to 4,400,000 (g / mol). If the molecular weight is lower than this, a complex having desired characteristics cannot be obtained. On the other hand, those having a too high molecular weight are difficult to produce and are not practical.
[0010]
The compound having a hydrogen-bondable site for forming the poly (γ-glutamic acid) salt complex of the present invention includes at least the carboxy anion (COO − ) of the poly (γ-glutamic acid) salt in an aqueous solution or aqueous solution. Any compound can be used as long as it can be partially bonded through a hydrogen bond. Particularly preferred as such a compound is chitosanamine having the following repeating unit (B).
[Chemical 9]
[0011]
By doing so, a polymer ion complex is formed between the polycation composed of the chitosanamine and the polyanion obtained from the poly (γ-glutamic acid) salt. In this case, the repeating unit (A) is 10 mol% or more with respect to the repeating unit (B), or the repeating unit (B) is 10 mol% or more with respect to the repeating unit (A). This is because if either one of the repeating unit (A) and the repeating unit (B) is too small compared to the other, a sufficient polymer ion complex cannot be produced.
[0012]
Formation of the polymer ion complex can be confirmed by measuring an infrared spectrum (IR) in tracking the reaction. That is, in addition to the peak near 1600 cm −1 derived from chitosan and γ-PGA, the formation of a polymer ion complex has characteristic absorption due to the formation of crosslinks near 1630 cm −1. The formation of a polymer ion complex can be confirmed.
This embodiment is advantageous in that chitosan existing in large quantities as biomass can be used.
[0013]
In another preferred embodiment of the present invention, urea, guanidine hydrochloride, guanidine sulfate, guanidine nitrate, tannin and the like can be used as the compound having a hydrogen bondable site. Particularly preferred is urea because it has a large protein denaturing effect. The concentration of these compounds is 0.1-5, preferably 0.1-2, in molar ratio to the poly (γ-glutamic acid) salt, so that the carboxy anion of the poly (γ-glutamic acid) salt The desired complex in which the compound is bonded via hydrogen bonds is obtained.
[0014]
Furthermore, in another preferable aspect of the present invention, a fiber reinforcing material (fibrous reinforcing material) is added together with a compound such as urea. Examples of the fiber reinforcing material include natural fibers such as silk and cotton. The fiber reinforcing material concentration is usually 0.1 to 5 wt%, preferably 0.1 to 2 wt%. When the fiber reinforcing material is added in this way, there is an advantage that improvement in hygroscopicity and high elongation is observed.
[0015]
The present inventor has established a method capable of easily obtaining a poly (γ-glutamic acid) salt complex as described above in a large amount. Therefore, the present invention provides, as another viewpoint, a method for producing a poly (γ-glutamic acid) salt complex. The method of the present invention uses poly (γ-glutamic acid) as water or water and a hydrophilic solvent. An aqueous solution of a poly (γ-glutamic acid) salt having the above-mentioned repeating unit (A) obtained by adding a water-soluble salt of alkali metal, alkaline earth metal or ammonium ion to a solution dissolved in a mixed solvent of And adding a compound having a site capable of hydrogen bonding to the carboxy anion of the poly (γ-glutamic acid) salt and mixing to form a poly (γ-glutamic acid) salt complex.
[0016]
In order to carry out such a production method, it is first necessary to prepare γ-PGA [poly (γ-glutamic acid)]. However, γ-PGA is a well-known substance. It can be obtained by various methods such as chemical synthesis. However, in order to obtain γ-PGA efficiently, a method using a fermentation method is preferable. Details of this method are described, for example, in JP-A-7-135991.
[0017]
Next, the obtained γ-PGA is converted to a γ-PGA salt. This is a salt of the γ-carboxylic acid at the γ-PGA. The γ-PGA salt here is not particularly limited, but for alkali metal salts, for example, γ-PGA sodium salt, γ-PGA potassium salt, γ-PGA lithium salt, etc., for alkaline earth metal salts, for example, γ- Examples thereof include PGA magnesium salt, γ-PGA calcium salt, γ-PGA barium salt, and γ-PGA ammonium salt. However, these illustrations do not limit the present invention.
[0018]
When converting γ-PGA into a γ-PGA salt, an aqueous solution in which γ-PGA is previously dissolved in water or a mixed solvent of water and a hydrophilic organic solvent, and then water-soluble salts are added to form a complete solution. Get.
Examples of the hydrophilic organic solvent used in the present invention include methanol, ethanol, acetone, isopropanol and the like. Examples of the water-soluble salts include sodium hydrogen carbonate, sodium hydroxide, calcium hydroxide, calcium chloride, ammonium acetate and the like. The γ-PGA ammonium salt can also be added by adding aqueous ammonia.
[0019]
In the method of the present invention, next, an aqueous solution of γ-PGA having the above-mentioned repeating unit (A) obtained in this way is combined with a hydrogen bonding compound (a carboxy anion of a γ-PGA salt can be hydrogen bonded). Compound having a different site).
The aqueous solution containing a γ-PGA salt obtained by adding an alkali metal, alkaline earth metal or ammonium water-soluble salt may be directly added with a hydrogen bonding compound. The aqueous solution is freeze-dried (dialysis is preferably performed before freeze-drying) to form a γ-PGA salt as a powder, and when adding hydrogen bonding, the γ-PGA salt powder is water or water and hydrophilic as described above. An aqueous solution is prepared by dissolving in a mixed solvent of an organic solvent (for example, water, water and methanol mixed solvent, water and ethanol mixed solvent, water and acetone mixed solvent, water and isopropanol mixed solvent, etc.), and has hydrogen bonding properties. Add compound. The solution concentration of the aqueous solution is 1 to 20 wt%, preferably 5 to 10 wt%.
[0020]
In order to produce a polymer ion complex formed from a polyanion comprising a γ-PGA salt and a polycation comprising a chitosan derivative according to the method of the present invention, the above repeating unit (B) is prepared by dissolving chitosan in an organic acid. A chitosan quaternary amine is formed, which is added as a hydrogen bonding compound to an aqueous solution containing a γ-PGA salt. To make chitosan into a quaternary amine salt, chitosan may be dissolved in a small amount of dilute organic acid. Generally, the organic acid is used at a ratio of 10 to 100 equivalents relative to chitosan 1. Examples of the diluted organic acid used in the present invention include formic acid, acetic acid, methanesulfonic acid and the like.
[0021]
Next, a poly (γ-glutamic acid) salt-containing aqueous solution is mixed with the chitosan solution in which the amino group is converted to a quaternary amine salt with a dilute organic acid. At this time, the desired polymer ion complex can be produced by setting the molar ratio of the repeating unit (A) to the repeating unit (B) from 1: 9 to 9: 1.
[0022]
The polymer ion complex solution thus obtained is useful as a raw material for forming a membrane or fiber as it is. A preferred application example of the polymer ion complex according to the present invention is that it can be formed into a film or a film by evaporating the solvent of such a polymer ion complex solution (film casting method). It can also be spun by melt molding. Film formation and spinning from a solution or melt can be carried out according to conventional methods. The membrane and fiber may be stretched.
[0023]
When urea, guanidine hydrochloride, guanidine sulfate, guanidine nitrate, tannin or the like is used as the hydrogen bonding compound, these compounds are added as they are to the aqueous solution of γ-PGA salt as described above, and further required. Accordingly, a desired poly (γ-glutamic acid) salt complex can be produced by adding a fiber reinforcing material and mixing them. As described above, the concentration of urea or the like is 0.1 to 5, preferably 0.1 to 2, in terms of molar ratio with respect to the γ-PGA salt, and the reinforcing material concentration is 0.1 to 5 wt. %, Preferably 0.1 to 2 wt%. Molding of the poly (γ-glutamic acid) salt complex thus obtained can be performed by a dry method and a wet method.
[0024]
【Example】
Examples are shown below to further clarify the features of the present invention, but the present invention is not limited by the description of these Examples.
Example 1 Production and Molding of Polymer Ion Complex [Preparation of γ-PGA Salt]
As the γ-PGA used as a raw material, for example, one produced by the method described in JP-A-7-135991 was used. γ-PGA (1.3 g) was dissolved in water (50 ml), and sodium hydrogen carbonate (0.84 g) was added at room temperature (25 ° C.). After the addition, the mixture was stirred for 60 minutes, and freeze-dried to obtain a powder of γ-PGA salt (sodium salt). In addition, when the molecular weight of this (gamma) -PGA salt was measured by the gel filtration chromatography, the peak molecular weight was 650,000.
[0025]
[Preparation of chitosan quaternary amine]
A quaternary amine salt was obtained by dissolving chitosan (0.16 g) [manufactured by Kyushu Katayama Chemical Co., Ltd.] in a formic acid solution (10 ml) diluted to 60%.
[0026]
[Preparation of polymer ion complex]
The aqueous γ-PGA solution obtained by dissolving the γ-PGA salt (sodium salt) powder obtained as described above in a solvent was added to the quaternary amine salt solution of chitosan obtained as described above at room temperature ( While stirring at 25 ° C.), the molar ratio of γ-PGA salt and chitosanamine was changed as shown in the following table and mixed to prepare a 2% concentration solution as a whole.
[0027]
[Table 1]
Samples 1 to 5 have an IR (infrared absorption spectrum) of 16
A characteristic absorption peak at 0 cm −1 was observed, and formation of a polymer ion complex was confirmed. However, for samples 6 and 7, this characteristic absorption peak was not observed.
[0029]
[Polymer ion complex molding]
By evaporating the obtained polymer ion complex solution (sample 1 to sample 5) at room temperature (25 ° C.) for 48 hours by a film casting method, a film (thickness 20 to 60 μm) can be obtained. It was. The obtained film did not show deterioration due to hygroscopicity as in the conventional film made of γ-PGA material, and maintained a stable shape even after one week.
[0030]
Example 2 Production of Complex Using Urea and Molding 5 g of γ-PGA was added to 100 ml of distilled water, and an aqueous sodium hydroxide solution was added until γ-PGA was dissolved to obtain a homogeneous solution. To this, 2.3 g of urea was added and mixed by stirring to obtain a γ-PGA complex solution. This was developed on a Teflon sheet and dried in a dryer at 60 ° C. for 6 hours to obtain a film (thickness: 50 to 100 μm). The obtained film was stable even after 1 week.
[0031]
Example 3 Production and Molding of Composite Using Urea + Fiber Reinforcement Material 10 g of γ-PGA was added to 100 ml of distilled water, and an aqueous sodium hydroxide solution was added until γ-PGA was dissolved to obtain a homogeneous solution. To this, 2.3 g of urea and 1 g of silk thread were added and mixed with stirring to obtain a γ-PGA complex solution. This was spread on a Teflon sheet and left to dry at room temperature for 24 hours to obtain a film (thickness 80 to 150 μm). The obtained film was stable even after 1 week.
[0032]
【The invention's effect】
The poly (γ-glutamic acid) salt complex of the present invention has no hygroscopic property and is flexible, and can be easily formed into a film or membrane that is stable for a long period of time. The manufacturing method is also simple.
Claims (5)
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| JP24887896A JP3647989B2 (en) | 1996-08-30 | 1996-08-30 | Poly (γ-glutamic acid) salt complex and method for producing the same |
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|---|---|---|---|
| JP24887896A JP3647989B2 (en) | 1996-08-30 | 1996-08-30 | Poly (γ-glutamic acid) salt complex and method for producing the same |
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| JP6488473B2 (en) * | 2012-11-21 | 2019-03-27 | 東洋紡株式会社 | Antifungal and coating agents |
| JP7267583B2 (en) * | 2019-03-27 | 2023-05-02 | 国立大学法人高知大学 | Method for producing ionic polymer |
| JP2023151060A (en) * | 2022-03-31 | 2023-10-16 | 東洋濾紙株式会社 | Method for producing poly-γ-glutamic acid ion complex |
| CN118725291B (en) * | 2024-09-03 | 2024-11-05 | 青岛溯博生物技术有限公司 | Modification method for improving polyglutamic acid activity, and product and application thereof |
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