JPH06100727A - Electrically conductive resin composition and its production - Google Patents
Electrically conductive resin composition and its productionInfo
- Publication number
- JPH06100727A JPH06100727A JP4210288A JP21028892A JPH06100727A JP H06100727 A JPH06100727 A JP H06100727A JP 4210288 A JP4210288 A JP 4210288A JP 21028892 A JP21028892 A JP 21028892A JP H06100727 A JPH06100727 A JP H06100727A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- fine particles
- resin
- resin composition
- treated
- 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.)
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- Conductive Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電性樹脂組成物及びそ
の製造方法に関するものであり、本発明の樹脂組成物は
導電性を有するため、このものを用いて得られる成形製
品は帯電防止性、電磁波の遮蔽性が要求される分野で有
利に使用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive resin composition and a method for producing the same, and since the resin composition of the present invention has conductivity, a molded product obtained using this composition has antistatic properties. , Is advantageously used in fields where electromagnetic wave shielding properties are required.
【０００２】[0002]
【従来の技術】コンピュータ等の電子機器用ハウジング
等には特に高度の電磁波遮蔽材料が要求されており、導
電性の高い金、銀、銅、ニッケル、アルミニウム、鉄等
の金属類あるいはカーボンブラック、黒鉛、炭素繊維等
の炭素化合物の繊維、微粒子を利用する方法が各種提案
されている。2. Description of the Related Art In particular, housings for electronic devices such as computers are required to have a high degree of electromagnetic wave shielding material, and highly conductive metals such as gold, silver, copper, nickel, aluminum, iron or carbon black, Various methods of using carbon compound fibers such as graphite and carbon fibers and fine particles have been proposed.
【０００３】銀、銅、ニッケル等の金属粉末あるいは黒
鉛粉末は主としてコンピュータハウジングの電磁波シー
ルド用に使用される導電性塗料の導電性フィラーとして
利用されたり、直接樹脂成分に練り込むなどの方法で使
用される。黒鉛に関しては、黒鉛を粉砕して得られる黒
鉛粒子として、天然黒鉛を公知公用の方法で３０μｍ以
下に粉砕することは、例えば特開昭６１−６８０１号公
報に記載されている。Metallic powder of silver, copper, nickel or the like or graphite powder is mainly used as a conductive filler of a conductive paint used for electromagnetic wave shielding of a computer housing, or is directly kneaded into a resin component. To be done. Regarding graphite, as graphite particles obtained by pulverizing graphite, pulverizing natural graphite to 30 μm or less by a known and publicly known method is described in, for example, JP-A-61-6801.
【０００４】また、キッシュ黒鉛等の人造黒鉛の微粉末
を使用することも特開昭６２−８８２６１号公報に記載
されている。さらに、酸処理黒鉛を膨張させて得られる
膨張化黒鉛を圧縮した黒鉛シートを、ヘンシェルミキサ
ーで４０μｍ程度に粉砕して使用する方法が特開昭６４
−１１１６１号公報に提案されている。The use of fine powder of artificial graphite such as Kish graphite is also described in JP-A-62-88261. Further, there is a method in which a graphite sheet obtained by expanding expanded graphite obtained by expanding acid-treated graphite is crushed to about 40 μm with a Henschel mixer and used.
It is proposed in Japanese Patent Publication No. -11161.
【０００５】[0005]
【発明が解決しようとする課題】このような従来の技術
により製造される黒鉛微粒子は、導電性付与あるいは電
磁波遮蔽の目的を達成するため、樹脂等に配合されて家
庭用あるいは工業用の電化製品、自動車の電子装置、電
子機器のハウジングの一部に利用されたり、また、導電
性付与あるいは電磁波遮蔽の目的を達成するために導電
性塗料に配合されて使用されている。ところが近年導電
性付与あるいは電磁波遮蔽に対する要求は極めて強くな
り、従来技術による黒鉛微粒子では配合量を増大させね
ばならず、その結果、樹脂加工時の作業効率、塗料の塗
工性または樹脂の物性面からの要求に答えられないとい
う問題がある。本発明の課題はこれらの産業上の要請に
答えるべく、樹脂に高い導電性を付与する黒鉛粒子を提
供することにある。The graphite fine particles produced by such a conventional technique are blended with a resin or the like in order to achieve the purpose of imparting conductivity or shielding electromagnetic waves, and household or industrial electric appliances. It is used as a part of a housing of an electronic device or an electronic device of an automobile, or is mixed with a conductive paint for the purpose of imparting conductivity or shielding electromagnetic waves. However, in recent years, the demand for imparting conductivity or shielding electromagnetic waves has become extremely strong, and the amount of graphite fine particles according to the prior art has to be increased. As a result, work efficiency at the time of resin processing, coating property of resin or physical properties of resin are There is a problem that we can not answer the request from. An object of the present invention is to provide graphite particles that impart high conductivity to a resin in order to meet these industrial demands.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、本発明者らは特定の黒鉛粉末を含有させることによ
り、樹脂に極めて高い導電性を付与させ、かつ黒鉛の配
合量を増大させても、樹脂加工時の作業効率、塗料の塗
工性または樹脂の物性面の要求を損なうという問題のな
い樹脂組成物を見い出し本発明を完成させた。In order to solve the above-mentioned problems, the present inventors have added a specific graphite powder to impart extremely high conductivity to the resin and increase the blending amount of graphite. However, the present invention has been completed by finding a resin composition having no problem of impairing the work efficiency at the time of resin processing, the coating property of the coating material, or the physical properties of the resin.
【０００７】すなわち、本発明の要旨は、（Ｉ）黒鉛微
粒子を５〜５０重量％含有して成る樹脂組成物であっ
て、該黒鉛微粒子が、平均粒子径２０μｍ以下かつ、嵩
密度０．１２ｇ／ｃｃ以下の膨張化黒鉛であることを特
徴とする導電性樹脂組成物、並びに（II）黒鉛微粒子を
５〜５０重量％含有して成る樹脂組成物を製造する際
に、該黒鉛微粒子として、酸処理黒鉛を膨張させて得ら
れる膨張化黒鉛をジェット粉砕機により平均粒子径が２
０μｍ以下、嵩密度が０．１２ｇ／ｃｃ以下となるよう
に粉砕して得られる膨張化黒鉛を用いることを特徴とす
る導電性樹脂組成物の製造方法、にある。That is, the gist of the present invention is a resin composition comprising (I) 5 to 50% by weight of graphite fine particles, the graphite fine particles having an average particle diameter of 20 μm or less and a bulk density of 0.12 g. / Cc or less expanded graphite, the conductive resin composition, and (II) when producing a resin composition containing 5 to 50% by weight of graphite fine particles, as the graphite fine particles, The expanded graphite obtained by expanding the acid-treated graphite has a mean particle size of 2 by a jet pulverizer.
A method for producing a conductive resin composition, characterized in that expanded graphite obtained by pulverizing to a particle size of 0 μm or less and a bulk density of 0.12 g / cc or less is used.
【０００８】以下、本発明を詳細に説明する。まず、本
発明においては、黒鉛微粒子として膨張性黒鉛を膨張さ
せた膨張化黒鉛が用いられる。熱膨張性黒鉛は、広義に
は種々の方法でつくられ、多様な組成物をあげることが
できるが、酸処理黒鉛が一般的である。酸処理黒鉛は、
天然黒鉛、熱分解黒鉛、キッシュ黒鉛などの黒鉛を、濃
厚な硫酸と強い酸化剤との混合物で処理した後、水洗
し、乾燥して得られるものをいい、黒鉛シートなどの製
造に用いられる工業的な熱膨張性黒鉛は通常このものに
相当する。The present invention will be described in detail below. First, in the present invention, expanded graphite obtained by expanding expandable graphite is used as the graphite fine particles. The heat-expandable graphite is produced by various methods in a broad sense, and various compositions can be mentioned, but acid-treated graphite is generally used. Acid-treated graphite is
Natural graphite, pyrolytic graphite, quiche graphite, and other graphite are treated with a mixture of concentrated sulfuric acid and a strong oxidizer, washed with water, and dried. Thermally expansive graphite usually corresponds to this.
【０００９】この酸処理黒鉛は、黒鉛の有する層状構造
の層間に硫酸が残留、固定されているものであり、約５
００℃以上に急激に加熱することにより層間に存在する
硫酸が膨張することによってＣ軸方向に数１０〜数１０
０倍に膨張する性質を有するものであって、熱膨張後の
黒鉛層は互いにゆるく接している構造となっている。本
発明においては、この急激な加熱によって膨張した状態
の黒鉛を膨張化黒鉛として用いる。This acid-treated graphite is one in which sulfuric acid remains and is fixed between the layers of the layered structure of graphite.
Sulfuric acid existing between layers is expanded by rapid heating to 00 ° C. or higher, so that several tens to several tens in the C-axis direction are expanded.
It has the property of expanding by a factor of 0, and the graphite layers after thermal expansion are in loose contact with each other. In the present invention, graphite expanded in this rapid heating is used as expanded graphite.
【００１０】本発明で使用される酸処理黒鉛は、原料黒
鉛、製造方法には特に制限はないが、その特性として
は、１０００℃で１０秒間、急激に加熱するときの膨張
度が１００〜３００ｃｃ／ｇであることが望ましい。こ
のような酸処理黒鉛は、例えば、９８％濃硫酸と６０％
過酸化水素水の混合物中におよそ３０〜１００メッシュ
に粉砕された黒鉛を、４５℃以下で１０分〜３０分接触
させ、水洗、乾燥を行うことにより製造することができ
る。The acid-treated graphite used in the present invention is a raw material graphite and the production method is not particularly limited, but the characteristic is that the expansion coefficient when rapidly heated at 1000 ° C. for 10 seconds is 100 to 300 cc. / G is desirable. Such acid-treated graphite is, for example, 98% concentrated sulfuric acid and 60%
It can be produced by contacting graphite crushed to about 30 to 100 mesh in a mixture of hydrogen peroxide water at 45 ° C. or less for 10 to 30 minutes, washing with water and drying.
【００１１】本発明において使用される膨張化黒鉛は、
通常、膨張度として１００〜３００ｃｃ／ｇ（膨張後の
嵩密度０．０１〜０．００３ｇ／ｃｃ）である酸処理黒
鉛を５００℃以上、好ましくは７００〜１５００℃で数
秒間、更に好ましくは８００〜１１００℃で２〜５秒間
加熱することにより熱膨張させて得られる。熱膨張は、
例えば所定の温度に制御された電気炉内あるいはガスバ
ーナー炉に連続的に酸処理黒鉛を供給することにより工
業的な規模で実施することができる。The expanded graphite used in the present invention is
Usually, acid-treated graphite having a degree of expansion of 100 to 300 cc / g (bulk density after expansion 0.01 to 0.003 g / cc) is 500 ° C. or higher, preferably 700 to 1500 ° C. for several seconds, more preferably 800. It is obtained by thermal expansion by heating at ˜1100 ° C. for 2 to 5 seconds. Thermal expansion
For example, it can be carried out on an industrial scale by continuously supplying acid-treated graphite in an electric furnace controlled to a predetermined temperature or in a gas burner furnace.
【００１２】尚、ここでいう「膨張度」とは、１０００
℃に保持された電気炉内に１０分以上保持して加熱され
た１５０ｃｃの石英ビーカを炉外に取り出し、直ちに酸
処理黒鉛０．５ｇを投入し、同じく１０００℃に保持さ
れた炉中に素早く入れ、そのまま１０秒間保持した後、
炉外に取り出し、自然冷却の後に、ビーカに付した目盛
りによって、膨張後の黒鉛層の上部位置を読み取って容
積を測定し、算出する値（単位：ｃｃ／ｇ）をいう。The term "expansion" as used herein means 1000
Remove the heated 150 cc quartz beaker, which was kept in the electric furnace maintained at ℃ for 10 minutes or more, out of the furnace, immediately add 0.5 g of acid-treated graphite, and quickly put it in the furnace maintained at 1000 ℃. Put it in and hold it for 10 seconds,
It is a value (unit: cc / g) calculated by taking out from the furnace and, after natural cooling, reading the upper position of the expanded graphite layer with a scale attached to a beaker to measure the volume.
【００１３】また、本発明における「嵩密度」について
は、ＪＩＳ Ｋ６８９１による方法で測定される見掛密
度と同値で、（単位：ｇ／ｃｃ）で表される。酸処理黒
鉛の膨張度が１００ｃｃ／ｇ未満である場合は、Ｃ軸方
向に対する膨張が不十分であり、そのため層状に形成さ
れている酸処理黒鉛の黒鉛結晶（原料黒鉛も層間化合物
である酸処理黒鉛もほぼ類似した層状結晶構造である）
を熱膨張させたとき、層間剥離が十分行われず、従って
個々の剥離片はＣ軸方向の厚みの大きなもの（剥離しな
い層が重層となっている）となり、その結果、平均粒子
径が同等で膨張度の高い膨張化黒鉛粉末を使用して得た
該黒鉛微粒子に比較して、導電性が付与できる黒鉛粉末
による鎖状連結の形成が十分となるためには、添加量を
増加させなければならない。また、酸処理黒鉛の膨張度
が３００ｃｃ／ｇを超えると、導電性付与に関してそれ
に見合う効果が期待できないばかりか、工業的に製造す
ることがきわめて難しく経済的な見地からは実用的では
ない。The "bulk density" in the present invention is the same value as the apparent density measured by the method according to JIS K6891, and is expressed in (unit: g / cc). When the degree of expansion of the acid-treated graphite is less than 100 cc / g, the expansion in the C-axis direction is insufficient, and therefore graphite crystals of the acid-treated graphite formed in layers (the raw graphite is also an acid-treated compound that is an intercalation compound). Graphite also has a similar layered crystal structure)
When thermal expansion was performed, delamination was not performed sufficiently, and therefore each exfoliated piece had a large thickness in the C-axis direction (layers that did not exfoliate were multi-layered), and as a result, the average particle diameter was the same. Compared with the graphite fine particles obtained by using an expanded graphite powder having a high expansion degree, in order to sufficiently form a chain connection by the graphite powder capable of imparting conductivity, the addition amount must be increased. I won't. In addition, when the expansion degree of the acid-treated graphite exceeds 300 cc / g, not only the effect corresponding to that for imparting conductivity cannot be expected, but also it is extremely difficult to industrially manufacture and it is not practical from an economical point of view.
【００１４】本発明において、該黒鉛微粒子の後述する
樹脂への配合は、樹脂組成物中の含量が５〜５０重量
％、好ましくは１０〜３０重量％となるように行なわれ
る。この配合量が５重量％未満であると本発明効果が得
られず好ましくない。また、配合量が５０重量％を超え
ると導電性は良好であるが、導電性付与に関してそれに
見合う効果が期待できないので好ましくない。In the present invention, the graphite fine particles are blended with the resin described below so that the content in the resin composition is 5 to 50% by weight, preferably 10 to 30% by weight. If the blending amount is less than 5% by weight, the effect of the present invention cannot be obtained, which is not preferable. Further, if the blending amount exceeds 50% by weight, the conductivity is good, but it is not preferable because an effect commensurate with the conductivity cannot be expected.
【００１５】本発明において、該黒鉛微粒子の平均粒子
径は２０μｍ以下、好ましくは２〜２０μｍである。該
黒鉛微粒子の平均粒子径が２０μｍを超えると、樹脂へ
の分散が悪く、樹脂中に分散できる粒子数が平均粒子径
２０μｍ以下の該黒鉛微粒子添加時に較べて少なく導電
性に劣る。加えて安定した導電性が得られにくい。更
に、塗料に添加して用いた場合、外観及び膜厚精度に問
題が生じるので好ましくない。なお、該黒鉛微粒子の平
均粒子径が２μｍ未満の場合は、粉砕の際、長時間を要
し経済的な見地からも実用的ではなく、また導電性付与
に関してそれに見合う効果が期待できないのであまり望
ましくない。In the present invention, the graphite fine particles have an average particle size of 20 μm or less, preferably 2 to 20 μm. When the average particle size of the graphite fine particles exceeds 20 μm, the dispersion in the resin is poor, and the number of particles that can be dispersed in the resin is small compared to when the graphite fine particles having an average particle size of 20 μm or less are added, resulting in poor conductivity. In addition, it is difficult to obtain stable conductivity. Further, when it is used by being added to a paint, it causes problems in appearance and film thickness accuracy, which is not preferable. When the average particle size of the graphite fine particles is less than 2 μm, it takes a long time during pulverization, which is not practical from an economical point of view, and it is not desirable because it cannot be expected to have an effect in terms of imparting conductivity. Absent.
【００１６】本発明において、該黒鉛微粒子の嵩密度は
０．１２ｇ／ｃｃ以下、好ましくは０．１０ｇ／ｃｃ以
下である。嵩密度が０．１２ｇ／ｃｃを超える該黒鉛微
粒子は、黒鉛粒子の解離が遅く、樹脂への分散性が低下
し、導電性に劣るので不適である。 以上のように、粉
砕により平均粒子径２０μｍ以下、嵩密度０．１２ｇ／
ｃｃ以下、の範囲に得られる該黒鉛微粒子は、膨張化黒
鉛自体の良導電性を損なうことなく微粒子化されたもの
で、混練機への供給が極めて容易であるばかりでなく、
短い混練時間で十分な分散を行うことができる。同様
に、塗料に添加した際の分散性も良好である。その結
果、少ない配合量で安定した高い導電性を有する樹脂組
成物が得られる。In the present invention, the graphite fine particles have a bulk density of 0.12 g / cc or less, preferably 0.10 g / cc or less. The graphite fine particles having a bulk density of more than 0.12 g / cc are not suitable because the graphite particles are slowly dissociated, the dispersibility in the resin is reduced, and the conductivity is poor. As described above, the average particle size of 20 μm or less and the bulk density of 0.12 g /
The graphite fine particles obtained in the range of cc or less are fine particles without impairing the good conductivity of the expanded graphite itself, and are not only very easily supplied to the kneading machine,
Sufficient dispersion can be achieved with a short kneading time. Similarly, the dispersibility when added to the paint is also good. As a result, a stable resin composition having high conductivity can be obtained with a small amount.
【００１７】本発明において、平均粒子径が２０μｍ以
下で、嵩密度が０．１２ｇ／ｃｃ以下となるように粉砕
を行う方法としては、次のような方法を挙げることがで
きる。例えばヘンシェルミキサー、ホモミキサーハンド
ミキサー、ハンマーミル、家庭用ジューサー等の粗砕機
で、直径１ｍｍ以下に粗粉砕し、これを、マイクロイフ
ィダー等の供給機を用いて、粒子間衝突方式であるジェ
ット粉砕により微粒子化を行うことにより調整される。
ジェット粉砕は、供給された原料が流体（圧縮空気、不
活性ガス、スチーム、ホットエアー等）と共に超音速に
加速され粉砕ゾーンに導かれそこで粒子間同士が相互衝
突、相互摩擦、微粉砕化される粉砕型式である。なお、
高速回転衝撃式粉砕の様な粉体粒子と打撃子が衝突する
粉砕方式においては、粒子径は２０μｍ以下としうる
が、嵩密度が０．１２ｇ／ｃｃ以下になり難いので好ま
しくない。In the present invention, the following method can be mentioned as a method of pulverizing so that the average particle diameter is 20 μm or less and the bulk density is 0.12 g / cc or less. For example, a crusher such as a Henschel mixer, a homomixer hand mixer, a hammer mill, and a household juicer is used to roughly crush the particles to a diameter of 1 mm or less. It is adjusted by pulverizing into fine particles.
In jet pulverization, the supplied raw material is accelerated to supersonic velocity together with fluid (compressed air, inert gas, steam, hot air, etc.) and guided to the pulverization zone where particles collide with each other, mutually rub, and finely pulverize. It is a crushing type. In addition,
In a pulverization method in which powder particles collide with a hitting element, such as high-speed rotary impact pulverization, the particle size can be 20 μm or less, but it is not preferable because the bulk density is less than 0.12 g / cc.
【００１８】本発明の樹脂組成物は塗料、直接押出しシ
ート、射出成形品などの成形品とすることもできるし、
発泡剤を添加して発泡成形品として使用できるが、マス
ターバッチ、コンパウンドとしてその他の樹脂類による
希釈、あるいは混合により成形品に供することが出来る
から、該黒鉛微粒子の配合量は所望の導電性に応じて、
本発明の範囲内で自由に設計できることはいうまでもな
い。樹脂としては、熱可塑性、熱硬化性のいずれも使用
しうる。The resin composition of the present invention can be used as a paint, a directly extruded sheet, a molded product such as an injection molded product, and the like.
Although it can be used as a foamed molded product by adding a foaming agent, it can be used as a masterbatch, diluted with other resins as a compound, or provided in a molded product by mixing. Depending on,
It goes without saying that the design can be freely made within the scope of the present invention. The resin may be either thermoplastic or thermosetting.
【００１９】熱可塑性樹脂としては、次に挙げるものを
例示することができる。即ち、ポリエチレン、ポリプロ
ピレン、ポリブチレン及びこれらのモノマーと酢酸ビニ
ル、アクリル酸エステルとの共重合体等のポレオレフィ
ン樹脂類、ポリ塩化ビニル樹脂類、ポリスチレン、アク
リルニトリル−スチレン共重合体、アクリルニトリル−
ブタジエン−スチレン共重合体等のポリスチレン系樹脂
類、ポリエチレンテレフタレート等のポリエステル系樹
脂類、ナイロン等のポリアミド系樹脂類、ポリオキシメ
チレン等のエーテル系樹脂類の他、塩素化ポリエチレ
ン、ポリブタジエン、ポリイソプレン等のエラストマー
類の各類を代表的に挙げることができる。The following can be exemplified as the thermoplastic resin. That is, polyolefins such as polyethylene, polypropylene, polybutylene and copolymers of these monomers with vinyl acetate and acrylic ester, polyvinyl chloride resins, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-
Polystyrene resins such as butadiene-styrene copolymer, polyester resins such as polyethylene terephthalate, polyamide resins such as nylon, ether resins such as polyoxymethylene, chlorinated polyethylene, polybutadiene, polyisoprene Each type of elastomers such as can be representatively mentioned.
【００２０】また、熱硬化性樹脂としては、フェノール
−ホルムアルデヒド、フェノール−フルフラール等のフ
ェノール樹脂類、エポキシ樹脂類、ユリア−ホルムアル
デヒド、エステル化ユリア等のユリア樹脂類、メラミン
−ホルムアルデヒド、アニリン−ホルムアルデヒド等の
メラミン樹脂類、珪素樹脂類、マレイン酸−エチレング
リコール縮合体等の不飽和ポリエステル樹脂類、アルキ
ド樹脂類、フタル酸ジアリル重合体、等を代表的に挙げ
ることができる。As the thermosetting resin, phenol resins such as phenol-formaldehyde and phenol-furfural, epoxy resins, urea resins such as urea-formaldehyde and esterified urea, melamine-formaldehyde, aniline-formaldehyde, etc. Representative examples thereof include unsaturated melamine resins, silicone resins, unsaturated polyester resins such as maleic acid-ethylene glycol condensates, alkyd resins, and diallyl phthalate polymers.
【００２１】本発明の樹脂組成物を製造する方法として
は、樹脂原料と所定量の膨張化黒鉛微粒子を、ヘンシェ
ルミキサー、リボンブレンダー等通常使用される混合装
置によって撹拌混合し、ついで単軸又は二軸スクリュー
押出機、ニーダー、バンバリーミキサー等通常使用され
る混練機で混練するか、あるいは、加熱二本ロール等を
使用して練和する方法を挙げることができる。As a method for producing the resin composition of the present invention, a resin raw material and a predetermined amount of expanded graphite fine particles are stirred and mixed by a commonly used mixing device such as a Henschel mixer, a ribbon blender, and then uniaxially or biaxially. Examples of the method include kneading with a kneader that is commonly used, such as an axial screw extruder, a kneader, a Banbury mixer, or kneading using a heated two-roll.
【００２２】練和する際の温度条件としては、使用する
樹脂が熱硬化性樹脂原料の場合、硬化温度以下で練和す
ることが望ましい。一方、熱可塑性樹脂原料の場合、当
樹脂の融点以上から融点＋１００℃程度の温度を挙げる
ことが出来るが、一般に膨張性黒鉛粉末の添加により混
合物の流動性が低下する傾向があるので融点＋３０℃以
上で練和することがより有利であり、又、上限温度は樹
脂の熱安定性によって左右される。When the resin used is a thermosetting resin raw material, it is desirable that the temperature conditions for kneading be kneading at a temperature not higher than the curing temperature. On the other hand, in the case of a thermoplastic resin raw material, a temperature of not less than the melting point of the resin to a melting point + 100 ° C or so can be mentioned. It is more advantageous to knead as described above, and the upper limit temperature depends on the thermal stability of the resin.
【００２３】一方、塗料に配合する際の方法としては、
例えば、熱可塑性樹脂原料を、シンナー等の炭化水素系
溶剤を加えて粘度が調整された塗料に、所定量の該黒鉛
微粒子を、混ぜ合わせこれを均一に分散させる事が挙げ
られる。分散方法としては、ラボスターラー、ホモミキ
サー等の通常用いられる撹拌機で容易に行われる。本発
明の樹脂組成物においては、通常のプラスチック製品及
び塗料に使用される一般的な添加剤、即ち、酸化防止
剤、帯電防止剤、滑剤、架橋剤、難燃剤、染顔料、導電
性フィラー、充填剤等が添加、配合されることに関して
は特別の制限はない。On the other hand, as a method for blending into the paint,
For example, a thermoplastic resin raw material may be mixed with a hydrocarbon solvent such as thinner to a paint whose viscosity is adjusted, and a predetermined amount of the graphite fine particles may be mixed and uniformly dispersed. As a dispersion method, a commonly used stirrer such as a lab stirrer or a homomixer is easily used. In the resin composition of the present invention, general additives used in ordinary plastic products and paints, that is, antioxidants, antistatic agents, lubricants, crosslinking agents, flame retardants, dyes and pigments, conductive fillers, There are no particular restrictions on the addition and blending of fillers and the like.
【００２４】また、本発明により製造される樹脂組成物
あるいはこれを用いた成形品については、更に、表面の
美装化、耐水化、難燃化等を目的として異種材料との組
合せによる複合材料を製造することも可能である。Further, regarding the resin composition produced by the present invention or a molded article using the same, a composite material obtained by combining different materials for the purpose of making the surface beautiful, water resistant, flame retardant, etc. It is also possible to manufacture
【００２５】[0025]
【発明の効果】本発明により、樹脂に良好な導電性を付
与することができるので、電気製品、電子製品のキャビ
ネット等に使用する際に帯電防止あるいは電磁波の遮蔽
に対して高い効果が期待される。また、本発明で使用さ
れる膨張化黒鉛粉末はきわめて軽量であり、完成製品の
軽量化に有利である。更に、本発明の製造方法は、極め
て容易に膨張化黒鉛粉末を樹脂に添加、分散することが
でき、所望の導電性を発揮させることができるものであ
る。According to the present invention, good conductivity can be imparted to the resin, and therefore, it is expected to have a high effect on the antistatic property or the electromagnetic wave shielding when it is used in cabinets of electric products and electronic products. It Further, the expanded graphite powder used in the present invention is extremely lightweight, which is advantageous for reducing the weight of the finished product. Further, in the production method of the present invention, the expanded graphite powder can be added and dispersed in the resin very easily, and the desired conductivity can be exhibited.
【００２６】[0026]
【実施例】以下本発明を実施例及び比較例により更に詳
細に説明するが、本発明はその要旨を超えない限り、以
下の実施例に限定されるものではない。なお、実施例等
に記載した各成分の量を示す「部」はすべて重量部であ
り、％はすべて重量％である。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist. In addition, all "parts" indicating the amounts of the respective components described in Examples and the like are parts by weight, and% are all% by weight.
【００２７】実施例１ 〈黒鉛粉粒子の製造〉固定炭素分９０％、灰分８％であ
るカナダ産出の天然鱗片状黒鉛（粒度；３６メッシュ〜
８０メッシュ）の各４０部を９８％硫酸１５０部、６０
％過酸化水素水２部の混合液に加えて、３０〜３５度で
１５分間反応させた。ついで反応物に１５０部の３０％
硫酸を加えて希釈した後、ガラス繊維濾紙（ＧＡ１０
０）を用いてヌッチェで吸引濾過し残さをとりだした。
この濾過残さを５００部の水中に投入し、３０秒間かき
混ぜ洗浄した後、再び吸引濾過により残さを分離した。
このときの残さを再び５００部の水中に投入し、３０秒
間かき混ぜ洗浄した後、同様に吸引濾過により残さを分
離した。ついでこの濾過残さを１０５℃の熱風循環式乾
燥器中で約９０分乾燥して酸処理黒鉛を得た。この酸処
理黒鉛の１０００℃、１０秒間の膨張度の測定結果は、
１９０ｃｃ／ｇｒ、嵩密度は０．００５３ｇ／ｃｃであ
った。Example 1 <Production of Graphite Powder Particles> Natural flake graphite produced in Canada with a fixed carbon content of 90% and an ash content of 8% (particle size: 36 mesh-
40 parts of 80 mesh), 150 parts of 98% sulfuric acid, 60 parts
% Hydrogen peroxide solution (2 parts), and the mixture was reacted at 30 to 35 ° C. for 15 minutes. Then 30% of 150 parts in the reaction product
After diluting by adding sulfuric acid, glass fiber filter paper (GA10
0) was used to suction-filter with a Nutsche and the residue was taken out.
The filtration residue was put into 500 parts of water, stirred and washed for 30 seconds, and then the residue was separated by suction filtration again.
The residue at this time was again put into 500 parts of water, and after stirring and washing for 30 seconds, the residue was similarly separated by suction filtration. Then, the filtration residue was dried in a hot air circulation dryer at 105 ° C. for about 90 minutes to obtain acid-treated graphite. The measurement result of the expansion degree of this acid-treated graphite at 1000 ° C. for 10 seconds is
The volume density was 190 cc / gr and the bulk density was 0.0053 g / cc.
【００２８】〈微粉砕方法〉ここで得た膨張化黒鉛粒子
をプレスにより常温で圧締して厚みがおよそ０．５ｍｍ
の圧縮黒鉛を得た。この圧縮黒鉛の密度は１．００ｇ／
ｃｃであった。この圧縮黒鉛を、ヘンシェルミキサーを
用いて粗粉砕を行い、膨張化黒鉛粒子Ａを得た。平均粒
子径は、４００μｍ、密度０．３ｇ／ｃｃであった。更
に、この膨張化黒鉛粒子Ａを用いて、旋回流型ジェット
ミル「ＣＰＮ−０４型」（セイシン企業（株）製）にて
フィード量５００ｇ／ｈ、空気圧７．５ｋｇ／ｃｍ2 で
粉砕を行った。得られた膨張化黒鉛微粒子は平均粒子径
４．８μｍ、嵩密度０．０８ｇ／ｃｃであった。<Fine pulverization method> The expanded graphite particles obtained here are pressed at room temperature by a press to have a thickness of about 0.5 mm.
Of compressed graphite was obtained. The density of this compressed graphite is 1.00 g /
It was cc. The compressed graphite was coarsely crushed using a Henschel mixer to obtain expanded graphite particles A. The average particle size was 400 μm and the density was 0.3 g / cc. Further, the expanded graphite particles A were pulverized by a swirling flow type jet mill “CPN-04 type” (manufactured by Seishin Enterprise Co., Ltd.) at a feed rate of 500 g / h and an air pressure of 7.5 kg / cm 2. It was The expanded graphite fine particles obtained had an average particle diameter of 4.8 μm and a bulk density of 0.08 g / cc.
【００２９】〈平均粒子径の測定〉平均粒子径６０μｍ
以上の場合、ふるい分けにより平均粒子径を、重量累積
５０％平均粒度として求めた。平均粒子径６０μｍ以下
の場合、遠心沈降光透過法により平均粒子径を、重量累
積５０％平均粒度として求めた。 装置：（「マイクロフォトサイザーＳＫＣ−２０００」
セイシン企業（株）製）<Measurement of average particle size> Average particle size 60 μm
In the above case, the average particle size was determined by sieving as the 50% weight cumulative average particle size. When the average particle size was 60 μm or less, the average particle size was determined as a 50% weight-average particle size by the centrifugal sedimentation light transmission method. Device: ("Micro Photosizer SKC-2000"
Seishin Enterprise Co., Ltd.)
【００３０】〈樹脂組成物の製造〉樹脂として次に示す
ものを用い、更に前記膨張化黒鉛粒子Ａをジェット粉砕
して得た膨張化黒鉛微粒子を用いて、又、次に示す練和
条件により樹脂組成物を製造した。 樹 脂； １．ポリエチレン：三菱化成（株）製「三菱ポリエチ−
ＬＤ Ｆ−２６１」 練和方法；ブラベンダー社製「ブラベンダープラスチコ
ーダー」のミキシングチャンバーを温度１８０℃、回転
数４５ｒｐｍに設定し、このチャンバーに、ポリエチレ
ン樹脂２８部を入れ、樹脂が流動状態で練和され始めた
状態になってから、引続き２８部の膨張化黒鉛微粒子を
約１分を要して添加した。膨張化黒鉛微粒子の添加を始
めた時から混練操作を３分間続けた。測定開始後３分経
過してからチャンバー内の混合物の温度を測定したとこ
ろ１８０±５℃であり、混練操作中殆ど設定値に近い温
度を示していた。３分間の混練が終了した後、チャンバ
ーより混合物を取り出した。 シート化方法；練和時の設定温度に予め設定された熱プ
レス装置に、１２０ｍｍ×１２０ｍｍ×１ｍｍの金属製
のスペーサーを設置し、前記練和操作の終了した混合物
１４部を２００ｋｇ／ｃｍ2 で３分間加熱圧締し、つい
で解圧してシートを得た。このシートは、目視観察後、
体積抵抗率測定用とした。<Production of Resin Composition> The following resins are used, and expanded graphite fine particles obtained by jet crushing the expanded graphite particles A are used, and the following kneading conditions are used. A resin composition was produced. Resin; 1. Polyethylene: "Mitsubishi Polyethylene" manufactured by Mitsubishi Kasei Co., Ltd.
LD F-261 "Kneading method: The temperature of the mixing chamber of" Blavender Plasticorder "manufactured by Brabender was set to 180 ° C and the rotation speed was 45 rpm, and 28 parts of polyethylene resin was put into this chamber, and the resin was in a fluid state. After the kneading started, 28 parts of expanded graphite fine particles were continuously added in about 1 minute. The kneading operation was continued for 3 minutes from the start of the addition of the expanded graphite fine particles. When the temperature of the mixture in the chamber was measured 3 minutes after the start of measurement, it was 180 ± 5 ° C., which was almost the same as the set value during the kneading operation. After the kneading for 3 minutes was completed, the mixture was taken out from the chamber. Sheeting method: A metal press spacer of 120 mm × 120 mm × 1 mm was installed on a hot press device preset to a set temperature during kneading, and 14 parts of the mixture after the kneading operation was completed at 200 kg / cm 2 . The sheet was heat-pressed for 3 minutes and then released to obtain a sheet. This sheet, after visual observation,
Used for measuring volume resistivity.
【００３１】〈体積抵抗率の測定〉４探針式抵抗率測定
方式により体積抵抗率を測定した。測定には「ロレスタ
ＡＰ」（三菱油化（株）製）を用いて室温にて行った。 〈引っ張り強度試験評価〉ＪＩＳ−Ｋ−７１１３に準
拠。<Measurement of Volume Resistivity> The volume resistivity was measured by a 4-probe resistivity measuring method. "Loresta AP" (manufactured by Mitsubishi Petrochemical Co., Ltd.) was used for the measurement at room temperature. <Evaluation of tensile strength test> In accordance with JIS-K-7113.
【００３２】実施例２ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、旋回流型ジェットミル「ＣＰＮ−０４型」（セイシ
ン企業（株）製）にてフィード量５５０ｇ／ｈ、空気圧
７．５ｋｇ／ｃｍ2 で粉砕を行った。得られた膨張化黒
鉛微粒子は、平均粒子径４．８μｍ、嵩密度０．０８ｇ
／ｃｃであった。これを第１表に示した配合量に基き実
施例１同様に樹脂組成物の製造、体積抵抗率、及び引っ
張り強度測定を行った。Example 2 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a swirling flow type jet mill "CPN-04 type" (manufactured by Seishin Enterprise Co., Ltd.) was used to feed 550 g / Milling was carried out at h and an air pressure of 7.5 kg / cm 2 . The expanded graphite fine particles obtained had an average particle diameter of 4.8 μm and a bulk density of 0.08 g.
Was / cc. Based on the blending amount shown in Table 1, the resin composition was manufactured, the volume resistivity and the tensile strength were measured in the same manner as in Example 1.
【００３３】実施例３ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、流動層式カウンタージェットミル「アルピネジェッ
トミル２００ＡＦＧ」（（株）イトマンエンジニアリン
グ製）にてフィード量４ｋｇ／ｈで、粉砕を行った。得
られた膨張化黒鉛微粒子は、平均粒子径１６．３μｍ、
嵩密度０．０８ｇ／ｃｃであった。これを第１表に示し
た配合量に基き実施例１同様に樹脂組成物の製造、体積
抵抗率の測定を行った。Example 3 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a fluidized bed type counter jet mill "Alpine Jet Mill 200AFG" (manufactured by Itoman Engineering Co., Ltd.) was used to feed Grinding was performed at 4 kg / h. The obtained expanded graphite fine particles had an average particle diameter of 16.3 μm,
The bulk density was 0.08 g / cc. Based on the blending amounts shown in Table 1, the resin composition was produced and the volume resistivity was measured in the same manner as in Example 1.
【００３４】実施例４ 実施例１で得られた膨張化黒鉛微粒子を以下に示す方法
で、塗料として用いた場合の樹脂組成物の製造を行っ
た。 〈樹脂組成物の製造〉樹脂として次に示すものを用い、
更に実施例１で得られた膨張化黒鉛微粒子を用いて、次
に示す塗布条件により熱可塑性樹脂及び熱硬化性樹脂組
成物を製造した。Example 4 A resin composition was produced when the expanded graphite fine particles obtained in Example 1 were used as a paint by the method shown below. <Production of resin composition> Using the following as a resin,
Further, the expanded graphite fine particles obtained in Example 1 were used to produce a thermoplastic resin and a thermosetting resin composition under the following coating conditions.
【００３５】１．アクリルラッカー ：関西ペイント
（株）製「ＡＣＲＩＣ１０００」固形分３７．５重量％ ２．ＰＶＣ（塩化ビニル樹脂）：ロックペイント（株）
製「パーマロック」固形分５７．５重量％ ３．フェノール ：日本化成（株）製「Ｓ−１
９１」（レゾール型）固形分４０．１重量％ ＊ 固形分の測定は塗料約１０ｇを秤量した後、シャー
レ上に薄く延ばし１０５℃で、１日以上乾燥させ残った
重量を固形分として初めの重量の割合で示した値であ
る。1. Acrylic lacquer: "ACRIC1000" manufactured by Kansai Paint Co., Ltd., solid content 37.5% by weight 2. PVC (vinyl chloride resin): Rock Paint Co., Ltd.
Made by "Permalock" solid content 57.5% by weight 3. Phenol: "S-1" manufactured by Nippon Kasei Co., Ltd.
91 "(resole type) solid content 40.1% by weight * The solid content is measured by weighing about 10 g of the coating material, spreading it thinly on a petri dish, and drying at 105 ° C. for 1 day or more. It is a value shown as a weight ratio.
【００３６】塗布方法；容量１５０ｃｃのラミネートカ
ップにアクリルラッカー２０重量部入れ次に、黒鉛微粉
末３．２１重量部添加した。これに粘度約１．２ポイズ
になる様希釈剤としてシンナー（フェノール樹脂につい
ては水。）適量添加したものを、「ラボスタラー」
（「ＥＹＥＬＡ Ｄ．Ｃ ＳＴＩＲＲＥＲ ＤＣＬ−Ｒ
Ｔ」東京理科機械（株）製）５００ｒｐｍで約３分間分
散を行った。このようにして得られた樹脂組成物塗料を
１２０ｍｍ×１２０ｍｍ×０．５ｍｍの塩ビ板上に、バ
ーコーターを用いて塗装を行った。これを室温にて、１
日以上乾燥、フェノール樹脂に関しては６０℃、３時間
以上で熱硬化させた。目視観察後、膜厚を測定し、体積
抵抗率測定用とした。又、膜厚の測定の際、「デジタル
ライナーゲージＤＧ−７５１」（小野測器（株）製）を
用いて中央部及び中央部より３ｃｍ離れた４隅を測定
し、それらの平均値を用いた。尚、ここでの配合率は黒
鉛微粉末重量を塗料の固形分重量と添加した黒鉛微粉末
重量とで除した割合である。（ｗｔ％）Coating method: 20 parts by weight of acrylic lacquer was put in a laminating cup having a capacity of 150 cc, and then 3.21 parts by weight of graphite fine powder was added. A suitable amount of thinner (water for phenol resin) was added as a diluent so that the viscosity would be about 1.2 poise.
("EYELA DC STIRRRER DCL-R
T ”manufactured by Tokyo Rika Kikai Co., Ltd. was dispersed at 500 rpm for about 3 minutes. The resin composition coating material thus obtained was coated on a 120 mm × 120 mm × 0.5 mm vinyl chloride plate using a bar coater. This at room temperature, 1
After drying for more than a day, the phenol resin was heat-cured at 60 ° C. for 3 hours or more. After visual observation, the film thickness was measured and used for volume resistivity measurement. In addition, when measuring the film thickness, a "digital liner gauge DG-751" (manufactured by Ono Sokki Co., Ltd.) was used to measure the central portion and four corners 3 cm away from the central portion, and the average value thereof was used. I was there. The blending ratio here is the ratio of the weight of the graphite fine powder divided by the weight of the solid content of the coating material and the weight of the added graphite fine powder. (Wt%)
【００３７】〈体積抵抗率の測定〉実施例１と同様。 〈鉛筆引っかき試験〉ＪＩＳ−Ｋ−５４００準拠。<Measurement of Volume Resistivity> The same as in Example 1. <Pencil scratch test> According to JIS-K-5400.
【００３８】実施例５ 実施例３の微粉砕方法で得られた膨張化黒鉛微粒子を用
いて、（平均粒子径１６．３μｍ、嵩密度０．０８ｇ／
ｃｃ）これを第１表に示した配合量に基き実施例４同様
に塗料としての樹脂組成物の製造、体積抵抗率の測定、
及び鉛筆引っかき試験を行った。Example 5 Using the expanded graphite fine particles obtained by the finely pulverizing method of Example 3, (average particle diameter 16.3 μm, bulk density 0.08 g /
cc) Based on the compounding amounts shown in Table 1, production of a resin composition as a coating material and measurement of volume resistivity in the same manner as in Example 4,
And a pencil scratch test was performed.
【００３９】実施例６ 実施例３の微粉砕方法で得られた膨張化黒鉛微粒子を用
いて、（平均粒子径１６．３μｍ、嵩密度０．０８ｇ／
ｃｃ）これを第１表に示した配合量に基き実施例４同様
に塗料としての樹脂組成物の製造、体積抵抗率の測定、
及び鉛筆引っかき試験を行った。Example 6 Using the expanded graphite fine particles obtained by the finely pulverizing method of Example 3, (average particle diameter 16.3 μm, bulk density 0.08 g /
cc) Based on the compounding amounts shown in Table 1, production of a resin composition as a coating material and measurement of volume resistivity in the same manner as in Example 4,
And a pencil scratch test was performed.
【００４０】実施例７ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、旋回流型ジェットミル「ＣＰＮ−０４型」（セイシ
ン企業（株）製）にてフィード量８０ｇ／ｈ、空気圧
７．５ｋｇ／ｃｍ2 で粉砕を行った。得られた膨張化黒
鉛微粒子は、平均粒子径２．２μｍ、嵩密度０．１０ｇ
／ｃｃであった。これを第１表に示した配合量に基き実
施例４同様に塗料としての樹脂組成物の製造、体積抵抗
率の測定、及び鉛筆引っかき試験を行った。Example 7 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a swirling flow type jet mill "CPN-04 type" (manufactured by Seishin Enterprise Co., Ltd.) was used to feed 80 g / Milling was carried out at h and an air pressure of 7.5 kg / cm 2 . The expanded graphite fine particles obtained had an average particle diameter of 2.2 μm and a bulk density of 0.10 g.
Was / cc. Based on the blending amounts shown in Table 1, a resin composition as a coating material was prepared, a volume resistivity was measured, and a pencil scratching test was performed in the same manner as in Example 4.
【００４１】実施例８ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、旋回流型ジェットミル「ＣＰＮ−０４型」（セイシ
ン企業（株）製）にてフィード量３６０ｇ／ｈ、空気圧
７．５ｋｇ／ｃｍ2 で粉砕を行った。得られた膨張化黒
鉛微粒子は、平均粒子径４．１μｍ、嵩密度０．０９ｇ
／ｃｃであった。これを第１表に示した配合量に基き実
施例４同様に塗料としての樹脂組成物の製造、体積抵抗
率の測定、及び鉛筆引っかき試験を行った。Example 8 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a swirling flow type jet mill "CPN-04 type" (manufactured by Seishin Enterprise Co., Ltd.) was used to feed at 360 g / Milling was carried out at h and an air pressure of 7.5 kg / cm 2 . The obtained expanded graphite fine particles have an average particle diameter of 4.1 μm and a bulk density of 0.09 g.
Was / cc. Based on the blending amounts shown in Table 1, a resin composition as a coating material was prepared, a volume resistivity was measured, and a pencil scratching test was performed in the same manner as in Example 4.
【００４２】比較例１ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、流動層式カウンタージェットミル「アルピネジェッ
トミル２００ＡＦＧ」（（株）イトマンエンジニアリン
グ製）にてフィード量６ｋｇ／ｈで、粉砕を行った。得
られた膨張化黒鉛微粒子は、平均粒子径３５．２μｍ、
嵩密度０．１０ｇ／ｃｃであった。これを第１表に示し
た配合量に基き実施例４同様に塗料としての樹脂組成物
の製造、体積抵抗率の測定、及び鉛筆引っかき試験を行
った。Comparative Example 1 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a fluidized bed type counter jet mill “Alpine Jet Mill 200AFG” (manufactured by Itoman Engineering Co., Ltd.) was used to feed Crushing was performed at 6 kg / h. The expanded graphite fine particles obtained had an average particle diameter of 35.2 μm,
The bulk density was 0.10 g / cc. Based on the blending amounts shown in Table 1, a resin composition as a coating material was prepared, a volume resistivity was measured, and a pencil scratching test was performed in the same manner as in Example 4.
【００４３】比較例２ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、高速回転衝撃式粉砕機「コスモマイザーII」
（（株）奈良機械製作所製）にて、フィード量４．７ｋ
ｇ／ｈ、回転数７０００ｒｐｍで、粉砕を行った。得ら
れた膨張化黒鉛微粒子は、平均粒子径８．６μｍ、嵩密
度０．１５ｇ／ｃｃであった。これを第１表に示した配
合量に基き実施例１同様に樹脂組成物の製造、体積抵抗
率の測定を行った。Comparative Example 2 Using the expanded graphite particles A obtained by the coarse crushing of Example 1, a high speed rotary impact crusher "Cosmomizer II" is used.
(Nara Machinery Co., Ltd.) feed amount 4.7k
Grinding was performed at g / h and a rotation speed of 7,000 rpm. The expanded graphite fine particles obtained had an average particle diameter of 8.6 μm and a bulk density of 0.15 g / cc. Based on the blending amounts shown in Table 1, the resin composition was produced and the volume resistivity was measured in the same manner as in Example 1.
【００４４】比較例３ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、高速回転衝撃式粉砕機「コスモマイザーII」
（（株）奈良機械製作所製）にて、フィード量４．７ｋ
ｇ／ｈ、回転数７０００ｒｐｍ、排気風量８Ｎｍ3 ／ｍ
ｉｎで、粉砕を行った。得られた膨張化黒鉛微粒子は、
平均粒子径８．６μｍ、嵩密度０．１５ｇ／ｃｃであっ
た。これを第１表に示した配合量に基き実施例４同様に
塗料としての樹脂組成物の製造、体積抵抗率の測定、及
び鉛筆引っかき試験を行った。Comparative Example 3 Using the expanded graphite particles A obtained by the coarse crushing of Example 1, a high-speed rotary impact crusher "Cosmomizer II" was used.
(Nara Machinery Co., Ltd.) feed amount 4.7k
g / h, rotation speed 7000 rpm, exhaust air volume 8 Nm 3 / m
Grinding was carried out in. The expanded graphite fine particles obtained are
The average particle size was 8.6 μm and the bulk density was 0.15 g / cc. Based on the blending amounts shown in Table 1, a resin composition as a coating material was prepared, a volume resistivity was measured, and a pencil scratching test was performed in the same manner as in Example 4.
【００４５】比較例４ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、高速回転衝撃式粉砕機「コスモマイザーII」
（（株）奈良機械製作所製）にて、フィード量４．７ｋ
ｇ／ｈ、回転数７０００ｒｐｍ、排気風量５Ｎｍ3 ／ｍ
ｉｎで、粉砕を行った。得られた膨張化黒鉛微粒子は、
平均粒子径４１．２μｍ、嵩密度０．４４ｇ／ｃｃであ
った。これを第１表に示した配合量に基き実施例４同様
に塗料としての樹脂組成物の製造、体積抵抗率の測定、
及び鉛筆引っかき試験を行った。Comparative Example 4 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a high-speed rotary impact pulverizer "Cosmomizer II" is used.
(Nara Machinery Co., Ltd.) feed amount 4.7k
g / h, rotation speed 7000 rpm, exhaust air volume 5 Nm 3 / m
Grinding was carried out in. The expanded graphite fine particles obtained are
The average particle diameter was 41.2 μm and the bulk density was 0.44 g / cc. Based on the compounding amounts shown in Table 1, the resin composition as a coating material was produced in the same manner as in Example 4, the volume resistivity was measured,
And a pencil scratch test was performed.
【００４６】比較例５ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、高速回転衝撃式粉砕機「コスモマイザーII」
（（株）奈良機械製作所製）にて、フィード量６．５ｋ
ｇ／ｈ、回転数５０００ｒｐｍ、排気風量３Ｎｍ3 ／ｍ
ｉｎで、粉砕を行った。得られた膨張化黒鉛微粒子は、
平均粒子径４１．２μｍ、嵩密度０．４４ｇ／ｃｃであ
った。これを第１表に示した配合量に基き実施例４同様
に塗料としての樹脂組成物の製造、体積抵抗率の測定、
及び鉛筆引っかき試験を行った。Comparative Example 5 Using the expanded graphite particles A obtained by the coarse crushing of Example 1, a high-speed rotary impact crusher "Cosmomizer II" was used.
(Nara Machinery Co., Ltd.) feed amount 6.5k
g / h, rotation speed 5000 rpm, exhaust air volume 3 Nm 3 / m
Grinding was carried out in. The expanded graphite fine particles obtained are
The average particle diameter was 41.2 μm and the bulk density was 0.44 g / cc. Based on the compounding amounts shown in Table 1, the resin composition as a coating material was produced in the same manner as in Example 4, the volume resistivity was measured,
And a pencil scratch test was performed.
【００４７】比較例６ 本発明の黒鉛粉末の代わりに、これを製造する際に使用
した膨張度１９０ｃｃ／ｇの膨張化黒鉛粉末を、媒体水
を用いて家庭用ジューサーにて３０秒間湿式粉砕をおこ
なった。得られた膨張化黒鉛粉末は、粒子径２００μ
ｍ、嵩密度０．０５ｇ／ｃｃであった。これを第１表に
示した配合量に基き実施例１同様に樹脂組成物の製造、
体積抵抗率の測定を行った。なお、樹脂に配合する際
に、嵩高さと滑りによる作業性不良のために、約３分を
要した。Comparative Example 6 Instead of the graphite powder of the present invention, the expanded graphite powder having an expansion degree of 190 cc / g used in the production of the graphite powder was wet pulverized for 30 seconds with a household juicer using medium water. I did it. The expanded graphite powder obtained had a particle size of 200 μ.
m and bulk density were 0.05 g / cc. Based on the compounding amounts shown in Table 1, the resin composition was produced in the same manner as in Example 1,
The volume resistivity was measured. In addition, it took about 3 minutes due to the bulkiness and poor workability due to slippage when blending with the resin.
【００４８】比較例７ 実施例１の粗粉砕で得られた膨張化黒鉛粒子Ａを用い
て、流動層式カウンタージェットミル「アルピネジェッ
トミル２００ＡＦＧ」（（株）イトマンエンジニアリン
グ製）にてフィード量４ｋｇ／ｈで、粉砕を行った。得
られた膨張化黒鉛微粒子は、平均粒子径１６．３μｍ、
嵩密度０．０８ｇ／ｃｃであった。これを第１表に示し
た配合量に基き実施例１同様に樹脂組成物の製造、体積
抵抗率の測定を行った。Comparative Example 7 Using the expanded graphite particles A obtained by the coarse pulverization of Example 1, a fluidized bed type counter jet mill "Alpine Jet Mill 200AFG" (manufactured by Itoman Engineering Co., Ltd.) was used to feed. Grinding was performed at 4 kg / h. The obtained expanded graphite fine particles had an average particle diameter of 16.3 μm,
The bulk density was 0.08 g / cc. Based on the blending amounts shown in Table 1, the resin composition was produced and the volume resistivity was measured in the same manner as in Example 1.
【００４９】比較例８ 本発明の黒鉛粉末の代わりに、これを製造する際に使用
した原料である天然黒鉛粉末を使用し、旋回流型ジェッ
トミル「ＣＰＮ−０４型」（セイシン企業（株）製）に
て、フィード量２．５ｋｇ／ｈ、空気圧７．５ｋｇ／ｃ
ｍ2 で粉砕を行った。得られた天然黒鉛微粒子は平均粒
子径６．９μｍ、嵩密度０．１７ｇ／ｃｃであった。こ
れを第１表に示した配合量に基き実施例１同様に樹脂組
成物の製造、体積抵抗率の測定を行った。Comparative Example 8 Instead of the graphite powder of the present invention, a natural graphite powder which is a raw material used for producing the graphite powder was used, and a swirling flow type jet mill “CPN-04 type” (Seishin Enterprise Co., Ltd.) was used. Manufactured), feed rate 2.5 kg / h, air pressure 7.5 kg / c
Grinding was carried out at m 2 . The obtained natural graphite fine particles had an average particle diameter of 6.9 μm and a bulk density of 0.17 g / cc. Based on the blending amounts shown in Table 1, the resin composition was produced and the volume resistivity was measured in the same manner as in Example 1.
【００５０】比較例９ 本発明の黒鉛粉末の代わりに、これを製造する際に使用
した原料である天然黒鉛粉末を使用し、旋回流型ジェッ
トミル「ＣＰＮ−０４型」（セイシン企業（株）製）に
て、フィード量１．８ｋｇ／ｈ、空気圧７．５ｋｇ／ｃ
ｍ2 で粉砕を行った。得られた天然黒鉛微粒子は平均粒
子径４．３μｍ、嵩密度０．１７ｇ／ｃｃであった。こ
れを第１表に示した配合量に基き実施例４同様に塗料と
しての樹脂組成物の製造、体積抵抗率の測定、及び鉛筆
引っかき試験を行った。第１表に示されるように、比較
例では何れも高い体積抵抗率を示しているのに対し、本
発明の実施例では何れも良好な導電性を示している。更
に樹脂物性（塗膜硬度）においては、塗膜硬度の低下が
防止されている。Comparative Example 9 Instead of the graphite powder of the present invention, a natural graphite powder which is a raw material used for producing the graphite powder was used, and a swirling flow type jet mill “CPN-04 type” (Seishin Enterprise Co., Ltd.) was used. Manufactured), feed rate 1.8 kg / h, air pressure 7.5 kg / c
Grinding was carried out at m 2 . The obtained natural graphite fine particles had an average particle diameter of 4.3 μm and a bulk density of 0.17 g / cc. Based on the blending amounts shown in Table 1, a resin composition as a coating material was prepared, a volume resistivity was measured, and a pencil scratching test was performed in the same manner as in Example 4. As shown in Table 1, all of the comparative examples show high volume resistivity, while all of the examples of the present invention show good conductivity. Further, in the physical properties of the resin (coating hardness), the coating hardness is prevented from decreasing.
【００５１】[0051]
【表１】 [Table 1]
【００５２】[0052]
【表２】 [Table 2]
【００５３】[0053]
【表３】 [Table 3]
【００５４】[0054]
【表４】 [Table 4]
Claims (2)
る樹脂組成物であって、該黒鉛微粒子が、平均粒子径２
０μｍ以下かつ、嵩密度０．１２ｇ／ｃｃ以下の膨張化
黒鉛であることを特徴とする導電性樹脂組成物。1. A resin composition containing 5 to 50% by weight of graphite fine particles, wherein the graphite fine particles have an average particle diameter of 2
An electrically conductive resin composition, which is expanded graphite having a bulk density of 0.12 g / cc or less and 0 μm or less.
る樹脂組成物を製造する際に、該黒鉛微粒子として、酸
処理黒鉛を膨張させて得られる膨張化黒鉛をジェット粉
砕機により平均粒子径が２０μｍ以下、嵩密度が０．１
２ｇ／ｃｃ以下となるように粉砕して得られる膨張化黒
鉛を用いることを特徴とする導電性樹脂組成物の製造方
法。2. When producing a resin composition containing 5 to 50% by weight of graphite fine particles, expanded graphite obtained by expanding acid-treated graphite as the graphite fine particles is averaged by a jet pulverizer. Diameter is 20 μm or less, bulk density is 0.1
A method for producing a conductive resin composition, which comprises using expanded graphite obtained by pulverizing so as to be 2 g / cc or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4210288A JPH06100727A (en) | 1992-08-06 | 1992-08-06 | Electrically conductive resin composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4210288A JPH06100727A (en) | 1992-08-06 | 1992-08-06 | Electrically conductive resin composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06100727A true JPH06100727A (en) | 1994-04-12 |
Family
ID=16586921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4210288A Pending JPH06100727A (en) | 1992-08-06 | 1992-08-06 | Electrically conductive resin composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06100727A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761743A1 (en) * | 1995-08-31 | 1997-03-12 | Alusuisse Technology & Management AG | Ultrafine thermoplasts |
| WO2001038220A1 (en) * | 1999-11-26 | 2001-05-31 | Timcal Ag | Method for producing graphite powder with an increased bulk density |
| JP2006152170A (en) * | 2004-11-30 | 2006-06-15 | Nichias Corp | Conductive epoxy resin composition and preparation process of the same |
| JP2010514599A (en) * | 2007-01-04 | 2010-05-06 | 日本パーカライジング株式会社 | Conductive organic coating with thin film and good moldability |
| JP2013018825A (en) * | 2011-07-08 | 2013-01-31 | Sekisui Chem Co Ltd | Flame-retardant resin composition, flame-retardant resin sheet, and flame-retardant multilayer sheet |
| CN102982877A (en) * | 2012-12-24 | 2013-03-20 | 揭阳市广福电子实业有限公司 | Audio and video signal transmission conduction wire |
| JP2013535402A (en) * | 2010-08-11 | 2013-09-12 | ティムカル ソシエテ アノニム | Grinding expanded graphite agglomerate, method for producing the same, and use thereof |
| WO2013172334A1 (en) | 2012-05-15 | 2013-11-21 | 日本ゼオン株式会社 | Conductive composition |
| JP2019011436A (en) * | 2017-06-30 | 2019-01-24 | 東洋インキＳｃホールディングス株式会社 | Conductive composition and method for producing conductor film |
-
1992
- 1992-08-06 JP JP4210288A patent/JPH06100727A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0761743A1 (en) * | 1995-08-31 | 1997-03-12 | Alusuisse Technology & Management AG | Ultrafine thermoplasts |
| WO2001038220A1 (en) * | 1999-11-26 | 2001-05-31 | Timcal Ag | Method for producing graphite powder with an increased bulk density |
| JP2003514753A (en) * | 1999-11-26 | 2003-04-22 | ティムカル アーゲー | Method for producing graphite powder with increased bulk density |
| KR100769531B1 (en) * | 1999-11-26 | 2007-10-23 | 팀칼 아게 | Method for producing graphite powder with an increased bulk density |
| JP2016175839A (en) * | 1999-11-26 | 2016-10-06 | イメリス グラファイト アンド カーボン スイッツァランド エスアー | Method for producing graphite powder with increased bulk density |
| JP2006152170A (en) * | 2004-11-30 | 2006-06-15 | Nichias Corp | Conductive epoxy resin composition and preparation process of the same |
| JP2010514599A (en) * | 2007-01-04 | 2010-05-06 | 日本パーカライジング株式会社 | Conductive organic coating with thin film and good moldability |
| US9187612B2 (en) | 2010-08-11 | 2015-11-17 | Imerys Graphite & Carbon Switzerland Sa | Ground expanded graphite agglomerates, methods of making, and applications of the same |
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| JP2013535402A (en) * | 2010-08-11 | 2013-09-12 | ティムカル ソシエテ アノニム | Grinding expanded graphite agglomerate, method for producing the same, and use thereof |
| JP2013018825A (en) * | 2011-07-08 | 2013-01-31 | Sekisui Chem Co Ltd | Flame-retardant resin composition, flame-retardant resin sheet, and flame-retardant multilayer sheet |
| WO2013172334A1 (en) | 2012-05-15 | 2013-11-21 | 日本ゼオン株式会社 | Conductive composition |
| US10283231B2 (en) | 2012-05-15 | 2019-05-07 | Zeon Corporation | Conductive composition |
| CN102982877A (en) * | 2012-12-24 | 2013-03-20 | 揭阳市广福电子实业有限公司 | Audio and video signal transmission conduction wire |
| JP2019011436A (en) * | 2017-06-30 | 2019-01-24 | 東洋インキＳｃホールディングス株式会社 | Conductive composition and method for producing conductor film |
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