JPH0632993A - Production of ultrafine graphite powder coating material excellent in oxidation resistance - Google Patents
Production of ultrafine graphite powder coating material excellent in oxidation resistanceInfo
- Publication number
- JPH0632993A JPH0632993A JP4189353A JP18935392A JPH0632993A JP H0632993 A JPH0632993 A JP H0632993A JP 4189353 A JP4189353 A JP 4189353A JP 18935392 A JP18935392 A JP 18935392A JP H0632993 A JPH0632993 A JP H0632993A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- water
- oxidation resistance
- particle size
- ultrafine
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/46—Graphite
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐酸化性に優れた超微粉
末黒鉛塗料の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ultrafine powder graphite paint having excellent oxidation resistance.
【０００２】[0002]
【従来の技術】従来の超微粉末黒鉛塗料の製造方法とし
ては、天然精製鱗状黒鉛あるいは人造黒鉛を、真空中あ
るいは窒素、水素などの気体中で乾式粉砕することによ
り、超微粉末黒鉛を得（たとえば、粉体工学研究会誌
６，87 (1969) ）、これを水などの媒体に分散させるこ
とによっていた。2. Description of the Related Art As a conventional method for producing ultrafine powder graphite paint, natural fine scaly graphite or artificial graphite is dry-pulverized in vacuum or in a gas such as nitrogen or hydrogen to obtain ultrafine powder graphite. (For example, Journal of Powder Engineering Research Society
6 , 87 (1969)) by dispersing it in a medium such as water.
【０００３】[0003]
【発明が解決しようとする課題】しかしこの方法による
と非常に表面積の大きな粉体が得られるために、塗料化
しても耐酸化性の悪いものしか得られない。またこの方
法では非常に粒度範囲の大きな粉末が得られるために、
極めて精密な分級をするか、分散方法に工夫をこらすな
どしなければ安定な分散体として取出すことが難しく、
また生産性が低く、品質が不安定であるなどの問題点が
あった。However, according to this method, a powder having a very large surface area can be obtained, so that even if it is made into a paint, only a poor oxidation resistance can be obtained. In addition, since a powder having a very large particle size range can be obtained by this method,
It is difficult to take it out as a stable dispersion unless it is classified extremely accurately or the dispersion method is devised.
Moreover, there are problems such as low productivity and unstable quality.
【０００４】更に、他の超微粉末黒鉛塗料の製造方法と
しては、上記黒鉛粉末を重クロム酸カリウムと硝酸など
の強力な酸化剤で酸化させて酸化黒鉛を得て、これを加
水分解させることにより超微粉末を得ていたが（たとえ
ば Kolloid Zeitschritt 78,105 (1937)、米国特許第1,
175,958 号明細書) 。この場合、洗浄などに大量な水が
必要であり、また表面に酸化物があるために、非常に酸
化しやすいものであった。Further, as another method for producing an ultrafine powder graphite coating, the above graphite powder is oxidized with a strong oxidizing agent such as potassium dichromate and nitric acid to obtain graphite oxide, which is hydrolyzed. Ultra fine powder was obtained (for example, Kolloid Zeitschritt 78, 105 (1937), U.S. Pat.
175,958 specification). In this case, a large amount of water is required for washing and the like, and since the surface has oxides, it is very easy to oxidize.
【０００５】また更に、土状黒鉛の場合、その一次粒子
は小さく、平均粒径が 0.5μm の分散体を作るのは容易
であったが、土状黒鉛にもともと存在する灰分を除去す
ることが難しく、この灰分のために耐酸化性が劣り実用
化に問題があった。従って本発明の目的は耐酸化性に優
れた超微粉末黒鉛塗料の製造方法を提供することにあ
る。Furthermore, in the case of earth-like graphite, the primary particles are small and it was easy to form a dispersion having an average particle diameter of 0.5 μm, but it was possible to remove the ash originally present in the earth-like graphite. It was difficult to use, and because of this ash content, the oxidation resistance was poor and there was a problem in practical application. Therefore, an object of the present invention is to provide a method for producing an ultrafine powder graphite coating material having excellent oxidation resistance.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成した本発
明の耐酸化性に優れた超微粉末黒鉛塗料の製造方法は、
天然土状黒鉛を粉砕した後、浮遊選鉱で物理精練し、次
いでアルカリ、酸処理により化学精練することにより灰
分が３％以下、表面積が 50m2 ／ｇ以下、平均粒子径が
0.5μm で且つ最大粒子径が 1.0μm 以下の高純度超微
粉末の黒鉛を得、この黒鉛を水または有機溶剤に分散さ
せることを特徴とする。Means for Solving the Problems The method for producing an ultrafine powder graphite paint excellent in oxidation resistance according to the present invention, which achieves the above objects, comprises:
After crushing natural earth graphite, it is physically refined by flotation, and then chemically refined by alkali and acid treatment, so that the ash content is 3% or less, the surface area is 50 m 2 / g or less, and the average particle size is
It is characterized in that high-purity ultrafine powder graphite having a particle size of 0.5 μm and a maximum particle size of 1.0 μm or less is obtained, and the graphite is dispersed in water or an organic solvent.
【０００７】本発明の超微粉末黒鉛塗料の製造方法にお
いては、先ず出発原料の天然土状黒鉛を粉砕するが、粉
砕は通常湿式粉砕機を用いて行い、最大粒径が1.0 μm
以下のものを得る。該粒径が 1.0μm より大になると分
散が悪くなり、塗料にした場合その隠蔽力が不足する。In the method for producing an ultrafine powder graphite coating material of the present invention, the starting material, natural earth-like graphite, is first pulverized. The pulverization is usually carried out using a wet pulverizer, and the maximum particle size is 1.0 μm.
Get the following: If the particle size is larger than 1.0 μm, the dispersion will be poor and the hiding power of the paint will be insufficient.
【０００８】このようにした粉砕された黒鉛は浮遊選鉱
により物理精練し、次いでアルカリ処理、例えば水酸化
ナトリウムまたは水酸化カリウムで処理し、酸処理、例
えば塩酸、硫酸または酢酸等で処理して化学精練して高
純度微粉末の黒鉛を得る。この黒鉛は灰分が３％以下、
表面積が 50m2 ／ｇ以下、平均粒子径が 0.5μm でかつ
最大粒子径が 1.0μm 以下であることが必要である。表
面積が 50m2 ／ｇより大になると耐酸化性が悪化し、平
均粒子径が 0.5μm より大で最大粒子径が 1.0 μm よ
り大では分散が悪くなり、塗料とした場合その隠蔽力が
不足する。The thus crushed graphite is physically refined by flotation, then treated with an alkali, for example, sodium hydroxide or potassium hydroxide, and treated with an acid, for example, hydrochloric acid, sulfuric acid or acetic acid, and chemically. It is refined to obtain high purity fine powder graphite. This graphite has an ash content of 3% or less,
It is necessary that the surface area is 50 m 2 / g or less, the average particle size is 0.5 μm, and the maximum particle size is 1.0 μm or less. If the surface area is more than 50 m 2 / g, the oxidation resistance will be poor, and if the average particle size is greater than 0.5 μm and the maximum particle size is greater than 1.0 μm, the dispersion will be poor and the hiding power will be insufficient when used as a paint. .
【０００９】上記高純度微粉末の黒鉛を、水または有機
溶剤、例えばアルコール、メチルエチルケトン、リグロ
イン等に分散させると塗料が得られる。この際分散剤と
して、水溶性高分子、例えばカルボキシメチルセルロー
スナトリウム（ＣＭＣ）、リグニンスルホン酸ナトリウ
ム、ポリカルボン酸ナトリウムまたはポリビニルアルコ
ール等を黒鉛の５〜50％の範囲で添加するのが好まし
い。A coating material can be obtained by dispersing the above high-purity fine powder graphite in water or an organic solvent such as alcohol, methyl ethyl ketone, ligroin, or the like. At this time, it is preferable to add a water-soluble polymer such as sodium carboxymethyl cellulose (CMC), sodium lignin sulfonate, sodium polycarboxylate or polyvinyl alcohol as a dispersant in the range of 5 to 50% of graphite.
【００１０】上記本発明の方法で得られた黒鉛塗料は、
タングステン線、モリブデン線、ステンレス線の線引用
潤滑剤として、例えば直径２〜５μm 極細線の線引きに
用いられる。このような潤滑剤の場合には黒鉛が細くな
いと線にのらない。また黒鉛塗料塗布後、500 〜900 ℃
のような高温での熱処理が必要であるので、耐酸化性に
すぐれていないと酸化燃焼し、潤滑性を失う。The graphite paint obtained by the method of the present invention is
Used as a wire drawing lubricant for tungsten wire, molybdenum wire, and stainless wire, for example, for drawing ultrafine wires having a diameter of 2 to 5 μm. In the case of such a lubricant, if the graphite is not fine, it will not line up. After applying the graphite paint, 500-900 ℃
Since heat treatment at a high temperature is required, if it is not excellent in oxidation resistance, it will oxidize and burn and lose lubricity.
【００１１】更に、上記黒鉛塗料は、またカラーブラウ
ン管のマトリックス用塗料等として用いられる。マトリ
ックス用塗料等として用いる場合にはこの塗料により直
径30〜100 μm のホールが形成される。この際黒鉛が細
くないとホールの形状が悪く、また隠蔽力がでない。黒
鉛塗料塗布後に高温の熱処理、例えば 450〜500 ℃で３
時間以上処理することが必要であるので、耐酸化性に優
れていないと酸化燃焼し隠蔽力が悪くなる。Further, the above graphite paint is also used as a paint for a matrix of a color cathode ray tube. When used as a matrix paint, etc., this paint forms holes with a diameter of 30 to 100 μm. At this time, if the graphite is not thin, the shape of the hole is bad and the hiding power is not good. After applying the graphite paint, heat treatment at high temperature, eg 3 at 450-500 ℃
Since it is necessary to treat for more than a time, if it is not excellent in oxidation resistance, it will oxidize and burn and the hiding power will deteriorate.
【００１２】[0012]
【実施例】以下本発明を実施例および比較例により説明
する。実施例 天然土状黒鉛（灰分15％）500 ｇと水２ lをボールミル
に投入し、粉砕した後、ファーレンワールド式浮遊機に
より物理精練を行った（灰分５％）。次いで25％水酸化
ナトリウム溶液中で２時間加熱し、次いで10％塩酸中で
80℃で２時間加熱し、十分に水洗を行い、表面積45 m2
／ｇ、平均粒径0.25μm 、灰分1.2 ％の超微粉末黒鉛を
得た。この黒鉛につき、（株）理学社製、熱分析装置を
用い、加熱による減量を測定し、結果を図１に熱減量曲
線で示す。EXAMPLES The present invention will be described below with reference to examples and comparative examples. Example 500 g of natural earth graphite (ash content: 15%) and 2 liters of water were put into a ball mill, pulverized, and then physically scoured by a Fahrenworld floater (ash content: 5%). Then heat in 25% sodium hydroxide solution for 2 hours, then in 10% hydrochloric acid.
Heat at 80 ° C for 2 hours, wash thoroughly with water, surface area 45 m 2
/ G, average particle size of 0.25 μm, and ash content of 1.2%, ultrafine powder graphite was obtained. With respect to this graphite, the weight loss due to heating was measured using a thermal analyzer manufactured by Rigaku Co., Ltd., and the result is shown in the heat loss curve in FIG.
【００１３】上記黒鉛粉末を50ｇのカルボキシメチルセ
ルロースナトリウムとともに４ｌの水に懸濁させ塗料を
得た。The above graphite powder was suspended in 4 liters of water together with 50 g of sodium carboxymethyl cellulose to obtain a paint.
【００１４】比較例 天然鱗状黒鉛（灰分15％）500 ｇを真空中で乾式ボール
ミルにより粉砕し、表面積250m2 ／ｇ，平均粒径0.25μ
m 、灰分1.5 ％の粉末黒鉛を得た。この黒鉛につき、実
施例の黒鉛と同様にして加熱による減量を測定し、結果
を図１に熱減量曲線で示す。上記黒鉛粉末を50ｇのカル
ボキシルメチルセルロースナトリウムとともに水に懸濁
させ塗料を得た。Comparative Example 500 g of natural scaly graphite (ash content: 15%) was crushed by a dry ball mill in vacuum to have a surface area of 250 m 2 / g and an average particle size of 0.25 μm.
A powdered graphite with m 2 and ash content of 1.5% was obtained. With respect to this graphite, the weight loss due to heating was measured in the same manner as the graphite of the example, and the result is shown in the heat loss curve in FIG. The above graphite powder was suspended in water together with 50 g of sodium carboxymethyl cellulose to obtain a paint.
【００１５】[0015]
【発明の効果】以上説明してきたように、本発明は、天
然土状黒鉛を湿式粉砕機で粉砕した後、浮遊選鉱で物理
精練し、次いでアルカリ処理、酸処理により化学精練す
ることにより規定する高純度微粉末の黒鉛を得、この黒
鉛を水または有機溶剤に分散させて塗料を製造するとい
う構成としたことにより、得られる超微粉末黒鉛塗料は
耐酸化性が著しく改善されるという効果が得られる。As described above, the present invention is defined by crushing natural earth graphite with a wet crusher, physically scouring by flotation, and then chemically scouring by alkali treatment and acid treatment. By obtaining a graphite of high purity fine powder and dispersing the graphite in water or an organic solvent to produce a coating, the obtained ultrafine powder graphite coating has the effect of significantly improving the oxidation resistance. can get.
【図１】実施例および比較例で得られた黒鉛の熱減量曲
線図である。FIG. 1 is a thermal loss curve diagram of graphite obtained in Examples and Comparative Examples.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 //(Ｃ１０Ｍ 173/02 103:02） Ｚ 9159−4Ｈ Ｃ１０Ｎ 20:06 Ｚ 8217−4Ｈ 30:10 40:24 Ｚ 8217−4Ｈ 70:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display area // (C10M 173/02 103: 02) Z 9159-4H C10N 20:06 Z 8217-4H 30: 10 40:24 Z 8217-4H 70:00
Claims (1)
後、浮遊選鉱で物理精練し、次いでアルカリ処理、酸処
理により化学精練することにより灰分を３％以下、表面
積が 50m2 ／ｇ以下、平均粒子径が 0.5μm 以下でかつ
最大粒子径が1.0 μm 以下の高純度超微粉末の黒鉛を
得、この黒鉛を水または有機溶剤に分散させることを特
徴とする耐酸化性に優れた超微粉末黒鉛塗料の製造方
法。1. The natural ash graphite is pulverized by a wet pulverizer, physically refined by flotation, and then chemically refined by an alkali treatment and an acid treatment to obtain an ash content of 3% or less and a surface area of 50 m 2 / g or less. , High-purity ultrafine powder graphite with an average particle diameter of 0.5 μm or less and a maximum particle diameter of 1.0 μm or less, and this graphite is dispersed in water or an organic solvent, which has excellent oxidation resistance. Method for producing fine powder graphite paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4189353A JPH0632993A (en) | 1992-07-16 | 1992-07-16 | Production of ultrafine graphite powder coating material excellent in oxidation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4189353A JPH0632993A (en) | 1992-07-16 | 1992-07-16 | Production of ultrafine graphite powder coating material excellent in oxidation resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0632993A true JPH0632993A (en) | 1994-02-08 |
Family
ID=16239909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4189353A Pending JPH0632993A (en) | 1992-07-16 | 1992-07-16 | Production of ultrafine graphite powder coating material excellent in oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0632993A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583360A (en) * | 2012-04-16 | 2012-07-18 | 丁慧贤 | Method for purifying graphite by using microwave |
| KR101439536B1 (en) * | 2012-07-24 | 2014-10-30 | 주식회사 태삼진 | Method of manufacturing natural flaky griphite by mechanical mill |
| CN109607527A (en) * | 2017-12-05 | 2019-04-12 | 湖南有色金属研究院 | A kind of purification by mineral method of low-grade micro crystal graphite |
| CN110077048A (en) * | 2019-05-16 | 2019-08-02 | 重庆云天化瀚恩新材料开发有限公司 | A kind of graphene heat-conducting piece and preparation method thereof |
-
1992
- 1992-07-16 JP JP4189353A patent/JPH0632993A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583360A (en) * | 2012-04-16 | 2012-07-18 | 丁慧贤 | Method for purifying graphite by using microwave |
| KR101439536B1 (en) * | 2012-07-24 | 2014-10-30 | 주식회사 태삼진 | Method of manufacturing natural flaky griphite by mechanical mill |
| CN109607527A (en) * | 2017-12-05 | 2019-04-12 | 湖南有色金属研究院 | A kind of purification by mineral method of low-grade micro crystal graphite |
| CN109607527B (en) * | 2017-12-05 | 2022-01-28 | 湖南有色金属研究院 | Beneficiation and purification method of low-grade microcrystalline graphite |
| CN110077048A (en) * | 2019-05-16 | 2019-08-02 | 重庆云天化瀚恩新材料开发有限公司 | A kind of graphene heat-conducting piece and preparation method thereof |
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