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WO2020009226A1 - Thermal insulation filler, thermal insulation material and thermal insulation structure - Google Patents

Thermal insulation filler, thermal insulation material and thermal insulation structure Download PDF

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Publication number
WO2020009226A1
WO2020009226A1 PCT/JP2019/026834 JP2019026834W WO2020009226A1 WO 2020009226 A1 WO2020009226 A1 WO 2020009226A1 JP 2019026834 W JP2019026834 W JP 2019026834W WO 2020009226 A1 WO2020009226 A1 WO 2020009226A1
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WO
WIPO (PCT)
Prior art keywords
mass
silica
heat
heat insulating
insulating filler
Prior art date
Application number
PCT/JP2019/026834
Other languages
French (fr)
Japanese (ja)
Inventor
航平 水田
浩徳 長崎
和人 田原
内藤　牧男
Original Assignee
デンカ株式会社
国立大学法人大阪大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デンカ株式会社, 国立大学法人大阪大学 filed Critical デンカ株式会社
Priority to JP2020529066A priority Critical patent/JP7377498B2/en
Publication of WO2020009226A1 publication Critical patent/WO2020009226A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B30/00—Compositions for artificial stone, not containing binders
    • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general

Definitions

  • the present invention relates to a heat insulating filler, a heat insulating material, and a heat insulating structure.
  • heat insulation materials are also attracting attention from the viewpoint of, for example, keeping the heat of internal combustion engines and fuel cells, and can be applied to various shapes not limited to molded bodies. Insulating materials are required.
  • porous body containing fine pores of 100 nm or less exhibits excellent heat insulating properties.
  • porous heat insulating materials include inorganic porous heat insulating materials using silica fine particles manufactured by a dry method as shown in Patent Documents 1 to 5. This exhibits excellent heat insulating properties because fluid heat transfer is suppressed by forming a fine porous structure by dry silica containing micropores.
  • the use form as a heat insulating material in the above-mentioned conventional technology is often based on a molded body formed by a mechanical press, and as described in the above-mentioned patent document, many studies have been made to improve dust generation and strength after molding. ing.
  • the powder to be used is required to have good fluidity that can be uniformly filled in a mold.
  • dry silica fine particles have a problem of handling properties during the manufacturing process because they exhibit a small bulk density and strong adhesiveness and squirt property derived from Coulomb force.
  • the heat insulating layer is formed by filling the space with the powder by the flow of the powder.
  • a heat insulating powder having an excellent filling property is required.
  • air in the target space is replaced with powder, so that dry silica fine particles having a very small bulk density are not suitable.
  • Patent Document 8 describes a method for producing a heat insulating material in which a mixture containing 1) silica fine particles as a main component, 2) reinforcing fibers, and 3) a liquid storage material impregnated with water is wet-formed and dried. are doing.
  • Patent Documents 9 and 10 describe heat insulating boards filled with two or more kinds of fine particles having different primary particle diameters. However, Patent Documents 8 to 10 do not describe the water content.
  • the present invention has been made in view of the above problems and background, and has an object to provide a heat-insulating filler that has good heat-insulating properties and can exhibit excellent filling properties.
  • the present inventors have conducted intensive studies, and as a result, the problem was solved by a heat insulating filler containing mixed silica powder obtained by mixing dry silica fine particles and wet silica fine particles at a predetermined ratio. We found that we could solve it. That is, the present invention is as follows.
  • An insulating filler comprising a mixed silica powder comprising 10% by mass to 80% by mass of dry silica and 20% by mass to 90% by mass of wet silica having a water content of 2% by mass or more.
  • the heat-insulating filler according to [1] containing 1 to 10 parts by mass of the inorganic fiber based on 100 parts by mass of the mixed silica powder.
  • [5] The heat-insulating filler according to any one of [1] to [4], wherein the average particle size of the dry silica is 0.8 ⁇ m or less, and the average particle size of the wet silica is 1 ⁇ m or more.
  • a heat insulating material comprising the heat insulating filler according to any one of [1] to [6].
  • [8] A heat insulating structure including the heat insulating material according to [7].
  • a heat insulating filler which has good heat insulating properties and can exhibit excellent filling properties.
  • an excellent heat insulating effect and a heat retaining effect can be provided for various shapes.
  • the heat-insulating filler according to one embodiment (the present embodiment) of the present invention is a mixture comprising 10% by mass to 80% by mass of dry silica and 20% by mass to 90% by mass of wet silica having a water content of 2% by mass or more. Contains silica powder.
  • a low thermal conductivity can be maintained by the fine pore structure formed by the fumed silica, and the charge on the surface is diffused by the moisture in the fumed silica, so that the adhesion is improved.
  • the fluidity is improved and excellent filling properties are exhibited.
  • the fluidity was further improved by the aggregation of the mixed silica powder obtained by mixing these and the addition of the mixed silica fine particles to the inorganic fibers.
  • Dry silica "used in the present invention is a general term for amorphous silica materials produced by a dry method, and those produced by any method such as a combustion method or an arc method can be used.
  • the combustion method refers to, for example, a method in which silicon tetrachloride is reacted in a high-temperature flame.
  • Dry silica (preferably dry silica fine particles) is a particle containing fine pores and gives a fine porous structure in the mixed silica powder. Therefore, from the viewpoint of reducing the thermal conductivity, the content is preferably 10% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. If the amount is less than 10% by mass, sufficient heat insulating properties may not be exhibited. If the amount exceeds 80% by mass, the fluidity of the powder cannot be sufficiently secured, and the filling property may be reduced.
  • wet silica "used in the present invention is a general term for amorphous silica substances produced by a wet method, and those produced by any method such as a precipitation method and a gel method can be used.
  • the sedimentation method refers to, for example, a method of neutralizing an aqueous solution of sodium silicate to precipitate silica, filtering and drying.
  • the wet silica preferably wet silica fine particles
  • the content is preferably from 20% by mass to 90% by mass, and more preferably from 30% by mass to 70% by mass from the viewpoint of fluidity and adhesion when the mixed silica powder is used. If the amount is less than 20% by mass, good handling properties may not be exhibited, and even if the amount exceeds 90% by mass, further enhancement of the effect cannot be expected.
  • the mixed silica powder is a powder containing dry silica and wet silica and obtained by mixing arbitrary inorganic fibers (and, if necessary, radiation scattering particles).
  • Water contained when mixing dry silica and wet silica has a role of suppressing van der Waals force acting on particles.
  • the water content is not particularly limited as long as it is 2% by mass or more based on the mass of the wet silica. If the amount is less than 2% by mass, the adhesion may increase due to static electricity acting on the particles, so that good handling properties may not be exhibited.
  • the water content of the wet silica is preferably from 3 to 15% by mass, more preferably from 5 to 10% by mass.
  • the water content of the mixed silica powder obtained by mixing the dry silica and the wet silica is preferably from 2 to 8% by mass, more preferably from 3 to 7% by mass from the viewpoint of good handling properties. preferable.
  • the average particle diameter of each of the dry silica and the wet silica (more specifically, the 50% integrated particle diameter D 50 measured by a laser diffraction type particle size analyzer (Model LS-230 manufactured by Coulter)) is 0.
  • the average particle diameter of the dry silica is preferably 10 ⁇ m or less from the viewpoint of suppressing the heat transfer of the fluid. Further, in order to improve the fluidity of the mixed silica powder and suppress the jetting property, it is preferable that the average particle diameter of wet silica is larger than that of dry silica.
  • the average particle size of the fumed silica is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and most preferably 0.5 ⁇ m or less.
  • the average particle size of the fumed silica is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, and most preferably 0.05 ⁇ m or more.
  • the average particle size of the wet silica is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and most preferably 5 ⁇ m or more.
  • the average particle diameter of the wet silica is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and most preferably 20 ⁇ m or less.
  • inorganic fibers it is preferable to further mix inorganic fibers with the mixed silica powder.
  • the inorganic fiber used in the present invention is not particularly limited as long as the filling property is improved by impregnating the mixed silica powder with the fiber, and any inorganic fiber can be used. Further, at the time of molding, it has a role of giving moldability to the heat insulating filler. Typical examples are artificial fibers with excellent heat resistance, such as silica fiber, alumina silica fiber, glass fiber, zirconia fiber, silicon carbide fiber, rock wool manufactured from minerals, natural mineral wollastonite, sepiolite, etc. And one or more of these can be used as necessary.
  • the average fiber diameter of the inorganic fibers is an average value of the diameters of 100 fibers confirmed by scanning electron microscope (SEM) observation.
  • the average fiber diameter is preferably from 0.1 ⁇ m to 50 ⁇ m, and more preferably 1 ⁇ m or more, most preferably 5 ⁇ m or more, since the probability of silica fine particles being attached is increased and the ejectability of the powder is suppressed.
  • the average fiber length of the inorganic fibers is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 15 to 35 ⁇ m, in consideration of the filling property of the mixed silica powder.
  • the average fiber length of the inorganic fibers can be determined as the average value of the fiber lengths of 100 fibers confirmed by scanning electron microscope (SEM) observation.
  • the content of the inorganic fiber is preferably from 1 to 10 parts by mass, more preferably from 3 to 7 parts by mass, per 100 parts by mass of the mixed silica powder.
  • the amount is 1 part by mass or more, sufficient moldability is easily exhibited, and when the amount is 10 parts by mass or less, contact between fibers is suppressed, material heat conduction is reduced, and thermal conductivity can be reduced.
  • the heat-insulating filler of the present invention may further contain radiation scattering particles in order to improve heat insulating properties at high temperatures (200 ° C. or higher).
  • the radiation scattering particles are not particularly limited as long as they can effectively scatter or absorb infrared rays.For example, silicon carbide, zirconium oxide, titanium oxide, copper oxide, and the like can be used, and one or more of these particles can be used. Seeds may be used.
  • the amount of the radiation scattering particles to be used is preferably 0.5% by mass to 35% by mass, more preferably 1.0% by mass to 20% by mass based on 100% by mass of the insulating filler.
  • the thermal conductivity of the heat-insulating filler obtained by the present invention is preferably 0.05 W / (m ⁇ K) or less at 25 ° C., and 0.029 W / (m ⁇ K) or less. Is more preferred.
  • the loose filling bulk density is a density obtained when powder is dropped and filled from a certain height into a ground container and then ground.
  • the heat-insulating filler obtained in the present invention preferably has a loose packing bulk density of 40 kg / m 3 or more, and more preferably 50 to 80 kg / m 3 , in a mixed silica powder state, from the viewpoint of approaching the designed packing density. More preferred. When it is 40 kg / m 3 or more, sufficient filling properties are exhibited, voids do not increase too much, and sufficient heat insulating properties are easily obtained.
  • the method for producing the heat-insulating filler is not particularly limited. For example, 10% to 80% by mass of dry silica and 20% to 90% by mass of wet silica having a water content of 2% by mass or more are several mm And a method of mixing them with a grinding mill having a clearance, and a method of mixing them with a metal blade while winding them up with an air current to obtain them by biaxial mixing.
  • the heat-insulating filler of the present embodiment as described above can be used as a solid. Further, among solids, it can be used as a powder.
  • Heat insulation material The heat insulation material according to the present embodiment is obtained by blending the above-mentioned heat insulation filler. Specifically, it refers to a heat insulating layer or a heat insulating material obtained by filling the above-described heat insulating filler as a raw material, for example, a heat insulating layer obtained by filling a space using the flow of powder. And a heat insulating material obtained by filling a mold with pressure.
  • the detailed method of obtaining by pressure filling is not particularly limited, but for example, it may be formed into a plate by a dry uniaxial press using a mold.
  • dry molding is preferred from the viewpoint of molding defects due to generation of voids and cracks during drying.
  • the heat insulating material according to the present embodiment may be formed by covering the whole of the above-mentioned heat insulating filler with a skin material.
  • the outer shell material is desirably in the form of sheet such as glass fiber, inorganic fiber woven fabric such as alumina fiber or inorganic fiber non-woven fabric, resin film, organic fiber woven fabric, organic fiber non-woven fabric, aluminum, metal foil such as copper foil, etc. There is no particular limitation.
  • the coating method is not particularly limited, and the filling rate of the heat-insulating filler can be appropriately set according to the intended use.
  • a heat-insulating filler formed by pressure molding may be covered with the above-described sheet, or a sheet-like processed sheet may be filled with the heat-insulating filler.
  • the heat insulation structure according to the present embodiment includes the above-described heat insulating material.
  • the heat-insulating filler according to the present embodiment may be used as it is as a heat insulating material, or may be combined with another heat insulating material to form a heat insulating structure.
  • a heat insulating structure configured by a laminated structure filled and laminated on another heat insulating material having different heat resistance
  • the heat insulating material to the heat insulating filler according to the present embodiment It can be said that this is a combined layered heat insulating structure.
  • a heat insulating structure in which a hollow box is filled with the heat insulating filler according to the present embodiment as a heat insulating material may be employed.
  • Example 1 Dry insulating silica and wet silica were mixed at a mixing ratio shown in Table 1, and 4.5 parts by mass of the inorganic fiber was mixed with 100 parts by mass of the mixture (mixed silica powder) to prepare an insulating filler.
  • Dry silica 1 (F1): CAB-O-SIL M-5 powder (trade name, manufactured by Cabot Specialty Chemicals), average particle size 0.20 ⁇ m, bulk density 70 g / L, water content 0.9 mass% Dry silica 2 (F2): AEROSIL 380 (trade name, manufactured by Nippon Aerosil Co., Ltd.), average particle size less than 0.05 ⁇ m, bulk density 50 g / L, water content 1.0 mass% Dry silica 3 (F3): NDK-N20 (trade name, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), average particle size 0.15 ⁇ m, bulk density 40 g / L, water content 1.2 mass%
  • Wet silica 1 CARPLEX # 80 powder (trade name, manufactured by Evonik Japan KK) Average particle size 15 ⁇ m, bulk density 145 g / L, water content 8.0 mass%
  • Wet silica 2 (W2): Toksil NP (trade name, manufactured by Oriental Silicas Corporation), average particle diameter 10 ⁇ m, bulk density 63 g / L, water content 6.2 mass%
  • Wet silica 3 (W3): Mizukasil P-527 (trade name, manufactured by Mizusawa Chemical Industry Co., Ltd.), average particle size 1.8 ⁇ m, bulk density 190 g / L, water content 5.2 mass%
  • Inorganic fiber 1 silica fiber sheet AS-300 (trade name, manufactured by Asahi Sangyo Co., Ltd.) Average fiber diameter 10 ⁇ m, 25 mm cutting and defibration processing (average fiber length: 25 mm)
  • the bulk density of the above-mentioned materials is a densely packed bulk density, which is measured by “Powder Tester PT-S” manufactured by Hosokawa Micron Corporation.
  • Water content The water content of dry silica, wet silica, and mixed silica powder was determined as the weight loss rate at 200 ° C. using a differential thermogravimetric analyzer TG-DTA 2000SR (trade name, Bruker AXS).
  • the loose filling bulk density was a density calculated by dropping the heat-insulating filler from the funnel into a stainless beaker having an inner diameter of 63 mm and a capacity of 200 mL at an interval of 150 mm, and performing abrasion filling.
  • a molded body (200 mm ⁇ 200 mm ⁇ 20 mm, density: about 230 kg / m 3 ) is produced from the produced heat-insulating filler by die molding using a uniaxial press, and a thermal conductivity measuring apparatus ( (Manufactured by Eiko Seiki Co., Ltd.) at 23 ° C.
  • a molded body (dimensions and the like were the same as above) was produced by die molding using a uniaxial press, and the moldability was visually evaluated. The case where no crack was observed in the molded body was evaluated as “O”, and the case where cracks or damage was observed was evaluated as “X”.
  • Example 2 Dry silica F1 was mixed at a ratio of 50% by mass and wet silica W1 was mixed at a ratio of 50% by mass, and inorganic fibers shown in Table 2 were used for the obtained mixture (mixed silica powder: Experiment No. 1-4), The procedure was performed in the same manner as in Experimental Example 1, except that the amount of the insulating filler was changed as shown in Table 2 to prepare the heat insulating filler. Table 2 shows the results.
  • Inorganic fiber 2 (Material used) Inorganic fiber 2 (IF2): glass fiber (manufactured by NEC Corporation), average fiber diameter 50 ⁇ m, average fiber length 25 mm
  • Inorganic fiber 3 (IF3): Alumina silica fiber (trade name: Denka-Alsen, manufactured by Denka) Average fiber diameter 5.0 ⁇ m, average fiber length 25 mm
  • Example 3 Experiment No. Except that the thermal conductivity (high-temperature thermal conductivity) at a high temperature (600 ° C.) was measured using the radiation-scattering particles shown in Table 3 using the formulation 1-4 and changing the blending amount as shown in Table 3. Was performed in the same manner as in Experimental Example 1.
  • a molded body (the dimensions and the like are the same as above) is produced from the produced heat-insulating filler by die molding using a uniaxial press, and a protective thermal plate method thermal conductivity measuring apparatus in accordance with JIS A 1412-1. It measured at 600 degreeC using (made by Eikoseiki).
  • the heat-insulating filler of the present invention configured as described above has excellent operability and filling properties, and has more heat resistance and heat insulating properties than before, so it can be applied to complicated shapes, It can contribute to energy saving of vehicles, airplanes, other internal combustion engines, and piping.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Insulation (AREA)
  • Silicon Compounds (AREA)

Abstract

A thermal insulation filler which contains a mixed silica powder that is composed of from 10% by mass to 80% by mass of dry silica and from 20% by mass to 90% by mass of wet silica having a moisture content of 2% by mass or more. It is preferable that from 1 part by mass to 10 parts by mass of inorganic fibers are contained per 100 parts by mass of the mixed silica powder; and it is also preferable that the inorganic fibers have an average fiber diameter of from 0.1 μm to 50 μm.

Description

断熱充填材、断熱材、断熱構造Insulation filler, insulation, insulation structure
　本発明は、断熱充填材、断熱材、断熱構造に関する。 The present invention relates to a heat insulating filler, a heat insulating material, and a heat insulating structure.
　近年、省エネルギーの観点から放熱エネルギーを抑制するために、断熱材の需要が益々大きくなってきている。また、従来の住宅や配管、溶鉱炉、電気炉といった用途だけでなく、例えば内燃機関や燃料電池等の保温といった観点からも断熱材は注目されており、成型体に限らない様々な形状に適応可能な断熱材が求められている。 In recent years, the demand for heat insulating materials has been increasing more and more in order to suppress heat radiation from the viewpoint of energy saving. In addition to conventional applications such as houses, pipes, blast furnaces, and electric furnaces, heat insulation materials are also attracting attention from the viewpoint of, for example, keeping the heat of internal combustion engines and fuel cells, and can be applied to various shapes not limited to molded bodies. Insulating materials are required.
　室温付近での空気の平均自由行程は１００ｎｍであるため、１００ｎｍ以下の微細気孔を含む多孔質体が優れた断熱性を示すことがよく知られている。このような多孔質断熱材には様々な種類があり、例えば特許文献１～５に示されるような乾式法によって製造されたシリカ微粒子を使用した無機系多孔質断熱材が挙げられる。これは、微細気孔を内包する乾式シリカによって微細な多孔質構造が形成されていることで流体熱伝達が抑制されるため、優れた断熱性を示す。 た め Since the mean free path of air near room temperature is 100 nm, it is well known that a porous body containing fine pores of 100 nm or less exhibits excellent heat insulating properties. There are various types of such porous heat insulating materials, and examples thereof include inorganic porous heat insulating materials using silica fine particles manufactured by a dry method as shown in Patent Documents 1 to 5. This exhibits excellent heat insulating properties because fluid heat transfer is suppressed by forming a fine porous structure by dry silica containing micropores.
　上記従来技術における断熱材としての使用形態は、機械プレスによる成型体をベースとしたものが多く、上述した特許文献のように、発塵性や成型後の強度を改善する検討が多く成されてきている。このとき、均一な成型体を得るために、使用粉体には金型に対して均一に充填出来る良好な流動性が求められる。しかしながら、乾式シリカ微粒子は、小さな嵩密度とクーロン力に由来する強い付着性、噴出性を示すために製造工程中でのハンドリング性が課題である。 The use form as a heat insulating material in the above-mentioned conventional technology is often based on a molded body formed by a mechanical press, and as described in the above-mentioned patent document, many studies have been made to improve dust generation and strength after molding. ing. At this time, in order to obtain a uniform molded body, the powder to be used is required to have good fluidity that can be uniformly filled in a mold. However, dry silica fine particles have a problem of handling properties during the manufacturing process because they exhibit a small bulk density and strong adhesiveness and squirt property derived from Coulomb force.
　また、特許文献６、７で袋状の外皮材中に粉末を充填することによって製造される断熱材について示されているように、粉末の流動によって空間に粉体を充填することで断熱層を形成する手法があり、充填性に優れる断熱性粉体が必要とされる。しかし、流動による充填では、対象空間中の空気を粉体へと置換するため、嵩密度が非常に小さな乾式シリカ微粒子では不向きである。 In addition, as shown in Patent Documents 6 and 7 regarding a heat insulating material manufactured by filling a powder in a bag-shaped outer material, the heat insulating layer is formed by filling the space with the powder by the flow of the powder. There is a forming method, and a heat insulating powder having an excellent filling property is required. However, in the case of filling by flow, air in the target space is replaced with powder, so that dry silica fine particles having a very small bulk density are not suitable.
　特許文献８は、１）主成分としてのシリカ微粒子と、２）補強繊維と、３）水を含浸させた蓄液性物質とを含む混合物を湿式成形し、乾燥する断熱材の製造方法を記載している。特許文献９、１０は、一次粒子径の異なる２種以上の微粒子が充填されてなる断熱ボードを記載している。しかし、特許文献８～１０は、含水率について記載がない。 Patent Document 8 describes a method for producing a heat insulating material in which a mixture containing 1) silica fine particles as a main component, 2) reinforcing fibers, and 3) a liquid storage material impregnated with water is wet-formed and dried. are doing. Patent Documents 9 and 10 describe heat insulating boards filled with two or more kinds of fine particles having different primary particle diameters. However, Patent Documents 8 to 10 do not describe the water content.
特許第４８６０００５号公報Japanese Patent No. 4860005 特開平７－２３７９５７号公報JP-A-7-237957 特許第０５０８１４６４号公報Japanese Patent No. 05081464 特許第４３６７６１２号公報Japanese Patent No. 4367612 特表平１１－５１３３４９号公報Japanese Patent Publication No. 11-513349 特許第５７８３７１７号公報Japanese Patent No. 5783717 特開２０１３－１５９６号公報JP 2013-1596 A 特許第５４０９９３９号公報Patent No. 5409939 特開平１－１９９０９５号公報JP-A-1-199095 特開平１－１３５９９８号公報JP-A-1-135998
　本発明は、上記課題と背景を鑑みてなされたものであり、良好な断熱性を有し、優れた充填性を発揮しうる断熱充填材を提供することを目的とする。 The present invention has been made in view of the above problems and background, and has an object to provide a heat-insulating filler that has good heat-insulating properties and can exhibit excellent filling properties.
　本発明者らは、上記課題と背景を鑑みて、鋭意検討を重ねた結果、乾式シリカ微粒子と湿式シリカ微粒子とを所定の割合で混合してなる混合シリカ粉末を含む断熱充填材により当該課題が解決できることを見出した。すなわち、本発明は下記のとおりである。 In view of the above problems and background, the present inventors have conducted intensive studies, and as a result, the problem was solved by a heat insulating filler containing mixed silica powder obtained by mixing dry silica fine particles and wet silica fine particles at a predetermined ratio. We found that we could solve it. That is, the present invention is as follows.
［１］　乾式シリカ１０質量％～８０質量％と、含水率が２質量％以上の湿式シリカ２０質量％～９０質量％とからなる混合シリカ粉末を含む断熱充填材。
［２］　前記混合シリカ粉末１００質量部に対して、無機繊維を１質量部～１０質量部含む［１］に記載の断熱充填材。
［３］　前記無機繊維が平均繊維径０．１μｍ～５０μｍである［２］に記載の断熱充填材。
［４］　輻射散乱粒子を含む［１］～［３］のいずれかに記載の断熱充填材。
［５］　前記乾式シリカの平均粒径が０．８μｍ以下であり、前記湿式シリカの平均粒径が１μｍ以上である［１］～［４］のいずれかに記載の断熱充填材。
［６］　固体である［１］～［５］のいずれかに記載の断熱充填材。
［７］　［１］～［６］のいずれかに記載の断熱充填材を配合してなる断熱材。
［８］　［７］に記載の断熱材を含む断熱構造。 [1] An insulating filler comprising a mixed silica powder comprising 10% by mass to 80% by mass of dry silica and 20% by mass to 90% by mass of wet silica having a water content of 2% by mass or more.
[2] The heat-insulating filler according to [1], containing 1 to 10 parts by mass of the inorganic fiber based on 100 parts by mass of the mixed silica powder.
[3] The heat insulating filler according to [2], wherein the inorganic fibers have an average fiber diameter of 0.1 μm to 50 μm.
[4] The heat-insulating filler according to any one of [1] to [3], containing radiation scattering particles.
[5] The heat-insulating filler according to any one of [1] to [4], wherein the average particle size of the dry silica is 0.8 μm or less, and the average particle size of the wet silica is 1 μm or more.
[6] The heat-insulating filler according to any one of [1] to [5], which is a solid.
[7] A heat insulating material comprising the heat insulating filler according to any one of [1] to [6].
[8] A heat insulating structure including the heat insulating material according to [7].
　本発明によれば、良好な断熱性を有し、優れた充填性を発揮しうる断熱充填材を提供できる。その結果、様々な形状物に対し優れた断熱効果、保温効果を提供できる。 According to the present invention, it is possible to provide a heat insulating filler which has good heat insulating properties and can exhibit excellent filling properties. As a result, an excellent heat insulating effect and a heat retaining effect can be provided for various shapes.
　以下、本発明の詳細を説明する。
［１．断熱充填材］
　本発明の一実施形態（本実施形態）に係る断熱充填材は、乾式シリカ１０質量％～８０質量％と、含水率が２質量％以上の湿式シリカ２０質量％～９０質量％とからなる混合シリカ粉末を含む。 Hereinafter, details of the present invention will be described.
[1. Insulation filler]
The heat-insulating filler according to one embodiment (the present embodiment) of the present invention is a mixture comprising 10% by mass to 80% by mass of dry silica and 20% by mass to 90% by mass of wet silica having a water content of 2% by mass or more. Contains silica powder.
　本実施形態においては、具体的には、乾式シリカによって形成される微細気孔構造で低熱伝導率を維持でき、上記湿式シリカ中の水分によって表面の電荷が拡散されるために付着性が改善されることで、流動性が向上し優れた充填性発揮されると推察される。さらにこれらを混合した混合シリカ粉末の凝集と無機繊維への混合シリカ微粒子の添着によって流動性がより向上することが見出された。 In the present embodiment, specifically, a low thermal conductivity can be maintained by the fine pore structure formed by the fumed silica, and the charge on the surface is diffused by the moisture in the fumed silica, so that the adhesion is improved. Thus, it is presumed that the fluidity is improved and excellent filling properties are exhibited. Further, it was found that the fluidity was further improved by the aggregation of the mixed silica powder obtained by mixing these and the addition of the mixed silica fine particles to the inorganic fibers.
　本発明で使用する「乾式シリカ」とは、乾式法によって製造される非晶質シリカ物質の総称であり、燃焼法もしくはアーク法等、いずれの方法で製造されたものも使用できる。燃焼法とは例えば、四塩化珪素を高温の炎の中で反応させる方法をいう。乾式シリカ（乾式シリカ微粒子が好ましい）は微細な気孔を含んだ粒子であり、混合シリカ粉末において微細な多孔質構造を与えるものである。そのため、熱伝導率低減の観点から、含有量は１０質量％～８０質量％とし、３０～７０質量％とすることが好ましい。１０質量％未満では十分な断熱性を発揮しない場合があり、８０質量％を超えると粉体流動性が十分に確保できず、充填性が低下する場合がある。 「" Dry silica "used in the present invention is a general term for amorphous silica materials produced by a dry method, and those produced by any method such as a combustion method or an arc method can be used. The combustion method refers to, for example, a method in which silicon tetrachloride is reacted in a high-temperature flame. Dry silica (preferably dry silica fine particles) is a particle containing fine pores and gives a fine porous structure in the mixed silica powder. Therefore, from the viewpoint of reducing the thermal conductivity, the content is preferably 10% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass. If the amount is less than 10% by mass, sufficient heat insulating properties may not be exhibited. If the amount exceeds 80% by mass, the fluidity of the powder cannot be sufficiently secured, and the filling property may be reduced.
　本発明で使用する「湿式シリカ」とは、湿式法によって製造される非晶質シリカ物質の総称であり、沈降法もしくはゲル法等、いずれの方法で製造されたものも使用できる。沈降法とは例えば、珪酸ソーダの水溶液を中和してシリカを析出し、濾過、乾燥する方法をいう。この湿式シリカ（湿式シリカ微粒子が好ましい）は、乾式シリカを自身の周囲に添着させることで、粉末の付着性および噴出性を抑える粒子である。また、含有量は、混合シリカ粉末とした時の流動性と付着性の観点から２０質量％～９０質量％とし、３０～７０質量％とすることが好ましい。２０質量％未満では良好なハンドリング性を発揮しない場合があり、９０質量％を超えて添加してもそれ以上の効果の増進は期待できない。ここで、混合シリカ粉末とは、乾式シリカと湿式シリカと含み、任意の無機繊維を（必要な場合は輻射散乱粒子も）混合することで得られる粉末のことである。 「" Wet silica "used in the present invention is a general term for amorphous silica substances produced by a wet method, and those produced by any method such as a precipitation method and a gel method can be used. The sedimentation method refers to, for example, a method of neutralizing an aqueous solution of sodium silicate to precipitate silica, filtering and drying. The wet silica (preferably wet silica fine particles) is a particle that suppresses powder adhesion and jetting properties by adhering dry silica to the periphery thereof. Further, the content is preferably from 20% by mass to 90% by mass, and more preferably from 30% by mass to 70% by mass from the viewpoint of fluidity and adhesion when the mixed silica powder is used. If the amount is less than 20% by mass, good handling properties may not be exhibited, and even if the amount exceeds 90% by mass, further enhancement of the effect cannot be expected. Here, the mixed silica powder is a powder containing dry silica and wet silica and obtained by mixing arbitrary inorganic fibers (and, if necessary, radiation scattering particles).
　乾式シリカと湿式シリカとの混合時に含まれる水分は粒子に働くファンデルワールス力を抑える役割がある。この含水率は、湿式シリカの質量に対して２質量％以上であれば特に限らない。２質量％未満では、粒子に働く静電気により付着性が増大するため、良好なハンドリング性を発揮しない場合がある。湿式シリカの含水率は３～１５質量％であることが好ましく、５～１０質量％であることがより好ましい。 水分 Water contained when mixing dry silica and wet silica has a role of suppressing van der Waals force acting on particles. The water content is not particularly limited as long as it is 2% by mass or more based on the mass of the wet silica. If the amount is less than 2% by mass, the adhesion may increase due to static electricity acting on the particles, so that good handling properties may not be exhibited. The water content of the wet silica is preferably from 3 to 15% by mass, more preferably from 5 to 10% by mass.
　また、乾式シリカと湿式シリカとを混合してなる混合シリカ粉末の含水率は、良好なハンドリング性の観点から、２～８質量％であることが好ましく、３～７質量％であることがより好ましい。 The water content of the mixed silica powder obtained by mixing the dry silica and the wet silica is preferably from 2 to 8% by mass, more preferably from 3 to 7% by mass from the viewpoint of good handling properties. preferable.
　上記乾式シリカ、湿式シリカ、混合シリカの含水率は、熱重量分析装置（ＴＧＡ）によって２００℃まで昇温し、昇温前の重量Ｘと減少した重量Ｘ１を用いて含水率Ｗを算出する。
　含水率Ｗ（質量％）＝（Ｘ１／Ｘ）×１００ The dry silica, wet silica, the water content of the mixed silica, thermogravimetric analyzer (TGA) by raising the temperature to 200 ° C., to calculate the water content W with reference to the weight X 1 was reduced with heated weight before X .
Water content W (% by mass) = (X 1 / X) × 100
　乾式シリカ及び湿式シリカのそれぞれの平均粒径（より具体的にはレーザー回折式粒度測定器（コールター社製「モデルＬＳ－２３０」型）によって測定される５０％積算粒子径Ｄ５０）は０．０１μｍ～１００μｍが好ましく、流体熱伝達を抑える観点から、乾式シリカの平均粒径は１０μｍ以下が好ましい。また、混合シリカ粉末とした時の流動性を向上させ、噴出性を抑えるために、湿式シリカの平均粒径は乾式シリカより大きいことが好ましい。 The average particle diameter of each of the dry silica and the wet silica (more specifically, the 50% integrated particle diameter D 50 measured by a laser diffraction type particle size analyzer (Model LS-230 manufactured by Coulter)) is 0. The average particle diameter of the dry silica is preferably 10 μm or less from the viewpoint of suppressing the heat transfer of the fluid. Further, in order to improve the fluidity of the mixed silica powder and suppress the jetting property, it is preferable that the average particle diameter of wet silica is larger than that of dry silica.
　乾式シリカの平均粒径は１μｍ以下が好ましく、０．８μｍ以下がより好ましく、０．５μｍ以下が最も好ましい。乾式シリカの平均粒径は０．０１μｍ以上が好ましく、０．０３μｍ以上がより好ましく、０．０５μｍ以上が最も好ましい。湿式シリカの平均粒径は、０．５μｍ以上が好ましく、１μｍ以上がより好ましく、５μｍ以上が最も好ましい。湿式シリカの平均粒径は、５０μｍ以下が好ましく、３０μｍ以下がより好ましく、２０μｍ以下が最も好ましい。 (4) The average particle size of the fumed silica is preferably 1 μm or less, more preferably 0.8 μm or less, and most preferably 0.5 μm or less. The average particle size of the fumed silica is preferably 0.01 μm or more, more preferably 0.03 μm or more, and most preferably 0.05 μm or more. The average particle size of the wet silica is preferably 0.5 μm or more, more preferably 1 μm or more, and most preferably 5 μm or more. The average particle diameter of the wet silica is preferably 50 μm or less, more preferably 30 μm or less, and most preferably 20 μm or less.
　本実施形態においては、混合シリカ粉末にさらに無機繊維を混合することが好ましい。
　本発明で使用する無機繊維は、混合シリカ粉末の繊維添着により充填性を向上させるものであれば特に限定されるものではなく、いかなるものでも使用できる。また、成形時には断熱充填材に成形性を与える役割を持つ。代表的なものとして、耐熱性に優れる人造繊維であるシリカ繊維、アルミナシリカ繊維、ガラス繊維、ジルコニア繊維、炭化ケイ素繊維、鉱物を原料として製造されるロックウール、天然鉱物のウォラストナイト、セピオライトなどが挙げられ、必要に応じてこれらを一種あるいは複数種使用することができる。 In the present embodiment, it is preferable to further mix inorganic fibers with the mixed silica powder.
The inorganic fiber used in the present invention is not particularly limited as long as the filling property is improved by impregnating the mixed silica powder with the fiber, and any inorganic fiber can be used. Further, at the time of molding, it has a role of giving moldability to the heat insulating filler. Typical examples are artificial fibers with excellent heat resistance, such as silica fiber, alumina silica fiber, glass fiber, zirconia fiber, silicon carbide fiber, rock wool manufactured from minerals, natural mineral wollastonite, sepiolite, etc. And one or more of these can be used as necessary.
　上記無機繊維の平均繊維径とは、走査型電子顕微鏡（ＳＥＭ）観察によって確認される繊維１００本の直径の平均値である。平均繊維径は０．１μｍ～５０μｍが好ましく、シリカ微粒子が付着する確率が増大し、粉体の噴出性を抑えられるため、１μｍ以上がより好ましく、５μｍ以上が最も好ましい。 平均 The average fiber diameter of the inorganic fibers is an average value of the diameters of 100 fibers confirmed by scanning electron microscope (SEM) observation. The average fiber diameter is preferably from 0.1 μm to 50 μm, and more preferably 1 μm or more, most preferably 5 μm or more, since the probability of silica fine particles being attached is increased and the ejectability of the powder is suppressed.
　上記無機繊維の平均繊維長は特に限定するものではないが、混合シリカ粉末の充填性を考慮すると１０μｍ以上が好ましく、１５～３５μｍがより好ましい。
　なお、上記無機繊維の平均繊維長は、走査型電子顕微鏡（ＳＥＭ）観察によって確認される繊維１００本の繊維長の平均値として求めることができる。 The average fiber length of the inorganic fibers is not particularly limited, but is preferably 10 μm or more, more preferably 15 to 35 μm, in consideration of the filling property of the mixed silica powder.
The average fiber length of the inorganic fibers can be determined as the average value of the fiber lengths of 100 fibers confirmed by scanning electron microscope (SEM) observation.
　上記無機繊維の含有量は、混合シリカ粉末１００質量部に対して、１質量部～１０質量部であることが好ましく、３～７質量部であることがより好ましい。
　１質量部以上であることで、十分な成形性が発揮されやすくなり、１０質量部以下であることで繊維同士の接触が抑えられ、物質熱伝導が小さくなり熱伝導率を低下させることができる。 The content of the inorganic fiber is preferably from 1 to 10 parts by mass, more preferably from 3 to 7 parts by mass, per 100 parts by mass of the mixed silica powder.
When the amount is 1 part by mass or more, sufficient moldability is easily exhibited, and when the amount is 10 parts by mass or less, contact between fibers is suppressed, material heat conduction is reduced, and thermal conductivity can be reduced. .
　本発明の断熱充填材は、高温中（２００℃以上）での断熱性を向上させるために輻射散乱粒子をさらに含有することができる。輻射散乱粒子は、赤外線を効果的に散乱又は吸収できるものであれば特に限定されるものではなく、例えば炭化ケイ素や酸化ジルコニウム、酸化チタン、酸化銅などが使用でき、これらの粒子を一種あるいは複数種使用してよい。
　輻射散乱粒子の使用量は、断熱充填材１００質量％に対して、０．５質量％～３５質量％が好ましく、１．０質量％～２０質量％がより好ましい。 The heat-insulating filler of the present invention may further contain radiation scattering particles in order to improve heat insulating properties at high temperatures (200 ° C. or higher). The radiation scattering particles are not particularly limited as long as they can effectively scatter or absorb infrared rays.For example, silicon carbide, zirconium oxide, titanium oxide, copper oxide, and the like can be used, and one or more of these particles can be used. Seeds may be used.
The amount of the radiation scattering particles to be used is preferably 0.5% by mass to 35% by mass, more preferably 1.0% by mass to 20% by mass based on 100% by mass of the insulating filler.
　本発明によって得られる断熱充填材の熱伝導率は、２５℃における熱伝導率が０．０５Ｗ／（ｍ・Ｋ）以下であることが好ましく、０．０２９Ｗ／（ｍ・Ｋ）以下であることがより好ましい。 The thermal conductivity of the heat-insulating filler obtained by the present invention is preferably 0.05 W / (m · K) or less at 25 ° C., and 0.029 W / (m · K) or less. Is more preferred.
　疎充填嵩密度とは、すり切り容器に対して一定の高さから粉体を落として充填し、すり切った際に得られる密度である。 The loose filling bulk density is a density obtained when powder is dropped and filled from a certain height into a ground container and then ground.
　本発明で得られる断熱充填材は、設計した充填密度に近づける観点から混合シリカ粉末の状態で疎充填嵩密度が４０ｋｇ／ｍ３以上であることが好ましく、５０～８０ｋｇ／ｍ３であることがより好ましい。４０ｋｇ／ｍ３以上であることで十分な充填性が発揮され、空隙が増大しすぎず、十分な断熱性が得られやすくなる。 The heat-insulating filler obtained in the present invention preferably has a loose packing bulk density of 40 kg / m 3 or more, and more preferably 50 to 80 kg / m 3 , in a mixed silica powder state, from the viewpoint of approaching the designed packing density. More preferred. When it is 40 kg / m 3 or more, sufficient filling properties are exhibited, voids do not increase too much, and sufficient heat insulating properties are easily obtained.
　断熱充填材の製造方法は特に限定するものではないが、例えば、乾式シリカ１０質量％～８０質量％と、含水率が２質量％以上の湿式シリカ２０質量％～９０質量％とを、数ｍｍのクリアランスを持たせた磨砕式ミルによって混合することで得る方法や、気流で巻き上げながら金属羽でこれらを混合する二軸混合によって得る方法等が挙げられる。
　以上のような本実施形態の断熱充填材は固体として使用できる。また、固体の中では、粉末として使用できる。 The method for producing the heat-insulating filler is not particularly limited. For example, 10% to 80% by mass of dry silica and 20% to 90% by mass of wet silica having a water content of 2% by mass or more are several mm And a method of mixing them with a grinding mill having a clearance, and a method of mixing them with a metal blade while winding them up with an air current to obtain them by biaxial mixing.
The heat-insulating filler of the present embodiment as described above can be used as a solid. Further, among solids, it can be used as a powder.
［２］断熱材
　本実施形態に係る断熱材は、既述の断熱充填材を配合してなる。
　具体的には、既述の断熱充填材を原料として充填することによって得られる断熱層又は断熱材のことであり、例えば、粉体の流動を利用して空間に充填することにより得られる断熱層であって、金型に加圧充填することによって得られる断熱材が挙げられる。 [2] Heat insulation material The heat insulation material according to the present embodiment is obtained by blending the above-mentioned heat insulation filler.
Specifically, it refers to a heat insulating layer or a heat insulating material obtained by filling the above-described heat insulating filler as a raw material, for example, a heat insulating layer obtained by filling a space using the flow of powder. And a heat insulating material obtained by filling a mold with pressure.
　加圧充填によって得る場合の詳細な手法は、特に限定するものではないが、例えば、金型を使用した乾式一軸プレスによって板状に成型してもよい。ただし、乾燥時の空隙や亀裂の発生による成型欠陥の観点から、乾式成形が好ましい。 詳細 The detailed method of obtaining by pressure filling is not particularly limited, but for example, it may be formed into a plate by a dry uniaxial press using a mold. However, dry molding is preferred from the viewpoint of molding defects due to generation of voids and cracks during drying.
　また、本実施形態に係る断熱材は、外皮材によって既述の断熱充填材の全体を被覆させてなるものでもよい。外皮材は、ガラス繊維、アルミナ繊維等の無機繊維織物や無機繊維不織布、樹脂フィルム、有機繊維織物、有機繊維不織布、アルミニウム、銅箔などの金属箔等シート形状のものが望ましいが、材質については特に限定されるものではない。 断 熱 Further, the heat insulating material according to the present embodiment may be formed by covering the whole of the above-mentioned heat insulating filler with a skin material. The outer shell material is desirably in the form of sheet such as glass fiber, inorganic fiber woven fabric such as alumina fiber or inorganic fiber non-woven fabric, resin film, organic fiber woven fabric, organic fiber non-woven fabric, aluminum, metal foil such as copper foil, etc. There is no particular limitation.
　被覆方法は特に限定されるものではなく、断熱充填材の充填率は使用用途によって適宜設定できる。例えば、加圧成型した断熱充填材を前述したシートによって被覆するものでもよく、シートを袋状に加工したものに断熱充填材を充填するものでもよい。 The coating method is not particularly limited, and the filling rate of the heat-insulating filler can be appropriately set according to the intended use. For example, a heat-insulating filler formed by pressure molding may be covered with the above-described sheet, or a sheet-like processed sheet may be filled with the heat-insulating filler.
［３］断熱構造
　本実施形態に係る断熱構造は既述の断熱材を含む。
　本実施形態に係る断熱充填材は、そのまま断熱材として使用してよいが、他の断熱材と組み合わせて、断熱構造としてもよい。他の断熱材と組み合わせて使用する場合、例えば、異なる耐熱性を有する他の断熱材上に充填積層させた積層構造によって構成される断熱構造は、本実施形態に係る断熱充填材に断熱材を組み合わせた層状の断熱構造といえる。また、中空の箱に本実施形態に係る断熱充填材を断熱材として充填した断熱構造としてもよい。 [3] Heat insulation structure The heat insulation structure according to the present embodiment includes the above-described heat insulating material.
The heat-insulating filler according to the present embodiment may be used as it is as a heat insulating material, or may be combined with another heat insulating material to form a heat insulating structure. When used in combination with other heat insulating materials, for example, a heat insulating structure configured by a laminated structure filled and laminated on another heat insulating material having different heat resistance, the heat insulating material to the heat insulating filler according to the present embodiment It can be said that this is a combined layered heat insulating structure. Further, a heat insulating structure in which a hollow box is filled with the heat insulating filler according to the present embodiment as a heat insulating material may be employed.
　以下、実施例及び比較例を挙げてさらに詳細に内容を説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the content will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
「実験例１」
　乾式シリカと湿式シリカを表１で示す混合比率で混合し、これらの混合物（混合シリカ粉末）１００質量部に対して無機繊維４．５質量部を混合することで、断熱充填材を作製した。 "Experimental example 1"
Dry insulating silica and wet silica were mixed at a mixing ratio shown in Table 1, and 4.5 parts by mass of the inorganic fiber was mixed with 100 parts by mass of the mixture (mixed silica powder) to prepare an insulating filler.
　これらの乾式シリカ、湿式シリカ、混合シリカ粉末や断熱充填材等について、含水率、疎充填嵩密度の割合及び熱伝導率をそれぞれ測定した。得られた結果を表１に示す。なお、使用材料は下記のとおりである。 に つ い て For these dry silica, wet silica, mixed silica powder, heat-insulating filler and the like, the water content, the ratio of loose bulk density and the thermal conductivity were measured. Table 1 shows the obtained results. The materials used are as follows.
（使用材料）
　乾式シリカ１（Ｆ１）：ＣＡＢ－Ｏ－ＳＩＬ　Ｍ－５粉末（商品名、Ｃａｂｏｔ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製）平均粒径０．２０μｍ、嵩密度７０ｇ／Ｌ、含水率０．９質量％
　乾式シリカ２（Ｆ２）：ＡＥＲＯＳＩＬ　３８０（商品名、日本アエロジル社製）平均粒径０．０５μｍ未満、嵩密度５０ｇ／Ｌ、含水率１．０質量％
　乾式シリカ３（Ｆ３）：ＮＤＫ－Ｎ２０（商品名、旭化成ワッカーシリコーン社製）平均粒径０．１５μｍ、嵩密度４０ｇ／Ｌ、含水率１．２質量％ (Material used)
Dry silica 1 (F1): CAB-O-SIL M-5 powder (trade name, manufactured by Cabot Specialty Chemicals), average particle size 0.20 μm, bulk density 70 g / L, water content 0.9 mass%
Dry silica 2 (F2): AEROSIL 380 (trade name, manufactured by Nippon Aerosil Co., Ltd.), average particle size less than 0.05 μm, bulk density 50 g / L, water content 1.0 mass%
Dry silica 3 (F3): NDK-N20 (trade name, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), average particle size 0.15 μm, bulk density 40 g / L, water content 1.2 mass%
　湿式シリカ１（Ｗ１）：ＣＡＲＰＬＥＸ　＃８０粉末（商品名、エボニック・ジャパン株式会社製）　平均粒径１５μｍ、嵩密度１４５ｇ／Ｌ、含水率８．０質量％
　湿式シリカ２（Ｗ２）：トクシール ＮＰ（商品名、Ｏｒｉｅｎｔａｌ　Ｓｉｌｉｃａｓ　Ｃｏｒｐｏｒａｔｉｏｎ製）平均粒径１０μｍ、嵩密度６３ｇ／Ｌ、含水率６．２質量％
　湿式シリカ３（Ｗ３）：ミズカシル Ｐ－５２７（商品名，水澤化学工業社製）平均粒径１．８μｍ、嵩密度１９０ｇ／Ｌ、含水率５．２質量％ Wet silica 1 (W1): CARPLEX # 80 powder (trade name, manufactured by Evonik Japan KK) Average particle size 15 μm, bulk density 145 g / L, water content 8.0 mass%
Wet silica 2 (W2): Toksil NP (trade name, manufactured by Oriental Silicas Corporation), average particle diameter 10 μm, bulk density 63 g / L, water content 6.2 mass%
Wet silica 3 (W3): Mizukasil P-527 (trade name, manufactured by Mizusawa Chemical Industry Co., Ltd.), average particle size 1.8 μm, bulk density 190 g / L, water content 5.2 mass%
　無機繊維１（ＩＦ１）：シリカファイバーシート　ＡＳ－３００（商品名、旭産業社製）平均繊維径１０μｍ、２５ｍｍ裁断解繊加工（平均繊維長さ：２５ｍｍ） Inorganic fiber 1 (IF1): silica fiber sheet AS-300 (trade name, manufactured by Asahi Sangyo Co., Ltd.) Average fiber diameter 10 μm, 25 mm cutting and defibration processing (average fiber length: 25 mm)
　上記使用材料の嵩密度は、密充填嵩密度のことであり、ホソカワミクロン（株）社製の「パウダテスターＰＴ－Ｓ型」により測定される。 嵩 The bulk density of the above-mentioned materials is a densely packed bulk density, which is measured by “Powder Tester PT-S” manufactured by Hosokawa Micron Corporation.
（評価方法）
　含水率：乾式シリカ、湿式シリカ、混合シリカ粉末の含水率は、示差熱重量分析装置ＴＧ－ＤＴＡ　２０００ＳＲ（商品名、ＢｒｕｋｅｒＡＸＳ社）を使用して、２００℃時点での重量減少率とした。 (Evaluation method)
Water content: The water content of dry silica, wet silica, and mixed silica powder was determined as the weight loss rate at 200 ° C. using a differential thermogravimetric analyzer TG-DTA 2000SR (trade name, Bruker AXS).
　疎充填嵩密度は、内径Φ６３ｍｍ、容量２００ｍＬのステンレスビーカーに対して、１５０ｍｍの間隔をあけて、漏斗から断熱充填材を落下させ、すり切り充填させることで算出される密度とした。疎充填嵩密度は大きいほど充填性が良好であり、好ましくは４０ｋｇ／ｍ３以上である。 The loose filling bulk density was a density calculated by dropping the heat-insulating filler from the funnel into a stainless beaker having an inner diameter of 63 mm and a capacity of 200 mL at an interval of 150 mm, and performing abrasion filling. The larger the loose packing bulk density is, the better the filling property is, preferably 40 kg / m 3 or more.
　熱伝導率：作製した断熱充填材を、一軸プレスを使用した金型成型によって成型体（２００ｍｍ×２００ｍｍ×２０ｍｍ、密度２３０ｋｇ／ｍ３程度）を作製し、ＩＳＯ８３０１に準拠した熱伝導率測定装置（英弘精機社製）を用いて２３℃で測定した。 Thermal conductivity: A molded body (200 mm × 200 mm × 20 mm, density: about 230 kg / m 3 ) is produced from the produced heat-insulating filler by die molding using a uniaxial press, and a thermal conductivity measuring apparatus ( (Manufactured by Eiko Seiki Co., Ltd.) at 23 ° C.
　成形性：一軸プレスを使用した金型成型によって成型体（寸法等は同上）を作製し、成形性を目視で評価した。成型体にひび割れが確認されなかった場合を○、ひび割れあるいは破損が確認された場合を×とした。 Formability: A molded body (dimensions and the like were the same as above) was produced by die molding using a uniaxial press, and the moldability was visually evaluated. The case where no crack was observed in the molded body was evaluated as “O”, and the case where cracks or damage was observed was evaluated as “X”.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　表１より、湿式シリカの割合が増大するに従い、熱伝導率に悪影響を及ぼすことなく粉体の充填性が向上し、含水率と疎充填嵩密度、及び成形性が向上していることがわかる。 From Table 1, it can be seen that as the proportion of the wet silica increases, the filling property of the powder is improved without adversely affecting the thermal conductivity, and the water content, the loosely packed bulk density, and the moldability are improved. .
「実験例２」
　乾式シリカＦ１を５０質量％、湿式シリカＷ１を５０質量％の比率で混合し、得られた混合物（混合シリカ粉末：実験Ｎｏ．１－４）に対して表２に示す無機繊維を使用し、表２の通りその配合量を変えて断熱充填材を作製したこと以外は実験例１と同様に行った。結果を表２に示す。 "Experimental example 2"
Dry silica F1 was mixed at a ratio of 50% by mass and wet silica W1 was mixed at a ratio of 50% by mass, and inorganic fibers shown in Table 2 were used for the obtained mixture (mixed silica powder: Experiment No. 1-4), The procedure was performed in the same manner as in Experimental Example 1, except that the amount of the insulating filler was changed as shown in Table 2 to prepare the heat insulating filler. Table 2 shows the results.
（使用材料）
　無機繊維２（ＩＦ２）：ガラス繊維（日本電気硝子社製）平均繊維径５０μｍ、平均繊維長２５ｍｍ
　無機繊維３（ＩＦ３）：アルミナシリカ繊維（商品名デンカアルセン、デンカ製）平均繊維径５．０μｍ、平均繊維長２５ｍｍ (Material used)
Inorganic fiber 2 (IF2): glass fiber (manufactured by NEC Corporation), average fiber diameter 50 μm, average fiber length 25 mm
Inorganic fiber 3 (IF3): Alumina silica fiber (trade name: Denka-Alsen, manufactured by Denka) Average fiber diameter 5.0 μm, average fiber length 25 mm
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　表２より、本発明の範囲内で無機繊維を配合することにより熱伝導率に悪影響を及ぼすことなく粉体の充填性が向上し、含水率と疎充填嵩密度、及び成形性が向上していることがわかる。 From Table 2, it can be seen that by blending the inorganic fibers within the scope of the present invention, the filling property of the powder is improved without adversely affecting the thermal conductivity, the water content, the loosely packed bulk density, and the moldability are improved. You can see that there is.
「実験例３」
　実験Ｎｏ．１－４の配合を使用し、表３に示す輻射散乱粒子を使用し、表３の通り配合量を変え、高温（６００℃）での熱伝導率（高温熱伝導率）を測定したこと以外は実験例１と同様に行った。 "Experimental example 3"
Experiment No. Except that the thermal conductivity (high-temperature thermal conductivity) at a high temperature (600 ° C.) was measured using the radiation-scattering particles shown in Table 3 using the formulation 1-4 and changing the blending amount as shown in Table 3. Was performed in the same manner as in Experimental Example 1.
（実験方法）
　高温熱伝導率：作製した断熱充填材を、一軸プレスを使用した金型成型によって成型体（寸法等は同上）を作製し、ＪＩＳ　Ａ　１４１２－１に準拠した保護熱板法熱伝導率測定装置（英弘精機社製）を用いて６００℃で測定した。 (experimental method)
High-temperature thermal conductivity: A molded body (the dimensions and the like are the same as above) is produced from the produced heat-insulating filler by die molding using a uniaxial press, and a protective thermal plate method thermal conductivity measuring apparatus in accordance with JIS A 1412-1. It measured at 600 degreeC using (made by Eikoseiki).
（使用材料）
　輻射散乱粒子（Ｒ１）：炭化ケイ素（デンカ製）平均粒径４．２μｍ
　輻射散乱粒子（Ｒ２）：酸化チタン（富士フイルム和光純薬社製）平均粒径５．０μｍ
　輻射散乱粒子（Ｒ３）：ケイ酸ジルコニウム　和光一級（富士フイルム和光純薬社製）平均粒径５．０μｍ (Material used)
Radiation scattering particles (R1): silicon carbide (made by Denka) average particle size 4.2 μm
Radiation scattering particles (R2): titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) average particle size 5.0 μm
Radiation scattering particles (R3): zirconium silicate Wako first class (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) average particle size 5.0 μm
Figure JPOXMLDOC01-appb-T000003
  
Figure JPOXMLDOC01-appb-T000003
  
　表３より、本発明の範囲内で輻射散乱粒子を配合することによりその他の物性に悪影響を及ぼすことなく高温熱伝導率が低減されていることがわかる。 From Table 3, it can be seen that blending radiation scattering particles within the scope of the present invention reduces the high-temperature thermal conductivity without adversely affecting other physical properties.
　以上のように構成された本発明の断熱充填材は優れた操作性と充填性を有し、かつ従来以上の耐熱性と断熱性を有するため、複雑な形状に対しても適応可能であり、車両や飛行機、その他内燃機関、配管の省エネルギー化に寄与することができる。 The heat-insulating filler of the present invention configured as described above has excellent operability and filling properties, and has more heat resistance and heat insulating properties than before, so it can be applied to complicated shapes, It can contribute to energy saving of vehicles, airplanes, other internal combustion engines, and piping.

Claims (8)

  1. 　乾式シリカ１０質量％～８０質量％と、含水率が２質量％以上の湿式シリカ２０質量％～９０質量％とからなる混合シリカ粉末を含む断熱充填材。 (4) An insulating filler containing a mixed silica powder comprising 10% by mass to 80% by mass of dry silica and 20% by mass to 90% by mass of wet silica having a water content of 2% by mass or more.
  2. 　前記混合シリカ粉末１００質量部に対して、無機繊維を１質量部～１０質量部含む請求項１に記載の断熱充填材。 The heat-insulating filler according to claim 1, wherein the filler contains 1 to 10 parts by mass of the inorganic fiber based on 100 parts by mass of the mixed silica powder.
  3. 　前記無機繊維が平均繊維径０．１μｍ～５０μｍである請求項２に記載の断熱充填材。 断 熱 The heat insulating filler according to claim 2, wherein the inorganic fibers have an average fiber diameter of 0.1 Pm to 50 Pm.
  4. 　輻射散乱粒子を含む請求項１～３のいずれか一項に記載の断熱充填材。 断 熱 The heat-insulating filler according to any one of claims 1 to 3, which contains radiation scattering particles.
  5. 　前記乾式シリカの平均粒径が０．８μｍ以下であり、前記湿式シリカの平均粒径が１μｍ以上である請求項１～４のいずれか一項に記載の断熱充填材。 (5) The heat-insulating filler according to any one of (1) to (4), wherein the average particle diameter of the dry silica is 0.8 μm or less, and the average particle diameter of the wet silica is 1 μm or more.
  6. 　固体である請求項１～５のいずれか一項に記載の断熱充填材。 断 熱 The heat-insulating filler according to any one of claims 1 to 5, which is a solid.
  7. 　請求項１～６のいずれか一項に記載の断熱充填材を配合してなる断熱材。 断 熱 A heat insulating material comprising the heat insulating filler according to any one of claims 1 to 6.
  8. 　請求項７に記載の断熱材を含む断熱構造。
     
     
     
          A heat insulating structure comprising the heat insulating material according to claim 7.



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