JPH0541586B2 - - Google Patents
Info
- Publication number
- JPH0541586B2 JPH0541586B2 JP58105745A JP10574583A JPH0541586B2 JP H0541586 B2 JPH0541586 B2 JP H0541586B2 JP 58105745 A JP58105745 A JP 58105745A JP 10574583 A JP10574583 A JP 10574583A JP H0541586 B2 JPH0541586 B2 JP H0541586B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- binder
- weight
- ceramic fibers
- unexpanded vermiculite
- 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 - Lifetime
Links
- 239000000835 fiber Substances 0.000 claims description 99
- 239000000919 ceramic Substances 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 55
- 239000011230 binding agent Substances 0.000 claims description 54
- 229910052902 vermiculite Inorganic materials 0.000 claims description 42
- 239000010455 vermiculite Substances 0.000 claims description 42
- 235000019354 vermiculite Nutrition 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 16
- 229920000620 organic polymer Polymers 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000004113 Sepiolite Substances 0.000 description 7
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 7
- 244000144992 flock Species 0.000 description 7
- 229910052624 sepiolite Inorganic materials 0.000 description 7
- 235000019355 sepiolite Nutrition 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- -1 sodium organic acid Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Nonwoven Fabrics (AREA)
Description
本発明は、未膨張バーミキユライト、セラミツ
ク繊維、結合剤からなり、常温から高温まで優れ
た弾力性と可撓性を有し、130℃程度の低温から
膨張する耐熱弾性シート状物に関するものであ
る。
従来、(1)特開昭50−55603号には膨張性雲母、
無機繊維材料、無機結合剤からなる膨張性シート
材料が示されており、また、(2)特開昭51−69507
号には膨張性雲母、無機繊維材料、有機弾性結合
剤からなる可撓−膨張性シート材料が示されてお
り、さらに(3)特開昭54−30218号には未膨張ヒル
石、無機繊維物質、有機エラストマー結合剤、無
機粘土結合剤からなる可撓性膨張性シート物質が
示されている。
しかし、無機結合剤を使用した従来例(1)のシー
ト材料は、本発明者の実験によれば、常温での可
撓性、弾力性に欠け、一方有機結合剤を使用した
従来例(2)のシート材料は、高温でこの結合剤が焼
失し強度が低下することがわかつている。更に、
有機と無機の結合剤を併用した従来例(4)のシート
物質でも使用している無機結合剤が硬化性のもの
であるため、有機結合剤が焼失する高温では、弾
性力、可撓性を失うことが本発明者の実験により
判明した。又、これら従来例(1)〜(3)によれば、製
造されるシート状物は高温になると非常に脆くな
り、更に結合剤の含有量が5%以上と多く、低温
での膨張が少なく弾性の小さいことが本発明者の
実験により判明した。
このように従来提案された材料は、耐熱性、可
撓性、弾力性などの特性において何らかの欠点を
有しており、その用途が大きく制限されるという
不利があつた。
本発明は、上記欠点を除去、改善したシート状
物を提供することを目的とし、特許請求の範囲記
載のシート状物を提供することにより前記目的を
達成するものである。
以下、本発明を詳細に説明する。
セラミツクス繊維は、一般的に高純度のシリカ
とアルミナのほぼ等量を電気溶融し、その細流を
高圧の空気または水蒸気で吹き飛ばすことにより
繊維化したもので、この繊維は200〜300℃で軟化
するガラス繊維と異なり850℃以上にならなけれ
ば結晶化せず、1000℃以上の高温に耐える優れた
耐火性を有する繊維である。しかし、上記細流を
繊維化する際には、繊維化されないシヨツト、繊
維の先端にくつついて残つているシヨツト、さら
に繊維の先端から折れ離脱したシヨツトなどが生
じる。このシヨツトの大きさは最初から繊維化さ
れないものは一般的に粗大で、150μ以上の粒径
を有するものが多い。また繊維の先端に残留もし
くは、これから離脱したものは一般的に微細で、
100〜44μ程度のものが多くこれらがシヨツトの
大半を占める。上記方法により製造されたセラミ
ツク繊維には通常前記シヨツトが50%程度含まれ
ている。
そして、これらのシヨツトは繊維の絡みの中に
取り込まれた状態で存在するものが多く、繊維の
絡みの中から繊維を破壊することなくシヨツトだ
けを分離し、除去することは極めて難かしい。
シヨツトは主として球状であるため、セラミツ
クス繊維あるいはバーミキユライトなどの材料と
は絡みにくく、また膨張性も有しないために、常
温及び高温におけるシートの強度、可撓性、弾力
性には何ら寄与せず本発明のシート状物にあつて
は十分取り除くことが望ましい。
従来、セラミツクス繊維の絡みの中に取り込ま
れた大粒のシヨツトのみでなく微細なシヨツトま
で除去するためには、繊維を破壊し細分化しなけ
ればならず、本発明のシート状物の使用に適する
シヨツト含有率が低く、しかも繊維長が長いセラ
ミツク繊維を工業的に大量に得ることは困難であ
つた。本発明のシート状物に使用するセラミツク
繊維に施こすシヨツト除去処理は、セラミツク繊
維を水中にて撹拌しセラミツク繊維フロツクのス
ラリーを形成させる工程、上記フロツクを、撹拌
羽根及び邪魔板を有し、ゆるやかな乱流を発生さ
せることができる角型の容器、あるいは側壁より
加圧水を送り込み、うず流を発生させることがで
きる円筒形容器内でほぐし、繊維を破壊すること
なく絡みの中に取り込まれているシヨツトを取り
出したり、繊維の先端にくつついているシヨツト
を折つたりしてセラミツク繊維とシヨツトを分離
する工程、さらに、分離されたシヨツトを除去す
ると同時に繊維を捕集する工程の3つの工程を、
各工程間に送液ポンプなどの繊維を破壊するよう
な輸送装置は何ら使用せず連続化した工程により
セラミツク繊維を流通させることにより行なわれ
る。このため、本発明において使用すセラミツク
繊維は、シヨツト含有率が低く、しかも繊維の長
さが長いという特徴を有し、これを使用したシー
ト状物は、高温で大きな強度、弾力性を有する。
次に、本発明のシート状物に用いるセラミツク
繊維であつてシヨツト含有率が30%以下のセラミ
ツク繊維を得る具体的方法の二例を説明する。
市販のセラミツクス繊維を水中に投入し撹拌し
てセラミツク繊維フロツクのスラリーを作成す
る。次に、このスラリーを撹拌羽根と邪魔板を有
する角型の容器に徐々に導びくと同時に水を容器
に供給しながら流速5〜50m/分のゆつくりとし
た乱流の中で解繊し、セラミツク繊維フロツクを
ほぐしシヨツトを分離する。絡みがほぐされたセ
ラミツクス繊維のスラリーを容器の上部より順
次、あふれ出させ移動しているエンドレスのスク
リーン上に導びき、シヨツトをふるい落とし繊維
を捕集する。
本発明のシート状物に用いるシヨツト含有率が
30%以下のセラミツク繊維を得る他の1つの方法
について説明する。
市販のセラミツク繊維を水中に投入し撹拌して
セラミツク繊維フロツクのスラリーを作成する。
次に、このスラリーを円筒容器に徐々に導びくと
同時に、この容器の側壁より加圧水を送り込み、
うず流を発生させ、そのうず流の中でセラミツク
繊維フロツクをほぐし、シヨツトを分離する。絡
みがほぐされたセラミツク繊維のスラリーをうず
流の中心部から順次、流出させ移動しているエン
ドレスのスクリーン上に導びき、シヨツトをふる
い落とし繊維を捕集する。
次に本発明において使用するセラミツク繊維中
のシヨツト含有率の測定方法を説明する。まず、
セラミツク繊維20gを秤量し、これを振動ミルに
て10秒間粉砕する。次に、この粉砕試料の全重量
を計量した後、容量5のビーカーに入れデカン
テーシヨンをくり返した後乾燥させ、ふるい分け
を行ない標準ふるい44μの上に残つたものをシヨ
ツトとする。
シヨツト含有率(%)=44μ以上のシヨツト量(g)
/100(g)×100
次に未膨張バーミキユライトについて説明す
る。バーミキユライトは、薄片多重構造を持つ粒
子で、Si−O四面体層とMg−O(OH)又はAl−
O八面体層から成るタルク状2:1型層構造を基
本とし、それらが層間に水を介してつながつた雲
母状構造の含水鉱物である。加熱すると脱水して
剥離膨張し10〜25倍に伸長するので弾力性、断熱
性などの特性を有する。ただ、層間の結合力が乏
しいため、少しの外力で薄片化してしまい単独に
て形態を維持することは難かしい。本発明に使用
するバーミキユライトは、有機酸ナトリウムによ
り処理することが有利である。これは未膨張バー
ミキユライトの膨張率や膨張力は粒径に比例して
大きくなるが、シート状物の製造には分散性の良
い小さい粒径のものを使用し、本発明のシート状
物には、粒径0.1〜2.8mmのものを使うのが有利で
ある。このような小さい粒径のバーミキユライト
を使用したシートは、膨張力、弾力性は小さくな
る。本発明者は、有機酸ナトリウムによりバーミ
キユライト粒子の層間のカチオンを置換すること
により、膨張力、弾力性が上昇し、更に置換して
いないバーミキユライトよりも低い温度から膨張
することを知見しており、本発明のようにバーミ
キユライトの粒径の小さいものを使用しても、有
機酸ナトリウムで処理をすれば、特性的に優れた
シートになることがわかつた。
上記有機酸ナトリウム水溶液中に未膨張のバー
ミキユライトを浸漬することにより、未膨張バー
ミキユライトの膨張力が向上する理由は、層間の
カルシウムイオン、又はマグネシウムイオンがナ
トリウムイオンに置換されることにより、加熱時
に層間の水が抜けにくくなるためであると考えら
れる。
次に、本発明のシート状物に用いる未膨張バー
ミキユライトの有機酸ナトリウムによる処理方法
について説明する。
所定量の未膨張バーミキユライトを1〜3規定
濃度の例えば酢酸ナトリウム水溶液に投入し、例
えば30分〜5時間、好ましくは1時間浸した後水
洗し、100℃にて乾燥する。
次に結合剤について説明する。
結合剤として有機質と無機質のそれぞれの結合
剤を併用し、有機質のものは特に、アクリロニト
リルブタジエン、スチレンブタジエン、アクリル
酸エステル、ポリウレタン、酢酸ビニル、メチル
セルロースなどが有効であり、又無機質のものと
しては、セピオライト、モンモリロナイトなどの
粘土質、アルミナゾル、シリカゾルなどのコロイ
ダル質のものが有効である。
さらに本発明者は、前記各材料からなるシート
状物の片面あるいは両面に有機高分子フイルムを
貼着するか又は、前記シート状物の全面を有機高
分子フイルムにて密封することにより、シート状
物の弾力性、膨張性などの優れた特性をそこなう
ことなく常温での取扱いに支障のない可撓性と強
度を有するシート状物を得ることが出来ることを
知見した。上記有機高分子フイルムのシート状物
への貼着又は密封は、公知の接着剤にて貼り付け
てもよく又シユリンクパツク、真空パツクなどの
方法により行なうことが出来る。しかし、上記の
ごとく貼着又は密封に使用する有機高分子フイル
ムの量は、多過ぎるとシート状物の弾力性、可撓
性に悪影響が出る。従つて本発明者の実験により
有機高分子フイルムの量は、貼着又は密封される
シート状物の重量の0.5%以下であることが望ま
しい。また、有機高分子フイルムの材質として
は、再生セルロース、セルロース誘導体、ポリオ
レフイン、ポリ塩化ビニル、ポリ塩化ビニリデ
ン、ポリビニルアルコール、ポリエステル、ポリ
エチレン、塩酸ゴム、ポリアミド、フツ素樹脂な
どが有利である。
本発明者は、これらの材料を使用することによ
り優れた特性を有するシート状物を製造できるこ
とを新規に知見した。以下に、これらの材料を使
用することによる作用効果並びにシート状物の特
性について説明する。
本発明のシート状物は、セラミツクス繊維、未
膨張バーミキユライトと含有量が0.5〜3.5重量%
と極めて少量の結合剤とを用いて作られたもので
あり、セラミツクス繊維や未膨張バーミキユライ
トが結合剤により強く拘束されないため、200℃
以下の低温から膨張を始め、また常温から高温ま
で弾力性を有する。セラミツク繊維と未膨張バー
ミキユライトのみからなるシート状物はその形状
維持が難かしいためその形状維持のためには結合
剤をある程度添加する必要がある。しかし、結合
剤はその量が多いとシートの弾力性あるいは柔軟
性が低下し、また結合剤の量が少ないとシート状
物の形成が難かしくなるという問題がある。本発
明者は、結合剤がシートの持つ特性をそこなわ
ず、シートの成形及び形状維持のために必要な結
合剤の量とセラミツク繊維の形態を組み合わせる
ことにより上記問題を解決出来ることを知見し
た。即ち、シヨツト含有率が30重量%以下のセラ
ミツク繊維を使用したシート状物は、繊維の割合
が高く、絡みが強いために結合剤は少ない量でも
その結合効果は常温から高温まで十分発揮され優
れた弾力性を有する。
次に、有機質と無機質の結合剤の併用効果につ
いてのべる。有機質結合剤のみを使用したシート
状物は常温では優れた柔軟性と弾力性を有する
が、加熱されると有機質結合剤が焼失し、更にバ
ーミキユライトの膨張によりシートが膨張し過ぎ
て形態を保つことが困難になるが、無機質の結合
剤を併用するとバーミキユライトの膨張を適度に
抑制し繊維の絡みを固定するのでシートの形状は
十分に保持され、又バーミキユライトの膨張が抑
制されているために常温のみならず高温において
も弾力性が発揮される。結合剤が特に良い効果を
示すのは、無機質結合剤と有機質結合剤の比率が
1/2〜1/10の時である。この比率より高い場合は
シートが硬くなり、低い場合は高温での強度が小
さく弾力性も低くなる。
上記のごとく、結合剤含有率が0.5〜3.5重量%
という少量からなる本発明のシート状物は、200
℃以下の低温においても膨張を開始するが、あら
かじめ有機酸ナトリウム水溶液にて処理された未
膨張バーミキユライトを使用することにより、シ
ート状物の低温での膨張率は向上する。さらにこ
の際、粒径が0.1〜2.83mmの未膨張バーミキユラ
イトを使用するとセラミツク繊維あるいは結合剤
と未膨張バーミキユライトが均一に混ざり合うた
め、シート状物の弾力性あるいは強度が向上す
る。従つて低温での膨張率あるいは膨張力を必要
とする場合には有機酸ナトリウム水溶液にて処理
された粒径が0−1〜2−83mmの未膨張バーミキ
ユライトを使用した本発明のシート状物が有利で
ある。また、未膨張バーミキユライトの処理に使
用する有機酸ナトリウムとしては酢酸ナトリウム
が有利である。
前記セラミツク繊維、未膨張バーミキユライ
ト、結合剤などの各材料よりなる本発明のシート
状物は、結合剤の含有量が少ないにもかかわら
ず、常温での通常の取扱いには特に支障はない
が、シートを折りたたむ場合など苛酷な取り扱い
をした場合には、シートの表面に亀裂が生じた
り、シートが切断されるなどの恐れがあ。苛酷な
取扱いをする場合には、上記シート状物の片面又
は両面に有機高分子フイルムを貼着するかまた
は、シート状物を有機高分子フイルムにて密封す
る必要がある。この際、使用する有機高分子フイ
ルムの重量はシート状物の重量の0.5重量%以下
であることが望ましく、これ以上多いと低温での
膨張率が若干低下する。このように有機高分子フ
イルムの貼着又は密封がなされた本発明のシート
状物は、常温から高温までの優れた弾力性と低温
からの膨張性を有するのみならず常温での苛酷な
取り扱いにも十分耐える優れた可撓性を有する。
次に、本発明のシート状物に使用する各材料の
混合割合を限定する理由を説明する。
未膨張バーミキユライトは、40重量%未満では
低温から有効な膨張が得られず弾力性が不足し、
一方83重量%を越えると結合剤を多量に使用しな
いとシートの形成が難かしくなるので40〜83重量
%の範囲内にする必要がある。
結合剤は、0.5重量%未満ではシートの成形が
困難になり、3.5重量%を越えると低温での弾力
性及び膨張率が不足するので0.5〜3.5重量%の範
囲内にする必要がある。
次に、本発明を実施例について説明する。
実施例 1
容量1m3の高速ミキサーに800の水とシヨツ
ト含有率52%の市販のセラミツク繊維8Kgを投入
し15分間撹拌してセラミツク繊維フロツクのスラ
リーを作成した。一方、容量25の円筒型容器の
側壁より流量170/分、水圧1.5Kg/cm2の加圧水
を送り込み、円筒型容器内にうず流を発生させ、
この円筒型容器上部よりうず流の中心部へ上記セ
ラミツク繊維フロツクのスラリーを80/分の流
量で導びき、セラミツク繊維フロツクをほぐした
後、このスラリーをうず流の中心部より流出させ
30メツシユの金網上へ導びきセラミツク繊維を捕
集した。このようにしてシヨツト含有率13%、平
均繊維長38mmのセラミツク繊維を得た。次に、セ
ピオライト1.7g、市販の未焼成南アフリカ産バ
ーミキユライト1号(粒径0.42〜1.41mm)208g、
上記セラミツク繊維126g、アクリロニトリルブ
タジエン系ラテツクス(固型分40%)26mlを8000
mlの水中に添加し充分撹拌、混合した。このスラ
リー中に市販のポリアクリルアミド系凝集剤0.1
%水溶液8ml、硫酸バンド10%水溶液5mlを添加
し撹拌、混合した。このようにして作成したスラ
リーを角型の手抄き機にて抄造し、厚さ約18mmの
抄造物を得た。この抄造物を100℃にて乾燥した
後ステンレス製の平板の間に入れプレスし、30×
30cm、厚さ5.5mmの本発明のシート状物を得た。
実施例 2
容量1m3の高速ミキサーに800の水とシヨツ
ト含有率52%の市販のセラミツク繊維8Kgを投入
し15分間撹拌してセラミツク繊維フロツクのスラ
リーを作成した。一方、容量25の円筒型容器の
側壁より流量170/分、水圧1.5Kg/cm2の加圧水
を送り込み円筒型容器内にうず流を発生させ、こ
の円筒型容器上部よりうず流の中心部へ上記セラ
ミツク繊維フロツクのスラリーを80/分の流量
で導き、セラミツク繊維フロツクをほぐした後、
このスラリーとうず流の中心部より流出させ30メ
ツシユの金網上へ導びきセラミツク繊維を捕集し
た。このようにしてシヨツト含有率21%、平均繊
維長38mmのセラミツク繊維を得た。次にセピオラ
イト1.7g、上記セラミツク繊維126g、濃度1規
定、温度70℃の酢酸ナトリウム水溶液中にて1時
間処理された市販の未焼成南アフリカ産バーミキ
ユライト208g、アクリロニトリルブタジエン系
ラテツクス(固型分40%)26mlを8000mlの水中に
添加し充分撹拌、混合した。このスラリー中に市
販のポリアクリルアミド系凝集剤0.1%水溶液8
ml、硫酸バンド10%水溶液5mlを添加し撹拌、混
合した。このようにして作成したスラリーを角型
の手抄き機にて抄造し、厚さ約17mmの抄造物を得
た。この抄造物を100℃にて乾燥した後ステンレ
ス製の平板の間に入れプレスし、30×30cm、厚さ
5.5mmの本発明のシート状物を得た。
実施例 3
容量1m3の高速ミキサーに800の水とシヨツ
ト含有率52%の市販のセラミツク繊維8Kgを投入
し15分間撹拌してセラミツク繊維フロツクのスラ
リーを作成した。一方、容量25の円筒型容器の
側壁より流量170/分、水圧1.5Kg/cm2の加圧水
を送り込み、円筒型容器内にうず流を発生させ、
この円筒型容器上部よりうず流の中心部へ上記セ
ラミツク繊維フロツクのスラリーを80/分の流
量で導びき、セラミツク繊維フロツクをほぐした
後、このスラリーをうず流の中心部より流出させ
30メツシユの金網上へ導びきセラミツク繊維を捕
集した。このようにしてシヨツト含有率13%平均
繊維長38mmのセラミツク繊維を得た。次にセピオ
ライト0.3g、上記セラミツク繊維206g、濃度1
規定、温度70℃の酢酸ナトリウム水溶液にて1時
間処理された市販の未焼成南アフリカ産バーミキ
ユライト139g、アクリロニトリルブタジエン系
ラテツクス(固型分40%)3.5mlを8000mlの水中
に添加し充分撹拌、混合した。このスラリー中に
市販のポリアクリルアミド系凝集剤0.1%水溶液
3ml、硫酸バンド10%水溶液3mlを添加し撹拌、
混合した。このようにして作成したスラリーを角
型の手抄き機にて抄造し、厚さ約16mmの抄造物を
得た。この抄造物を100℃にて乾燥した後ステン
レス製の平板の間に入れプレスし、30×30cm、厚
さ5.5のシート状物を得た。このシート状物を厚
さ10μのポリエチレンフイルムにて密封し本発明
のシート状物を得た。
実施例 4
容量1m3の高速ミキサーに800の水とシヨツ
ト含有率52%の市販のセラミツク繊維8Kgを投入
し15分間撹拌してセラミツクス繊維フロツクのス
ラリーを作成した。一方、容量25の円筒型容器
の側壁より流量170/分、水圧1.5Kg/cm2の加圧
水を送り込み、円筒型容器内にうず流を発生さ
せ、この円筒型容器上部よりうず流の中心部へ上
記セラミツク繊維フロツクのスラリーを80/分
の流量で導びき、セラミツク繊維フロツクをほぐ
した後、このスラリーをうず流の中心部より流出
させ30メツシユの金網上へ導びきセラミツク繊維
を捕集した。このようにしてシヨツト含有率21
%、平均繊維長38mmのセラミツク繊維を得た。次
にセピオライト1.7g、上記セラミツク繊維57g、
濃度1規定、温度70℃の酢酸ナトリウム水溶液に
て1時間処理された市販の未焼成南アフリカ産バ
ーミキユライト277g、アクリロニトリルブタジ
エン系ラテツクス(固型分40%)26mlを8000mlの
水中に添加し充分撹拌、混合した。このスラリー
中に市販のポリアクリルアミド系凝集剤0.1%水
溶液8ml、硫酸バンド10%水溶液5mlを添加し撹
拌、混合した。このようにして作成したスラリー
を角型の手抄き機にて抄造し、厚さ約10mmの抄造
物を得た。この抄造物を100℃にて乾燥した後ス
テンレス製の平板の間に入れプレスし、30×30
cm、厚さ5.5のシート状物を得た。
比較例 1
市販のセラミツク繊維(シヨツト含有率50%)
104g、市販の未焼成南アフリカ産バーミキユラ
イト1号(粒径0.42〜1.41mm)208g、セピオラ
イト17g、アクリロニトリルブタジエン系ラテツ
クス(固型分40%)43ml、市販のポリアクリルア
ミド系凝集剤0.1%水溶液80ml、硫酸バンド10%
水溶液11mlを用い、実施例1と同様の方法にて30
×30cm、厚さ5.5mmのシート状物を得た。
比較例 2
市販のセラミツク繊維(シヨツト含有率50%)
139g、市販の未焼成南アフリカ産バーミキユラ
イト1号(粒径0.42〜1.41mm)139g、セピオラ
イト35g、アクリロニトリルブタジエン系ラテツ
クス(固型分40%)87ml、市販のポリアクリルア
ミド系凝集剤0.1%水溶液170ml、硫酸バンド10%
水溶液17mlを用い、実施例1と同様の方法にて30
×30cm、厚さ5.5mmのシート状物を得た。
上記実施例1〜4のシート状物について、以下
に示す常温及び高温の弾力性、可撓性、膨張率の
評価試験を実施し、その結果を比較例と共に第1
表に示した。
本発明のシート状物について実施した常温での
弾力性評価試験は、ASTM F−36−79の変形法
に基く試験で、該変形法は、ペネトレーターを直
径10cmのアンビルで置き換え、25mm平方の試験片
に12.5Kgの荷重を加え圧縮率と復元率を測定する
方法である。又、高温での弾力性評価試験とは、
20mm平方の試験片に900℃の雰囲気下にて元の厚
さの40%までの繰り返し圧縮を行ない、その時の
シートの圧縮復元力を測定し、その繰り返しに伴
なう変化を記録するという方法である。この復元
力の値が大きく、しかも繰り返しによる減少率が
小さい程、弾力性が優れているとの評価が成され
る。
さらに、可撓性の評価試験は、折れることなく
巻くことができるロールの半径を測定する方法で
ある。また、膨張率は、25mm平方のシート材料を
120〜400℃の雰囲気の炉で1時間焼成し、冷間に
てその膨張量を測定し算出したものである。
The present invention relates to a heat-resistant elastic sheet made of unexpanded vermiculite, ceramic fibers, and a binder, which has excellent elasticity and flexibility from room temperature to high temperatures, and expands from a low temperature of about 130°C. be. Conventionally, (1) Unexamined Patent Publication No. 50-55603 contains expandable mica,
An expansible sheet material composed of an inorganic fiber material and an inorganic binder is disclosed, and (2) Japanese Patent Application Laid-Open No. 51-69507
In JP-A-54-30218, a flexible-expandable sheet material consisting of expandable mica, an inorganic fiber material, and an organic elastic binder is disclosed. A flexible expandable sheet material is shown comprising a material, an organic elastomeric binder, and an inorganic clay binder. However, according to the inventor's experiments, the sheet material of the conventional example (1) using an inorganic binder lacks flexibility and elasticity at room temperature, while the sheet material of the conventional example (2) using an organic binder lacks flexibility and elasticity at room temperature. It is known that the bonding agent in the sheet material of ) is burned out at high temperatures, resulting in a decrease in strength. Furthermore,
The inorganic binder used in the sheet material of conventional example (4), which uses a combination of organic and inorganic binders, is hardening, so at high temperatures where the organic binder is burned out, elasticity and flexibility are reduced. It was found through experiments by the inventor that this loss occurs. Furthermore, according to these conventional examples (1) to (3), the sheet-like products produced become extremely brittle at high temperatures, and furthermore, the binder content is as high as 5% or more, resulting in little expansion at low temperatures. The inventor's experiments revealed that the elasticity was low. As described above, the conventionally proposed materials have some drawbacks in properties such as heat resistance, flexibility, and elasticity, and have the disadvantage that their uses are greatly limited. An object of the present invention is to provide a sheet-like product that eliminates and improves the above-mentioned drawbacks, and achieves the above-mentioned object by providing a sheet-like product as described in the claims. The present invention will be explained in detail below. Ceramic fibers are generally made into fibers by electrically melting approximately equal amounts of high-purity silica and alumina, and then blowing the resulting stream with high-pressure air or steam. This fiber softens at 200 to 300°C. Unlike glass fiber, it does not crystallize unless the temperature reaches 850℃ or higher, and it has excellent fire resistance and can withstand high temperatures of 1000℃ or higher. However, when the above-mentioned rivulet is turned into fibers, some shots are not turned into fibers, some shots remain stuck to the tips of the fibers, and some shots break off from the tips of the fibers. The size of these shots is generally coarse if they are not made into fibers from the beginning, and many have a particle size of 150μ or more. In addition, the materials remaining at the tips of the fibers or separated from them are generally fine,
Most of the shots are about 100 to 44μ, and these make up the majority of shots. Ceramic fibers produced by the above method usually contain about 50% of the shots. Many of these shots exist in a state of being incorporated into the tangle of fibers, and it is extremely difficult to separate and remove only the shot from the tangle of fibers without destroying the fibers. Because shots are mainly spherical, they do not easily entangle with materials such as ceramic fibers or vermiculite, and they do not have expansion properties, so they do not contribute to the strength, flexibility, or elasticity of the sheet at room or high temperatures. First, in the case of the sheet-like material of the present invention, it is desirable to remove them sufficiently. Conventionally, in order to remove not only the large shots trapped in the entanglement of ceramic fibers but also the fine shots, the fibers had to be broken and fragmented, and the shot suitable for use in the sheet-like product of the present invention is It has been difficult to industrially obtain large quantities of ceramic fibers with a low content and a long fiber length. The shot removal treatment performed on the ceramic fibers used in the sheet-like product of the present invention includes a step of stirring the ceramic fibers in water to form a slurry of ceramic fiber flocs, and a step of stirring the flocs with a stirring blade and a baffle plate. The fibers are loosened in a rectangular container that can generate a gentle turbulent flow, or a cylindrical container that can generate a vortex flow by pumping pressurized water through the side wall, so that the fibers are incorporated into the tangles without breaking them. The process consists of three steps: separating the shot from the ceramic fiber by taking out the shot that is stuck to the end of the fiber and breaking off the shot stuck to the tip of the fiber, and then removing the separated shot and collecting the fiber at the same time. ,
The process is carried out by circulating the ceramic fibers in a continuous process without using any transportation device such as a liquid pump that would destroy the fibers between each process. Therefore, the ceramic fiber used in the present invention has a low shot content and a long fiber length, and a sheet-like product using the ceramic fiber has high strength and elasticity at high temperatures. Next, two examples of specific methods for obtaining ceramic fibers having a shot content of 30% or less, which are used in the sheet-like article of the present invention, will be explained. Commercially available ceramic fibers are placed in water and stirred to create a slurry of ceramic fiber flock. Next, this slurry is gradually introduced into a rectangular container equipped with stirring blades and baffles, and at the same time, water is supplied to the container and defibrated in a slow turbulent flow at a flow rate of 5 to 50 m/min. , loosen the ceramic fiber flock and separate the shot. A slurry of disentangled ceramic fibers is sequentially overflowed from the top of the container and guided onto a moving endless screen, where the shot is sieved and the fibers are collected. The shot content used in the sheet material of the present invention is
Another method for obtaining ceramic fibers of 30% or less will be described. Commercially available ceramic fibers are poured into water and stirred to create a slurry of ceramic fiber flocs.
Next, this slurry is gradually introduced into a cylindrical container, and at the same time pressurized water is pumped through the side wall of this container.
A vortex is generated, which loosens the ceramic fiber flock and separates the shot. A slurry of disentangled ceramic fibers is sequentially flowed out from the center of the eddy stream and guided onto a moving endless screen, which sieves the shots and collects the fibers. Next, a method for measuring the shot content in the ceramic fiber used in the present invention will be explained. first,
Weigh 20g of ceramic fiber and crush it for 10 seconds in a vibrating mill. Next, after weighing the total weight of this pulverized sample, it is placed in a 5-capacity beaker, decanted repeatedly, dried, and sieved, and what remains on a standard 44μ sieve is used as shot. Shot content (%) = Shot amount of 44μ or more (g)
/100(g)×100 Next, unexpanded vermiculite will be explained. Vermiculite is a particle with a flake multilayer structure, consisting of a Si-O tetrahedral layer and Mg-O(OH) or Al-
It is a hydrous mineral with a mica-like structure, which has a basic talc-like 2:1 layer structure consisting of O octahedral layers, which are connected through water between the layers. When heated, it dehydrates, peels and expands, stretching 10 to 25 times, so it has properties such as elasticity and heat insulation. However, due to the poor bonding strength between the layers, it becomes flaky with the slightest external force, making it difficult to maintain its shape by itself. The vermiculite used in the invention is advantageously treated with a sodium organic acid. This is because the expansion rate and expansion power of unexpanded vermiculite increase in proportion to the particle size, but when manufacturing sheet-like products, small particle sizes with good dispersibility are used, and the sheet-like products of the present invention It is advantageous to use particles with a particle size of 0.1 to 2.8 mm. A sheet using vermiculite with such a small particle size has low expansion force and elasticity. The present inventor has discovered that by replacing the cations between the layers of vermiculite particles with sodium organic acid, the expansion force and elasticity increase, and furthermore, vermiculite expands from a lower temperature than unsubstituted vermiculite. It was found that even if vermiculite with a small particle size is used as in the present invention, a sheet with excellent properties can be obtained if treated with sodium organic acid. The reason why the expansion power of unexpanded vermiculite is improved by immersing unexpanded vermiculite in the organic acid sodium aqueous solution is that calcium ions or magnesium ions between the layers are replaced with sodium ions. This is thought to be because water between the layers becomes difficult to escape during heating. Next, a method for treating unexpanded vermiculite used in the sheet material of the present invention with organic acid sodium will be described. A predetermined amount of unexpanded vermiculite is put into an aqueous sodium acetate solution having a concentration of 1 to 3 normal, and immersed for example for 30 minutes to 5 hours, preferably 1 hour, then washed with water and dried at 100°C. Next, the binder will be explained. Both organic and inorganic binders are used as binders, and organic binders are particularly effective, such as acrylonitrile butadiene, styrene butadiene, acrylic esters, polyurethane, vinyl acetate, and methyl cellulose, and inorganic binders include: Clay materials such as sepiolite and montmorillonite, and colloidal materials such as alumina sol and silica sol are effective. Furthermore, the present inventor has developed a method for forming a sheet by pasting an organic polymer film on one or both sides of a sheet made of each of the above-mentioned materials, or by sealing the entire surface of the sheet with an organic polymer film. It has been found that it is possible to obtain a sheet-like product that has flexibility and strength that can be handled at room temperature without impairing the product's excellent properties such as elasticity and expansibility. The above-mentioned organic polymer film may be attached or sealed to the sheet-like material using a known adhesive, or may be carried out by a shrink packing method, a vacuum packing method, or the like. However, as mentioned above, if the amount of organic polymer film used for pasting or sealing is too large, the elasticity and flexibility of the sheet material will be adversely affected. Therefore, according to experiments conducted by the present inventors, the amount of organic polymer film is desirably 0.5% or less of the weight of the sheet material to be adhered or sealed. Further, as the material for the organic polymer film, regenerated cellulose, cellulose derivatives, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyester, polyethylene, hydrochloric acid rubber, polyamide, fluororesin, etc. are advantageous. The present inventors have newly found that by using these materials, sheet-like products having excellent properties can be manufactured. The effects of using these materials and the properties of the sheet-like material will be explained below. The sheet material of the present invention contains ceramic fibers and unexpanded vermiculite in a content of 0.5 to 3.5% by weight.
and a very small amount of binder, and because the ceramic fibers and unexpanded vermiculite are not strongly constrained by the binder, it can be heated to 200℃.
It begins to expand at low temperatures below, and remains elastic from room temperature to high temperatures. Since it is difficult to maintain the shape of a sheet made only of ceramic fibers and unexpanded vermiculite, it is necessary to add a certain amount of binder to maintain the shape. However, there is a problem that if the amount of binder is large, the elasticity or flexibility of the sheet will be reduced, and if the amount of binder is small, it will be difficult to form a sheet-like product. The present inventor has discovered that the above problem can be solved by combining the amount of binder and the morphology of the ceramic fibers necessary for forming and maintaining the shape of the sheet without the binder impairing the properties of the sheet. . In other words, sheet materials using ceramic fibers with a shot content of 30% by weight or less have a high proportion of fibers and are highly intertwined, so even with a small amount of binder, the binding effect is fully demonstrated from room temperature to high temperature, making it excellent. It has good elasticity. Next, we will discuss the combined effects of organic and inorganic binders. Sheet materials using only an organic binder have excellent flexibility and elasticity at room temperature, but when heated, the organic binder burns out and the sheet expands too much due to the expansion of vermiculite, causing it to lose its shape. However, when an inorganic binder is used in combination, the expansion of vermiculite is moderately suppressed and the entanglement of fibers is fixed, so the shape of the sheet is sufficiently maintained, and the expansion of vermiculite is suppressed. Because of this, it exhibits elasticity not only at room temperature but also at high temperatures. The binder exhibits particularly good effects when the ratio of the inorganic binder to the organic binder is 1/2 to 1/10. If the ratio is higher than this, the sheet will be hard; if it is lower, the strength at high temperatures will be low and the elasticity will be low. As mentioned above, binder content is 0.5-3.5% by weight
The sheet material of the present invention consists of a small amount of 200
Expansion starts even at low temperatures below .degree. C., but by using unexpanded vermiculite that has been previously treated with an organic acid sodium aqueous solution, the expansion rate of the sheet material at low temperatures is improved. Furthermore, if unexpanded vermiculite with a particle size of 0.1 to 2.83 mm is used at this time, the ceramic fibers or binder and unexpanded vermiculite are uniformly mixed, so that the elasticity or strength of the sheet material is improved. Therefore, when expansion coefficient or expansion power at low temperatures is required, the sheet form of the present invention using unexpanded vermiculite with a particle size of 0-1 to 2-83 mm treated with an aqueous solution of sodium organic acid may be used. Things are advantageous. Furthermore, sodium acetate is advantageously used as the organic acid sodium used in the treatment of unexpanded vermiculite. Although the sheet-like product of the present invention made of materials such as the ceramic fiber, unexpanded vermiculite, and binder has a low binder content, there is no particular problem in normal handling at room temperature. However, if the seat is handled harshly, such as when folded, there is a risk that the surface of the seat may crack or the seat may be cut. If the sheet is to be handled harshly, it is necessary to attach an organic polymer film to one or both sides of the sheet, or to seal the sheet with an organic polymer film. At this time, it is desirable that the weight of the organic polymer film used is 0.5% by weight or less of the weight of the sheet-like material; if it is more than this, the expansion coefficient at low temperatures will decrease slightly. The sheet material of the present invention to which the organic polymer film is attached or sealed in this way not only has excellent elasticity from room temperature to high temperature and expandability from low temperature, but also has the ability to withstand harsh handling at room temperature. It has excellent flexibility to withstand even the most severe conditions. Next, the reason for limiting the mixing ratio of each material used in the sheet-like article of the present invention will be explained. If unexpanded vermiculite is less than 40% by weight, it will not be able to expand effectively at low temperatures and will lack elasticity.
On the other hand, if it exceeds 83% by weight, it becomes difficult to form a sheet unless a large amount of binder is used, so the content must be within the range of 40 to 83% by weight. If the binder is less than 0.5% by weight, it will be difficult to form a sheet, and if it exceeds 3.5% by weight, the elasticity and expansion rate at low temperatures will be insufficient, so the content must be within the range of 0.5 to 3.5% by weight. Next, the present invention will be described with reference to examples. Example 1 800 g of water and 8 kg of commercially available ceramic fibers with a shot content of 52% were charged into a high-speed mixer with a capacity of 1 m 3 and stirred for 15 minutes to prepare a slurry of ceramic fiber floc. On the other hand, pressurized water with a flow rate of 170/min and a water pressure of 1.5 Kg/cm 2 was sent from the side wall of a cylindrical container with a capacity of 25 to generate an eddy flow inside the cylindrical container.
The slurry of the ceramic fiber flocs is introduced into the center of the vortex from the top of this cylindrical container at a flow rate of 80/min, and after loosening the ceramic fiber flocs, the slurry is allowed to flow out from the center of the vortex.
Ceramic fibers were collected by guiding them onto a 30-mesh wire mesh. Ceramic fibers with a shot content of 13% and an average fiber length of 38 mm were thus obtained. Next, 1.7 g of sepiolite, 208 g of commercially available unfired South African vermiculite No. 1 (particle size 0.42 to 1.41 mm),
126g of the above ceramic fiber and 26ml of acrylonitrile butadiene latex (solid content 40%) for 8000
ml of water and thoroughly stirred and mixed. In this slurry, commercially available polyacrylamide flocculant 0.1
% aqueous solution and 5 ml of a 10% sulfuric acid band aqueous solution were added and mixed with stirring. The slurry thus prepared was made into paper using a square hand paper machine to obtain a paper product with a thickness of approximately 18 mm. After drying this paper product at 100℃, it was placed between stainless steel plates and pressed.
A sheet-like product of the present invention having a size of 30 cm and a thickness of 5.5 mm was obtained. Example 2 800 g of water and 8 kg of commercially available ceramic fibers with a shot content of 52% were charged into a high-speed mixer with a capacity of 1 m 3 and stirred for 15 minutes to prepare a slurry of ceramic fiber floc. On the other hand, pressurized water with a flow rate of 170/min and a water pressure of 1.5 Kg/cm 2 is sent from the side wall of a cylindrical container with a capacity of 25 to generate an eddy flow inside the cylindrical container, and from the top of the cylindrical container to the center of the eddy flow as described above. After introducing the slurry of ceramic fiber flock at a flow rate of 80/min to loosen the ceramic fiber flock,
This slurry was flowed out from the center of the whirlpool and guided onto a 30-mesh wire mesh to collect ceramic fibers. Ceramic fibers with a shot content of 21% and an average fiber length of 38 mm were thus obtained. Next, 1.7 g of sepiolite, 126 g of the above ceramic fibers, 208 g of commercially available unfired South African vermiculite treated in a sodium acetate aqueous solution with a concentration of 1N and a temperature of 70°C for 1 hour, and acrylonitrile butadiene latex (solid content 40 %) was added to 8000 ml of water and thoroughly stirred and mixed. In this slurry, a commercially available polyacrylamide flocculant 0.1% aqueous solution 8
ml and 5 ml of a 10% aqueous solution of band sulfate were added and stirred and mixed. The slurry thus prepared was made into paper using a square hand paper machine to obtain a paper product with a thickness of approximately 17 mm. After drying this paper product at 100℃, it was placed between stainless steel plates and pressed.
A 5.5 mm sheet-like product of the present invention was obtained. Example 3 800 g of water and 8 kg of commercially available ceramic fibers with a shot content of 52% were charged into a high-speed mixer with a capacity of 1 m 3 and stirred for 15 minutes to prepare a slurry of ceramic fiber floc. On the other hand, pressurized water with a flow rate of 170/min and a water pressure of 1.5 Kg/cm 2 was sent from the side wall of a cylindrical container with a capacity of 25 to generate an eddy flow inside the cylindrical container.
The slurry of the ceramic fiber flocs is introduced into the center of the vortex from the top of this cylindrical container at a flow rate of 80/min, and after loosening the ceramic fiber flocs, the slurry is allowed to flow out from the center of the vortex.
Ceramic fibers were collected by guiding them onto a 30-mesh wire mesh. In this way, ceramic fibers with a shot content of 13% and an average fiber length of 38 mm were obtained. Next, 0.3g of sepiolite, 206g of the above ceramic fiber, concentration 1
Add 139 g of commercially available uncalcined South African vermiculite treated with an aqueous sodium acetate solution at a specified temperature of 70°C for 1 hour, and 3.5 ml of acrylonitrile butadiene latex (solid content 40%) to 8000 ml of water and stir thoroughly. Mixed. To this slurry, 3 ml of a commercially available polyacrylamide flocculant 0.1% aqueous solution and 3 ml of a 10% sulfuric acid aqueous solution were added and stirred.
Mixed. The slurry thus prepared was made into paper using a square hand paper machine to obtain a paper product with a thickness of approximately 16 mm. After drying this paper product at 100°C, it was placed between stainless steel flat plates and pressed to obtain a sheet-like product measuring 30 x 30 cm and 5.5 cm thick. This sheet-like product was sealed with a polyethylene film having a thickness of 10 μm to obtain a sheet-like product of the present invention. Example 4 800 g of water and 8 kg of commercially available ceramic fibers with a shot content of 52% were charged into a high-speed mixer with a capacity of 1 m 3 and stirred for 15 minutes to prepare a slurry of ceramic fiber floc. On the other hand, pressurized water with a flow rate of 170/min and a water pressure of 1.5 Kg/cm 2 is sent from the side wall of a cylindrical container with a capacity of 25 to generate an eddy flow inside the cylindrical container, and from the top of the cylindrical container to the center of the eddy flow. The slurry of the ceramic fiber flock was introduced at a flow rate of 80/min to loosen the ceramic fiber flock, and then the slurry was flowed out from the center of the eddy flow and introduced onto a 30-mesh wire gauze to collect the ceramic fibers. In this way, shot content 21
%, and the average fiber length was 38 mm. Next, 1.7g of sepiolite, 57g of the above ceramic fiber,
277 g of commercially available uncalcined South African vermiculite treated with an aqueous solution of sodium acetate at a concentration of 1N and a temperature of 70°C for 1 hour, and 26 ml of acrylonitrile butadiene latex (solid content 40%) were added to 8000 ml of water and stirred thoroughly. , mixed. To this slurry were added 8 ml of a commercially available 0.1% aqueous solution of polyacrylamide flocculant and 5 ml of a 10% aqueous solution of sulfuric acid, followed by stirring and mixing. The slurry thus prepared was made into paper using a square hand paper machine to obtain a paper product with a thickness of approximately 10 mm. After drying this paper product at 100℃, it was placed between stainless steel plates and pressed.
A sheet-like product with a thickness of 5.5 cm and a thickness of 5.5 cm was obtained. Comparative example 1 Commercially available ceramic fiber (shot content 50%)
104g, commercially available uncalcined South African Vermiculite No. 1 (particle size 0.42-1.41mm) 208g, sepiolite 17g, acrylonitrile butadiene latex (solid content 40%) 43ml, commercially available polyacrylamide coagulant 0.1% aqueous solution 80ml , sulfate band 10%
Using 11 ml of aqueous solution, 30
A sheet-like product with a size of 30 cm and a thickness of 5.5 mm was obtained. Comparative example 2 Commercially available ceramic fiber (shot content 50%)
139g, commercially available uncalcined South African Vermiculite No. 1 (particle size 0.42-1.41mm) 139g, sepiolite 35g, acrylonitrile butadiene latex (solid content 40%) 87ml, commercially available polyacrylamide coagulant 0.1% aqueous solution 170ml , sulfate band 10%
Using 17 ml of aqueous solution, 30
A sheet-like product with a size of 30 cm and a thickness of 5.5 mm was obtained. The following evaluation tests of elasticity, flexibility, and expansion coefficient at room temperature and high temperature were conducted on the sheet-like materials of Examples 1 to 4 above, and the results were evaluated in the first test together with the comparative examples.
Shown in the table. The elasticity evaluation test at room temperature conducted on the sheet material of the present invention was a test based on the modified method of ASTM F-36-79, in which the penetrator was replaced with an anvil of 10 cm in diameter, and a 25 mm square test was performed. This method applies a load of 12.5 kg to a piece and measures the compression ratio and recovery ratio. Also, what is the elasticity evaluation test at high temperature?
A method in which a 20 mm square test piece is repeatedly compressed to 40% of its original thickness in an atmosphere of 900°C, the compression restoring force of the sheet at that time is measured, and the change due to the repetition is recorded. It is. The larger the value of this restoring force and the smaller the rate of decrease due to repetition, the better the elasticity is evaluated. Furthermore, the flexibility evaluation test is a method of measuring the radius of a roll that can be rolled without breaking. Also, the expansion rate is 25mm square sheet material.
Calculated by firing in a furnace at 120 to 400°C for 1 hour and measuring the amount of expansion in the cold.
【表】
第1表からわかるように、本発明の当初52%あ
つたシヨツトを、除去処理によつて21%以下に低
下させた実施例1〜3に示したシート状物は、い
ずれも常温で30%以上圧縮率と86%以上の高い復
元率を有していた。一方高温での弾力性も150回
のくり返し圧縮に対して圧縮復元力は30%程度し
か減少せず、又可撓性も1〜5cmの半径のロール
に巻くことが出来るなど本発明のシート状物は優
れた弾力性と可撓性を有していた。さらに本発明
のシート状物は、130℃程度の低温から既に膨張
が始まつており、結合剤含有量が少ない効果が表
われている。また、酢酸ナトリウム水溶液にて処
理された未膨張バーミキユライトを使用した実施
例2、3および4のシート状物は、極めて高い膨
張率を有していた。
以上、本発明のシート状物は、少ない量の結合
剤とシヨツトの少ないセラミツク繊維の組み合わ
せにより、実施例によりわかるように従来この種
の材料には見られなかつた常温から高温までの優
れた弾力性、可撓性、低温からの膨張性を有する
新規な材料であり、各種シール材、パツキング材
として広い用途が期待できる。[Table] As can be seen from Table 1, the sheet materials shown in Examples 1 to 3, in which the initial 52% shot of the present invention was reduced to 21% or less by removal treatment, were all heated at room temperature. It had a compression rate of over 30% and a high restoration rate of over 86%. On the other hand, regarding elasticity at high temperatures, the compression restoring force decreases by only about 30% after 150 repeated compressions, and the sheet shape of the present invention has flexibility, such as being able to be rolled into rolls with a radius of 1 to 5 cm. The material had excellent elasticity and flexibility. Furthermore, the sheet-like material of the present invention already begins to expand at a low temperature of about 130° C., demonstrating the effect of the low binder content. In addition, the sheet materials of Examples 2, 3, and 4 using unexpanded vermiculite treated with an aqueous sodium acetate solution had extremely high expansion rates. As mentioned above, the sheet-like material of the present invention has excellent elasticity from room temperature to high temperature, which has not been seen in conventional materials of this type, as can be seen from the examples, due to the combination of a small amount of binder and ceramic fibers with few shots. It is a new material that has properties such as strength, flexibility, and expandability at low temperatures, and is expected to have a wide range of uses as various sealing materials and packing materials.
Claims (1)
結合剤と有機結合剤の比が1/2〜1/10からなる結
合剤0.5〜3.5重量%、残部がシヨツト含有率30%
以下のセラミツク繊維からなることを特徴とする
耐熱弾性シート状物。 2 前記未膨張バーミキユライトの粒径は、0.1
〜2.83mmの範囲内にあることを特徴とする特許請
求の範囲第1項に記載のシート状物。 3 前記セラミツク繊維は、主としてシリカとア
ルミナを電気溶融し、その細流を高圧の空気また
は水蒸気によつて吹き飛ばしてなる結晶化温度が
850℃以上の繊維であることを特徴とする特許請
求の範囲第1項または第2項のいずれかに記載の
シート状物。 4 未膨張バーミキユライト40〜83重量%、無機
結合剤と有機結合剤の比が1/2〜1/10からなる結
合剤0.5〜3.5重量%、残部がシヨツト含有率30%
以下のセラミツク繊維からなり、ASTM F−36
−79試験に基づき2インチ平方のアンビルを使い
12.5Kgの荷重下で試験した時30%以上の圧縮と85
%以上の回復をすることを特徴とする特許請求の
範囲第1項ないし第3項のいずれか1つに記載の
シート状物。 5 未膨張バーミキユライト40〜83重量%、無機
結合剤と有機結合剤の比が1/2〜1/10からなる結
合剤0.5〜3.5重量%、残部実質的にセラミツク繊
維からなるシート状物の片面または両面に有機高
分子フイルムを貼着してなり、ASTM F−36−
79試験に基づき2インチ平方のアンビルを使い
12.5Kgの荷重下で試験した時30%以上の圧縮と85
%以上の回復をすることを特徴とする特許請求の
範囲第1項ないし第3項のいずれか1つに記載の
シート状物。 6 未膨張バーミキユライト40〜83重量%、無機
結合剤と有機結合剤の比が1/2〜1/10からなる結
合剤0.5〜3.5重量%、残部がシヨツト含有率30%
以下のセラミツク繊維からなるシート状物であつ
て、その全面が有機高分子フイルムで密封されて
なることを特徴とする耐熱弾性シート状物。 7 前記未膨張バーミキユライトの粒径は、0.1
〜2.83mmの範囲内にあることを特徴とする特許請
求の範囲第6項に記載のシート状物。 8 前記セラミツク繊維は、主としてシリカとア
ルミナを電気溶融し、その細流を高圧の空気また
は水蒸気によつて吹き飛ばしてなる結晶化温度が
850℃以上の繊維であることを特徴とする特許請
求の範囲第6項または第7項のいずれかに記載の
シート状物。 9 前記有機高分子フイルムは、その重量が前記
シート状物の重量の0.5重量%以下であることを
特徴とする特許請求の範囲第6項ないし第8項の
いずれか1つの記載のシート状物。 10 未膨張バーミキユライト40〜83重量%、無
機結合剤と有機結合剤の比が1/2〜1/10からなる
結合剤0.5〜3.5重量%、残部実質的にセラミツク
繊維からなるシート状物の全面を有機高分子フイ
ルムで密封してなり、ASTM F−3679試験に基
づき2インチ平方のアンビルを使い12.5Kgの荷重
下で試験した時30%以上の圧縮と85%以上の回復
をすることを特徴とする特許請求の範囲第6項な
いし第9項のいずれか1つに記載のシート状物。[Scope of Claims] 1. 40 to 83% by weight of unexpanded vermiculite, 0.5 to 3.5% by weight of a binder with a ratio of inorganic binder to organic binder of 1/2 to 1/10, and the remainder being shot content. 30%
A heat-resistant elastic sheet material comprising the following ceramic fibers. 2 The particle size of the unexpanded vermiculite is 0.1
The sheet-like article according to claim 1, characterized in that the thickness is within the range of ~2.83 mm. 3. The ceramic fibers are produced by electrically melting silica and alumina, and blowing the resulting stream with high-pressure air or water vapor.
The sheet-like article according to claim 1 or 2, which is a fiber having a temperature of 850°C or higher. 4 40 to 83% by weight of unexpanded vermiculite, 0.5 to 3.5% by weight of a binder with a ratio of inorganic binder to organic binder of 1/2 to 1/10, the remainder being shot content 30%
Made of the following ceramic fibers, ASTM F-36
-Using a 2 inch square anvil based on the 79 test.
Compression of over 30% and 85 when tested under a load of 12.5Kg
The sheet-like material according to any one of claims 1 to 3, wherein the sheet-like material has a recovery rate of % or more. 5. A sheet-like material consisting of 40 to 83% by weight of unexpanded vermiculite, 0.5 to 3.5% by weight of a binder with a ratio of inorganic binder to organic binder of 1/2 to 1/10, and the remainder substantially consisting of ceramic fibers. An organic polymer film is attached to one or both sides of the
Based on 79 tests using a 2 inch square anvil.
Compression of over 30% and 85 when tested under a load of 12.5Kg
The sheet-like material according to any one of claims 1 to 3, wherein the sheet-like material has a recovery rate of % or more. 6 40 to 83% by weight of unexpanded vermiculite, 0.5 to 3.5% by weight of a binder with a ratio of inorganic binder to organic binder of 1/2 to 1/10, the remainder being shot content 30%
1. A heat-resistant elastic sheet-like material comprising the following ceramic fibers, the entire surface of which is sealed with an organic polymer film. 7 The particle size of the unexpanded vermiculite is 0.1
The sheet-like article according to claim 6, characterized in that the thickness is within the range of ~2.83 mm. 8 The ceramic fibers are produced by electrically melting mainly silica and alumina, and blowing out the trickle with high-pressure air or water vapor.
The sheet-like article according to claim 6 or 7, which is a fiber having a temperature of 850°C or higher. 9. The sheet-like article according to any one of claims 6 to 8, wherein the weight of the organic polymer film is 0.5% by weight or less of the weight of the sheet-like article. . 10 A sheet-like material consisting of 40 to 83% by weight of unexpanded vermiculite, 0.5 to 3.5% by weight of a binder with a ratio of inorganic binder to organic binder of 1/2 to 1/10, and the remainder substantially consisting of ceramic fibers. The entire surface is sealed with an organic polymer film, and when tested under a load of 12.5 kg using a 2-inch square anvil based on the ASTM F-3679 test, it must compress by more than 30% and recover by more than 85%. A sheet-like article according to any one of claims 6 to 9, characterized in that:
Priority Applications (1)
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---|---|---|---|
JP58105745A JPS59230737A (en) | 1983-06-15 | 1983-06-15 | Elastic heat resisting sheet-shaped article |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58105745A JPS59230737A (en) | 1983-06-15 | 1983-06-15 | Elastic heat resisting sheet-shaped article |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59230737A JPS59230737A (en) | 1984-12-25 |
JPH0541586B2 true JPH0541586B2 (en) | 1993-06-23 |
Family
ID=14415792
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JP58105745A Granted JPS59230737A (en) | 1983-06-15 | 1983-06-15 | Elastic heat resisting sheet-shaped article |
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JP (1) | JPS59230737A (en) |
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KR100854409B1 (en) * | 2007-11-06 | 2008-08-26 | (주)정진브이앤피 | Artificial stone comprising vermiculite |
JP5971894B2 (en) | 2011-01-31 | 2016-08-17 | スリーエム イノベイティブ プロパティズ カンパニー | Contamination control element holding material, manufacturing method thereof and contamination control apparatus |
KR20200115048A (en) * | 2019-03-25 | 2020-10-07 | 더 프록터 앤드 갬블 캄파니 | Multi-layer soluble solid article and method for manufacturing same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430218A (en) * | 1977-08-08 | 1979-03-06 | Minnesota Mining & Mfg | Flexible and expandable sheet material |
JPS5692155A (en) * | 1979-11-28 | 1981-07-25 | Minnesota Mining & Mfg | Flexible intumescent sheet |
JPS5895636A (en) * | 1981-11-30 | 1983-06-07 | イビデン株式会社 | Heat-resistant elastic sheet and manufacture |
-
1983
- 1983-06-15 JP JP58105745A patent/JPS59230737A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430218A (en) * | 1977-08-08 | 1979-03-06 | Minnesota Mining & Mfg | Flexible and expandable sheet material |
JPS5692155A (en) * | 1979-11-28 | 1981-07-25 | Minnesota Mining & Mfg | Flexible intumescent sheet |
JPS5895636A (en) * | 1981-11-30 | 1983-06-07 | イビデン株式会社 | Heat-resistant elastic sheet and manufacture |
Also Published As
Publication number | Publication date |
---|---|
JPS59230737A (en) | 1984-12-25 |
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