JP5154738B2 - Heat resistant ceramic sheet - Google Patents
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- JP5154738B2 JP5154738B2 JP2004217426A JP2004217426A JP5154738B2 JP 5154738 B2 JP5154738 B2 JP 5154738B2 JP 2004217426 A JP2004217426 A JP 2004217426A JP 2004217426 A JP2004217426 A JP 2004217426A JP 5154738 B2 JP5154738 B2 JP 5154738B2
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- 239000000919 ceramic Substances 0.000 title claims description 135
- 239000000835 fiber Substances 0.000 claims description 143
- 239000003365 glass fiber Substances 0.000 claims description 95
- 239000011230 binding agent Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 32
- 229910010272 inorganic material Inorganic materials 0.000 claims description 31
- 239000011147 inorganic material Substances 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004113 Sepiolite Substances 0.000 claims description 10
- 229910052624 sepiolite Inorganic materials 0.000 claims description 10
- 235000019355 sepiolite Nutrition 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 239000002734 clay mineral Substances 0.000 claims description 4
- 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 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 239000011214 refractory ceramic Substances 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 description 29
- 239000011521 glass Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 8
- 229920003043 Cellulose fiber Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、断熱材、耐熱濾過材、耐熱絶縁材、耐熱シール材、耐熱パッキン材、耐熱緩衝材、耐熱クッション材、耐熱触媒担持材等として使用される耐熱セラミックシート、特に、２００〜１６００℃の任意の温度領域で使用し得る汎用性の高い耐熱セラミックシートに関する。 The present invention relates to a heat-resistant ceramic sheet used as a heat insulating material, heat-resistant filter material, heat-resistant insulating material, heat-resistant sealing material, heat-resistant packing material, heat-resistant buffer material, heat-resistant cushion material, heat-resistant catalyst support material, etc., particularly 200 to 1600 ° C. It relates to a heat-resistant ceramic sheet with high versatility that can be used in any temperature range.
従来、耐熱セラミックシートとしては、シリカ−アルミナ繊維、アルミナ繊維、シリカ−アルミナ−ジルコニア繊維等のセラミック繊維に、少量の有機バインダーを添加して湿式抄造されたものが主流として使用されている。
耐熱用途として用いられる耐熱セラミックシートの使用温度は通常６００〜１６００℃であるが、前記有機バインダーの耐熱温度はせいぜい４５０℃までである。つまり、前記耐熱セラミックシートは、有機バインダーの分解が始まる２００〜３００℃近辺の温度に達すると、機械的強度が大きく低下し、４００℃以上では、殆どの有機バインダーが分解又は焼失し、有機バインダーによるバインダー効果は殆どなくなり、耐熱セラミックシートの実質的な構成物は前記セラミック繊維のみとなる。一般的なセラミック繊維（例えば、シリカ−アルミナ繊維等）の繊維径は３μｍ程度であるため、セラミック繊維のみとなった耐熱セラミックシートでは、繊維の絡みによる強度確保が殆ど期待できず、ハンドリング性がなくなり、綿状に崩れてしまう。
Conventionally, as a heat-resistant ceramic sheet, a wet-paper made by adding a small amount of an organic binder to a ceramic fiber such as silica-alumina fiber, alumina fiber, silica-alumina-zirconia fiber or the like is mainly used.
The use temperature of the heat-resistant ceramic sheet used for heat-resistant applications is usually 600 to 1600 ° C, but the heat-resistant temperature of the organic binder is 450 ° C at most. That is, when the temperature of the heat-resistant ceramic sheet reaches a temperature in the vicinity of 200 to 300 ° C. where the decomposition of the organic binder starts, the mechanical strength is greatly reduced. Above 400 ° C., most of the organic binder is decomposed or burned out. The binder effect is almost eliminated, and the substantial constituent of the heat-resistant ceramic sheet is only the ceramic fiber. Since the diameter of a general ceramic fiber (for example, silica-alumina fiber) is about 3 μm, a heat-resistant ceramic sheet composed of only ceramic fibers can hardly be expected to ensure strength due to the entanglement of the fibers, and has handling properties. It disappears and collapses into a cotton-like shape.
そこで、特許文献１には、セラミック繊維と、６００〜８００℃で軟化する中軟化ガラス繊維、８００℃以上で軟化する高軟化ガラス繊維の２種類のガラス繊維とを混合使用するか、あるいは、セラミック繊維と、３５０〜６００℃で軟化する低軟化ガラス繊維、６００〜８００℃で軟化する中軟化ガラス繊維、８００℃以上で軟化する高軟化ガラス繊維の３種類のガラス繊維とを混合使用するようにし、有機バインダーが分解又は焼失した後も、一定レベルの機械的強度を維持できるようにした耐熱セラミックシートが提案されている。
この耐熱セラミックシートでは、前記ガラス繊維として繊維径１μｍ以下の微細径ガラス繊維を少なくともその一部に用いるようにしており、前記中軟化ガラス繊維と前記高軟化ガラス繊維の２種類のガラス繊維を混合使用した場合には、有機バインダーによるバインダー効果が失われ始める２００℃近辺から、中軟化ガラス繊維のバインダー効果が発揮され始める６００℃近辺までの温度領域において、前記微細径ガラス繊維の絡み効果により一定レベルの機械的強度が維持される。また、前記低軟化ガラス繊維と前記中軟化ガラス繊維と前記高軟化ガラス繊維の３種類のガラス繊維を混合使用した場合では、前記微細径ガラス繊維の絡み効果に加え、前記低軟化ガラス繊維の軟化によるバインダー効果が発揮され、２００〜６００℃近辺の温度領域における機械的強度が更に高められる。
In this heat-resistant ceramic sheet, a fine glass fiber having a fiber diameter of 1 μm or less is used as at least a part of the glass fiber, and the two kinds of glass fibers of the medium softened glass fiber and the highly softened glass fiber are mixed. When used, in a temperature range from around 200 ° C. at which the binder effect due to the organic binder begins to be lost to around 600 ° C. at which the binder effect of the medium-softened glass fiber begins to be exhibited, it is constant due to the entanglement effect of the fine glass fiber. A level of mechanical strength is maintained. In addition, in the case of mixing and using three types of glass fibers, the low-softening glass fiber, the medium-softening glass fiber, and the high-softening glass fiber, in addition to the entanglement effect of the fine-diameter glass fiber, the softening of the low-softening glass fiber The binder effect is exhibited, and the mechanical strength in the temperature range near 200 to 600 ° C. is further increased.
しかしながら、前記特許文献１の前記中軟化ガラス繊維と前記高軟化ガラス繊維の２種類のガラス繊維を混合使用した耐熱セラミックシートでは、有機バインダーによるバインダー効果が失われる２００〜６００℃近辺の温度領域においても、微細径ガラス繊維の絡み効果により一定レベルの機械的強度が維持できるとされているが、耐熱セラミックシートの全繊維材料中に５〜５０質量％程度しか含まれない微細径ガラス繊維の絡み効果だけでは、実際に維持できる機械的強度のレベルは低い。この微細径ガラス繊維の絡み効果だけでより高い機械的強度を確保しようとすると、ガラス繊維の配合量をできるだけ多くしなければならず、セラミック繊維の配合量が減り、耐熱セラミックシートの耐熱性の低下を招く。したがって、耐熱セラミックシートの耐熱性を落とすことなく２００〜６００℃近辺での高い機械的強度を確保することはできない。
また、前記特許文献１の前記低軟化ガラス繊維と前記中軟化ガラス繊維と前記高軟化ガラス繊維の３種類のガラス繊維を混合使用した耐熱セラミックシートでは、前記微細径ガラス繊維の絡み効果に加え、前記低軟化ガラス繊維の軟化によるバインダー効果が発揮され、同じく２００〜６００℃近辺の温度領域での機械的強度はある程度高いレベルが確保されるものの、低軟化ガラス繊維を使用したことにより副作用的にもたらされる共融作用により、セラミック繊維の融点が低下し、耐熱セラミックシートの耐熱性が大きく低下する（例えば、６００℃以上、特に８００℃以上の温度で、面収縮率及び線収縮率が大きくなり、反り等の変形を生じる）。しかも、前記低軟化ガラス繊維の軟化によるバインダー効果が発揮され始めるのは３５０℃以上の温度領域においてであり、少なくとも２００〜３５０℃近辺の温度領域においては、高いレベルの機械的強度を確保することはできない。
However, in the heat-resistant ceramic sheet in which the two types of glass fibers of the medium-softened glass fiber and the highly-softened glass fiber of Patent Document 1 are mixed and used, in a temperature region around 200 to 600 ° C. where the binder effect due to the organic binder is lost. Although it is said that a certain level of mechanical strength can be maintained due to the entanglement effect of the fine diameter glass fiber, the entanglement of the fine diameter glass fiber that is contained only in about 5 to 50% by mass in the total fiber material of the heat-resistant ceramic sheet. By effect alone, the level of mechanical strength that can actually be maintained is low. In order to secure higher mechanical strength only by the entanglement effect of this fine glass fiber, the glass fiber content must be increased as much as possible, the ceramic fiber content is reduced, and the heat resistance of the heat-resistant ceramic sheet is reduced. Incurs a decline. Therefore, high mechanical strength in the vicinity of 200 to 600 ° C. cannot be ensured without reducing the heat resistance of the heat-resistant ceramic sheet.
In addition, in the heat-resistant ceramic sheet using the three kinds of glass fibers of the low-softening glass fiber, the medium-softening glass fiber, and the high-softening glass fiber in Patent Document 1, in addition to the entanglement effect of the fine-diameter glass fiber, Although the binder effect due to the softening of the low-softening glass fiber is exhibited and the mechanical strength in the temperature region around 200 to 600 ° C. is also secured to a certain level, it is side effects by using the low-softening glass fiber. The resulting eutectic action lowers the melting point of the ceramic fiber and greatly reduces the heat resistance of the heat-resistant ceramic sheet (for example, the surface shrinkage rate and the linear shrinkage rate increase at a temperature of 600 ° C. or higher, particularly 800 ° C. or higher). , Causing deformation such as warping). Moreover, the binder effect due to the softening of the low-softening glass fiber begins to be exerted in a temperature range of 350 ° C. or higher, and a high level of mechanical strength is ensured in a temperature range of at least 200 to 350 ° C. I can't.
一方、従来の耐熱セラミックシートは、前述の通り、使用温度が６００〜１６００℃であるごく限られた特殊用途での使用が一般的であったが、セラミックシートの持つ優れたクッション性、柔軟性、耐候性、耐薬品性、耐熱性等により、近年では、使用温度が２００〜６００℃である一般用途にも使用されるようになってきている。これに伴い、耐熱セラミックシートの用途も耐熱クッション材、耐熱緩衝材、耐熱パッキン材等と多岐に亘ってきており、耐熱セラミックシートには、２００〜６００℃の温度領域における、加圧や衝撃等、更には、繰り返しの加圧や衝撃等にも耐え得る高い機械的強度と良好な形状保持性（繊維の脱落の生じ難さも含む）が求められるようになっている。
そこで、本発明は、このような従来の問題点に鑑み、セラミック繊維をバインダーで結着してなる耐熱セラミックシートにおいて、耐熱セラミックシートの耐熱性を落とすことなく２００〜６００℃近辺での高い機械的強度を確保し、２００〜１６００℃の任意の温度領域を使用温度とした断熱材、耐熱濾過材、耐熱絶縁材、耐熱シール材、耐熱パッキン材、耐熱緩衝材、耐熱クッション材、耐熱触媒担持材等として好適に使用し得る汎用性の高い耐熱セラミックシートを提供することを目的とする。
On the other hand, as described above, the conventional heat-resistant ceramic sheet is generally used for a very limited special purpose in which the operating temperature is 600 to 1600 ° C. However, the excellent cushioning property and flexibility of the ceramic sheet are common. In recent years, due to weather resistance, chemical resistance, heat resistance, and the like, it has come to be used in general applications where the operating temperature is 200 to 600 ° C. Along with this, the use of heat-resistant ceramic sheets has been wide-ranging such as heat-resistant cushioning materials, heat-resistant cushioning materials, heat-resistant packing materials, etc., and heat-resistant ceramic sheets have pressure, impact, etc. in a temperature range of 200 to 600 ° C. Furthermore, high mechanical strength that can withstand repeated pressurization and impact, and good shape retention (including the difficulty of fiber detachment) are required.
Therefore, in view of such conventional problems, the present invention is a heat resistant ceramic sheet formed by binding ceramic fibers with a binder, and a high machine around 200 to 600 ° C. without reducing the heat resistance of the heat resistant ceramic sheet. Heat insulation, heat-resistant filter material, heat-resistant insulation material, heat-resistant seal material, heat-resistant packing material, heat-resistant buffer material, heat-resistant cushioning material, heat-resistant catalyst support, ensuring sufficient strength and using any temperature range of 200-1600 ° C An object of the present invention is to provide a highly versatile heat-resistant ceramic sheet that can be suitably used as a material.
本発明の耐熱セラミックシートは、前記目的を達成するべく、請求項１に記載の通り、セラミック繊維６０〜９５質量％と、軟化点が６００〜８００℃で平均繊維径１μｍ以下のガラス短繊維２〜８質量％と、軟化点が６００℃以上で平均繊維径５〜２０μｍのガラス長繊維０〜１０質量％と、乾燥固結性無機物３〜２０質量％とを少なくとも含み、軟化点が６００℃未満のガラス繊維を含まないこれら材料が有機バインダーで結着された、湿式法によって形成される密度０．３０ｇ／ｃｍ３以下のシートであり、前記セラミック繊維、前記ガラス短繊維、前記ガラス長繊維、前記乾燥固結性無機物を含む材料を水中で分散・混合し、高分子凝集剤を添加し、前記セラミック繊維表面に前記乾燥固結性無機物を吸着・担持して得た抄紙原料液を用いて湿式抄造してなるものであることを特徴とする。
また、請求項２記載の耐熱セラミックシートは、請求項１記載の耐熱セラミックシートにおいて、前記乾燥固結性無機物が焼結性を有することを特徴とする。
また、請求項３記載の耐熱セラミックシートは、請求項１又は２記載の耐熱セラミックシートにおいて、前記乾燥固結性無機物が、セピオライト、アタパルジャイトから選択される鉱物微細繊維、シリカゾル、アルミナゾル、チタニアゾル、ジルコニアゾルから選択されるゾル状物又はゲル状物、シリカフレーク、シリカ−チタニアフレークから選択される表面に多数の水酸基を有する鱗片状物、カオリン、クレー、モンモリロナイトから選択される粘土鉱物の中から選択された少なくとも１種であることを特徴とする。
また、請求項４記載の耐熱セラミックシートは、請求項３記載の耐熱セラミックシートにおいて、前記乾燥固結性無機物が、セピオライト、アタパルジャイトから選択される鉱物微細繊維であることを特徴とする。
また、請求項５記載の耐熱セラミックシートは、請求項１乃至４の何れか１項に記載の耐熱セラミックシートにおいて、前記有機バインダーの配合量が、前記セラミック繊維と前記ガラス短繊維と前記ガラス長繊維と前記乾燥固結性無機物を含む無機材料の合計配合量に対して０．３〜５外質量％であることを特徴とする。
In order to achieve the above object, the heat-resistant ceramic sheet of the present invention is composed of 60 to 95% by mass of ceramic fibers and short glass fibers 2 having a softening point of 600 to 800 ° C. and an average fiber diameter of 1 μm or less as described in claim 1. -8 % by mass, a softening point of 600 ° C. or higher and an average fiber diameter of 5-20 μm long glass fibers of 0-10% by mass and a dry solidifying inorganic substance of 3-20% by mass, with a softening point of 600 ° C. A sheet having a density of 0.30 g / cm 3 or less formed by a wet method in which these materials not containing less glass fibers are bound with an organic binder, and the ceramic fibers, the glass short fibers, and the glass long fibers. A papermaking raw material liquid obtained by dispersing and mixing the material containing the dry-solidifying inorganic substance in water, adding a polymer flocculant, and adsorbing and supporting the dry-solidifying inorganic substance on the ceramic fiber surface Characterized in that it is made of by wet papermaking using.
The heat-resistant ceramic sheet according to claim 2 is characterized in that, in the heat-resistant ceramic sheet according to claim 1, the dry consolidated inorganic substance has sinterability.
The heat-resistant ceramic sheet according to claim 3 is the heat-resistant ceramic sheet according to claim 1 or 2, wherein the dry solidifying inorganic material is selected from mineral fine fibers selected from sepiolite and attapulgite, silica sol, alumina sol, titania sol, zirconia. Selected from sol or gel selected from sol, silica flakes, scales having many hydroxyl groups on the surface selected from silica-titania flakes, kaolin, clay, clay mineral selected from montmorillonite It is characterized by being at least one kind.
The heat-resistant ceramic sheet according to claim 4, wherein, in the heat-resistant ceramic sheet according to claim 3, wherein the drying caking inorganic material, sepiolite, you being a mineral fine fibers selected from attapulgite.
Also, temperature ceramic sheet according to claim 5, wherein, in the heat-resistant ceramic sheet according to any one of claims 1 to 4, the amount of the organic binder, the said ceramic fiber and said short glass fibers Glass It is 0.3-5 mass% with respect to the total compounding quantity of the inorganic material containing a long fiber and the said dry-consolidating inorganic substance, It is characterized by the above-mentioned.
本発明の耐熱セラミックシートは、セラミック繊維６０〜９５質量％と、軟化点が６００〜８００℃で平均繊維径１μｍ以下のガラス短繊維２〜８質量％と、軟化点が６００℃以上で平均繊維径５〜２０μｍのガラス長繊維０〜１０質量％と、乾燥固結性無機物３〜２０質量％とを少なくとも含み、軟化点が６００℃未満のガラス繊維を含まないこれら材料が有機バインダーで結着された、湿式法によって形成される密度０．３０ｇ／ｃｍ3以下のシートとして構成したため、耐熱セラミックシート本来の耐熱性を維持しつつ、従来の耐熱セラミックシートでは不十分とされていた２００〜６００℃の温度領域での機械的強度を高められたことで、常温〜１６００℃に亘る全温度領域で高い機械的強度を確保できるようになり、２００〜１６００℃の任意の温度領域を使用温度とした断熱材、耐熱濾過材、耐熱絶縁材、耐熱シール材、耐熱パッキン材、耐熱緩衝材、耐熱クッション材、耐熱触媒担持材等として好適に使用し得る汎用性の高い耐熱セラミックシートとすることができる。 The heat-resistant ceramic sheet of the present invention comprises 60 to 95% by mass of ceramic fibers, 2 to 8% by mass of short glass fibers having a softening point of 600 to 800 ° C. and an average fiber diameter of 1 μm or less, and an average fiber having a softening point of 600 ° C. or more. These materials that contain at least 0 to 10% by weight of long glass fibers having a diameter of 5 to 20 μm and 3 to 20% by weight of dry-solidifying inorganic substances and that do not contain glass fibers having a softening point of less than 600 ° C. are bound with an organic binder. 200-600, which is considered to be insufficient with conventional heat-resistant ceramic sheets, while maintaining the original heat resistance of the heat-resistant ceramic sheet because it is configured as a sheet having a density of 0.30 g / cm 3 or less formed by a wet method. By increasing the mechanical strength in the temperature range of ° C., it becomes possible to ensure high mechanical strength in the entire temperature range from room temperature to 1600 ° C. General-purpose material that can be suitably used as a heat insulating material, heat-resistant filter material, heat-resistant insulating material, heat-resistant sealing material, heat-resistant packing material, heat-resistant cushioning material, heat-resistant cushioning material, heat-resistant catalyst support material, etc. with an arbitrary temperature range of ℃ Highly heat resistant ceramic sheet.
本発明の耐熱セラミックシートは、セラミック繊維６０〜９５質量％と、軟化点が６００〜８００℃で平均繊維径１μｍ以下のガラス短繊維２〜８質量％と、軟化点が６００℃以上で平均繊維径５〜２０μｍのガラス長繊維０〜１０質量％と、乾燥固結性無機物３〜２０質量％とを少なくとも含み、軟化点が６００℃未満のガラス繊維を含まないこれら材料が有機バインダーで結着された、湿式法によって形成される密度０．３０ｇ／ｃｍ3以下のシートであり、湿式抄造により形成されるシートであることが好ましい。 The heat-resistant ceramic sheet of the present invention comprises 60 to 95% by mass of ceramic fibers, 2 to 8 % by mass of short glass fibers having a softening point of 600 to 800 ° C. and an average fiber diameter of 1 μm or less, and an average fiber having a softening point of 600 ° C. or more. These materials that contain at least 0 to 10% by weight of long glass fibers having a diameter of 5 to 20 μm and 3 to 20% by weight of dry-solidifying inorganic substances and that do not contain glass fibers having a softening point of less than 600 ° C. are bound with an organic binder. The sheet is formed by a wet method and has a density of 0.30 g / cm 3 or less, and is preferably a sheet formed by wet papermaking.
前記乾燥固結性無機物は、乾燥固結性と共に焼結性を有するものであることが好ましい。尚、本願において、乾燥固結性とは、水で練ることによって可塑性を生じ乾燥によって適度な強度を有して固まる性質、あるいは、一旦水に分散させた後にその分散液を乾燥させるとそれ自身が固結する性質のことを指す。
このような乾燥固結性無機物としては、セピオライト、アタパルジャイト等の鉱物微細繊維、シリカゾル、アルミナゾル、チタニアゾル、ジルコニアゾル等からなるゾル状物又はゲル状物、シリカフレーク、シリカ−チタニアフレーク等の表面に多数の水酸基を有する鱗片状物、カオリン、クレー、モンモリロナイト等の粘土鉱物が挙げられる。これらの乾燥固結性無機物は、湿式法によってシート形成されると、無機物表面に存在する水酸基による水素結合の作用によりバインダー効果が発揮され、更に、加熱により、脱水縮合反応や焼結反応を起こし強固に固結化していく特性を有する。上記した乾燥固結性無機物の中から、実際の耐熱セラミックシートの用途や求められる機能・特性等に合わせて、適切な１種又は２種以上を選択して使用することができる。特に、少量の添加で高いバインダー効果が得られ、湿式抄造時の歩留りが良好である点から、セピオライト、アタパルジャイト等の鉱物微細繊維の使用が好ましい。
このような乾燥固結性無機物を配合して湿式法によりシート形成された耐熱セラミックシートは、常温において、乾燥固結性無機物が前記セラミック繊維等の繊維材料を結着状態に固定しているため、常温〜６００℃程度の温度領域において、耐熱セラミックシートの機械的強度の向上に大きく寄与する。また、前記乾燥固結性無機物が焼結性を有する場合、その焼結温度以上にて前記耐熱セラミックシートが使用される場合においては、その焼結温度から使用温度上限までの温度領域において、乾燥固結性無機物の焼結によるバインダー効果により、機械的強度が更に高まる。
尚、前記特許文献１に記載された従来の３５０〜６００℃で軟化する低軟化ガラス繊維を配合して３５０〜６００℃の温度領域での機械的強度向上を図った耐熱セラミックシートでは、低軟化ガラス繊維の添加による共融作用によりセラミック繊維の融点が低下し、耐熱セラミックシートの耐熱性が大きく低下するという問題があったが、本発明においては、同様に、有機バインダーのバインダー効果が失われ始める２００℃近辺からガラス短繊維の軟化によるバインダー効果が発揮され始める６００℃近辺までの温度領域における機械的強度確保の手段として、前記乾燥固結性無機物を配合しているが、前記乾燥固結性無機物は１０００℃以上の耐熱性を有しており、同様の問題は生じない。
It is preferable that the dry-consolidating inorganic material has sinterability as well as dry-consolidating property. In the present application, dry caking property means the property that plasticity is produced by kneading with water and solidifies with an appropriate strength by drying, or once the dispersion is dried after being dispersed in water. Refers to the nature of solidification.
Examples of such dry-consolidating inorganic substances include mineral fine fibers such as sepiolite and attapulgite, sol-like or gel-like substances composed of silica sol, alumina sol, titania sol, zirconia sol, silica flakes, silica-titania flakes, and the like. Examples thereof include scale minerals having a large number of hydroxyl groups, clay minerals such as kaolin, clay and montmorillonite. When these dry-solidified inorganic materials are formed into a sheet by a wet method, the binder effect is exerted by the action of hydrogen bonding by hydroxyl groups present on the surface of the inorganic material, and further, heating causes dehydration condensation reaction and sintering reaction. It has the property of solidifying firmly. From the above-mentioned dry-solidifying inorganic material, one or more appropriate types can be selected and used according to the actual use of the heat-resistant ceramic sheet and the required functions and characteristics. In particular, the use of fine mineral fibers such as sepiolite and attapulgite is preferred because a high binder effect can be obtained with a small amount of addition and the yield during wet papermaking is good.
A heat-resistant ceramic sheet formed by a wet method by blending such a dry-solidifying inorganic substance has a dry-solidifying inorganic substance fixing the fiber material such as the ceramic fiber in a bound state at room temperature. In the temperature range from room temperature to about 600 ° C., it greatly contributes to improvement of the mechanical strength of the heat-resistant ceramic sheet. Further, when the dry-consolidating inorganic material has sinterability, in the case where the heat-resistant ceramic sheet is used at a temperature equal to or higher than the sintering temperature, drying is performed in a temperature range from the sintering temperature to the upper limit of the use temperature. The mechanical strength is further increased by the binder effect caused by the sintering of the caking inorganic substance.
The heat resistant ceramic sheet described in the above-mentioned Patent Document 1 and blended with the low-softening glass fiber that softens at 350 to 600 ° C. to improve the mechanical strength in the temperature range of 350 to 600 ° C. There was a problem that the melting point of the ceramic fiber was lowered due to the eutectic action due to the addition of the glass fiber, and the heat resistance of the heat-resistant ceramic sheet was greatly lowered, but in the present invention, the binder effect of the organic binder was similarly lost. As a means for ensuring mechanical strength in the temperature range from around 200 ° C. to around 600 ° C. where the binder effect due to softening of short glass fibers begins to be exhibited, the dry-solidified inorganic material is blended. The inorganic substance has a heat resistance of 1000 ° C. or higher, and the same problem does not occur.
前記セラミック繊維としては、結晶質繊維のアルミナ繊維（平均繊維径３〜４μｍ程度、耐熱温度１６００℃程度）や、非晶質繊維のシリカ繊維（平均繊維径０．５〜４μｍ程度、耐熱温度１０００℃程度）、シリカ−アルミナ繊維（平均繊維径３〜４μｍ程度、耐熱温度１２００℃程度）、シリカ−アルミナ−ジルコニア繊維（平均繊維径３〜４μｍ程度、耐熱温度１４００℃程度）等が使用できる。これらのセラミック繊維の中から、耐熱セラミックシートの実際の用途に合わせ、その用途に求められる機能や特性等に応じて、適宜適切なセラミック繊維を選択して使用すればよい。セラミック繊維としては最も一般的なシリカ−アルミナ繊維は、比較的安価で入手し易い点で有利である。シリカ繊維は、１μｍ以下の微細径繊維を使用できる点で有利であるが、他のセラミック繊維に比べて非常に高価であり、不純物を嫌う耐熱触媒担持材等の特殊用途以外には通常適さない。 Examples of the ceramic fibers include crystalline fibers of alumina fibers (average fiber diameter of about 3 to 4 μm, heat resistance temperature of about 1600 ° C.) and amorphous fibers of silica fibers (average fiber diameter of about 0.5 to 4 μm, heat resistance temperature of 1000). ), Silica-alumina fiber (average fiber diameter of about 3 to 4 μm, heat resistance temperature of about 1200 ° C.), silica-alumina-zirconia fiber (average fiber diameter of about 3 to 4 μm, heat resistance temperature of about 1400 ° C.), and the like can be used. From these ceramic fibers, an appropriate ceramic fiber may be appropriately selected and used in accordance with the function and characteristics required for the application in accordance with the actual application of the heat-resistant ceramic sheet. Silica-alumina fiber, which is the most common ceramic fiber, is advantageous in that it is relatively inexpensive and easily available. Silica fibers are advantageous in that fine fibers having a diameter of 1 μm or less can be used, but they are very expensive compared to other ceramic fibers and are usually not suitable except for special uses such as heat-resistant catalyst support materials that do not like impurities. .
前記ガラス短繊維としては、前述の通り、軟化点が６００〜８００℃で、平均繊維径が１μｍ以下であるガラス短繊維を使用する。
前記ガラス短繊維として繊維径１μｍ以下の微細径ガラス短繊維を使用したことにより、有機バインダーによるバインダー効果が失われ始める２００℃近辺から、前記ガラス短繊維の軟化によるバインダー効果が発揮され始める前記ガラス短繊維の軟化点（６００〜８００℃）近辺までの温度領域において、前記ガラス短繊維の絡み効果により一定レベルの機械的強度が耐熱セラミックシートに付与される。繊維材料の配合により絡み効果が発現される条件としては、繊維径１μｍ以下の繊維が含まれていることが目安とされており、１μｍを超える繊維径の繊維のみからなる繊維材料では、絡み効果は発現されにくい。したがって、前記平均繊維径１μｍ以下の条件の範囲では、できるだけ平均繊維径の小さいガラス短繊維を使用し、使用する繊維材料の繊維径分布において、１μｍ以下となる繊維の比率がより高くなるようにすることが好ましい。このことから、前記ガラス短繊維の平均繊維径は０．８μｍ以下であることが好ましく、そのような繊維径分布を有したガラス短繊維材料を単独使用することが好ましい。
また、前記ガラス短繊維として軟化点が６００〜８００℃のガラス短繊維を使用したことにより、前記軟化点以上の温度領域において、前記ガラス短繊維の軟化によるバインダー効果が発揮されるので、６００℃以上の温度領域においては、前記乾燥固結性無機物によるバインダー効果と併せ、機械的強度が高められる。
尚、本発明の耐熱セラミックシートでは、前記ガラス短繊維として軟化点が６００℃以上のガラス短繊維を使用しているので、前記特許文献１に記載された従来の３５０〜６００℃で軟化する低軟化ガラス繊維を配合した耐熱セラミックシートのように、低軟化ガラス繊維の添加による共融作用によりセラミック繊維の融点が低下し、耐熱セラミックシートの耐熱性が大きく低下するという問題は生じず、耐熱セラミックシート本来の耐熱性が確保される。
As the short glass fiber, as described above, a short glass fiber having a softening point of 600 to 800 ° C. and an average fiber diameter of 1 μm or less is used.
By using a fine glass short fiber having a fiber diameter of 1 μm or less as the short glass fiber, the binder effect due to softening of the short glass fiber starts to be exhibited from around 200 ° C. at which the binder effect due to the organic binder starts to be lost. In a temperature range up to the softening point (600 to 800 ° C.) of the short fiber, a certain level of mechanical strength is imparted to the heat-resistant ceramic sheet by the entanglement effect of the short glass fiber. As a condition for the entanglement effect to be manifested by the blending of the fiber material, it is a standard that fibers having a fiber diameter of 1 μm or less are included. Is difficult to express. Therefore, within the range of the condition of the average fiber diameter of 1 μm or less, the short glass fiber having the smallest average fiber diameter is used, and the fiber diameter distribution of the fiber material to be used is higher in the ratio of fibers that are 1 μm or less. It is preferable to do. From this, the average fiber diameter of the short glass fibers is preferably 0.8 μm or less, and it is preferable to use a short glass fiber material having such a fiber diameter distribution alone.
Moreover, since the binder effect by softening of the said short glass fiber is exhibited in the temperature range more than the said softening point by using the short glass fiber whose softening point is 600-800 degreeC as said short glass fiber, 600 degreeC In the above temperature range, the mechanical strength is enhanced together with the binder effect by the dry-solidifying inorganic material.
In the heat-resistant ceramic sheet of the present invention, since the short glass fiber having a softening point of 600 ° C. or higher is used as the short glass fiber, the low temperature softening at 350 to 600 ° C. described in Patent Document 1 is used. As with heat-resistant ceramic sheets blended with softened glass fibers, the melting point of the ceramic fibers decreases due to the eutectic action caused by the addition of low-softened glass fibers, and the heat resistance of the heat-resistant ceramic sheets does not significantly decrease. The inherent heat resistance of the sheet is ensured.
前記耐熱セラミックシートには、前述の通り、軟化点が６００℃以上で、平均繊維径が５〜２０μｍであるガラス長繊維（ガラスチョップド繊維）を、必要に応じて添加することができる。
このようなガラス長繊維を添加することにより、耐熱セラミックシートの機械的強度、特に、引裂強度や耐折強度が更に高められるので、耐熱セラミックシートにこのような特性が求められる場合には好適である。
尚、前記ガラス短繊維の場合と同様、本発明の耐熱セラミックシートでは、前記ガラス長繊維として軟化点が６００℃以上のガラス長繊維を使用しているので、前記特許文献１に記載された従来の耐熱セラミックシートのような耐熱性低下の問題は生じず、耐熱セラミックシート本来の耐熱性が確保される。
As described above, a long glass fiber (glass chopped fiber) having a softening point of 600 ° C. or higher and an average fiber diameter of 5 to 20 μm can be added to the heat-resistant ceramic sheet as necessary.
By adding such long glass fibers, the mechanical strength of the heat-resistant ceramic sheet, in particular, the tear strength and folding strength, can be further increased. Therefore, it is suitable when such characteristics are required for the heat-resistant ceramic sheet. is there.
As in the case of the short glass fiber, the heat resistant ceramic sheet of the present invention uses a long glass fiber having a softening point of 600 ° C. or more as the long glass fiber. Thus, there is no problem of a decrease in heat resistance unlike the heat resistant ceramic sheet, and the original heat resistance of the heat resistant ceramic sheet is ensured.
前記有機バインダーとしては、アクリル樹脂エマルジョン、塩化ビニリデン樹脂エマルジョン、ポリエステル樹脂エマルジョン、ミクロフィブリル化セルロース等を使用することができるが、特に、少量の添加で高いバインダー効果が得られ、湿式抄造時の分散性及び歩留りが良好である点から、ミクロフィブリル化セルロース（微細セルロース繊維）の使用が好ましい。 As the organic binder, acrylic resin emulsion, vinylidene chloride resin emulsion, polyester resin emulsion, microfibrillated cellulose, and the like can be used. In particular, a high binder effect can be obtained with a small amount of addition, and dispersion during wet papermaking. From the viewpoint of good properties and yield, the use of microfibrillated cellulose (fine cellulose fiber) is preferred.
前記耐熱セラミックシートは、例えば、前記セラミック繊維６０〜９５質量％と、前記ガラス短繊維２〜８質量％と、前記ガラス長繊維０〜１０質量％と、前記乾燥固結性無機物３〜２０質量％と、これら無機材料の合計量１００質量％に対して０．３〜５外質量％の有機バインダーを添加し、水中で分散・混合して抄紙原料液を得、これを湿式抄造によりシート化し、加熱乾燥することによって得ることができる。
前記セラミック繊維の配合量は、耐熱セラミックシートの良好な耐熱性を確保するため、６０質量％以上の配合量とすることが必要であり、適宜、耐熱セラミックシートの用途、すなわち、耐熱セラミックシートに求められる耐熱性に応じて適切な配合量を選択すればよく、例えば、耐熱セラミックシートが１０００℃以上の耐熱性を必要とする場合には、８５質量％以上の配合量とすることが好ましい。尚、前記セラミック繊維の配合量が９５質量％を超える場合は、相対的に、耐熱セラミックシートのバインダーとして機能させる前記ガラス短繊維、前記乾燥固結性無機物、前記有機バインダーの配合量が少なくなり、耐熱セラミックシートの常温〜１６００℃の任意の温度領域における十分な機械的強度が得られなくなるため不適である。
また、前記ガラス短繊維の配合量は、耐熱セラミックシートの全体に均一分散状態に介在させ、前記した良好なバインダー効果を発揮させるため、２質量％以上の配合量とすることが必要であるが、２０質量％を超えると、相対的に、前記セラミック繊維の配合量が少なくなり、耐熱セラミックシートの十分な耐熱性が得られなくなるため不適である。尚、前記耐熱セラミックシートがより高い耐熱性、柔軟性、クッション性を必要とする場合は、前記ガラス短繊維の配合量は１５質量％以下、より好ましくは１０質量％以下とすることが好ましい。
また、前記ガラス長繊維は、耐熱セラミックシートがより高い引裂強度や耐折強度を必要とする場合に、必要に応じて適当量を配合することができるが、配合量が１０質量％を超えると、相対的に、前記セラミック繊維、前記ガラス短繊維、前記乾燥固結性無機物の配合量が少なくなるとともに、湿式抄造によりシート形成する場合に、抄紙原料液中での前記ガラス長繊維の均一分散が得られにくくなるため、不適である。
また、前記乾燥固結性無機物の配合量は、耐熱セラミックシートの全体に均一分散状態に介在させ、前記した良好なバインダー効果を発揮させるため、３質量％以上の配合量とすることが必要であるが、２０質量％を超えると、相対的に、前記セラミック繊維の配合量が少なくなり、耐熱セラミックシートの十分な機械的強度が得られなくなるため不適である。尚、前記耐熱セラミックシートがより高い柔軟性、クッション性を必要とする場合は、前記乾燥固結性無機物の配合量は１５質量％以下、より好ましくは８質量％以下とすることが好ましい。
また、前記有機バインダーは、耐熱セラミックシートを常温〜２００℃近辺の温度領域において取り扱う際の適度なハンドリング性を得ることのできる最小限の量を配合すればよく、前記セラミック繊維と前記ガラス短繊維と前記ガラス長繊維と前記乾燥固結性無機物を含む無機材料の合計配合量に対して０．３〜５外質量％の配合量とすることが好ましい。尚、前記有機バインダーの配合量を多くし過ぎると、有機バインダーの焼失時に発生する臭気性ガス量が多くなるので好ましくない。
また、上記製造例のように、前記乾燥固結性無機物を、前記セラミック繊維、前記ガラス短繊維等と共に抄紙原料液中に配合・混合して湿式抄造する場合は、抄紙原料液中に高分子凝集剤を適量添加し、セラミック繊維表面に乾燥固結性無機物を吸着・担持させた上で、シート化する。このようにすることで、繊維表面に乾燥固結性無機物が吸着した状態のセラミック繊維同士が絡み合ってシート化されるようになるので、必然的に前記セラミック繊維同士の接触交絡点には前記乾燥固結性無機物が介在されるようになり、該乾燥固結性無機物の乾燥固結性により、前記セラミック繊維同士が確実に結着される。
また、前記乾燥固結性無機物として前記シリカゾル、アルミナゾル、チタニアゾル、ジルコニアゾル等からなるゾル状物又はゲル状物を使用し、前記セラミック繊維、前記ガラス短繊維等と共に抄紙原料液中に配合・混合して湿式抄造する場合は、前記ゾル状物又はゲル状物の湿式抄造時の歩留りが良好でないため、乾燥固結性無機物として、前記した他の乾燥固結性無機物、すなわち、セピオライト、アタパルジャイト等の鉱物微細繊維、シリカフレーク、シリカ−チタニアフレーク等の表面に多数の水酸基を有する鱗片状物、カオリン、クレー、モンモリロナイト等の粘土鉱物の中から少なくとも１種を併用するようにすることが好ましい。
また、前記乾燥固結性無機物として前記シリカゾル、アルミナゾル、チタニアゾル、ジルコニアゾル等からなるゾル状物を使用する場合は、前述の通り、湿式抄造時の歩留りが良好でないことから、湿式抄造後のシートに付着させて介在させるようにしてもよい。具体的には、湿式抄造後の湿紙状態又は乾紙状態のシートに、前記ゾル状物を、含浸、スプレー塗布、表面コート等により付着処理するようにすればよい。この場合、前記ゾル状物の配合量は１０質量％以下、より好ましくは５質量％以下とすることが好ましい。前記ゾル状物の配合量が１０質量％（５質量％）を超えると、耐熱セラミックシートの機械的強度は高くなるが、逆に、柔軟性が低下するため好ましくない。
また、前記有機バインダーは、前記セラミック繊維、前記ガラス短繊維等と共に抄紙原料液中に配合・混合して湿式抄造するようにしても、湿式抄造後のシートに付着させて介在させるようにしてもよい。
The heat-resistant ceramic sheet is, for example, 60 to 95% by mass of the ceramic fiber, 2 to 8 % by mass of the short glass fiber, 0 to 10% by mass of the long glass fiber, and 3 to 20% by mass of the dry-solidifying inorganic substance. %, And an organic binder of 0.3 to 5% by mass with respect to 100% by mass of the total amount of these inorganic materials is added, and dispersed and mixed in water to obtain a papermaking raw material liquid, which is made into a sheet by wet papermaking It can be obtained by heating and drying.
In order to ensure good heat resistance of the heat-resistant ceramic sheet, the amount of the ceramic fiber needs to be 60% by mass or more, and is appropriately used for the heat-resistant ceramic sheet, that is, the heat-resistant ceramic sheet. What is necessary is just to select a suitable compounding quantity according to the heat resistance calculated | required, for example, when a heat resistant ceramic sheet requires the heat resistance of 1000 degreeC or more, it is preferable to set it as the compounding quantity of 85 mass% or more. In addition, when the blending amount of the ceramic fiber exceeds 95% by mass, the blending amount of the short glass fiber, the dry-solidifying inorganic substance, and the organic binder that function as a binder of the heat-resistant ceramic sheet is relatively reduced. The heat resistant ceramic sheet is not suitable because sufficient mechanical strength in an arbitrary temperature range from room temperature to 1600 ° C. cannot be obtained.
Further, the blending amount of the short glass fibers is required to be 2% by mass or more in order to interpose the entire heat-resistant ceramic sheet in a uniformly dispersed state and exhibit the above-described good binder effect. When the content exceeds 20% by mass, the amount of the ceramic fiber is relatively small, so that sufficient heat resistance of the heat-resistant ceramic sheet cannot be obtained. In addition, when the said heat resistant ceramic sheet requires higher heat resistance, a softness | flexibility, and cushioning properties, it is preferable that the compounding quantity of the said glass short fiber shall be 15 mass% or less, More preferably, it is 10 mass% or less.
In addition, the glass long fiber can be blended in an appropriate amount as required when the heat-resistant ceramic sheet requires higher tear strength and folding strength, but when the blending amount exceeds 10% by mass. In addition, when the amount of the ceramic fiber, the short glass fiber, and the dry-solidifying inorganic material is relatively reduced, and the sheet is formed by wet papermaking, the long glass fiber is uniformly dispersed in the papermaking raw material liquid. Is difficult to obtain.
Further, the blending amount of the dry-solidifying inorganic substance is required to be 3% by mass or more in order to interpose the entire heat-resistant ceramic sheet in a uniformly dispersed state and exhibit the above-described good binder effect. However, if it exceeds 20% by mass, the amount of the ceramic fiber is relatively small, and it is not suitable because sufficient mechanical strength of the heat-resistant ceramic sheet cannot be obtained. In addition, when the said heat resistant ceramic sheet requires higher flexibility and cushioning properties, the blending amount of the dry-solidifying inorganic material is preferably 15% by mass or less, more preferably 8% by mass or less.
The organic binder may be blended in a minimum amount capable of obtaining an appropriate handling property when the heat-resistant ceramic sheet is handled in a temperature range from room temperature to around 200 ° C. The ceramic fiber and the short glass fiber It is preferable that the blending amount is 0.3 to 5% by mass with respect to the total blending amount of the inorganic material including the long glass fiber and the dry-solidifying inorganic substance. An excessive amount of the organic binder is not preferable because the amount of odorous gas generated when the organic binder is burned out increases.
Further, as in the above production example, when the dry-solidifying inorganic substance is blended and mixed in the papermaking raw material liquid together with the ceramic fibers, the short glass fibers, etc., a polymer in the papermaking raw material liquid is used. An appropriate amount of an aggregating agent is added, and a dry solidifying inorganic substance is adsorbed and supported on the surface of the ceramic fiber, and then formed into a sheet . In this way, since the ceramic fibers in a state where the dry solidifying inorganic substance is adsorbed on the fiber surface are entangled with each other to form a sheet, the contact entanglement point between the ceramic fibers inevitably becomes the dry. A caking inorganic substance comes to intervene, and the ceramic fibers are reliably bound to each other by the dry caking property of the dry caking inorganic substance.
Further, as the dry-solidifying inorganic substance, a sol-like or gel-like substance composed of the silica sol, alumina sol, titania sol, zirconia sol, etc. is used and blended and mixed in the papermaking raw material liquid together with the ceramic fiber, the short glass fiber, etc. In the case of wet papermaking, since the yield during wet papermaking of the sol or gel is not good, as the dry solidified inorganic material, other dry solidified inorganic materials described above, that is, sepiolite, attapulgite, etc. It is preferable to use at least one kind of clay minerals such as scales having a large number of hydroxyl groups on the surface, such as fine mineral fibers, silica flakes, silica-titania flakes, kaolin, clay and montmorillonite.
In addition, when using a sol-like material composed of the silica sol, alumina sol, titania sol, zirconia sol, etc. as the dry-solidifying inorganic material, since the yield during wet papermaking is not good as described above, the sheet after wet papermaking You may make it interpose by attaching to. Specifically, the sol-like material may be attached to the wet paper sheet or dry paper sheet after wet papermaking by impregnation, spray coating, surface coating, or the like. In this case, the amount of the sol-like material is preferably 10% by mass or less, more preferably 5% by mass or less. When the amount of the sol-like material exceeds 10% by mass (5% by mass), the mechanical strength of the heat-resistant ceramic sheet increases, but conversely, the flexibility decreases, which is not preferable.
In addition, the organic binder may be mixed and mixed in the papermaking raw material together with the ceramic fibers, the short glass fibers, etc., and may be wet-made, or may be attached to the sheet after wet-making. Good.
次に、本発明の実施例について比較例及び従来例と共に詳細に説明する。
（実施例１）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８７質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％と、乾燥固結性無機物としてセピオライト５質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、更に高分子凝集剤を添加して、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
Next, examples of the present invention will be described in detail together with comparative examples and conventional examples.
Example 1
As ceramic fibers, 87% by mass of silica-alumina fibers having an average fiber diameter of 4 μm, as glass short fibers, 8% by mass of C glass short fibers having an average fiber diameter of 0.6 μm (softening point of about 650 ° C.), and as a dry-solidifying inorganic substance To 100% by mass of the total amount of inorganic material with 5% by mass of sepiolite, 3% by mass of fine cellulose fibers with Canadian standard freeness of 0 ml are added as an organic binder, and a polymer flocculant is further added. The sheet was formed by wet papermaking with a square sheet machine, and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
（実施例２）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８２質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％と、乾燥固結性無機物としてカオリン１０質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、更に高分子凝集剤を添加して、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Example 2)
82% by mass of silica-alumina fiber having an average fiber diameter of 4 μm as ceramic fiber, 8% by mass of C glass short fiber (softening point of about 650 ° C.) having an average fiber diameter of 0.6 μm as short glass fiber, and dry solidified inorganic substance To 100% by mass of the total amount of inorganic material with 10% by mass of kaolin, add 3% by mass of fine cellulose fibers with Canadian standard freeness of 0 ml as an organic binder, and further add a polymer flocculant. The sheet was formed by wet papermaking with a square sheet machine, and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
（実施例３）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８２質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％と、ガラス長繊維として繊維径７μｍ、繊維長６ｍｍのＥガラスチョップド繊維（軟化点約８４０℃）５質量％と、乾燥固結性無機物としてセピオライト５質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてアクリル樹脂バインダーを固形分で５外質量％となる量を添加し、更に高分子凝集剤を添加して、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Example 3)
82% by mass of silica-alumina fiber having an average fiber diameter of 4 μm as ceramic fiber, 8% by mass of C short glass fiber (softening point of about 650 ° C.) having an average fiber diameter of 0.6 μm as short glass fiber, and fiber diameter as long glass fiber An acrylic resin as an organic binder for 5% by mass of E glass chopped fiber (softening point of about 840 ° C.) of 7 μm and a fiber length of 6 mm and a total amount of 100% by mass of an inorganic material of 5% by mass of sepiolite as a dry solidifying inorganic substance Add an amount of 5% by mass of the binder as a solid content, add a polymer flocculant, wet form with a square sheet machine for hand making, and dry at 150 ° C., A heat-resistant ceramic sheet was obtained.
（実施例４）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８２質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％と、ガラス長繊維として繊維径７μｍ、繊維長６ｍｍのＥガラスチョップド繊維（軟化点約８４０℃）５質量％と、乾燥固結性無機物としてセピオライト３質量％及びシリカゾルを固形分で２質量％となる量との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、更に高分子凝集剤を添加して、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
Example 4
82% by mass of silica-alumina fiber having an average fiber diameter of 4 μm as ceramic fiber, 8% by mass of C short glass fiber (softening point of about 650 ° C.) having an average fiber diameter of 0.6 μm as short glass fiber, and fiber diameter as long glass fiber 7 μm, fiber length 6 mm E glass chopped fiber (softening point about 840 ° C.) 5% by mass, dry solidified inorganic material 3% by mass and silica sol 2% by mass in solid content Add 100% by mass of Canadian standard freeness of fine cellulose fiber 3% by mass as organic binder to 100% by mass, add polymer flocculant and wet paper making with hand-made square sheet machine And formed into a sheet and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
（比較例１）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８７質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％と、ガラス長繊維として繊維径７μｍ、繊維長６ｍｍのＥガラスチョップド繊維（軟化点約８４０℃）５質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Comparative Example 1)
87% by mass of silica-alumina fiber having an average fiber diameter of 4 μm as ceramic fiber, 8% by mass of C glass short fiber (softening point of about 650 ° C.) having an average fiber diameter of 0.6 μm as short glass fiber, and fiber diameter as long glass fiber 3% by mass of fine cellulose fibers having a Canadian standard freeness of 0 ml as an organic binder with respect to a total amount of 100% by mass of an inorganic material with 5% by mass of E glass chopped fiber (softening point of about 840 ° C.) of 7 μm and a fiber length of 6 mm. Was added, and was wet-processed with a square sheet machine for hand-making to form a sheet and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
（比較例２）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８７質量％と、ガラス短繊維として平均繊維径０．６μｍのＥガラス短繊維（軟化点約８４０℃）１３質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Comparative Example 2)
Total amount of inorganic material 100% of silica-alumina fibers having an average fiber diameter of 4 μm as ceramic fibers and 13% by weight of E glass short fibers (softening point of about 840 ° C.) having an average fiber diameter of 0.6 μm as glass short fibers 100 Add 3% by mass of fine cellulose fiber with Canadian standard freeness of 0ml as organic binder to mass%, make wet sheet with square sheet machine for handmaking, dry at 150 ° C, A heat-resistant ceramic sheet was obtained.
（比較例３）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維８７質量％と、ガラス短繊維として平均繊維径０．６μｍのＣガラス短繊維（軟化点約６５０℃）８質量％及び平均繊維径０．６μｍのＥガラス短繊維（軟化点約８４０℃）５質量％との無機材料の合計量１００質量％に対し、有機バインダーとしてカナディアン標準濾水度０ｍｌの微細セルロース繊維３外質量％を添加し、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Comparative Example 3)
As ceramic fibers, 87% by mass of silica-alumina fibers having an average fiber diameter of 4 μm, and as glass short fibers, 8% by mass of C glass short fibers having an average fiber diameter of 0.6 μm (softening point of about 650 ° C.) and an average fiber diameter of 0.6 μm. To the total amount of 100% by mass of inorganic material with 5% by mass of E glass short fibers (softening point of about 840 ° C.), 3% by mass of fine cellulose fibers with Canadian standard freeness of 0 ml are added as organic binder. The sheet was formed by wet papermaking with a square sheet machine, and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
（従来例）
セラミック繊維として平均繊維径４μｍのシリカ−アルミナ繊維１００質量％に、有機バインダーとしてアクリル樹脂バインダーを固形分で５外質量％となる量を添加し、手抄き用角型シートマシンにて湿式抄造してシート化し、１５０℃で乾燥して、耐熱セラミックシートを得た。
(Conventional example)
Add 100% by mass of silica-alumina fiber with an average fiber diameter of 4 μm as ceramic fiber, and add an acrylic resin binder as an organic binder in an amount of 5% by mass in solid content. And formed into a sheet and dried at 150 ° C. to obtain a heat-resistant ceramic sheet.
次に、上記にて得られた実施例１〜４、比較例１〜３、従来例の各耐熱セラミックシートについて、厚さ、坪量、密度、常温引張強度、引張強度保持率を以下の方法により測定した。結果を表１に示す。
〈厚さ〉
ダイヤルシックネスゲージを用いて、加重１９．６ｋＰａにて測定した。
〈坪量〉
０．１ｍ2の質量を測定し、これを１０倍して坪量とした。
〈密度〉
坪量（ｇ／ｍ2）÷厚さ（ｍｍ）÷１０００の計算値。
〈常温引張強度〉
等速度引張試験機により常温での引張強度を測定した。測定条件は、引張速度２５ｍｍ／分、チャック間距離１００ｍｍとして行った。
〈加熱後の引張強度〉
２００〜１０００℃の所定温度にて１時間加熱後、常温にて等速度引張試験機により引張強度を測定し、加熱後の引張強度とした。引張強度の測定条件は、引張速度２５ｍｍ／分、チャック間距離１００ｍｍとして行った。
〈引張強度保持率〉
前記常温引張強度、前記加熱後の引張強度の各測定結果を基に、次式により引張強度保持率を算出した。
引張強度保持率（％）＝（加熱後の引張強度）÷（常温引張強度）×１００
Next, with respect to each of the heat-resistant ceramic sheets of Examples 1 to 4, Comparative Examples 1 to 3, and the conventional example obtained above, the thickness, basis weight, density, room temperature tensile strength, and tensile strength retention are as follows. It was measured by. The results are shown in Table 1.
<thickness>
Measurement was performed using a dial thickness gauge at a load of 19.6 kPa.
<Weight>
A mass of 0.1 m 2 was measured, and this was multiplied by 10 to obtain a basis weight.
<density>
Calculated value of basis weight (g / m 2 ) ÷ thickness (mm) ÷ 1000.
<Normal temperature tensile strength>
Tensile strength at room temperature was measured with a constant velocity tensile tester. The measurement conditions were a tensile speed of 25 mm / min and a distance between chucks of 100 mm.
<Tensile strength after heating>
After heating at a predetermined temperature of 200 to 1000 ° C. for 1 hour, the tensile strength was measured with a constant velocity tensile tester at room temperature to obtain the tensile strength after heating. The tensile strength was measured under the conditions of a tensile speed of 25 mm / min and a distance between chucks of 100 mm.
<Tensile strength retention>
Based on the measurement results of the normal temperature tensile strength and the tensile strength after heating, the tensile strength retention was calculated by the following formula.
Tensile strength retention rate (%) = (tensile strength after heating) ÷ (room temperature tensile strength) × 100
表１の結果から、以下のようなことが分かった。
（１）本発明の実施例１〜４の耐熱セラミックシートは、乾燥固結性無機物を適当量配合したことにより、比較例１〜３及び従来例の耐熱セラミックシートと比較して、常温引張強度が同等で、２００〜１０００℃加熱後の引張強度が、特に３００〜５００℃程度において改善され、１０００℃までの全温度領域において１０Ｎ／２５ｍｍ幅以上の引張強度を確保できることが確認できた。
（２）実施例１の耐熱セラミックシートでは、乾燥固結性無機物として、少量の添加で高いバインダー効果の得られるセピオライトを使用したため、乾燥固結性無機物の配合量を５質量％という比較的少量に留めるとともに、セラミック繊維の配合量を多くし、実施例２の耐熱セラミックシートと比較し、２００〜６００℃程度での引張強度を同等以上に維持しながら、６００〜１０００℃程度での引張強度を高めることができた。
From the results in Table 1, the following was found.
(1) The heat-resistant ceramic sheets of Examples 1 to 4 of the present invention were blended with an appropriate amount of a dry-solidifying inorganic material, so that the room temperature tensile strength was higher than that of Comparative Examples 1 to 3 and the conventional heat-resistant ceramic sheets. It was confirmed that the tensile strength after heating at 200 to 1000 ° C. was improved particularly at about 300 to 500 ° C., and a tensile strength of 10 N / 25 mm width or more could be secured in the entire temperature range up to 1000 ° C.
(2) In the heat-resistant ceramic sheet of Example 1, sepiolite, which can obtain a high binder effect with a small amount of addition, was used as the dry-solidifying inorganic material. Therefore, the amount of the dry-solidifying inorganic material is relatively small at 5% by mass. As compared with the heat-resistant ceramic sheet of Example 2, the tensile strength at about 600 to 1000 ° C. is maintained while maintaining the tensile strength at about 200 to 600 ° C. or higher as compared with the heat resistant ceramic sheet of Example 2. I was able to increase.
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