JP3412975B2 - Method for producing fullerene-containing fine particles - Google Patents
Method for producing fullerene-containing fine particlesInfo
- Publication number
- JP3412975B2 JP3412975B2 JP20853495A JP20853495A JP3412975B2 JP 3412975 B2 JP3412975 B2 JP 3412975B2 JP 20853495 A JP20853495 A JP 20853495A JP 20853495 A JP20853495 A JP 20853495A JP 3412975 B2 JP3412975 B2 JP 3412975B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- fullerene
- particularly limited
- present
- containing fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010419 fine particle Substances 0.000 title claims description 48
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 35
- 229910003472 fullerene Inorganic materials 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- -1 acryl group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- 239000003085 diluting agent Substances 0.000 description 2
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- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007902 hard capsule Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000007918 intramuscular administration Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000007911 parenteral administration Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
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Description
【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明は、フラーレンおよび
／またはフラーレン誘導体を含有する微粒子に関する。
【０００２】
【従来の技術】フラーレンはその環上に広がるπ共役系
に起因した様々な機能を有する。有機超伝導、光電変換
及び非線形効果等の電気、光学的機能はもとより、最近
では、抗腫瘍効果も確認されている。
【０００３】
【発明が解決しようとする課題】このフラーレンをフラ
ーレンとしての機能を損なうことなく扱いやすくするこ
とが望まれている。
【０００４】
【課題を解決するための手段】本発明は、かかる課題を
克服するためになされたものである。フラーレンが有す
る機能をより効果的に発現するために微粒子化するもの
である。
【０００５】すなわち、本発明は、（ａ）フラーレンお
よび／またはフラーレン誘導体および（ｂ）有機化合物
を含有してなる微粒子に関する。
【０００６】
【発明の実施の態様】以下、本発明について詳細に説明
する。本発明において使用するフラーレンとは、一般式
Ｃｘで規定される球状炭素化合物である。ここで、ｘは
特に限定されず、６０〜１３６から選ばれる偶数であ
り、好ましくは、６０、７０、７６、７８、８２、８
４、９０、９６である。
【０００７】本発明で使用しうるフラーレン誘導体とし
ては、フラーレンの２重結合に炭素数が１〜２０のアル
キル基、アクリル基およびアリル基等の不飽和二重結合
を有する基、シリル基、又はＰＥＧ（ポリエチレングリ
コール）鎖等が付加した化合物が例示されるが、これら
に特に限定されない。また、フラーレンに導入した基の
数は、特に限定されず１〜ｘである。これらフラーレン
誘導体は、公知の例えばオレフィンの二重結合に上記反
応基を付加させる方法等と同様にして得ることができ
る。
【０００８】本発明で用いる微粒子の調製法は、特に限
定されないが、懸濁重合法、乳化重合法、界面重合法、
不溶化反応法、相分離法、界面沈殿法、スプレードライ
イング法および気中懸濁被覆法等が例示される。
【０００９】本発明で用いる微粒子の材質は、特に限定
されず、有機化合物、無機化合物を問わないが、光透過
性であることが好ましい。このような微粒子を形成する
材質として有機化合物としては、ＰＭＭＡ（ポリメチル
メタクリレート）、ポリカーボネートおよびポリエステ
ル等、無機化合物としては、二酸化ケイ素等が例示され
る。
【００１０】本発明で用いる微粒子の粒子径は、特に限
定されないが、１０ｎｍ〜１ｍｍ、好ましくは１０ｎｍ
〜０．１ｍｍである。
【００１１】フラーレン類を微粒子に含有させる方法
は、特に限定されないが、微粒子を調製する際に微粒子
の原料にフラーレン類を溶解および／または分散してお
く方法、微粒子調製後に含浸する方法が例示される。含
有させるフラーレン類の量は、特に限定されないが、微
粒子に対して０．０１〜１０重量％である。
【００１２】フラーレン類を微粒子に含有させる際に、
必要に応じて溶媒を用いてもよい。使用されうる溶媒
は、特に限定されないが、具体的にはテトラヒドロフラ
ン、ジメチルホルムアミド、ベンゼンもしくはトルエン
等が例示され、これら溶媒は混合して使用してもよい。
ここで、反応溶媒の使用量は、フラーレン類が溶解する
量であれば特に限定されない。
【００１３】通常、これら含有工程は室温で行うが、必
要に応じて加熱してもよい。加熱温度は、特に限定され
ないが、３０〜２００℃、好ましくは、５０〜１００℃
である。
【００１４】この様にして得られた本発明のフラーレン
含有微粒子は、フラーレンが有する機能と微粒子が有す
る機能を合わせ持つため、様々な用途に応用可能であ
る。これら用途は特に限定されないが、光機能的用途と
して波長変換材料、光スイッチおよびレーザー素子等、
医学的用途として抗腫瘍剤等が例示される。
【００１５】用途の１つとして、レーザー素子を例示す
る。微粒子がレーザー発振することはよく知られている
が、その微粒子中に非線形材料であるフラーレン類を含
有させることにより、高次高調波発生とレーザー発振を
同時に行うことが可能となるので、短波長レーザーとし
て使用できる。
【００１６】本発明の微粒子は、フィルム、ファイバー
等の光導波路中で用いることが望ましい。これら光導波
路の形成中に、必要に応じてポーリングを行ってもよ
い。
【００１７】光導波路を形成するにおいて、該微粒子を
光学的に透明なマトリックス中に均一に分散させること
が好ましい。マトリックスとしては、特に限定されない
が、微粒子より屈折率が低いものが好ましく、ポリメチ
ルメタクリレート、ポリカーボネートもしくはポリエス
テル等の有機高分子または二酸化ケイ素等の無機高分子
が例示される。
【００１８】本発明の微粒子を有機高分子中に分散させ
る方法は、特に限定されないが、上記マトリックスを得
る際のモノマーに該微粒子を均一に分散した後、硬化前
もしくは硬化中にキャストもしくは紡糸等により成型す
る方法、または、該有機高分子及び該微粒子を例えばメ
チルイソブチルケトン、ジメチルスルホキシドのような
有機溶媒に均一に分散し、キャストもしくは紡糸等の成
型中もしくは成型後、溶媒を除去し成型する方法が例示
される。
【００１９】本発明の微粒子を無機高分子中に分散させ
る方法は、特に限定されないが、ジ、トリもしくはテト
ラアルコキシシラン中に該微粒子を均一に分散し、塩酸
等の酸を添加し重合させながら、キャストもしくは紡糸
等の成型を施す方法が例示される。
【００２０】応用例の２つめとして、本発明の微粒子を
抗腫瘍剤として用いる場合を例示する。この場合、その
剤形及び投与方法は特に限定されず、顆粒剤、散財、錠
剤、硬カプセル剤、軟カプセル剤、シロップ剤、乳剤、
懸濁剤もしくはその他の内服液剤等にして経口投与する
方法、注射剤として、もしくは注射用の粉末にして用時
調製して、動脈投与、静脈投与、筋肉投与もしくは皮下
投与する方法、または坐剤として投与する方法が例示さ
れる。
【００２１】本発明の微粒子を含む上記製剤を調製する
場合、製剤担体に対する該微粒子の含有量は、特に制限
されず、０．１〜９９．９重量％である。また、これら
製剤の製法は常法に従う。
【００２２】製剤化に際し、その製剤化助剤として、有
機もしくは無機の、固体もしくは液体の担体または希釈
剤を用いても良い。固体製剤を調製する際に用いられる
賦形剤は、特に限定されないが、乳糖、蔗糖、でんぷ
ん、タルク、セルロース、デキストリン、カオリンもし
くは炭酸カルシウム等が例示される。
【００２３】経口投与用の液体製剤を調製する際に用い
られる希釈剤は、一般に用いられる不活性なものであれ
ば特に限定されず、水もしくは植物油等が例示される。
これら製剤は、上記不活性希釈剤のほかに添加剤とし
て、湿潤剤、懸濁補助剤、甘味剤、着色剤もしくは保存
剤等を含有していても良い。さらに、液体製剤とした
後、ゼラチン等の吸収生物質に含浸させカプセルとして
も良い。
【００２４】注射剤もしくは坐剤等の非経口投与用製剤
を調製する場合、水、プロピレングリコール、ポリエチ
レングリコール、ベンジルアルコール、オレイン酸エチ
ルもしくはレシチン等の溶剤または懸濁化剤を使用して
も良い。坐剤を調製する場合、カカオ油、乳化カカオ
油、ラウリン油もしくはウィテップゾール等の基剤を用
いても良い。
【００２５】臨床投与量は、経口もしくは注射投与に限
らず、特に制限されず、年齢、病態及び症状により適宜
増減することが望ましい。経口投与の場合、成人に対し
該化合物として、１日あたり０．０１〜１０００ｍｇが
好ましい。経口投与の方法は、特に制限されず、上記１
日量の薬剤を１回、適当な間隔をおいて２〜４回もしく
は間欠して投与しても良い。
【００２６】抗腫瘍効果の発現にあたり、エネルギー線
を本発明の微粒子に照射しても良い。エネルギー線は特
に限定されず、Ｘ線、γ線、（遠）紫外線、可視光、も
しくは（遠）赤外線等が例示される。
【００２７】以下に、実施例に基づいて本発明をさらに
詳細に説明するが、本発明はこれら実施例に限定される
ものではない。
【００２８】実施例１
撹拌機、冷却管、窒素導入口を付けた２００ｍｌの４つ
口丸底フラスコに、水；１１８．５ｇを取り、ゴーセノ
ール；ＧＬ−０５（日本合成化学（株）製）；１．５ｇ
を溶解した。メチルメタクリレート；３０ｇ、エチレン
グリコールジメタクリレート；０．０６ｇ、Ｖ−６５
（和光純薬（株）製）；０．０１５ｇを均一に溶解した
後加え、回転数４００ｒ．ｐ．ｍで分散した。次いで、
系内の温度を５０℃にし５時間反応させ、ろ過、水洗、
乾燥し微粒子（Ａ）を得た。Ｃ６０；０．１ｇをトルエ
ン；５０ｍｌに溶解した溶液に、微粒子（Ａ）２５ｇを
加え、室温で１晩撹拌し、ろ過、水洗、乾燥し、平均粒
径３０μｍの本発明のフラーレン含有微粒子を約２５ｇ
得た。この微粒子の赤外吸収スペクトルを測定したとこ
ろ、５２６ｃｍ-1および５７６ｃｍ-1にＣ６０由来のピ
ークが観測され、Ｃ６０の存在が確認された。
【００２９】実施例２
エチレングリコールジメタクリレートを０．０３ｇに変
えた以外は、実施例１と同様な操作を行い、平均粒径４
０μｍの本発明のフラーレン含有微粒子を約２４ｇ得
た。
【００３０】実施例３
モノアクリロイル基置換Ｃ６０（モノアクリロイル基当
量６００ｇ／ｅｑ）；０．１ｇをトルエン；５０ｍｌに
溶解した溶液に、実施例１で得られた微粒子（Ａ）２５
ｇを加え、室温で１晩撹拌し、ろ過、水洗、乾燥し、平
均粒径４２μｍの本発明のフラーレン含有微粒子を約２
５ｇ得た。
【００３１】実施例４
モノ（トリフェニルシリル）基置換Ｃ６０（モノ（トリ
フェニルシリル）基当量８００ｇ／ｅｑ）；０．１ｇを
トルエン；５０ｍｌに溶解した溶液に、実施例１で得ら
れた微粒子（Ａ）２５ｇを加え、室温で１晩撹拌し、ろ
過、水洗、乾燥し、平均粒径４１μｍの本発明のフラー
レン含有微粒子を約２５ｇ得た。
【００３２】実施例５
撹拌機、冷却管、窒素導入口を付けた２００ｍｌの４つ
口丸底フラスコに、ｎ−ヘプタン；１１８．５ｇを取
り、組成比（重量）がブチルアクリレート：メチルアク
リレート：アクリル酸＝５０：４５：５の高分子；１．
５ｇを溶解した。Ｎ−イソプロピルアクリルアミド；３
０ｇ、ＶＡ−５４５（和光純薬（株）製）；０．０１５
ｇを水；３０ｇに均一に溶解した後加え、回転数４００
ｒ．ｐ．ｍで分散した。次いで、系内の温度を５０℃に
し５時間反応させ、ろ過、水洗、乾燥し微粒子（Ｂ）を
得た。Ｃ６０；０．１ｇを組成比（重量）がトルエン：
ＴＨＦ（テトラヒドロフラン）＝１：１の混合溶媒；５
０ｍｌに溶解した溶液に、微粒子（Ｂ）２５ｇを加え、
室温で１晩撹拌し、ろ過、水洗、乾燥し、平均粒径５５
μｍの本発明のフラーレン含有微粒子を約２５ｇ得た。
【００３３】実施例６
撹拌機、冷却管、窒素導入口を付けた２００ｍｌの４つ
口丸底フラスコに、水；１１８．５ｇを取り、ゴーセノ
ール；ＧＬ−０５（日本合成化学（株）製）；１．５ｇ
を溶解した。Ｃ６０；０．０５ｇをトルエン；２５ｍｌ
に溶解した溶液に、メチルメタクリレート；５ｇ、エチ
レングリコールジメタクリレート；０．０１ｇ、Ｖ−６
５（和光純薬（株）製）；０．００３ｇを均一に溶解し
た後加え、回転数４００ｒ．ｐ．ｍで分散した。次い
で、系内の温度を５０℃にし５時間反応させ、ろ過、水
洗、乾燥し、平均粒径４０μｍの本発明のフラーレン含
有微粒子を２５ｇ得た。
【００３４】
【発明の効果】本発明のフラーレン含有微粒子は、フラ
ーレンが有する機能と微粒子が有する機能を合わせ持つ
ため、光機能的用途として波長変換材料、光スイッチお
よびレーザー素子等、医学的用途として抗腫瘍剤等に応
用可能である。Description: TECHNICAL FIELD [0001] The present invention relates to fine particles containing fullerene and / or a fullerene derivative. [0002] Fullerene has various functions due to a π-conjugated system spreading on its ring. Recently, antitumor effects have been confirmed as well as electric and optical functions such as organic superconductivity, photoelectric conversion and nonlinear effects. [0003] It is desired to make this fullerene easy to handle without impairing its function as a fullerene. [0004] The present invention has been made to overcome such problems. In order to more effectively express the function of fullerenes, they are made into fine particles. That is, the present invention relates to fine particles comprising (a) a fullerene and / or a fullerene derivative and (b) an organic compound. Hereinafter, the present invention will be described in detail. The fullerene used in the present invention is a spherical carbon compound defined by the general formula Cx. Here, x is not particularly limited, and is an even number selected from 60 to 136, and preferably, 60, 70, 76, 78, 82, 8
4, 90, 96. The fullerene derivative usable in the present invention includes a group having an unsaturated double bond such as an alkyl group having 1 to 20 carbon atoms, an acryl group and an allyl group, a silyl group, Compounds to which a PEG (polyethylene glycol) chain or the like is added are exemplified, but are not particularly limited thereto. Further, the number of groups introduced into the fullerene is not particularly limited and is 1 to x. These fullerene derivatives can be obtained, for example, in the same manner as in the known method of adding the above reactive group to the double bond of an olefin. The method for preparing the fine particles used in the present invention is not particularly limited, but may be a suspension polymerization method, an emulsion polymerization method, an interfacial polymerization method,
Examples include an insolubilization reaction method, a phase separation method, an interfacial precipitation method, a spray drying method, and an air suspension coating method. The material of the fine particles used in the present invention is not particularly limited and may be an organic compound or an inorganic compound, but is preferably light-transmitting. Examples of a material forming such fine particles include an organic compound such as PMMA (polymethyl methacrylate), polycarbonate and polyester, and an inorganic compound such as silicon dioxide. The particle diameter of the fine particles used in the present invention is not particularly limited, but is 10 nm to 1 mm, preferably 10 nm.
０．１0.1 mm. The method for incorporating the fullerenes into the fine particles is not particularly limited. Examples thereof include a method of dissolving and / or dispersing the fullerenes in the raw material of the fine particles when preparing the fine particles, and a method of impregnating the fine particles after the preparation. You. The amount of the fullerenes to be contained is not particularly limited, but is 0.01 to 10% by weight based on the fine particles. When fullerenes are contained in fine particles,
A solvent may be used if necessary. The solvent that can be used is not particularly limited, but specific examples thereof include tetrahydrofuran, dimethylformamide, benzene, and toluene. These solvents may be used as a mixture.
Here, the amount of the reaction solvent used is not particularly limited as long as the fullerenes are dissolved. Usually, these containing steps are carried out at room temperature, but may be carried out if necessary. The heating temperature is not particularly limited, but 30 to 200 ° C, preferably 50 to 100 ° C.
It is. The thus obtained fullerene-containing fine particles of the present invention have both the function of fullerene and the function of fine particles, and can be applied to various uses. Although these applications are not particularly limited, wavelength conversion materials, optical switches and laser devices as optical functional applications,
Antitumor agents and the like are exemplified as medical uses. As one of applications, a laser element will be exemplified. It is well known that fine particles oscillate in laser.However, by including fullerenes as a nonlinear material in the fine particles, high-order harmonic generation and laser oscillation can be performed at the same time. Can be used as a laser. The fine particles of the present invention are desirably used in optical waveguides such as films and fibers. Polling may be performed as needed during the formation of these optical waveguides. In forming an optical waveguide, it is preferable that the fine particles are uniformly dispersed in an optically transparent matrix. The matrix is not particularly limited, but preferably has a lower refractive index than the fine particles, and examples thereof include organic polymers such as polymethyl methacrylate, polycarbonate, and polyester, and inorganic polymers such as silicon dioxide. The method for dispersing the fine particles of the present invention in an organic polymer is not particularly limited, but after uniformly dispersing the fine particles in the monomer used to obtain the matrix, cast or spun before or during curing. Or the organic polymer and the fine particles are uniformly dispersed in an organic solvent such as methyl isobutyl ketone or dimethyl sulfoxide, and the solvent is removed during or after molding such as casting or spinning, and then molded. A method is illustrated. The method for dispersing the fine particles of the present invention in an inorganic polymer is not particularly limited, but the fine particles are uniformly dispersed in di-, tri- or tetraalkoxysilane, and an acid such as hydrochloric acid is added thereto for polymerization. And a method of performing molding such as casting or spinning. As a second application example, a case where the fine particles of the present invention are used as an antitumor agent will be exemplified. In this case, the dosage form and administration method are not particularly limited, and granules, splinters, tablets, hard capsules, soft capsules, syrups, emulsions,
A method for oral administration in the form of a suspension or other internal solution, a method for injection, or a powder for injection, prepared at the time of administration, and an arterial, intravenous, intramuscular or subcutaneous administration, or a suppository Is exemplified. When the above-mentioned preparation containing the fine particles of the present invention is prepared, the content of the fine particles with respect to the preparation carrier is not particularly limited, and is 0.1 to 99.9% by weight. The preparation of these preparations follows conventional methods. Upon formulation, an organic or inorganic solid or liquid carrier or diluent may be used as a formulation aid. The excipient used for preparing the solid preparation is not particularly limited, and examples thereof include lactose, sucrose, starch, talc, cellulose, dextrin, kaolin, and calcium carbonate. The diluent used for preparing a liquid preparation for oral administration is not particularly limited as long as it is an inert agent generally used, and examples thereof include water and vegetable oil.
These preparations may contain, as additives, wetting agents, suspending aids, sweetening agents, coloring agents, preservatives and the like in addition to the inert diluents. Further, after a liquid preparation is prepared, it may be impregnated with an absorbent biomaterial such as gelatin to form a capsule. When preparing a preparation for parenteral administration such as injection or suppository, a solvent or suspending agent such as water, propylene glycol, polyethylene glycol, benzyl alcohol, ethyl oleate or lecithin may be used. . When preparing suppositories, a base such as cocoa oil, emulsified cocoa oil, lauric oil or witepsol may be used. The clinical dose is not limited to oral or injection administration, and is not particularly limited, and it is desirable to appropriately increase or decrease it according to age, disease state and symptoms. In the case of oral administration, the compound is preferably 0.01 to 1000 mg per day for an adult. The method of oral administration is not particularly limited.
The daily dose of the drug may be administered once, two to four times at appropriate intervals, or intermittently. For the expression of the antitumor effect, the fine particles of the present invention may be irradiated with an energy ray. The energy ray is not particularly limited, and examples thereof include X-rays, γ-rays, (far) ultraviolet rays, visible light, and (far) infrared rays. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 118.5 g of water was placed in a 200 ml four-necked round-bottomed flask equipped with a stirrer, a condenser and a nitrogen inlet, and then gohsenol; GL-05 (manufactured by Nippon Synthetic Chemical Co., Ltd.) 1.5 g
Was dissolved. Methyl methacrylate; 30 g, ethylene glycol dimethacrylate; 0.06 g, V-65
(Manufactured by Wako Pure Chemical Industries, Ltd.); p. m. Then
The temperature in the system was raised to 50 ° C and reacted for 5 hours.
After drying, fine particles (A) were obtained. 25 g of fine particles (A) was added to a solution of 0.1 g of C60 in 50 ml of toluene, and the mixture was stirred at room temperature overnight, filtered, washed with water, and dried to obtain the fullerene-containing fine particles of the present invention having an average particle diameter of 30 μm. 25g
Obtained. The The infrared absorption spectrum of the particles was measured, a peak derived from C60 to 526cm -1 and 576cm -1 is observed, the presence of C60 was observed. Example 2 The same operation as in Example 1 was carried out except that the amount of ethylene glycol dimethacrylate was changed to 0.03 g, and the average particle size was 4%.
About 24 g of 0 μm fullerene-containing fine particles of the present invention were obtained. Example 3 The fine particles (A) 25 obtained in Example 1 were dissolved in a solution prepared by dissolving 0.1 g of monoacryloyl group-substituted C60 (monoacryloyl group equivalent: 600 g / eq) in 50 ml of toluene.
g, stirred at room temperature overnight, filtered, washed with water, and dried to obtain about 2 μm of the fullerene-containing fine particles of the present invention having an average particle size of 42 μm.
5 g were obtained. Example 4 Mono (triphenylsilyl) group-substituted C60 (mono (triphenylsilyl) group equivalent: 800 g / eq); 0.1 g of a solution obtained by dissolving 0.1 g of toluene in 50 ml of the fine particles obtained in Example 1 (A) 25 g was added, the mixture was stirred at room temperature overnight, filtered, washed with water and dried to obtain about 25 g of fullerene-containing fine particles of the present invention having an average particle diameter of 41 μm. Example 5 In a 200 ml four-necked round-bottomed flask equipped with a stirrer, a condenser, and a nitrogen inlet, 118.5 g of n-heptane was taken, and the composition ratio (weight) was butyl acrylate: methyl acrylate: Acrylic acid = polymer of 50: 45: 5;
5 g were dissolved. N-isopropylacrylamide; 3
0 g, VA-545 (manufactured by Wako Pure Chemical Industries, Ltd.); 0.015
g after dissolving it uniformly in 30 g of water.
r. p. m. Next, the temperature in the system was raised to 50 ° C., and the reaction was carried out for 5 hours, followed by filtration, washing with water and drying to obtain fine particles (B). C60; 0.1 g in a composition ratio (weight) of toluene:
A mixed solvent of THF (tetrahydrofuran) = 1: 1; 5
25 g of the fine particles (B) are added to the solution dissolved in 0 ml,
Stir at room temperature overnight, filter, wash and dry, average particle size 55
About 25 g of the fullerene-containing fine particles of the present invention having a size of μm was obtained. Example 6 In a 200-ml four-necked round-bottomed flask equipped with a stirrer, a condenser, and a nitrogen inlet, 118.5 g of water was placed, and gohsenol; 1.5 g
Was dissolved. C60: 0.05 g of toluene; 25 ml
5 g of methyl methacrylate; 0.01 g of ethylene glycol dimethacrylate; V-6
5 (manufactured by Wako Pure Chemical Industries, Ltd.); 0.003 g was uniformly dissolved, and added. p. m. Next, the temperature in the system was raised to 50 ° C., and the reaction was performed for 5 hours, followed by filtration, washing with water, and drying, to obtain 25 g of fullerene-containing fine particles of the present invention having an average particle diameter of 40 μm. The fullerene-containing fine particles of the present invention have both the function of fullerene and the function of fine particles. Therefore, they can be used as optical functional applications such as wavelength conversion materials, optical switches, and laser devices. It can be applied to antitumor agents and the like.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 69/00 Ｃ０８Ｌ 69/00 (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/00 - 31/36 ＩＮＳＰＥＣ（ＤＩＡＬＯＧ) ＪＩＣＳＴファイル（ＪＯＩＳ) ＷＰＩ（ＤＩＡＬＯＧ)Continuation of the front page (51) Int.Cl. 7 identification code FI C08L 69/00 C08L 69/00 (58) Investigated field (Int.Cl. 7 , DB name) C01B 31/00-31/36 INSPEC (DIALOG ) JICST file (JOIS) WPI (DIALOG)
Claims (1)
体を有機溶媒に溶解した溶液に有機高分子からなる微粒
子を添加、攪拌し、フラーレンおよび／またはフラーレ
ン誘導体を該微粒子に含浸させた後、得られた微粒子を
濾別することを特徴とするフラーレンおよび／またはフ
ラーレン誘導体含有微粒子の製造方法。(57) [Claim 1] A fine particle comprising an organic polymer is added to a solution in which fullerene and / or a fullerene derivative is dissolved in an organic solvent and stirred, and fullerene and / or a fullerene derivative is added to the fine particle. A method for producing fullerene and / or fullerene derivative-containing fine particles, comprising filtering the obtained fine particles after impregnation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853495A JP3412975B2 (en) | 1995-07-25 | 1995-07-25 | Method for producing fullerene-containing fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853495A JP3412975B2 (en) | 1995-07-25 | 1995-07-25 | Method for producing fullerene-containing fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0940412A JPH0940412A (en) | 1997-02-10 |
| JP3412975B2 true JP3412975B2 (en) | 2003-06-03 |
Family
ID=16557787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20853495A Expired - Fee Related JP3412975B2 (en) | 1995-07-25 | 1995-07-25 | Method for producing fullerene-containing fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3412975B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3606855B2 (en) * | 2002-06-28 | 2005-01-05 | ドン ウン インターナショナル カンパニー リミテッド | Method for producing carbon nanoparticles |
| JP2005097329A (en) * | 2003-08-28 | 2005-04-14 | Mitsubishi Chemicals Corp | COMPOSITION CONTAINING FULLERENE DERIVATIVE, AND METHOD FOR PRODUCING COATING AND POWDER USING THE COMPOSITION |
| JP4612392B2 (en) * | 2004-10-20 | 2011-01-12 | 帝人株式会社 | Polyester resin composition and process for producing the same |
| JP4843932B2 (en) * | 2004-10-29 | 2011-12-21 | 東レ株式会社 | Method for producing epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| JP4489741B2 (en) * | 2006-09-01 | 2010-06-23 | 独立行政法人科学技術振興機構 | Fullerene polymer composite and production method thereof |
| CN117203156A (en) * | 2021-03-01 | 2023-12-08 | 赞迪亚制药公司 | Alzheimer's Disease Treatments and Methods |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308481A (en) | 1992-06-02 | 1994-05-03 | Analytical Bio-Chemistry Laboratories, Inc. | Chemically bound fullerenes to resin and silica supports and their use as stationary phases for chromatography |
-
1995
- 1995-07-25 JP JP20853495A patent/JP3412975B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308481A (en) | 1992-06-02 | 1994-05-03 | Analytical Bio-Chemistry Laboratories, Inc. | Chemically bound fullerenes to resin and silica supports and their use as stationary phases for chromatography |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0940412A (en) | 1997-02-10 |
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