JP2003112910A - Method for hydrophilizing carbon molding - Google Patents
Method for hydrophilizing carbon moldingInfo
- Publication number
- JP2003112910A JP2003112910A JP2001309853A JP2001309853A JP2003112910A JP 2003112910 A JP2003112910 A JP 2003112910A JP 2001309853 A JP2001309853 A JP 2001309853A JP 2001309853 A JP2001309853 A JP 2001309853A JP 2003112910 A JP2003112910 A JP 2003112910A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- oxygen
- gas
- container
- treatment
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Carbon And Carbon Compounds (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、本来は疎水性であ
るカーボン成形体を親水性にする方法に関するものであ
る。本発明方法によれば、燃料電池のセパレーターに用
いられるカーボン成形体を親水性とすることができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for making a carbon molded body, which is originally hydrophobic, hydrophilic. According to the method of the present invention, the carbon molding used for the separator of the fuel cell can be made hydrophilic.
【０００２】[0002]
【従来の技術】黒鉛、カーボンブラック、コークス、炭
素繊維のようなカーボン材料と、樹脂やピッチのような
炭素質材料とを混合し、成形したのち必要に応じて焼成
してカーボン成形体を製造することは広く行われてい
る。カーボン成形体は種々の用途に用いられているが、
最近では燃料電池のセパレーターとしての用途が注目さ
れている。2. Description of the Related Art Carbon materials such as graphite, carbon black, coke, and carbon fibers are mixed with carbonaceous materials such as resin and pitch, molded, and then fired if necessary to produce a carbon molded body. Things to do are widespread. Carbon molded bodies are used for various purposes,
Recently, its use as a separator for fuel cells has been drawing attention.
【０００３】カーボン成形体は一般に疎水性なので、親
水性を必要とする用途には、製造に際し予じめ親水性物
質を含有させたり、成形体の表面に親水性物質を塗布し
て親水性を付与することが提案されている。しかしこれ
らの方法は成形体の他の特性を低下させることが多く、
望ましい方法ではない。また、ポリオレフィンなどの親
水化処理に有効とされているコロナ放電処理、紫外線照
射処理、プラズマ処理、フッ素ガス処理などの方法を適
用することも検討されている。これらの方法のなかでも
フッ素ガス処理は、複雑な形状のものにも適用でき、か
つ親水化処理の効果も比較的持続するので、好ましい方
法と考えられる。Since a carbon molded body is generally hydrophobic, for applications that require hydrophilicity, a hydrophilic substance may be contained in advance during manufacture, or a hydrophilic substance may be applied to the surface of the molded body to make it hydrophilic. It is proposed to give. However, these methods often deteriorate other properties of the molded body,
Not the preferred method. Further, application of methods such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, and fluorine gas treatment, which are considered to be effective for hydrophilizing polyolefins, has also been studied. Among these methods, the fluorine gas treatment is considered to be a preferable method since it can be applied to a complicated shape and the effect of the hydrophilic treatment is relatively long-lasting.
【０００４】[0004]
【発明が解決しようとする課題】しかしながらカーボン
成形体は、一般に表面形状が単純でフッ素ガスとの反応
面積が小さいためか、フッ素ガス処理を行っても処理直
後は親水性を示すが、時間が経過すると親水性が低下す
るという問題がある。従って本発明は、カーボン成形体
に長期間に亘り安定した親水性を付与することができ、
従って燃料電池のセパレータのように永続的な親水性が
要求される用途に好適な、カーボン成形体のフッ素ガス
処理方法を提供しようとするものである。However, probably because the carbon molded body generally has a simple surface shape and a small reaction area with the fluorine gas, it shows hydrophilicity immediately after the fluorine gas treatment, but There is a problem that the hydrophilicity decreases with the passage of time. Therefore, the present invention can impart stable hydrophilicity to the carbon molded body for a long period of time,
Accordingly, it is an object of the present invention to provide a fluorine gas treatment method for a carbon molded body, which is suitable for applications where permanent hydrophilicity is required such as a separator of a fuel cell.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、カーボ
ン成形体をフッ素を含むガスで２段階で処理し、かつ第
１段階の処理をフッ素と酸素とを含む混合ガスを用いて
行い、第２段階の処理を第１段階で用いたガスよりもフ
ッ素に対する酸素の比率が小さいガスを用いて行うこと
により、カーボン成形体に長期間に亘り安定した親水性
を付与することができる。According to the present invention, a carbon molded body is treated with a gas containing fluorine in two stages, and the first stage treatment is carried out using a mixed gas containing fluorine and oxygen. By performing the treatment of the second stage using a gas having a smaller ratio of oxygen to fluorine than the gas used in the first stage, it is possible to impart stable hydrophilicity to the carbon molded body for a long period of time.
【０００６】[0006]
【発明の実施の形態】本発明で親水化処理の対象とする
カーボン成形体としては、任意の方法で調製したものを
用いることができる。通常は種々の黒鉛、カーボンブラ
ック、コークス更には炭素繊維などのカーボン材料と、
バインダーとしての熱硬化性樹脂、熱可塑性樹脂、ゴ
ム、ピッチなどの炭素質材料とを混合して成形し、更に
必要に応じて焼成したものが用いられる。なお、カーボ
ン成形体の調製に際しては、作業性などを向上させるた
め、滑剤、架橋促進剤、可塑剤その他の助剤を原材料に
添加してもよい。BEST MODE FOR CARRYING OUT THE INVENTION As the carbon molded body to be subjected to the hydrophilization treatment in the present invention, those prepared by any method can be used. Usually, various graphite, carbon black, coke and carbon materials such as carbon fiber,
A thermosetting resin as a binder, a thermoplastic resin, rubber, a carbonaceous material such as pitch, and the like are mixed, molded, and fired if necessary. When preparing the carbon molded body, a lubricant, a crosslinking accelerator, a plasticizer and other auxiliaries may be added to the raw materials in order to improve workability.
【０００７】本発明ではこのカーボン成形体を、２段階
のフッ素ガス処理により親水化する。その第１段階で
は、カーボン成形体をフッ素と酸素とを含む混合ガスで
処理する。この混合ガスによる親水化の機構は不明であ
るが、成形体表面にフッ素が作用して表面を活性化し、
この活性化された部位に酸素が作用して親水性基が生成
するものと考えられる。この第１段階の処理は、酸素に
対するフッ素のモル比が１．０未満の混合ガスを用いて
行うのが好ましい。処理に用いる混合ガスは、フッ素及
び酸素以外に窒素ガスなどの不活性ガスを含有していて
もよい。混合ガス中の酸素の分圧は通常は１００Ｔｏｒ
ｒ以上であり、２００Ｔｏｒｒ以上であるのが好まし
い。また、フッ素の分圧は通常は６０Ｔｏｒｒ以上であ
り、１００Ｔｏｒｒ以上であるのが好ましい。処理温度
は通常−３０〜２００℃であるが、−１０〜７０℃が好
ましい。特に好ましいのは室温近辺の５〜４０℃であ
る。温度が高いと反応は速いが、高温に過ぎると炭素と
フッ素とでＣＦ結合が生じ、目的とする親水性の発現の
障害となるおそれがある。逆に低温では反応の進行が遅
くなる。反応に要する時間は温度にもよるが、通常は１
分間以上であり、最長でも２４時間も反応させれば十分
である。In the present invention, this carbon compact is made hydrophilic by a two-step fluorine gas treatment. In the first stage, the carbon molded body is treated with a mixed gas containing fluorine and oxygen. The mechanism of hydrophilization by this mixed gas is unknown, but fluorine acts on the surface of the molded body to activate the surface,
It is considered that oxygen acts on this activated site to generate a hydrophilic group. This first-stage treatment is preferably performed using a mixed gas having a molar ratio of fluorine to oxygen of less than 1.0. The mixed gas used for the treatment may contain an inert gas such as nitrogen gas in addition to fluorine and oxygen. The partial pressure of oxygen in the mixed gas is usually 100 Tor
It is at least r, preferably at least 200 Torr. Further, the partial pressure of fluorine is usually 60 Torr or more, and preferably 100 Torr or more. The treatment temperature is usually -30 to 200 ° C, preferably -10 to 70 ° C. Particularly preferred is 5 to 40 ° C. near room temperature. If the temperature is high, the reaction is fast, but if the temperature is too high, CF bond is formed between carbon and fluorine, which may hinder the desired hydrophilicity. On the contrary, the reaction proceeds slowly at low temperature. The time required for the reaction depends on the temperature, but is usually 1
It is more than one minute, and it is enough to react for at least 24 hours.
【０００８】第２段階のフッ素ガス処理は、第１段階で
用いた混合ガスよりもフッ素に対する酸素のモル比率の
小さいガスを用いて行う。好ましくはフッ素に対する酸
素のモル比が０．３以下のガスを用いる。最も好ましく
は酸素を実質的に含有しないガスを用いる。すなわち第
２段階のフッ素ガス処理では、酸素の存在は親水化処理
にとってむしろ有害であるとも考えられる。第２段階の
フッ素ガス処理に用いるガス中のフッ素の分圧も、通常
は６０Ｔｏｒｒ以上であり、１００Ｔｏｒｒ以上である
のが好ましい。またこのガスも窒素ガスなどの不活性ガ
スを含有していてもよい。第２段階のフッ素ガス処理の
温度及び時間は、前述の第１段階のそれと同様である。The second stage fluorine gas treatment is performed using a gas having a smaller molar ratio of oxygen to fluorine than the mixed gas used in the first stage. A gas having a molar ratio of oxygen to fluorine of 0.3 or less is preferably used. Most preferably, a gas containing substantially no oxygen is used. That is, in the second stage fluorine gas treatment, it is considered that the presence of oxygen is rather harmful to the hydrophilic treatment. The partial pressure of fluorine in the gas used for the second stage fluorine gas treatment is also usually 60 Torr or more, preferably 100 Torr or more. This gas may also contain an inert gas such as nitrogen gas. The temperature and time for the second stage fluorine gas treatment are the same as those for the first stage described above.
【０００９】本発明によるカーボン成形体の親水化処理
は、通常は密閉し得る容器中で回分方式で行われる。す
なわち密閉し得る容器にカーボン成形体を収容し、排気
して容器内を真空にする。これに第１段階処理用のガス
を導入し、所定の反応条件下に維持する。次いで排気し
て容器内を真空にしたのち、第２段階処理用のガスを導
入して所定の反応条件下に維持することにより、カーボ
ン成形体が親水化処理される。第１段階及び第２段階と
も処理圧力は任意であるが、安全性及び経済性の点から
して、常圧ないしは減圧が好ましい。また処理用のガス
を導入する前には十分に減圧にするのが好ましい。これ
によりカーボン成形体内部にまで処理用のガスを行きわ
たらせることができる。なお、第１段階の処理では、フ
ッ素と酸素とを別々に容器内に導入してもよいが、その
場合には酸素を先に導入するのが好ましい。The hydrophilic treatment of the carbon molded body according to the present invention is usually carried out in a batchable manner in a container which can be closed. That is, the carbon molded body is housed in a container that can be closed and evacuated to create a vacuum inside the container. A gas for the first stage treatment is introduced into this and maintained under predetermined reaction conditions. Next, the interior of the container is evacuated to form a vacuum, and then the gas for the second stage treatment is introduced to maintain the reaction under predetermined reaction conditions, whereby the carbon molded body is subjected to the hydrophilic treatment. The treatment pressure is arbitrary in both the first stage and the second stage, but from the viewpoint of safety and economy, normal pressure or reduced pressure is preferable. Further, it is preferable to sufficiently reduce the pressure before introducing the processing gas. As a result, the processing gas can be spread to the inside of the carbon molded body. In the first-stage treatment, fluorine and oxygen may be separately introduced into the container, but in that case, it is preferable to introduce oxygen first.
【００１０】[0010]
【実施例】以下に実施例により本発明を更に具体的に説
明する。
実施例１
天然黒鉛とフェノール樹脂とを３：１（重量比）で混合
し、この混合物を１５０℃、４００ｋｇ／ｃｍ2で１０
分間加圧して成形体とし、これを更に機械加工して１５
×１５×３０ｍｍのカーボン成形体とした。内容積１リ
ットルの容器にこのカーボン成形体を収容し、排気して
容器内を真空にした。これにフッ素、酸素及び窒素の混
合ガスを導入して容器内を常圧とした。容器内のフッ素
分圧は１００Ｔｏｒｒ、酸素分圧は２６０Ｔｏｒｒ、窒
素分圧は４００Ｔｏｒｒである。１０分間室温で保持し
たのち排気して容器内を真空とし、次いでフッ素と窒素
との混合ガスを導入して容器内を常圧とした。容器内の
フッ素分圧は１００Ｔｏｒｒ、窒素分圧は６６０Ｔｏｒ
ｒである。１０分間室温で保持したのち容器を開放し、
容器内を窒素ガスで置換したのちカーボン成形体を取出
した。このカーボン成形体について、協和界面科学
（株）製接触角計ＣＡ−Ｄ型を用いて、水滴接触角を測
定した。結果を表−１に示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. Example 1 Natural graphite and phenol resin were mixed at a ratio of 3: 1 (weight ratio), and this mixture was mixed at 150 ° C. and 400 kg / cm 2 for 10 minutes.
It is pressed for a minute to form a compact, which is further machined to 15
A carbon molded body of × 15 × 30 mm was prepared. The carbon molded body was placed in a container having an internal volume of 1 liter, and the container was evacuated to create a vacuum inside the container. A mixed gas of fluorine, oxygen and nitrogen was introduced into this to bring the inside of the container to normal pressure. The fluorine partial pressure in the container is 100 Torr, the oxygen partial pressure is 260 Torr, and the nitrogen partial pressure is 400 Torr. After being kept at room temperature for 10 minutes, the interior of the container was evacuated to form a vacuum, and then a mixed gas of fluorine and nitrogen was introduced to bring the interior of the container to a normal pressure. Fluorine partial pressure in the container is 100 Torr, nitrogen partial pressure is 660 Torr
r. After holding at room temperature for 10 minutes, open the container,
After the inside of the container was replaced with nitrogen gas, a carbon molded body was taken out. The water drop contact angle of this carbon molded body was measured using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table-1.
【００１１】比較例１
内容積１リットルの容器に実施例１で用いたのと同様な
カーボン成形体を収容し、排気して容器内を真空にし
た。これにフッ素、酸素及び窒素の混合ガスを導入して
容器内を常圧とした。容器内のフッ素の分圧は１００Ｔ
ｏｒｒ、酸素分圧は２６０Ｔｏｒｒ、窒素分圧は４００
Ｔｏｒｒである。室温で１０分間保持したのち容器を開
放し、容器内を窒素ガスで置換してからカーボン成形体
を取出した。このカーボン成形体の水滴接触角を表−１
に示す。Comparative Example 1 A carbon molded body similar to that used in Example 1 was placed in a container having an internal volume of 1 liter, and the container was evacuated to create a vacuum inside the container. A mixed gas of fluorine, oxygen and nitrogen was introduced into this to bring the inside of the container to normal pressure. The partial pressure of fluorine in the container is 100T
orr, oxygen partial pressure is 260 Torr, nitrogen partial pressure is 400
Torr. After holding at room temperature for 10 minutes, the container was opened, the inside of the container was replaced with nitrogen gas, and then the carbon molded body was taken out. The water drop contact angle of this carbon compact is shown in Table-1.
Shown in.
【００１２】比較例２
内容積１リットルの容器に実施例１で用いたのと同様な
カーボン成形体を収容し、排気して容器内を真空にした
のちフッ素ガスを導入して常圧に復帰させた。室温で１
０分間保持したのち排気して容器を真空とし、次いでフ
ッ素、酸素及び窒素の混合ガスを導入して容器内を常圧
とした。容器内のフッ素分圧は１００Ｔｏｒｒ、酸素分
圧は２６０Ｔｏｒｒ、窒素分圧は４００Ｔｏｒｒであ
る。室温で１０分間保持したのち容器を開放し、容器内
を窒素ガスで置換してからカーボン成形体を取出した。
このカーボン成形体の水滴接触角を表−１に示す。Comparative Example 2 A carbon molded body similar to that used in Example 1 was housed in a container having an internal volume of 1 liter, and the container was evacuated to evacuate the container, and then fluorine gas was introduced to restore normal pressure. Let 1 at room temperature
After holding for 0 minutes, the container was evacuated to a vacuum, and then a mixed gas of fluorine, oxygen and nitrogen was introduced to bring the inside of the container to normal pressure. The fluorine partial pressure in the container is 100 Torr, the oxygen partial pressure is 260 Torr, and the nitrogen partial pressure is 400 Torr. After holding at room temperature for 10 minutes, the container was opened, the inside of the container was replaced with nitrogen gas, and then the carbon molded body was taken out.
The water drop contact angle of this carbon molded product is shown in Table 1.
【００１３】実施例２
黒鉛板を機械加工して１５×１５×３０ｍｍとしたもの
を用いた以外は、実施例１と同様にしてカーボン成形体
の親水化処理を行った。結果を表−１に示す。Example 2 A carbon molded body was hydrophilized in the same manner as in Example 1 except that a graphite plate was machined to have a size of 15 × 15 × 30 mm. The results are shown in Table-1.
【００１４】[0014]
【表１】 [Table 1]
Claims (6)
段階で処理して親水化する方法であって、第１段階の処
理をフッ素と酸素とを含む混合ガスを用いて行い、第２
段階の処理を第１段階で用いたガスよりもフッ素に対す
る酸素のモル比率が小さいガスを用いて行うことを特徴
とする方法。1. A carbon compact is treated with a gas containing fluorine.
In the method, the first step is performed by using a mixed gas containing fluorine and oxygen.
A method characterized in that the step treatment is carried out using a gas having a smaller molar ratio of oxygen to fluorine than the gas used in the first step.
対するフッ素のモル比が１．０未満のものであることを
特徴とする請求項１記載の方法。2. The method according to claim 1, wherein the gas used for the first-stage treatment has a molar ratio of fluorine to oxygen of less than 1.0.
分圧が６０Ｔｏｒｒ以上であり、酸素の分圧が１００Ｔ
ｏｒｒ以上であり、かつ酸素に対するフッ素のモル比が
１．０未満のものであることを特徴とする請求項１又は
２記載の方法。3. The partial pressure of fluorine of the gas used in the first stage treatment is 60 Torr or more, and the partial pressure of oxygen is 100 T.
The method according to claim 1 or 2, wherein the molar ratio of fluorine to oxygen is less than 1.0.
に対する酸素のモル比が０．３以下のものであることを
特徴とする請求項１ないし３のいずれかに記載の方法。4. The method according to claim 1, wherein the gas used in the second-stage treatment has a molar ratio of oxygen to fluorine of 0.3 or less.
実質的に含まないものであることを特徴とする請求項１
ないし４のいずれかに記載の方法。5. The gas used in the second-step treatment is substantially free of oxygen.
5. The method according to any one of 4 to 4.
ーに用いるものであることを特徴とする請求項１ないし
５のいずれかに記載の方法。6. The method according to claim 1, wherein the carbon molded body is used for a separator of a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001309853A JP4075343B2 (en) | 2001-10-05 | 2001-10-05 | Method for hydrophilizing carbon molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001309853A JP4075343B2 (en) | 2001-10-05 | 2001-10-05 | Method for hydrophilizing carbon molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003112910A true JP2003112910A (en) | 2003-04-18 |
| JP4075343B2 JP4075343B2 (en) | 2008-04-16 |
Family
ID=19128932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001309853A Expired - Lifetime JP4075343B2 (en) | 2001-10-05 | 2001-10-05 | Method for hydrophilizing carbon molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4075343B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106550614A (en) * | 2014-05-30 | 2017-03-29 | Sei株式会社 | Electrode material and its manufacture method and lithium battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015068559A1 (en) | 2013-11-11 | 2015-05-14 | 株式会社神戸製鋼所 | Titanium separator material for fuel cells, and method for producing titanium separator material for fuel cells |
-
2001
- 2001-10-05 JP JP2001309853A patent/JP4075343B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106550614A (en) * | 2014-05-30 | 2017-03-29 | Sei株式会社 | Electrode material and its manufacture method and lithium battery |
| CN106550614B (en) * | 2014-05-30 | 2020-03-20 | Sei株式会社 | Electrode material, method for producing same, and lithium battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4075343B2 (en) | 2008-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101576052B1 (en) | carbon dioxide separation membrane comprising porous hollow titanium dioxide nanoparticle and manufacturing method thereof | |
| EP2889334A1 (en) | Flaked graphite resin composite material and method for producing same | |
| EP1059991B1 (en) | Methods for reforming polymer surface for improved wettability | |
| CN1019401B (en) | Process for preparing open pore polyethylene foam | |
| US6860910B2 (en) | Carbon foam abrasives | |
| JPH02269134A (en) | Method for producing smooth surface on object comprising polymer of ethylene, propylene, butadiene, and styrene, and object comprising hdpe | |
| US4124691A (en) | Method for the preparation of reticulate carbon structures | |
| JP2003112910A (en) | Method for hydrophilizing carbon molding | |
| US4698233A (en) | Production of aluminum material having an aluminum nitride layer | |
| SE447429B (en) | PROCEDURE FOR THE PREPARATION OF FUEL EXTENSIONS OF FLEXIBLE NUCLEAR FUEL CONTAINING URAND Dioxide | |
| JPH01275639A (en) | Surface modification | |
| US4855093A (en) | Process of making a diaphragm of carbonaceous materials for a speaker | |
| Kurokawa et al. | Trapping sites of polypropylene mechano-radicals | |
| US10167198B2 (en) | Method for producing flake graphite, and flake graphite | |
| JP2004339344A (en) | Method for producing modified polytetrafluoroethylene film | |
| JPH059812A (en) | Porous carbon fiber, its production, production of porous graphite fiber and treatment of porous carbon fiber | |
| JPS61146522A (en) | Preparation of porous body made of polytetrafluoroethylene resin | |
| JPH0625709A (en) | Production of sintered hard alloy parts | |
| JPS58463B2 (en) | New manufacturing method for ion exchange membranes | |
| JP3237003B2 (en) | Porous carbon material and method for producing the same | |
| JP4773737B2 (en) | Polar liquid supplier for fuel cell, method for producing the same, and fuel cell | |
| JPH08171883A (en) | Carbon material for ion implantating device | |
| JPS63166759A (en) | Manufacture of carbon material | |
| JP2004035835A (en) | Preparation of foamed body using supercritical fluid | |
| JPS63229123A (en) | Membrane for gas separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040604 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070307 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070807 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071004 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080108 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080121 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4075343 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110208 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120208 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120208 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130208 Year of fee payment: 5 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |