JPS6058688B2 - clay mineral sheet material - Google Patents
clay mineral sheet materialInfo
- Publication number
- JPS6058688B2 JPS6058688B2 JP55018644A JP1864480A JPS6058688B2 JP S6058688 B2 JPS6058688 B2 JP S6058688B2 JP 55018644 A JP55018644 A JP 55018644A JP 1864480 A JP1864480 A JP 1864480A JP S6058688 B2 JPS6058688 B2 JP S6058688B2
- Authority
- JP
- Japan
- Prior art keywords
- vermiculite
- sheet material
- flakes
- clay mineral
- thickness
- 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.)
- Expired
Links
Landscapes
- Gasket Seals (AREA)
- Laminated Bodies (AREA)
- Sealing Material Composition (AREA)
Description
【発明の詳細な説明】 本発明は、粘土鉱物シート材に関するものである。[Detailed description of the invention] The present invention relates to clay mineral sheet materials.
従来、粘土鉱物シートとしては、雲母やモンモリロナ
イト等の層状粘土鉱物を主原料とするものが知られてい
る。BACKGROUND ART Conventionally, clay mineral sheets whose main raw materials are layered clay minerals such as mica and montmorillonite are known.
しかし、これらは、シート材としての柔軟性を得るには
、非常に薄いシートしか得られない。また、耐熱性シー
トとしては、他にカオウールやセピオライト等の繊維状
物質を主原料とするものが知られている。しかし、これ
らは厚さ方向に対する弾性率が小さい。また、繊維状原
料は、高価なものや、入手困難な物質であることが多い
。 本発明はひる石を主原料とする新規な無機質耐熱シ
ート材、すなわち、ひる石を粉砕して得られ る薄片を
主要成分とし、該薄片が積層されて相互に結合され、シ
ート状に形成された構造をもつことを特徴とする粘土鉱
物シート材を提供するものである。However, with these materials, only a very thin sheet can be obtained to obtain flexibility as a sheet material. In addition, other heat-resistant sheets are known that use fibrous substances such as Kao wool and sepiolite as main raw materials. However, these have a small elastic modulus in the thickness direction. Furthermore, fibrous raw materials are often expensive or difficult to obtain materials. The present invention is a novel inorganic heat-resistant sheet material that uses vermiculite as the main raw material, that is, the main component is flakes obtained by crushing vermiculite, and the flakes are laminated and bonded to each other to form a sheet. The present invention provides a clay mineral sheet material that is characterized by having a structure.
本発明のシート材はシート材としての柔軟性を有する
と同時に、製造が容易、原料が廉価、厚さ方向の弾性係
数が高い、電気抵抗が高い、耐油・耐薬品性を有する、
耐熱性、耐酸化性を有する、人体に対して無害である等
の優れた性質を兼ね備えている。The sheet material of the present invention has flexibility as a sheet material, is easy to manufacture, uses inexpensive raw materials, has a high elastic modulus in the thickness direction, has high electrical resistance, and has oil and chemical resistance.
It has excellent properties such as heat resistance, oxidation resistance, and is harmless to the human body.
またひる石の成分組成によつては金属光沢を有し、赤外
線に対する反射率が高いといつた性質も兼備する。 こ
こでひる石は珪酸アルミニウム層を基本とする層状鉱物
であり、四面***置に存在する珪素原子が無秩序にアル
ミニウム等で置換され、その代表的化学式は(E0.6
〜0.9)(M&)〔Si、Al)。Depending on the composition of vermiculite, it also has metallic luster and high reflectance to infrared rays. Here, vermiculite is a layered mineral based on an aluminum silicate layer, and silicon atoms existing in tetrahedral positions are randomly substituted with aluminum etc., and its typical chemical formula is (E0.6
~0.9) (M&) [Si, Al).
O、O(OH)2・ml。O(ここでEは交換性陽イオ
ン)であられされる。一方、同じ層状鉱物である雲母は
(に)・(MgO)〔Si。Al)。O、O(OH)O
で表わされ、Jモンモリロナイトは(Eo・3 ・3)
・ 〔A15/。・ Mg、/。〕 ・ 〔51、〕O
、O(OH)2・ml。oで表わされる。ひる石は、化
学成分において、特に、Al2O3/5102比におい
て、および層間イオンの組成において、雲母やモンモリ
ロナイトとは区別さ7れ、その他X線回折におけるピー
ク位置やピーク幅、四面***置の他のイオンによる置換
の様子、層間水の状態、陽イオン交換容量、有機物に対
する膨潤性等の点で雲母やモンモリロナイトと異つてい
る。ひる石を1000℃程度で焼成するとアコーディオ
ン状に膨張することが知られており、この膨張ひる石は
園芸用の土質改良材や軽量コンクリート用骨材等に利用
されている。O, O(OH)2·ml. O (where E is an exchangeable cation). On the other hand, mica, which is also a layered mineral, is (ni)・(MgO) [Si. Al). O, O(OH)O
It is expressed as J-montmorillonite (Eo・3・3)
・ [A15/.・Mg, /. ] ・ [51,] O
, O(OH)2·ml. It is represented by o. Vermiculite is distinguished from mica and montmorillonite in its chemical composition, particularly in the Al2O3/5102 ratio and in the composition of interlayer ions, and also has other differences in peak position, peak width, and tetrahedral position in X-ray diffraction. It differs from mica and montmorillonite in terms of the manner of substitution by ions, the state of interlayer water, cation exchange capacity, and swelling ability with respect to organic substances. It is known that when vermiculite is fired at about 1000°C, it expands into an accordion shape, and this expanded vermiculite is used as a soil conditioner for gardening, aggregate for lightweight concrete, and the like.
本発明のシート材の主要成分となるひる石を原料とする
薄片はこの膨張ひる石を粉砕することにより容易に得ら
れる。この薄片は珪酸アルミニウムを主成分とする板状
体であり、ひる石の層間に含まれている水が飛散し、ひ
る石の基体となる珪酸アルミニウム層が分離したもので
ある。ここで薄片は、珪酸アルミニウム層が一層から数
千層重なつたもので、厚さは100μ以下であり、表面
積の平方根の値の厚さに対する比(アスペクト比)が5
以上のものである。The flakes made from vermiculite, which is the main component of the sheet material of the present invention, can be easily obtained by crushing the expanded vermiculite. This flake is a plate-like body whose main component is aluminum silicate, and the water contained between the layers of vermiculite is scattered, and the aluminum silicate layer, which is the base of vermiculite, is separated. Here, the flakes are composed of one to several thousand aluminum silicate layers, the thickness is 100μ or less, and the ratio of the square root of the surface area to the thickness (aspect ratio) is 5.
That's all.
個々の薄片は、厚さが小さいためそれ自身ある程度の柔
軟性を有する。また、比較的大きいアスペクト比のため
、自然沈降、淵過、圧縮成型、あるいは抄造法により、
珪酸アルミニウム層のC軸が一定方向を向く性質を有す
る。この薄片は厚さに対して表面積が大きい、いわゆる
アクペクト比が大きいことに大きな特徴があり、本発明
のシート材は主としてこの大きなアクペクト比を利用し
たものである。薄片の形状、アクペクト比は粉砕方法、
時間により異り、アクペクト比は通常、ミキサー粉砕〉
摩砕〉ボールミル粉砕の順になる。粉砕は乾式でも湿式
でもよい。例えば、焼成ひる石を水中5〜3紛間ミキサ
ーで粉砕した結果、主として、厚jさが0.1〜10μ
、表面積が2500μ2〜1000000μ2程度のも
のが得られた。また焼成ひる石をボールミルを用いて1
0時間湿式粉砕した結果、厚さ0.5μ以下で一表面積
が1〜100μ2程度のものが得られた。
3本発明のシート材は上記
薄片を主要成分とするものである。シート材はこの薄片
のみで構成することも、また、他の添加物を配合して構
成することもできる。添加物としては強度向上を目的と
してウィスカあるいは鉱物繊維等の繊維材料、酸化4ス
ズ等の表面反射率を高めるための材料、結合材としての
有機無機のバインダー、その他の性質向上、付加をねら
つた種々の材料を添加することができる。かかる添加物
は薄片の表面に付着したり、薄片の間に介在する。より
具体的にはカオウールやセピオライト等の繊維状物質を
混合することにより、より柔軟なシートが、モンモリロ
ナイト等有機物に対し膨潤性を有する粘土鉱物を混合す
ることにより、油等の有機物や水に対して膨潤性を有す
るシートが、また、未焼成ひる石の微粉を混合すること
により、高温において再膨張するシートが得られる。ま
た、シート状ひる石をシラン処理することにより、ひる
石層間水あるいは吸着水により、シラン化合物の加水分
解によるシラノール化が進行し、粒子間の結合をより強
固にすると同時に、撥水性を有するシートが得られる。
本発明の粘土鉱物シート材は上記した薄片を積層し相互
に結合させてシート状に形成したもので7ある。薄片を
積層させる方法としては、水等の液体に分散させ自然沈
降あるいは強制的に枦過して、底面あるいはフィルター
状に薄片を積層させる方法、紙のように抄造する方法、
薄片と適当な液体でスラリーを作り平面状に塗布して積
層させ・る方法等の種々の方法がある。薄片どうしを互
いに結合させる方法としては、薄片の積層体が液体を含
有している場合には、その液体を蒸散させ、蒸散にとも
なう結合力を利用するもの、あるいは積層体の上下方向
をブレスして重圧を作用させ、それにより薄片どうしを
結合させることができる。また結合力を高めるために有
機無機の結合剤を使用することも可能である。かかる結
合剤としては熱可塑性の合成樹脂、熱硬化性合成樹脂、
アルギン酸ソーダ等の粘着剤、水ガラス等の無機結合剤
を使用することができる。水に分散した薄片をろ過し得
られた積層体をブレスして本発明のシート材を製造する
方法においては、薄片としてアスペクト比の大きいもの
を用いる場合に特に有効であり強度の大きいシート材が
得られる。The individual flakes have a certain degree of flexibility themselves due to their small thickness. In addition, due to its relatively large aspect ratio, natural sedimentation, perforation, compression molding, or papermaking methods can be used to
The aluminum silicate layer has a property that the C axis is oriented in a certain direction. A major feature of this thin piece is that it has a large surface area relative to its thickness, that is, a large aspect ratio, and the sheet material of the present invention mainly utilizes this large aspect ratio. The shape of the flakes, the aspect ratio, the grinding method,
Varies depending on time, aspect ratio is usually mixer grinding>
The order is grinding> ball mill grinding. Grinding may be done dry or wet. For example, as a result of crushing calcined vermiculite in an underwater 5-3 mill mixer, the thickness j is mainly 0.1-10μ.
, a surface area of approximately 2,500 μ2 to 1,000,000 μ2 was obtained. In addition, calcined vermiculite was milled using a ball mill.
As a result of wet milling for 0 hours, a product with a thickness of 0.5 μm or less and a surface area of about 1 to 100 μ2 was obtained.
3. The sheet material of the present invention has the above flakes as a main component. The sheet material may be composed only of this thin piece, or may be composed of other additives. Additives include whiskers or fibrous materials such as mineral fibers to improve strength, materials to increase surface reflectance such as tetratin oxide, organic and inorganic binders as binding materials, and other materials intended to improve or add properties. Various materials can be added. Such additives may adhere to the surface of the flakes or be present between the flakes. More specifically, by mixing fibrous substances such as Kao wool and sepiolite, a more flexible sheet can be obtained, and by mixing clay minerals that have swelling properties against organic substances such as montmorillonite, it is resistant to organic substances such as oil and water. In addition, by mixing fine powder of unburned vermiculite, a sheet that re-expands at high temperatures can be obtained. In addition, by silane treatment of sheet-like vermiculite, water between the layers of vermiculite or adsorbed water promotes silanolization through hydrolysis of the silane compound, which strengthens the bond between particles and at the same time provides a sheet with water repellency. is obtained.
The clay mineral sheet material of the present invention is formed into a sheet by laminating the above-mentioned flakes and bonding them to each other. Methods for laminating thin pieces include a method of dispersing them in a liquid such as water and allowing them to settle naturally or being forced to pass through, and then layering the thin pieces on the bottom or in the shape of a filter, a method of making paper like paper,
There are various methods such as making a slurry with thin pieces and a suitable liquid and applying it on a flat surface and layering it. Methods for bonding thin pieces to each other include, if the stack of flakes contains liquid, evaporating the liquid and utilizing the bonding force accompanying the evaporation, or pressing the stack in the vertical direction. Pressure can then be applied to bond the flakes together. It is also possible to use an organic or inorganic binder to increase the bonding strength. Such binders include thermoplastic synthetic resins, thermosetting synthetic resins,
Adhesives such as sodium alginate and inorganic binders such as water glass can be used. The method of producing the sheet material of the present invention by filtering the thin flakes dispersed in water and pressing the obtained laminate is particularly effective when using thin flakes with a large aspect ratio, and the sheet material has high strength. can get.
スラリーを塗布し乾燥してシートを製造する方法では薄
片の粒度が細いものに有効で、薄くて強度の大きいもの
が得られる。The method of manufacturing a sheet by applying a slurry and drying it is effective for producing thin flakes with a fine particle size, and can produce thin flakes with high strength.
しかし乾燥に時間がかかる。抄造方でシート材を製造す
る方法ではアスペクト比の大きいものに有効である。However, it takes time to dry. The method of manufacturing sheet materials by papermaking is effective for materials with large aspect ratios.
しかし強度の高いものは得られにくいため結合剤の使用
が必要とされる場合がある。実施例1
粒度(5)(日本工業規格JISA5OO9−1972
)の日本産金色焼成ひる石を原料とし、原料30fと水
道水1000ccの混合物を、鋼製て直径約5577!
77!の4枚の攪拌羽根を有するミキサーを用いて、毎
分約10000回転で10分間粉砕した。However, since it is difficult to obtain a material with high strength, it may be necessary to use a binder. Example 1 Particle size (5) (Japanese Industrial Standard JISA5OO9-1972
) made from Japanese golden calcined vermiculite, a mixture of 30 f raw materials and 1000 cc of tap water, and made of steel with a diameter of approximately 5,577 mm.
77! The mixture was pulverized for 10 minutes at about 10,000 revolutions per minute using a mixer with four stirring blades.
このようにして得られた粉末は厚さ0.1ミクロン〜数
十ミクロン、大きさ数十〜数百ミクロンの薄片であつた
(アクペクト比10〜5000)。この薄片の水中懸濁
液を、ブフナーロート(直径約16(7n)、吸引びん
(内容積約8e)、ろ紙(NO5A直径15C!RL)
を用い、水流ポンプにより吸引びん内を減圧にすること
により、強制的にろ過し、しかる後に55℃で1(転)
間乾燥することによりひる石板を得た。上記分量(ひる
石30ダ、水1000cc)では、ろ過は4〜5回に分
けて行ない、その結果、直径約13cff1、厚さ約0
.1〜0.57n:mのひる石板が4〜5枚得られた。
このひる石板を打ち抜きにより、内径60TSn1外径
7『のドーナツ状の板とし、この板を約1敗重ね、内径
6『,外径7『の管状成型体成型用の金型中に入れ、油
圧ブレス機により、1000k9/Cltの圧力で圧縮
することにより、内径60Tn!N,外径7『、厚さ約
2順〜5wnのドーナツ状ひる石成型体を得た。この成
型体の特性を第1表に示す。この成型体をオートクレー
ブ用ガスケットとして用いた。オートクレーブ温度23
0℃、水蒸気圧28気圧、241寺間使用し、室温まで
冷却した。この加熱(加圧)冷却を10回繰り返した後
もこのひる石板を用いたガスケットは何ら変化なく良い
気密性を保有してした。実施例2
粒度(5)、日本産金焼成ひる石を15yおよび未焼成
中国産ひる石15f1水道水1000ccを実施例1と
同じミキサーを用いて、10,000rpm×1紛間粉
砕した。The powder thus obtained was flakes with a thickness of 0.1 micron to several tens of microns and a size of several tens to hundreds of microns (aspect ratio 10 to 5000). A suspension of this flake in water was placed in a Buchner funnel (diameter approx. 16 (7n), suction bottle (inner volume approx. 8e), filter paper (NO5A diameter 15C!RL)
Using a water jet pump to reduce the pressure inside the suction bottle, filtration was forcibly performed, and then 1 (inversion) was carried out at 55°C.
By drying for a while, a vermiculite slab was obtained. With the above amount (30 da of vermiculite, 1000 cc of water), filtration was performed in 4 to 5 times, and as a result, the diameter was about 13 cff1 and the thickness was about 0.
.. Four to five vermiculite plates of 1 to 0.57 n:m were obtained.
This vermiculite plate is punched to form a donut-shaped plate with an inner diameter of 60TSn1 and an outer diameter of 7'', and the plates are stacked approximately once, placed in a mold for forming a tubular molded body with an inner diameter of 6'' and an outer diameter of 7'', and the By compressing with a pressure of 1000k9/Clt using a press machine, the inner diameter is 60Tn! A doughnut-shaped vermiculite molded body having an outer diameter of 7'' and a thickness of about 2 to 5 wn was obtained. The properties of this molded body are shown in Table 1. This molded body was used as a gasket for an autoclave. Autoclave temperature 23
The temperature was 0°C, the water vapor pressure was 28 atm, and the temperature was 241°C, and the temperature was cooled to room temperature. Even after this heating (pressure) cooling was repeated 10 times, the gasket using the vermiculite plate maintained good airtightness without any change. Example 2 Using the same mixer as in Example 1, 15y of Japanese gold calcined vermiculite and 15f of uncalcined Chinese vermiculite with particle size (5) and 1000 cc of tap water were pulverized at 10,000 rpm x 1 using the same mixer as in Example 1.
このようにして得られた、焼成および未焼成ひる石の混
合物薄片をブフナーロート(直径約16cm)、吸引び
ん(内容物8e)ろ紙(NO.5A,l5OTfOnφ
)を用いた水流ポンプにより吸引びん内を減圧すること
により強制的に数回に分けてろ過し、しかる後に、55
℃で1叫間乾燥することにより、直径約13cm1厚さ
0.2〜0.5wnのひる石板を得た。このひる石板か
ら事務ハサミにより10X50TfrInの大きさの板
を切り取り、この板を約10枚重ね、それを10×50
Tf0nの金型に入れ、油圧ブレスにより2000k9
/Cltの圧力で圧縮成型することにより10×50T
nIn,2WrIn〜5薗厚さの成型体を得た。この成
型体を900′Cに保持した電気炉中へ入れ、2分間保
持後、試料を取り出し、室温へ冷却した。この処理によ
り、上記成型体はアコーデオン状に膨張し、厚さはもと
の厚さの1.2〜2倍に変化した。このようにして得ら
れた試料(試料1とする)、およびこれをジクロルジメ
チルシラン中に約2分間浸漬して得られた試料(試料2
とする)の特性を第2表に示す。このようにして得られ
た成型体は、自動車用ガスケット材として必要と思われ
る・特性を具備している。7実施例3
粒度(5)、日本産金色焼成ひる石を25y1カオウー
ルを5y1水道水1000mLを実施例1と同じミキサ
ーを用いて、5000rpm×5分間粉砕した。The thus obtained mixed flakes of calcined and uncalcined vermiculite were placed in a Buchner funnel (approximately 16 cm in diameter), in a suction bottle (contents 8e), and on filter paper (NO. 5A, 15OTfOnφ).
) is used to reduce the pressure inside the suction bottle, and the filtration is forcibly divided into several times.
By drying at ℃ for one hour, a vermiculite plate with a diameter of about 13 cm and a thickness of 0.2 to 0.5 wn was obtained. Cut out a board with the size of 10x50TfrIn from this stone board with office scissors, stack about 10 of these boards, and then cut out a board with a size of 10x50TfrIn.
Put it in a Tf0n mold and use a hydraulic press to make it 2000k9.
10×50T by compression molding at a pressure of /Clt
A molded body having a thickness of nIn, 2WrIn to 5 mm was obtained. This molded body was placed in an electric furnace maintained at 900'C, and after being maintained for 2 minutes, the sample was taken out and cooled to room temperature. As a result of this treatment, the molded body expanded into an accordion shape, and its thickness changed to 1.2 to 2 times its original thickness. The sample thus obtained (referred to as sample 1), and the sample obtained by immersing this in dichlorodimethylsilane for about 2 minutes (sample 2).
Table 2 shows the characteristics of The molded product thus obtained has properties considered necessary as an automobile gasket material. 7 Example 3 Particle size (5): 25y1 of Japanese golden calcined vermiculite, 5y1 of Kao wool, and 1000 mL of tap water were ground using the same mixer as in Example 1 at 5000 rpm for 5 minutes.
Claims (1)
薄片が積層されて相互に結合され、シート状に形成され
た構造をもつことを特徴とする粘土鉱物シート材。 2 薄片は、平均的な厚さが0.1μ〜100μであり
、平均的な一平面の面積が2500μ^2以上である特
許請求の範囲第1項記載の粘土鉱物シート材。 3 粘土鉱物シートの厚さは0.01mm〜10mm、
密度は1.0g/cm^3〜2.5/cm^3である特
許請求の範囲第1項記載の粘土鉱物シート材。[Claims] 1. A clay mineral sheet material, characterized in that the main component is flakes obtained by crushing vermiculite, and the flakes are laminated and bonded to each other to form a sheet-like structure. . 2. The clay mineral sheet material according to claim 1, wherein the flakes have an average thickness of 0.1 μm to 100 μm and an average plane area of 2500 μ^2 or more. 3 The thickness of the clay mineral sheet is 0.01 mm to 10 mm,
The clay mineral sheet material according to claim 1, having a density of 1.0 g/cm^3 to 2.5/cm^3.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55018644A JPS6058688B2 (en) | 1980-02-18 | 1980-02-18 | clay mineral sheet material |
DE19813105860 DE3105860A1 (en) | 1980-02-18 | 1981-02-18 | PLATE OR TABLET-SHAPED MINERAL TONE PRODUCT |
US06/506,222 US4486235A (en) | 1980-02-18 | 1983-06-21 | Clay mineral sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55018644A JPS6058688B2 (en) | 1980-02-18 | 1980-02-18 | clay mineral sheet material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56114877A JPS56114877A (en) | 1981-09-09 |
JPS6058688B2 true JPS6058688B2 (en) | 1985-12-21 |
Family
ID=11977308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP55018644A Expired JPS6058688B2 (en) | 1980-02-18 | 1980-02-18 | clay mineral sheet material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6058688B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0611954B2 (en) * | 1985-03-27 | 1994-02-16 | 日本ピラ−工業株式会社 | Spiral gasket filler material |
CN105531341B (en) * | 2013-08-01 | 2018-03-16 | 霓佳斯株式会社 | The thin slice and its manufacture method being made up of laminar clay mineral |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US343917A (en) * | 1886-06-15 | Punching and shearing machine | ||
US3434917A (en) * | 1966-03-07 | 1969-03-25 | Grace W R & Co | Preparation of vermiculite paper |
JPS5339318A (en) * | 1976-09-23 | 1978-04-11 | Ici Ltd | Manufacture of moulded products from vermiculite |
JPS56104768A (en) * | 1980-01-23 | 1981-08-20 | Nippon Asbestos Co Ltd | Vermiculite sheet material |
-
1980
- 1980-02-18 JP JP55018644A patent/JPS6058688B2/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US343917A (en) * | 1886-06-15 | Punching and shearing machine | ||
US3434917A (en) * | 1966-03-07 | 1969-03-25 | Grace W R & Co | Preparation of vermiculite paper |
JPS5339318A (en) * | 1976-09-23 | 1978-04-11 | Ici Ltd | Manufacture of moulded products from vermiculite |
JPS56104768A (en) * | 1980-01-23 | 1981-08-20 | Nippon Asbestos Co Ltd | Vermiculite sheet material |
Also Published As
Publication number | Publication date |
---|---|
JPS56114877A (en) | 1981-09-09 |
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