【考案の詳細な説明】[Detailed explanation of the idea]
〈産業上の利用分野〉
本考案は適度な剛性と可撓性を有する複合シー
ト材に関する。
〈従来の技術〉
膨張黒鉛を圧縮成型した可撓性黒鉛シート材料
の製造法が特公昭44−23966号として知られてい
る。
この可撓性黒鉛シート材料は膨張黒鉛を結合剤
の不存在下で加圧成型して得られるものである。
その特徴は可撓性を有し、不浸透性であり、圧
縮に対する復元率がよいというものである。
しかしながらこの可撓性黒鉛シート材料は、剛
性が小さく脆いため、変形破損し易く、取扱いが
困難であるという欠点があつた。また、膨張黒鉛
に結合剤を添加した黒鉛シート材料でも剛性の向
上は望めなかつた。（特開昭49−115905号公報）
そこで穿孔、爪立加工した金属薄板を可撓性黒
鉛シートの間に内挿圧延したメタルインサートシ
ートが考えられた。
しかしながら、このシート材料は逆に可撓性に
劣る欠点があつた。
さらに、特公昭46−14803号公報では黒鉛成形
体中に銅系金網を埋め込む方法が開示されている
が、この黒鉛成形体は高荷重制動用炭素成形体用
であつて、これに用いられる銅系金網は黒鉛成形
体の摺動面に主として用いられ、目開きも大き
く、得られる黒鉛成形体は可撓性不浸透性に問題
点がある。
〈本考案が解決しようとする問題点〉
本考案の目的は、可撓性、不浸透性、耐食性等
にすぐれた複合シート材を提供するものである。
さらに本考案の目的は、圧縮復元性にすぐれ、
変形、破損が少なく取扱いが容易で、各種の形状
に容易に成形し得る複合シート材を提供するもの
である。
〈問題を解決するための手段〉
線径0.01〜0.5mm、目開き0.02〜１mmの金網を膨
張黒鉛又は結合剤を含む膨張黒鉛にインサート
し、ついで加圧成形してなる複合シート材は可撓
性、不浸透性、耐熱性、耐食性等を損うことなく
剛性が大きく、かつ圧縮復元性にすぐれ変形、破
損が少なく、取扱いが容易で、各種の形状に容易
に成形できるとの知見を得て本考案を完成した。
〈作用〉
本考案において使用される膨張黒鉛とは天然黒
鉛、熱分解黒鉛、キツシユ黒鉛等の黒鉛粉を濃硫
酸、濃硝酸、硝酸ナトリウム、過マンガン酸カリ
ウムまたは硫酸と硝酸の酸化剤の混合物等、臭
素、ハロゲン化物により層間化合物を形成させて
得た黒鉛粒子を急激に高温（例えば1200℃）で熱
処理することにより、黒鉛粒子内にガス圧を発生
させ、それによつて黒鉛の層間を拡張させて得ら
れるものである。
この場合、層平面に直角の方向をＣ方向とする
と、本願で使用される膨張黒鉛は、Ｃ方向寸法が
原粒子のそれの10倍以上のものである。膨張率が
10倍未満であると自己接着性や機械的強度等に難
があり好ましくない。
結合剤は、機械的強度、耐食性等の向上のため
に用いられるが、耐熱性、耐食性にすぐれた無機
質結合剤や合成樹脂が好ましい。例えば無機質結
合剤としては酸化黒鉛（添加量３〜50wt％）、ホ
ウ酸（添加量３〜15wt％）、リン酸アルミニウム
（添加量0.1〜30％）等が好ましく、又合成樹脂と
してはフツ素樹脂（添加量１〜50wt％）が好ま
しい。
金網の材料としては、鉄、銅、黄銅、洋白、ア
ルミニウム、ニツケル、リン青銅、ステンレス鋼
等の金属が用いられる。
金網の線径や目開きを適宜選定することにより
適度の剛性と可撓性を有する複合シート材を得る
ことが出来るが、例えば線径は0.01〜0.5mm、目
の開きは0.02〜１mm程度であれば良好な結果が得
られる。金網の種類は平織、あや織、畳織、すだ
れ織や金属線を単に格子状に配列し結合したもの
やひし形状のもの等が用いられる。
金網は膨張黒鉛又は結合剤を含む膨張黒鉛にイ
ンサートし、ついで加圧成形して第１図および第
２図の断面図に示すような複合シート材が得られ
る。
図において１，１１は膨張黒鉛又は、結合剤を
含む膨張黒鉛、２，１２は金網を示す。
膨張黒鉛又は結合剤を含む膨張黒鉛は自己接着
性を有するため、そのまま或いはシート状に成形
したものに金網をインサートして圧縮成型或いは
ロール成型等により常温又は加熱法にて複合シー
ト材が製造される。しかし特に必要があればエポ
キシ樹脂、フエノール樹脂等の接着剤を金網に塗
布したものを用いてもよい。
金網と膨張黒鉛又は結合剤を含む膨張黒鉛との
容積比は１：99〜50：50であれば剛性向上に効果
があり、可撓性が失われることもない。
以下に本考案の実施例について述べる。
実施例 １−１〜１−５
天然黒鉛粉末（24メツシユ下〜48メツシユ上の
粒度80％含有）100重量部を濃硫酸840重量部と硝
酸ナトリウム50重量部を混合した液中で16時間反
応させた。この酸処理した天然黒鉛粒子を十分に
水洗いした後、約100℃で乾燥させた。乾燥後こ
の粒子を1300℃で10秒間急速に加熱して黒鉛粒子
のＣ方向に、原寸法の約300倍に膨張した膨張黒
鉛粒子を得た。
次に、下記に示す仕様の金網を５種類用意し、
各々を膨張黒鉛に介挿しロール成形し、第１図に
示すごとき形状に膨張黒鉛を被覆した本考案の複
合シート材料を得た。これらの特性を第１表に示
す。
金網の仕様
線径（mm） 目開き（mm）
(1)ステンレス網 0.30 0.84
(2) 〃 0.18 0.42
(3) 〃 0.11 0.25
(4) 〃 0.11 0.18
(5) 銅 0.11 0.18
実施例 ２
実施例１の方法により得られた膨張黒鉛に結合
剤として酸化黒鉛を15wt％添加した。以下実施
例１に準じて金網のそれぞれを前記膨張黒鉛と結
合剤との混合組成物に介挿し、ついでロール成形
し、第１図に示すごとき形状の本考案の複合シー
ト材料を得た。それぞれの特性を求め、第１表に
示す。
比較例
実施例１の方法で得られた膨張黒鉛をロール成
形し、厚みが0.3mmの複合材料を得た。その特性
を第１表に示す。
<Industrial Application Field> The present invention relates to a composite sheet material having appropriate rigidity and flexibility. <Prior Art> A method for producing a flexible graphite sheet material by compression molding expanded graphite is known as Japanese Patent Publication No. 44-23966. This flexible graphite sheet material is obtained by pressure molding expanded graphite in the absence of a binder. Its characteristics are that it is flexible, impermeable, and has a good recovery rate against compression. However, this flexible graphite sheet material has low rigidity and is brittle, so it is easily deformed and damaged and has the drawback of being difficult to handle. Furthermore, even graphite sheet materials made by adding a binder to expanded graphite could not be expected to improve rigidity. (Japanese Unexamined Patent Publication No. 115905/1982) Therefore, a metal insert sheet was devised in which a perforated and pronged metal thin plate was inserted and rolled between flexible graphite sheets. However, this sheet material had the disadvantage of poor flexibility. Furthermore, Japanese Patent Publication No. 46-14803 discloses a method of embedding a copper-based wire mesh in a graphite molded body, but this graphite molded body is intended for a carbon molded body for high-load braking, and the copper wire used in this The wire mesh is mainly used for the sliding surface of graphite molded bodies, and the openings are large, and the obtained graphite molded bodies have problems in flexibility and impermeability. <Problems to be Solved by the Present Invention> The purpose of the present invention is to provide a composite sheet material having excellent flexibility, impermeability, corrosion resistance, etc. Furthermore, the purpose of this invention is to have excellent compression and decompression properties,
The object of the present invention is to provide a composite sheet material that is easy to handle with little deformation or damage, and can be easily formed into various shapes. <Means for solving the problem> A composite sheet material made by inserting a wire mesh with a wire diameter of 0.01 to 0.5 mm and an opening of 0.02 to 1 mm into expanded graphite or expanded graphite containing a binder, and then pressure forming it is flexible. It has been found that it has high rigidity without compromising its properties, impermeability, heat resistance, corrosion resistance, etc., has excellent compression recovery properties, has little deformation or breakage, is easy to handle, and can be easily molded into various shapes. The present invention was completed. <Operation> What is the expanded graphite used in this invention? Graphite powder such as natural graphite, pyrolytic graphite, and Kitshu graphite is mixed with concentrated sulfuric acid, concentrated nitric acid, sodium nitrate, potassium permanganate, or a mixture of oxidizing agents of sulfuric acid and nitric acid. By rapidly heat-treating graphite particles obtained by forming intercalation compounds with bromine and halides at high temperatures (for example, 1200°C), gas pressure is generated within the graphite particles, thereby expanding the interlayers of graphite. This can be obtained by In this case, assuming that the direction perpendicular to the layer plane is the C direction, the expanded graphite used in the present application has a dimension in the C direction that is 10 times or more that of the original particles. The expansion rate
If it is less than 10 times, self-adhesiveness and mechanical strength will be poor, which is not preferable. The binder is used to improve mechanical strength, corrosion resistance, etc., and preferably an inorganic binder or synthetic resin has excellent heat resistance and corrosion resistance. For example, as the inorganic binder, graphite oxide (addition amount 3 to 50 wt%), boric acid (addition amount 3 to 15 wt%), aluminum phosphate (addition amount 0.1 to 30%), etc. are preferable, and as the synthetic resin, fluorine Resin (addition amount 1 to 50 wt%) is preferred. As the material for the wire mesh, metals such as iron, copper, brass, nickel silver, aluminum, nickel, phosphor bronze, and stainless steel are used. A composite sheet material with appropriate rigidity and flexibility can be obtained by appropriately selecting the wire diameter and opening of the wire mesh. Good results can be obtained. Types of wire mesh used include plain weave, twill weave, tatami weave, blind weave, wire mesh simply arranged in a lattice pattern and joined together, and diamond-shaped wire mesh. The wire mesh is inserted into expanded graphite or expanded graphite containing a binder, and then pressure molded to obtain a composite sheet material as shown in the cross-sectional views of FIGS. 1 and 2. In the figure, 1 and 11 are expanded graphite or expanded graphite containing a binder, and 2 and 12 are wire meshes. Expanded graphite or expanded graphite containing a binder has self-adhesive properties, so composite sheet materials can be manufactured by inserting wire mesh into the sheet as it is or by compression molding or roll molding at room temperature or by heating. Ru. However, if particularly necessary, a wire mesh coated with an adhesive such as epoxy resin or phenol resin may be used. If the volume ratio of wire mesh to expanded graphite or expanded graphite containing a binder is 1:99 to 50:50, it is effective in improving rigidity and flexibility is not lost. Examples of the present invention will be described below. Examples 1-1 to 1-5 100 parts by weight of natural graphite powder (containing 80% particle size below 24 meshes to above 48 meshes) was reacted for 16 hours in a mixture of 840 parts by weight of concentrated sulfuric acid and 50 parts by weight of sodium nitrate. I let it happen. After thoroughly washing the acid-treated natural graphite particles with water, they were dried at about 100°C. After drying, the particles were rapidly heated at 1300° C. for 10 seconds to obtain expanded graphite particles that expanded to about 300 times their original size in the C direction of the graphite particles. Next, prepare five types of wire mesh with the specifications shown below.
Each was inserted into expanded graphite and roll-formed to obtain a composite sheet material of the present invention coated with expanded graphite in the shape shown in FIG. These properties are shown in Table 1. Wire mesh specifications Wire diameter (mm) Opening (mm) (1) Stainless steel mesh 0.30 0.84 (2) 〃 0.18 0.42 (3) 〃 0.11 0.25 (4) 〃 0.11 0.18 (5) Copper 0.11 0.18 Example 2 Example 1 15 wt% of graphite oxide was added as a binder to the expanded graphite obtained by the method described above. Thereafter, each of the wire meshes was inserted into the mixed composition of expanded graphite and a binder according to Example 1, and then roll-formed to obtain a composite sheet material of the present invention having the shape shown in FIG. The characteristics of each were determined and shown in Table 1. Comparative Example Expanded graphite obtained by the method of Example 1 was roll-molded to obtain a composite material with a thickness of 0.3 mm. Its characteristics are shown in Table 1.
【表】
〈効果〉
本考案の複合シート材は金網を強化材料として
使用されているため、膨張黒鉛シートの可撓性、
不浸透性、耐熱性、耐食性等を損なうことなく剛
性を大巾に向上できる。
また、圧縮復元性にすぐれ、変形、破損が少な
く、取扱いが容易で、各種の形状に容易に成形で
きる特長を有する。[Table] <Effects> Since the composite sheet material of the present invention uses wire mesh as a reinforcing material, the flexibility of the expanded graphite sheet,
Rigidity can be greatly improved without impairing impermeability, heat resistance, corrosion resistance, etc. In addition, it has excellent compression recovery properties, less deformation and damage, is easy to handle, and can be easily molded into various shapes.
【図面の簡単な説明】[Brief explanation of drawings]
第１図は金網が介挿された状態の本考案品の断
面図、第２図は金属線を単に格子状に配列し接合
した金網を介挿された状態の本考案品の断面図を
示す。
１，１１……膨張黒鉛又は結合剤を含む膨張黒
鉛、２，１２……金網。
Figure 1 is a cross-sectional view of the product of the present invention with a wire mesh inserted, and Figure 2 is a cross-sectional view of the product of the present invention with a wire mesh made by simply arranging and bonding metal wires in a lattice pattern. . 1, 11... Expanded graphite or expanded graphite containing a binder, 2, 12... Wire mesh.