JPH07223809A - Graphite material and production thereof - Google Patents
Graphite material and production thereofInfo
- Publication number
- JPH07223809A JPH07223809A JP6037671A JP3767194A JPH07223809A JP H07223809 A JPH07223809 A JP H07223809A JP 6037671 A JP6037671 A JP 6037671A JP 3767194 A JP3767194 A JP 3767194A JP H07223809 A JPH07223809 A JP H07223809A
- Authority
- JP
- Japan
- Prior art keywords
- graphitized
- graphite material
- mesophase
- mesophase spherules
- pulverized
- 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
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- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、樹脂に添加される摺動
用などの充填剤、面状発熱体、各種プリント基板や電子
材料における導電材料、非水電解質二次電池の負極材料
などとして有用な黒鉛材料およびその製造方法に関す
る。INDUSTRIAL APPLICABILITY The present invention is useful as a filler added to a resin for sliding, a sheet heating element, a conductive material in various printed boards and electronic materials, a negative electrode material for non-aqueous electrolyte secondary batteries, and the like. Graphite material and its manufacturing method.
【０００２】[0002]
【従来の技術】メソフェーズ小球体（メソカーボンマイ
クロビーズ）は、高度に配向した黒鉛類似の結晶構造を
有する球状の炭素微粒子である。このメソフェーズ小球
体は、他の炭素材にはみられない特異な構造および形状
を有しているため、これらの性質を有効に活用すべく、
多くの検討がなされている。2. Description of the Related Art Mesophase microspheres (mesocarbon microbeads) are spherical carbon fine particles having a highly oriented graphite-like crystal structure. Since this mesophase microsphere has a unique structure and shape not found in other carbon materials, in order to effectively utilize these properties,
Many studies have been made.
【０００３】前記メソフェーズ小球体は自己焼結性を有
し、バインダーを添加することなく成形および焼成でき
るとともに、従来の炭素材よりも、高密度および高強度
で均質性の高い等方性炭素ブロックを少ない工程で製造
することが可能である。そのため、一元（１成分）系炭
素材の原料として、炭素材メーカーでは広く使用されて
いる。The mesophase spherules are self-sintering, can be molded and fired without adding a binder, and are isotropic carbon blocks having higher density and higher strength and higher homogeneity than conventional carbon materials. Can be manufactured in a small number of steps. Therefore, it is widely used by carbon material manufacturers as a raw material of a unitary (one component) type carbon material.
【０００４】一方、メソフェーズ小球体の黒鉛化物を樹
脂組成物へ添加すると、従来の黒鉛材料では発現し得な
い新たな機能が発現することが明らかにされている。し
かし、粒度分布が１〜１００μｍ程度であるメソフェー
ズ小球体のうち、２０μｍ以上の粒子径を有するもの
は、樹脂複合材とする場合に、必要量以上のバインダー
を必要とするため、通常、使用することが困難である
が、それらを有効に活用するため、メソフェーズ小球体
を粉砕して使用することも考えられる。On the other hand, it has been clarified that when a graphitized mesophase spherule is added to a resin composition, a new function that cannot be exhibited by a conventional graphite material is exhibited. However, among the mesophase small spheres having a particle size distribution of about 1 to 100 μm, those having a particle size of 20 μm or more require a binder in an amount more than necessary when used as a resin composite material, and thus are usually used. However, in order to make effective use of them, it is possible to crush and use the mesophase microspheres.
【０００５】また、黒鉛材料において、メソフェーズ小
球体の異方性を低減するため、メソフェース小球体の黒
鉛化物を粉砕することも考えられる。しかし、黒鉛化し
たメソフェーズ小球体を粉砕すると、黒鉛結晶構造の配
向面で劈開が生じ、鱗片状、半球状、すり鉢状などのい
びつな形状となる。そのため、メソフェーズ小球体の黒
鉛化物を粉砕して樹脂などに添加しても、均質な混合物
を得ることが困難であるとともに、得られた複合材に異
方性が発現し、種々の特性に方向性が生じる。また、メ
ソフェーズ小球体の破砕面に、結晶破壊によるエッジが
残存し、破砕物の比表面積が大きくなるため、複合材に
要求される強度を得るためには、過剰量の樹脂を使用す
る必要がある。そのため、樹脂複合材本来の機能が損わ
れる。さらに、粉砕時の衝撃により、結晶構造に変化が
生じ、粉砕前の黒鉛化物とは物性値が異なる粉砕物しか
得られない。Further, in the graphite material, it may be considered to grind the graphitized mesophase spheres in order to reduce the anisotropy of the mesophase spheres. However, when the graphitized mesophase spherules are crushed, cleavage occurs in the orientation plane of the graphite crystal structure, and the spheroidal, hemispherical, and mortar-like shapes are formed. Therefore, it is difficult to obtain a homogeneous mixture even when the graphitized mesophase spherules are pulverized and added to a resin, etc., and the obtained composite material exhibits anisotropy, and it has various properties. Sexuality occurs. In addition, the crushed surface of the mesophase spherules has an edge due to crystal destruction, which increases the specific surface area of the crushed material.Therefore, it is necessary to use an excessive amount of resin to obtain the strength required for the composite material. is there. Therefore, the original function of the resin composite material is impaired. Furthermore, the impact during pulverization causes a change in the crystal structure, and only pulverized products having physical properties different from those of the graphitized product before pulverization can be obtained.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、粉砕するにも拘らず、メソフェーズ小球体の黒鉛化
物が有している優れた特性を保持しているとともに、樹
脂複合材などに等方性を付与できる黒鉛材料およびその
製造方法を提供することにある。Therefore, an object of the present invention is to retain the excellent properties of the graphitized mesophase spheroids despite being pulverized, and to provide a resin composite material and the like. It is to provide a graphite material capable of imparting isotropy and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記目的
を達成するため鋭意検討の結果、メソフェーズ小球体を
予め粉砕して炭素化又は黒鉛化すると、得られた黒鉛材
料がメソフェーズ小球体の黒鉛化物の特性をそのまま維
持していることを見いだし、本発明を完成した。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that when the mesophase spherules are preliminarily crushed and carbonized or graphitized, the obtained graphite material is mesophase spherules. The inventors have found that the characteristics of the graphitized product of No. 1 are maintained as they are, and completed the present invention.
【０００８】すなわち、本発明の方法では、メソフェー
ズ小球体を炭素化および黒鉛化する方法において、炭素
化又は黒鉛化に先立ってメソフェーズ小球体を粉砕し、
黒鉛材料を製造する。この方法において、メソフェーズ
小球体を粉砕した後、炭素化し、黒鉛化してもよく、メ
ソフェーズ小球体を炭素化した後、粉砕し、黒鉛化して
もよい。That is, according to the method of the present invention, in the method for carbonizing and graphitizing mesophase microspheres, the mesophase microspheres are crushed prior to carbonization or graphitization,
Manufacture graphite material. In this method, the mesophase spherules may be crushed and then carbonized and graphitized, or the mesophase spherules may be carbonized and then crushed and graphitized.
【０００９】本発明の材料は、前記の方法により得られ
た黒鉛材料である。この黒鉛材料の平均粒径は、例え
ば、２〜２０μｍ程度であってもよい。前記黒鉛材料
は、メソフェーズ小球体の黒鉛化物の特性をそのまま備
えているという特色がある。The material of the present invention is a graphite material obtained by the above method. The average particle size of this graphite material may be, for example, about 2 to 20 μm. The graphite material is characterized in that it has the same characteristics as the graphitized product of mesophase spherules.
【００１０】なお、本明細書において、「炭素化」と
は、特に言及しない限り、非酸化性雰囲気中、例えば４
５０〜１５００℃程度の温度で焼成処理することを言
う。また、黒鉛化とは、特に言及しない限り、非酸化性
雰囲気中、例えば、１５００〜３０００℃程度の温度で
焼成処理することを言い、結晶構造が黒鉛構造でないと
きも黒鉛化の概念に含める。In the present specification, the term "carbonization" is used in a non-oxidizing atmosphere, for example, 4 unless otherwise stated.
It means firing at a temperature of about 50 to 1500 ° C. Further, unless otherwise specified, the graphitization refers to a baking treatment in a non-oxidizing atmosphere at a temperature of, for example, about 1500 to 3000 ° C., and the graphitization concept also includes the case where the crystal structure is not the graphite structure.
【００１１】メソフェーズ小球体（メソカーボンマイク
ロビーズ）は、コールタール、コールタールピッチ、石
油系重質油（例えば、アスファルト）やエチレンボトム
油などの歴青物を、例えば、常圧〜２０ｋｇ／ｃｍ2 ・
Ｇ、温度３５０〜４５０℃程度の条件で熱処理し、生成
した球晶を分離精製することにより得られる。前記球晶
は、マトリックスピッチとは異なる相を形成しており、
ピッチの加熱処理過程において、アンチソルベント法、
遠心分離法等により単離できる。The mesophase microspheres (mesocarbon microbeads) include bituminous substances such as coal tar, coal tar pitch, petroleum heavy oil (eg asphalt) and ethylene bottom oil, for example, atmospheric pressure to 20 kg / cm 2.・
It is obtained by heat-treating under the conditions of G and temperature of 350 to 450 ° C., and separating and refining the generated spherulite. The spherulites form a phase different from the matrix pitch,
In the heat treatment process of pitch, anti-solvent method,
It can be isolated by a centrifugation method or the like.
【００１２】メソフェーズ小球体は、高度に結晶が配向
し、炭素六員環網目が層状に積層した構造を有する球晶
であり、異方性を有する球状の微小粒子である。前記メ
ソフェーズ小球体のＢＥＴ比表面積は、通常、７０ｍ2
／ｇ以下（好ましくは１〜１０ｍ2 ／ｇ程度）である。
前記メソフェーズ小球体は、例えば、１〜１００μｍ程
度の粒度分布を有している場合が多く、その平均粒子径
は、例えば、２〜８０μｍ程度である。The mesophase spherules are spherulites having a structure in which crystals are highly oriented and a carbon six-membered ring network is laminated in layers, and are spherical fine particles having anisotropy. The BET specific surface area of the mesophase microspheres is usually 70 m 2
/ G or less (preferably about 1 to 10 m 2 / g).
The mesophase microspheres often have a particle size distribution of, for example, about 1 to 100 μm, and the average particle size thereof is, for example, about 2 to 80 μm.
【００１３】このようなメソフェーズ小球体は、少なく
とも黒鉛化に先立って粉砕される。すなわち、本発明の
方法には、（１）メソフェーズ小球体を粉砕した後、炭
素化および黒鉛化する方法、（２）メソフェーズ小球体
を炭素化した後、粉砕して黒鉛化する方法が含まれる。Such mesophase spherules are crushed at least prior to graphitization. That is, the method of the present invention includes (1) a method of pulverizing mesophase spherules and then carbonizing and graphitizing, and (2) a method of carbonizing the mesophase spherules and then pulverizing and graphitizing. .
【００１４】メソフェーズ小球体の粉砕方法は特に制限
されず、種々の粉砕手段が利用できる。粉砕手段として
は、機械的に摩砕する手段、例えば、ボールミル、ハン
マーミル、ＣＦミル、アトマイザーミル、パルベライザ
ーなど、風力を利用した粉砕手段、例えば、ジェットミ
ルなどが例示される。また、粉砕時の発熱を抑制して粉
砕効率を高めるため、冷凍又は凍結粉砕機なども利用で
きる。さらに必要であれば、粉砕に際して、分散助剤を
添加して分散性を高めることも可能である。The method for pulverizing the mesophase microspheres is not particularly limited, and various pulverizing means can be used. Examples of the pulverizing means include means for mechanically pulverizing, for example, ball mill, hammer mill, CF mill, atomizer mill, pulverizer and the like, pulverizing means utilizing wind power, for example, jet mill. Further, in order to suppress heat generation during crushing and increase crushing efficiency, a freezing or freeze crushing machine or the like can be used. Further, if necessary, it is possible to add a dispersion aid during pulverization to enhance the dispersibility.
【００１５】メソフェーズ小球体の粉砕物またはメソフ
ェーズ小球体の炭素化物の粉砕物の粒径は、広い範囲で
選択でき、例えば、平均粒径１〜２０μｍ、好ましくは
１〜１０μｍ程度である。粉砕物の平均粒径が１μｍ未
満では、粒子サイズが小さすぎてカーボンブラックに近
い粒径となるとともに、吸油量が多くなるので、樹脂と
の均一な混合が困難となることに加えて、複合化しても
機能が有効に発現しない場合がある。また、平均粒径が
２０μｍを越えると、通常の添加量では複合材の十分な
強度を確保することが困難であるため、必要以上の樹脂
を使用する必要性が生じ、複合材本来の機能が損われ易
い。The particle size of the pulverized product of mesophase spherules or the pulverized product of carbonized mesophase spherules can be selected within a wide range, and for example, the average particle size is 1 to 20 μm, preferably about 1 to 10 μm. If the average particle size of the pulverized product is less than 1 μm, the particle size is too small and the particle size is close to that of carbon black, and the amount of oil absorption increases, which makes it difficult to uniformly mix with the resin. The function may not be effectively expressed even if it is turned into a solid. Further, if the average particle size exceeds 20 μm, it is difficult to secure sufficient strength of the composite material with a normal addition amount, so that it becomes necessary to use more resin than necessary, and the original function of the composite material is It is easily damaged.
【００１６】メソフェーズ小球体の炭素化は、固定床ま
たは流動床方式の炭化炉で行なうことができ、所定の温
度まで昇温できる炉であれば炭素化炉の加熱方式や種類
は特に限定されない。炭素化炉としては、例えば、リー
ドハンマー炉、トンネル炉、単独炉などが例示される。The carbonization of the mesophase spherules can be carried out in a fixed bed or fluidized bed carbonization furnace, and the heating system and type of the carbonization furnace are not particularly limited as long as it can raise the temperature to a predetermined temperature. Examples of the carbonization furnace include a lead hammer furnace, a tunnel furnace, and a single furnace.
【００１７】炭素化は、前記の条件で行なえばよいが、
好ましくは、非酸化性雰囲気、特に不活性雰囲気下、最
終到達温度４５０〜１５００℃、さらに好ましくは６０
０〜１５００℃程度で行なうことができる。処理温度が
４５０℃未満では、メソフェーズ小球体を粉砕して炭素
化および黒鉛化処理する場合、メソフェーズ小球体に残
存する未炭化の芳香族化合物が流出し、それらがバイン
ダーとなって粉砕したメソフェーズ小球体を再度焼結さ
せたり、流出物が黒鉛化炉に付着して炉を損傷させる場
合がある。なお、メソフェーズ小球体をそのまま炭素化
する場合、通常、流出物の処理装置を備えた炭化炉で炭
素化する場合が多いため、特に大きな問題とはならな
い。また処理温度が１５００℃を越える場合には、最終
的に黒鉛化炉でそれ以上の温度で再度加熱処理するため
経済的ではない。Carbonization may be carried out under the above conditions,
Preferably, in a non-oxidizing atmosphere, particularly an inert atmosphere, the final temperature reached is 450 to 1500 ° C., more preferably 60.
It can be performed at about 0 to 1500 ° C. When the treatment temperature is lower than 450 ° C, when the mesophase spherules are crushed for carbonization and graphitization, uncarbonized aromatic compounds remaining in the mesophase spherules flow out, and they serve as a binder to pulverize the mesophase spherules. The spheres may be re-sintered or the effluent may stick to the graphitization furnace and damage it. When the mesophase spherules are carbonized as they are, they are usually carbonized in a carbonization furnace equipped with an effluent treatment device, so that they are not particularly serious problems. Further, when the treatment temperature exceeds 1500 ° C., the heat treatment is finally performed again at a temperature higher than that in the graphitization furnace, which is not economical.
【００１８】非酸化性雰囲気下での炭素化は、例えば、
窒素、ヘリウム、アルゴン、ネオン、二酸化炭素などの
不活性ガス雰囲気や、真空下で行なうことができる。Carbonization under a non-oxidizing atmosphere is carried out, for example, by
It can be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, neon, carbon dioxide, or under vacuum.
【００１９】メソフェーズ小球体を粉砕した後、炭素化
する場合や、メソフェーズ小球体をそのまま炭素化する
場合、炭素化時の焼結を避けるため、メソフェーズ小球
体の粉砕物の表面を軽度に酸化処理し、粘結成分量をコ
ントロールするのが望ましい。前記酸化処理は、例え
ば、酸素、空気、一酸化炭素などの酸化性雰囲気下、１
００〜４００℃程度の温度で熱処理することにより行な
うことができる。When the mesophase spherules are pulverized and then carbonized, or when the mesophase spherules are carbonized as they are, the surface of the pulverized mesophase spherules is slightly oxidized to avoid sintering during carbonization. However, it is desirable to control the amount of caking components. The oxidation treatment is carried out, for example, in an oxidizing atmosphere of oxygen, air, carbon monoxide, etc.
This can be performed by heat treatment at a temperature of about 00 to 400 ° C.
【００２０】なお、メソフェーズ小球体の粉砕物を炭素
化する場合、メソフェーズ小球体から発生する未炭化の
芳香族成分は、粉砕されたメソフェーズ小球体の破断面
に滲出するようである。このような滲出物を炭素化させ
ると、粉砕時の破断面が滲出部位の滲出物で被覆される
ためか、破断面のエッジを包み隠し、破砕物を球状に近
い形状とすることができる。そのため、粉砕しても、黒
鉛化物の比表面積がさほど増大しないという利点があ
る。When carbonizing a pulverized product of mesophase spherules, an uncarbonized aromatic component generated from the mesophase spherules seems to exude to the fracture surface of the pulverized mesophase spherules. If such exudate is carbonized, the edge of the fractured surface can be covered and the crushed material can be made into a shape close to a spherical shape, probably because the fractured surface at the time of crushing is covered with the exudate at the exuded portion. Therefore, even if pulverized, there is an advantage that the specific surface area of the graphitized product does not increase so much.
【００２１】メソフェーズ小球体の粉砕物の炭化物、ま
たはメソフェーズ小球体の炭化物の粉砕物は、黒鉛化処
理され、本発明の黒鉛材料が得られる。前記炭化物や粉
砕物の黒鉛化は、所定の温度に到達し得る炉であれば黒
鉛化炉の加熱方式や種類は特に限定されない。黒鉛化炉
としては、例えば、アチソン炉、直接通電黒鉛化炉、真
空炉などが例示される。なお、黒鉛化は、必要に応じ
て、コークス、黒鉛、炭などの還元剤の存在下で行なっ
てもよい。The carbonized material of the pulverized mesophase spherules or the pulverized material of the mesophase spheroids is graphitized to obtain the graphite material of the present invention. For the graphitization of the carbide or pulverized product, the heating system and type of the graphitization furnace are not particularly limited as long as the furnace can reach a predetermined temperature. Examples of the graphitization furnace include an Acheson furnace, a direct current graphitization furnace, and a vacuum furnace. The graphitization may be carried out in the presence of a reducing agent such as coke, graphite or charcoal, if necessary.
【００２２】黒鉛化処理は、前記の黒鉛化条件で行なえ
ばよいが、好ましくは、非酸化性雰囲気、特に不活性雰
囲気下、１５００〜３０００℃、好ましくは２４００〜
３０００℃、さらに好ましくは２５００〜３０００℃程
度で行なうことができる。非酸化性雰囲気下での黒鉛化
は、例えば、窒素、ヘリウム、アルゴン、ネオンなどの
不活性ガス雰囲気や、真空下で行なうことができる。The graphitization treatment may be carried out under the above-mentioned graphitization conditions, but is preferably 1500 to 3000 ° C., preferably 2400 to 3000 ° C. in a non-oxidizing atmosphere, particularly an inert atmosphere.
It can be carried out at 3000 ° C., more preferably about 2500 to 3000 ° C. Graphitization in a non-oxidizing atmosphere can be performed, for example, in an atmosphere of an inert gas such as nitrogen, helium, argon or neon, or in vacuum.
【００２３】このように、黒鉛化に至るまでの行程で、
粉砕されたメソフェーズ小球体の表面は、その粉粒体の
周囲に残存する微少量の酸素により、酸化されるようで
ある。特に炭素化処理し、粉砕工程を経た後、黒鉛化処
理する場合には、粉砕した粉粒体のエッジ部が選択的に
酸化され、より球形に近い形状となる効果が大きい。こ
のような黒鉛化処理により、メソフェーズ小球体の黒鉛
化物と同様な特性を有する黒鉛材料が得られる。In this way, in the process leading to graphitization,
The surface of the crushed mesophase globule appears to be oxidized by the small amount of oxygen remaining around the granules. In particular, when the carbonization treatment is performed and the graphitization treatment is performed after the pulverization step, the edge portion of the pulverized powder or granules is selectively oxidized, and the effect of forming a more spherical shape is great. By such graphitization treatment, a graphite material having properties similar to those of the graphitized mesophase spheres can be obtained.
【００２４】前記本発明の方法により得られた黒鉛化材
料の平均粒径は、粉砕物の粒径に対応して、例えば、１
〜５０μｍ、好ましくは１〜２０μｍ程度である。ま
た、黒鉛材料のＢＥＴ比表面積は、例えば、１０ｍ2 ／
ｇ以下、好ましくは０．１〜１０ｍ2 ／ｇ、さらに好ま
しくは１〜１０ｍ2 ／ｇ、特に３〜８ｍ2 ／ｇ程度であ
る。また、Ｘ線回折法（学振法）によるｃ軸方向の結晶
子の厚みＬｃは、例えば、６５０〜９００オングストロ
ーム、好ましくは７００〜８５０オングストローム程度
である。The average particle size of the graphitized material obtained by the method of the present invention corresponds to the particle size of the pulverized product, for example, 1
It is about 50 μm, preferably about 1 to 20 μm. The BET specific surface area of the graphite material is, for example, 10 m 2 /
g or less, preferably 0.1 to 10 m 2 / g, more preferably 1 to 10 m 2 / g, and particularly about 3 to 8 m 2 / g. Further, the thickness Lc of the crystallite in the c-axis direction by the X-ray diffraction method (Gakushin method) is, for example, about 650 to 900 angstroms, preferably about 700 to 850 angstroms.
【００２５】このような黒鉛材料は、樹脂複合材などの
種々の複合材、例えば、摺動部材、面状発熱体、二次電
池用電極材などに、等方性を付与する上で有用である。
樹脂複合材を形成する場合、樹脂としては、例えば、フ
ェノール樹脂、フラン樹脂、エポキシ樹脂、ビニルエス
テル樹脂、不飽和ポリエステル樹脂、尿素樹脂、ポリイ
ミドなどの熱硬化性樹脂；ポリアミド、アクリル樹脂、
ポリアクリロニトリル、芳香族ポリエステルなどの飽和
ポリエステル、ポリアセタール、ポリカーボネート、フ
ッ素樹脂などの熱可塑性樹脂などが例示できる。樹脂複
合材は、例えば、前記黒鉛材料と樹脂とを混合し、成形
することにより形成でき、成形法には圧縮成形、射出成
形、押出し成形などの慣用の成形法が採用できる。Such a graphite material is useful for imparting isotropy to various composite materials such as resin composite materials such as sliding members, sheet heating elements, and secondary battery electrode materials. is there.
When forming a resin composite material, examples of the resin include thermosetting resins such as phenol resin, furan resin, epoxy resin, vinyl ester resin, unsaturated polyester resin, urea resin, and polyimide; polyamide, acrylic resin,
Examples thereof include polyacrylonitrile, saturated polyester such as aromatic polyester, polyacetal, polycarbonate, and thermoplastic resin such as fluororesin. The resin composite material can be formed, for example, by mixing the graphite material and a resin and molding, and as the molding method, a conventional molding method such as compression molding, injection molding, or extrusion molding can be adopted.
【００２６】[0026]
【発明の効果】本発明では、粉砕工程を含むにも拘ら
ず、メソフェーズ小球体の黒鉛化物が有している優れた
特性を保持した黒鉛材料を簡単な方法で製造できる。ま
た、粉砕されたメソフェーズ小球体の黒鉛化物を用いる
にも拘らず、本発明の黒鉛材料を用いることにより、樹
脂複合材などに等方性を付与できる。INDUSTRIAL APPLICABILITY According to the present invention, a graphite material which retains the excellent properties of the graphitized mesophase spheroids despite the pulverization step can be produced by a simple method. Further, although the pulverized mesophase spheroidized graphitized product is used, isotropic property can be imparted to the resin composite material and the like by using the graphite material of the present invention.
【００２７】[0027]
【実施例】以下に、実施例に基づいて本発明をより詳細
に説明する。EXAMPLES The present invention will be described in more detail based on the following examples.
【００２８】実施例１ コールタールを３９８℃で１８時間熱処理し、生成した
球晶を分離精製し、平均粒径１１．２μｍのメソフェー
ズ小球体を得た。この小球体を、ジェットミルを用い、
フィード量１８．６ｋｇ／ｈｒ、エアー圧力４ｋｇ／ｃ
ｍ2 の条件で粉砕し、平均粒径３．５μｍの粉粒状物を
得た。Example 1 Coal tar was heat-treated at 398 ° C. for 18 hours, and the produced spherulite was separated and purified to obtain mesophase microspheres having an average particle size of 11.2 μm. Using a jet mill, this small sphere,
Feed rate 18.6 kg / hr, air pressure 4 kg / c
It was pulverized under the condition of m 2 to obtain a powdery material having an average particle diameter of 3.5 μm.
【００２９】粉砕物を、窒素雰囲気下、２℃／分の昇温
速度で１０００℃まで加熱処理し、さらにアチソン炉で
２８００℃で黒鉛化した。得られた粉砕メソフェーズ小
球体の黒鉛化物の粒径は３．１μｍであり、Ｘ線回折法
による結晶子の厚みＬｃは７６０オングストローム、Ｂ
ＥＴ法による比表面積は５．２ｍ2 ／ｇであった。な
お、得られた黒鉛化物の粒子構造を図１に示す。The pulverized product was heat-treated under a nitrogen atmosphere at a heating rate of 2 ° C./min to 1000 ° C., and further graphitized at 2800 ° C. in an Acheson furnace. The particle size of the graphitized product of the obtained pulverized mesophase spherules was 3.1 μm, and the thickness Lc of the crystallite by the X-ray diffraction method was 760 Å, B
The specific surface area according to the ET method was 5.2 m 2 / g. The particle structure of the obtained graphitized product is shown in FIG.
【００３０】実施例２ 実施例１と同様にして得たメソフェーズ小球体を、窒素
雰囲気下、２℃／分の昇温速度で１０００℃まで加熱処
理して炭素化し、炭素化物を、ジェットミルを用いて、
フィード量１５．２ｋｇ／ｈｒ、エアー圧力４ｋｇ／ｃ
ｍ2 の条件で粉砕し、平均粒径４．２μｍの粉粒状物を
得た。次いで、アチソン炉を用い２８００℃で黒鉛化し
た。得られた粉砕メソフェーズ小球体の黒鉛化品の粒径
は４．０μｍであり、Ｘ線回折法による結晶子の厚みＬ
ｃは７４２オングストローム、ＢＥＴ法による比表面積
は６．７ｍ2 ／ｇであった。Example 2 The mesophase small spheres obtained in the same manner as in Example 1 were carbonized by heat-treating them to 1000 ° C. in a nitrogen atmosphere at a temperature rising rate of 2 ° C./min, and the carbonized product was jet-milled. make use of,
Feed rate 15.2 kg / hr, air pressure 4 kg / c
It was pulverized under the condition of m 2 to obtain a powdery material having an average particle diameter of 4.2 μm. Then, it was graphitized at 2800 ° C. using an Acheson furnace. The particle size of the obtained graphitized product of pulverized mesophase spherules was 4.0 μm, and the thickness L of the crystallite measured by the X-ray diffraction method was L.
c was 742 Å, and the specific surface area according to the BET method was 6.7 m 2 / g.
【００３１】比較例１ 実施例１と同様にして得たメソフェーズ小球体を、窒素
雰囲気下、２℃／分の昇温速度で１０００℃まで加熱処
理して炭素化し、さらにアチソン炉を用いて２８００℃
で黒鉛化した。ジェットミルを用いて、フィード量１．
８ｋｇ／ｈｒ、エアー圧力７ｋｇ／ｃｍ2 の条件で、前
記黒鉛化物を粉砕し、平均粒径５．２μｍの粉粒状物を
得た。この黒鉛化物の粉砕物は、Ｘ線回折法による結晶
子の厚みＬｃが６２０オングストローム、ＢＥＴ法によ
る比表面積は１２．２ｍ2 ／ｇであった。なお、得られ
た黒鉛化物の粒子構造を図２に示す。Comparative Example 1 Mesophase spherules obtained in the same manner as in Example 1 were carbonized by heat treatment to 1000 ° C. at a temperature rising rate of 2 ° C./min in a nitrogen atmosphere, and then 2800 using an Acheson furnace. ℃
Graphitized with. Feed amount 1.
The graphitized product was pulverized under the conditions of 8 kg / hr and an air pressure of 7 kg / cm 2 to obtain a powdery granular material having an average particle size of 5.2 μm. The pulverized product of this graphitized product had a crystallite thickness Lc determined by X-ray diffraction of 620 angstroms and a specific surface area determined by BET of 12.2 m 2 / g. The particle structure of the obtained graphitized product is shown in FIG.
【００３２】[0032]
【表１】 実施例３ 実施例１と同様の方法で得た粉砕メソフェーズ小球体の
黒鉛化物４０重量部と、四フッ化エチレン樹脂（旭硝子
（株）製：フルオンＧ）１００重量部とをヘンシェルミ
キサーを用いて混合した。得られた混合物を円筒状の金
型（５０ｍｍφ）に充填し、７５０ｋｇ／ｃｍ2 の圧力
で予備成形した後、３６０℃で１時間加熱し、続いて８
００ｋｇ／ｃｍ2 の圧力で加圧した後、冷却した。[Table 1] Example 3 40 parts by weight of graphitized pulverized mesophase microspheres obtained by the same method as in Example 1 and 100 parts by weight of tetrafluoroethylene resin (Fluon G manufactured by Asahi Glass Co., Ltd.) were used in a Henschel mixer. Mixed. The obtained mixture was filled in a cylindrical mold (50 mmφ), preformed at a pressure of 750 kg / cm 2 , and then heated at 360 ° C. for 1 hour, and then 8
After pressurizing with a pressure of 00 kg / cm 2 , it was cooled.
【００３３】得られたフッ素樹脂複合材から、プレス軸
に対して平行方向及び垂直方向にテストピースを切り出
し、曲げ強度、体積固有抵抗、摩擦係数、摩耗係数を測
定した。Test pieces were cut out from the obtained fluororesin composite material in the directions parallel and perpendicular to the press axis, and the bending strength, volume resistivity, friction coefficient and wear coefficient were measured.
【００３４】なお、前記曲げ強度は、テストピース（１
０ｍｍ×１０ｍｍ×３０ｍｍ）を用い、３点曲げ法で測
定した。体積固有抵抗は、曲げ強度と同様のテストピー
スについて定電流４点法で測定した。摩擦摩耗特性は、
スラスト式摩擦試験機において相手材としてＳＵＪ−２
を使用し、摩擦係数は、滑り速度１００ｍ／分、荷重１
ｋｇ／ｃｍ2 の条件で、摩耗係数は、滑り速度１２８ｍ
／分、荷重１．６ｋｇ／ｃｍ2 の条件で測定した。In addition, the bending strength is the test piece (1
(0 mm × 10 mm × 30 mm), and the measurement was performed by the three-point bending method. The volume resistivity was measured by a constant current four-point method for a test piece similar to bending strength. Friction and wear characteristics
SUJ-2 as the mating material in the thrust type friction tester
The friction coefficient is 100 m / min for sliding speed and 1 for load.
The wear coefficient is a sliding speed of 128 m under the condition of kg / cm 2.
/ Min, and a load of 1.6 kg / cm 2 were measured.
【００３５】実施例４ 実施例２と同様の方法で得た粉砕メソフェーズ小球体の
黒鉛化物を用いる以外、実施例３と同様にして、フッ素
樹脂複合材の特性を測定し、表２に示した。Example 4 The characteristics of the fluororesin composite material were measured in the same manner as in Example 3 except that the graphitized pulverized mesophase microspheres obtained in the same manner as in Example 2 were used. .
【００３６】比較例２ 比較例１と同様の方法で得た粉砕メソフェーズ小球体の
黒鉛化物を用いる以外、実施例３と同様にして、フッ素
樹脂複合材の特性を測定し、表２に示した。Comparative Example 2 The properties of the fluororesin composite material were measured in the same manner as in Example 3 except that the graphitized pulverized mesophase spherules obtained in the same manner as in Comparative Example 1 were used. .
【００３７】[0037]
【表２】 [Table 2]
【図１】図１は実施例１で得られた黒鉛化物の粒子構造
を示す写真である。FIG. 1 is a photograph showing the particle structure of the graphitized product obtained in Example 1.
【図２】図２は比較例１で得られた黒鉛化物の粒子構造
を示す写真である。FIG. 2 is a photograph showing the particle structure of the graphitized product obtained in Comparative Example 1.
Claims (7)
化する方法であって、炭素化または黒鉛化に先立ってメ
ソフェーズ小球体を粉砕する黒鉛材料の製造方法。1. A method for carbonizing and graphitizing mesophase spherules, which comprises crushing the mesophase spherules prior to carbonization or graphitization.
化し、黒鉛化する請求項１記載の黒鉛材料の製造方法。2. The method for producing a graphite material according to claim 1, wherein the mesophase spherules are crushed, then carbonized and graphitized.
化性雰囲気下、４５０〜１５００℃で炭素化し、非酸化
性雰囲気下、２４００〜３０００℃で黒鉛化する請求項
２記載の黒鉛材料の製造方法。3. The production of a graphite material according to claim 2, wherein the mesophase spherules are pulverized, carbonized at 450 to 1500 ° C. in a non-oxidizing atmosphere, and graphitized at 2400 to 3000 ° C. in a non-oxidizing atmosphere. Method.
砕し、黒鉛化する請求項１記載の黒鉛材料の製造方法。4. The method for producing a graphite material according to claim 1, wherein the mesophase spherules are carbonized, then pulverized and graphitized.
下、４５０〜１５００℃で炭素化した後、粉砕し、非酸
化性雰囲気下、２４００〜３０００℃で黒鉛化する請求
項４記載の黒鉛材料の製造方法。5. The graphite material according to claim 4, wherein the mesophase spherules are carbonized at 450 to 1500 ° C. in a non-oxidizing atmosphere, then crushed and graphitized at 2400 to 3000 ° C. in a non-oxidizing atmosphere. Manufacturing method.
材料。6. A graphite material obtained by the method according to claim 1.
記載の黒鉛材料。7. The average particle size is 1 to 20 μm.
The described graphite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6037671A JPH07223809A (en) | 1994-02-09 | 1994-02-09 | Graphite material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6037671A JPH07223809A (en) | 1994-02-09 | 1994-02-09 | Graphite material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07223809A true JPH07223809A (en) | 1995-08-22 |
Family
ID=12504105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6037671A Pending JPH07223809A (en) | 1994-02-09 | 1994-02-09 | Graphite material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07223809A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998029335A1 (en) * | 1996-12-25 | 1998-07-09 | Sumitomo Metal Industries, Ltd. | Graphite powder suitable for negative electrode material of lithium ion secondary cell |
| EP0955684A1 (en) * | 1998-04-21 | 1999-11-10 | Sony Corporation | Graphite powders suited for negative electrode material of lithium ion secondary battery |
| WO2011126078A1 (en) * | 2010-04-08 | 2011-10-13 | 大豊工業株式会社 | Sliding material based on graphite-containing resin, and sliding member |
| WO2012074107A1 (en) | 2010-12-02 | 2012-06-07 | 大豊工業株式会社 | Swash plate for swash plate compressor |
| WO2013051340A1 (en) | 2011-10-07 | 2013-04-11 | 大豊工業株式会社 | Scroll compressor |
| JP2013083301A (en) * | 2011-10-07 | 2013-05-09 | Taiho Kogyo Co Ltd | Slide bearing made of graphite added resin-based material, for pinion gear of planetary gear mechanism |
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-
1994
- 1994-02-09 JP JP6037671A patent/JPH07223809A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6576369B1 (en) | 1996-12-25 | 2003-06-10 | Sumitomo Metal Industries, Ltd. | Graphite powder suitable for negative electrode material of lithium ion secondary batteries |
| WO1998029335A1 (en) * | 1996-12-25 | 1998-07-09 | Sumitomo Metal Industries, Ltd. | Graphite powder suitable for negative electrode material of lithium ion secondary cell |
| EP0955684A1 (en) * | 1998-04-21 | 1999-11-10 | Sony Corporation | Graphite powders suited for negative electrode material of lithium ion secondary battery |
| US6764767B2 (en) | 1998-04-21 | 2004-07-20 | Sony Corporation | Graphite powders suited for negative electrode material of lithium ion secondary battery |
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| WO2011126078A1 (en) * | 2010-04-08 | 2011-10-13 | 大豊工業株式会社 | Sliding material based on graphite-containing resin, and sliding member |
| CN102971379A (en) * | 2010-04-08 | 2013-03-13 | 大丰工业株式会社 | Sliding material based on graphite-containing resin, and sliding member |
| US9512378B2 (en) | 2010-04-08 | 2016-12-06 | Taiho Kogyo Co., Ltd. | Sliding material based on graphite-added resin and sliding member |
| JP5683571B2 (en) * | 2010-04-08 | 2015-03-11 | 大豊工業株式会社 | Graphite-added resin-based sliding material and sliding member |
| WO2012074107A1 (en) | 2010-12-02 | 2012-06-07 | 大豊工業株式会社 | Swash plate for swash plate compressor |
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| JP2013083301A (en) * | 2011-10-07 | 2013-05-09 | Taiho Kogyo Co Ltd | Slide bearing made of graphite added resin-based material, for pinion gear of planetary gear mechanism |
| US9453509B2 (en) | 2011-10-07 | 2016-09-27 | Taiho Kogyo Co., Ltd. | Scroll compressor |
| WO2013051340A1 (en) | 2011-10-07 | 2013-04-11 | 大豊工業株式会社 | Scroll compressor |
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Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20041116 |