WO2012090566A1 - Matériau d'isolation thermique et procédé de production de celui-ci - Google Patents

Matériau d'isolation thermique et procédé de production de celui-ci Download PDF

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WO2012090566A1
WO2012090566A1 PCT/JP2011/073003 JP2011073003W WO2012090566A1 WO 2012090566 A1 WO2012090566 A1 WO 2012090566A1 JP 2011073003 W JP2011073003 W JP 2011073003W WO 2012090566 A1 WO2012090566 A1 WO 2012090566A1
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heat insulating
insulating material
particles
mass
less
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PCT/JP2011/073003
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English (en)
Japanese (ja)
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ちひろ 飯塚
新納　英明
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旭化成ケミカルズ株式会社
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Priority claimed from JP2010290902A external-priority patent/JP5775691B2/ja
Priority claimed from JP2011110590A external-priority patent/JP5876668B2/ja
Priority claimed from JP2011133315A external-priority patent/JP2013001596A/ja
Priority claimed from JP2011165753A external-priority patent/JP5824272B2/ja
Priority claimed from JP2011189750A external-priority patent/JP5824298B2/ja
Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to KR1020137014362A priority Critical patent/KR101506413B1/ko
Publication of WO2012090566A1 publication Critical patent/WO2012090566A1/fr

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    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0067—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the density of the end product
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • 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
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to a heat insulating material and a method for manufacturing the heat insulating material.
  • the average free path of air molecules at room temperature is about 100 nm. Therefore, in a porous body having voids with a diameter of 100 nm or less, convection due to air and heat transfer due to conduction are suppressed, and such a porous body exhibits an excellent heat insulating action.
  • Patent Document 1 describes a heat insulating material obtained by independently forming an ultrafine powder of silica into a porous body.
  • the heat insulating material has a bulk density of 0.2 to 1.5 g / cm 3 and a BET specific surface area.
  • porous particles are formed by coating particles made of a radiation absorption / scattering material or the like with ultrafine particles associated in a ring shape or a spiral shape so that the inner diameter of the ring becomes 0.1 ⁇ m or less.
  • Patent Document 3 discloses a microporous body composed of two or more kinds of fine particles having different primary particle diameters.
  • fumed silica is selected as a material having low thermal conductivity, and ceramic fiber and heat resistance of a special particle size and particle size distribution are used as an infrared opacifier in order to reduce infrared transmission.
  • a method is disclosed in which a metal oxide is blended and a hole is provided so as to reduce the cross-sectional area of the heat passage.
  • JP 2007-169158 A Japanese Patent No. 4367612 JP-A-1-103968 Special table 2008-542592
  • the microporous structure contributes to reducing the heat conduction of the heat insulating material, but increasing the ratio of the holes leads to reducing the strength of the heat insulating material.
  • it is desirable to process it into a complicated shape depending on the application but if the strength of the heat insulating material is not sufficient, it cannot withstand processing such as cutting, drilling, punching, etc. There is a problem.
  • processing such as cutting it is necessary that the load resistance at the time of compression by 5% is large. Specifically, the maximum load at a compression rate of 0 to 5% is required. It was found necessary to be 0.7 MPa or more.
  • Non-Patent Document 1 (trade name, manufactured by Nippon Microtherm Co., Ltd.) is a panel type having a density of 200 to 275 kg / m 3 and the load at a compression rate of 5% is 2 kg / cm 2. It is. Further, for the same type of insulation from the graph listed (Non-Patent Document # 1 "compression resistant FIG Microtherm"), to about 10% compressive deformation at a load of about 4.5 kg / cm 2 When the inventor studied, the heat insulating material described in Non-Patent Document 1 did not have sufficient strength, and it was easy to collapse when trying to cut.
  • Non-Patent Document 2 describes that a microtherm is a solid or flexible plate-like molded body, and the compression strength at 5% compression is 75 to 600 kN / m 2 depending on the density.
  • the strength test method is described as measuring the relationship between compressive load and deformation rate.
  • Non-Patent Document 2 introduces a strength measurement example (ASTM Test Method C 165) based on a standardized measurement standard of ASTM (American Society for Testing for Materials and Materials) compression strength of ASTM (American Society for Testing and Materials). . According to this, heat insulation is measured with a normal testing machine, but it does not show a pattern that collapses with a certain stress, so it is described that a load-deformation curve is drawn and compared with a load at a certain deformation rate. Yes. As described above, when the heat insulating material is greatly compressed and deformed by the load, the heat insulating performance is likely to be deteriorated, and a gap is generated due to the compressive deformation, the strength of the portion is decreased, and the material is easily collapsed.
  • ASTM American Society for Testing for Materials and Materials
  • the heat insulating materials described in Patent Documents 1 to 3 are excellent in terms of heat insulating performance, the compression strength is insufficient, and the possibility of compressive deformation during use of the heat insulating material is very high. Furthermore, when industrially using a heat insulating material mainly composed of ultrafine particles as described in Patent Documents 1 to 3, the heat insulating material mainly composed of ultrafine particles is very bulky and has a loosely packed bulk density. Due to the small size, the following problems occur. For example, when molding by pressure, it is very easy to scatter and difficult to fill the mold, and when the heat insulating material aggregates in the supply process to the mold, the bulk density of the loose filling depends on the remaining amount of the heat insulating material in the storage tank hopper. Because it changes, stable continuous supply may be difficult. Such agglomeration of the forming raw material may lead to insufficient filling of the mold, resulting in a significant reduction in productivity.
  • the powdery heat insulating material needs to deaerate air at the time of pressure molding, it has a large amount of air in advance and, as described in Patent Document 3, contains ultrafine particles as a main component. Since the porous body has a small pore diameter, it tends to be required for a long time for deaeration by reduced pressure or the like, and the productivity is low.
  • the stroke tends to be large when pressure-molding a bulky heat insulating material mainly composed of ultrafine particles. When the stroke is large, the powder in the vicinity of the pressurization location is likely to become insufficient as the distance from the pressurization location increases even if the powder is sufficiently consolidated.
  • Lamination refers to a phenomenon in which a molded product obtained by pressure molding is peeled into two or more layers mainly in the thickness direction. If such delamination occurs, it cannot be handled as a product, and the yield decreases, which is not preferable.
  • Patent Document 4 includes a plurality of glass particles and a binder composition for melting glass when the heat insulating compound is exposed to a temperature higher than 1000 ° C., and has a rubber-like layered ceramic-like structure. Insulating composites with low porosity are disclosed. Although the heat insulation composite currently disclosed by patent document 4 is hard to compress-deform, it cannot be said that heat insulation performance is enough.
  • the present invention has been made in view of such problems of the prior art, is not easily collapsed or deformed during compression, can be processed without cutting and can be shaped and cut, and has heat insulation properties. It aims at providing the manufacturing method of the heat insulating material excellent in material and productivity.
  • the present inventor is a heat insulating material containing silica and / or alumina, which contains small particles of a specific particle diameter and exhibits a specific compressive strength. It has been found that high heat insulation is exhibited even in applications where the load is large, and the present invention has been completed. That is, the present invention is as follows.
  • the present invention is molded include silica and / or aluminum, it comprises a plurality of small particles having a particle diameter D S is 5nm or more 30nm or less, the maximum load in the compression ratio 0-5% is 0.7MPa or more Provided is a heat insulating material having a thermal conductivity at 30 ° C. of 0.05 W / m ⁇ K or less.
  • the heat insulating material of the present invention preferably has a bulk density of 0.2 g / cm 3 or more and 1.5 g / cm 3 or less.
  • the heat insulating material of the present invention preferably has a pore volume of 0.5 mL / g or more and 2 mL / g or less.
  • the heat insulating material of the present invention has an integrated fine pore diameter of 0.05 ⁇ m or more and 0.5 ⁇ m or less with respect to an integrated pore volume V 0.003 of pores having a pore diameter of 0.003 ⁇ m or more and 150 ⁇ m or less.
  • the ratio R of the pore volume V is preferably 70% or more.
  • the heat insulating material of the present invention further contains infrared opaque particles, and preferably has a thermal conductivity at 800 ° C. of 0.2 W / m ⁇ K or less.
  • the infrared opaque particles contained in the heat insulating material of the present invention have an average particle size of 0.5 ⁇ m or more and 30 ⁇ m or less, and the content of the infrared opaque particles is 0.1 based on the total mass of the heat insulating material. It is preferable that they are mass% or more and 39.5 mass% or less.
  • the heat insulating material of the present invention includes silica and / or aluminum, and includes a plurality of large particles having a particle diameter DL of 50 nm to 100 ⁇ m, and the mass of the large particles relative to the sum of the mass of the small particles and the mass of the large particles
  • the ratio RL is preferably 60% by mass or more and 90% by mass or less.
  • the heat insulating material of the present invention includes at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements and germanium, and at least selected from the group consisting of alkali metal elements and alkaline earth metals.
  • the content is 0.005 mass% or more and 5 mass% or less based on the total mass of the heat insulating material, and when containing germanium, the content is the total of the heat insulating material. It is preferable that it is 10 mass ppm or more and 1000 mass ppm or less on the basis of mass.
  • At least one element selected from the group consisting of the above alkali metal elements, alkaline earth metal elements and germanium is contained in the large particles in the heat insulating material of the present invention.
  • the heat insulating material of the present invention further contains inorganic fibers, and the content of the inorganic fibers is preferably more than 0% by mass and 20% by mass or less based on the total mass of the heat insulating material.
  • the heat insulating material of the present invention contains phosphorus (P), and the content of phosphorus (P) is preferably 0.002% by mass or more and 6% by mass or less based on the total mass of the heat insulating material.
  • the heat insulating material of the present invention contains iron (Fe), and the content of iron (Fe) is preferably 0.002% by mass or more and 6% by mass or less based on the total mass of the heat insulating material.
  • the present invention also provides the above heat insulating material housed in a jacket material.
  • the jacket material contains inorganic fibers or the jacket material is a resin film.
  • the present invention is also a method for producing the above-described heat insulating material, wherein a housing step of housing an inorganic mixture containing silica and / or alumina and containing small particles having an average particle diameter of 5 nm to 30 nm in a mold, and A molding step for molding the inorganic mixture, and the molding step is (a) a step of heating the inorganic mixture to 400 ° C. or higher while pressurizing it with a mold, or (b) after the inorganic mixture is molded by pressurization.
  • a method for producing a heat insulating material which is a step of performing a heat treatment at a temperature of 400 ° C. or higher.
  • the inorganic mixture preferably contains silica and / or alumina, and further contains large particles having an average particle size of 50 nm to 100 ⁇ m.
  • the ratio RL of the mass of the large particles to the sum of the mass of the small particles and the mass of the large particles is mixed at 60 mass% to 90 mass% to obtain an inorganic mixture. It is preferable to further have.
  • the large particles preferably contain at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements, and germanium.
  • the molding pressure it is preferable to set the molding pressure so that the bulk density of the molded heat insulating material is 0.2 g / cm 3 or more and 1.5 g / cm 3 or less.
  • the method further includes a cutting step of cutting a part of the molded body obtained in the molding step.
  • the present invention it is possible to provide a heat insulating material and a method for manufacturing the heat insulating material that are unlikely to be collapsed or deformed during compression and that can be cut and shaped without collapsing.
  • the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
  • this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
  • Heat insulating material [1] Silica, alumina
  • the heat insulating material of the present embodiment includes a plurality of small particles of silica and / or alumina.
  • the component which does not satisfy the size of “small particles” described later may contain silica and / or alumina, and the content of silica and / or alumina in the heat insulating material (the small particles and the silica in the components other than the small particles and It is preferable that the mass of alumina (which is expressed by the ratio of the mass to the mass of the heat insulating material) is 50% by mass or more because heat transfer by solid conduction is small.
  • silica and / or alumina particles that do not satisfy the sizes of “small particles” and “small particles” are collectively referred to as “silica particles” and “alumina particles”.
  • the content of silica particles and / or alumina particles is 75% by mass or more of the powder because the adhesion between the powders increases and the powder scattering decreases.
  • silica particles, other particles comprised of component represented by the composition formula SiO 2 refers to a material containing SiO 2, a metal component or the like in addition to SiO 2, containing other inorganic compounds Includes particles.
  • the silica particles may contain salts and complex oxides with Si and various other elements, or may contain hydrated oxides such as hydroxides. It may have a silanol group.
  • the alumina particles are widely encompassing concept of a material containing Al 2 O 3, in addition to Al 2 O 3 Includes particles containing other inorganic compounds such as metal components.
  • the alumina particles may contain salts and composite oxides with Al and various other elements, or may contain hydrated oxides such as hydroxides.
  • the alumina in the silica particles and / or the alumina particles may be crystalline, amorphous, or a mixture thereof. This is preferable because the heat transfer by is small and the heat insulation performance is high.
  • silica particles include the following.
  • An oxide of silicon called “silica” or “quartz”.
  • Partial oxide of silicon Silicon complex oxide such as silica alumina and zeolite. Any one of silicate (glass) of Na, Ca, K, Mg, Ba, Ce, B, Fe and Al.
  • silicate (glass) of Na, Ca, K, Mg, Ba, Ce, B, Fe and Al Any one of silicate (glass) of Na, Ca, K, Mg, Ba, Ce, B, Fe and Al.
  • SiC and SiN oxides any one of silicate (glass) of Na, Ca, K, Mg, Ba, Ce, B, Fe and Al.
  • silicate (glass) of Na, Ca, K, Mg, Ba, Ce, B, Fe and Al Any one of silicate (glass) of Na, Ca, K, M
  • alumina particles include the following.
  • An oxide of aluminum called “alumina”.
  • Alumina called ⁇ -alumina, ⁇ -alumina, ⁇ -alumina.
  • Partial oxide of aluminum Aluminum complex oxides such as silica alumina and zeolite. Any one of Na, Ca, K, Mg, Ba, Ce, B, Fe and Si aluminate (glass).
  • the silica particles and / or alumina particles are thermally stable at the temperature at which the heat insulating material is used. Specifically, it is preferable that the weight of silica particles and / or alumina particles does not decrease by 10% or more when held for 1 hour at the maximum use temperature of the heat insulating material. Moreover, it is preferable that a silica particle and / or an alumina particle have water resistance from a viewpoint of maintaining heat insulation performance and a viewpoint of the shape maintenance at the time of shape
  • the specific gravity of the silica particles and alumina particles is preferably 2.0 or more and 5.0 or less. It is more preferable that it is 2.0 or more and 4.5 or less because the bulk density of the heat insulating material is small, and it is further more preferable that it is 2.0 or more and 4.2 or less.
  • the specific gravity of silica particles and alumina particles refers to the true specific gravity determined by the pycnometer method.
  • a porous body having voids with a diameter of 100 nm or less has a low thermal conductivity and is suitable for a heat insulating material.
  • the following void diameter 100nm are formed in the green body, in order to facilitate indicates thermal insulation, or less 30nm particle diameter D S 5 nm or more "small particles".
  • the content of the following small particles 30nm or 5nm particle diameter D S is not particularly limited, the present inventors have investigated However, in addition to the small particles, as the large particles, a particle containing silica and / or alumina and having a particle diameter DL of 50 nm or more and 100 ⁇ m or less is selected, and the large particles with respect to the sum of the mass of the small particles and the mass of the large particles is selected.
  • the ratio RL of the mass of particles is in the range of 60% by mass or more and 90% by mass or less, the volume of the powder before pressurization does not become too large, and it is easy to fill the mold. It has been found that powders that are difficult to scatter and aggregate can be obtained.
  • the methods for producing the heat insulating material of the present embodiment a process of heating a raw material powder (inorganic mixture) while being pressure-molded, or heating after pressure-molding is performed.
  • the heat insulating material contains particles having different particle diameters, for example, small particles and large particles, depending on the heating temperature, there is a tendency that heat shrinkage is less likely to occur when heated compared to heat insulating materials mainly composed of small particles. is there. The reason for this is not clear, but is estimated as follows.
  • the particles and inorganic fibers constituting the heat insulating material and the surfaces thereof are softened and melted, and the particles constituting the heat insulating material and the particles and inorganic fibers are fused to be strong. It is presumed that a simple joint is formed. As a result, it is estimated that the heat insulating material hardens and exhibits excellent compressive strength. At this time, if the heat insulating material contains large particles, joints are formed at the interfaces between the particles or between the particles and the inorganic fibers, but the particle size of the large particles themselves is kept approximately the same as before heating.
  • the heat shrinkage is small compared to the case where the main component of the heat insulating material is small particles, and at the same time, a state in which pores are present in the heat insulating material can be formed. For this reason, it is speculated that it is possible to achieve both heat insulation performance and compressive strength even if large particles with larger heat transfer due to solid conduction are included than small particles. If the heat shrinkage due to heating is large, the loss of the heat insulating material after heating with respect to the heat insulating material before heating, that is, the heat insulating material of the product becomes large.
  • the heat insulating material preferably contains two or more kinds of silica particles and / or alumina particles, and particularly when two kinds of particles having different particle diameters, that is, small particles and large particles made of silica and / or alumina,
  • the mass ratio RL of the large particles is preferably 60% by mass or more and 90% by mass or less based on the sum of the mass of the small particles and the mass of the large particles.
  • the content ratio of large particles is more preferably 60% by mass or more and 85% by mass or less, and further preferably 65% by mass or more and 85% by mass or less from the viewpoint of heat insulation performance.
  • Non-patent document 3 the heat-insulating material precursor mainly composed of ultrafine particles is molded when the pressure is released after pressure molding.
  • the body tends to be large and easy to swell. This expansion is called springback.
  • a molded body obtained by pressure-molding ultrafine particles containing ultrafine powder as a main component has a problem that a springback occurs and a molding defect occurs in some cases. .
  • the microporous structure contributes to reducing the heat conduction of the heat insulating material, but spring back is likely to occur if the air is not sufficiently vented during pressure molding.
  • the occurrence of springback during molding tends to be suppressed as compared to the case consisting of only small particles, but the suppression effect is significant when the blending ratio is 25% by mass or more.
  • the ratio of the large particles to the small particles of the heat insulating material is the scatterability of the powder used as the raw material of the heat insulating material. It is preferable to determine the balance so that the spring back suppression and the thermal conductivity of the heat insulating material become desired values.
  • a crack-shaped molding defect occurs on a surface perpendicular to the press surface during pressure molding. If such a molding defect exists in the heat insulating material, the heat insulating material may be damaged, and the heat insulating performance is also deteriorated, so that it cannot be handled as a product and the yield is reduced, which is not preferable. Further, a heat insulating material mainly composed of ultrafine particles also tends to cause lamination after being pressure-molded. Lamination refers to a phenomenon in which a molded product obtained by pressure molding is peeled into two or more layers mainly in the thickness direction.
  • the loosely packed bulk density of the powder (inorganic mixture) used as the raw material for the heat insulating material is preferably 0.030 g / cm 3 or more and 0.35 g / cm 3 or less.
  • the loosely packed bulk density is less than 0.030 g / cm 3 , the volume of the heat insulating material is large, and, for example, a device necessary for pressure molding tends to increase in size, and it tends to remarkably scatter and aggregate. Therefore, it is not preferable. If the loosely packed bulk density is more than 0.35 g / cm 3 , the heat insulation performance tends to be lowered, which is not preferable.
  • 0.035 g / cm 3 or more 0.3 g / cm 3 or less from the viewpoint of facilitating the filling of the mold, 0.040 g / cm in terms of thermal insulation performance 3 to 0.25 g / cm 3 or less is more preferred.
  • the heat-insulating material contains infrared opaque particles, there is a strong tendency to require heat insulation performance at a high temperature, so that the volume before pressurization is appropriately sized and the mold can be easily filled.
  • loose packing bulk density is preferably 0.045 g / cm 3 or more 0.25 g / cm 3 or less, and more is 0.05 g / cm 3 or more 0.25 g / cm 3 or less preferably, further preferably 0.05 g / cm 3 or more 0.20 g / cm 3 or less. Details of the infrared opaque particles will be described later.
  • the “loosely packed bulk density” refers to a value obtained according to the measurement procedure of “initial bulk density” of JIS R 1628.
  • (1) to (4) that is, (1) The mass of the measurement container is measured with a scale. (2) Place the sample in the measuring container until it overflows through the sieve. At this time, the measurement container should not be vibrated or the sample should not be compressed. (3) Grind the powder that has risen from the upper end surface of the measurement container using a grinding plate. At this time, the ground plate is used by being inclined backward from the direction of grinding so as not to compress the powder.
  • the entire measurement container is weighed with a scale, and the mass of the sample is calculated by subtracting the weight of the measurement container.
  • Measure based on JIS R 1628 is an index based on the premise that the difference between the initial bulk density and the bulk density of this measurement is within 0.3%, whereas in the case of the powdery heat insulating material of this embodiment, the initial The difference between the bulk density and the original bulk density may be greatly different.
  • the present inventor has found that the initial bulk density is an important indicator for the ease of lamination when pressure-forming a powdery heat insulating material. Completed the invention.
  • An example of an apparatus for measuring loosely packed bulk density is shown in FIG. The distance between the tip of the funnel attached to the lower part of the sieve and the measuring container shall be 20-30 mm.
  • the content of small particles and large particles can be calculated, for example, by separating small particles and large particles from the heat insulating material and measuring their masses.
  • the method for separating the small particles and the large particles is not particularly limited.
  • the particles can be separated using a classification method or a classification machine described in the revised sixth edition, Chemical Engineering Handbook (Maruzen).
  • Known classification methods include wet classification and dry classification.
  • Wet classification machines include gravity classifiers (sediment classifiers), spitz casters, hydraulic classifiers, siphon sizers, centrifugal classifiers, liquid cyclones, jet sizers, rake classifiers, Aikens types, spiral classifiers, bowl classifiers. Machine, hydro separator, decanter and the like.
  • Machines for dry classification include sieving machines such as vibrating screens, in-plane screens, rotary screens, double cylinder type screens, gravity classifiers, zigzag classifiers, wind classifiers, free vortex type centrifugal classifiers, cyclones, Perfusion separator, forced vortex type centrifugal classifier, turbo classifier, microplex, micron separator, Accucut, super separator, startervant type classifier, turboplex, cyclone air separator, centrifugal classifier such as O-SEPA, louver type classifier And inertia classifiers such as a fanton gelen classifier, elbow jet, and improved virtual impactor.
  • the classifier may be selected according to the particle size of small particles and large particles to be separated, and these classifiers may be used in combination.
  • the particle diameter of the silica particles and alumina particles can be measured by observing the cross section of the heat insulating material with a field emission scanning electron microscope (FE-SEM).
  • FE-SEM field emission scanning electron microscope
  • When measuring the particle size of small particles set the magnification so that particles of 5 nm or more and 30 nm or less can be observed (for example, 10000 times), and randomly extract “representative cross-sectional field of view” for the thermal insulation.
  • “Representative cross-sectional field of view” means a field of view in which the state of the cross-sectional shape is common to some extent in arbitrarily selected cross-sections, not a specific surface in the cross-section of the heat insulating material.
  • a typical cross-sectional visual field is observed, and two or more small particles are observed in the visual field, it can be determined that the heat insulating material is “contains small particles”.
  • a typical sectional visual field is observed in 100 visual fields and a total of 100 small particles can be observed, “contain small particles”.
  • the particles do not necessarily have to be circular particles, and may have an irregular shape.
  • the diameter of the particles is determined by the equivalent area equivalent circle diameter.
  • the equivalent area equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particles, and is also called the Heywood diameter. Even if there are irregularly shaped particles, if the area is 78 nm 2 (corresponding to the area of a circle having a particle diameter of 10 nm), the particle diameter is considered to be 10 nm.
  • the particle size of each particle may be determined by the equivalent area circle equivalent diameter, so it is not essential to determine the average value of the particle size, but the entire set of small particles If the average value of the particle diameter is determined for the purpose of grasping the tendency of the physical properties of the heat insulating material, the magnification is set so that particles of 5 nm to 30 nm can be observed, and 100 or more particles are observed. What is necessary is just to calculate
  • the cross section of the heat insulating material can be observed with the following conditions and apparatus, for example.
  • a cross section polisher (SM-09010, manufactured by JEOL Ltd.)
  • BIB broad ion beam processing was applied to the insulation material as a sample under the conditions of acceleration voltage 4.0 kV and processing time 9 hours, obtain.
  • This sample is loaded on a sample stage and Os coating of about 2 nm is applied to prepare a sample for speculum.
  • the Os coating can be applied using, for example, an osmium coater (HPC-1SW type, manufactured by Vacuum Device Corporation).
  • HPC-1SW osmium coater
  • a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.) is used, and measurement is performed under the condition of an acceleration voltage of 1.0 kV.
  • Particle diameter D S of the small particles is preferably 5nm or more 30nm or less. If D S is in 5nm or more, compared to the case D S is outside the above numerical range, they tend small particles are chemically stable, heat-insulating performance may stable tendency. If D S is a 30nm or less, compared with the case D S is outside the above numerical range, small contact area between the small particles, less heat transfer due to the powder of the solid conduction, tends low thermal conductivity There is.
  • D S is, if it is 5nm or 25nm or less, from the viewpoint of thermal conductivity, more preferable to be 5nm or more 20nm or less, more preferable to be 5nm or more 18nm or less, and particularly preferably 7nm more 14nm or less.
  • the particle diameter D L of the large particles satisfies D S ⁇ D L.
  • D L is preferably at 50nm or more 100 ⁇ m or less.
  • D L is obtained by the same method as D S described above.
  • DL is 50 nm or more
  • the heat insulating material when the heat insulating material is molded, the spring back in the molded product tends to be small.
  • DL is 100 ⁇ m or less, the thermal conductivity tends to be small.
  • Particle diameter D L of the larger particles if it is 50nm or more 50 ⁇ m or less, because heat insulating material is easy uniform mixing thereof with the case containing the inorganic fibers and the infrared opacifying particles, preferably.
  • D L is, if it is 50nm or more 10 ⁇ m or less, increase adhesion of the particles, for separation of particles from the powder is small, and still more preferably 50nm or more 5 ⁇ m or less.
  • D L is at least twice the D S, since the spring-back is reduced in the case of molding the heat insulator, preferred.
  • D L is the is more than three times D S, large bulk density of the mixed powder of small particles and large particles, because of their high workability powder volume is small, more preferred.
  • D L is the is more than 4 times the D S, large difference in particle size of the small particles and large particles, since it is easy to disperse for small particles of large particles when mixed with small particles and large particles, further preferable. From the viewpoint of solid heat transfer due to particle aggregation, it is preferable that each particle is dispersed. That is, it is preferable that there are no locations where large particles are in direct contact with each other and connected.
  • the voids between the large particles generated when the large particles are not directly connected are filled with small particles, and the large particles are difficult to directly contact each other. Therefore, there is no heat transfer path with large solid conduction in the heat insulating material, and the heat conductivity of the whole heat insulating material tends to be low. Furthermore, by filling the gaps between the large particles with small particles, the size of the gaps present in the heat insulating material is reduced, and air convection and heat transfer are suppressed, so the thermal conductivity of the entire heat insulating material is reduced. It tends to be low.
  • the heat insulating material preferably contains a water repellent from the viewpoint of suppressing deterioration of handling properties, deformation of the heat insulating material, cracking, and the like when water is immersed in the heat insulating material.
  • the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicon-based water repellents such as silicon resin, polydimethylsiloxane, and alkylalkoxysilane; Fluorine-based water repellents such as carboxylates, perfluoroalkyl phosphate esters and perfluoroalkyltrimethylammonium salts, silane coupling agents such as alkoxysilanes containing alkyl groups and perfluoro groups, trimethylsilyl chloride and 1,1,1 And silylating agents such as 3,3,3-hexamethyldisilazane.
  • a method in which the powder is stirred and dried while adding a solution obtained by diluting these water repellents with a solvent such as water or alcohol examples include a method of dispersing in a solvent such as water or alcohol to form a slurry, adding a water repellent thereto, stirring and filtering, and drying, and steaming with chlorotrimethylsilane.
  • wax-based water repellents and silicon-based water repellents are preferably used in the present embodiment.
  • the content of the water repellent in the inorganic mixture is preferably 100/30 to 100 / 0.1 in terms of the mass of the whole inorganic mixture / the mass of the water repellent from the viewpoint of imparting a sufficient water repellent effect. 20 to 100 / 0.5 is more preferable, and 100/10 to 100/1 is more preferable.
  • the heat insulating material preferably contains inorganic fiber from the viewpoint of ease of molding.
  • the heat insulating material containing inorganic fibers has an advantage that, in pressure molding, there is little dropout of particles from the formed heat insulating material, and the productivity is high.
  • the heat insulating material containing an inorganic fiber has the advantage that it is hard to disintegrate and is easy to handle. Even in the state of powder as a raw material of the heat insulating material, it is preferable in handling because it is less scattered.
  • the term “inorganic fiber” means that the ratio of the average length of the inorganic fiber to the average thickness (aspect ratio) is 10 or more.
  • the aspect ratio is preferably 10 or more, and when molding a heat insulating material, 50 or more is more preferable from the viewpoint of enabling molding with a small pressure and improving the productivity of the heat insulating material, from the viewpoint of the bending strength of the heat insulating material. 100 or more is more preferable.
  • the aspect ratio of the inorganic fiber can be obtained from the average value of the thickness and length of 1000 inorganic fibers measured by FE-SEM. It is preferable that the inorganic fibers are monodispersed and mixed in the powder, but the inorganic fibers may be mixed in a state in which the inorganic fibers are entangled with each other or a bundle in which a plurality of inorganic fibers are aligned in the same direction. .
  • the inorganic fibers may be aligned in the same direction.
  • the inorganic fibers are oriented in a direction perpendicular to the heat transfer direction. It is preferable.
  • the method for orienting the inorganic fibers perpendicularly to the heat transfer direction is not particularly limited.For example, when filling the mold with the powder as the raw material of the heat insulating material, the powder is dropped from a high place to the filling point. By filling, the inorganic fibers tend to be oriented perpendicular to the heat transfer direction. In the case of pressure molding, for example, by pressing in the same direction as the heat transfer direction, the inorganic fibers that have been oriented in the heat transfer direction can be easily oriented in a direction perpendicular to the heat transfer direction.
  • inorganic fibers examples include long glass fibers (filaments) (SiO 2 —Al 2 O 3 —B 2 O 3 —CaO), glass fibers, glass wool (SiO 2 —Al 2 O 3 —CaO—Na 2 O).
  • Alkali resistant glass fiber SiO 2 —ZrO 2 —CaO—Na 2 O
  • rock wool basalt wool
  • slag wool SiO 2 —
  • ceramic fiber mullite fiber
  • silica fiber SiO 2
  • alumina fiber Al 2 O 3 —SiO 2
  • potassium titanate fiber Alumina whisker, silicon carbide whisker, silicon nitride whisker, calcium carbonate whisker, basic magnesium sulfate whisker Car, calcium sulfate whisker (gypsum fiber), zinc oxide whisker, zirconia fiber, carbon fiber, graphite whisker, phosphate fibers, AES (Alkaline Earth Silicate) fiber (SiO 2 -CaO-MgO), natural mineral wollast
  • biosoluble AES fibers Alkaline Earth Silicate Fiber
  • examples of the AES fiber include SiO 2 —CaO—MgO inorganic glass (inorganic polymer).
  • the average thickness of the inorganic fibers is preferably 1 ⁇ m or more from the viewpoint of preventing scattering. In the case of a heat insulating material, the thickness is preferably 20 ⁇ m or less from the viewpoint of suppressing heat transfer by solid conduction.
  • the average thickness of the inorganic fibers can be obtained by calculating the thickness of 1000 inorganic fibers by FE-SEM and averaging the thicknesses.
  • the content of the inorganic fibers in the heat insulating material is preferably more than 0% by mass with respect to the total mass of the heat insulating material from the viewpoint of suppressing the detachment of the powder, and the heat conductivity is 0.05 W / m ⁇ K or less. It is preferable that it is 20 mass% or less.
  • the content of the inorganic fiber is more preferably 0.5% by mass or more and 18% by mass or less from the viewpoint of easy mixing with the infrared opaque particles. From the viewpoint of reducing the loosely packed bulk density of the powder as the raw material of the material, it is more preferably 0.5% by mass or more and 16% by mass or less.
  • the content of the inorganic fiber can be obtained, for example, by classification from a powder using the inorganic fiber as a raw material for the heat insulating material.
  • the heat insulating material contains infrared opacifying particles when heat insulating performance at a high temperature is required.
  • the infrared opaque particles refer to particles made of a material that reflects, scatters, or absorbs infrared rays. When infrared opaque particles are mixed in the heat insulating material, heat transfer due to radiation is suppressed, so that the heat insulating performance is particularly high in a high temperature region of 200 ° C. or higher.
  • infrared opaque particles examples include zirconium oxide, zirconium silicate, titanium dioxide, iron titanium oxide, iron oxide, copper oxide, silicon carbide, gold ore, chromium dioxide, manganese dioxide, graphite and other carbonaceous materials, carbon fibers , Spinel pigments, aluminum particles, stainless steel particles, bronze particles, copper / zinc alloy particles, and copper / chromium alloy particles.
  • the above metal particles or nonmetal particles known as infrared opaque materials may be used alone or in combination of two or more.
  • zirconium oxide, zirconium silicate, titanium dioxide or silicon carbide is particularly preferable.
  • the composition of the infrared opaque particles is obtained by FE-SEM EDX.
  • the average particle diameter of the infrared opaque particles is preferably 0.5 ⁇ m or more from the viewpoint of heat insulation performance at 200 ° C. or more, and preferably 30 ⁇ m or less from the viewpoint of heat insulation performance at less than 200 ° C. due to suppression of solid conduction.
  • the average particle diameter of the infrared opaque particles is determined by the same method as that for silica particles and alumina particles. Depending on the size of the inorganic fibers, silica particles, and alumina particles, when the silica particles and / or alumina particles are 5 nm to 100 ⁇ m, the infrared opaque particles can be used from the viewpoint of easy mixing with the silica particles and / or alumina particles.
  • the average particle size is more preferably from 0.5 ⁇ m to 10 ⁇ m, and even more preferably from 0.5 ⁇ m to 5 ⁇ m.
  • the content of the infrared opaque particles in the heat insulating material is preferably 0.1% by mass or more and 39.5% by mass or less. If the content of the infrared opaque particles is larger than 39.5% by mass, heat transfer by solid conduction is large, so that the heat insulation performance at less than 200 ° C. tends to be low. In order to improve the heat insulation performance at 200 ° C. or higher, the content of the infrared opaque particles is more preferably 0.5% by mass to 35% by mass, and further preferably 1% by mass to 30% by mass.
  • the content of the infrared opaque particles in the heat insulating material when the content of the infrared opaque particles in the heat insulating material is within the above range, it tends to be more than 0% by volume and 5% by volume or less based on the volume of the whole heat insulating material. According to the studies by the inventors, the infrared reflection, scattering or absorption efficiency of the infrared opaque particles tends to depend on the volume ratio of the infrared opaque particles contained in the heat insulating material, and the infrared opaque particles in the heat insulating material.
  • the content of is preferably more than 0% by volume and 5% by volume or less based on the volume of the whole heat insulating material.
  • the content of the infrared opaque particles is greater than 5% by volume, heat transfer by solid conduction is large, and thus the heat insulation performance at less than 200 ° C. tends to be low.
  • the content of the infrared opaque particles is more preferably 0.02% by volume or more and 5% by mass or less, and further preferably 0.03% by volume or more and 4% by volume or less.
  • Thermal insulation containing infrared opacifying particles tends to have a small thermal shrinkage, for example, when it is suddenly exposed to excessive heat, it has the effect of delaying the shape change or the thermal insulation collapse. is there.
  • Insulating materials containing infrared opacifying particles tend to have less powder falling off the insulating material, the belt conveyor that transports the insulating material in the production line is less likely to get dirty, and hands are less likely to get dirty when holding the insulating material.
  • the place where the heat insulating material comes into contact is hard to get dirty. If there is little powder fall off from the heat insulating material, for example, when a resin film is used as the covering material and the heat insulating material is vacuum-packed, there is an advantage that the powder hardly adheres to the sealing surface of the resin film and the workability is excellent.
  • the content of the infrared opaque particles can be determined, for example, by measuring the composition of the infrared opaque particles with FE-SEM EDX and quantifying the elements contained only in the infrared opaque particles by fluorescent X-ray analysis. it can.
  • the heat insulating material of the present embodiment is unlikely to be collapsed or deformed during compression, can be shaped without cutting, and can be processed such as cutting.
  • the maximum load in the range of ⁇ 5% is preferably 0.7 MPa or more.
  • the pressure is more preferably 2.0 MPa or more, further preferably 3.0 MPa or more, and particularly preferably 6.29 MPa or more.
  • the upper limit of the maximum load in the range where the compression rate is 0 to 5% is not particularly limited, but 30 MPa or less is appropriate from the viewpoint of heat insulation performance.
  • the compression rate can be calculated from the sample thickness at the time of compressive strength measurement, that is, the stroke (push-in distance) with respect to the length of the sample in the compression direction. For example, when the compression strength is measured using a sample in which the molded body has a cubic shape of 1 cm ⁇ 1 cm ⁇ 1 cm, a state where the stroke is 0.5 mm is defined as a compression rate of 5%.
  • the pattern of the load-compressibility curve drawn when measuring the compressive strength is not particularly limited. That is, when the compression ratio is in the range of 0 to 5%, the molded body as a sample may collapse and show a clear breaking point, or may not collapse. When the compact as a sample collapses and exhibits a fracture point when the compression ratio is in the range of 0 to 5%, the maximum load of the compact is defined as the load at the fracture point.
  • the load at the breaking point is preferably 0.7 MPa or more, more preferably 2.0 MPa or more, and further preferably 3.0 MPa or more. If the sample does not collapse, it is evaluated using the maximum load value indicated by the compression ratio in the range of 0-5%.
  • ⁇ is the compressive strength (MPa) of the heat insulating material used as a sample
  • F max is the recorded maximum load (N)
  • a 0 is the cross-sectional area (mm 2 ) of the sample before measurement.
  • a precision universal testing machine As a measuring device, a precision universal testing machine, Autograph AG-100KN (manufactured by Shimadzu Corporation) is used, and the compressive strength is measured at an indentation speed of 0.5 mm / min as in JIS R1608.
  • the thermal conductivity of this embodiment has a thermal conductivity at 30 ° C. of 0.05 W / m ⁇ K or less. From the viewpoint of heat insulation performance, the thermal conductivity is preferably 0.045 W / m ⁇ K or less, more preferably 0.040 W / m ⁇ K or less, still more preferably 0.037 W / m ⁇ K or less, and 0.0213 W / m. -K or less is particularly preferable.
  • the heat insulating material containing the infrared opaque particles is preferable particularly when heat insulating performance in a high temperature region of 200 ° C. or higher is required. When the powder contains infrared opaque particles, the thermal conductivity at 800 ° C.
  • the heat insulating material may contain RL in the range of 60% by mass to 90% by mass. It is preferable to measure the thermal conductivity after preparing. When the thermal conductivity is more than 0.05 W / m ⁇ K, it is preferable to change the mixing amount within a range in which the content rate is maintained.
  • the mixing amount can be similarly determined when using inorganic fibers and infrared opaque particles. If the mixing amount of the inorganic fiber and the infrared opaque particles is excessive, the heat insulating property may be lowered. Therefore, it is preferable to appropriately prepare while measuring and confirming the thermal conductivity.
  • the mixing ratio of the inorganic fibers is preferably 18% by mass or less.
  • the mixing ratio of infrared opaque particles is preferably 23% by mass or less.
  • the bulk density of the heat insulating material of the present embodiment is preferably 0.2 g / cm 3 or more and 1.5 g / cm 3 or less. If the bulk density of the heat insulating material is smaller than 0.2 g / cm 3 , the compressive strength of the heat insulating material tends to decrease. If the bulk density of the heat insulating material is larger than 1.5 g / cm 3 , the heat insulating performance tends to be reduced, and the burden when the heat insulating material is transported increases.
  • the bulk density is defined by measuring and calculating the size and mass of the heat insulating material in a form in which the heat insulating material is actually used. For example, in the case where the heat insulating material has a layer structure, the bulk density of only the specific layer is not measured, but the dimensions and mass are measured in the form actually used, that is, in the state of the layer structure.
  • the mass of the heat insulating material is measured at normal temperature and normal pressure. That is, measurement is performed including the air that the heat insulating material has in its pores.
  • the volume of the heat insulating material is calculated based on the outer dimensions. That is, it is set as the volume of a heat insulating material also including the pore volume of a heat insulating material.
  • the pore volume is preferably 0.5 mL / g or more and 2 mL / g or less.
  • the pore volume is defined by a value measured by a mercury intrusion method to be described later, and means an integrated pore volume V 0.003 of pores having a pore diameter of 0.003 ⁇ m to 150 ⁇ m.
  • the pore volume is larger than 2 mL / g, the compressive strength of the heat insulating material tends to decrease, and when the pore volume is less than 0.5 mL / g, the heat insulating performance tends to decrease.
  • a pore volume of 0.5 mL / g or more and 2 mL / g or less means that the heat insulating material has pores.
  • the pore volume is within this range, it is estimated that appropriate pores exist in the heat insulating material, heat transfer due to solid conduction is suppressed, and excellent heat insulating performance can be exhibited.
  • the strength that can suppress the compressive deformation is expressed by the pore volume of the heat insulating material not being too large.
  • the above-described bulk density range tends to be easily achieved.
  • the pore volume is more preferably 0.8 mL / g or more and 1.8 mL / g or less, and further preferably 0.8 mL / g or more and 1.6 mL / g or less.
  • the ratio R of the accumulated pore volume V of pores having a pore diameter of 0.05 ⁇ m to 0.5 ⁇ m is 0. It is preferable that it is 70% or more with respect to the cumulative pore volume V 0.003 of the pores which are 003 ⁇ m or more and 150 ⁇ m or less.
  • R may be expressed as (V / V 0.003 ) ⁇ 100.
  • the pore distribution of the heat insulating material with R of less than 70% is as follows: (1) When there are many pores with a pore diameter of less than 0.05 ⁇ m, (2) Fine pores with a pore diameter of more than 0.5 ⁇ m.
  • R is more preferably 75% or more and further preferably 80% or more with respect to the total pore volume of the heat insulating material. The upper limit of R is 100%.
  • the powder of the present embodiment comprises an alkali metal element, It is preferable to include at least one element selected from the group consisting of an alkaline earth metal element and germanium.
  • at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements include lithium, sodium, potassium, Examples thereof include alkali metals such as rubidium and cesium, and alkaline earth metals such as magnesium, calcium, strontium and barium.
  • Only one basic element may be included, or two or more basic elements may be included.
  • Sodium, potassium, magnesium, and calcium are preferable at the point which can be hardened by comparatively low-temperature heat processing, when improving the adhesiveness of particle
  • the heat insulating material contains basic element or Ge, so that the basic element melts or is a main component of the heat insulating material such as silica or alumina.
  • the inventor presumes that the melting point of the metal contributes to the curing of the heat insulating material by lowering the melting point.
  • silica particles it is considered that the silica particles are fused to each other at the particle interface, and a bond such as Si—O—Si is generated to form a strong joint.
  • Si and Ge are elements belonging to the periodic table, and the oxides are tetravalent, such as SiO 2 and GeO 2 , respectively, so that they are easily incorporated into the crystal structure and form a strong structure. It is conceivable that. It is considered that the formation of such strong joints and structures acts to stabilize the structure formed by silica particles or alumina particles, and as a result, the heat insulating material as a whole is cured and the compressive strength is improved. Further, it is presumed that P and Fe also have the above-described action.
  • the content of the basic element is preferably 0.005% by mass or more and 5% by mass or less based on the total mass of the heat insulating material. Is preferably 10 mass ppm or more and 1000 mass ppm or less, and the P content is preferably 0.002 mass% or more and 6 mass% or less.
  • the content of Fe is preferably 0.005% by mass or more and 6% by mass or less. Moreover, it is preferable that the content rate of P is 0.002 mass% or more and 6 mass% or less. Further, the basic element content is 0.005 mass% to 3 mass%, the Ge content is 20 mass ppm to 900 mass ppm, and the P content is 0.002 mass% to 5.5 mass%.
  • the Fe content is preferably 0.005 mass% or more and 3 mass% or less from the viewpoint of improving adhesion between particles and fluidity and suppressing aggregation.
  • the basic element content is 0.005 mass% to 2 mass%
  • the Ge content is 20 mass ppm to 800 mass ppm
  • the P content is 0.002 mass% to 5 mass%
  • the Fe content is 0.005 mass% or more and 2 mass% or less.
  • the content of the basic elements, Ge, P, and Fe in the heat insulating material can be quantified by XRF (fluorescence X-ray analysis).
  • the content of the basic elements and Ge, P, and Fe contained in the large particles can be determined, for example, by separating the small particles from the large particles by the above-described method and measuring by the fluorescent X-ray analysis method.
  • the manufacturing method of the heat insulating material of the present embodiment accommodates an inorganic mixture containing small particles containing silica and / or alumina and having an average particle diameter of 5 nm to 30 nm in a mold.
  • a housing step and a molding step for molding the inorganic mixture wherein the molding step includes (a) a step of heating the inorganic mixture to 400 ° C. or higher while pressurizing the inorganic mixture with a mold, or (b) an inorganic mixture by pressurization. After the molding, a step of performing a heat treatment at a temperature of 400 ° C. or higher is included.
  • the average particle size of the small particles is preferably 5 nm or more and 25 nm or less from the viewpoint of thermal conductivity, more preferably 5 nm or more and 20 nm or less, further preferably 5 nm or more and 18 nm or less, and 7 nm or more and 14 nm or less. And particularly preferred. It is simple and preferable to use small particles and large particles having a known average particle diameter as a raw material for the heat insulating material. When the average particle size is specified for commercially available small particles and large particles, the value can be regarded as the average particle size of each particle.
  • the average particle diameter is 5 nm to 30 nm in the usual measurement method. If there is, it is certain that a plurality of small particles having a particle size of 5 nm or more and 30 nm or less are contained, and the average particle size of the large particles is not a difference because it does not affect the properties of the heat insulating material.
  • the specific surface area s [m 2 / g] can be measured using nitrogen as an adsorption gas (nitrogen adsorption method).
  • the BET method is adopted for the specific surface area.
  • a gas adsorption measuring apparatus Autosorb 3MP, can be used Yuasa Ionics Corporation.
  • Density ⁇ [g / cm 3] refers to the true specific gravity obtained by pycnometer method.
  • an automatic wet true density measuring device Auto True Densor MAT-7000, manufactured by Seishin Enterprise Co., Ltd.
  • the average particle size of large particles can be determined in the same manner as small particles.
  • Silica particles, alumina particles are particles having a silica component and an alumina component, respectively, and the mixing ratio of small particles and large particles and the thermal conductivity may be adjusted. it can.
  • the silica particles may be particles produced by condensing silicate ions by a wet method under acidic or alkaline conditions.
  • Silica particles may be obtained by hydrolyzing and condensing alkoxysilane by a wet method, or by baking a silica component produced by a wet method, or by producing a silicon compound such as chloride in the gas phase. You may have done.
  • the silica particles may be produced by oxidizing and burning silicon gas obtained by heating a raw material containing silicon metal or silicon.
  • the silica particles may be produced by melting silica or the like.
  • the alumina particles may be obtained by precipitating and filtering aluminum hydroxide from an aqueous solution of a soluble aluminum salt and igniting it. It may be obtained by the Bayer method based on the principle of manufacturing sodium aluminate by treating with gibbsite or boehmite with sodium hydroxide, or by giving gibbsite, boehmite, diaspore, clay, alumite, sulfuric acid, nitric acid, etc. It may be obtained by purifying the aluminum salt by treating with, separating the acid groups by precipitation with ammonia or pyrolysis, and baking.
  • Silica particles and alumina particles may contain components other than silica and components other than alumina, and examples thereof include those present as impurities in the raw material in the above production method. Components other than silica and alumina may be added during the production process of silica and alumina.
  • silica synthesized by wet method Gel silica made from sodium silicate and made acidic. Precipitated silica made from sodium silicate and made alkaline. Silica synthesized by hydrolysis and condensation of alkoxysilanes.
  • Known methods for producing alumina include the following. Alumina obtained by acid method. Alumina obtained by the buyer method (alkali method). Sintered alumina obtained by granulating, drying and firing calcined alumina made by the Bayer method. Fused alumina obtained by melting the raw material in an electric furnace and crystallizing it. White fused alumina made from calcined alumina made by the buyer method. Brown electrofused alumina mainly made of bauxite. Fumed alumina. Alumina obtained by vaporizing and oxidizing metal at high temperatures.
  • silica obtained by each manufacturing method gel method silica made acidic using sodium silicate as a raw material, precipitation method silica made alkaline using sodium silicate as a raw material, silica synthesized by hydrolysis and condensation of alkoxysilane Fumed silica made by burning silicon chloride, silica made by burning silicon metal gas, silica produced by arc method or plasma method, fumed alumina causes molding defects during pressure molding It's easy to do. Furthermore, they tend to scatter and tend to aggregate.
  • silica particles and alumina particles obtained by other production methods, a plurality of It is preferable to mix silica particles or alumina particles.
  • Silica fume by-produced during ferrosilicon production fused silica that melts and spheroidizes crushed silica powder in a flame, alumina obtained by the Bayer method, sintered alumina, fused alumina (white fused alumina, brown Fused alumina) has a thermal conductivity of more than 0.05 W / m ⁇ K. Therefore, using only silica and alumina obtained by this production method as a raw material for silica particles and alumina particles is not a preferable aspect in terms of thermal conductivity, but is less scattered and excellent in handling. It may be useful in terms of cost.
  • the thermal conductivity it is possible to adjust the thermal conductivity to 0.05 W / m ⁇ K or less by mixing silica obtained by other manufacturing methods, so when using silica fume, sintered alumina, etc. as a raw material It is preferable to mix silica particles and alumina particles obtained by other production methods. For example, fumed silica made by burning silicon chloride, silica made by burning silicon metal gas, silica particles containing silica fume, sintered alumina, and / or alumina by mixing fumed alumina. The thermal conductivity of the particles can be reduced.
  • silica and alumina fumed silica, silica produced by burning silicon metal gas, silica fume, fused silica, fumed alumina, alumina obtained by the Bayer method, sintered alumina from the viewpoint of productivity and cost It is more preferable to use
  • natural silicate minerals as silica particles.
  • natural minerals include olivine, chlorite, quartz, feldspar, zeolite and the like.
  • Natural minerals can be used as an example of alumina particles.
  • alumina natural minerals include bauxite, porphyry shale, mullite, sillimanite, kyanite, andalusite, and chamotte.
  • the mullite may be synthetic mullite, sintered mullite, or electrofused mullite.
  • a natural mineral is subjected to a treatment such as pulverization to adjust the particle diameter, and can be used as silica particles and / or alumina particles constituting the powder.
  • Alkali metal element, alkaline earth metal element, Ge, P, Fe During the manufacturing process of silica and alumina and the manufacturing process of the heat insulating material, they may be added as compounds containing basic elements, Ge, P and Fe, respectively, but a sufficient amount of basic elements, Ge, P and Fe are added. It is good also considering the silica particle and / or alumina particle which are contained beforehand as a raw material of a heat insulating material.
  • the compound containing a basic element, Ge, P, Fe is not particularly limited.
  • inorganic compound particles containing silica containing basic elements, Ge, P, and Fe as impurities as a raw material of the powder is a preferable embodiment from the viewpoint of productivity, cost, and workability.
  • Such inorganic compound particles containing silica can be obtained, for example, as silica fume that replicates during the production of silica gel-derived particles or ferrosilicon produced by a precipitation method.
  • the method of adding a compound containing each of basic elements, Ge, P, and Fe is not particularly limited. For example, it may be added to silica obtained by the above wet method or dry method, alumina obtained by the acid method or alkali method, sintered alumina, electrofused alumina, or added in each of the above production steps of silica or alumina. May be.
  • the compound containing each basic element, Ge, P, and Fe may be water-soluble or insoluble in water. It may be added as an aqueous solution of a compound containing basic elements, Ge, P, and Fe, and may be dried as necessary, or a compound containing basic elements, Ge, P, and Fe may be solid or liquid. You may add in a state.
  • the compound containing each of the basic elements, Ge, P, and Fe may be previously pulverized to a predetermined particle diameter, or may be preliminarily coarsely pulverized.
  • silica particles or alumina particles contain an excessive amount of basic elements, Ge, P, Fe
  • some processing is performed during the silica or alumina manufacturing process or the heat insulating material manufacturing process to contain the elements.
  • the amount may be adjusted to a predetermined range.
  • the method for adjusting an excessive amount of basic elements, Ge, P, and Fe to a predetermined range is not particularly limited.
  • a substitution method, extraction method, removal method, etc. with an acidic substance or other elements After treating inorganic compound particles containing silica with nitric acid or aqua regia, It can be dried and used as a raw material for powder.
  • Adjustment of an excessive amount of basic elements, Ge, P, and Fe may be performed after previously pulverizing inorganic compound particles containing silica and / or alumina to a desired particle diameter, or basic elements, Ge, P, and the like.
  • the silica particles and alumina particles may be pulverized after adjusting Fe to a predetermined range.
  • Silica particles and / or alumina particles, infrared opacifying particles and inorganic fibers used are known powder mixers, for example, those listed in the Revised Sixth Edition Chemical Engineering Handbook (Maruzen) And can be mixed. At this time, it is possible to mix two or more kinds of inorganic compound particles containing silica, or a compound containing each of basic elements, Ge, P, and Fe, or an aqueous solution thereof.
  • Known powder mixers include a horizontal cylindrical type, a V type (which may be equipped with a stirring blade), a double cone type, a cubic type, and a shaking type as a container rotating type (the container itself rotates, vibrates and swings).
  • Dynamic rotation type mechanical agitation type (container is fixed and agitated with blades, etc.), single axis ribbon type, double axis paddle type, rotary saddle type, biaxial planetary agitation type, conical screw type, high speed agitation type, rotation
  • the disk type, the rotating container type with roller, the rotating container type with stirring, the high-speed elliptical rotor type, and the fluid stirring type include an airflow stirring type and a non-stirring type by gravity. You may use combining these mixers.
  • silica particles and / or alumina particles, infrared opacifying particles and inorganic fibers can be performed by using a material known as a pulverizer, for example, those listed in the Revised Sixth Edition, Chemical Engineering Handbook (Maruzen). You may carry out, grind
  • pulverizers include roll mills (high pressure compression roll mills, roll rotating mills), stamp mills, edge runners (fret mills, Chillian mills), cutting / shearing mills (cutter mills, etc.), rod mills, self-pulverizing mills (erofall mills, Cascade mills, vertical roller mills (ring roller mills, rollerless mills, ball race mills), high-speed rotary mills (hammer mills, cage mills, disintegrators, screen mills, disc pin mills), high-speed rotary mills with built-in classifiers (fixed) Impact plate mill, turbo mill, centrifugal classification mill, annular mill, container drive medium mill (rolling ball mill (pot mill, tube mill, conical mill)), vibration ball mill (circular vibration mill, rotational vibration mill, centrifugal mill) ), Planetary mill, centrifugal fluidization mill), medium Stirring mill (tower crusher, stirring tank mill, horizontal flow tank mill, vertical flow tank mill, annular mill), airflow grinder (airflow
  • powder mixers with stirring blades, high-speed rotary mills, high-speed rotary mills with built-in classifiers, container drive medium mills, and compaction shear mills improve the dispersibility of particles and inorganic fibers. Therefore, it is preferable.
  • the peripheral speed of the tip of the stirring blade, rotating plate, hammer plate, blade, pin, etc. it is preferable to set the peripheral speed of the tip of the stirring blade, rotating plate, hammer plate, blade, pin, etc. to 100 km / h or more, more preferably 200 km / h or more, More preferably, it is 300 km / h or more.
  • silica particles and / or alumina particles When mixing a plurality of types of silica particles and / or alumina particles, it is preferable to introduce the silica particles and / or alumina particles into a stirrer or pulverizer in the order of increasing bulk specific gravity.
  • silica particles and / or alumina particles When inorganic fibers and infrared opaque particles are included, it is preferable to add and mix infrared opaque particles after mixing silica particles and / or alumina particles, and then add and mix inorganic fibers.
  • a metal oxide sol may be added to silica particles or alumina particles.
  • the metal oxide sol becomes an inorganic binder, and a molded article having high compressive strength can be easily obtained.
  • the metal oxide sol is added. It is preferable to mix.
  • the peripheral speed at the tip of the stirring blade is 100 km / h.
  • the peripheral speed at the tip of the stirring blade is preferably 100 km / h or more, and there is less contact between large particles. In view of the above, 200 km / h or more is more preferable, and 300 km / h or more is more preferable.
  • the metal oxide sol examples include silica sol, alumina sol, zirconia sol, ceria sol, and titania sol.
  • Silica sol and alumina sol are preferable from the viewpoint of reducing thermal conductivity and heat resistance.
  • the particle size of the metal oxide sol is preferably 2 nm or more and 450 nm or less, more preferably 4 nm or more and 300 nm or less, and further preferably 4 nm or more and 200 nm or less from the viewpoint of reducing the thermal conductivity.
  • the amount of the metal oxide sol added is The content of the solid content of the metal oxide sol with respect to the total mass of is preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and further preferably 2% by mass or more and 25% by mass or less. preferable.
  • the heat insulating material of the present embodiment can be obtained by pressure-molding an inorganic mixture as a raw material.
  • the pressure treatment and the heat treatment are simultaneously performed (a).
  • heat treatment may be performed after the pressure treatment. That is, (a) a method of pressurizing a mold (molding die) filled (contained) with an inorganic mixture while heating may be used, or (b) an inorganic mixture is pressurized by pressurizing the mold with the inorganic mixture filled.
  • the obtained heat insulating material may be taken out from the mold or heated in a state of being put in the mold. In both embodiments, the preferred pressure and heating temperature are approximately the same.
  • molding may be performed by a conventionally known ceramic pressure molding method such as a die press molding method (ram type pressure molding method), a rubber press method (hydrostatic pressure molding method), or an extrusion molding method. It can. From the viewpoint of productivity, a die press molding method is preferable.
  • a die press molding method is preferable.
  • the powdered heat insulating material is vibrated, etc., so that the thickness of the molded body is uniform. Therefore, it is preferable.
  • Filling the mold with a powdery heat insulating material while reducing the pressure and degassing the mold is preferable from the viewpoint of productivity because the mold can be filled in a short time.
  • the bulk density of the resulting molded body is set under conditions for pressure molding from the viewpoint of making the maximum load and / or thermal conductivity at a compression rate of 0 to 5% as desired and reducing the burden during transportation. If preferably set to be less than 0.2 g / cm 3 or more 1.5 g / cm 3. If the molding conditions are controlled by the pressurized pressure, the pressure is maintained depending on the slipperiness of the powder used as the raw material for the heat insulating material, the amount of air taken in between the particles of the powder and the pores, etc. Since the pressure value changes with time, production management tends to be difficult. On the other hand, the method of controlling the bulk density is preferable in that the load of the heat insulating material obtained without requiring time control can be easily set to the target value.
  • the bulk density of the heat insulating material is more preferably 0.25 g / cm 3 or more and 1.2 g / cm 3 or less, and further preferably 0.30 g / cm 3 or more and 1.0 g / cm 3 or less.
  • the molding pressure at which the bulk density of the molded body is 0.2 g / cm 3 or more and 1.5 g / cm 3 or less is, for example, a pressure of 0.01 MPa or more and 50 MPa or less, and 0.25 g / cm 3 or more and 1.2 g.
  • / cm 3 as a molding pressure equal to or less than is the pressure below 40MPa example 0.01MPa or more, as the molding pressure equal to or less than 0.30 g / cm 3 or more 1.0 g / cm 3 30 MPa or less, for example 0.01MPa or more Pressure.
  • the weight of the necessary inorganic mixture is obtained from the volume of the heat insulating material and the bulk density.
  • the weighed inorganic mixture is filled in a mold and pressed to a predetermined thickness and molded.
  • the powder when producing a molded body having a volume ⁇ cm 3 and a bulk density of ⁇ g / cm 3 (where ⁇ is larger than the loosely packed bulk density of the powder), the powder is weighed by ⁇ g, and the powder Is compressed so as to have a volume ⁇ .
  • Heat treatment method The heat insulating material during or after pressure molding is heat-dried within the range of temperature and time sufficient for the heat resistance of the heat insulating material, and the adsorbed water of the heat insulating material. It is preferable to put it to practical use after removing it because the thermal conductivity is lowered. Furthermore, you may heat-process.
  • Molding may be only pressure molding, but it is preferable to heat-treat the pressure-molded one.
  • the heat treatment may be performed during pressure molding.
  • the heat insulating material preferably contains an alkali metal element, an alkaline earth metal element, Ge, P, or Fe, and particularly preferably contained in a large particle.
  • the heat treatment temperature is preferably higher than the maximum use temperature of the heat insulating material.
  • 400 to 1400 degreeC is preferable specifically, More preferably, it is 500 to 1300 degreeC, More preferably, it is 600 to 1200 degreeC.
  • the heat insulating material can contain the metal oxide sol as described above.
  • the heat insulating material contains a metal oxide sol, the heat insulating material tends to be hardened at a lower heat treatment temperature.
  • the heat insulating material is preferably 200 ° C. or higher and 1400 ° C. or lower, more preferably 300 ° C. or higher and 1300 ° C. It is 400 degreeC or more, More preferably, it is 1200 degreeC or less.
  • the heat treatment atmosphere of the heat insulating material is in the air (or in the air), in an oxidizing atmosphere (oxygen, ozone, nitrogen oxide, carbon dioxide, hydrogen peroxide, hypochlorous acid, inorganic / organic peroxide, etc.) And in an inert gas atmosphere (helium, argon, nitrogen, etc.). Water vapor may be added to the atmosphere.
  • the heat treatment time may be appropriately selected according to the heat treatment temperature and the amount of the heat insulating material.
  • the heat treatment may be performed after the heat insulating material is installed at a place where the heat insulating material is used, or may be applied in advance to the heat insulating material before installation or construction.
  • the heat insulating material of the present embodiment can be cut to obtain a cut heat insulating material.
  • molding comprises silica and / or alumina, a housing step of the inorganic mixture having a particle diameter D S contains small particles is 5nm or 30nm or less, to accommodate the mold, the inorganic mixture A forming step, that is, a step of heating to 400 ° C. or higher while pressing the inorganic mixture with a mold, or a step of forming a heat treatment at a temperature of 400 ° C. or higher after forming the inorganic mixture by pressing, and a molding step A cutting step of cutting a part of the obtained heat insulating material.
  • the cutting means for the heat insulating material is not particularly limited.
  • a vertical machining center, a horizontal machining center, a milling machine such as a 5-axis machine can be used, and a hand saw, a lathe, and a milling machine are particularly preferable.
  • large particles having an inorganic compound containing silica and / or alumina and having a particle diameter DL of 50 nm or more and 100 ⁇ m or less are used. It is preferable to include the step of mixing the large particles with a ratio RL of the mass of the large particles to the total mass of the small particles and the large particles being 60% by mass to 90% by mass to obtain an inorganic mixture.
  • the large particles preferably contain at least one element selected from the group consisting of alkali metal elements, alkaline earth metal elements, and germanium.
  • the bulk density of the heat insulating material is 0.2 g / cm. 3 to 1.5 g / cm 3 by setting the molding pressure to be less than is preferred.
  • Heat insulation enveloping body provided with outer covering material It is preferable that the heat insulating material is an insulating material enveloping body provided with the heat insulating material and the outer covering material that accommodates the heat insulating material.
  • a heat insulating material enveloping body provided with a covering material has an advantage that it is easy to handle and easy to construct as compared with a heat insulating material not including a covering material.
  • the heat insulating material accommodated in the jacket material may be referred to as a core material.
  • FIG. 3 is an example of a schematic cross-sectional view of a heat insulating material enveloping body according to the present embodiment.
  • FIG. 4 is an example of a schematic cross-sectional view of small particles and large particles according to the present embodiment.
  • the heat insulating material encapsulating body 1 according to the present embodiment includes a plurality of small particles S and a plurality of large particles L having a particle diameter larger than that of the small particles S. 2 and a jacket material 3 for housing the heat insulating material 2.
  • the small particles S and the large particles L are mixed, and the small particles S exist around the large particles L.
  • cover material is not particularly limited as long as it can accommodate a heat insulating material as a core material.
  • examples thereof include inorganic fiber fabrics such as glass cloth, alumina fiber cloth, silica cloth, and inorganic fibers. Knitted fabric, polyester film, polyethylene film, polypropylene film, nylon film, polyethylene terephthalate film, resin film such as fluororesin film, plastic-metal film, metal foil such as aluminum foil, stainless steel foil, copper foil, ceramic paper, inorganic fiber
  • Nonwoven fabric, organic fiber nonwoven fabric, glass fiber paper, carbon fiber paper, rock wool paper, inorganic filler paper, organic fiber paper, ceramic coating, fluororesin coating, siloxane resin coating, and other resin coatings can be exemplified.
  • the thickness of the jacket material is thin.
  • the jacket material is made of a material that is stable at the temperature at which the core material is used, the jacket material is in a state of accommodating a heat insulating material that is the core material even during use.
  • a jacket material having high heat resistance is preferable from the viewpoint of easy handling of the core material after use.
  • the jacket material protects the core material only during transportation and construction, and includes those that melt and / or volatilize during use. Therefore, the organic material contained in the jacket material itself or the jacket material is the core. It may melt or disappear at the use temperature of the material.
  • inorganic fiber fabrics such as glass cloth, alumina fiber cloth, silica cloth, inorganic fiber knitted fabric, polyester film, polyethylene film, polypropylene film, nylon film, polyethylene terephthalate film, fluorine Resin film such as plastic resin film, plastic-metal film, metal foil such as aluminum foil, stainless steel foil, copper foil, ceramic paper, inorganic fiber nonwoven fabric, organic fiber nonwoven fabric, glass fiber paper, carbon fiber paper, rock wool paper, inorganic Sheet shapes such as filled paper and organic fiber paper are preferred.
  • inorganic fiber fabrics such as glass cloth, alumina fiber cloth, silica cloth, inorganic fiber knitted fabric, polyester film, polyethylene film, polypropylene film, nylon film, polyethylene terephthalate film, fluorine Resin film such as plastic resin film, plastic-metal film, metal foil such as aluminum foil, stainless steel foil, copper foil, ceramic paper, inorganic fiber nonwoven fabric, organic fiber nonwoven fabric, glass fiber paper, carbon fiber paper, rock wool paper, inorganic Sheet shapes such
  • the covering material is made of an inorganic fiber woven fabric such as glass cloth, alumina fiber cloth, silica cloth, or inorganic fiber knitted fabric from the viewpoint of thermal stability. Ceramic paper and inorganic fiber nonwoven fabric are more preferable.
  • the jacket material is more preferably an inorganic fiber fabric from the viewpoint of strength.
  • the method of coating the core material with the jacket material is not particularly limited, and the core material may be prepared or molded and coated with the jacket material at the same time, or the core material may be coated with the jacket material after preparation or molding. May be.
  • Cover material is inorganic fiber fabric, resin film, plastic-metal film, metal foil, ceramic paper, inorganic fiber nonwoven fabric, organic fiber nonwoven fabric, glass fiber paper, carbon fiber paper, rock wool paper, inorganic filler paper, organic fiber paper, etc.
  • the sheet-like form for example, it is possible to cover with stitching with inorganic fiber yarn or resin fiber yarn, adhesion fixing of the jacket material, and both stitching and adhesion.
  • the jacket material is a resin film, a plastic-metal film, a metal foil or the like, a vacuum pack or a shrink pack is preferable from the viewpoint of easy coating process.
  • the core material can be covered with the jacket material by applying to the core material with a brush or spray.
  • a linear depression in a heat insulating material composed of a pressure-molded core material and a jacket material to give flexibility to the heat insulating material.
  • a linear shape, a curved shape, a broken line shape, or the like can be selected according to the use state of the heat insulating material, and two or more of these may be combined.
  • the thickness of the line and the depth of the depression are determined according to the thickness, strength, and usage of the heat insulating material.
  • the outer jacket material may cover the entire surface of the core material, or may partially cover the core material.
  • the heat insulating material of the present embodiment is a heat absorbing material, a sound absorbing material, a sound insulating material, a sound insulating material, an anti-reflection material, a sound deadening material, an abrasive, a catalyst carrier, an adsorbent, a fragrance, a bactericide, and the like. It can also be suitably used for a carrier that adsorbs water, a deodorant, a deodorant, a humidity control material, a filler, a pigment, and the like.
  • Heat insulation method The heat insulating material of the present embodiment is adhered to a heat resistant container to maintain the temperature in the container or prevent the heat in the container from diffusing. It is possible to use suitably for the heat insulation method.
  • a heat insulating material is provided so as to be interposed between the heat source and the container, heat transfer from the heat source to the container can be suppressed.
  • the heat insulating material is shaped to fit into the container (for example, when the container is cylindrical, the heat insulating material is formed into a cylindrical shape having the same outer diameter as the inner diameter of the container), etc.
  • a sticking is a preferable aspect from a viewpoint of stability of a heat insulating material.
  • the heat-resistant container is not particularly limited, and examples thereof include a molten iron container, a ladle, a tundish, a topped car, a glass manufacturing container, a melting furnace, a boiler, a steel plate duct, a steam tank, and an engine.
  • the “heat-resistant container” may have any shape that can be accommodated therein, and is not limited in size and mobility, and is a concept that includes what is generally called “furnace”.
  • steel heating furnaces used in steel plants metal heat treatment furnaces used in non-ferrous metal production, aluminum melting furnaces, aluminum holding furnace lids, various industrial furnaces such as glass production, carbon firing furnaces, naphtha cracking furnaces,
  • various furnaces such as ceramic firing furnaces, semiconductor heat treatment furnaces, refuse incinerators, reforming furnaces, kiln furnaces, firing furnaces, heating furnaces, kilns, various towers or tanks, and containers constituting heat exchangers and turbines
  • the shape is also included in the heat resistant container. Since the heat insulating material of this embodiment is excellent in pressure resistance, it can be suitably used particularly in a place where pressure is applied.
  • the sticking method is not particularly limited, a method of sticking through a binder and / or a refractory is preferable from the viewpoint of ease of construction.
  • the binder has the function of fixing the heat insulating material to the heat resistant container, the function of absorbing the vibration of the heat resistant container and / or the heat insulating material, the heat from the joint filled with the heat insulating material, and the contents of the heat resistant container ( Those having a function of suppressing the outflow of gas (including gas) are also included.
  • binder examples include mortar, adhesive, fixing agent, and bonding agent, and various tapes such as a tape, a double-sided tape, and an acrylic resin-based adhesive tape can be used as the binder.
  • the adhesive include silica-based adhesive, ceramic, cement, solder, inorganic adhesive such as water glass (sodium silicate, sodium silicate), organic adhesive, asphalt, gum arabic, albumin, lacquer, glue, pine Natural adhesives such as, acrylic resin adhesive, acrylic resin anaerobic adhesive, ⁇ -olefin adhesive, urethane resin adhesive, ethylene-vinyl acetate resin emulsion adhesive, epoxy resin adhesive, epoxy resin Emulsion adhesive, vinyl acetate resin emulsion adhesive, cyanoacrylate adhesive, silicone adhesive, aqueous polymer-isocyanate adhesive, phenol resin adhesive, modified silicone adhesive, polyimide adhesive, polyacetic acid Synthetic adhesives such as vinyl resin solution adhesives, polybenzimidazole adhesives, etc. And the like.
  • Refractories include heat-resistant bricks, refractory bricks, irregular refractories, refractory mortars, refractory stamp materials, and refractory insulation bricks. Moreover, even if it is generally classified as a heat insulating brick, it is contained in a refractory material as long as it has fire resistance. Refractories can be classified into acidic refractories, neutral refractories, basic refractories, non-oxide refractories, and composite refractories. Examples of acidic refractories include feldspar, fused quartz, waxy, clay, high alumina, zircon, AZS, and zirconia refractories.
  • Examples of neutral refractories include alumina and chromia refractories.
  • Examples of basic refractories include calcareous, dolomite, magnesia, chromium magnesia, and spinel refractories.
  • Examples of the non-oxide refractories include carbonaceous, silicon carbide, silicon carbide-graphite, and silicon nitride refractories.
  • Examples of the composite refractories include alumina / carbonaceous, magnesia / carbonaceous, and silicon carbide-containing refractories.
  • the heat insulating material of the present embodiment may be attached to a heat-resistant container through a binder, may be attached to a heat-resistant container through a refractory, or a heat-resistant container through both a binder and a refractory. You may stick to.
  • a mode in which the molded body and / or the encapsulated body is attached to a heat-resistant container via a refractory is suitable for applications that require heat resistance in addition to heat insulation. For example, when a container to be insulated contains a heat source and a heat insulating material is provided outside the container for heat insulation, the heat insulating material is thermally deteriorated due to the presence of a refractory between the heat insulating material and the container.
  • heat conduction to the heat-resistant container can be suppressed while preventing deterioration of the heat insulating material.
  • the heat insulating material and / or the refractory does not need to cover the entire surface of the container, and even if it is partially, there is an effect of heat insulation and / or prevention of deterioration accordingly.
  • each cover the entire inner surface since the effect of heat insulation or the like is reduced by heat transfer from the uncoated portion, it is preferable that each cover the entire inner surface.
  • the heat insulating material and the refractory material may have substantially the same shape as the container, but the thickness of each may be appropriately set according to the required heat insulation and / or fire resistance performance.
  • the heat insulating material different from the present embodiment may be sandwiched between the heat insulating material of the present embodiment and / or the heat insulating material.
  • the heat insulating material of this embodiment can be attached to a heat-resistant container using screws.
  • the screw includes a bolt, a nut, and a screw.
  • the heat insulating material of this embodiment can be drilled with a hand drill or the like and screwed.
  • a screw may be used.
  • the area and / or weight of the heat insulating material to be used is large, the heat resistance performance of the adhesive is insufficient, and when screws are used for construction on the ceiling surface, there is a tendency that adhesion is easy.
  • a sticking location vibrates there exists a tendency for fixation by screwing to be effective.
  • the heat insulating material has a jacket material or when the location where the heat insulating material is pasted is a curved surface, the use of a binder tends to be suitable, but the type of heat insulating material, the situation of the location where it is to be pasted
  • the binder, the refractory, and the screw may be appropriately selected according to the contents of the sticking process.
  • the heat insulating material according to the present embodiment is housed in a housing to maintain the temperature in the housing, to diffuse the heat in the housing, and to prevent the housing from taking in external heat. It is also possible to use it suitably.
  • the housing is not particularly limited, and examples include a fuel cell unit, a fuel cell module housing, a fuel cell power generation unit, a stove, and a water heater.
  • the method of housing in the housing is not particularly limited, and it may be simply filled and arranged in the housing, or may be attached to the inner wall of the housing, for example, via the binder and / or refractory as described above, or screwed. It can be housed in a case by sticking and fixing using a binder, or sticking using a binder, a refractory, and a screw.
  • the heat insulation method of covering the heat-resistant containers and pipes with the heat insulating material is effective for maintaining the internal temperature of the heat-resistant containers and pipes and conversely preventing heat from entering them.
  • a method of forming the heat insulating material in a shape slightly larger than the heat-resistant container and the pipe and fitting the heat-resistant container and the pipe therein can be adopted.
  • a semi-cylindrical shaped body having a slightly larger radius than the pipe may be produced and fitted so as to cover the pipe.
  • a method of winding an elongated cylindrical enveloping body around the pipe is simple and effective.
  • the heat insulating material is processed to a length of 2 cm, a width of 2 cm, and a thickness of 2 cm, and the compressive strength is measured at an indentation speed of 0.5 mm / min using a precision universal testing machine Autograph AG-100KN (manufactured by Shimadzu Corporation).
  • a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.) is used, and one field of view is observed under the condition of an acceleration voltage of 1.0 kV.
  • 100 visual fields or more are observed to check whether 100 or more particles having an equivalent area equivalent circle diameter of 5 nm to 30 nm are present.
  • the In calculating the particle diameter D S of the small particles equal area circle equivalent diameter by increasing the field number to be observed as needed to 30nm or smaller particles than 5nm were observed more than 100, the number average about 100 particles It shows the calculated values in the examples as the particle diameter D S of the small particles.
  • Measurement is performed by mercury porosimetry using a pore distribution measuring device Autopore 9520 (manufactured by Shimadzu Corporation).
  • the formed heat insulating material is cut into a rectangular parallelepiped so as to enter the cell, one is taken into a low-sensitivity cell, and the pressure is measured under conditions of an initial pressure of about 7 kPa (about 1 psia, pore diameter of about 180 ⁇ m).
  • the mercury parameters are set at the instrument default mercury contact angle of 130 degrees and the mercury surface tension of 485 dynes / cm.
  • a powdered heat insulating material is pulverized in a menor mortar, filled into a 30 mm ⁇ polyvinyl chloride ring, and pressure-molded with an XRF tablet molding machine to produce a tablet, which is used as a measurement sample. This is measured with a fluorescent X-ray analyzer RIX-3000 manufactured by Rigaku Corporation. Also in the case of the molded heat insulating material, the content of the alkali metal element or the like can be similarly measured by pulverizing with a menor mortar after making the size into a menor mortar.
  • Example 1 A silica powder was obtained in which 25% by mass of silica powder (small particles) having an average particle size of 14 nm and 75% by mass of silica powder (large particles) having an average particle size of 150 nm were uniformly mixed by a hammer mill.
  • a molded body with a length of 30 cm, a width of 30 cm, a thickness of 20 mm, and a bulk density of 0.50 g / cm 3
  • 900 g of silica powder is filled in a mold having an inner dimension of 30 cm in length and 30 cm in width, and pressure molding is performed. As a result, a molded body having a bulk density of 0.50 g / cm 3 was obtained.
  • Example 1 of the cross section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more. Then such change the field of view as required to measure the particle diameter of the total of 100 small particles, the number average result, D S is 16 nm, the thermal conductivity at 30 °C 0.0269W / m ⁇
  • the heat insulating material was cut in the vertical direction to produce 25 cut heat insulating materials having a length of 6 cm, a width of 6 cm, and a thickness of 20 mm.
  • the bulk density of the heat insulating material of Example 1 is 0.50 g / cm 3
  • the pore volume, that is, the cumulative pore volume V 0.003 of pores having a pore diameter of 0.003 ⁇ m to 150 ⁇ m is 0.
  • the ratio of the cumulative pore volume V of pores having a pore diameter of 0.05 ⁇ m or more and 0.5 ⁇ m or less to R, ie, V 0.003 was 97.8%.
  • Example 2 A silica powder in which 15% by mass of silica powder (small particles) having an average particle size of 12 nm and 85% by mass of silica powder (large particles) having an average particle size of 10 ⁇ m were uniformly mixed by a hammer mill was obtained. Using 1980 g of this silica powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 1000 ° C. for 10 hours to obtain a heat insulating material of Example 2.
  • Example 2 of the cross section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • Example 3 A silica powder in which 90% by mass of silica powder (small particles) having an average particle diameter of 7.5 nm and 10% by mass of silica powder (large particles) having an average particle diameter of 60 ⁇ m were uniformly mixed by a hammer mill was obtained. . Using 396 g of this silica powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Example 3. Example 3 of the cross section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 9 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 3, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 1.14 MPa.
  • the bulk density of the heat insulating material of Example 3 was 0.22 g / cm 3
  • the pore volume was 2.701 mL / g
  • R was 48.7%.
  • Example 4 A silica powder in which 50% by mass of silica powder (small particles) having an average particle size of 14 nm and 50% by mass of silica powder (large particles) having an average particle size of 80 nm were uniformly mixed by a hammer mill was obtained. Using 558 g of this silica powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 1000 ° C. for 5 hours to obtain a heat insulating material of Example 4.
  • Example 4 a cross-section of heat insulating material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 15 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 4, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 0.98 MPa.
  • the bulk density of the heat insulating material of Example 4 was 0.32 g / cm 3
  • the pore volume was 1.703 mL / g
  • R was 67.4%.
  • Example 5 A silica powder in which 30% by mass of silica powder (small particles) having an average particle diameter of 7.5 nm and 70% by mass of silica powder (large particles) having an average particle diameter of 6 ⁇ m were uniformly mixed by a hammer mill was obtained. . Using 882 g of this silica powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 24 hours to obtain a heat insulating material of Example 5.
  • Example 5 of the cross section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 9 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 5, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 0.77 MPa.
  • the bulk density of the heat insulating material of Example 5 was 0.49 g / cm 3
  • the pore volume was 1.048 mL / g
  • R was 47.2%.
  • Example 6 A silica powder in which 80% by mass of silica powder (small particles) having an average particle diameter of 14 nm and 20% by mass of silica powder (large particles) having an average particle diameter of 150 nm was uniformly mixed by a hammer mill was obtained. Using 450 g of this silica powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 24 hours to obtain a heat insulating material of Example 6. Example 6 result the cross section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 16 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 6, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 1.14 MPa.
  • the bulk density of the heat insulating material of Example 6 was 0.25 g / cm 3
  • the pore volume was 2.426 mL / g
  • R was 47.6%.
  • Example 7 A powder in which 20% by mass of silica powder (small particles) having an average particle size of 14 nm and 80% by mass of alumina powder (large particles) having an average particle size of 200 nm were uniformly mixed by a hammer mill was obtained. Using 1296 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, and then heat treatment was performed at 1100 ° C. for 5 hours to obtain a heat insulating material of Example 7. Example 7 result the cross section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 19 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 as in Example 1, but none of these cut heat insulating materials were chipped or damaged.
  • the sample collapsed to show a breaking point at a compression rate of 4.3%, and the load at this time was 1.12 MPa.
  • the bulk density of the heat insulating material of Example 7 was 0.73 g / cm 3
  • the pore volume was 1.252 mL / g
  • R was 87.6%.
  • Example 8 A silica powder was obtained in which 25% by mass of silica powder (small particles) having an average particle size of 22 nm and 75% by mass of silica powder (large particles) having an average particle size of 150 nm were uniformly mixed by a hammer mill. Using 936 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Example 8. Example 8 result the cross section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 23 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 8, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 3.49 MPa.
  • the bulk density of the heat insulating material of Example 8 was 0.52 g / cm 3
  • the pore volume was 1.518 mL / g
  • R was 90.0%.
  • Example 9 A silica powder was obtained in which 25% by mass of silica powder (small particles) having an average particle size of 14 nm and 75% by mass of silica powder (large particles) having an average particle size of 80 nm were uniformly mixed by a hammer mill. 792 g of this powder was subjected to pressure molding in the same manner as in Example 1 to obtain a molded body, and then subjected to heat treatment at 1100 ° C. for 3 hours to obtain a heat insulating material of Example 9.
  • Example 9 a cross-section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 18 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 9, but there was no chipping or breakage in any of these cut heat insulating materials.
  • the maximum load at a compression rate of 5.0% was 2.59 MPa.
  • the bulk density of the heat insulating material of Example 9 was 0.47 g / cm 3 , the pore volume was 1.195 mL / g, and R was 90.6%.
  • Example 10 A silica powder was obtained by uniformly mixing 40% by mass of silica powder (small particles) with an average particle size of 7.5 nm and 60% by mass of silica powder (large particles) with an average particle size of 100 ⁇ m using a hammer mill. . Using 846 g of this powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 2 hours to obtain a heat insulating material of Example 10. Example 10 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 9 nm
  • 25 heat-insulating materials were cut and cut in the same manner as in Example 1 of the heat-insulating material of Example 10, but none of these cut-insulated materials were chipped or damaged.
  • the sample collapsed to show a breaking point at a compression rate of 4.9%, and the load at this time was 6.29 MPa.
  • the bulk density of the heat insulating material of Example 10 was 0.60 g / cm 3
  • the pore volume was 0.581 mL / g
  • R was 32.87%.
  • Example 11 A powder in which 15% by mass of alumina powder (small particles) having an average particle size of 7 nm and 85% by mass of silica powder (large particles) having an average particle size of 80 nm were uniformly mixed by a hammer mill was obtained. Using 972 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, and then heat treatment was performed at 1100 ° C. for 5 hours to obtain a heat insulating material of Example 11. Example 11 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 8 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 11, but none of these cut heat insulating materials were chipped or damaged.
  • the sample collapsed to show a breaking point when the compression rate was 4.6%, and the load at this time was 2.83 MPa.
  • the bulk density of the heat insulating material of Example 11 was 0.59 g / cm 3
  • the pore volume was 0.965 mL / g
  • R was 91.3%.
  • Example 12 A powder in which 15% by mass of silica powder (small particles) having an average particle size of 14 nm and 85% by mass of silica powder (large particles) having an average particle size of 320 nm was uniformly mixed by a hammer mill was obtained. Using 972 g of this powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 10 hours to obtain a heat insulating material of Example 12. Example 12 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 16 nm
  • 25 heat insulating materials were cut and cut as in Example 1 in the same manner as in Example 1, but none of these cut heat insulating materials were chipped or damaged.
  • the sample collapsed to show a breaking point at a compression rate of 4.7%, and the load at this time was 1.09 MPa.
  • the bulk density of the heat insulating material of Example 12 was 0.54 g / cm 3
  • the pore volume was 1.027 mL / g
  • R was 85.0%.
  • Example 13 A powder in which 20% by mass of silica powder (small particles) having an average particle size of 7.5 nm and 80% by mass of silica powder (large particles) having an average particle size of 10 ⁇ m were uniformly mixed by a hammer mill was obtained. Using 1260 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 1000 ° C. for 10 hours to obtain a heat insulating material of Example 13. Example 13 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 10 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 13 of the heat insulating material of Example 13, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 0.97 MPa.
  • the bulk density of the heat insulating material of Example 13 was 0.72 g / cm 3 , the pore volume was 1.425 mL / g, and R was 79.8%.
  • Example 14 After uniformly mixing 21% by mass of silica powder (small particles) with an average particle size of 14 nm and 63% by mass of silica powder (large particles) with an average particle size of 150 nm using a hammer mill, the average particle size is 1 ⁇ m. Then, 16% by mass of zirconium silicate, which is an infrared opaque particle, was added and mixed uniformly to obtain a powder. Using 1044 g of this powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Example 14.
  • Example 14 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more. Then, to observe the plurality of field as necessary to measure the particle size of the total of 100 small particles, the number average result this, D S is 16 nm, the thermal conductivity at 30 °C 0.0413W / M ⁇ K, 25 heat insulation materials were cut and cut in the same manner as in Example 1 in Example 14, but none of these cut insulation materials were chipped or damaged. .
  • Example 14 Furthermore, as a result of measuring the compressive strength in the same manner as in Example 1, the sample collapsed to show a breaking point at a compression rate of 4.5%, and the load at this time was 3.58 MPa. Moreover, the bulk density of the heat insulating material of Example 14 was 0.58 g / cm 3 , the pore volume was 1.212 mL / g, and R was 89.3%. Moreover, after using this powder and performing pressure forming using a cylindrical mold having an inner diameter of 30 cm to obtain a molded body, it was subjected to a heat treatment at 900 ° C.
  • Example 15 After 24% by mass of silica powder (small particles) having an average particle diameter of 14 nm and 71% by mass of silica powder (large particles) having an average particle diameter of 150 nm are uniformly mixed with a hammer mill, the average fiber diameter is 11 ⁇ m, 5 mass% of glass fibers having an average fiber length of 6.4 mm and a heat resistant temperature of 1050 ° C. were added and mixed with a high-speed shear mixer to obtain silica powder. Using 936 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Example 15.
  • Example 15 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more. Then, to observe the plurality of field as necessary to measure the particle size of the total of 100 small particles, the number average result this, D S is 16 nm, the thermal conductivity at 30 °C 0.0343W It was / m ⁇ K, and 25 sheets of the heat insulating material were cut and cut in the same manner as in Example 1 in Example 15, but none of these cut heat insulating materials were chipped or damaged. .
  • Example 14 Furthermore, as a result of measuring the compressive strength in the same manner as in Example 1, the sample collapsed to show a breaking point at a compression rate of 4.7%, and the load at this time was 3.84 MPa. Moreover, the bulk density of the heat insulating material of Example 14 was 0.52 g / cm 3 , the pore volume was 1.324 mL / g, and R was 83.5%.
  • Example 16 After uniformly mixing 21% by mass of silica powder (small particles) with an average particle size of 14 nm and 63% by mass of silica powder (large particles) with an average particle size of 80 nm using a hammer mill, the average particle size is 1 ⁇ m. Then, 15 mass% of zirconium silicate which is an infrared opaque particle is added and mixed uniformly. Further, 1 mass% of glass fiber having an average fiber diameter of 11 ⁇ m, an average fiber length of 6.4 mm, and a heat resistant temperature of 1050 ° C. The mixture was added and mixed with a high-speed shear mixer to obtain a powder.
  • Example 16 Using 864 g of this powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 1000 ° C. for 5 hours to obtain a heat insulating material of Example 16.
  • Example 16 a cross-section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 18 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 of Example 16, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 0.90 MPa.
  • the bulk density of the heat insulating material of Example 16 was 0.48 g / cm 3
  • the pore volume was 1.613 mL / g
  • R was 50.2%.
  • Example 17 After uniformly mixing 20% by mass of silica powder (small particles) with an average particle size of 14 nm and 60% by mass of silica powder (large particles) with an average particle size of 150 nm using a hammer mill, the average particle size is 1 ⁇ m. Then, 15 mass% of zirconium silicate which is an infrared opaque particle is added and mixed uniformly. Further, 5 mass% of glass fiber having an average fiber diameter of 11 ⁇ m, an average fiber length of 6.4 mm and a heat resistance temperature of 1050 ° C. The mixture was added and mixed with a high-speed shear mixer to obtain a powder.
  • Example 17 Using 702 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Example 17.
  • Example 17 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 17 nm
  • 25 heat insulating materials were cut by cutting the heat insulating material of Example 17 in the same manner as in Example 1, and none of these cut heat insulating materials were chipped or damaged.
  • the sample collapsed to show a breaking point when the compression rate was 4.4%, and the load at this time was 0.98 MPa.
  • the bulk density of the heat insulating material of Example 17 was 0.39 g / cm 3 , the pore volume was 1.247 mL / g, and R was 76.93%.
  • this powder and performing pressure forming using a cylindrical mold having an inner diameter of 30 cm to obtain a molded body it was subjected to heat treatment at 900 ° C. for 5 hours to have a diameter of 30 cm and a thickness of Two disk-shaped heat insulating materials having a bulk density of 20 mm and a bulk density of 0.39 g / cm 3 were obtained. Using these two heat insulating materials, the heat conductivity at 800 ° C. was measured, and it was 0.0982 W / m ⁇ K.
  • Example 18 After uniformly mixing 19% by mass of silica powder (small particles) with an average particle size of 14 nm and 57% by mass of silica powder (large particles) with an average particle size of 80 nm using a hammer mill, the average particle size is 1 ⁇ m. Then, 14 mass% of zirconium silicate which is an infrared opaque particle is added and mixed uniformly, and further, 10 mass% of glass fiber having an average fiber diameter of 11 ⁇ m, an average fiber length of 6.4 mm and a heat resistant temperature of 1050 ° C. The mixture was added and mixed with a high-speed shear mixer to obtain a powder.
  • Example 18 Using 972 g of this powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 1000 ° C. for 24 hours to obtain a heat insulating material of Example 18.
  • Example 18 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 18 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 in Example 18, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 4.56 MPa.
  • the bulk density of the heat insulating material of Example 18 was 0.58 g / cm 3
  • the pore volume was 1.048 mL / g
  • R was 93.3%.
  • Example 19 After uniformly mixing 21% by mass of silica powder (small particles) with an average particle size of 14 nm and 63% by mass of silica powder (large particles) with an average particle size of 150 nm using a hammer mill, the average particle size is 1 ⁇ m. Then, 15 mass% of zirconium silicate which is an infrared opaque particle is added and mixed uniformly. Further, 1 mass% of glass fiber having an average fiber diameter of 11 ⁇ m, an average fiber length of 6.4 mm and a heat resistant temperature of 1050 ° C. is added. The mixture was added and mixed with a high-speed shear mixer to obtain a powder.
  • Example 19 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 16 nm
  • 25 heat insulation materials were cut and cut in the same manner as in Example 1 in Example 19, but none of these cut insulation materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 4.96 MPa.
  • the bulk density of the heat insulating material of Example 19 was 0.51 g / cm 3
  • the pore volume was 1.279 mL / g
  • R was 77.2%.
  • Example 20 After mixing 27% by mass of silica powder (small particles) with an average particle size of 14 nm and 51% by mass of silica powder (large particles) with an average particle size of 6 ⁇ m using a hammer mill, the average particle size is 1 ⁇ m. Then, 21 mass% of zirconium silicate which is an infrared opaque particle is added and mixed uniformly. Further, 1 mass% of glass fiber having an average fiber diameter of 11 ⁇ m, an average fiber length of 6.4 mm, and a heat resistant temperature of 1050 ° C. The mixture was added and mixed with a high-speed shear mixer to obtain a powder.
  • Example 20 Using 1242 g of this powder, pressure molding was carried out in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 24 hours to obtain a heat insulating material of Example 20.
  • Example 20 a result of the cross-section of the heat insulating material was observed as described in [Measurement of particle diameter D S of the small particles] of equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more.
  • D S is 17 nm
  • 25 heat insulating materials were cut and cut in the same manner as in Example 1 of the heat insulating material of Example 20, but none of these cut heat insulating materials were chipped or damaged.
  • the maximum load at a compression rate of 5.0% was 0.75 MPa.
  • the bulk density of the heat insulating material of Example 20 was 0.69 g / cm 3 , the pore volume was 1.135 mL / g, and R was 48.1%.
  • Table 1 shows the content of Na, K, Mg, Ca, Ge, P, and Fe in the heat insulating materials of Examples 1 to 20 on the basis of the total mass of the heat insulating material.
  • Table 2 shows the content of Na, K, Mg, Ca, Ge, P, and Fe contained in the large particles in the heat insulating materials of Examples 1 to 20 on the basis of the total mass of the large particles.
  • the rate was 0.119 W / m ⁇ K, and 25 heat-insulating materials were prepared by cutting the heat-insulating material of Comparative Example 1 in the same manner as in Example 1. However, none of these heat-insulating materials were cut. There was no damage. Furthermore, as a result of measuring the compressive strength in the same manner as in Example 1, the maximum load at a compression rate of 5.0% was 17 MPa.
  • Example 3 A heat insulating material was prepared in the same manner as in Example 1 except that the heat treatment was not performed, and the heat insulating material of Comparative Example 3 was obtained.
  • the heat conductivity of the heat insulating material of Comparative Example 3 at 30 ° C. is 0.0273 W / m ⁇ K, and the heat insulating material of Comparative Example 3 was cut and cut in the same manner as in Example 1 to create 25 heat insulating materials. However, chipping or breakage was observed on 21 out of 25 sheets. Furthermore, as a result of measuring the compressive strength in the same manner as in Example 1, the maximum load at a compression rate of 5.0% was 0.23 MPa.
  • Comparative Example 4 A silica powder in which 5% by mass of silica powder (small particles) having an average particle size of 7.5 nm and 95% by mass of silica powder (large particles) having an average particle size of 100 ⁇ m were uniformly mixed by a hammer mill was obtained. . Using 3060 g of this silica powder, pressure molding was performed in the same manner as in Example 1 to obtain a molded body, followed by heat treatment at 900 ° C. for 5 hours to obtain a heat insulating material of Comparative Example 4.
  • Comparative Example 4 of the cross section of the insulation material [Measurement of particle diameter D S of the small particles] result of observation as described, equal area circle equivalent diameter was confirmed 30nm or smaller particles than 5nm is 2 or more. Then, to observe the plurality of field as necessary to measure the particle size of the total of 100 small particles, the number average result this, D S is 9 nm, the thermal conductivity at 30 °C 0.284W / M ⁇ K, 25 heat insulating materials were cut by cutting the heat insulating material of Comparative Example 4 in the same manner as in Example 1, but none of these cut heat insulating materials were chipped or damaged. . Furthermore, as a result of measuring the compressive strength in the same manner as in Example 1, the maximum load at a compression rate of 5.0% was 19 MPa.
  • Example 5 A silica powder in which 85% by mass of silica powder (small particles) having an average particle size of 12 nm and 15% by mass of silica powder (large particles) having an average particle size of 80 nm were uniformly mixed by a hammer mill was obtained. Using 594 g of this silica powder, pressure molding was performed in the same manner as in Example 1 to obtain a heat insulating material of Comparative Example 5. The heat conductivity of the heat insulating material of Comparative Example 5 at 30 ° C. is 0.0198 W / m ⁇ K, and the heat insulating material of Comparative Example 5 is cut and cut in the same manner as in Example 1 to create 25 heat insulating materials.
  • the present invention it is possible to provide a heat insulating material and a method for manufacturing the heat insulating material that are unlikely to be collapsed or deformed during compression and that can be cut and shaped without collapsing.

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Abstract

L'objet de la présente invention concerne : un matériau d'isolation thermique qui prend en compte les problèmes de la technologie classique, est peu susceptible de s'affaisser ou de se déformer quand il est comprimé, est capable d'être coupé ou façonné d'une autre manière sans s'affaisser et présente des propriétés d'isolation thermique ; et un procédé de production hautement productif pour le matériau d'isolation thermique. Le matériau d'isolation thermique est formé en incluant de la silice et/ou de l'aluminium, inclut une pluralité de petites particules présentant un diamètre de particules (Ds) de 5-30 nm, présente une charge maximale de 0,7 MPa min. à 0-5% de compression et présente un coefficient de transfert de chaleur de 0,05 W/m·K max., à 30°C.
PCT/JP2011/073003 2010-12-27 2011-10-05 Matériau d'isolation thermique et procédé de production de celui-ci WO2012090566A1 (fr)

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WO2014091665A1 (fr) * 2012-12-11 2014-06-19 ニチアス株式会社 Matière d'isolation et son procédé de fabrication
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JP2015143532A (ja) * 2014-01-31 2015-08-06 ニチアス株式会社 断熱材及びその製造方法
JP2016088819A (ja) * 2014-11-07 2016-05-23 旭化成ケミカルズ株式会社 粉体、その成形体及び被包体
JP6414835B1 (ja) * 2018-03-29 2018-10-31 株式会社エスコ 断熱材
CN112778885A (zh) * 2021-01-08 2021-05-11 中国科学院青海盐湖研究所 一种超疏水涂层材料及其制备方法、超疏水涂层
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