WO2013099090A1 - Highly flexible inorganic fibrous shaped body - Google Patents

Highly flexible inorganic fibrous shaped body Download PDF

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Publication number
WO2013099090A1
WO2013099090A1 PCT/JP2012/007284 JP2012007284W WO2013099090A1 WO 2013099090 A1 WO2013099090 A1 WO 2013099090A1 JP 2012007284 W JP2012007284 W JP 2012007284W WO 2013099090 A1 WO2013099090 A1 WO 2013099090A1
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weight
inorganic
fibrous shaped
inorganic fibrous
product according
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PCT/JP2012/007284
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French (fr)
Japanese (ja)
Inventor
鉄也 石原
賢 米内山
太一 白鳥
智彦 岸木
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ニチアス株式会社
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Publication of WO2013099090A1 publication Critical patent/WO2013099090A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions

Definitions

  • the present invention relates to an inorganic fibrous shaped body.
  • the present invention relates to a felt-like inorganic fibrous shaped body having a high flexibility formed without using an inorganic binder.
  • Inorganic fibers are lightweight, easy to handle, and excellent in heat resistance, and thus are used as, for example, heat-resistant sealing materials.
  • problems have recently been pointed out that inorganic fibers are inhaled into the human body and enter the lungs.
  • biosoluble inorganic fibers have been developed that do not cause problems even when inhaled by the human body, or are unlikely to occur (for example, Patent Documents 1 and 2).
  • the biosoluble inorganic fiber is subjected to secondary processing according to the application.
  • An object of the present invention is to provide an inorganic fiber shaped body having rigidity and self-supporting property and having high compression recovery property and cushioning property.
  • the following inorganic fibrous shaped body is provided.
  • An organic binder is an inorganic fibrous shaped body that does not contain thermosetting resin and inorganic binder.
  • composition SiO 2 66-82% by weight CaO 10-34% by weight MgO 0-3 wt% Al 2 O 3 0-5% by weight 2.
  • thermoplastic resin is one or more selected from acrylic resin, acrylic-styrene copolymer, polyester, polyethylene, polypropylene, polystyrene, polyamide, and polyvinyl alcohol. 4). Furthermore, the inorganic fibrous fixed form body in any one of 1-3 containing a fixing agent. 5. 5. The inorganic fibrous fixed body according to 4, wherein the fixing agent is one or more selected from aluminum, magnesium, calcium, sodium and salts thereof. 6). Furthermore, the inorganic fibrous fixed form in any one of 1-5 containing a pH adjuster. 7). 7. The inorganic fibrous molded article according to 6, wherein the pH adjuster is one or more selected from ammonia water and sodium hydroxide.
  • the inorganic fibrous shaped product according to any one of 1 to 10 wherein the compression recovery rate is 91% or more when the compression rate is 30%.
  • an inorganic fibrous shaped body having rigidity and self-supporting property and having high compression recovery and cushioning properties.
  • the inorganic fibrous shaped body of the present invention includes at least a predetermined inorganic fiber (hereinafter also referred to as a specific inorganic fiber) and an organic binder.
  • a predetermined inorganic fiber hereinafter also referred to as a specific inorganic fiber
  • an organic binder By including such an organic binder, flexibility can be expressed.
  • the inorganic fibrous fixed body of the present invention does not contain colloidal silica and metal alkoxide, which are typical inorganic binders.
  • thermoplastic resin examples include acrylic resin, acrylic-styrene copolymer, polyester, polyethylene, polypropylene, polystyrene, polyamide, polyvinyl alcohol and the like. Acrylic resin is preferable. Acrylic resin is highly transparent and resistant to discoloration at high temperatures.
  • the shaped product of the present invention may contain the organic binder in an unmelted state.
  • Pulp, starch, etc. can be further included as an organic binder.
  • pulp When pulp is included, the strength of the fibrous shaped body can be improved while maintaining flexibility.
  • the inorganic fibrous shaped product of the present invention can further contain a fixing agent, a pH adjuster, an antifoaming agent, and an aggregating agent.
  • a fixing agent include aluminum, magnesium, calcium, sodium and potassium sulfate, nitrate, acetate, hydrochloride and the like.
  • pH adjusters include ammonia water and sodium hydroxide.
  • the inorganic fibrous shaped body of the present invention does not need to contain a heat-expandable inorganic powder such as unfired vermiculite, shirasu, nacre, obsidian, and heat-expandable graphite.
  • a heat-expandable inorganic powder such as unfired vermiculite, shirasu, nacre, obsidian, and heat-expandable graphite.
  • the specific inorganic fiber used in the present invention has the following composition. Fibers having the following composition are excellent in biosolubility and fire resistance after heating. This fiber is different from rock wool and glass fiber. SiO 2 66-82% by weight CaO 10-34% by weight MgO 3 wt% or less Al 2 O 3 5 wt% or less Total of SiO 2 , CaO, MgO, Al 2 O 3 98 wt% or more
  • SiO 2 66-82 wt% (for example, it can be 68-80 wt%, 70-80 wt%, 71-80 wt% or 71-76 wt%)
  • CaO 10-34% by weight (for example, it can be 20-30% by weight or 21-26% by weight)
  • MgO 3 wt% or less eg, 1 wt% or less
  • Al 2 O 3 5% by weight or less eg, 3.5% by weight or less or 3% by weight or less.
  • Other oxides ⁇ 2% by weight
  • the Al 2 O 3 content can be, for example, 3.4% by weight or less or 3.0% by weight or less. Moreover, it can be 1.1 weight% or more or 2.0 weight% or more. The content is preferably 0 to 3% by weight, more preferably 1 to 3% by weight. If Al 2 O 3 is contained within this range, the strength becomes high.
  • the above inorganic fibers include other oxides such as alkali metal oxides (K 2 O, Na 2 O, etc.), Fe 2 O 3 , ZrO 2 , P 2 O 5 , B 2 O 3 , TiO 2 , MnO, R 2 O 3 (R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, or a mixture thereof) The above may or may not be included. Other oxides may be 0.2 wt% or less or 0.1 wt% or less, respectively.
  • the alkali metal oxide may contain 0.2% by weight or less of each oxide, and the total of the alkali metal oxides may be 0.2% by weight or less.
  • the total of SiO 2 , CaO, MgO and Al 2 O 3 may be more than 98 wt% or more than 99 wt%.
  • the fibers having the above composition are biosoluble.
  • the biosoluble inorganic fiber is, for example, an inorganic fiber having a physiological saline dissolution rate at 40 ° C. of 1% or more.
  • the physiological saline dissolution rate is measured, for example, as follows. That is, first, 1 g of a sample prepared by pulverizing inorganic fibers to 200 mesh or less and 150 mL of physiological saline are placed in an Erlenmeyer flask (volume: 300 mL) and placed in an incubator at 40 ° C. Next, a horizontal vibration of 120 revolutions per minute is continuously applied to the Erlenmeyer flask for 50 hours.
  • the concentration (mg / L) of each element contained in the filtrate obtained by filtration is measured with an ICP emission analyzer. Then, based on the measured concentration of each element and the content (% by weight) of each element in the inorganic fiber before dissolution, the physiological saline dissolution rate (%) is calculated. That is, for example, when the measurement element is silicon (Si), magnesium (Mg), calcium (Ca), and aluminum (Al), the physiological saline dissolution rate C (%) is calculated by the following equation.
  • C (%) [filtrate amount (L) ⁇ (a1 + a2 + a3 + a4) ⁇ 100] / [weight of inorganic fiber before dissolution (mg) ⁇ (b1 + b2 + b3 + b4) / 100].
  • a1, a2, a3 and a4 are the measured concentrations of silicon, magnesium, calcium and aluminum (mg / L), respectively, and b1, b2, b3 and b4 are respectively in the inorganic fibers before dissolution. It is content (weight%) of silicon, magnesium, calcium, and aluminum.
  • Examples of the method for producing the specific inorganic fiber include known methods such as a blowing method and a spinning method.
  • the inorganic fibrous shaped body can contain other inorganic fibers in addition to the specific inorganic fibers described above.
  • the specific inorganic fibers can be 50% by weight or more, 60% by weight or more, 80% by weight or more, or 100% by weight.
  • refractory fibers mainly composed of silica and alumina (silica 4 to 35% by weight, alumina 75 to 96% by weight (for example, silica 20 to 30% by weight, alumina 80 to 70% by weight mullite fiber)). Can do.
  • the compression recovery rate can be further improved.
  • biosoluble fibers such as rock wool
  • the compression recovery rate can be further improved.
  • the chemical composition of rock wool can vary depending on the raw material.
  • the SiO 2 content is 30 to 50% by mass
  • the Al 2 O 3 content is 10 to 20% by mass
  • the MgO content is 1 to 10%
  • CaO A fiber having a content of 20 to 40% by mass
  • a Fe 2 O 3 content of 0 to 3% by mass and a MnO content of 0 to 1% by mass.
  • the specific inorganic fiber may be used alone, or may be used by mixing with other inorganic fibers.
  • Other inorganic fibers include carbon fiber, slag wool, glass wool, silica fiber, silicon carbide fiber, boron nitride fiber, zirconia fiber, calcium silicate fiber, and other natural mineral fibers.
  • the inorganic fibrous shaped body can contain an antifoaming agent, an aggregating agent, a pH adjusting agent and the like in addition to the inorganic fiber, the organic binder, and the fixing agent.
  • the amount of the organic binder is usually 0.01 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2.5 to 40 parts by weight when the total amount of all inorganic fibers contained in the shaped product is 100 parts by weight. Part, more preferably 2.5 to 15 parts by weight.
  • the fixing agent is usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 0.6 to 10 parts by weight when the total amount of inorganic fibers is 100 parts by weight. Part, particularly preferably 0.6 to 4 parts by weight.
  • the inorganic fibrous shaped body may be configured to occupy 90% by weight, 95% by weight, 98% by weight or 99% by weight of the total inorganic fiber, organic binder and fixing agent.
  • the inorganic fibrous shaped body is preferably in the form of a cloth or plate such as felt. Since the fixed body of the present invention has high flexibility, it is easy to change its shape, for example, it is easy to push between joints. Moreover, since the compression recovery rate is high, it is difficult to drop off even during use or after use at high temperatures, and the sealing property can be maintained.
  • the thickness is not particularly limited, but is usually 5 mm or more, preferably 10 to 50 mm.
  • the inorganic fibrous shaped body of the present invention does not contain an inorganic binder, the compression recovery rate can be improved. Moreover, since an inorganic binder is not included, the restorability of the inorganic fibrous shaped body is maintained even after use at high temperatures.
  • So-called blankets manufactured by needle punching inorganic fibers do not contain organic binders, have poor rigidity and self-supporting properties, and are inferior to felt as in the present invention.
  • So-called boards containing inorganic binders such as colloids produced by vacuum dehydration molding similar to felts of inorganic fibers are superior to blankets and felts in terms of rigidity and independence, but inferior to flexibility and cushioning properties. .
  • the compression / decompression rate is, for example, 91 to 100%, preferably 95 to 99% when the compression rate is 30%. Further, for example, when the compression rate is 60%, it is 71 to 97%, preferably 85 to 95%. For example, when the compression ratio is 70%, it is 66 to 93%, preferably 75 to 90%.
  • the method for measuring the compression recovery rate is as described in the examples.
  • the amount of sagging in the overhunting test is, for example, 1 to 80 mm, preferably 5 to 20 mm when the shift amount is 200 mm, 2 to 140 mm, preferably 10 to 30 mm, and 300 mm when the shift amount is 250 mm.
  • the bulk density of the shaped product of the present invention is not particularly limited, but is usually 70 to 300 kg / cm 2 , or limited to 130 to 250 kg / cm 2 .
  • the fixed body can be manufactured by wet molding. Specifically, the inorganic fiber containing the specific inorganic fiber, the raw material containing the organic binder, and the dispersion medium are mixed to form a slurry, and the slurry is cast into a mold and dried. Preferably, drying is performed at a melting temperature or lower.
  • a thermoplastic resin is used as the organic binder, it is preferably blended in the form of an emulsion or an aqueous solution.
  • the shaped product of the present invention can be produced using a used shaped product, but it is not usually used because it is difficult to control the amount of organic matter. When the amount of organic matter increases, the amount of gas generated when heated increases.
  • Examples 1-8 (1) felt manufacturing SiO 2 73 wt%, the CaO 24 wt%, the MgO 0.3 wt%, the inorganic fibers A comprising Al 2 O 3 2 wt%, mullite fiber (SiO 2 30 wt%, Al 2 O 3 ( 70 wt%), rock wool (SiO 2 40 wt%, CaO 35 wt%, MgO 5 wt%, Al 2 O 3 13 wt%) and inorganic fibers selected from carbon fibers, acrylic emulsion (organic binder) , Aluminum sulfate (fixing agent), aqueous ammonia (pH adjusting agent), silicon emulsion (antifoaming agent), dimethylaminoethyl methacrylate (flocculating agent), water, mixed and dehydrated and molded at 100 ° C to 130 ° C.
  • the inorganic fibers A comprising Al 2 O 3 2 wt%, mullite fiber (SiO 2 30
  • the amount of each component is 5 parts by weight of an organic binder, 1.3 parts by weight of a fixing agent, 0.1 part by weight of a pH adjusting agent, 0.1 part by weight of an antifoaming agent, and 100 parts by weight of inorganic fibers. 3 parts by weight, 0.06 part by weight of a flocculant, and 5000 parts by weight of water.
  • the amount of inorganic fibers was changed as shown in Table 1.
  • the test piece was compressed until the thickness reached a predetermined compression rate (30%, 60%, 70%). After reaching the predetermined compression ratio, the pressure is held for about 30 seconds, and then the compression is released. The thickness was measured with calipers or a compression tester after about 30 seconds had passed after releasing the compression.
  • Comparative Example 1 (Blanket) After manufacturing the inorganic fiber A into a blanket with a needle punch, it was cut into a length of 600 mm ⁇ width of 50 mm ⁇ thickness of 25 mm, and then evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
  • Comparative Example 2 100 parts by weight of inorganic fiber A, 3 parts by weight of starch (organic binder), 8 parts by weight of colloidal silica (inorganic binder), 2 parts by weight of polyacrylamide (flocculating agent), 5000 parts by weight of water are mixed, dehydrated and dried.
  • the felt of Example 1 is more rigid and self-supporting than the blanket of Comparative Example 1, and the felts of Examples 1 to 8 are more flexible and have a compression recovery rate than the board of Comparative Example 2. I understand that it is expensive.
  • Examples 9-13 Inorganic fiber A, acrylic emulsion (organic binder), aluminum sulfate (fixing agent), ammonia water (pH adjusting agent), antifoaming agent, and flocculant are mixed, and in the same manner as in Example 1, length 600 mm ⁇ width 50 mm X A felt with a thickness of 25 mm was produced.
  • the blending amount of each component is 0.06 parts by weight of the flocculant with respect to 100 parts by weight of the inorganic fiber A in Examples 9 to 13, and the amount of the organic binder, antifoaming agent, fixing agent, and pH adjuster.
  • Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
  • Examples 14 and 15 Inorganic fiber A, acrylic emulsion (organic binder), aluminum sulfate (fixing agent), aqueous ammonia (pH adjusting agent), antifoaming agent, flocculant, and pulp are mixed, and the length is 600 mm ⁇ as in Example 1. A felt having a width of 50 mm and a thickness of 25 mm was produced.
  • the amount of each component is 0.06 parts by weight of the flocculant, 100 parts by weight of the inorganic fiber A, 5 parts by weight of the organic binder, 0.3 parts by weight of the antifoaming agent, and the fixing agent.
  • 1.3 parts by weight and 0.1 parts by weight of the pH adjuster, and the amount of pulp was changed as shown in Table 4. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.
  • the inorganic fibrous shaped body of the present invention can be used in various applications as a heat insulating material or as a substitute for asbestos.

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Abstract

An inorganic fibrous shaped body which comprises both an inorganic fiber component that contains at least a bio-soluble inorganic fiber having a specific composition and an organic binder other than thermosetting resins, with the proviso that the shaped body contains neither a thermosetting resin nor colloidal silica nor a metal alkoxide, and which is obtained by subjecting a slurry that contains the inorganic fiber component and the organic binder to dewatering and forming.

Description

柔軟性の高い無機繊維質定形体Highly flexible inorganic fiber shaped body
　本発明は、無機繊維質定形体に関する。特に、無機バインダーを用いずに成形した柔軟性が高いフェルト状の無機繊維質定形体に関する。 The present invention relates to an inorganic fibrous shaped body. In particular, the present invention relates to a felt-like inorganic fibrous shaped body having a high flexibility formed without using an inorganic binder.
　無機繊維は、軽量で扱いやすく、且つ耐熱性に優れるため、例えば、耐熱性のシール材として使用されている。一方、近年、無機繊維が人体に吸入されて肺に侵入することによる問題が指摘されている。そこで、人体に吸入されても問題を起こさない又は起こしにくい生体溶解性無機繊維が開発されている（例えば、特許文献１，２）。生体溶解性無機繊維は、用途に応じて二次加工される。 Inorganic fibers are lightweight, easy to handle, and excellent in heat resistance, and thus are used as, for example, heat-resistant sealing materials. On the other hand, problems have recently been pointed out that inorganic fibers are inhaled into the human body and enter the lungs. In view of this, biosoluble inorganic fibers have been developed that do not cause problems even when inhaled by the human body, or are unlikely to occur (for example, Patent Documents 1 and 2). The biosoluble inorganic fiber is subjected to secondary processing according to the application.
　様々な加工品のうち、工業窯炉内又は焼却炉内の目地材、耐火タイル、断熱レンガ、鉄皮、モルタル耐火物等の隙間を埋める目地材、曲面施工用断熱材として、柔軟性、クッション性がある成形品が求められている。特に、家電、給湯器、工業炉・電気炉等の炉蓋用熱シール材に用いる場合には、高い柔軟性とクッション性が求められる。
　さらに、このような成形品は、高温装置に用いられるため、使用中に変形しないように、加熱収縮率が小さいことも求められる。 Among various processed products, joint materials in industrial kilns or incinerators, fireproof tiles, heat insulating bricks, iron skins, mortar refractories, etc. There is a need for a molded article that is compatible. In particular, when used as a heat sealing material for furnace lids such as home appliances, water heaters, industrial furnaces and electric furnaces, high flexibility and cushioning properties are required.
Furthermore, since such a molded article is used in a high temperature apparatus, it is also required that the heat shrinkage rate is small so as not to be deformed during use.
　また、目地等の施工には、加工精度や寸法精度が必要となるため、ある程度の硬さが求められる。また、加工の容易性が必要となるため、自立性も求められる。 In addition, the construction of joints and the like requires processing accuracy and dimensional accuracy, and therefore a certain degree of hardness is required. In addition, since ease of processing is required, self-sustainability is also required.
特許公報第３７５３４１６号Japanese Patent Publication No. 3753416 特表２００５－５１４３１８号公報JP-T-2005-514318 特開２００６－３１６３６６号公報JP 2006-316366 A
　本発明の目的は、硬直性、自立性を有しかつ圧縮復元性及びクッション性の高い無機繊維質定形体を提供することである。 An object of the present invention is to provide an inorganic fiber shaped body having rigidity and self-supporting property and having high compression recovery property and cushioning property.
　本発明によれば、以下の無機繊維質定形体が提供される。
１．以下の組成を有する生体溶解性無機繊維を少なくとも含む無機繊維と、
　有機バインダーとを含み、
　ただし、熱硬化性樹脂と無機バインダーは含まない無機繊維質定形体。
［組成］
　ＳｉＯ２　　６６～８２重量％
　ＣａＯ　　　１０～３４重量％
　ＭｇＯ　　　０～３重量％
　Ａｌ２Ｏ３　　０～５重量％
２．前記有機バインダーが熱可塑性樹脂である１記載の無機繊維質定形体。
３．前記熱可塑性樹脂が、アクリル樹脂、アクリル－スチレン共重合体、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド及びポリビニルアルコールから選択される１以上である２に記載の無機繊維質定形体。
４．さらに定着剤を含む１～３のいずれか記載の無機繊維質定形体。
５．前記定着剤が、アルミニウム、マグネシウム、カルシウム、ナトリウム及びこれらの塩から選択される１以上である４記載の無機繊維質定形体。
６．さらにｐＨ調整剤を含む１～５のいずれか記載の無機繊維質定形体。
７．前記ｐＨ調整剤が、アンモニア水及び水酸化ナトリウムから選択される１以上である６記載の無機繊維質成形体。
８．前記無機繊維全量を１００重量部としたとき、前記有機バインダーを０．０１～５０重量部含む１～７のいずれか記載の無機繊維質定形体。
９．前記無機繊維と前記有機バインダーで、９０重量％以上を占める１～８のいずれか記載の無機繊維質定形体。
１０．フェルト状である１～９のいずれか記載の無機繊維質定形体。
１１．圧縮復元率が、圧縮率３０％のときに９１％以上である１～１０のいずれか記載の無機繊維質定形体。
１２．圧縮復元率が、圧縮率６０％のときに７１％以上である１～１１のいずれか記載の無機繊維質定形体。
１３．圧縮復元率が、圧縮率７０％のときに６６％以上である１～１２のいずれか記載の無機繊維質定形体。
１４．オーバーハンチング試験によるだれ量が、ずらし量が２００ｍｍのときは１～８０ｍｍである１～１３のいずれか記載の無機繊維質定形体。
１５．少なくとも以下の組成を有する生体溶解性無機繊維を含む無機繊維と、有機バインダーとを混合し、
　成形し、
　前記成形品を溶融温度以下で乾燥する１記載の無機繊維質定形体の製造方法。
［組成］
　ＳｉＯ２　　６６～８２重量％
　ＣａＯ　　　１０～３４重量％
　ＭｇＯ　　　０～３重量％
　Ａｌ２Ｏ３　　０～５重量％
１６．前記有機バインダーが、エマルジョン又は水溶液の形態の熱可塑性樹脂である１５記載の無機繊維質定形体の製造方法。 According to the present invention, the following inorganic fibrous shaped body is provided.
1. Inorganic fibers containing at least biosoluble inorganic fibers having the following composition;
An organic binder,
However, it is an inorganic fibrous shaped body that does not contain thermosetting resin and inorganic binder.
[composition]
SiO 2 66-82% by weight
CaO 10-34% by weight
MgO 0-3 wt%
Al 2 O 3 0-5% by weight
2. 2. The inorganic fibrous shaped product according to 1, wherein the organic binder is a thermoplastic resin.
3. 3. The inorganic fibrous shaped product according to 2, wherein the thermoplastic resin is one or more selected from acrylic resin, acrylic-styrene copolymer, polyester, polyethylene, polypropylene, polystyrene, polyamide, and polyvinyl alcohol.
4). Furthermore, the inorganic fibrous fixed form body in any one of 1-3 containing a fixing agent.
5. 5. The inorganic fibrous fixed body according to 4, wherein the fixing agent is one or more selected from aluminum, magnesium, calcium, sodium and salts thereof.
6). Furthermore, the inorganic fibrous fixed form in any one of 1-5 containing a pH adjuster.
7). 7. The inorganic fibrous molded article according to 6, wherein the pH adjuster is one or more selected from ammonia water and sodium hydroxide.
8). 8. The inorganic fibrous shaped product according to any one of 1 to 7, comprising 0.01 to 50 parts by weight of the organic binder, when the total amount of the inorganic fibers is 100 parts by weight.
9. 9. The inorganic fibrous fixed body according to any one of 1 to 8, wherein the inorganic fiber and the organic binder account for 90% by weight or more.
10. 10. The inorganic fibrous fixed body according to any one of 1 to 9, which is in the form of a felt.
11. 11. The inorganic fibrous shaped product according to any one of 1 to 10, wherein the compression recovery rate is 91% or more when the compression rate is 30%.
12 The inorganic fibrous shaped product according to any one of 1 to 11, wherein the compression recovery rate is 71% or more when the compression rate is 60%.
13. 13. The inorganic fibrous fixed body according to any one of 1 to 12, wherein the compression recovery rate is 66% or more when the compression rate is 70%.
14 14. The inorganic fibrous shaped body according to any one of 1 to 13, wherein the amount of droop in the overhunting test is 1 to 80 mm when the shift amount is 200 mm.
15. Mixing inorganic fibers including biosoluble inorganic fibers having at least the following composition and an organic binder,
Molded,
2. The method for producing an inorganic fibrous shaped product according to 1, wherein the molded product is dried at a melting temperature or lower.
[composition]
SiO 2 66-82% by weight
CaO 10-34% by weight
MgO 0-3 wt%
Al 2 O 3 0-5% by weight
16. 16. The method for producing an inorganic fibrous shaped product according to 15, wherein the organic binder is a thermoplastic resin in the form of an emulsion or an aqueous solution.
　本発明によれば、硬直性、自立性を有しかつ圧縮復元性及びクッション性の高い無機繊維質定形体を提供できる。 According to the present invention, it is possible to provide an inorganic fibrous shaped body having rigidity and self-supporting property and having high compression recovery and cushioning properties.
実施例におけるオーバーハング試験を説明するための図である。It is a figure for demonstrating the overhang test in an Example.
　本発明の無機繊維質定形体は、少なくとも、所定の無機繊維（以下、特定無機繊維ともいう）及び有機バインダーを含む。ただし、フェノール樹脂、エポキシ樹脂等の熱硬化性樹脂は含まない。このような有機バインダーを含むことにより柔軟性を発現できる。本発明の無機繊維質定形体は、典型的な無機バインダーであるコロイダルシリカ、金属アルコキシドは含まない。 The inorganic fibrous shaped body of the present invention includes at least a predetermined inorganic fiber (hereinafter also referred to as a specific inorganic fiber) and an organic binder. However, thermosetting resins such as phenol resins and epoxy resins are not included. By including such an organic binder, flexibility can be expressed. The inorganic fibrous fixed body of the present invention does not contain colloidal silica and metal alkoxide, which are typical inorganic binders.
　有機バインダーとして熱可塑性樹脂を用いることが好ましい。熱可塑性樹脂の例として、アクリル樹脂、アクリル－スチレン共重合体、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド、ポリビニルアルコール等が挙げられる。好ましくはアクリル樹脂である。アクリル樹脂は透明性が高く、高温における変色に強い。本発明の定形体は有機バインダーを実質的に溶融していないで状態で含むようにしてよい。 It is preferable to use a thermoplastic resin as the organic binder. Examples of the thermoplastic resin include acrylic resin, acrylic-styrene copolymer, polyester, polyethylene, polypropylene, polystyrene, polyamide, polyvinyl alcohol and the like. Acrylic resin is preferable. Acrylic resin is highly transparent and resistant to discoloration at high temperatures. The shaped product of the present invention may contain the organic binder in an unmelted state.
　有機バインダーとしてさらにパルプ、澱粉等を含むことができる。パルプを含むと柔軟性を維持したまま繊維質定形体の強度を向上できる。 Pulp, starch, etc. can be further included as an organic binder. When pulp is included, the strength of the fibrous shaped body can be improved while maintaining flexibility.
　本発明の無機繊維質定形体は、さらに定着剤、ｐＨ調整剤、消泡剤、凝集剤を含むことができる。定着剤として、アルミニウム、マグネシウム、カルシウム、ナトリウム及びカリウムのそれぞれ硫酸塩、硝酸塩、酢酸塩、塩酸塩等を例示できる。ｐＨ調整剤として、アンモニア水、水酸化ナトリウム等を例示できる。消泡剤及び凝集剤は市販のものを適量添加することで、成形体の製造を容易にすることができる。
　また、本発明の無機繊維質定形体は、未焼成バーミキュライト、シラス、真珠岩、黒曜石、熱膨張性黒鉛等の加熱膨張性無機質粉末を含む必要はない。 The inorganic fibrous shaped product of the present invention can further contain a fixing agent, a pH adjuster, an antifoaming agent, and an aggregating agent. Examples of the fixing agent include aluminum, magnesium, calcium, sodium and potassium sulfate, nitrate, acetate, hydrochloride and the like. Examples of pH adjusters include ammonia water and sodium hydroxide. By adding appropriate amounts of commercially available antifoaming agents and flocculants, it is possible to facilitate the production of the molded body.
In addition, the inorganic fibrous shaped body of the present invention does not need to contain a heat-expandable inorganic powder such as unfired vermiculite, shirasu, nacre, obsidian, and heat-expandable graphite.
　本発明で用いる特定無機繊維は以下の組成を有する。以下の組成の繊維は加熱後の生体溶解性、耐火性に優れる。尚、この繊維はロックウールやガラス繊維とは異なる。
　ＳｉＯ２　６６～８２重量％
　ＣａＯ　１０～３４重量％
　ＭｇＯ　３重量％以下
　Ａｌ２Ｏ３　５重量％以下
　ＳｉＯ２、ＣａＯ、ＭｇＯ、Ａｌ２Ｏ３の合計　９８重量％以上 The specific inorganic fiber used in the present invention has the following composition. Fibers having the following composition are excellent in biosolubility and fire resistance after heating. This fiber is different from rock wool and glass fiber.
SiO 2 66-82% by weight
CaO 10-34% by weight
MgO 3 wt% or less Al 2 O 3 5 wt% or less Total of SiO 2 , CaO, MgO, Al 2 O 3 98 wt% or more
　好ましくは、以下の組成を例示できる。
　ＳｉＯ２　６６～８２重量％（例えば、６８～８０重量％、７０～８０重量％、７１～８０重量％又は７１～７６重量％とできる）
　ＣａＯ　１０～３４重量％（例えば、２０～３０重量％又は２１～２６重量％とできる）
　ＭｇＯ　３重量％以下（例えば、１重量％以下とできる）
　Ａｌ２Ｏ３　５重量％以下（例えば３．５重量％以下又は３重量％以下とできる。また、１重量％以上又は２重量％以上とできる）
　他の酸化物　２重量％未満 Preferably, the following compositions can be exemplified.
SiO 2 66-82 wt% (for example, it can be 68-80 wt%, 70-80 wt%, 71-80 wt% or 71-76 wt%)
CaO 10-34% by weight (for example, it can be 20-30% by weight or 21-26% by weight)
MgO 3 wt% or less (eg, 1 wt% or less)
Al 2 O 3 5% by weight or less (eg, 3.5% by weight or less or 3% by weight or less. Also, 1% by weight or more or 2% by weight or more)
Other oxides <2% by weight
　ＳｉＯ２が上記範囲であると耐熱性に優れる。ＣａＯとＭｇＯが上記範囲であると加熱前後の生体溶解性に優れる。 When SiO 2 is in the above range, the heat resistance is excellent. When CaO and MgO are in the above range, the biosolubility before and after heating is excellent.
　Ａｌ２Ｏ３含有量は、例えば、３．４重量％以下又は３．０重量％以下とできる。また、１．１重量％以上又は２．０重量％以上とできる。好ましくは０～３重量％、より好ましくは１～３重量％である。この範囲でＡｌ２Ｏ３を含むと強度が高くなる。 The Al 2 O 3 content can be, for example, 3.4% by weight or less or 3.0% by weight or less. Moreover, it can be 1.1 weight% or more or 2.0 weight% or more. The content is preferably 0 to 3% by weight, more preferably 1 to 3% by weight. If Al 2 O 3 is contained within this range, the strength becomes high.
　上記の無機繊維は、他の酸化物として、アルカリ金属酸化物（Ｋ２Ｏ、Ｎａ２Ｏ等）、Ｆｅ２Ｏ３、ＺｒＯ２、Ｐ２Ｏ5、Ｂ２Ｏ３、ＴｉＯ２、ＭｎＯ、Ｒ２Ｏ３（ＲはＳｃ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ，Ｙ又はこれらの混合物から選択される）等を１以上含んでもよく、含まなくてもよい。他の酸化物は、それぞれ、０．２重量％以下又は０．１重量％以下としてよい。アルカリ金属酸化物は各酸化物を０．２重量％以下としてもよく、アルカリ金属酸化物の合計を０．２重量％以下としてもよい。 The above inorganic fibers include other oxides such as alkali metal oxides (K 2 O, Na 2 O, etc.), Fe 2 O 3 , ZrO 2 , P 2 O 5 , B 2 O 3 , TiO 2 , MnO, R 2 O 3 (R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, or a mixture thereof) The above may or may not be included. Other oxides may be 0.2 wt% or less or 0.1 wt% or less, respectively. The alkali metal oxide may contain 0.2% by weight or less of each oxide, and the total of the alkali metal oxides may be 0.2% by weight or less.
　また、ＳｉＯ２、ＣａＯ、ＭｇＯ、Ａｌ２Ｏ３の合計を９８重量％超又は９９重量％超としてよい。 Further, the total of SiO 2 , CaO, MgO and Al 2 O 3 may be more than 98 wt% or more than 99 wt%.
　上記の組成の繊維は生体溶解性である。一般に、生体溶解性無機繊維は、例えば、４０℃における生理食塩水溶解率が１％以上の無機繊維である。
　生理食塩水溶解率は、例えば、次のようにして測定される。すなわち、先ず、無機繊維を２００メッシュ以下に粉砕して調製された試料１ｇ及び生理食塩水１５０ｍＬを三角フラスコ（容積３００ｍＬ）に入れ、４０℃のインキュベーターに設置する。次に、三角フラスコに、毎分１２０回転の水平振動を５０時間継続して加える。その後、ろ過により得られた濾液に含有されている各元素の濃度（ｍｇ／Ｌ）をＩＣＰ発光分析装置により測定する。そして、測定された各元素の濃度と、溶解前の無機繊維における各元素の含有量（重量％）と、に基づいて、生理食塩水溶解率（％）を算出する。すなわち、例えば、測定元素が、ケイ素（Ｓｉ）、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）及びアルミニウム（Ａｌ）である場合には、次の式により、生理食塩水溶解率Ｃ（％）を算出する；Ｃ（％）＝［ろ液量（Ｌ）×（ａ１＋ａ２＋ａ３＋ａ４）×１００］／［溶解前の無機繊維の重量（ｍｇ）×（ｂ１＋ｂ２＋ｂ３＋ｂ４）／１００］。この式において、ａ１、ａ２、ａ３及びａ４は、それぞれ測定されたケイ素、マグネシウム、カルシウム及びアルミニウムの濃度（ｍｇ／Ｌ）であり、ｂ１、ｂ２、ｂ３及びｂ４は、それぞれ溶解前の無機繊維におけるケイ素、マグネシウム、カルシウム及びアルミニウムの含有量（重量％）である。 The fibers having the above composition are biosoluble. In general, the biosoluble inorganic fiber is, for example, an inorganic fiber having a physiological saline dissolution rate at 40 ° C. of 1% or more.
The physiological saline dissolution rate is measured, for example, as follows. That is, first, 1 g of a sample prepared by pulverizing inorganic fibers to 200 mesh or less and 150 mL of physiological saline are placed in an Erlenmeyer flask (volume: 300 mL) and placed in an incubator at 40 ° C. Next, a horizontal vibration of 120 revolutions per minute is continuously applied to the Erlenmeyer flask for 50 hours. Thereafter, the concentration (mg / L) of each element contained in the filtrate obtained by filtration is measured with an ICP emission analyzer. Then, based on the measured concentration of each element and the content (% by weight) of each element in the inorganic fiber before dissolution, the physiological saline dissolution rate (%) is calculated. That is, for example, when the measurement element is silicon (Si), magnesium (Mg), calcium (Ca), and aluminum (Al), the physiological saline dissolution rate C (%) is calculated by the following equation. C (%) = [filtrate amount (L) × (a1 + a2 + a3 + a4) × 100] / [weight of inorganic fiber before dissolution (mg) × (b1 + b2 + b3 + b4) / 100]. In this formula, a1, a2, a3 and a4 are the measured concentrations of silicon, magnesium, calcium and aluminum (mg / L), respectively, and b1, b2, b3 and b4 are respectively in the inorganic fibers before dissolution. It is content (weight%) of silicon, magnesium, calcium, and aluminum.
　上記の特定無機繊維の製造方法として、ブローイング法とスピニング法等公知の方法が挙げられる。 Examples of the method for producing the specific inorganic fiber include known methods such as a blowing method and a spinning method.
　無機繊維質定形体は、上記の特定無機繊維に加えて、他の無機繊維を含むことができる。無機繊維合計１００重量部のうち、特定無機繊維を５０重量％以上、６０重量％以上、８０重量％以上又は１００重量％とすることができる。 The inorganic fibrous shaped body can contain other inorganic fibers in addition to the specific inorganic fibers described above. Of the total 100 parts by weight of inorganic fibers, the specific inorganic fibers can be 50% by weight or more, 60% by weight or more, 80% by weight or more, or 100% by weight.
　例えば、シリカとアルミナを主成分とする耐火性繊維（シリカ４～３５重量％、アルミナ７５～９６重量％（例えばシリカ２０～３０重量％、アルミナ８０～７０重量％のムライトファイバー））を含むことができる。このような繊維を含むと圧縮復元率をさらに向上できる。 For example, containing refractory fibers mainly composed of silica and alumina (silica 4 to 35% by weight, alumina 75 to 96% by weight (for example, silica 20 to 30% by weight, alumina 80 to 70% by weight mullite fiber)). Can do. When such fibers are included, the compression recovery rate can be further improved.
　また、ロックウール等の生体溶解性繊維を含むこともできる。このような繊維を含むと圧縮復元率をさらに向上できる。
　ロックウールの化学組成は、その原料によって変わり得るが、例えば、ＳｉＯ２含有量が３０～５０質量％、Ａｌ２Ｏ３含有量が１０～２０質量％、ＭｇＯ含有量が１～１０質量、ＣａＯ含有量が２０～４０質量％、Ｆｅ２Ｏ３含有量が０～３質量％、ＭｎＯ含有量が０～１質量％の繊維である。 Moreover, biosoluble fibers, such as rock wool, can also be included. When such fibers are included, the compression recovery rate can be further improved.
The chemical composition of rock wool can vary depending on the raw material. For example, the SiO 2 content is 30 to 50% by mass, the Al 2 O 3 content is 10 to 20% by mass, the MgO content is 1 to 10%, CaO A fiber having a content of 20 to 40% by mass, a Fe 2 O 3 content of 0 to 3% by mass, and a MnO content of 0 to 1% by mass.
　本発明は上記特定無機繊維を単独で用いてもよいし、他の無機繊維と混合して用いてもよい。他の無機繊維として、カーボンファイバー、スラグウール、グラスウール、シリカ繊維、炭化ケイ素繊維、窒化ホウ素繊維、ジルコニア繊維、珪酸カルシウム繊維、その他の天然鉱物繊維が挙げられる。 In the present invention, the specific inorganic fiber may be used alone, or may be used by mixing with other inorganic fibers. Other inorganic fibers include carbon fiber, slag wool, glass wool, silica fiber, silicon carbide fiber, boron nitride fiber, zirconia fiber, calcium silicate fiber, and other natural mineral fibers.
　上述したように、無機繊維質定形体は、無機繊維、有機バインダー、定着剤の他、消泡剤、凝集剤、ｐＨ調整剤等を含むことができる。 As described above, the inorganic fibrous shaped body can contain an antifoaming agent, an aggregating agent, a pH adjusting agent and the like in addition to the inorganic fiber, the organic binder, and the fixing agent.
　有機バインダーの量は、定形体に含まれる全ての無機繊維合計を１００重量部としたとき、通常０．０１～５０重量部、好ましくは１～４５重量部、より好ましくは２．５～４０重量部、さらに好ましくは２．５～１５重量部含まれる。 The amount of the organic binder is usually 0.01 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2.5 to 40 parts by weight when the total amount of all inorganic fibers contained in the shaped product is 100 parts by weight. Part, more preferably 2.5 to 15 parts by weight.
　定着剤は、無機繊維合計を１００重量部としたとき、通常０～２０重量部、好ましくは０～１５重量部、より好ましくは０．５～１０重量部、さらに好ましくは０．６～１０重量部、特に好ましくは０．６～４重量部含まれる。 The fixing agent is usually 0 to 20 parts by weight, preferably 0 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 0.6 to 10 parts by weight when the total amount of inorganic fibers is 100 parts by weight. Part, particularly preferably 0.6 to 4 parts by weight.
　無機繊維質定形体は、無機繊維合計、有機バインダー及び定着剤で、９０重量％以上、９５重量％以上、９８重量％以上又は９９重量％以上を占めるように構成してもよい。 The inorganic fibrous shaped body may be configured to occupy 90% by weight, 95% by weight, 98% by weight or 99% by weight of the total inorganic fiber, organic binder and fixing agent.
　無機繊維質定形体は、好ましくはフェルト等の布状又は板状の形状である。本発明の定形体は柔軟性が高いため、形を変えやすく、例えば、目地の間に押し込み易い。また、圧縮復元率が高いため、高温で使用中又は使用後であっても脱落しにくく、シール性を保つことができる。厚みは特に限定はされないが、通常５ｍｍ以上、好ましくは、１０～５０ｍｍである。 The inorganic fibrous shaped body is preferably in the form of a cloth or plate such as felt. Since the fixed body of the present invention has high flexibility, it is easy to change its shape, for example, it is easy to push between joints. Moreover, since the compression recovery rate is high, it is difficult to drop off even during use or after use at high temperatures, and the sealing property can be maintained. The thickness is not particularly limited, but is usually 5 mm or more, preferably 10 to 50 mm.
　本発明の無機繊維質定形体は、無機バインダーを含まないため、圧縮復元率を向上させることができる。また、無機バインダーを含まないため、高温で使用した後でも無機繊維質定形体の復元性が保たれる。 Since the inorganic fibrous shaped body of the present invention does not contain an inorganic binder, the compression recovery rate can be improved. Moreover, since an inorganic binder is not included, the restorability of the inorganic fibrous shaped body is maintained even after use at high temperatures.
無機繊維をニードルパンチして製造されるいわゆるブランケットは有機バインダーを含まず、硬直性、自立性に乏しく、圧縮復元性、クッション性も本発明のようなフェルトより劣るため、加工や施工がしずらい。　　　 So-called blankets manufactured by needle punching inorganic fibers do not contain organic binders, have poor rigidity and self-supporting properties, and are inferior to felt as in the present invention. Rai. *
無機繊維をフェルトと同様な真空脱水成形等により製造されたコロイド等の無機バインダーを含有するいわゆるボードは、硬直性、自立性に関してはブランケット、フェルトより優れている反面、柔軟性、クッション性に劣る。 So-called boards containing inorganic binders such as colloids produced by vacuum dehydration molding similar to felts of inorganic fibers are superior to blankets and felts in terms of rigidity and independence, but inferior to flexibility and cushioning properties. .
　圧縮復元率は、例えば、圧縮率３０％のときは９１～１００％、好ましくは９５～９９％である。また、例えば、圧縮率６０％のときは７１～９７％、好ましくは８５～９５％である。また、例えば、圧縮率７０％のときは６６～９３％、好ましくは７５～９０％である。圧縮復元率の測定方法は実施例に記載の通りである。 The compression / decompression rate is, for example, 91 to 100%, preferably 95 to 99% when the compression rate is 30%. Further, for example, when the compression rate is 60%, it is 71 to 97%, preferably 85 to 95%. For example, when the compression ratio is 70%, it is 66 to 93%, preferably 75 to 90%. The method for measuring the compression recovery rate is as described in the examples.
　オーバーハンチング試験によるだれ量は、例えば、ずらし量が２００ｍｍのときは１～８０ｍｍ、好ましくは５～２０ｍｍ、ずらし量が２５０ｍｍのときは２～１４０ｍｍ、好ましくは１０～３０ｍｍ、ずらし量が３００ｍｍのときは３～２２０ｍｍ、好ましくは４０～７０ｍｍ、ずらし量が３５０ｍｍのときは３～２８０ｍｍ、好ましくは１００～１５０ｍｍ、ずらし量が４００ｍｍのときは３～３４０ｍｍ、好ましくは２００～３００ｍｍ、ずらし量が４５０ｍｍのときは３～３９０ｍｍ、好ましくは２５０～３５０ｍｍ、ずらし量が５００ｍｍのときは３～４４０ｍｍ、好ましくは３００～４００ｍｍである。 The amount of sagging in the overhunting test is, for example, 1 to 80 mm, preferably 5 to 20 mm when the shift amount is 200 mm, 2 to 140 mm, preferably 10 to 30 mm, and 300 mm when the shift amount is 250 mm. Is 3 to 220 mm, preferably 40 to 70 mm, 3 to 280 mm when the shift amount is 350 mm, preferably 100 to 150 mm, 3 to 340 mm when the shift amount is 400 mm, preferably 200 to 300 mm, and the shift amount is 450 mm 3 to 390 mm, preferably 250 to 350 mm, and when the shift amount is 500 mm, 3 to 440 mm, preferably 300 to 400 mm.
　本発明の定形体の嵩密度は特に限定されないが、通常７０～３００ｋｇ／ｃｍ２、又は限定して１３０～２５０ｋｇ／ｃｍ２である。 The bulk density of the shaped product of the present invention is not particularly limited, but is usually 70 to 300 kg / cm 2 , or limited to 130 to 250 kg / cm 2 .
　定形体は湿式成形により製造できる。具体的には、特定無機繊維を含む無機繊維、有機バインダーを含む原料と分散媒とを混合してスラリーを形成し、このスラリーを型に流して成形して、乾燥する。好ましくは溶融温度以下で乾燥する。有機バインダーとして熱可塑性樹脂を用いるとき、エマルジョン又は水溶液の形態で配合することが好ましい。本発明の定形体は使用済みの定形体を使用して製造することはできるが、有機物量をコントロールし難いため通常使用しない。有機物量が多くなると、加熱した際の発生ガスが大量になる。 The fixed body can be manufactured by wet molding. Specifically, the inorganic fiber containing the specific inorganic fiber, the raw material containing the organic binder, and the dispersion medium are mixed to form a slurry, and the slurry is cast into a mold and dried. Preferably, drying is performed at a melting temperature or lower. When a thermoplastic resin is used as the organic binder, it is preferably blended in the form of an emulsion or an aqueous solution. The shaped product of the present invention can be produced using a used shaped product, but it is not usually used because it is difficult to control the amount of organic matter. When the amount of organic matter increases, the amount of gas generated when heated increases.
実施例１～８
（１）フェルトの製造
　ＳｉＯ２を７３質量％、ＣａＯを２４質量％、ＭｇＯを０．３質量％、Ａｌ２Ｏ３を２質量％含む無機繊維Ａ、ムライトファイバー（ＳｉＯ２３０重量％、Ａｌ２Ｏ３７０重量％）、ロックウール（ＳｉＯ２４０重量％、ＣａＯ３５重量％、ＭｇＯ５重量％、Ａｌ２Ｏ３１３重量％）及びはカーボンファイバーから選択される無機繊維、アクリルエマルジョン（有機バインダー）、硫酸アルミニウム（定着剤）、アンモニア水（ｐＨ調整剤）、シリコンエマルジョン（消泡剤）、メタクリル酸ジメチルアミノエチル（凝集剤）、水を混合し、脱水成形して、１００℃～１３０℃で乾燥させ、長さ６００ｍｍ×幅５０ｍｍ×厚さ２５ｍｍのフェルトを製造した。各成分の配合量は、実施例１～８において、無機繊維１００重量部に対し、有機バインダー５重量部、定着剤１．３重量部、ｐＨ調整剤０．１重量部、消泡剤０．３重量部、凝集剤０．０６重量部、水５０００重量部であり、無機繊維の量は表１に示す通り変えた。 Examples 1-8
(1) felt manufacturing SiO 2 73 wt%, the CaO 24 wt%, the MgO 0.3 wt%, the inorganic fibers A comprising Al 2 O 3 2 wt%, mullite fiber (SiO 2 30 wt%, Al 2 O 3 ( 70 wt%), rock wool (SiO 2 40 wt%, CaO 35 wt%, MgO 5 wt%, Al 2 O 3 13 wt%) and inorganic fibers selected from carbon fibers, acrylic emulsion (organic binder) , Aluminum sulfate (fixing agent), aqueous ammonia (pH adjusting agent), silicon emulsion (antifoaming agent), dimethylaminoethyl methacrylate (flocculating agent), water, mixed and dehydrated and molded at 100 ° C to 130 ° C. It was dried to produce a felt having a length of 600 mm × width of 50 mm × thickness of 25 mm. In Examples 1 to 8, the amount of each component is 5 parts by weight of an organic binder, 1.3 parts by weight of a fixing agent, 0.1 part by weight of a pH adjusting agent, 0.1 part by weight of an antifoaming agent, and 100 parts by weight of inorganic fibers. 3 parts by weight, 0.06 part by weight of a flocculant, and 5000 parts by weight of water. The amount of inorganic fibers was changed as shown in Table 1.
（２）フェルトの評価
　得られたフェルトについて以下の評価をした。結果を表１，２に示す。
（ｉ）圧縮復元率
　圧縮後の復元率は以下のように測定した。すなわち、フェルトの任意の箇所から、横５０ｍｍ、縦５０ｍｍの試験片を３つずつ切り出し、各試験片の厚さ（圧縮前の厚さ）をノギスまたは圧縮試験機で測定した。 (2) Evaluation of felt The following evaluation was performed on the obtained felt. The results are shown in Tables 1 and 2.
(I) Compression recovery rate The compression recovery rate after compression was measured as follows. That is, three test pieces each having a width of 50 mm and a length of 50 mm were cut out from arbitrary portions of the felt, and the thickness of each test piece (thickness before compression) was measured with a caliper or a compression tester.
　次いで、この圧縮前の厚さを１００％として、その厚さが所定の圧縮率（３０％、６０％、７０％）になるまで試験片を圧縮した。所定の圧縮率に達した後、約３０秒間保持し、その後圧縮を開放する。圧縮を開放した後に約３０秒間経過後に厚さをノギスまたは圧縮試験機で測定した。 Next, assuming that the thickness before compression was 100%, the test piece was compressed until the thickness reached a predetermined compression rate (30%, 60%, 70%). After reaching the predetermined compression ratio, the pressure is held for about 30 seconds, and then the compression is released. The thickness was measured with calipers or a compression tester after about 30 seconds had passed after releasing the compression.
　そして、試験片の圧縮前の厚さに対する圧縮開放後の厚さの割合（％）を復元率として算出した。 And the ratio (%) of the thickness after compression release to the thickness before compression of the test piece was calculated as the restoration rate.
（ii）嵩密度
　（ｉ）記載のサンプルの横、縦、厚さをノギスにて測定し、重量を天秤にて測定し嵩密度を測定した。 (Ii) Bulk density The width, length, and thickness of the sample described in (i) were measured with calipers, the weight was measured with a balance, and the bulk density was measured.
（iii）オーバーハンチング試験
　縦６００ｍｍ、横５０ｍｍ、厚さ２５ｍｍのフェルトを、図１に示すように、机の上に試料を載せて、試料の一部が机からはみ出す様にずらしていった。机からずれる量が多くなるにつれ、机の面方向（水平方向）から、試料の端が垂れる量も多くなる。ずらした量とだれ量を測定した。ずらし量（ｍｍ）に対するだれ量（ｍｍ）を表２に示す。 (Iii) Overhunting test As shown in FIG. 1, a felt of 600 mm in length, 50 mm in width, and 25 mm in thickness was placed on a desk and shifted so that a part of the sample protruded from the desk. As the amount of deviation from the desk increases, the amount by which the end of the sample hangs from the desk surface direction (horizontal direction) also increases. The amount of displacement and the amount of drool were measured. Table 2 shows the amount of droop (mm) relative to the amount of shift (mm).
比較例１（ブランケット）
　無機繊維Ａをニードルパンチでブランケットに製造した後、長さ６００ｍｍ×幅５０ｍｍ×厚さ２５ｍｍに切断した後、実施例１と同様に評価した。結果を表１及び表２に示す。 Comparative Example 1 (Blanket)
After manufacturing the inorganic fiber A into a blanket with a needle punch, it was cut into a length of 600 mm × width of 50 mm × thickness of 25 mm, and then evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
比較例２（ボード）
　無機繊維Ａ１００重量部、澱粉（有機バインダー）３重量部、コロイダルシリカ（無機バインダー）８重量部、ポリアクリルアミド（凝集剤）２重量部、水５０００重量部を混合し、脱水成形して、乾燥させて、長さ６００ｍｍ×幅５０ｍｍ×厚さ２５ｍｍのボードを製造し、実施例１と同様に評価した。結果を表１及び表２に示す。 Comparative Example 2 (Board)
100 parts by weight of inorganic fiber A, 3 parts by weight of starch (organic binder), 8 parts by weight of colloidal silica (inorganic binder), 2 parts by weight of polyacrylamide (flocculating agent), 5000 parts by weight of water are mixed, dehydrated and dried. A board having a length of 600 mm, a width of 50 mm and a thickness of 25 mm was manufactured and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２より、実施例１のフェルトは、比較例１のブランケットより硬直性・自立性が高く、実施例１～８のフェルトは、比較例２のボードより柔軟性があり圧縮復元率が高いことが分かる。 From Tables 1 and 2, the felt of Example 1 is more rigid and self-supporting than the blanket of Comparative Example 1, and the felts of Examples 1 to 8 are more flexible and have a compression recovery rate than the board of Comparative Example 2. I understand that it is expensive.
実施例９～１３
　無機繊維Ａ、アクリルエマルジョン（有機バインダー）、硫酸アルミニウム（定着剤）、アンモニア水（ｐＨ調整剤）、消泡剤、凝集剤を混合し、実施例１と同様にして、長さ６００ｍｍ×幅５０ｍｍ×厚さ２５ｍｍのフェルトを製造した。各成分の配合量は、実施例９～１３において、無機繊維Ａ１００重量部に対し、凝集剤は０．０６重量部であり、その他、有機バインダー、消泡剤、定着剤、ｐＨ調整剤の量は表３に示す通り変えた。実施例１と同様に評価した。結果を表３に示す。 Examples 9-13
Inorganic fiber A, acrylic emulsion (organic binder), aluminum sulfate (fixing agent), ammonia water (pH adjusting agent), antifoaming agent, and flocculant are mixed, and in the same manner as in Example 1, length 600 mm × width 50 mm X A felt with a thickness of 25 mm was produced. The blending amount of each component is 0.06 parts by weight of the flocculant with respect to 100 parts by weight of the inorganic fiber A in Examples 9 to 13, and the amount of the organic binder, antifoaming agent, fixing agent, and pH adjuster. Were changed as shown in Table 3. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３より、実施例９～１３のフェルトは、比較例２のボードより柔軟性がありで圧縮復元率が高いことが分かる。 From Table 3, it can be seen that the felts of Examples 9 to 13 are more flexible and have a higher compression recovery rate than the board of Comparative Example 2.
実施例１４，１５
　無機繊維Ａ、アクリルエマルジョン（有機バインダー）、硫酸アルミニウム（定着剤）、アンモニア水（ｐＨ調整剤）、消泡剤、凝集剤、パルプを混合し、実施例１と同様にして、長さ６００ｍｍ×幅５０ｍｍ×厚さ２５ｍｍのフェルトを製造した。各成分の配合量は、実施例１４，１５において、無機繊維Ａ１００重量部に対し、凝集剤は０．０６重量部であり、有機バインダー５重量部、消泡剤０．３重量部、定着剤１．３重量部、ｐＨ調整剤０．１重量部とし、パルプの量は表４に示す通り変えた。実施例１と同様に評価した。結果を表４に示す。 Examples 14 and 15
Inorganic fiber A, acrylic emulsion (organic binder), aluminum sulfate (fixing agent), aqueous ammonia (pH adjusting agent), antifoaming agent, flocculant, and pulp are mixed, and the length is 600 mm × as in Example 1. A felt having a width of 50 mm and a thickness of 25 mm was produced. In Examples 14 and 15, the amount of each component is 0.06 parts by weight of the flocculant, 100 parts by weight of the inorganic fiber A, 5 parts by weight of the organic binder, 0.3 parts by weight of the antifoaming agent, and the fixing agent. 1.3 parts by weight and 0.1 parts by weight of the pH adjuster, and the amount of pulp was changed as shown in Table 4. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４から、無機繊維とともにパルプを入れても、圧縮復元性に影響を及ぼさないことがわかる。 From Table 4, it can be seen that even if the pulp is added together with the inorganic fiber, it does not affect the compression recovery property.
　本発明の無機繊維質定形体は、断熱材、またアスベストの代替品として、様々な用途に用いることができる。 The inorganic fibrous shaped body of the present invention can be used in various applications as a heat insulating material or as a substitute for asbestos.
　上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
　この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.

Claims (15)

  1. 　以下の組成を有する生体溶解性無機繊維を少なくとも含む無機繊維と、
    　熱硬化性樹脂以外の有機バインダーを含み、
    　ただし、熱硬化性樹脂、コロイダルシリカ及び金属アルコキシドは含まない、無機繊維と有機バインダーを含むスラリーを脱水成形して得られた無機繊維質定形体。
    ［組成］
    　ＳｉＯ２　　６６～８２重量％
    　ＣａＯ　　　１０～３４重量％
    　ＭｇＯ　　　０～３重量％
    　Ａｌ２Ｏ３　　０～５重量％
    　ＳｉＯ２、ＣａＯ、ＭｇＯ、Ａｌ２Ｏ３の合計　９８重量％以上     Inorganic fibers containing at least biosoluble inorganic fibers having the following composition;
    Including organic binders other than thermosetting resins,
    However, an inorganic fibrous shaped body obtained by dehydrating a slurry containing inorganic fibers and an organic binder, which does not contain thermosetting resin, colloidal silica, and metal alkoxide.
    [composition]
    SiO 2 66-82% by weight
    CaO 10-34% by weight
    MgO 0-3 wt%
    Al 2 O 3 0-5% by weight
    Total of SiO 2 , CaO, MgO, Al 2 O 3 98% by weight or more
  2. 　前記有機バインダーが熱可塑性樹脂を含む請求項１記載の無機繊維質定形体。 The inorganic fibrous shaped product according to claim 1, wherein the organic binder contains a thermoplastic resin.
  3. 　前記熱可塑性樹脂が、アクリル樹脂、アクリル－スチレン共重合体、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド及びポリビニルアルコールから選択される１以上である請求項２に記載の無機繊維質定形体。 The inorganic fibrous shaped product according to claim 2, wherein the thermoplastic resin is at least one selected from an acrylic resin, an acrylic-styrene copolymer, polyester, polyethylene, polypropylene, polystyrene, polyamide, and polyvinyl alcohol.
  4. 　さらに定着剤を含む請求項１～３のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 3, further comprising a fixing agent.
  5. 　前記定着剤が、アルミニウム、マグネシウム、カルシウム、ナトリウム及びこれらの塩から選択される１以上である請求項４記載の無機繊維質定形体。 The inorganic fibrous shaped product according to claim 4, wherein the fixing agent is one or more selected from aluminum, magnesium, calcium, sodium and salts thereof.
  6. 　さらにｐＨ調整剤を含む請求項１～５のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 5, further comprising a pH adjuster.
  7. 　前記ｐＨ調整剤が、アンモニア水及び水酸化ナトリウムから選択される１以上である請求項６記載の無機繊維質定形体。 The inorganic fibrous shaped product according to claim 6, wherein the pH adjuster is one or more selected from ammonia water and sodium hydroxide.
  8. 　前記無機繊維全量を１００重量部としたとき、前記有機バインダーを０．０１～５０重量部含む請求項１～７のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 7, comprising 0.01 to 50 parts by weight of the organic binder when the total amount of the inorganic fibers is 100 parts by weight.
  9. 　前記無機繊維と前記有機バインダーで、９０重量％以上を占める請求項１～８のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 8, wherein the inorganic fiber and the organic binder occupy 90% by weight or more.
  10. 　厚みが５～５０ｍｍである請求項１～９のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 9, wherein the thickness is 5 to 50 mm.
  11. 　圧縮復元率が、圧縮率３０％のときに９１％以上である請求項１～１０のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped body according to any one of claims 1 to 10, wherein the compression restoration rate is 91% or more when the compression rate is 30%.
  12. 　圧縮復元率が、圧縮率６０％のときに７１％以上である請求項１～１１のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 11, wherein the compression restoration rate is 71% or more when the compression rate is 60%.
  13. 　圧縮復元率が、圧縮率７０％のときに６６％以上である請求項１～１２のいずれか記載の無機繊維質定形体。 The inorganic fibrous shaped product according to any one of claims 1 to 12, wherein the compression restoration rate is 66% or more when the compression rate is 70%.
  14. 　少なくとも以下の組成を有する生体溶解性無機繊維を含む無機繊維と、熱硬化性樹脂以外の有機バインダーとを混合し、
    　成形し、
    　前記成形品を溶融温度以下で乾燥する請求項１記載の無機繊維質定形体の製造方法。
    ［組成］
    　ＳｉＯ２　　６６～８２重量％
    　ＣａＯ　　　１０～３４重量％
    　ＭｇＯ　　　０～３重量％
    　Ａｌ２Ｏ３　　０～５重量％
    　ＳｉＯ２、ＣａＯ、ＭｇＯ、Ａｌ２Ｏ３の合計　９８重量％以上     Mixing inorganic fibers containing biosoluble inorganic fibers having at least the following composition and an organic binder other than thermosetting resin,
    Molded,
    The method for producing an inorganic fibrous shaped product according to claim 1, wherein the molded article is dried at a melting temperature or lower.
    [composition]
    SiO 2 66-82% by weight
    CaO 10-34% by weight
    MgO 0-3 wt%
    Al 2 O 3 0-5% by weight
    Total of SiO 2 , CaO, MgO, Al 2 O 3 98% by weight or more
  15. 　前記有機バインダーが、エマルジョン又は水溶液の形態の熱可塑性樹脂を含む請求項１４記載の無機繊維質定形体の製造方法。 The method for producing an inorganic fibrous shaped product according to claim 14, wherein the organic binder contains a thermoplastic resin in the form of an emulsion or an aqueous solution.
PCT/JP2012/007284 2011-12-28 2012-11-13 Highly flexible inorganic fibrous shaped body WO2013099090A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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JP2011287378A JP5166598B1 (en) 2011-12-28 2011-12-28 Highly flexible inorganic fiber shaped body

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