WO1998038140A1 - Sound absorbing and heat insulating material, and method of manufacturing same - Google Patents
Sound absorbing and heat insulating material, and method of manufacturing same Download PDFInfo
- Publication number
- WO1998038140A1 WO1998038140A1 PCT/JP1997/000598 JP9700598W WO9838140A1 WO 1998038140 A1 WO1998038140 A1 WO 1998038140A1 JP 9700598 W JP9700598 W JP 9700598W WO 9838140 A1 WO9838140 A1 WO 9838140A1
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- Prior art keywords
- sound
- insulating material
- tensile strength
- absorbing heat
- absorbing
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- H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
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- C04B2111/00853—Uses not provided for elsewhere in C04B2111/00 in electrochemical cells or batteries, e.g. fuel cells
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/52—Sound-insulating materials
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/25—Coating or impregnation absorbs sound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2926—Coated or impregnated inorganic fiber fabric
- Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
Definitions
- the present invention relates to a sound-absorbing heat-insulating material using carbon fibers, and more particularly, to a sound-absorbing heat-insulating material using non-electrolytically fine carbon fibers.
- the sound-absorbing heat-insulating material according to the present invention is not limited to a sound-absorbing heat-insulating material, but may be used exclusively as a sound-absorbing material or as a heat-insulating material exclusively used for heat insulation. Can also be used. Background technology
- Sound-absorbing insulation is increasingly important as a component for creating energy-saving and comfortable living spaces, or as a component for protecting people and equipment from harsh external environments. waiting.
- natural fibers and synthetic resins have been used for the sound-absorbing heat insulating material.
- these fibers are generally flammable, and generate toxic gas in the event of a fire. Thus, there is a problem with safety.
- inorganic materials are now being used in place of these materials, and glass fibers in particular have good fire safety, moldability and workability. However, it has been widely used as a material for sound absorbing insulation.
- glass fiber is a specific gravity of 2. 4 ⁇ 2. 6 g / cm 3 degree and have come large. For this reason, there is a problem that the sound-absorbing heat-insulating material using glass fiber does not have sufficient sound-absorbing heat insulating properties per unit weight. In addition, glass fibers are gradually degraded by absorbing moisture, and have low mechanical strength. Therefore, there is a problem that the sound-absorbing heat-insulating material using glass fiber has insufficient durability.
- the present invention has excellent sound absorbing properties and heat insulating properties using carbon fibers, but also has durability, mechanical strength, compression restoring property, light weight, chemical stability, and difficulty. It is an object of the present invention to provide a sound-absorbing heat insulating material that is excellent in flammability, not generating toxic gas in a fire, hardly absorbing moisture, and has excellent non-electrocorrosive and non-conductive properties.
- carbon fibers generally have high electrical conductivity, excellent antistatic properties, and relatively high electromotive force. Therefore, such characteristics of carbon fiber have been conventionally used for antistatic and the like. However, this property of carbon fiber is not preferred as a material for sound absorbing insulation.
- a sound-absorbing insulation material is made of a material with high electrical conductivity, the sound-absorbing insulation material itself will cause an electrical short circuit, Pieces of material that fall off and float into the interior of electrical circuits, etc., can cause internal short circuits.
- the material has an electromotive force, an electrochemical reaction occurs with other members around the material, and as a result, other members may be corroded.
- an object of the present invention is to provide a sound-absorbing and heat-insulating material that can be mounted on a high-speed railway vehicle, an aircraft, or the like.
- high-speed railcars and the like generally use metal as a main constituent material and have a lot of electric wiring. Therefore, the problem of the present invention cannot be solved even if the sound-absorbing heat insulating material is simply composed of carbon fibers instead of glass fibers.
- the present inventors have diligently studied means for achieving the above object using carbon fibers. As a result, they found that by setting the carbonization temperature of carbon fiber appropriately, it was possible to improve the strength and sound-absorbing insulation performance of the sound-absorbing heat insulating material, and at the same time, to improve the electrocorrosion. . We also found that electrical corrosion caused by sound-absorbing insulation made of carbon fiber can be substantially prevented by setting the galvanic current of the sound-absorbing insulation to 10 A or less. Based on this knowledge, we have completed a group of inventions of the following configuration.
- the quality of the electrical conductivity and the electrical corrosion are not necessarily in a unique relationship. Therefore, the galvanic current value specified in the present invention is extremely important as a requirement for a sound-absorbing heat insulating material that does not cause electric corrosion.
- the invention of the group has the following constitution.
- the fibers of a flocculent carbon fiber aggregate composed of carbon fibers having an average fiber diameter of 0.5 m to 5 m and an average fiber length of 1 mm to 15 mm are bonded to each other with a thermosetting resin.
- This is a sound-absorbing heat insulating material that has been characterized.
- the second invention is based on the first invention, wherein the sound absorbing and heat insulating material is used as one electrode, the aluminum plate is used as the other electrode, and 0.45% by weight of sodium chloride is used.
- a galvanic current in a galvanic cell using an aqueous solution as an electrolytic solution is 10 A or less.
- the maximum tensile strength of the acoustic insulation material is to 1. O g Z mm 2 or more in which this and the FEATURE:.
- a fifth invention is characterized in that, in the first to fourth inventions, the compression / restoration rate of the sound-absorbing heat insulating material is 70% or more.
- a minimum tensile strength in a direction orthogonal to a maximum tensile strength direction of the sound absorbing heat insulating material is 0.04 times or more of the maximum tensile strength.
- a tensile strength in a direction perpendicular to both the direction of the maximum tensile strength and the direction of the minimum tensile strength is 0.76 times or more of the maximum tensile strength.
- the seventh invention is characterized in that in the first to sixth inventions, the thermal conductivity of the sound absorbing heat insulating material is 0.039 W / m ⁇ ° C or less. .
- An eighth invention is based on the first to seventh inventions, wherein a normal incidence sound absorption coefficient at a frequency of 100 Hz at a thickness of 25 mm of the sound absorbing heat insulating material is 48% or more. This is the feature.
- an anisotropic pitch obtained by polymerizing a condensed polycyclic hydrocarbon is heated and melted, and the melt is discharged from a spinning nozzle.
- a spinning step of spinning by jetting a heating gas from the periphery of the nozzle in the same direction as the discharge direction of the molten material; and after infusing the spun fiber, at a temperature of at least
- a method for producing a sound-absorbing heat insulating material comprising: a spray deposition step; and a heat forming step of heating and forming the spray deposited material.
- the eleventh invention is the eleventh invention according to the tenth invention, wherein the spraying and depositing step comprises: a depositing step of depositing the non-electrolytic corrosion carbon fibers in a flocculent form; And a spraying step of spraying a thermosetting resin liquid.
- a twenty-second invention is the invention according to the tenth or eleventh invention, wherein the spray deposition step or the deposition method in the deposition step comprises reducing at least a carbon fiber opened by air. It is characterized by being dropped on a plane from a height of 100 cm or more.
- the thermal conductivity is a value measured at a temperature of 22 ° C according to ASTM C-518 (American Society for Testing and Material; heat flow meter method).
- the normal incidence sound absorption coefficient is a value measured in accordance with JISA-145.
- Compression recovery ratio 1 0 O mmx 1 0 O mm X thickness 2 5 mm sound absorbing sectional heated material sample piece to a weight of 0. 7 K / cm 2 in the thickness direction in ⁇ Ko diameter 7 6 mm The thickness was measured after repeating the cycle of adding 30 minutes and removing the weight 24 times, and expressed as a percentage of the original thickness (25 mm).
- the galvanic current is the current value when the cell diagram is measured with a galvanic cell represented by a carbon fiber electrode I 0.45 wt% sodium chloride aqueous solution I aluminum electrode. Say. Details will be described later. Brief explanation of drawings
- Figure 1 is a graph showing the relationship between carbonization temperature of carbon fiber, galvanic current, and electrical corrosion.
- Figure 2 is a graph showing the relationship between the carbonization temperature of carbon fibers and the tensile strength of single fibers.
- Figure 3 is a graph showing the relationship between the carbonization temperature of carbon fibers and the tensile strength of a sound-absorbing heat-insulating material using this carbon fiber.
- Figure 4 is a graph showing the relationship between the carbonization temperature of carbon fibers (anisotropic pitch and isotropic pitch) and the tensile strength of single fibers.
- Figure 5 shows the carbonization of carbon fibers (anisotropic pitch and isotropic pitch). This is a graph showing the relationship between the temperature and the tensile strength of a sound-absorbing heat insulating material using this carbon fiber.
- Figure 6 is a graph showing the relationship between the fiber diameter of carbon fiber and the thermal conductivity of the sound-absorbing insulation.
- Fig. 7 is a graph showing the relationship between the fiber diameter of carbon fiber and the normal incidence sound absorption coefficient at 1000 Hz of the sound absorbing and insulating material.
- Fig. 8 is a graph showing the sound absorption characteristics of a sound-absorbing heat insulating material mainly composed of carbon fiber.
- Figure 9 is a graph showing the relationship between the bulk density and the heat insulation (1 / s) of a sound-absorbing heat insulating material mainly composed of carbon fiber.
- FIG. 10 is a graph showing the relationship between the bulk density of a sound-absorbing heat insulating material mainly composed of carbon fibers and the heat insulating performance per unit bulk density ⁇ ((1 / ⁇ ) I ⁇ ).
- FIG. 11 is a distribution diagram of the fiber diameter of the carbon fiber precursor used in Examples 1 to 6 and Comparative Examples 1 to 2 described later.
- Figure 12 is a schematic drawing of a galvanic cell.
- FIG. 13 is an explanatory diagram for explaining the electric corrosion test.
- Fig. 14 is a conceptual diagram showing the bonding state (joining points) between the carbon fibers constituting the CF sound absorbing heat insulating material.
- FIG. 15 is a diagram for explaining a method of measuring the tensile strength (width direction, longitudinal direction).
- Fig. 16 shows Fig. 5 for explaining the method of measuring the tensile strength (in the thickness direction).
- the average fiber diameter was 1.3 m (fiber diameter 0.5 111 to 3'.5 m) and the average fiber length was 5 mm (fiber length 1 mm to 15 mm).
- the sound-absorbing heat insulating material formed by joining the intersections of carbon fibers with each other with a thermosetting resin is referred to as “CF sound-absorbing heat insulating material”, and the conventional sound-absorbing heat insulating material made of glass fiber is referred to as glass. It is called a fiber acoustic insulation (GF in the figure).
- Figure 12 shows a galvanic current measuring device.
- 1 is a carbon fiber electrode (one electrode).
- the carbon fiber electrode 1 is formed by assembling 100 mg of the carbon fiber into an aggregate having a thickness of lmm, a width of 40 mm, and a height of 50 mm. These were used as carbon fiber electrodes.
- the CF sound absorbing insulation material prepared to the same size as above was used as the carbon fiber electrode.
- Reference numeral 2 denotes an aluminum electrode (the other electrode) made of an aluminum alloy 204 with a thickness of lmm, a width of 40 mm, and a height of about 50 mm.
- 3a is a 0.2 mm-thick glass cross interposed between the carbon fiber electrode 1 and the aluminum electrode 2 in order to regulate the distance between the two electrodes.
- 4 is a glass plate. This glass plate 4 prevents carbon fibers from falling off. As described above, it plays a role of pressing the other surface of the carbon fiber electrode 1 through the glass cross 3b (0.2 mm thick).
- Reference numeral 5 denotes an electrolytic solution composed of a 0.45% by weight aqueous solution of sodium chloride (200 ml).
- 7 is a resistance-free ammeter (HM-1004, manufactured by Hokuto Denko KK).
- 8 is a glass beaker (300 ml).
- an electrode group 9 composed of 1, 2, 3a, 3b., And 4 is immersed in an electrolyte solution 5, and the electrodes 1 and 2 are connected via a lead wire 6 attached to the upper end thereof. Connected to resistance-less ammeter 7.
- the above test specimen 12 was left in a room with a relative humidity of 90% and a temperature of 40 ° C for 24 hours, and after 24 hours, it was returned to a normal room (temperature 18 to 27 ° C, relative humidity 40 to 7). 0%) and leave it here for 24 hours. Twenty-four hours later, the cycle of returning to the room with a relative humidity of 90% s and a temperature of 40 ° C was repeated 15 times (30 days). After 15 times (after 30 days), the aluminum mirror surface is visually observed. If the aluminum mirror surface remains as it was at the beginning, “No electric corrosion (1)” If there is slight cloudiness on the aluminum mirror surface, it is judged as "Electric corrosion is low (Sat)”. If the aluminum mirror surface is clearly corroded, it is indicated as "Electro-corrosion.” (10) ”.
- the tensile strength, thermal conductivity, normal incidence sound absorption coefficient, and compression recovery rate of the sound absorbing heat insulating material were measured by the above-described methods.
- the tensile strength of the single fiber was measured according to JISR-7601. Details of this measurement method are described in the relevant section.
- FIG. 1 shows the anisotropic pitch obtained by polymerizing condensed polycyclic hydrocarbons, spun to an average fiber diameter of 1.3 ⁇ m and an average fiber length of 5 mm.
- FIG. 4 is a graph showing the relationship between carbon fiber after carbonization treatment and the galvanic current of a CF sound-absorbing heat-insulating material manufactured using the carbon fiber, and the relationship with the presence or absence of electric corrosion ( ⁇ ). .
- ⁇ indicates the galvanic current of carbon fiber
- X – X indicates the galvanic current of the acoustic insulation made of CF.
- the horizontal axis (galvanic current) in Fig. 1 is shown on a logarithmic scale.
- the galvanic current increased exponentially.
- the presence or absence of electrolytic corrosion slight electrical corrosion was observed at a galvanic current of 20 A, but no electrical corrosion was observed below 10 A.
- the carbonization temperature is preferably 800 ° C or less to form carbon fibers that do not cause electrical corrosion. It can be seen that it is better to set the temperature to 75 ° C or lower.
- the carbonization temperature should be set at 550 ° C to 800 ° C or lower, more preferably at 50 ° C or lower.
- FIG. 2 shows the relationship between the carbonization temperature and the tensile strength (K gmm 2 ) and elongation of a single fiber. Also, shows the relationship between the carbonization temperature of the carbon fiber composition 3 tensile strength in a longitudinal direction of the upper to the CF thermal-(g / mm 2) and CF thermal-this, Figure 3 below The side shows the relationship between the compression recovery rate (%) of the CF material and the carbonization temperature.
- the tensile strength of a single fiber is a value measured in accordance with JISR-7601, but the tensile strength of an ultrafine fiber having a fiber diameter of 0.5 m to 3.5 m (average fiber diameter of 1.3 um) is measured. It is difficult to measure. Then, under the same conditions except for the fiber diameter, a carbon fiber with a fiber diameter of 10 to 13 am was produced, and the tensile strength was measured using this fiber. It is shown after conversion.
- the CF sound-absorbing insulation material was composed of only a carbon fiber three-dimensional structure (bulk density: 4.8 K / m 3 ), and was measured under the conditions described in [Tensile strength measurement conditions] below. Value.
- the tensile strength of the carbon fiber itself increased linearly as the carbonization temperature increased.
- the elongation had a maximum value at around 65 ° C.
- the pattern showed a large value between 625 ° C. and 800 ° C. and no change after 800 ° C.
- the tensile strength of the CF sound-absorbing heat insulating material had a maximum value near 700 ° C. and a minimum value near 800 ° C. (upper part in FIG. 3).
- Figure 14 is a conceptual diagram showing the bonding state (joining points,) of the carbon fibers that make up the CF sound absorbing thermal insulation.
- the shape of the mesh changes so that each line constituting the mesh faces the stretching direction.
- the line segments have different lengths. Therefore, a large tensile force is applied to the line segment that constitutes a specific side, so that the line segment is cut or the joining point “ ⁇ ” that bonds the line segment comes off. That is.
- the mesh when the mesh is composed of a line segment (carbon fiber) having a large elongation, if a large tensile force is applied to a specific side (line segment), the side is stretched. By the drag combined with the other side, it becomes possible to resist the pulling force.
- the mesh can act as a network as a network, cutting of the line segments and detachment of the junction " ⁇ " are reduced, and the tensile strength as a whole is increased. Become. It is considered that the tensile strength of such a network is maximized when the elongation and the tensile strength of the single fiber are appropriately balanced. In other words, the results in FIGS.
- Figure 4 shows the carbonization of carbon fiber from anisotropic pitch made of polymerized condensed polycyclic hydrocarbons and carbon fiber made from isotropic pitch made of coal tar. The relationship between temperature and tensile strength is shown.
- Fig. 5 shows the carbon fiber treatment temperature and the tensile strength of the CF sound absorbing insulation material (bulk density: 4.8 Kg / m 3 ) composed of these carbon fibers. (Tensile strength in the longitudinal direction).
- the carbon fiber using anisotropic pitch as the raw material had a significantly higher tensile strength than the carbon fiber using the isotropic pitch as the raw material.
- the tensile strength of the sound absorbing insulation material made of carbon F using carbon fiber made of isotropic pitch is the maximum value as in the case of anisotropic pitch. Did not have a local minimum. From these experimental results, it can be said that the existence of the maximum and minimum values is a characteristic characteristic of carbon fiber made of an anisotropic pitch obtained by polymerizing a condensed polycyclic hydrocarbon. Therefore, the existence of the maximum value and the minimum value is extremely important in improving the performance and production efficiency of the CF sound absorbing thermal insulation according to the present invention.
- the carbon fiber precursor is made by polymerizing condensed polycyclic hydrocarbons. It is better to use anisotropic pitch as a raw material.
- galvanic corrosion From the viewpoint of tensile strength and elongation, the carbonization temperature of the carbon fiber precursor is not less than 550 ° C, less than 800 ° C, preferably 550 to 750 ° C, more preferably. Or between 65 ° C and 75 ° C.
- FIGS. 6 and 7 show the relationship between the thermal conductivity ⁇ (W / m- ° C) of 5 mm) and the average diameter of the carbon fibers constituting the sound-absorbing heat insulating material.
- Fig. 7 shows the relationship between the average diameter of the carbon fibers of the CF sound absorbing and insulating material and the normal incidence sound absorption coefficient at 1000 Hz.
- the thermal conductivity of a fiber length of 1 Omm) or the sound absorption coefficient at normal incidence is also shown (Plot X).
- FIGS. 6 and 7 were obtained due to a trial error.
- the thermal conductivity increases as the diameter of the carbon fiber increases.
- the CF material is made of carbon fiber with an average diameter of 5 m or less
- the glass has an average diameter of 1 m. It can be seen that heat insulation performance equal to or higher than that of acoustic insulation made of fiberglass (thermal conductivity 5: 0.039 WZ m ⁇ ° C) can be obtained. In other words, inside and outside the numerical limit of an average diameter of 5 m, It is meaningful to distinguish whether sound insulation can maintain heat insulation performance equal to or greater than that of glass fiber sound insulation with an average diameter of 1 m.
- the average diameter of the carbon fiber is preferably 5 m or less, more preferably 2 m or less from the viewpoint of sound absorption coefficient, but carbon fiber with an average fiber diameter of less than 0.50 m is produced. Doing so is difficult at present. Therefore, the average diameter of the carbon fiber is set to be not less than 0 and not more than 5 m, and more preferably not more than 2 / m.
- the length of carbon fibers (fiber length) it is not easy to produce carbon fibers with an average fiber diameter of 0.5 m to 5 / zm, and an average fiber length of more than 15 mm for ultrafine carbon fibers of 5 mm. .
- the orientation of the fibers is It is not preferable because it is easily oriented originally.
- the average carbon fiber length is less than 1 mm, short carbon fibers are unlikely to be entangled with each other, so that a good three-dimensional structure cannot be formed, and the carbon fibers easily fall off the structure. However, the dropped carbon fibers may enter the surrounding electric circuit, for example, and cause problems such as failure of the electric equipment.
- the average fiber length is 3 mm to 8 mm, it is easy to manufacture and easily oriented three-dimensionally.
- the average fiber length should be 1 mm or more and 15 mm or less, and more preferably 3 mm or more and 8 mm or less.
- Fig. 8 shows the frequency-normal incidence sound absorption coefficient curve of a CF sound absorbing and insulating material manufactured using carbon fibers having an average fiber diameter of 1.3 m or 13 m. From a comparison between the two, it is understood that the sound absorbing thermal insulation made of CF using ultrafine carbon fibers having an average fiber diameter of 1.3 m has good sound absorbing properties especially in the high frequency range. Bulk density and thermal insulation
- FIG. 9 shows the measurement results in the relationship between the bulk density and 1 / ⁇ (insulation). Based on this figure, the relationship between the bulk density and the heat insulation (1 nos) of the CF sound absorbing heat insulating material will be described.
- Fig. 9 shows the results (Hata- ⁇ ) of the sound absorbing and insulating material made of CF (having a thickness of 25 mm), the average fiber diameter of 1.0 m or 2.5 m, and the average fiber length of 5 to 15 mm. Both conventional sound-absorbing insulation materials (X) are shown.
- FIG. 10 shows a diagram in which the abscissa represents the bulk density, and the abscissa represents the value ((1 nos) / p) obtained by dividing the heat insulation (1I) by the bulk density p.
- the heat insulation performance per unit bulk density (heat insulation performance per weight) of the sound absorbing heat insulating material becomes clear. That is, in FIG. 10, as the bulk density increases, the heat insulation performance per unit bulk density decreases almost linearly, and the lower the bulk density, the better the heat insulation performance per weight. You can see this. Also, it can be seen that the CF sound-absorbing heat insulating material has better heat insulation performance per weight ((1 / ⁇ ) / ⁇ ) than the glass fiber sound-absorbing heat insulating material (X).
- the heat insulation performance is almost the same. From these results, if the bulk density of the CF sound absorbing insulation material is set to 10 kg / m 3 or less, at least the typical sound absorbing insulation material of glass fiber, which has been used in the past, has been used at least. It can be seen that insulation performance equal to or higher than that of the heat insulating material (bulk density: 6.7 Kg / m 3 ) can be guaranteed.
- the compression recovery ratio is one of the characteristics that reflects the mechanical strength of CF sound absorbing insulation. If a sound-absorbing heat-insulating material with a small compression recovery rate is used, for example, under conditions where vibration or a compressive force accompanying vibration is applied, the initial sound-absorbing heat-insulating effect cannot be obtained within a short period of time. The reason is that if the compression / decompression ratio is poor, the volume gradually becomes smaller when subjected to vibration or compression.
- One of the objects of the present invention is to provide a CF fiber having a performance equal to or higher than that of a conventional glass fiber sound-absorbing and heat-insulating material. It is intended to provide a sound-absorbing heat-insulating material. Therefore, it is necessary to secure at least the same compression restoration rate as that of the acoustic insulation made of glass fiber.
- the compression recovery ratio of a typical acoustic absorption material made of glass fiber (bulk density: 6.7 K / m 3 ), which has been conventionally used, is 70% (see Comparative Example 4 in Table 4 below).
- the compression / restoration rate of the CF sound-absorbing heat insulating material is preferably at least 70% or more, more preferably 85% or more. If the compression / recovery ratio is 85% or more, it can withstand external forces during manufacturing and mounting, and can be used even in situations where vibration and compression force are constantly applied.
- the present invention is intended to provide a lightweight and high-performance CF sound-absorbing insulation material using ultra-fine carbon fiber, and is used in applications where vibration and compression force are constantly applied, such as in high-speed rail vehicles and aircraft.
- the mechanical strength is lower than that of a material having a large bulk density using medium-thick fibers. Therefore, it tends to be inferior in handleability, workability, and durability.
- the minimum tensile strength in a direction orthogonal to the maximum tensile strength direction of the sound-absorbing heat insulating material is 4% or more of the maximum tensile strength.
- the tensile strength in a direction perpendicular to both of the directions of the minimum tensile strength is 35% or more of the maximum tensile strength.
- Table 1 shows the results of measuring the tensile strength of the sound-absorbing heat-insulating material in which only the bulk density was changed from three directions of the longitudinal direction, the width direction, and the thickness direction.
- Table 2 shows the ratio of the tensile strength in the minimum tensile strength direction and the tensile strength in the intermediate tensile strength direction to the tensile strength in the maximum tensile strength direction, and the ratio of the tensile strength in the minimum tensile strength direction to the tensile strength in the intermediate tensile strength direction. (Expressed as a percentage).
- the minimum tensile strength direction is the thickness direction
- the maximum tensile strength is the longitudinal direction or the width direction
- the intermediate tensile strength direction is the direction of the tensile strength located between the maximum tensile strength and the minimum tensile strength
- the width direction is usually the intermediate tensile strength direction.
- the measurement was performed using a constant-speed tension type tensile tester under the following conditions.
- the tensile strength in the thickness direction was measured by a method in which a plate was attached to both sides (the stretched portion in Fig. 16) of the sound absorbing insulation material made of CF, and this plate was pulled in the direction of the arrow.
- the sound insulating insulation made of glass fiber used as the comparison object is made of glass fiber with an average fiber diameter of 1 ⁇ m and an average fiber length of 10 mm.
- the sound absorbing insulation material made of CF had higher tensile strength than the sound absorbing insulation material made of glass fiber.
- a large difference was observed in the tensile strength between the two in the width direction and the thickness direction.
- the tensile strength direction of the thickness direction of the CF thermal-acoustic insulation material, 8.5-fold Der fiberglass thermal-acoustic insulation material with a bulk density 5 K gm 3 is, bulk density 1 0 K g Roh m 3 It was 15 times that of acoustic insulation made of glass fiber.
- the intermediate tensile strength direction Z outermost Obiki Zhang strength direction of the ratio of the CF thermal-acoustic insulation material, Te bulk density 3 K g / m 3 ⁇ 1 0 K g / m 3 odor, there at 8 6% or more was.
- the ratio of the minimum tensile strength direction / maximum tensile strength direction was 5.4 or more at a bulk density of 3 kg / m 3 to 7 kg Zm 3 .
- an anisotropic pitch is prepared by polymerizing a condensed polycyclic hydrocarbon by a known method (Japanese Patent Application Laid-Open No. 63-146920).
- the pitch is heated and melted, and is discharged from the spinning nozzle.
- a heating gas is jetted from the periphery of the spinning nozzle in the same direction as the discharging direction (preferably, in the direction parallel to the discharging direction). Then, a spun fiber is produced. This heating gas prevents the discharged material from cooling immediately and plays a role in obtaining fibers of an appropriate length.
- the above spun fibers are collected, for example, by a net and subjected to infusibilization treatment (oxidation treatment). Thereby, a carbon fiber precursor can be produced.
- This carbon fiber precursor is carbonized at a temperature of 65 ° C. to 75 ° C. in an inert gas to form a carbon fiber.
- the diameter of the discharge port of the spinning nozzle is varied in the range of 0.5 mm to 0.2 mm, and the heating melting temperature and discharge speed of the pitch, and the temperature and ejection speed of the heating gas are adjusted.
- the average diameter and average fiber length of the spun fiber can be arbitrarily changed.
- the fiber diameter / fiber length slightly changes due to the infusibilization treatment and carbonization treatment. However, when the measurement error is considered, there is no substantial difference between the size of the spun fiber and the size of the carbon fiber, and no substantial difference occurs in the average fiber diameter and the average fiber length.
- a CF sound absorbing and insulating material according to the present invention is produced as follows.
- the carbon fibers collected by a net or the like are opened by a method such as blowing air, and the carbon fibers are dropped and deposited while spraying a thermosetting resin liquid (spray deposition method).
- a method in which unwoven carbon fibers are dropped and deposited in a planar shape to form a coarse flocculent aggregate, and a thermosetting resin liquid is sprayed on the aggregate (sedimentation-spray method) Then, a carbon fiber aggregate (spray deposit) sprayed with thermosetting resin is produced.
- the spray deposit is usually lightly compressed with two pressing plates from the thickness direction, and heated in this state to cure the thermosetting resin.
- the pressure plate may be applied from a direction perpendicular to the thickness direction.
- the CF sound-absorbing heat-insulating material according to the present invention may be composed only of the above-mentioned carbon fiber and a thermosetting resin, or may be composed mainly of the above-mentioned carbon fiber. It may also contain other fibers as long as the sound absorbing and heat insulating properties are not impaired. Examples of such fibers include glass fibers, polyester fibers, and ceramic fibers. .
- the preferred and rather adjusting the interval as a 1. Less than 3 K gm 3 bulk density (except rather bulk density b) carbon fiber aggregate, when the thermoforming Shi said two pressing plates To form a molded product (carbon fiber three-dimensional structure) having the desired bulk density. Why al, 1. 3 K g when the assembly of Z m 3 less coarse bulk density, the fibers are oriented in fully run-dam. Thus, a bulky (small bulk density) carbon fiber three-dimensional structure in which only the intersections of the fibers are adhered to each other can be obtained. The tensile strength in the direction becomes more uniform.
- the opened carbon fiber is dropped on a plane from a height of 100 cm.
- the fibers can be randomly oriented without using special equipment. The reason is that if a lightweight carbon fiber with an average fiber diameter of 0.5 m to 2 m and an average fiber length of 3 mm to 8 mm is dropped from a height of 100 cm, air resistance Thus, some are oriented in the direction of gravity, and some are oriented in a direction perpendicular to the direction of gravity. That is, a bulky carbon fiber deposit (cotton fiber aggregate) oriented in a random direction is obtained. Therefore, if a thermosetting resin liquid is sprayed on the sediment, a randomly oriented carbon fiber three-dimensional structure can be obtained.
- the orientation of the fibers can be controlled, so that a fiber aggregate having a desired bulk density can be easily produced.
- thermosetting resin used above for example, a phenol resin, a melamine resin, or a silicone resin can be used.
- the amount of use is usually 10 to 40% by weight, and preferably 20 to 30% by weight, based on the sound absorbing and heat insulating material made of CF. If the content exceeds 40% by weight, the amount of the binder is too large, and it is not preferable because the portions other than the intersections between the carbon fibers are bonded. On the other hand, if it is less than 10% by weight, the intersection cannot be sufficiently bonded, so that the tensile strength and the compression recovery rate become too small.
- the heating temperature at the time of the above-mentioned heat molding of the phenol resin is 150 to 250 ° C, and usually 180 ° C to 220 ° C.
- the CF sound absorbing and heat insulating material of the present invention having the above-mentioned various physical properties can be obtained.
- the present invention will be described more specifically based on examples.
- a pitch having a softening point of 280 ° C obtained by polymerizing a condensed polycyclic hydrocarbon is melted at 320 ° C, and a molten pitch is obtained from a spinning nozzle having a discharge hole of 0.225 mm in diameter.
- a heating gas of 320 ° C. is discharged from the periphery of the discharge hole in the same direction as the discharge direction of the molten pitch and in the same direction as the discharge direction.
- the fibers were spun into fibers while blowing out to the line, and collected by a net.
- the diameter of the carbon fiber precursor was about 0.5 to 3.5 m (average fiber diameter 1.3 m), and the fiber length was 1 to 15 mm (average fiber length 5 mm).
- Figure 11 shows the diameter distribution of the carbon fibers produced under these conditions.
- the fiber is heated at 300 ° C for 30 minutes in an air atmosphere to make it infusible, and then heated to a predetermined temperature (800 ° C at 6'50 ° C, 700 ° C, 750 ° C). Carbonization was performed by heating for 30 minutes in an inert gas atmosphere of C). In this way, four types of carbon fibers having different carbonization temperatures were obtained. The diameter and fiber length of these carbon fibers were almost the same as those of the carbon fiber precursor.
- CF sound-absorbing insulation materials were produced using the above four types of carbon fibers. Specifically, air is blown onto the carbon fibers in which the fibers are intertwined to open the fiber, and the spread carbon fiber naturally falls on a flat surface so as to fall snow from a height of 100 cm. By dropping, a flocculent aggregate (unbound state) having a thickness of 120 mm and a bulk density of about 0.7 Kgm 3 was produced.
- the carbon fiber aggregate was sprayed with a 150 wt% phenolic resin solution of 20 wt% to the carbon fiber aggregate, and the press was equipped with a press machine having two pressing plates. It was compressed to a thickness of about 25 mm (no compression in the vertical and horizontal directions), and heated to 200 ° C in this state to completely cure the phenolic resin.
- carbon fiber three-dimensional structures four types having a length of 1.5 m, a width of 0.5 m, a thickness of 25 mm, and a bulk density of 4.8 Kg / m 3 were produced. This was used as CF sound absorbing insulation.
- Example 5 The same as in Examples 1 to 4 except that the carbonization temperature was set to 700 ° C. and the thickness of the carbon fiber aggregate was set to 100 mm. As a result, a CF sound-absorbing heat insulating material of Example 5 having a bulk density of 4. OK g Z m 3 was produced. The size and thickness are the same as in Examples 1 to 4.
- Example 6 Except that the carbonization temperature was set to 700 ° C. and the thickness of the carbon fiber aggregate was set to 17.5 mm, the bulk density was set to 7.75 ° C. in the same manner as in Examples 1 to 4.
- Examples 1 to 10 were repeated except that carbon fiber having a diameter of 13 m and an average fiber length of 25 mm was obtained by using a coal-based isotropic pitch as a raw material and carbonizing at 950 ° C.
- a sound absorbing and heat insulating sound absorbing material according to Comparative Example 3 was produced in the same manner as in Example 4.
- Glass fiber sound-absorbing insulation material (thickness: 25 m) consisting of glass fibers joined together with phenolic resin with an average fiber diameter of 1.0 m and an average fiber length of 10 mm m and bulk density of 6.7 Kg / m 3 ) were taken as Comparative Example 4.
- Comparative Example 1 galvanic current of 56 A at carbonization temperature of 850
- Comparative Example 2 carbonization temperature of 900 ° C, galvanic current
- Comparative Example 3 carbonization temperature: 950 ° C, galvanic current: 36 aA
- the reason why no electrical corrosion was observed in Comparative Example 4 was that glass fibers did not generate galvanic current.
- the thermal conductivity (W / m * ° C) was as follows: Examples 1-4 with a bulk density of 4.8 Kg Zm 3 , 0.035-0.037, and a bulk density of 4.0 kg.
- the bulk density was 0.037
- the density of OK g Zm 3 was 0.033.
- the thermal conductivity of Comparative Example 4 (sound-absorbing insulating material made of glass fiber) having a bulk density of 6.7 Kg / m 3 was 0.039. From these results, it was proved that the CF sound-absorbing heat-insulating material according to the present invention had a lower bulk density and higher heat-insulating performance than the glass fiber sound-absorbing heat-insulating material.
- the magnitude of the thermal conductivity is inversely related to the quality of the heat insulation.
- the 1000 HZ normal incidence sound absorption coefficient (%) at a thickness of 25 mm is as follows: bulk density 4.SK g Zm 3 of Examples 1 to 4 was 52 to 55, bulk density 4.OK g.
- Example 5 of Zm 3 was 50 and the bulk density was 7. OK g.
- Example 6 of Zm 3 was strong and 60. This was paired, bulk density 6. 7 K g / Comparative example m 3 4 2 5 m that put the thickness 1 0 0 0 HZ normal incidence sound absorption coefficient of the (glass fiber thermal-acoustic insulation material) (%) 4 It was eight.
- each subject of the present invention can be sufficiently achieved.
- a sound-absorbing heat-insulating material having excellent tensile strength and compression restoring property in addition to excellent heat-insulating properties and sound-absorbing properties.
- the sound-absorbing heat insulating material of the present invention has carbon fiber as a main constituent material, it has favorable characteristics that carbon fiber has, namely light weight, chemical stability, flame retardancy, and toxic gas at the time of fire. It also has properties that do not occur and are less likely to absorb moisture.
- the sound-absorbing heat insulating material of the present invention has improved electrical corrosiveness and non-conductive properties, which are weak points of the sound-absorbing heat insulating material made of carbon fiber, and also has mechanical properties such as tensile strength and compression recovery rate. It has been greatly improved.
- the present invention not only can it be used as a component for realizing energy saving in a house or the like, but also there is a constant vibration, a large amount of metal material is used,
- a sound absorbing insulation material made of CF which can be suitably used in, for example, an aircraft, a high-speed railway vehicle, a spacecraft, and the like on which various electric devices are mounted. Therefore, the industrial significance of the present invention is great.
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Description
Claims
Priority Applications (5)
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DE69726765T DE69726765T2 (de) | 1997-02-27 | 1997-02-27 | Schallabsorbierendes und wärmedämmendes material, und verfahren zur herstellung desselben |
US09/180,432 US6855398B1 (en) | 1997-02-27 | 1997-02-27 | Sound absorbing and heat insulating material, and method of manufacturing same |
EP97905419A EP0963964B1 (en) | 1997-02-27 | 1997-02-27 | Sound absorbing and heat insulating material, and method of manufacturing same |
JP10537490A JP3009479B2 (ja) | 1997-02-27 | 1997-02-27 | 吸音断熱材及びその製造方法 |
PCT/JP1997/000598 WO1998038140A1 (en) | 1997-02-27 | 1997-02-27 | Sound absorbing and heat insulating material, and method of manufacturing same |
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EP (1) | EP0963964B1 (ja) |
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WO2003078716A1 (fr) * | 2002-03-20 | 2003-09-25 | Osaka Gas Company Limited | Feutres en fibre de carbone et materiaux thermo-isolants |
WO2005045115A1 (ja) * | 2003-11-10 | 2005-05-19 | Teijin Limited | 炭素繊維不織布、その製造方法および用途 |
WO2006112487A1 (ja) * | 2005-04-18 | 2006-10-26 | Teijin Limited | ピッチ系炭素繊維、マットおよびそれらを含む樹脂成形体 |
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WO2002032639A2 (en) * | 2000-06-05 | 2002-04-25 | Dunstan Walter Runciman | Materials which have sound absorbing properties |
US20020160252A1 (en) * | 2001-02-28 | 2002-10-31 | Mitsubishi Chemical Corporation | Conductive carbonaceous-fiber sheet and solid polymer electrolyte fuel cell |
CA2665352C (en) | 2008-05-06 | 2016-02-23 | Moderco Inc. | An acoustic face of polymer and embedded coarse aggregates and an acoustic panel assembly |
US9136536B2 (en) | 2011-08-12 | 2015-09-15 | Yazaki Corporation | Method of making cohesive carbon assembly and its applications |
DE102014226266A1 (de) * | 2014-12-17 | 2016-06-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Dämm- und Filterstoff und seine Verwendung als inertes schallabsorbierendes Material |
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JPH06116032A (ja) * | 1992-10-08 | 1994-04-26 | Mitsubishi Kasei Corp | 炭素繊維強化炭素複合材とその製造方法及びそれを用いた摺動材 |
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JPH08217556A (ja) * | 1995-02-15 | 1996-08-27 | Unitika Ltd | 軽量炭素材及びその製造方法 |
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JPS59145286A (ja) * | 1983-02-08 | 1984-08-20 | Fuji Standard Res Kk | 高強度炭素繊維用原料として好適なメソフエ−スピツチ |
US4997716A (en) * | 1987-10-28 | 1991-03-05 | The Dow Chemical Company | Fire shielding composite structures |
JP2646140B2 (ja) * | 1989-11-21 | 1997-08-25 | 株式会社ペトカ | 炭素繊維複合体およびその製造方法 |
JP2678513B2 (ja) * | 1990-01-26 | 1997-11-17 | 株式会社ペトカ | 炭素繊維構造体、炭素炭素複合材及びそれらの製造方法 |
-
1997
- 1997-02-27 EP EP97905419A patent/EP0963964B1/en not_active Expired - Lifetime
- 1997-02-27 US US09/180,432 patent/US6855398B1/en not_active Expired - Fee Related
- 1997-02-27 DE DE69726765T patent/DE69726765T2/de not_active Expired - Fee Related
- 1997-02-27 WO PCT/JP1997/000598 patent/WO1998038140A1/ja active IP Right Grant
- 1997-02-27 JP JP10537490A patent/JP3009479B2/ja not_active Expired - Fee Related
Patent Citations (3)
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JPH08502768A (ja) * | 1992-09-14 | 1996-03-26 | サイテク・テクノロジー・コーポレーシヨン | ハイブリッド金属/複合構造体のガルバニック分解の減少 |
JPH06116032A (ja) * | 1992-10-08 | 1994-04-26 | Mitsubishi Kasei Corp | 炭素繊維強化炭素複合材とその製造方法及びそれを用いた摺動材 |
JPH08217556A (ja) * | 1995-02-15 | 1996-08-27 | Unitika Ltd | 軽量炭素材及びその製造方法 |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003078716A1 (fr) * | 2002-03-20 | 2003-09-25 | Osaka Gas Company Limited | Feutres en fibre de carbone et materiaux thermo-isolants |
WO2005045115A1 (ja) * | 2003-11-10 | 2005-05-19 | Teijin Limited | 炭素繊維不織布、その製造方法および用途 |
JP2009079346A (ja) * | 2003-11-10 | 2009-04-16 | Teijin Ltd | 炭素繊維不織布およびその用途 |
WO2006112487A1 (ja) * | 2005-04-18 | 2006-10-26 | Teijin Limited | ピッチ系炭素繊維、マットおよびそれらを含む樹脂成形体 |
US7651767B2 (en) | 2005-04-18 | 2010-01-26 | Teijin Limited | Pitch-based carbon fiber, web and resin molded product containing them |
US7767302B2 (en) | 2005-04-18 | 2010-08-03 | Teijin Limited | Pitch-based carbon fiber, web and resin molded product containing them |
CN101163825B (zh) * | 2005-04-18 | 2011-09-14 | 帝人株式会社 | 沥青类碳纤维、毡以及含有它们的树脂成型体 |
Also Published As
Publication number | Publication date |
---|---|
EP0963964A1 (en) | 1999-12-15 |
US6855398B1 (en) | 2005-02-15 |
EP0963964A4 (en) | 2001-11-21 |
DE69726765T2 (de) | 2004-11-04 |
DE69726765D1 (de) | 2004-01-22 |
EP0963964B1 (en) | 2003-12-10 |
JP3009479B2 (ja) | 2000-02-14 |
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