WO2017170447A1 - 吸音材 - Google Patents
吸音材 Download PDFInfo
- Publication number
- WO2017170447A1 WO2017170447A1 PCT/JP2017/012472 JP2017012472W WO2017170447A1 WO 2017170447 A1 WO2017170447 A1 WO 2017170447A1 JP 2017012472 W JP2017012472 W JP 2017012472W WO 2017170447 A1 WO2017170447 A1 WO 2017170447A1
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- WIPO (PCT)
- Prior art keywords
- fibers
- absorbing material
- coat film
- sound
- nonwoven fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/162—Selection of materials
- G10K11/168—Plural layers of different materials, e.g. sandwiches
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/1095—Coating to obtain coated fabrics
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/326—Polyureas; Polyurethanes
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
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- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/162—Selection of materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
Definitions
- the present invention relates to a sound absorbing material.
- Vehicles such as automobiles and trains are required to achieve both light weight and quietness, and in order to ensure quietness, they are affixed to the walls, floors and ceilings of vehicles to absorb sound outside the vehicle.
- the material is used.
- Sound absorbing materials for vehicles, particularly automobiles, are required to absorb sound in a wide frequency range from low frequencies to high frequencies. Due to the characteristics of sound-absorbing materials, a certain amount of thickness is required for sound absorption in the low and medium frequency ranges, but in order to secure a wider cabin, sound absorption in the low and medium frequency ranges is required. It is necessary to balance sex.
- a sound absorbing material As a sound absorbing material, a non-woven fabric made only of organic fibers such as cinsalate (manufactured by 3M) is known. However, although such a sound absorbing material can be made relatively thin, it has not been possible to achieve sufficient sound absorbing properties.
- a wet method glass nonwoven fabric comprising a glass fiber and a binder component for bonding the glass fiber, wherein the wet method glass nonwoven fabric containing a component having a sulfur atom and a rubber component in the binder is tensioned for decorative board applications. It has been reported that the strength does not decrease (Patent Document 1).
- the inventors of the present invention have found the following. (1) Even if a nonwoven fabric made only of inorganic fibers such as glass fibers was used as a sound absorbing material, sufficient sound absorbing properties could not be obtained. (2) Therefore, in a non-woven fabric composed only of inorganic fibers, if the fiber diameter of the inorganic fibers is reduced, the sound absorption is improved in a wide frequency range from a low frequency to a high frequency. However, since the sound absorption is reduced by resonance, a new problem has arisen that sufficient sound absorption cannot be obtained particularly in the middle frequency range (500 to 1600 Hz). (3) In general, it is generally considered that the use of a material having a relatively low elastic modulus as a fiber constituent material or a fiber coating material improves sound absorption. However, even if such a material is used, a new problem arises in that sufficient sound absorption is still not obtained in the middle frequency range (500 to 1600 Hz) because sound absorption is reduced due to resonance.
- An object of the present invention is to provide a sound absorbing material that achieves sufficient sound absorption in a wide frequency range from a low frequency to a high frequency, particularly in a middle frequency range (500 to 1600 Hz).
- the present invention is a sound absorbing material comprising a fiber group consisting of inorganic fibers, organic fibers or mixed fibers thereof,
- the present invention relates to a sound-absorbing material coated with a polymer coat film having a loss coefficient of 0.1 or more at least between the fibers in the fiber group.
- the sound absorbing material of the present invention achieves sufficient sound absorption in a wide frequency range from a low frequency to a high frequency, particularly in the middle frequency range.
- the sound absorbing material of the present invention also has excellent heat insulating properties.
- the sound-absorbing material of the present invention includes a group of fibers composed of inorganic fibers, organic fibers, or mixed fibers thereof.
- any inorganic fiber used in the field of sound-absorbing material can be used, and examples thereof include glass fiber, carbon fiber, and mixed fiber thereof.
- any organic fiber used in the field of sound-absorbing material can be used, and examples thereof include polyester fiber, polyamide fiber, polyacrylic fiber, polyethylene fiber, and mixed fibers thereof.
- the form of the fiber group is not particularly limited, and may be, for example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like, but a nonwoven fabric is preferable from the viewpoint of further improving sound absorption.
- a nonwoven fabric is a group of randomly oriented sheet fibers in which relatively short fibers are entangled or bonded to each other.
- a preferred non-woven fabric from the viewpoint of further improving sound absorption is one in which fibers are entangled with each other. This is because by using a non-woven fabric in which fibers are entangled with each other and bonding (adhering) the fibers with a polymer coat film, which will be described later, the sound absorbing property, particularly the sound absorbing property in the middle frequency range is further improved.
- the average fiber diameter of the fibers constituting the fiber group is not particularly limited.
- the average fiber diameter is usually 1 to 100 ⁇ m, and 1 to 20 ⁇ m is preferable from the viewpoint of further improving sound absorption.
- the average fiber length of the fibers constituting the nonwoven fabric is not particularly limited.
- the average fiber length is usually 2 to 1000 mm, and 20 to 200 mm is preferable from the viewpoint of further improving sound absorption.
- the nonwoven fabric may be produced by any method, for example, so-called needle punch method, dry method, wet method, spun bond method, melt blow method, thermal bond method, chemical bond method, spun lace method, stitch bond method, steam jet method. May be manufactured.
- a preferred manufacturing method is a needle punch method.
- the basis weight of the fiber group is not particularly limited as long as the porosity of the fiber group is 80 to 99.9%, particularly 90 to 99.5%.
- the porosity is a volume content of air, and a value measured by a method described in detail later is used.
- the bonding point between fibers is covered with the polymer coat film. That the bonding point between fibers is covered with the polymer coat film means that the intersection (contact point) of the fibers is covered or adhered with the polymer coat film. Specifically, when the fibers are already bonded, the bonding point may be covered with the polymer coat film. When fibers are not yet bonded, bonding (adhesion) between fibers may be achieved by the polymer coat film.
- At least the bonding points between the fibers are covered with the polymer coat film means that not only the bonding points between the fibers but also at least a part of the fiber surface may be covered with the polymer coat film. From the viewpoint of further improving sound absorption, preferably, not only the bonding point between fibers but also the entire surface of the fiber is covered with a polymer coat film.
- the polymer coat film has a loss coefficient of 0.1 or more, and is preferably 0.2 or more, more preferably 0.3 or more, and further preferably from the viewpoint of further improving sound absorption, particularly sound absorption in the middle frequency range.
- the upper limit value of the loss coefficient of the polymer coat film is not particularly limited, and is usually 5, particularly 3.
- the polymer coat film may be formed of any material (for example, a coating material) as long as it has the above loss coefficient, and is formed of, for example, a thermosetting material such as a thermosetting polymer or a thermosetting elastomer.
- thermosetting polymer is a polymer in which a network structure is three-dimensionally formed by heating with a curing agent as desired.
- thermosetting elastomer is a polymer in which a network structure is three-dimensionally formed by heating together with a curing agent (crosslinking agent) if desired, and elasticity is developed.
- thermosetting material As such a thermosetting material, commercially available coating materials such as paints and adhesives may be used.
- Examples of commercially available paints include urethane paints, vinyl chloride paints, silicone paints, and epoxy paints.
- Examples of commercially available adhesives include urethane adhesives, vinyl chloride adhesives, silicone adhesives, and epoxy adhesives.
- thermosetting materials from the viewpoint of further improving sound absorption are urethane paints, vinyl chloride paints, urethane adhesives, and vinyl chloride adhesives, and more preferred thermosetting materials are urethane paints and urethanes. Adhesive.
- the loss coefficient of the polymer coat film is a loss coefficient when the film thickness is 100 ⁇ m, the measurement frequency is 10 Hz, and the measurement temperature is 23 ° C., and can be measured by a method described in detail later.
- thermosetting material or a coating material (commercially available product) having a loss factor within a predetermined range may be selected, and a polymer coat film may be formed using the selected material.
- the coating liquid A that can form a polymer coating film having a loss factor within a predetermined range
- the coating liquid A is applied to the fiber group, and then heated, dried, and cured to form the polymer coating film. can do.
- coating liquid A examples include urethane adhesive W-222 (manufactured by Yokohama Rubber), vinyl chloride adhesive # 1551A (manufactured by Sunstar Giken), urethane paint SH3400M (manufactured by ASM), and urethane paint SH3400S (manufactured by ASM). Can be used. These adhesives and paints may be one-component or two-component, but are usually one-component.
- Coating liquid A preferably contains a polyrotaxane from the viewpoint of further improving sound absorption.
- the content of the polyrotaxane is usually 5 to 50% by mass, particularly 5 to 20% by mass, based on the solid content of the coating liquid A.
- the polyrotaxane may form a chemical bond with the polymer molecules constituting the polymer coat film, or may be dispersed in the polymer coat film without forming a chemical bond. The same applies to the case where a polyrotaxane is contained in the coating liquid B described later.
- the loss coefficient of the polymer coat film obtained by containing and dispersing the loss coefficient improving material in the coating liquid B can be controlled within the predetermined range.
- the polymer coat film can be formed by applying the loss factor improving material-containing coating liquid B to the fiber group, followed by heating, drying and curing.
- the loss factor improving material is a material that can increase the loss factor, and examples thereof include a pulverized polymer coat film (cured product) having a loss factor within a predetermined range, polyrotaxane, and the like.
- the average particle size of the pulverized product is usually 5 ⁇ m or less, preferably 10 to 1000 nm.
- the content of the loss factor improving material is not particularly limited as long as the loss factor of the polymer coat film can be controlled within a predetermined range, and is, for example, 10 to 100% by mass, particularly 20 to 60%, based on the solid content of the coating liquid B. % By mass.
- the pulverized product is contained in the coating liquid B, the pulverized product is usually dispersed in the polymer coat film without forming a chemical bond with the polymer molecules constituting the polymer coat film.
- urethane paint R2250 Nihon Bee Chemical
- pigments, dyes, dispersants, emulsifiers, UV absorbers, antifoaming agents, thickeners, leveling agents, plasticizers, coupling agents, water repellents, hygroscopic agents, antibacterial agents may be contained.
- the present invention does not prevent the polymer coat film from being formed from a thermoplastic material such as a thermoplastic polymer.
- a thermoplastic polymer usually has a loss factor of less than 0.1, the loss of the polymer coat film obtained by containing and dispersing the loss factor improver as in the case of using the coating liquid B described above is lost. It is necessary to control the coefficient within the predetermined range. In the case of using a thermoplastic polymer, drying is simply performed by heating. The thermoplastic polymer is a polymer that is softened and melted by heating and then solidified by cooling.
- the coating liquid application method, solid content concentration and heating conditions are not particularly limited as long as a polymer coat film having a predetermined loss factor can be formed on the fiber surface.
- any coating method can be used, and examples thereof include a dip method and a spray method.
- the fiber group is impregnated with the coating solution by a dip method.
- the solid content concentration of the coating liquid is usually 0.1 to 40% by mass, preferably 0.5 to 30% by mass, and more preferably 8 to 25% by mass.
- the heating conditions are usually 80 to 180 ° C., preferably 85 to 170 ° C. for 2 to 6 hours, preferably 4 to 5.5 hours. In the case of moisture curing or the like, heating is not necessary.
- the coating amount of the polymer coat film on the fiber group is usually 5 to 90% by mass, preferably 8 to 85% by mass, more preferably 15 to 85% by mass from the viewpoint of further improving the sound absorption and reducing the weight of the sound absorbing material. More preferably, it is 40 to 85% by mass.
- the porosity of the sound absorbing material is equal to or slightly smaller than the porosity of the fiber group used in the production of the polymer coat film.
- the porosity of the sound absorbing material is usually 70 to 99.9%, particularly 80 to 99.5%.
- the measuring method of physical property values in the examples is as follows.
- the coating amount is a value represented by (XY) / X, where X is the mass after the coating treatment and Y is the mass before the coating treatment.
- Examples A1 to A4 Glass wool having an average fiber diameter of about 7 to 8 ⁇ m was formed into a sheet shape with a needle punch so that the porosity was 96% and the thickness was 10 mm, to obtain a nonwoven fabric (A).
- the nonwoven fabric (A) was cut into a columnar shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (B), and the mass was measured with an electronic balance. Thereafter, the coating material shown in Table 1 was diluted with toluene to a solid content concentration of 10% to obtain a coating solution.
- the cylindrical nonwoven fabric (B) was dipped in the coating liquid, and the voids of the cylindrical nonwoven fabric (B) were completely impregnated with the coating liquid.
- the cylindrical nonwoven fabric (B) taken out from the coating solution was placed in a hot air drying furnace and heated under the curing conditions shown in Table 1 to dry and cure the coating solution. Thereafter, the cylindrical nonwoven fabric (B) was taken out from the hot air drying furnace and further allowed to stand at room temperature for 7 days to obtain a sound absorption coefficient test piece (C) in which fiber intersections were adhered with a polymer coat film. After measuring the mass of the sound absorption coefficient test piece (C), it was observed with a scanning electron microscope to confirm that the polymer coat film adhered the intersections of the fibers. The results of measuring the sound absorption rate are also shown in Table 1.
- Examples B1 to B6 Glass wool having an average fiber diameter of about 3 to 4 ⁇ m was formed into a sheet shape with a needle punch so that the porosity was 98% and the thickness was 10 mm to obtain a nonwoven fabric (D).
- the nonwoven fabric (D) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (E), and the mass was measured with an electronic balance. Thereafter, the coating material shown in Table 2 was diluted with toluene so as to have a solid content concentration shown in Table 2 to obtain a coating solution.
- the cylindrical nonwoven fabric (E) was dipped in the coating solution, and the coating solution was completely impregnated in the voids of the cylindrical nonwoven fabric (E).
- the cylindrical nonwoven fabric (E) taken out from the coating solution was placed in a hot air drying furnace and heated under the curing conditions shown in Table 2 to dry and cure the coating solution. Thereafter, the cylindrical nonwoven fabric (E) was taken out from the hot air drying oven and allowed to stand at room temperature for 7 days to obtain a sound absorption coefficient test piece (F) in which the intersections of the fibers were adhered with a polymer coat film. After measuring the mass of the sound absorption coefficient test piece (F), it was confirmed by observation with a scanning electron microscope that the polymer coat film adhered the intersections of the fibers. The results of measuring the sound absorption rate are shown together in Table 2.
- Example B7 Urethane paint B was applied with a blade onto a steel sheet coated with a release agent, and cured at 160 ° C. for 1 h using a hot-air drying furnace to produce a film (G) having a thickness of 100 ⁇ m.
- the powder obtained by pulverizing the film (G) is dispersed in toluene, pulverized with a disperser for 10 minutes, and then filtered with 5 C filter paper as defined in JIS P 3801. Elastomer particles (H) of 1 ⁇ m or less were obtained.
- elastomer particles (H) was added to 39.4 g of urethane paint C diluted to a solid content concentration of 3.7%, and stirred for 30 minutes with a disperser to prepare a coating solution. Then, said cylindrical nonwoven fabric (E) was dipped in the coating liquid, and the voids of the cylindrical nonwoven fabric (E) were completely impregnated with the coating liquid. The cylindrical nonwoven fabric (E) taken out from the coating solution was placed in a hot air drying furnace and heated under the curing conditions shown in Table 2 to dry and cure the coating solution.
- the cylindrical nonwoven fabric (E) was taken out from the hot air drying oven and further allowed to stand at room temperature for 7 days to obtain a sound absorption coefficient test piece (I) in which the intersections of the fibers were adhered with a polymer coat film.
- a sound absorption coefficient test piece (I) After measuring the mass of the sound absorption coefficient test piece (I), it was observed with a scanning electron microscope to confirm that the polymer coat film adhered the intersections of the fibers. The results of measuring the sound absorption rate are shown together in Table 2.
- Example C1 A PET fiber having a fiber length of 51 mm and a fineness of 2.2 denier was formed into a sheet shape with a needle punch so as to have a porosity of 96% and a thickness of 5 mm, to obtain a nonwoven fabric (J).
- the nonwoven fabric (J) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 5 mm to produce a cylindrical nonwoven fabric (K), and the mass was measured with an electronic balance. Thereafter, the coating material shown in Table 3 was diluted with toluene to a solid content concentration of 10% to obtain a coating solution.
- the cylindrical nonwoven fabric (B) was dipped in the coating liquid, and the voids of the cylindrical nonwoven fabric (K) were completely impregnated with the coating liquid.
- the cylindrical nonwoven fabric (K) taken out from the coating solution was placed in a hot air drying furnace and heated under the curing conditions shown in Table 3 to dry and cure the coating solution. Thereafter, the cylindrical nonwoven fabric (K) was taken out from the hot air drying furnace and further allowed to stand at room temperature for 7 days to obtain a sound absorption coefficient test piece (L) in which the intersections of the fibers were adhered with a polymer coat film. After measuring the mass of the sound absorption coefficient test piece (L), it was confirmed by observation with a scanning electron microscope that the polymer coat film adhered the intersections of the fibers. Table 3 shows the results of measuring the sound absorption coefficient by stacking two sound absorption coefficient test pieces (L).
- Comparative Example A1 Glass wool having an average fiber diameter of about 7 to 8 ⁇ m was formed into a sheet shape with a needle punch so that the porosity was 96% and the thickness was 10 mm, to obtain a nonwoven fabric (A).
- the nonwoven fabric (A) was cut into a columnar shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (B), and the mass was measured with an electronic balance. Then, the result of having measured the sound absorption rate of the cylindrical nonwoven fabric (B) is shown in Table 1.
- Comparative Example A2 The coating material shown in Table 1 was diluted with toluene to a solid content concentration of 10% to obtain a coating solution. Glass wool having an average fiber diameter of about 7 to 8 ⁇ m was dipped in the coating solution. The dipped glass wool was placed so that the fibers did not overlap each other, placed in a hot air drying furnace, heated under the curing conditions shown in Table 1, and the coating liquid coated on the fiber surface was dried and cured. Thereafter, the glass wool was taken out from the hot air drying furnace and allowed to stand at room temperature for 7 days to obtain glass wool (M) in which fibers were coated with a polymer coat film.
- M glass wool
- Glass wool (M) was formed into a sheet shape with a needle punch so that the porosity was 96% and the thickness was 10 mm to obtain a nonwoven fabric (N).
- the nonwoven fabric (N) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (O), and the mass was measured with an electronic balance. Then, the result of having measured the sound absorption rate of the cylindrical nonwoven fabric (O) was shown in Table 1. When the cylindrical nonwoven fabric (O) was observed with a scanning electron microscope, it was confirmed that the intersection of the fibers was not adhered by the polymer coat film.
- Comparative Example B1 Glass wool having an average fiber diameter of about 3 to 4 ⁇ m was formed into a sheet shape with a needle punch so that the porosity was 98% and the thickness was 10 mm to obtain a nonwoven fabric (D).
- the nonwoven fabric (D) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (E), and the mass was measured with an electronic balance. Then, the result of having measured the sound absorption rate of the cylindrical nonwoven fabric (E) is shown in Table 2.
- Comparative Example B2 Glass wool having an average fiber diameter of about 3 to 4 ⁇ m was formed into a sheet shape with a needle punch so that the porosity was 98% and the thickness was 10 mm to obtain a nonwoven fabric (D).
- the nonwoven fabric (D) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 10 mm to produce a cylindrical nonwoven fabric (E), and the mass was measured with an electronic balance. Thereafter, the coating material shown in Table 2 was diluted to a solid content concentration of 5% to obtain a coating solution.
- the cylindrical nonwoven fabric (E) was dipped in the coating solution, and the coating solution was completely impregnated in the voids of the cylindrical nonwoven fabric (E).
- the cylindrical nonwoven fabric (E) taken out from the coating solution was placed in a hot air drying furnace and heated under the curing conditions shown in Table 2 to dry and cure the coating solution. Thereafter, the cylindrical nonwoven fabric (E) was taken out from the hot air drying oven and allowed to stand at room temperature for 7 days to obtain a sound absorption coefficient test piece (P) in which the intersections of the fibers were adhered with a polymer coat film. After measuring the mass of the sound absorption coefficient test piece (P), it was observed with a scanning electron microscope to confirm that the polymer coat film adhered the intersection of the fibers. The results of measuring the sound absorption rate are shown together in Table 2.
- Comparative Example C1 A PET fiber having a fiber length of 51 mm and a fineness of 2.2 denier was formed into a sheet shape with a needle punch so as to have a porosity of 96% and a thickness of 5 mm, to obtain a nonwoven fabric (J).
- the nonwoven fabric (J) was cut into a cylindrical shape with a diameter of 40 mm and a thickness of 5 mm to produce a cylindrical nonwoven fabric (K), and the mass was measured with an electronic balance. Then, the result of having measured two sheets of cylindrical nonwoven fabrics (K) and having measured the sound absorption rate was shown in Table 3.
- Glass wool A Glass fiber with an average fiber diameter of about 7 to 8 ⁇ m and an average fiber length of 30 to 150 mm
- Glass wool B Glass fiber with an average fiber diameter of about 3 to 4 ⁇ m and an average fiber length of 30 to 150 mm PET nonwoven fabric: Fiber length of 51 mm, fineness 2.2 Denier (fiber diameter of about 16 ⁇ m) PET fiber urethane adhesive (moisture curable polymer): W-222 (manufactured by Yokohama Rubber); Polyrotaxane content is 0% by mass: Vinyl chloride adhesive (thermosetting elastomer): # 1551A (manufactured by Sunstar Giken); content of polyrotaxane is 0% by mass: Urethane paint A (thermosetting elastomer): SH3400M (manufactured by ASM); the content of polyrotaxane is 5 to 20% by mass with respect to the solid content of the paint: Urethane paint B (
- the sound-absorbing material of the present invention is useful as a sound-absorbing material used by being affixed to walls, floors, and ceilings of vehicles such as automobiles and trains.
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Abstract
Description
(1)ガラス繊維などの無機繊維のみからなる不織布を吸音材として使用しても、十分な吸音性は得られなかった。
(2)そこで、無機繊維のみからなる不織布において、無機繊維の繊維径を低減すると、低周波数から高周波数までの広い周波数域で吸音性が向上する。しかしながら、共振により、吸音性が低下するため、特に中周波数域(500~1600Hz)において、十分な吸音性が得られない、という新たな課題が生じた。
(3)また、繊維の構成材料として、または繊維の被覆材料として、弾性率が比較的低いものを用いると、吸音性が向上すると考えるのが一般的である。しかしながら、そのような材料を用いても、共振により、吸音性が低下するため、中周波数域(500~1600Hz)において、十分な吸音性がやはり得られない、という新たな課題が生じた。
前記繊維群における少なくとも繊維間の結合点が0.1以上の損失係数を有するポリマーコート膜で被覆されている吸音材に関する。
メトラー社製 電子天秤 AE160を使用し、被覆処理前の質量の測定を行い、素材の比重と試験片の体積から空隙率(サンプル材料中の空気の体積含有率)を算出した。
表1~表3のコーティング液で厚み100μmのフィルムを作製し、5mm×30mmの短冊状にカットしたサンプルを測定試験片として用いた。アイティー計測制御社製 垂動的粘弾性計測装置 DVA-220を使用し、測定周波数10Hz、昇温速度2℃/分にて測定を行い、測定温度23℃時のtanδを求めた。
メトラー社製 電子天秤 AE160を使用し、被覆処理前後の質量の測定を行い、被覆量を算出した。被覆量は、被覆処理後の質量をX、被覆処理前の質量をYとしたとき、(X-Y)/Xで表される値である。
日本音響エンジニアリング社製 垂直入射吸音率測定システム WinZacMTXを使用し、測定周波数範囲 200~4800Hz(1/3オクターブバンド)、内径40mmの音響管を用いた垂直入射吸音率測定(JIS A 1405-2、ISO 10534-2準拠)を行い、500~1600Hzの平均垂直入射吸音率を算出した。ポリマーコート膜を形成しなかったときの吸音率からの増加率を合わせて算出した。
平均繊維径約7~8μmからなるグラスウールを、空隙率96%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(A)を得た。不織布(A)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(B)を作製し、電子天秤にて質量を測定した。その後、表1に示す被覆材をトルエンで固形分濃度10%になるよう希釈し、コーティング液を得た。円柱状不織布(B)をコーティング液中にディップし、コーティング液を円柱状不織布(B)の空隙部に完全に含浸させた。コーティング液から取り出した円柱状不織布(B)を熱風乾燥炉に入れ、表1に示す硬化条件で加熱し、コーティング液を乾燥および硬化させた。その後、円柱状不織布(B)を熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維の交点が接着された吸音率測定試験片(C)を得た。吸音率測定試験片(C)の質量を測定した後、走査型電子顕微鏡で観察してポリマーコート膜が繊維の交点を接着していることを確認した。吸音率を測定した結果を併せて表1に示した。
平均繊維径約3~4μmからなるグラスウールを、空隙率98%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(D)を得た。不織布(D)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(E)を作製し、電子天秤にて質量を測定した。その後、表2に示す被覆材をトルエンで表2に示す固形分濃度になるよう希釈し、コーティング液を得た。円柱状不織布(E)をコーティング液中にディップし、コーティング液を円柱状不織布(E)の空隙部に完全に含浸させた。コーティング液から取り出した円柱状不織布(E)を熱風乾燥炉に入れ、表2に示す硬化条件で加熱し、コーティング液を乾燥および硬化させた。その後、円柱状不織布(E)を熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維の交点が接着された吸音率測定試験片(F)を得た。吸音率測定試験片(F)の質量を測定した後、走査型電子顕微鏡で観察してポリマーコート膜が繊維の交点を接着していることを確認した。吸音率を測定した結果を併せて表2に示した。
離型剤を被覆処理した鋼板上にウレタン塗料Bをブレードで塗布し、熱風乾燥炉を用いて160℃×1hで硬化させ、厚み100μmのフィルム(G)を作製した。フィルム(G)を粉砕した粉をトルエン中に分散させ、ディスパーサーで10分間解砕した後、JIS P 3801に規定される5種Cの濾紙で濾過し、分散液を乾固させ、粒径1μm以下のエラストマ粒子(H)を得た。固形分濃度3.7%に希釈したウレタン塗料C39.4gにエラストマ粒子(H)を0.6g加え、ディスパーサーで30分間撹拌しコーティング液を作製した。その後、上記の円柱状不織布(E)をコーティング液中にディップし、コーティング液を円柱状不織布(E)の空隙部に完全に含浸させた。コーティング液から取り出した円柱状不織布(E)を熱風乾燥炉に入れ、表2に示す硬化条件で加熱し、コーティング液を乾燥および硬化させた。その後、円柱状不織布(E)を熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維の交点が接着された吸音率測定試験片(I)を得た。吸音率測定試験片(I)の質量を測定した後、走査型電子顕微鏡で観察してポリマーコート膜が繊維の交点を接着していることを確認した。吸音率を測定した結果を併せて表2に示した。
繊維長51mm、繊度2.2デニールのPET繊維を、空隙率96%、厚み5mmになるよう、ニードルパンチにてシート状に成形し、不織布(J)を得た。不織布(J)を直径40mm、厚み5mmの円柱状にくり抜いて円柱状不織布(K)を作製し、電子天秤にて質量を測定した。その後、表3に示す被覆材をトルエンで固形分濃度10%になるよう希釈し、コーティング液を得た。円柱状不織布(B)をコーティング液中にディップし、コーティング液を円柱状不織布(K)の空隙部に完全に含浸させた。コーティング液から取り出した円柱状不織布(K)を熱風乾燥炉に入れ、表3に示す硬化条件で加熱し、コーティング液を乾燥および硬化させた。その後、円柱状不織布(K)を熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維の交点が接着された吸音率測定試験片(L)を得た。吸音率測定試験片(L)の質量を測定した後、走査型電子顕微鏡で観察してポリマーコート膜が繊維の交点を接着していることを確認した。吸音率測定試験片(L)を2枚重ねて吸音率を測定した結果を併せて表3に示した。
平均繊維径約7~8μmからなるグラスウールを、空隙率96%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(A)を得た。不織布(A)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(B)を作製し、電子天秤にて質量を測定した。その後、円柱状不織布(B)の吸音率を測定した結果を表1に示した。
表1に示す被覆材をトルエンで固形分濃度10%になるよう希釈し、コーティング液を得た。平均繊維径約7~8μmからなるグラスウールをコーティング液中にディップした。ディップしたグラスウールを各繊維同士が重ならないように配置して熱風乾燥炉に入れ、表1に示す硬化条件で加熱し、繊維表面にコートされたコーティング液を乾燥および硬化させた。その後、グラスウールを熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維を被覆したグラスウール(M)を得た。グラスウール(M)を、空隙率96%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(N)を得た。不織布(N)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(O)を作製し、電子天秤にて質量を測定した。その後、円柱状不織布(O)の吸音率を測定した結果を表1に示した。円柱状不織布(O)を走査型電子顕微鏡で観察したところ、繊維の交点がポリマーコート膜により接着されていないことを確認した。
平均繊維径約3~4μmからなるグラスウールを、空隙率98%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(D)を得た。不織布(D)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(E)を作製し、電子天秤にて質量を測定した。その後、円柱状不織布(E)の吸音率を測定した結果を表2に示した。
平均繊維径約3~4μmからなるグラスウールを、空隙率98%、厚み10mmになるよう、ニードルパンチにてシート状に成形し、不織布(D)を得た。不織布(D)を直径40mm、厚み10mmの円柱状にくり抜いて円柱状不織布(E)を作製し、電子天秤にて質量を測定した。その後、表2に示す被覆材を固形分濃度5%になるよう希釈し、コーティング液を得た。円柱状不織布(E)をコーティング液中にディップし、コーティング液を円柱状不織布(E)の空隙部に完全に含浸させた。コーティング液から取り出した円柱状不織布(E)を熱風乾燥炉に入れ、表2に示す硬化条件で加熱し、コーティング液を乾燥および硬化させた。その後、円柱状不織布(E)を熱風乾燥炉から取り出し、さらに常温で7日間放置して、ポリマーコート膜で繊維の交点が接着された吸音率測定試験片(P)を得た。吸音率測定試験片(P)の質量を測定した後、走査型電子顕微鏡で観察してポリマーコート膜が繊維の交点を接着していることを確認した。吸音率を測定した結果を併せて表2に示した。
繊維長51mm、繊度2.2デニールのPET繊維を、空隙率96%、厚み5mmになるよう、ニードルパンチにてシート状に成形し、不織布(J)を得た。不織布(J)を直径40mm、厚み5mmの円柱状にくり抜いて円柱状不織布(K)を作製し、電子天秤にて質量を測定した。その後、円柱状不織布(K)を2枚重ねて吸音率を測定した結果を表3に示した。
グラスウールA:平均繊維径約7~8μmおよび平均繊維長30~150mmからなる硝子繊維
グラスウールB:平均繊維径約3~4μmおよび平均繊維長30~150mmからなる硝子繊維
PET不織布:繊維長51mm、繊度2.2デニール(繊維径約16μm)のPET繊維
ウレタン系接着剤(湿気硬化性ポリマー):W-222(横浜ゴム製);ポリロタキサンの含有量は0質量%である:
塩化ビニル系接着剤(熱硬化性エラストマー):#1551A(サンスター技研製);ポリロタキサンの含有量は0質量%である:
ウレタン塗料A(熱硬化性エラストマー):SH3400M(ASM製);ポリロタキサンの含有量は当該塗料の固形分に対して5~20質量%である:
ウレタン塗料B(熱硬化性エラストマー):SH3400S(ASM製);ポリロタキサンの含有量は当該塗料の固形分に対して5~20質量%である:
ウレタン塗料C(熱硬化性ポリマー):R2250(日本ビー・ケミカル);ポリロタキサンの含有量は0質量%である:
エラストマ粒子:ウレタン塗料Bを硬化・粉砕した粒子
Claims (9)
- 無機繊維、有機繊維またはこれらの混合繊維からなる繊維群を備えた吸音材であって、
前記繊維群における少なくとも繊維間の結合点が0.1以上の損失係数を有するポリマーコート膜で被覆されている吸音材。 - 前記繊維群における繊維間の結合点および繊維表面が前記ポリマーコート膜で被覆されている、請求項1に記載の吸音材。
- 前記ポリマーコート膜が熱硬化性ポリマーまたは熱硬化性エラストマーから構成される、請求項1または2に記載の吸音材。
- 前記ポリマーコート膜がポリロタキサンを含む、請求項1~3のいずれかに記載の吸音材。
- 前記繊維群が不織布の形態を有する、請求項1~4のいずれかに記載の吸音材。
- 前記繊維群が、ガラス繊維および炭素繊維からなる群から選択される1種以上の無機繊維からなる、請求項1~5のいずれかに記載の吸音材。
- 前記繊維群が、ポリエステル繊維、ポリアミド繊維、ポリアクリル繊維およびポリエチレン繊維からなる群から選択される1種以上の有機繊維からなる、請求項1~5のいずれかに記載の吸音材。
- 前記ポリマーコート膜の繊維群に対する被覆量が5~90質量%である、請求項1~7のいずれかに記載の吸音材。
- 請求項1~8のいずれかに記載の吸音材の製造方法であって、
前記繊維群に、損失係数が0.1以上のポリマーコート膜を形成するためのコーティング液を塗布した後、加熱する、吸音材の製造方法。
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| CN201780003277.1A CN108885862B (zh) | 2016-03-31 | 2017-03-27 | 吸声材料 |
| US15/763,078 US10943576B2 (en) | 2016-03-31 | 2017-03-27 | Sound absorbing material |
| DE112017000099.8T DE112017000099T5 (de) | 2016-03-31 | 2017-03-27 | Schalldämpfungsmaterial |
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|---|---|---|---|---|
| JP6955722B2 (ja) * | 2017-03-13 | 2021-10-27 | 株式会社Asm | ポリロタキサンを有して形成される架橋体を含有する吸音材 |
| EP3988514A4 (en) * | 2019-06-19 | 2022-08-17 | Sumitomo Electric Industries, Ltd. | RESIN COMPOSITION, SECONDARY COATING MATERIAL FOR OPTICAL FIBER, OPTICAL FIBER AND METHOD FOR MANUFACTURING OPTICAL FIBER |
| WO2022123969A1 (ja) * | 2020-12-07 | 2022-06-16 | 住友電気工業株式会社 | 樹脂組成物、光ファイバ及び光ファイバの製造方法 |
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| WO2018102331A1 (en) * | 2016-11-30 | 2018-06-07 | Basf Se | Aqueous polymer emulsions for sound damping applications |
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- 2017-03-27 DE DE112017000099.8T patent/DE112017000099T5/de not_active Withdrawn
- 2017-03-27 WO PCT/JP2017/012472 patent/WO2017170447A1/ja not_active Ceased
- 2017-03-27 CN CN201780003277.1A patent/CN108885862B/zh active Active
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| Publication number | Publication date |
|---|---|
| JP2017181902A (ja) | 2017-10-05 |
| US10943576B2 (en) | 2021-03-09 |
| JP6376167B2 (ja) | 2018-08-22 |
| US20180277088A1 (en) | 2018-09-27 |
| CN108885862B (zh) | 2023-09-26 |
| CN108885862A (zh) | 2018-11-23 |
| DE112017000099T5 (de) | 2018-06-21 |
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