JPS58120505A - Cubic system boron nitride particle - Google Patents

Abstract

PURPOSE:To enhance the micro-chipping property of cubic system boron nitride particles, the joining property to other material and the sinterability by introducing a specified amount of carbon into the particles. CONSTITUTION:The titled cubic system boron nitride (cBN) particles contain 0.02-2.0wt% carbon. Hexagonal system BN and a catalytic substance are blended as principal starting materials in a blending ratio equal to that in the conventional manufacture of cBN, and a carbonaceous material is added to the blend. They are held in a high temp. and high pressure region where cBN is thermodynamically stable like the conventional method synthesize cBN particles contg. carbon.

Description

【発明の詳細な説明】 この発明は研削・研摩用砥石の砥粒等に使用される立方
晶窒化ホウ素粒子に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cubic boron nitride particles used as abrasive grains for grinding and polishing wheels.

立方晶窒化ホウ素（以下ｃＢＮと記す）はダイヤモンド
に次ぐ硬さを持つばかシでなく、化学的安定性、熱的安
定性はダイヤモンドよりも優れ、しかも鉄とは容易に反
応しないことから籍に銅系材料の研削あるいは研磨等に
極めて有用な材料として知られておシ、主として研削用
砥石や研摩用砥石の砥粒として使用されるほか、切断用
１ブレード、ラッピング加工用ラップ、さらには微粉焼
結体として切削用チップ等にも使用されてｉる。Cubic boron nitride (hereinafter referred to as cBN) has a hardness that is second only to diamond, and its chemical stability and thermal stability are superior to diamond, and it does not easily react with iron, making it a popular choice. It is known as an extremely useful material for grinding or polishing copper-based materials, and is mainly used as abrasive grains for grinding wheels and polishing wheels, as well as for cutting blades, lapping laps, and even fine powder. It is also used as a sintered body for cutting tips and the like.

ところで研削・研摩用砥石の砥粒に要求される特性とし
ては、極めて硬質であることのほか、結合剤（ボンド）
の種類によって次のような種々の特性が要求される。す
なわちメタルボンドを用い九砥石では、強固なボンドに
よりて砥粒が強力に保持されるため、いわゆる重研削用
として砥粒自体が強靭な結合を有するタフなものが望ま
れる。By the way, the characteristics required of the abrasive grains for grinding and polishing wheels include extremely hardness, as well as a binder (bond).
The following various characteristics are required depending on the type. That is, in a nine-grinding wheel using a metal bond, since the abrasive grains are strongly held by a strong bond, a tough one in which the abrasive grain itself has a strong bond is desired for so-called heavy grinding.

一方結合剤として樹脂（レジノイドボンド）を用−る場
合には、研削中の被剛材の焼けを防止すること、および
メタルボンド等と比較して砥粒に対する保持力が小さい
ことから、砥粒自体が適度な微小チッピング（マイクロ
チッピング）を起しながら自刃作用を生じる砥粒が望ま
れる。さらにレジノイドボンドを用いる場合、研削中の
熱放散性を良好にするとともに、砥粒に対するレジンの
保持力を強化するため、砥粒表面に特殊な金属コーティ
ングを施す仁とが広く行なわれているが、この場合砥粒
特性として金属コーティング層との接着性が良好なこと
が望まれる。またこのほか粘土尋の窯業原料からなるビ
トリファイドボンドを用いた砥石、あるいは電着によっ
て砥粒を保持した電着砥石等があるが、これらの場合に
おφても前記同様にボンドと砥粒との接着性が良好なこ
とが砥石としての性能を充分に発揮する上において極め
て重要である。一方、微粉を焼結して切削用チップ等に
使用する場合には、当然のことなから自校同士の焼結性
が良好なことが望まれる。On the other hand, when resin (resinoid bond) is used as a bonding agent, it is necessary to prevent burning of the rigid material during grinding, and because it has a smaller holding power for the abrasive grains than metal bond etc. It is desired that the abrasive grain itself has a self-sharpening action while causing appropriate microchipping (microchipping). Furthermore, when using resinoid bond, a special metal coating is widely applied to the surface of the abrasive grain in order to improve heat dissipation during grinding and to strengthen the resin's holding power to the abrasive grain. In this case, it is desired that the abrasive grain has good adhesion to the metal coating layer. In addition, there are whetstones that use vitrified bond made from ceramic raw material of thick clay, and electrodeposited whetstones that hold abrasive grains by electrodeposition, but in these cases, the bond and abrasive grains are separated in the same way as described above. Good adhesion is extremely important for fully demonstrating the performance of a grindstone. On the other hand, when fine powder is sintered and used for cutting tips or the like, it is naturally desired that the sinterability of the particles be good.

従来、砥粒用のｃＢＮ粒子として数種のものが開発され
てお妙、それらのうちで特に前述のマイクロチクピング
性を良好にしたものとして、ｃＢＮ組成のＢとＮの原子
比を若干Ｂリッチ側にコントロールした改質ｃＢＮ粒子
が知られている。この型式の改質ｃＢＮ粒子はＢリッチ
とするととくよって上述のようにマイクロチッピングが
生じ鳥くな）、そのため通常のＢ　ＩＪプツチ岐ないｃ
ＢＮ粒子を用いた砥石と比較して格段にレジノイドボン
ドを用ｉた場合の砥石性能が良好となる。しかしながら
この型式の改質ｃＢＮ粒子はＢリッチに制御することに
よって改質はするものの、製造時においてはＢを成分に
添加しても実際に３３１Ｊツチとなりて−るｃＢＮ粒子
が得られる収率は極端に低く、を九す富化奮もばらつく
ためマイクロチッピングの１１度を自由に制御できない
等の問題があり、さらには上述のような改質ｃＢＮ粒子
におしても通常のｃＢＮ粒子と比較して金属やガラス質
物質あるいは粘土系物質などの他の物質との接着性は特
に良好とならず、また自校同士の焼結性も特に良好とは
ならない。In the past, several types of cBN particles have been developed for use as abrasive grains. Among them, one with particularly good microchipability as mentioned above is that the atomic ratio of B and N in the cBN composition is slightly increased by B. Modified cBN particles whose richness is controlled are known. If this type of modified cBN particles is B-rich, it will cause microchipping as described above), and therefore it will not be as fine as normal B IJ.
The performance of the grindstone using resinoid bond is much better than that of the grindstone using BN particles. However, although this type of modified cBN particles is modified by controlling it to be rich in B, even if B is added to the ingredients during production, the actual yield of cBN particles of 331 J is low. There are problems such as the inability to freely control the 11 degrees of microchipping because the enrichment rate is extremely low and the enrichment rate varies, and furthermore, even with modified cBN particles as mentioned above, compared to normal cBN particles. The adhesion to other materials such as metals, glassy substances, or clay-based substances is not particularly good, and the sinterability between self-sintering materials is not particularly good either.

この発明は以上の事情に鑑みてなされたもので、従来の
通常のｃＢＮ粒子よりもマイクロチッピング性が良好で
しかも前述の改質ｃＢＮ粒子のごとく製造時における収
率が低くなったりすることなく、かつまた靭性を自由に
制御してマイクロチッピングの程度を制御し得るように
なし、さらには従来の通常のｃＢＮ粒子中改質ｃＢＮ粒
子と比較して金属や粘土質物質等との接合性が良好でし
かも自校同士の焼結性も良好なｃＢＮ粒子を提供すると
をを目的とするものである。This invention was made in view of the above circumstances, and has better microchipping properties than conventional ordinary cBN particles, and does not have a low yield during production like the above-mentioned modified cBN particles. In addition, the degree of microchipping can be controlled by freely controlling the toughness, and the bondability with metals, clay materials, etc. is better than that of conventional modified cBN particles in ordinary cBN particles. Moreover, it is an object of the present invention to provide cBN particles that have good sintering properties between themselves.

本発明者等は上述の目的を達成するべく鋭意実験・検討
を重ねた結果、ｃＢＮ粒子中に炭素を０．０２〜２．０
係含有させることによってマイクロチクピング性、他物
質との接合性、自校同士の焼結性のいずれをも向上させ
ることができ、しかも収率も低下せずかつＣ添加量を制
御するだゆで粒自体の靭性を容易に制御し得ることを見
出し、この発明をなすに至った。し九がってこの発明の
ｃＢＮ粒子は、その粒子中に炭素を０．０２〜２−〇−
金含有せたことを特徴とするものである。As a result of extensive experiments and studies to achieve the above-mentioned purpose, the present inventors have found that 0.02 to 2.0 carbon is added to cBN particles.
By adding C, it is possible to improve microchipability, bondability with other materials, and sinterability between self-containing materials.Moreover, the yield does not decrease and the amount of carbon added can be controlled. It was discovered that the toughness of the grains themselves can be easily controlled, and this invention was accomplished. Therefore, the cBN particles of this invention contain 0.02 to 2-2% of carbon in the particles.
It is characterized by containing gold.

以下この発明についてさらに具体的に説明する。This invention will be explained in more detail below.

この発明のｃＢＮ粒子を製造するＫＩｈ九りては、通常
のｃＢＮ粒子を製造する場合と同様な配合割合で主原料
としての六方晶窒化ホウ素（以下ｈＢＮと記す）と触媒
物質とを配合し、さらにこれに炭素質物質を添加して、
従来法と同様にｃＢＮが熱力学的に安定である高温、高
圧領域に保持して合成すれば良い。ここで触媒物質とし
ては従来と同様にアルカリ金−もしくはアルカリ土類金
属の窒化物、例えばＬｉ　、Ｎ　＋ＣａｘＮ２　、ある
−はアルカリ金属もしくはアルカリ土類金属と窒素およ
びホウ素からなる窒化ホウ素系３元化合物、例えばＣａ
５Ｂ、Ｎ４ヤＬｉ、ＢＮ２等を使用すれば良く、さらに
は本発明者が先に提案した新規な窒化ホウ素系４元化合
物すなわちＬ　ｉ　Ｃａ　ＢＮ　２を用いても良い。　
　　　−一方炭素質、物質としては広い意味で炭素を含
むものであれば良く、例えば黒鉛あるいは無定形炭素、
カーボンブラック等の炭素単体物質のみならず、ｃＢＮ
合成のための高温高圧下において分解して炭素残液を残
す有機物、例えば各種合成樹脂類、油脂類、アルコール
類、さらＫはカーバイド等の炭化物等を使用することが
できる。このような炭素質物質を添加する方法としては
、その炭素質物質の性状に応じて適当な方法を選択すれ
ば良い０例えばｈＢＮ粉末および触媒粉末に直接炭素質
物質粉末を混合しても良く、あるいは予めｈＢＮ粉末と
触媒粉末との混合粉体を成形しておき、その成形体を液
体状の炭素質物質または炭素質物質溶液中に浸漬して含
浸させたシ、あるいはｈＢＮや触媒の粉末粒子もしくは
それらの成形体に炭素質物質を蒸着もしくはデーティン
グしても良い、を九従来から、予めｈＢＮ粉末および触
媒粉末をそれぞれ各別に薄い板状に圧粉成形し、ｈＢＮ
粉末の圧粉成形板と触媒粉末の圧粉成形板とを交互に積
層して高温高圧下に供する方法も知られておシ、この場
合いずれか一方の圧粉成形板に予め前述のような各種の
方法で炭素質物質を添加しておいても良１０上述のよう
に炭素質物質を添加した原料に高温高圧を加えてｃＢＮ
を合成する装置としては種々考えられるが、例えば第１
図に示すようなガードル型高圧発生装置を使用すること
ができる。第１図において１，１′は高圧を上下方向か
ら加える丸めのアノビルであり、そのアンビル１，１′
の先端面間には、パイロフィライト等からなる断熱板２
゜２′および鋼等からなる通電リング３．３’、モリブ
デン等からなる通電板４，４′を介して円筒状の試料容
器５が配置されて−る。この試料容ｌＩ５は、パイロフ
ィライトからなる外周壁６の内側に黒鉛からなる筒状の
発熱体７およびパイロフィライトからなる絶縁スリーブ
８がその順に配設され、かつ上下両面に黒鉛からなる通
電板９，９′およびパイロフィライトからなる断熱板１
０　、１０’を配置した構成とされておシ、その上下の
断熱板１０゜１０′および絶縁スリーブ８の間に反応試
料、すなわち前述の炭素質物質を添加した原料１１が収
容される。なお試料容器５の周囲はシリンダコア１２に
よって取囲まれてお妙、またそのシリンダコア１２と上
下のアノビル１．１′との間にはパイロフィライトから
なるガスケット１３　、１３’が介挿されている。KIh Kuritate, which manufactures the cBN particles of the present invention, mixes hexagonal boron nitride (hereinafter referred to as hBN) as the main raw material and a catalyst material in the same mixing ratio as when manufacturing ordinary cBN particles, Furthermore, by adding carbonaceous substances to this,
As in the conventional method, cBN may be synthesized while being maintained at a high temperature and high pressure region where it is thermodynamically stable. Here, the catalyst material is a nitride of alkali gold or alkaline earth metal, such as Li, N +CaxN2, and a boron nitride-based ternary compound consisting of an alkali metal or alkaline earth metal, nitrogen, and boron, as in the past. , for example Ca
5B, N4, Li, BN2, etc. may be used, and furthermore, a novel boron nitride-based quaternary compound previously proposed by the present inventor, ie, Li Ca BN 2 may be used.
-On the other hand, carbonaceous substances may be substances that contain carbon in a broad sense, such as graphite or amorphous carbon,
Not only simple carbon substances such as carbon black, but also cBN
It is possible to use organic substances that decompose under high temperature and high pressure for synthesis and leave carbon residues, such as various synthetic resins, oils and fats, alcohols, and carbides such as carbides. As a method for adding such a carbonaceous substance, an appropriate method may be selected depending on the properties of the carbonaceous substance. For example, the carbonaceous substance powder may be directly mixed with the hBN powder and the catalyst powder, Alternatively, a mixed powder of hBN powder and catalyst powder is molded in advance, and the molded product is immersed in a liquid carbonaceous material or carbonaceous material solution to impregnate it, or hBN or catalyst powder particles are used. Alternatively, a carbonaceous material may be vapor-deposited or dated on these molded bodies. Conventionally, hBN powder and catalyst powder are individually compacted into thin plate shapes, and hBN
There is also a known method of stacking powder compacting plates and catalyst powder compacting plates alternately and subjecting them to high temperature and high pressure. Carbonaceous substances may be added by various methods.10 As mentioned above, cBN is produced by applying high temperature and high pressure to the raw material to which carbonaceous substances have been added.
There are various possible devices for synthesizing the
A girdle type high pressure generator as shown in the figure can be used. In Fig. 1, 1 and 1' are rounded anvils that apply high pressure from above and below;
A heat insulating plate 2 made of pyrophyllite or the like is placed between the tip surfaces of the
A cylindrical sample container 5 is disposed via a current-carrying ring 3, 3' made of steel or the like, and current-carrying plates 4, 4' made of molybdenum or the like. This sample container II5 has a cylindrical heating element 7 made of graphite and an insulating sleeve 8 made of pyrophyllite disposed in that order inside an outer circumferential wall 6 made of pyrophyllite, and has an energized upper and lower surface made of graphite. Insulating board 1 consisting of plates 9, 9' and pyrophyllite
The reaction sample, that is, the raw material 11 to which the carbonaceous substance mentioned above is added, is housed between the upper and lower heat insulating plates 10 and 10' and the insulating sleeve 8. The sample container 5 is surrounded by a cylinder core 12, and gaskets 13 and 13' made of pyrophyllite are inserted between the cylinder core 12 and the upper and lower annovils 1.1'. ing.

上記に例示したような高圧発生装置によって原料に高温
高圧を加えればこの発明の目的とする炭素を含有するｃ
ＢＮが得られるが、ここで加える高温高圧は要は前述の
ようにｃＢＮが熱力学的に安定な領域となるように設定
すれば良く、具体的には１３００〜１６００℃の高温下
で４０〜６０ｋｂａｒの高圧を加え、５〜４０分間保持
すれば良い。By applying high temperature and high pressure to the raw material using the high pressure generator as exemplified above, carbon containing carbon, which is the object of this invention, can be produced.
BN is obtained, but the high temperature and high pressure applied here should be set so that cBN is thermodynamically stable as mentioned above, specifically, at a high temperature of 1300 to 1600 ° C. A high pressure of 60 kbar may be applied and held for 5 to 40 minutes.

このようにして得られたｃＢＮ結晶粒には、その内部に
炭素が含まれる。この炭素は固溶されている状態となっ
ているかある−は単に包有されているだけであるかは不
明であるが、一定限界までは固溶し、それを越えた分が
包有物として結晶粒内にとり込まれて−るものと解する
のが妥当である。The cBN crystal grains thus obtained contain carbon inside them. It is unclear whether this carbon is in a solid solution state or whether it is simply included, but it remains in a solid solution up to a certain limit, and beyond that it becomes an inclusion. It is reasonable to understand that it is incorporated into crystal grains.

ｃＢＮ結晶粒内の炭素含有量は０．０２〜２．０％の範
囲とする必°堤があり、０．０２Ｓ未満ではこの発明の
目的とする効果、すなわちマイクロチッピング性？他物
質との接合性、自校同士の焼結性等の向ヒ効束がほとん
ど得られず、これに対し２．Ｏｌをなお上述のように炭
素含有量を制御するためＫは東料中に添加する炭素質物
質の添加量を制御すれば良いことは勿論である。It is necessary that the carbon content in the cBN crystal grains be in the range of 0.02 to 2.0%, and if it is less than 0.02S, the desired effect of this invention, ie, microchipability? Hardly any ferrous properties such as bondability with other materials or sinterability between self-containing materials can be obtained, whereas 2. Of course, in order to control the carbon content of Ol as described above, K can be controlled by controlling the amount of carbonaceous material added to the Toryo.

以トのように炭素質物質を含有するｃＢＮ粒子は、復水
する実施例に示すようにマイクロチッピングを起こし易
く、しかも金属との接合性が従来の通常のｃＢＮ粒子や
Ｂを富化したｃＢＮ粒子と比較して格段に良好であるか
ら金属コーティングを施してレジメイドボンドを用−た
砥石に使用すれば砥粒の脱落も少なくなり、さらには炭
素含有量を制御することによって粒子の靭性を制御して
マイクロチッピングの程度を制御し得る等、特にレジノ
イドボンドを用いる砥石用の砥粒として最適である。As shown in the examples below, cBN particles containing carbonaceous substances tend to cause microchipping as shown in the examples of condensation, and their bondability with metals is higher than that of conventional ordinary cBN particles or B-enriched cBN. Since it is much better than grains, if it is coated with a metal and used in a grindstone that uses remade bond, it will reduce the amount of abrasive grains falling off, and by controlling the carbon content, the toughness of the grains can be improved. It is particularly suitable as an abrasive grain for grinding wheels using resinoid bond, as it can control the degree of microchipping.

ま友上述のように金属との接合性が良好であってかつま
た他の粘土系物質やガラス系物質との接合性も従来の他
のｃＢＮ粒子と比較して格段に良好であることから、ビ
トリファイドボンドやメタルボンドを用いた砥石あるい
は電着砥石等においてもマイクロチッピングが要求され
る用途に社有用となる。さらに、粒子自体の焼結性も従
来の他のｃＢＮ粒子と比較して格段に良好であシ、その
ため微粉を焼結して切削用焼結チップ等とする場合に用
いても最適である。さらに、この発明のｃＢＮ粒子を製
造するにあたっては、Ｂリッチに制御したｃＢＮ粒子の
ごとく収率が低下することなく、従来の通常のｃＢＮ粒
子と同程度の収率で得ることができる。As mentioned above, Mayu has good bonding properties with metals, and also has much better bonding properties with other clay-based materials and glass-based materials compared to other conventional cBN particles. It is also useful for applications that require microchipping in grindstones using vitrified bond or metal bond, or electroplated grindstones. Furthermore, the sinterability of the particles themselves is much better than that of other conventional cBN particles, and therefore, they are optimal for use when sintering fine powder to make sintered chips for cutting, etc. Furthermore, in producing the cBN particles of the present invention, the yield does not decrease as in the case of cBN particles controlled to be rich in B, and can be obtained at a yield comparable to that of conventional ordinary cBN particles.

以下にこの発明の実施例および比較例を記す。Examples and comparative examples of this invention are described below.

実施例１ ｈＢＮ粉末とＬ　ｉ　ｓＮ粉末と黒鉛粉末とを重量比で
５：１：０．２の割合で混合した混合粉体４．５？を直
径１５■、長さ１５■の円筒状に成形し、その密度ρ；
１．７の成形体を第１図に示す装置に装填し、圧力５５
ｋｂａｒ、温度１５００℃において３０分間保持した後
、先ず温度を下降させ、次いで圧力を下げてから試料を
取出し友、この試料から未反応のｈＢＮおよび黒鉛を分
離して粒径３０〜２００μｍの黒色光沢を有する粒子が
１．３５７　（収率３７チ）得られた。この黒色粒子を
Ｘ線回折に付したところ、ｃＢＮであることが確認され
た。またこのｃＢＮ粒子には炭素が０．０８−程度含有
されていることが確認され丸。Example 1 A mixed powder of hBN powder, LisN powder, and graphite powder mixed in a weight ratio of 5:1:0.2 was 4.5? is formed into a cylindrical shape with a diameter of 15 cm and a length of 15 cm, and its density ρ;
1.7 was loaded into the apparatus shown in Fig. 1, and the pressure was 55.
kbar and a temperature of 1500°C for 30 minutes, first lower the temperature, then lower the pressure, and then take out the sample. Unreacted hBN and graphite were separated from this sample and a black gloss with a particle size of 30-200 μm was obtained. 1.357 particles (yield: 37) were obtained. When this black particle was subjected to X-ray diffraction, it was confirmed that it was cBN. It was also confirmed that this cBN particle contained approximately 0.08-carbon.

実施例２ 黒鉛粉末の代りにカーボンブラックを用−九点以外は実
施例１と同様にして実験を行った。これにより粒径３０
〜２００μｍの黒色光沢を有するｃＢＮ粒子が１．４２
　ｔ　（収率３９慢）得られた。ｔたその炭素含有量は
０．１１程度であつ九。Example 2 An experiment was conducted in the same manner as in Example 1, except that carbon black was used instead of graphite powder. This results in a particle size of 30
1.42 cBN particles with ~200 μm black gloss
t (yield 39%) was obtained. Its carbon content is about 0.11.

実施例３ 黒鉛粉末の代りにフェノール樹脂粉末を用いた点以外は
実施例１と同様にし工実験を行った。その結果粒径３０
〜２００μｍの黒色光沢を有するｃＢＮ粒子が１．８７
　（収率５０嗟）得られ九、その炭素含有量は０．２チ
程度であった。Example 3 A construction experiment was carried out in the same manner as in Example 1 except that phenol resin powder was used instead of graphite powder. As a result, the particle size is 30
1.87 cBN particles with ~200 μm black gloss
(Yield: 50 cm) was obtained, and its carbon content was about 0.2 h.

実施例４ 黒鉛粉末の代りにカルシウムカーパイＦ”　（ＣａＣ２
）を用いた点以外は実施例１と同様にして実験を行っ九
、千の結果粒径３０〜２００μｍの黒色光沢を有するｃ
ＢＮ粒子が０．８）（収率２２９Ｇ）得られた。Example 4 Calcium Carpai F” (CaC2
) The experiment was carried out in the same manner as in Example 1 except that 9,000 particles were used.
BN particles (0.8) (yield 229G) were obtained.

その炭素含有量は１．１チ程度であった。Its carbon content was about 1.1 inches.

実施例５ ｈＢＮ粉末とＬｔｘＮ粉末とを重量比で５：１の割合で
混合した粉体４．５？を直径１５■、長さ１５■の円筒
状に成形し、これをエチルアルコール中へ浸漬した後、
第１図に示す装置に装填し、圧カ５２ｋｂａｒ１温度１
５００℃で２０分間保持し死後、温度を降下させ続いて
圧力を下げて試料を取出した。この試料を精製して粒径
２ｏ〜２００Ｊ１ｍの黒色光沢を有するｃＢＮ粒子を１
．６　ｔ　（収率４３囁）得ることができた。そのｃＢ
Ｎ粒子の炭素含有量は０．５−程度であった。Example 5 Powder 4.5? was prepared by mixing hBN powder and LtxN powder at a weight ratio of 5:1. was formed into a cylindrical shape with a diameter of 15 cm and a length of 15 cm, and after immersing it in ethyl alcohol,
Loaded into the apparatus shown in Figure 1, pressure: 52 kbar, temperature: 1.
After death by holding at 500° C. for 20 minutes, the temperature was lowered and the pressure was subsequently lowered to take out the sample. This sample was purified to obtain 1 cBN particle with a black luster and a particle size of 2o~200J1m.
．． 6t (yield 43cm) could be obtained. That cB
The carbon content of the N particles was about 0.5-.

実施例６ アルコールの代ＤＫケロシンを用いた点以外は実施例５
と同様に実験を行った。その結果粒径２０〜２００μｍ
の黒色光沢を有するｃＢＮ粒子が０、９　ｉ　（収率２
４−）得られた。その炭素含有量Ｆｉ０．８−程度で６
つ九。Example 6 Example 5 except that DK kerosene was used instead of alcohol.
The experiment was conducted in the same way. As a result, the particle size is 20 to 200 μm.
cBN particles with a black gloss of 0.9 i (yield 2
4-) Obtained. Its carbon content Fi0.8-6
Nineteen.

実施例７ ｈＢＮ粉末とＣａ　ｓＮ２粉末とを重量比で１０：１の
割合で混合し、これに数滴のメカニックオイルを加えて
混合した後、その４．５ｔを外径１５■、直径１５１１
ｍに成形して第１図の装置に充填し、圧力５３ｋｂａｒ
、温度１５５０℃にて４０分保持した後試料を取出し、
精製したところ、粒径２０〜２００μｍの黒色光沢を有
するｃＢＮ粒子が１．０２　Ｆ（収率２５チ）得られ丸
。その炭素含有量は０．８襲程度であった。Example 7 hBN powder and Ca sN2 powder were mixed at a weight ratio of 10:1, a few drops of mechanic oil was added and mixed, and then 4.5 tons of the mixture was mixed with an outer diameter of 15 cm and a diameter of 1511 cm.
m and filled into the apparatus shown in Fig. 1 under a pressure of 53 kbar.
After holding the temperature at 1550°C for 40 minutes, take out the sample.
When purified, 1.02 F (yield: 25 F) of cBN particles with a black luster and a particle size of 20 to 200 μm were obtained. Its carbon content was about 0.8%.

実施例８ ｈＢＮ粉末の圧粉成形体を直径１５■、厚さ３−の円板
状に加工し、一方Ｌ１３Ｎ粉末に５ｗｔ−の黒鉛粉末を
混合して直径１５■、厚さ１．５〜２５■の円板状に成
形し、両者の円板状成形体を交互に積１して第１図に示
す装置内に装填した。そして圧力５６　ｋｂａｒ　、温
度１５５０℃にて３０分保持した後、試料を取出して精
製したところ、粒径５０〜３００　ｌｔｍの黒色光沢を
有するｃＢＮ粒子が０．６１（収率１５チ）得られた。Example 8 A compacted body of hBN powder was processed into a disc shape with a diameter of 15 cm and a thickness of 3 mm, and on the other hand, a 5 wt- graphite powder was mixed with L13N powder to form a compact with a diameter of 15 cm and a thickness of 1.5 to 1.5 mm. It was molded into a 25-inch disc, and the two disc-shaped molded bodies were stacked alternately and loaded into the apparatus shown in FIG. After holding at a pressure of 56 kbar and a temperature of 1550°C for 30 minutes, the sample was taken out and purified, and 0.61 (yield: 15 cm) of cBN particles with a black luster and a particle size of 50 to 300 ltm were obtained. .

その炭素含有量は０．９−程度であった。Its carbon content was about 0.9-.

実施例９ ｈＢＮ粉末に１　ａｔ　ｑ＆のカーボンブラックを混合
した後、その粉体を直径１５ＩＩＩ１１厚さ２．５〜３
．５■の円板状に成形し、一方Ｌ　ｉｓＮ粉末とＣａ、
Ｎ２粉末を重量比で１：１の割合で混合した粉体を直径
１５■、厚さ１．５〜２．５箇の円板状に成形し、両者
の成形体を交互に積層して、実施例８と同様な条件で処
理した。その結果粒径５０〜３５０μｍの黒色光沢を有
するｃＢＮ粒子が０．７　ｉ　（収率］９−）得られた
。その炭素含有量は０．９５ａ程度であった。Example 9 After mixing 1 at q& of carbon black with hBN powder, the powder was mixed with a diameter of 15III11 and a thickness of 2.5~3.
．． Formed into a 5-inch disk shape, and on the other hand, LisN powder and Ca,
A powder prepared by mixing N2 powder at a weight ratio of 1:1 was molded into a disc shape with a diameter of 15 cm and a thickness of 1.5 to 2.5 parts, and both molded bodies were laminated alternately. The treatment was carried out under the same conditions as in Example 8. As a result, 0.7 i (yield: 9-) of cBN particles having a particle size of 50 to 350 μm and having black luster were obtained. Its carbon content was about 0.95a.

比較例１ 黒鉛粉末を配合しない点以外は実施例１と同様にして実
験を行った。その結果粒径２０〜１５０μｍ程度のｃＢ
Ｎ粒子がｔｔＦ（収率２６慢）得られた。このｃＢＮ粒
子を分析したところ、不純物として炭素が０００１〜０
．０１９６含有されて埴ることが確認された。Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that graphite powder was not blended. As a result, cB with a particle size of about 20 to 150 μm
N particles were obtained from ttF (yield: 26%). When this cBN particle was analyzed, it was found that carbon was present as an impurity in the range of 0001 to 0.
．． It was confirmed that 0196 was contained.

比較例２ ｈＢＮ粉末とＬ＠５Ｎ粉末とホウ素粉末とを重量比で５
：１：０．２の割合で混合し、以下実施例１と同様に処
理した。その結果粒径３０〜２００μｍの黒色ｃＢＮ粒
子が０．６　Ｆ　（収率１６％）得られた。Comparative Example 2 hBN powder, L@5N powder and boron powder in a weight ratio of 5
:1:0.2 and treated in the same manner as in Example 1. As a result, black cBN particles having a particle size of 30 to 200 μm were obtained at 0.6 F (yield: 16%).

そのｃＢＮ”ｌｆ９．子を分析したところ、Ｂはｃｌｌ
Ｎの化学当量よりも０．１参過剰であに、またＣは不純
物として０．００１　％程度含有されていることが判明
した。When I analyzed that cBN"lf9. child, B was cll
It was found that C was contained in an amount of 0.1 in excess of the chemical equivalent of N, and about 0.001% of C was contained as an impurity.

上述のような各実施例によシ得られたｃＢＮ粒子のうち
、炭素含有量がｏ、　ｏ　８　嗟であるｃＢＮ粒子と、
比較例１によるＩＲ票無添加のｃＢＮ粒子（但し不純物
としての炭素ｏ、　ｏ　ｏ　ｓ％）、および比較例２に
よるＢ　ＩＪタッチしたｃＢＮ粒子（Ｂｏ、１１Ｇ％不
純物としての炭素０．００１嗟）Ｋ）−て表面に重量比
で６０噂のＮｉコートを施して砥粒とし、それらの砥粒
によりレジノイドダンドを用ｉて砥石を成して研削試験
を行った。但し砥粒の粒度は−ずれも＋１４０メツシエ
、−１７０メツシユであり、研削試験の条件は次の通シ
である。Among the cBN particles obtained in each example as described above, cBN particles having a carbon content of o, o 8 o,
cBN particles without IR tag added according to Comparative Example 1 (however, carbon o, o s% as impurities) and B IJ-touched cBN particles according to Comparative Example 2 (Bo, 11G% carbon 0.001 mo as impurities) A grinding test was conducted using abrasive grains by coating the surface with Ni at a weight ratio of 60, and using these abrasive grains to form a grindstone using a resinoid dand. However, the particle size of the abrasive grains was -140 mesh and -170 mesh, and the conditions for the grinding test were as follows.

研削態様　二平面研削 砥石周速　：　１５００　ｆ％／ｎｉｍ切込み　　：２
０μｍ クロス送り：２■ 砥石寸法　：直径１５０１１１Ｘ厚さ７■（但しｃＢＮ
層厚が１．５■） 冷却剤　　：ソリエフール 被削材　　：　ＳＫＨ−ｓ　７　（硬度Ｈ１ｃ６２−６
３　）この研削試験の結果を第１表に示す。Grinding mode Biplane grinding wheel peripheral speed: 1500 f%/nim depth of cut: 2
0 μm Cross feed: 2 ■ Grinding wheel dimensions: Diameter 150111 x thickness 7 ■ (However, cBN
Layer thickness is 1.5■) Coolant: Soliefour Work material: SKH-s 7 (Hardness H1c62-6
3) The results of this grinding test are shown in Table 1.

第１表 第１表に示す結果からこの発明のｅＢＮ粒子を用いた砥
石にあっては、ホウ素リッチとしたｃＢＮ粒子を用いた
砥石および通常のｃＢＮ粒子（炭素無添加、ホウ孝非リ
ッチ）を用いた砥石と比較して研削抵抗が少ないことが
明らかであり、また研削後の砥粒表面を調べたところマ
イクロチッピングを起こしており、しかも砥粒の砥石面
からの脱落も少ないことが確認された。また被剛材の焼
け４はとんど生じていないことが確認された。これらの
事実から炭素を含有するこの発明のｅＢＮ粒子はマイク
ロチッピング性が良好でしかも金属コート層との接合性
も良好なことが明らかである。Table 1 From the results shown in Table 1, the grindstone using the eBN particles of the present invention is superior to the grindstone using the boron-rich cBN particles and the normal cBN particles (carbon-free, non-boron-rich). It is clear that the grinding resistance is lower than that of the grinding wheel used, and when the surface of the abrasive grains was examined after grinding, it was confirmed that microchipping had occurred, and that there was little falling off of the abrasive grains from the surface of the grinding wheel. Ta. Furthermore, it was confirmed that burnout 4 of the stiffened material hardly occurred. From these facts, it is clear that the carbon-containing eBN particles of the present invention have good microchipping properties and also have good bonding properties with the metal coating layer.

一方、炭素含有量を０〜２．０％の範囲で種々変化させ
たｃＢＮ粒子（＋１４０、−１２０メツシエ）について
強度（靭性）を調べた結果を第２図に示す。但しこの試
験は、０．５７のｃＢＮ粒子を鋼球とともに容器内に入
れて一定時間振動粉砕し、１４０メツシユの篩上に残留
し九粒子の割合を調べ、その割合をもって粒子強度の目
安とした。この場合篩上の残留割合が大き電柵靭性が高
いタフな粒子である。第゛２図に示すように炭素含有量
を変えればそれに伴って粒子の靭性が変化し、したがっ
て炭素含有量を制御することによって粒子の靭性を制御
し得ることが明らかである。On the other hand, FIG. 2 shows the results of examining the strength (toughness) of cBN particles (+140, -120 Messier) whose carbon content was varied in the range of 0 to 2.0%. However, in this test, cBN particles of 0.57 were placed in a container together with a steel ball and crushed by vibration for a certain period of time, and the proportion of nine particles remaining on a 140-mesh sieve was determined, and that proportion was used as a measure of particle strength. . In this case, the residual ratio on the sieve is large and the particles are tough and have high toughness. As shown in FIG. 2, if the carbon content is changed, the toughness of the particles changes accordingly, and it is therefore clear that the toughness of the particles can be controlled by controlling the carbon content.

また前述の各実施例と比較例１．２を比較すれば、炭素
を添加したこの発明のｃＢＮ粒子の製造時の収率は、Ｂ
リッチとしたｃＢＮ粒子（比較例２）の収率よりも格段
に良好でありて、炭素を添加せずしかもＢリッチとしな
い従来の通常のｃＢＮ粒子の収率とほぼ同等であること
が明らかである。Furthermore, when comparing each of the above-mentioned Examples and Comparative Example 1.2, the yield during production of cBN particles of the present invention with added carbon is as follows:
It is clear that the yield is much better than the yield of enriched cBN particles (Comparative Example 2) and almost the same as the yield of conventional cBN particles that are not added with carbon and are not enriched with B. be.

以上のように炭素を０，０２〜２．０チ含有するこの発
明のｃＢＮ粒子は、砥粒として使用した場合のマイクロ
チッピング性が良好でしかも金属や粘土系物質との接合
性も良好であり、また炭素含有量を制御するだけで容易
に粒子の靭性を制御することができ、さらには０粒同士
の焼結性が良好でしかも粒子製造時の収率も良好である
等の各種の長所がアリ、シたがってビトリファイドボン
ドを用％ｈｆｔ砥石の他、各種砥石の砥粒として有用で
あ抄、また焼結体として切削用チップ等にも有用である
。As described above, the cBN particles of the present invention containing 0.02 to 2.0 g of carbon have good microchipping properties when used as abrasive grains, and also have good bonding properties with metals and clay-based substances. In addition, the toughness of the particles can be easily controlled simply by controlling the carbon content, and furthermore, the sinterability of zero particles is good, and the yield during particle production is also good. Therefore, vitrified bond is useful as abrasive grains for various types of whetstones in addition to hft whetstones, and is also useful as a sintered body for cutting tips.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図はこの発明のｃＢＮ粒子の製造に使用される高圧
発生装置および試料容器の一例を示す断面図、第２図は
ｃＢＮ粒子の炭素含有量と粒子の靭性試験における篩上
残留割合との関係を示す相関図である。 出願人　昭和電工株式会社 代理人　弁理士豊田武久Figure 1 is a cross-sectional view showing an example of a high-pressure generator and sample container used in the production of cBN particles of the present invention, and Figure 2 shows the relationship between the carbon content of cBN particles and the percentage remaining on a sieve in a particle toughness test. It is a correlation diagram showing a relationship. Applicant: Showa Denko Co., Ltd. Agent: Takehisa Toyota, patent attorney

Claims (1)

【特許請求の範囲】[Claims] 炭素成分を重量比で０．０２〜２．０％含むことを特徴
とする立方晶窒化ホウ素粒子。Cubic boron nitride particles containing 0.02 to 2.0% by weight of a carbon component.