JP2019193980A - Laminate and sound absorbing material using the same - Google Patents

Abstract

To provide a laminate obtained by using, as a base material, a resin molded product having high sound absorbing performance even though being thin, particularly having a high sound absorbing property at a low frequency around 1000 Hz, high thermal insulation performance, a strength, and a self-standing property, as well as a sound absorbing material including the laminate.SOLUTION: The laminate of the present invention includes: a surface material (I) including a fiber assembly; and a base material (II) including a resin molded product having a communication void. The fiber assembly includes a nonwoven fabric A containing ultra fine fibers whose average fiber diameter is less than or equal to 6 μm, and having a weight per unit area of 10 to 1500 g/m. The resin molded product is a molded product including solid resin particles including resin and having a depressed outer shape part, the resin particles being fused to each other. A continuous void part is provided between the fused resin particles, with the porosity of 15 to 80%, and the thickness of 5.0 to 80 mm. The sound absorbing material of the present invention is a sound absorbing material including the laminate of the present invention.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a laminate and a sound absorbing material comprising the laminate. Specifically, the laminate includes a base material including a resin molded body obtained by fusing and molding resin particles having a special shape and a face material including a fiber assembly, and a sound absorbing material including the laminate. Regarding materials.

  As a substitute for conventional solid resin materials and metal materials, resin foam materials obtained by foaming resin have low density, high heat insulation properties, and buffer properties as components for automobiles and electronic devices. Is being used effectively.

  In particular, in an automobile, there is a movement to encapsulate the engine with a heat insulating material or the like in order to provide heat insulation so that the engine room is not cooled from the viewpoint of energy saving when the engine is restarted after idling stop. In recent years, there has been an increasing demand for reducing acceleration noise, and countermeasures against sound absorption in an engine room that generates sound are required, and there is a movement to encapsulate an engine and surround a pump that generates sound. However, the engine room is hot and heat resistance is required, and the space is very narrow, and unless it is a self-supporting sound absorbing material, it may adhere to the engine due to vibration during traveling. May deteriorate or melt due to heat. In addition, since the distance from the sound source changes, the initial sound absorption performance cannot be maintained. Furthermore, in the engine room, there is a lot of noise in the low frequency region around 1,000Hz, such as low sound emitted from the engine and pumps, and reverberation in the engine room due to the rolling sound from the ground. However, the use of a resin material having heat insulating properties, sound absorbing properties and sound insulating properties is expected.

However, although the resin foam material has a high heat insulating property, on the other hand, the range of use has been limited in terms of sound absorption and sound insulation.
The reason for this is that the sound absorption and sound insulation properties are not characteristics that are expressed in general foams, but depend on the cell structure, and the foam of the closed cell structure is a structure in which adjacent cells of the foam structure are separated by resin partition walls. While the body is excellent in rigidity and mechanical strength, the sound absorption and sound insulation performance is very low, whereas the foam of the open cell structure in which the bubble partition wall is destroyed or disappeared is excellent in sound absorption and sound insulation performance while rigidity and mechanical strength In other words, the properties tend to conflict with each other, making it difficult to achieve both.

  In general, examples of open cell type resin foams include foamed urethane resin and foamed melamine resin, which are generally called sponges. The main applications are sponge applications that absorb fluid, flexibility, and impact. It is a cushioning material application using the absorbability. Since these are excellent in sound absorption, they are widely used as light-weight sound-absorbing materials compared to inorganic materials, but because they have low rigidity and strength, they are mainly laminated with other structural materials rather than as self-supporting structural materials. Used as a laminated material.

The main production methods of foam include a bead foam molding method and an extrusion foam molding method. In the bead foam molding method, granular resin foam particles obtained by pre-foaming resin particles are formed into a desired shape. This is a method of forming by a mechanism for forming a molded product by fusion of resin expanded particles by thermal expansion after filling into a molding die, and has various complicated three-dimensional shapes as an advantage compared with the extrusion foam molding method. Various foam materials for structural members, such as the ability to produce foam products with high productivity, the absence of material loss caused by cutting, and the ability to produce molding dies at low cost. This is a particularly preferable method as the molding method.
However, the foam molding process of the bead foam molding method is a closed cell in which bubble cells are separated by a resin film, and is based on a mechanism in which the foam particles are fused to each other due to the expansion of the bubbles. Since the cell structure is basically a closed cell structure, the sound absorption performance is generally inferior.

  On the other hand, as exemplified below, a void structure that is continuous in the foam by a bead foam molding method, that is, a foam having a continuous void structure and a method for producing the same are proposed and known to be usable as a sound-absorbing foam. ing.

Patent Document 1 discloses a granular resin foam particle having a void structure by impregnating a physical foam material into a thermoplastic resin foam particle satisfying a specific bulk density and true density relationship and having a shape parameter satisfying a specific condition. Describes a thermoplastic resin molded article having a continuous void formed by foaming in a mold and is excellent in water permeability and sound absorption.
Prior art document that suggests the sound absorption effect of a foam formed by fusing a granular foam that forms a communication void whose shape parameter satisfies a specific condition for a general-purpose resin of polyolefin resin as in Patent Document 1 Exists.

Furthermore, as a soundproof material having high sound absorption performance, a laminate in which a nonwoven fabric is laminated on an open-cell foam is known, and examples thereof are given below.
Patent Document 2 describes a laminate in which a skin portion made of a synthetic resin layer having fine pores is directly attached to at least one surface of a base material made of a nonwoven fabric or a continuous resin foam without using an adhesive. ing. Examples of the base material include foams such as polyethylene resin, polypropylene resin, polyurethane resin, polyester resin, acrylic resin, polystyrene resin, and cross-linked foam as continuous resin foams, which are preferable in terms of sound absorption. As an example, a flexible urethane foam is mentioned.

Japanese Patent Laid-Open No. 7-137063 JP 2008-146001 A

  The foam exemplified in Patent Document 1 is a foam in which voids are formed by hollow and cross-shaped granular foams of ethylene propylene random polymer and low density polyethylene, and sound absorbing performance is obtained only with a sound absorbing material having a void structure. Is insufficient. In addition, since the foamed molded product is molded by fusing and fusing particles, the beads themselves need to be foamed, resulting in a problem that the strength of the foam is weak.

  Moreover, the structure of the foam described in Patent Document 2 has only fine pores, and the sound absorbing performance is insufficient. As a use, a cushioning adhesive material has been proposed as an interior for vehicles, and many foams that do not have a main purpose of sound absorption and have insufficient sound absorption performance are included. In addition, since the foamed molded product itself has no strength, the strength is insufficient at a location where vibration is applied, such as in an engine room.

  In other general resins, foam molded products with a void structure and their manufacturing technology are considered to be unestablished, especially resins other than general-purpose resins used in engine rooms, such as heat-resistant deformation and solvent resistance. , Resin foam particles that form communication voids made of so-called engineering resins having excellent functions such as flame retardancy, and technology for producing foamed molded products having communication voids formed by fusing them; The sound absorption performance of is currently unknown.

  Further, in recent years, there is a demand for a thin structure that is further excellent in sound absorption performance, particularly in a low frequency region around 1000 Hz that is required in an engine room of an automobile.

  The problem to be solved by the present invention is based on a resin molded body having high sound absorption performance even when thin, particularly high sound absorption performance at a low frequency of around 1000 Hz, high heat insulation performance, strength and self-supporting properties. It is providing the laminated body used as a material, and the sound-absorbing material which consists of this laminated body.

As a result of diligent investigations for solving the problems, the present inventors have surprisingly found a novel non-foamed resin molded article having a communication void having a specific structure formed by a process of heat-sealing resin particles having a specific shape. It has been found that by including a base material containing a specific surface material and a specific face material, even a thin structure, which has been impossible in the past, exhibits high sound absorption performance and has heat insulation performance.
In particular, only a resin molded body having a communication gap exhibits a sound absorption performance only in the middle and high frequency range, but by including a specific face material, a low frequency range around 1000 Hz, which is particularly required in the engine room of an automobile. It was found that the sound absorption performance was shifted without greatly changing the thickness.
Furthermore, by selecting a thermoplastic resin with a specific range of surface tension as the raw material resin, performance selected from mechanical strength, heat resistance, heat deformation resistance, flame resistance, solvent resistance, and rigidity, and higher sound absorption The present invention has been completed by finding that it can be a self-supporting laminated sound-absorbing structure material having performance.

That is, the present invention is as follows.
[1]
A laminate including a face material (I) including a fiber assembly and a base material (II) including a resin molded body having a communication gap,
The fiber assembly includes a non-woven fabric A containing ultrafine fibers having an average fiber diameter of 6 μm or less and having a weight per unit area of 10 to 1500 g / m ² .
The resin molded body is a solid resin particle containing a resin, including a resin particle having a concave outer shape portion, the molded resin body fused to each other, and between the fused resin particles Having continuous voids, porosity of 15-80%,
A laminate having a thickness of 5.0 to 80 mm.
[2]
The face material (I) is a fiber assembly in which the nonwoven fabric A and at least one nonwoven fabric B each having an average fiber diameter of 7 to 40 μm and a weight per unit area of 30 to 2000 g / m ² are laminated. The laminated body according to [1], wherein 1 to 15 bodies are laminated.
The laminate according to claim 1.
[3]
The laminate according to [1] or [2], wherein the resin particles have an average particle diameter of 1.0 to 4.0 mm.
[4]
The laminate according to any one of [1] to [3], wherein the resin molded body includes a thermoplastic resin having a surface tension of 37 to 60 mN / m at 20 ° C.
[5]
The laminate according to any one of [1] to [4], wherein the air permeability of the fiber assembly is 0.1 to 25 cc / (cm ² · sec).
[6]
The laminate according to any one of [1] to [5], wherein the thickness of the face material (I) is 0.1 to 6.0 mm.
[7]
The laminate according to any one of [1] to [6], wherein the nonwoven fabric B is made of short fibers.
[8]
The laminate according to any one of [1] to [7], which is a self-supporting soundproof material.
[9]
A sound-absorbing material comprising the laminate according to any one of [1] to [8].

  According to the present invention, even if it is thin, it has a high sound absorption performance, in particular, a high sound absorption performance at a low frequency of around 1000 Hz, a high heat insulation performance, and a strength and self-supporting laminate based on a resin molded body. A sound absorbing material comprising the body and the laminate can be provided.

It is a figure which shows an example of sectional drawing of the resin particle used for the laminated body of this embodiment. It is a perspective view of the resin particle used for the laminated body of this embodiment. It is a figure which shows sectional drawing which shows the discharge port shape of the unusual shape extrusion die used in Examples 1-12, and the concave outer shape part of the obtained resin particle. It is a figure which shows the relationship between the frequency of the laminated body of this embodiment, and a normal incidence sound absorption coefficient.

[Laminate]
The laminate of this embodiment is a laminate comprising a face material (I) containing a fiber assembly, and a base material (II) containing a resin molded product having a communicating void,
The fiber assembly includes a non-woven fabric A containing ultrafine fibers having an average fiber diameter of 6 μm or less and having a weight per unit area of 10 to 1500 g / m ² .
The resin molded body includes solid resin particles having a concave outer shape, the resin particles are fused to each other, and has a continuous void portion between the fused resin particles. The rate is 15-80%,
The thickness is 5.0 to 80 mm.

  In addition to the face material (I) and the base material (II), the laminate of the present embodiment includes a gas barrier layer, an antistatic layer, a surface hardened layer, an electromagnetic shielding layer, a lubricant layer, a conductive layer, a dielectric layer, Other layers such as an insulating layer, an antifogging layer, a magnetic layer, a printed layer, and a decorative layer may be included. Further, a resin layer having a mirror surface or a textured surface on the outermost surface may be provided on the opposite surface of the face material (I) to the base material (II) in order to impart design properties. Especially, it is preferable that it consists only of face material (I) and base material (II) from a viewpoint which is further excellent in sound absorption performance.

  The thickness of the laminate of this embodiment is 5.0 to 80 mm, preferably 10 to 50 mm, more preferably 12 to 30 mm, from the viewpoint of excellent sound absorption performance, rigidity, balance between strength and lightness. is there.

(Substrate (II))
The base material (II) including the resin molded body having a communication gap and forming the laminate of the present embodiment will be described below. It is preferable that the resin molding which has the said communicating space | gap is a resin molding obtained by carrying out the fusion molding of the resin particle as follows.
The base material (II) includes the resin molded body. Among these, it is preferable to consist only of the resin molded body. The base material (II) may include a resin layer containing additives such as inorganic or organic particles, a flame retardant, and a stabilizer in addition to the resin molded body.

  The thickness of the base material (II) is preferably from 2.0 to 79.9 mm, more preferably from 3.0 to 49.9 mm, from the viewpoint of excellent sound absorption performance, rigidity, balance between strength and lightness. More preferably, it is 5.0-29.9 mm.

-Resin foam particles-
The resin particles are preferably resin particles having a concave outer shape (resin particles having a concave shape in the outer shape viewed from at least one direction).
In the present specification, having a concave outer shape means that there is a direction in which an orthographic image in which the orthographic image of the resin particles is a concave figure is obtained. Further, in this specification, the concave figure means that at least a part (preferably the whole line segment) connecting the two points on the outer surface of the orthographic image figure to be a concave figure passes through the outer region of the resin particle. Say that it is possible to select two points to be line segments. An example of a concave figure is shown in FIG.
Moreover, the said concave external shape part is a structure different from the foaming bubble produced by a water | moisture content etc. when a resin particle is heated.

The concave outer shape portion may be one or plural.
The concave outer shape portion may be one or a plurality of through holes that connect the surfaces of the resin particles, may be one or a plurality of concave portions that do not penetrate the particles, or may be one or a plurality of concave portions. The through hole and one or a plurality of recesses may be mixed. Here, the through-hole may be a cavity connecting two holes formed on the outer surface of the resin foam particle, and in the orthographic image in which the cavity is reflected, the orthographic image in which the cavity is surrounded by the resin particles It is good also as a structure from which (the orthogonal projection image in which the cavity forms the isolated cavity in the resin particle) is obtained.

  In the resin particle, as the concave portion, in an orthogonal projection image in which the concave portion can be confirmed, a region surrounded by a straight line circumscribing the concave portion at least two points and an outer surface of the resin particle with respect to a region occupied by the resin particle The ratio of A (area A / area occupied by the resin particles) is preferably 10% or more, and more preferably 30% or more. Especially, it is preferable to satisfy the above-mentioned range in an orthogonal projection image including the deepest part of the concave portion. Here, the deepest portion of the concave portion may be a portion where the distance to the intersection with the outer surface of the concave portion of the perpendicular line circumscribing the concave portion at least two or more is the longest.

  When the concave outer shape portion is a through hole, the area of the through hole is preferably 10% or more with respect to the total area of the orthographic image of the resin particle in the orthogonal projection image in which the through hole of the resin particle can be confirmed. More preferably, it is 30% or more. Especially, it is preferable to satisfy the above range in an orthographic image in which the area of the through hole of the resin particle is the largest. Further, in the cross section where the hollow shape through which the through hole can be confirmed, the area of the hollow shape is preferably 10% or more, more preferably 30% with respect to the total area of the resin particles on the cross section. That's it. The through hole preferably has at least one cross-section satisfying the above-mentioned area of the cavity shape, and more preferably satisfies the above-mentioned range in the entire cross-section.

  By selecting the shape of the resin particles so that the concave outer shape portion satisfies the conditions of the concave portion and / or the conditions of the through hole, the communication void (continuous void, It is possible to satisfactorily form a communication gap).

  The concave outer shape portion of the resin particle may or may not be a through hole, but the resin particle is particularly preferably in a shape having a concave portion. By adopting a shape with recesses, there is a filling state that was not found in conventional resin particles, and the structure of the communication voids of the resin molded body obtained after molding realizes a particularly excellent balance in both sound absorption performance and mechanical strength can do.

A particularly excellent shape as the shape having the concave portion includes a structure in which a groove-shaped concave portion is provided in the resin particle. When the resin particles are heat-sealed between the resin particles at the time of manufacturing the resin molded body, the resin particle adjacent to the groove-shaped concave portion is By joining in an interlocking filling state and forming a resin molded body having a large joint area between the resin particles and a high strength, and when joining in a form in which the grooves of adjacent resin particles are joined together, Spans, i.e., communicating voids.
As the groove-shaped recess, for example, a shape (FIGS. 2A and 2B) in which a cross section (FIG. 1) of a shape (C shape, U shape, etc.) obtained by cutting a part of a hollow substantially circle is overlapped, hollow The shape etc. which piled up the cross section (FIG. 1) which cut off some polygons (triangle, square, etc.) of these are mentioned. Here, the hollow in the hollow substantially circle and the hollow substantially polygonal shape may be a substantially circular shape or a substantially polygonal shape, but is preferably the same shape as the shape surrounding the hollow. . In addition, it is preferable that the center of the hollow shape overlaps the center of the shape surrounding the hollow (for example, concentric circles).

  Examples of the recess include, for example, a bowl-like shape obtained by curving a disk shape having a certain thickness, a shape formed by bending or bending the disk in an out-of-plane direction, and a single or a plurality on a cylindrical outer surface. The structure etc. which provided the recessed part of this are mentioned. Among the particle shapes, as an example of a particularly preferable particle shape in terms of ease of manufacture, excellent productivity, and easy shape control, the same having a common axis having an outer diameter smaller than the outer diameter from a cylinder The shape (FIG. 2) etc. which cut and excised the part within a fixed angle seeing from the axial direction of the cylinder which cut | disconnected the column of height were mentioned. Hereinafter, this shape is referred to as a C-shaped cross-section partial cylindrical shape, and it is possible to form an equivalent void in the resin molded body even if the shape is substantially the same shape that is slightly deformed based on this shape. If the above conditions are satisfied, it can be used within the scope of the present invention. FIG. 2 shows a preferable example of a C-shaped cross-section partial cylindrical shape in which the size of the portion to be cut out and cut is different.

  The recesses preferably have the same shape when the cross section is continuously formed in one specific direction of the resin particles. For example, as shown in FIG. 2, the shape of the recess in the cross section with respect to one direction of resin particles (vertical direction in FIG. 2, extrusion direction) is the same as the shape of the recess in a different cross section formed by shifting in one direction. It is preferable.

  It can be confirmed that the resin particles have a concave outer shape by observing and determining a transmission image of the resin particles while changing the observation direction of the particles with an optical microscope.

The resin particles are solid, and in the resin particles, for example, the ratio ρ ₀ / ρ ₁ between the density ρ ₀ of the resin contained in the resin particles and the true density ρ ₁ of the resin particles is less than 1.20. Preferably, it is 1.10 or less, and more preferably 1.05 or less.
In this specification, the true density ρ ₁ is a value M / V ₁ obtained by dividing resin particles having a predetermined weight M by the true volume V ₁ of the resin particles at the weight M. The density ρ ₀ of the resin is the density of the raw material resin, and is a density measured by a submersion method using a weight scale. At this time, the density ρ ₀ of the resin is measured by using a mixer, a press, a cutter, a mill, or the like to make the raw resin into a fine powder of 1 mm or less in order to eliminate the influence of pores on the surface and partially generated voids. It is preferable. In the present specification, ρ ₀ and ρ ₁ all mean values obtained by measurement in an environment of 20 ° C. and 0.10 MPa.

The average particle diameter of the resin particles can be measured by classifying 100 g of resin particles using a standard sieve defined in JIS Z8801. It is preferable that the average particle diameter of the said resin particle is 1.0-4.0 mm, More preferably, it is 1.2-3.0 mm. If the average particle size is less than 1.0 mm, handling in the production process is difficult, and if it exceeds 4.0 mm, the surface accuracy of a complicated molded product tends to decrease, which is not preferable.
In addition, the shape of the resin particle of this embodiment is not specifically limited, It is good in various shapes.

  As the method for producing the resin particles, a method using the thermoplasticity of a thermoplastic resin, a method by post-processing such as cutting of particles in a solid state, etc. are possible, and any method can be used as long as it can give a desired outer shape to the particles. Applicable. Among them, a modified extrusion method using a die provided with a discharge section having a special shape can be suitably used as a method capable of producing particles having excellent productivity and stable shape. Resin particles are obtained by foaming pellets obtained by melting and extruding a thermoplastic resin by an extruder having a die having a discharge section with a special shape and pelletizing by a method commonly used in industry such as strand cutting or underwater cutting. The method of obtaining is mentioned.

The resin particles include a resin. Examples of the resin include thermoplastic resins.
Examples of the thermoplastic resin include polystyrene, poly α-methylstyrene, styrene maleic anhydride copolymer, blend or graft polymer of polyphenylene oxide and polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene terpolymer, styrene-butadiene. Copolymer, Styrene polymer such as high impact polystyrene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, post chlorinated polyvinyl chloride, vinyl chloride polymer such as ethylene or copolymer of propylene and vinyl chloride, polyvinylidene chloride Copolymer resin, nylon-6, nylon-6,6, single and copolymer polyamide resin, polyethylene terephthalate, single and copolymer polyester resin, modified polyphenylene Ether resin (polyphenylene ether - polystyrene alloy resin), polycarbonate resin, methacryl imide resin, polyphenylene sulfide, polysulfone, polyether sulfone, polyester resins, phenolic resins, urethane resins, polyolefin resins, and the like.

  Examples of the polyolefin resin include polypropylene, ethylene-propylene random copolymer, propylene-butene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-butene polymerized using a Ziegler catalyst or a metallocene catalyst. Polypropylene resins such as ternary copolymers, low density polyethylene, medium density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl Polyethylene resins such as methacrylate copolymers and ionomer resins are used alone or in combination.

As said resin, it is preferable that the surface tension in 20 degreeC is 37-60 mN / m, More preferably, it is 38-55 mN / m. If the surface tension is within the above range, a sound-absorbing resin molded product having high mechanical strength can be obtained, which is particularly preferable.
As the surface tension of the resin, a value measured by a method in which the temperature is changed to 20 ° C. in the method described in JIS K6768 “Plastic-film and sheet-wetting tension test method” is used.

  Particularly preferable thermoplastic resins include polyamide resins, polyester resins, polyether resins, methacrylic resins, modified polyether resins (phenylene ether-polystyrene alloy resins) and the like whose surface tension is within the above range. Among them, polyamide resins are excellent as heat resistance, chemical resistance and solvent resistance, and are suitable for high heat resistant structural materials, and modified polyether resins (phenylene ether-polystyrene alloy) as resins excellent in heat resistance and high temperature rigidity. Resin).

  The thermoplastic resin may be used in a non-crosslinked state, but may be used after being crosslinked with peroxide or radiation.

  If necessary, the resin particles may be prepared by using conventional compounding agents such as antioxidants, light stabilizers, ultraviolet absorbers, flame retardants, dyes, pigments and other colorants, plasticizers, lubricants, crystallization nucleating agents, talc. Further, an inorganic filler such as charcoal cal may be included depending on the purpose.

  As the flame retardant, bromine-based or phosphorus-based flame retardants can be used, and as the antioxidant, phenol-based, phosphorus-based, sulfur-based, etc. antioxidants can be used. As the agent, light stabilizers such as hindered amines and benzophenones can be used.

-Resin molding-
The resin molded body is a molded body in which the resin particles are fused to each other. That is, the resin molded body of the present embodiment is a molded body having at least a portion where at least two of the resin particles are fused to each other. There are fused portions and voids between the fused resin particles.
The resin molded body has continuous voids between the resin particles fused as described above, and the porosity is 15 to 80%, preferably 18 to 80%, more preferably 20 to 75%. It is.
The said porosity can be measured by the method as described in the below-mentioned Example.

  In the resin molded body, it is preferable that the ratio of the resin particles to the entire resin molded body is 98% by mass or more because the performance of resin particles having a substantially concave outer shape can be obtained.

The resin molded body is a molded body obtained by fusing the aggregates of the resin particles to each other, and it is necessary to have continuous voids between the resin particles. In the present specification, the term “continuous void portion” means that a void portion which is continuous between the fused resin particles is formed between two opposing surfaces (between two surfaces) of the resin molded body. It means that continuous voids are generated and the fluid can flow. It is preferable that the said resin molding has a space | gap part continuous in at least one direction, and it is preferable to have a space | gap part continuous in the thickness direction. As the communication gap, a unit length flow resistance measured by an AC method defined in international standard ISO9053 is 200,000 N · s / m ⁴ or less using a flat resin molded body sample having a thickness of 10 mm. It is preferably 150,000 N · s / m ⁴ or less.

The resin molded body can have heat insulation performance by having such voids. As the heat insulation performance, the thermal conductivity of the resin molded body is preferably 0.025 to 0.15 W / m · K, more preferably 0.027 to 0.13 W / m · K, and still more preferably 0.8. 030 to 0.12 W / m · K. When the thermal conductivity of the resin molded body is less than 0.025 W / m · K, the porosity is too high, resulting in insufficient strength of the molded body, which exceeds 0.15 W / m · K. And the heat insulation property is low, and there is a possibility that the heat energy loss becomes large.
The thermal conductivity can be measured by the method described in Examples described later.

  The fusion strength of the resin molded body is evaluated from the tensile elongation at break (%) of the resin molded body by measuring the tensile strength based on JIS K6767A. The breaking elongation is preferably 2% or more, and more preferably 2% or more. If the elongation at break is less than 2%, the resin molded body may be damaged by vibration during traveling or vibration of the power system when installed in the engine room.

  The resin molded body is produced by filling the resin particles in a closed mold and heating them, but filling the molds that cannot be sealed and heating them to heat the resin particles together. May be. Depending on the resin type and molding conditions, a general-purpose in-mold foaming automatic molding machine can be used.

  However, in a normal in-mold automatic foaming machine and mold, the particles are fused by utilizing the foaming of the resin particles. Since the resin particles of the present invention are solid resin particles and do not foam, it is preferable to pressurize the inside of the mold cavity filled with the particles during heating in order to obtain higher fusing properties. A preferable method is a method in which the inside of the mold cavity is pressurized during heating by using a mechanism in which a part or the entire surface of the mold is compressed. For this purpose, a structure in which the particle surface of the mold is used as a seal and can be compressed in the middle, or a structure in which the cavity can be pressurized by pressing the top by sliding the top of the mold can be mentioned. Securing power by changing the program of the molding machine and creating a program that operates by attaching a hydraulic mechanism, motor, compressor, etc. for sliding the tops separately from the power to open and close the mold I can do it.

  By producing resin moldings by mixing resin particles having a concave outer shape and particles having a general shape such as an oval, cylindrical, or polygonal column without a concave outer shape at an arbitrary ratio The balance of desired sound absorption performance and mechanical strength can be adjusted.

  Although only the resin molded product of the present embodiment exhibits a high sound absorption rate, the sound absorption pattern has a peak around 2000 Hz, and the sound absorption performance around 1000 Hz particularly required in an automobile engine room or the like is low. By laminating the face material (I) comprising the fiber assembly of the present embodiment on this resin molded body, the sound absorption peak can be peak-shifted around 1000 to 1500 Hz and the decrease in the sound absorption peak can be suppressed. It becomes possible to express sound absorption at around 1000 Hz. FIG. 4 shows the relationship between the frequency and the normal incident sound absorption coefficient in an example described later.

(Face material (I))
Next, the face material (I) including the fiber assembly forming the laminate of the present embodiment will be described below.
The face material (I) includes the fiber assembly. Among these, it is preferable to consist only of the fiber assembly. In addition to the fiber assembly, the face material (I) includes an antioxidant, a light stabilizer, a UV absorber, a flame retardant, a colorant such as a dye and a pigment, a plasticizer, a lubricant, a crystallization nucleating agent, talc, A resin phase containing an inorganic filler such as charcoal cal may be included. In addition, for the purpose of imparting coloring, water repellency, flame retardancy, etc. to the face material (I), functions such as coloring processing such as dyeing, water repellency processing such as a fluorine resin, and processing of a flame retardant such as phosphorus are given. Processing may be performed.
The face material (I) preferably has 1 to 50 fiber assemblies laminated, more preferably 1 to 30 sheets, and still more preferably 1 to 20 sheets. In particular, in the case of a fiber assembly in which at least one non-woven fabric A and non-woven fabric B, which will be described later, are laminated, 1 to 15 fiber assemblies are preferably laminated, more preferably 1 to 12 pieces. More preferably, the number is 1 to 10.

  As thickness of the said face material (I), 0.1-6.0 mm is preferable, More preferably, it is 0.1-5.5 mm, More preferably, it is 0.2-5.0 mm. If it is 6.0 mm or less, it is preferable in terms of weight reduction and heat insulation, and if it is 0.1 mm or more, the strength of the face material (I) can be sufficiently obtained.

Air permeability of the surface material (I) is preferably ^{0.1~25cc / (cm 2 · sec)} , more preferably ^{1~20cc / (cm 2 · sec)} , more preferably 3～15Cc / (Cm ² · sec). When the air permeability of the face material (I) is less than 0.1 cc / (cm ² · sec), the thermal conductivity is increased, and the heat insulation performance is lowered, which is not preferable. If the air permeability exceeds 25 cc / (cm ² · sec), the shift of the sound absorbing performance to the low frequency band in the sound absorbing performance is not preferable.
The air permeability of the face material (I) can be measured by the method described in Examples described later.

-Fiber assembly-
The fiber assembly includes the nonwoven fabric A containing ultrafine fibers having an average fiber diameter of 6 μm or less and having a weight per unit area of 10 to 1500 g / m ² .
The number of laminated nonwoven fabrics contained in the fiber assembly is preferably 20 or less. When the number is more than 20, the weight increases, the thermal conductivity increases, and the heat insulating property may be lowered. More preferably, it is 1-15, and more preferably 10.

  The thickness of the fiber assembly is preferably 5.0 mm or less. In order to obtain the strength of the fiber assembly, the thickness is preferably 0.1 mm or more.

Weight per unit area of the fiber aggregate (basis weight) is preferably from 50 to 1500 g / m ^2, more preferably 70~1200g / m ^2, more preferably from 100 to 1000 g / m ^2. If the basis weight is less than 50 g / m ² , the face material (I) may become too thin to obtain sufficient strength. If the basis weight of the fiber assembly is 1500 g / m ^{2 or} less, it is good from the viewpoint of thickness and light weight.
The basis weight of the fiber assembly can be measured by the method described in Examples described later.

The bulk density of the fiber aggregate is preferably 0.10~1.0g / cm ^3, more preferably 0.12~0.90g / cm ^3, more preferably 0.15～0.80G / cm ³ . When the bulk density is less than 0.10 g / cm ³ , the sound absorption performance of the laminate is deteriorated, and when the bulk density of the fiber assembly exceeds 1.0 g / cm ³ , the denseness is increased, and the face material and the base The adhesion stability of the material decreases.
The bulk density of the fiber assembly is obtained by dividing the basis weight of the fiber assembly by the thickness, and can be measured by the method described in Examples described later.

Air permeability of the fiber aggregate is preferably ^{0.1~25cc / (cm 2 · sec)} , more preferably ^{0.2~25cc / (cm 2 · sec)} , more preferably 0.3 25 cc / (cm ² · sec). If the air permeability of the fiber assembly is less than 0.1 cc / (cm ² · sec), the sound absorption rate shifts to the low frequency side, but sound reflection occurs on the surface of the fiber assembly, and the sound absorption rate decreases overall. This is not preferable. When the air permeability exceeds 25 cc / (cm ² · sec), the effect of laminating the fiber assembly is small, which is not preferable.
The air permeability of the fiber assembly can be measured by the method described in Examples described later.

The fiber aggregate preferably has a thermal conductivity of 0.02 to 0.15 W / m · K, more preferably 0.02 to 0.12 W / m · K. If the thermal conductivity of the fiber assembly is less than 0.02 W / m · K, the sound absorption performance becomes insufficient, and if it exceeds 0.15 W / m · K, the heat insulation performance is insufficient and the thermal energy loss is large. There is a possibility.
The thermal conductivity can be measured by the method described in Examples described later.

--Nonwoven fabric A--
The nonwoven fabric A contained in the fiber assembly contains ultrafine fibers having an average fiber diameter of 6 μm or less, and the weight per unit area is 10 to 1500 g / m ² .
Specific examples of the resin constituting the nonwoven fabric A include, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene 1,4-cyclohexanedimethanol (PCT), polylactic acid (PLA), and / or Alternatively, thermoplastic polymers such as polypropylene (PP), polyacrylonitrile, polyacetate, and polyamide resin can be used. Among these, PET, PP, and polyamide can be used from the viewpoint of cost and ease of processing. Furthermore, from the viewpoint of weight reduction, PP having a lighter specific gravity can be used.

  The nonwoven fabric A preferably contains 30% by mass or more of ultrafine fibers having a fiber diameter of 6 μm or less, more preferably 50% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the nonwoven fabric A. It is. The whole nonwoven fabric A may be comprised only with the said ultrafine fiber. When the content of the ultrafine fiber is less than 30% by mass, it is difficult to obtain a sound absorption lowering effect due to resonance due to the ultrafine fiber characteristics.

The average fiber diameter of the ultrafine fibers is 6 μm or less, more preferably 0.3 to 5 μm, and most preferably 0.5 to 5 μm.
The average fiber diameter can be measured by the method described in Examples described later.

The nonwoven fabric A has a weight per unit area of 10 to 1500 g / m ² . When the weight per unit area is smaller than 10 g / m ^2, the effect of the sound absorption performance of the ultrafine fiber is insufficient, and when it exceeds 1500 g / m ² , the ultrafine fiber has a high bulk density. When the load is increased, the sound absorption performance may vary due to the decrease in thickness. Preferably it is 10-1000 g / m < ² >, More preferably, it is 10-800 g / m < ² >.

  It is preferable that 1-30 sheets of the nonwoven fabric A is contained in a fiber assembly, More preferably, it is 1-15 sheets, More preferably, it is 1-10 sheets. When 1 to 30 nonwoven fabrics A are included, the sound absorption performance due to resonance can be improved.

Although the manufacturing method of the nonwoven fabric A is not specifically limited, The spun bond method or the melt blow method is preferable.
Although the spunbond method is not particularly limited, the molten polymer is extruded from a nozzle, and is drawn by a high-speed suction gas, and then collected on a moving conveyor to form a web. A method of forming a sheet by entanglement or the like is preferable.
The melt blown method is not particularly limited, but a production method in which a fiber raw material is processed to be thinner by melting a resin raw material and blowing a high-temperature air current onto a fibrous resin extruded from a nozzle is preferable.

--Nonwoven fabric B--
The fiber assembly may further include a non-woven fabric B. Nonwoven fabric B has an average fiber diameter of 7 to 40 μm and a weight per unit area of 30 to 2000 g / m ² .
Specifically, as the resin constituting the nonwoven fabric B, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene 1,4-cyclohexanedimethanol (PCT), polylactic acid (PLA) and / or Examples thereof include thermoplastic polymers such as polypropylene (PP), polyacrylonitrile, polyacetate, and polyamide resins. Among these, PET, PP, and polyamide can be used from the viewpoint of cost and ease of processing. Furthermore, from the viewpoint of weight reduction, PP having a lighter specific gravity can be used.

The nonwoven fabric B preferably has an average fiber diameter of 7 to 40 μm, more preferably 7 to 30 μm, and still more preferably 7 to 20 μm. If the average fiber diameter is thinner than 7 μm, the sound absorption performance of the fiber assembly may be deteriorated. Moreover, since there is no waist of a fiber assembly, handling property may worsen. If the average fiber diameter is larger than 40 μm, the contribution to the sound absorbing performance tends to be small.
The average fiber diameter can be measured by the method described in Examples described later.

The fibers of the nonwoven fabric B may be continuous long fibers, short fibers, or a mixture thereof. The longer the fiber length, the more likely the entanglement between the fibers, and the higher the sound absorbing performance.
When short fibers are used, the fiber length is preferably 38 to 150 mm, more preferably 45 to 150 mm, and still more preferably 50 to 150 mm. If the fiber length is less than 38 mm, entanglement between the fibers is difficult to occur, and the sound absorption performance tends to be greatly reduced. The short fiber may be a single component, or may be a composite fiber composed of a mixture of two or more types of short fibers having different short fiber lengths or a plurality of types of short fibers.
Moreover, in order to adjust the waist of the nonwoven fabric B, a thick fiber having a fiber diameter of more than 40 μm and not more than 100 μm may be mixed. From the viewpoint of not changing the properties of the nonwoven fabric B, the content is 100% by mass of the nonwoven fabric B. It is preferable that it is 30 mass% or less with respect to it, and it is more preferable that it is 20 mass% or less. If the thick fiber exceeds 30% by mass, problems such as the texture of the nonwoven fabric becoming too hard are likely to occur.
Furthermore, it is also preferable to use heat-fusible fibers having different melting points from the viewpoint of improving dimensional stability.

  It is preferable that 1-25 sheets of the nonwoven fabric B is contained in a fiber assembly, More preferably, it is 1-15 sheets, More preferably, it is 1-10 sheets. When 1 to 25 non-woven fabrics B are included, the face material 1 is lumped and is easily laminated.

Although it does not specifically limit as a method of manufacturing the nonwoven fabric B from the continuous long fiber, The nonwoven fabric obtained by the spun bond method or the melt blow method is preferable.
The spunbond method is not particularly limited, but in general, a molten polymer is extruded from a nozzle, sucked and stretched with a high-speed suction gas, and then collected on a moving conveyor to form a web. The manufacturing method which makes it a sheet form by giving heat processing, an entanglement, etc. continuously is preferable.
The melt blown method is not particularly limited, but generally, a production method is preferred in which the resin raw material is melted and the fiber diameter is processed by blowing a high-temperature air current onto the fibrous resin extruded from the nozzle.

It does not specifically limit as a method of manufacturing the nonwoven fabric B from a short fiber, The resin bond method, the thermal bond method, the spunlace method etc. are mentioned.
In general, the resin bond method is a manufacturing method in which fibers are bonded together by bonding a fiber web with an adhesive.
The thermal bond method is a manufacturing method in which a fiber web or a binder fiber is partially melted and bonded.
The spunlace method is a manufacturing method in which a fiber web is entangled using a high-pressure water stream.
The thermal bond method or the spunlace method is preferable from the viewpoint of obtaining a large gap between fibers.

The nonwoven fabric B preferably has a weight per unit area of 30 to 2000 g / m ² . If it is less than 30 g / m ^2, handling is difficult because there is no waist of the fiber assembly. If it is 2000 g / m ² or more, the thickness becomes too thick, the weight is heavy, and the thermal conductivity is increased, so that the heat insulation performance may be lowered. The weight per unit area of the nonwoven fabric B is more preferably 40-1500 g / m ² , and still more preferably 50-1200 g / m ² .

Both the nonwoven fabric A and the nonwoven fabric B are preferably bonded between the fibers so that the fibers do not move and become non-uniform in the plane. In this case, the powder is bonded by heat using a powdery binder or a fibrous binder. It is preferable to do so. More preferably, it is a fibrous binder fiber. In particular, the melting point of the low melting point portion of the binder is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, even more preferably, because it can withstand environmental resistance tests, such as when used as a sound absorbing material for automobile engine rooms. Is 120 ° C. or higher.
As the resin constituting the low melting point portion of the binder, for example, low melting point polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE) and the like can be used. For example, when polybutylene terephthalate (PBT) having a melting point of around 220 ° C. is used as the meltblown fiber, low melting point polyethylene terephthalate (PET) having a melting point of 110 ° C. can be used as the binder.
The binder may be in the form of powder or fiber, and preferably has a fiber shape, and the cross-sectional diameter and length are not particularly limited, but in order to increase dispersibility in the meltblown fiber, it is preferably a short fiber. . For example, staple fibers having a fiber length of 10 mm to 100 mm manufactured by cutting a spun fiber can be used. Since the fibrous binder has a high contact density with the fiber at least in part, it is possible to efficiently melt and bond the fibers and suppress the necessary amount of the binder fiber.

The binder fiber need not be a material having a uniform melting point as a whole, as long as it has a low melting point portion on at least the surface of the high melting point fiber.
For example, a core-sheath fiber, a core having a high melting point (for example, a melting point of 220 to 300 ° C.), and polyester resin fibers such as polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate, and copolyester Or polyamide resin fibers such as nylon 6, nylon 11, nylon 66, etc., and the sheath part has a low melting point (for example, a melting point of 90 ° C. or higher and lower than 180 ° C., and a melting point of 140 to 210 ° C. lower than the high melting point component of the core) Ingredients such as low melting point polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polyester elastomer can be used. The average fiber diameter of the core part is preferably 5 to 20 μm, and the thickness of the sheath part is preferably 5.0 to 20 μm. If fibers having such a core-sheath structure are used, when the fibers are mixed, only the sheath portion having a low melting point is melted, and the core portion remains as a fiber, so that the air permeability can be increased without impairing the properties of the fiber. It can be reduced.
The difference between the melting point of the synthetic resin fiber constituting the low melting point part of the binder and the melting point of the synthetic resin fiber constituting the other part is preferably 10 ° C. or more. The fibrous binder that can be partially melted has an effect of bonding between the fibers by being melted and lowering the air permeability of the fibers. Further, since the fiber structure can be fixed, the stability of the air permeability can be increased and handling can be facilitated.

Weight per unit area of the binder (basis weight) is preferably 1 to 40 g / m ^2, more preferably from 5~35g / m ^2. If the amount is less than 1 g / m ² , the amount of binder may be insufficient, the fiber structure cannot be sufficiently melt bonded and stably fixed, and the thickness is easily recovered during use, so the air permeability is constant. May not be maintained. On the other hand, if the binder exceeds 40 g / m ² , the effect of lowering the air permeability by the fibers may be diminished.

  The fiber aggregate may be the nonwoven fabric A alone, or at least one nonwoven fabric A and nonwoven fabric B may be laminated. The laminated structure may be a non-woven fabric A / non-woven fabric B, non-woven fabric B / non-woven fabric A / non-woven fabric B, non-woven fabric A / non-woven fabric B / non-woven fabric A, etc. A structure including a portion in which the same nonwoven fabric is continuously laminated, such as nonwoven fabric B / nonwoven fabric A / nonwoven fabric A, may be used.

  In addition, the fiber assembly has a laminated structure of nonwoven fabric B-1 / nonwoven fabric A / nonwoven fabric B-2 using nonwoven fabric B-1 and nonwoven fabric B-2 having different weights per unit area as the nonwoven fabric B, for example. You may do it. Moreover, when the nonwoven fabric B is two types of nonwoven fabrics having different average fiber diameters, they may be laminated in the same manner. The same applies to the nonwoven fabric A.

  The method for laminating the nonwoven fabric A and the nonwoven fabric B is not particularly limited, and is a method of collecting on the same net at the time of fabric production and integrating them by self-fusion, Examples thereof include a thermal bonding method in which integration is performed using a sonic embossing roll and the like, and a mechanical kneading method in which separately woven nonwoven fabrics are integrated by a needle punch, a water punch, or the like. It is also possible to bond using an adhesive, a binder resin, or the like, but a method of collecting on the same net at the time of fabric production and integrating by self-fusion or a needle punch method is preferable. As the needle punch method, basically, a method described in detail in “Basics and Applications of Nonwoven Fabrics” edited by the Japan Society of Warfare Mechanical Engineers Nonwoven Fabric Research Group can be adopted.

  As a method of laminating a plurality of the fiber aggregates, a method similar to the laminating method of the non-woven fabric A and the non-woven fabric B can be adopted. However, the surface material (1) is simply overlapped to form the base material (II The method of fixing together when laminating | stacking is also mentioned.

Next, the lamination | stacking system of face material (I) and base material (II) in the laminated body of this embodiment is demonstrated.
Examples of means for laminating the base material (II) including the resin molded body on one side of the face material (I) including the fiber assembly include a method of laminating and integrating via an adhesive in addition to a method using thermal bonding. However, it is preferable to simply superimpose the face material (I) and the base material (II) without using an adhesive to form a laminate (composite sound absorbing material). By not using an adhesive, air permeability can be reliably ensured between the face material (I) and the base material (II), and stable sound absorbing performance can be maintained. In this way, when the layers are simply overlapped and stacked, they are preferably integrated by fitting into a predetermined frame (frame) and fixing at least the end portions. In the case of stacking and integrating via an adhesive, air permeability may be ensured by partially disposing the adhesive. If the adhesive forms a film to form an adhesive layer and the air permeability is impaired, sound penetration from the face material (I) to the base material (II) is hindered, and the sound absorption performance may be lowered. As a method for causing the adhesive to partially exist in this way, a powdery or fibrous thermal adhesive may be used. Further, the face material (I) and the base material (II) are fixed around the front surface, the side surface, or the back surface of the base material (II), and the face material (I) is fixed to the base material (II) through an air layer. May be equipped. In addition, in the base material (II), the surface of the base material (II) which is the surface on the face material (I) side of the fiber assembly laminate is heated and melted and bonded to the face material (I) such as the fiber assembly laminate. It can also be bonded and integrated by a method.

  As a specific example of the laminating method by thermal bonding between the face material (I) and the base material (II), heating that softens or melts the fibers contained in the face material (I) and the resin contained in the base material (II). Thermal bonding method that heats and pressurizes with a net, roll, etc. in an atmosphere; hot melt powder, adhesive, etc. are applied to the face material and / or substrate by spray, roll, etc., and heat treatment Adhesive method for bonding such as non-woven fabric containing low melting point fiber, web-like non-woven fabric, tape yarn cloth, photomelt film, mesh sheet, etc. The method of fixing by driving in, etc .; The bonding may be a surface or may be bonded at a plurality of points.

  In this embodiment, when two or more fiber assembly laminates are stacked as the face material (I), a method of sequentially laminating individual fiber assembly laminates or two or more fiber assembly laminates simultaneously. It can also be laminated.

  The laminate (composite sound absorbing material) of the present embodiment is used by being installed so that the face material (I) side including the fiber assembly is positioned on the sound incident side. By arranging the face material (I) side including the fiber assembly on the sound incident side, the sound absorption performance can be effectively improved.

  In the laminate of this embodiment, the base material (II) has a sound absorption performance with a sound absorption peak around 2000 Hz, and the face material (I) also has a sound absorption performance. However, the face material (I) is applied to the base material (II). By laminating, the sound absorption peak around 2000 Hz of the base material (II) can be shifted to the vicinity of 1000 to 1500 Hz while suppressing a decrease in sound absorption rate, and high sound absorption at 1000 Hz is expressed. It becomes possible to suppress low-frequency noise around 1000 Hz generated in the engine room of an automobile.

The sound absorption coefficient at 1000 Hz of the laminate of the present embodiment is preferably 0.30 or more, more preferably 0.35 or more, and further preferably 0.40 or more.
The sound absorption coefficient can be measured by the method described in Examples described later.

The laminate of the present embodiment, it is preferable that the thermal energy loss is less 245.0W / m ² · hr, and more preferably 240.0W / m ² · hr less, still more preferably 235.0W / m ² · hr or less. If the thermal energy loss of the laminated body exceeds 245.0 W / m ² · hr, the heat inside the laminated body will go out to the outside. For example, when the engine is stopped at an idling stop, Since the engine cools down, extra energy is required at the time of restart, and the fuel efficiency of gasoline and diesel may be deteriorated.
The thermal energy loss can be measured by the method described in Examples described later.

  The laminated body of this embodiment can be used as a member that shields various noises, such as a soundproof member in an engine room for a vehicle such as an automobile. In particular, by selecting a hard thermoplastic resin as a base material, it can be used as a self-supporting soundproofing material that can be self-supported only by the laminate of the present embodiment without further laminating other members.

  Embodiments of the present invention will be described below with reference to examples. However, the scope of the present invention is not limited by the examples.

  The evaluation methods used in the examples and comparative examples are described below.

(1) Average particle diameter D (mm) of resin particles
100 g of resin particles are defined in JIS Z8801, nominal dimensions are d ₁ = 5.6 mm, d ₂ = 4.75 mm, d ₃ = 4 mm, d ₄ = 3.35 mm, d ₅ = 2.36 mm, d ₆ = 1.7mm, d ₇ = 1.4mm, followed by classification using a sieve standard is d ₈ = 1 mm, sieve through the d _i, old d _{i + 1} the weight ratio of particles to stop in X _i, The average particle diameter D of all particle aggregates was determined by the following formula.
D = ΣX _i (d _i · d _{i + 1} ) ^1/2
(I represents an integer of 1 to 7)

(2) Resin density ρ ₀ (g / cm ³ ) and resin particle true density ρ ₁ (g / cm ³ )
500 g of the raw material resin is rotated at 8,000 revolutions per minute using a sentry cutter UCM150 (manufactured by Nihon Coke Kogyo Co., Ltd.), and laser diffraction / scattering method particle size distribution measuring device LS13 320 manufactured by Beckman Coulter, Inc. The measured average particle size was 500 μm or less. After measuring the mass W (g) of this powder, the volume V (cm ³ ) is measured by the submerging method, and W / V (g / cm ³ ) is obtained as the resin density ρ ₀ (g / cm ³ ). It was.
After measuring the mass W (g) of the resin particles obtained in Examples and Comparative Examples, the volume V (cm ³ ) was measured by a submerging method, and W / V (g / cm ³ ) was determined as the true density of the resin particles. ρ ₁ (g / cm ³ ) was determined.
Ρ ₀ / ρ ₁ was calculated from the measurement result.

(3) Porosity of resin molding (%)
The porosity of the resin molded body was determined from the following formula.
Porosity (%) of resin molded product = [(BC) / B] × 100
However, B: apparent volume (cm ³ ) of the resin molded body, C: true volume (cm ³ ) of the resin molded body, the apparent volume is a volume calculated from the outer dimensions of the molded body, and the true volume C is It means the actual volume excluding the voids of the molded body. The true volume C can be obtained by measuring an increased volume when the resin molded body is submerged in a liquid (for example, alcohol).

(4) Presence / absence of continuous voids The unit length was determined as follows from the measurement of flow resistance.
As a measuring method of the unit length flow resistance value, the AC method of the international standard ISO9053 was applied and the flow resistance measurement system AirReSys type manufactured by Nippon Acoustic Engineering Co., Ltd. was used. That is, using a flat resin molded body sample having a thickness of 20 mm, the pressure difference P (Pa) between the front and back surfaces of the material is measured in a flowing state in a uniform flow rate F = 0.5 mm / s. It calculated | required as P / (t * F) (N * s / m < ⁴ >) from thickness t (m). When the unit length flow resistance value is 200,000 N · s / m ⁴ or less, there is a continuous void (○), and when it exceeds 200,000 N · s / m ⁴ , the continuous void is not evaluated (×) did.

(5) Strength of molded body The tensile strength of a resin molded body and a laminate is measured based on JIS K6767A, and the strength is excellent when the fracture elongation of the resin molded body is 2% or more (◯), and the elongation at break is 2%. The strength was inferior when the strength was less than (x).

(6) Weight per unit area of nonwoven fabric and fiber assembly (weight per unit area) (g / m ² )
The value evaluated according to the method described in JIS L-1913 “General Nonwoven Test Method” per unit area (ISO method) was defined as the weight per unit area of the nonwoven fabric and fiber assembly (weight per unit area).

(7) Average fiber diameter (μm) of nonwoven fabric and fiber assembly
The “average geometric diameter” of the fibers was measured by image analysis of SEM micrographs of the web specimens of each production example. A 1 cm × 1 cm test piece was cut out from the web test piece and directly attached to a sample stage of a scanning electron microscope. The sample stage on which the test piece was placed was inserted into a scanning microscope, and image observation was performed using an acceleration voltage of 20 KV, a working distance of 15 mm, and a 0 ° sample tilt in the low vacuum mode. Fiber diameter was measured using backscattered electron images taken at 500x and 1000x magnification. In the electron micrograph of each sample, 100 fibers were arbitrarily selected, the fiber diameter was measured, and the number average average fiber diameter was calculated.

(8) Air permeability of the fiber assembly (cc / (cm ² · sec))
The measurement was performed according to the method described in JIS L-1096 “Testing method for fabrics and knitted fabrics”.

(9) Sound absorption characteristics of laminate and sound absorption coefficient at 1000 Hz The normal incident sound absorption coefficient was measured based on JIS A1405-2. Samples (30 mm × 30 mm × thickness of each production example) obtained by individually or overlaying each production example of a resin molded body or fiber assembly, samples of examples and comparative examples (30 mm × 30 mm × (base material thickness 20 mm +) A disc having a diameter of 41 mm is cut out from the thickness of each face material used in the examples and comparative examples), and a rigid body made of aluminum is directly placed on the back side of the sample, and a normal incident sound absorption measurement system WinZacMTX type manufactured by Nippon Acoustic Engineering Co., Ltd. is used. The normal incident sound absorption coefficient at a frequency of 160 to 5000 Hz was measured at 20 ° C. 200, 250Hz, 315Hz, 400Hz, 500Hz, 630Hz, 800Hz, 1000Hz, 1250Hz, 1600Hz, 2000Hz, the sound absorption coefficient of the 1/3 octave band with 11 points as the center frequency is measured, and the sound absorption of the average sound absorption coefficient of 11 bands Sound absorption characteristics are excellent when there are 5 or more frequencies with a rate of 30% or more (◎), sound absorption characteristics are good when frequencies with a frequency of 30% or more are 3 or more and 4 or less, and sound absorption rate is 30%. The case where the above frequency was 2 points or less was evaluated as having poor sound absorption characteristics (x). Among them, the sound absorption rate at 1000 Hz was measured. The sound absorption rate at 1000 Hz was evaluated.

(10) Thermal conductivity (W / m · K) and thermal energy loss (W / m ² · hr)
Test pieces of each production example of resin molded body and fiber assembly (30 mm × 30 mm × thickness of each production example), test pieces of examples and comparative examples (30 mm × 30 mm × (thickness of substrate 20 mm + examples and comparative examples) The thickness of each face material used in 1) was prepared, and based on ISO 22007-6, the thermal conductivity in the thickness direction of each test piece was measured using Mobile-10 manufactured by Eye Phase. Next, the size of each test piece 1 m × 1 m is prepared, the environmental temperature on one side of the high temperature side 1 m × 1 m is set to 100 ° C., the environmental temperature on the opposite side is set to 20 ° C., and the surface of the test piece on the 20 ° C. side is measured. The surface temperature was measured and the thermal energy loss was calculated based on JIS A9501. In addition, although there is no front and back when a test piece is a single layer, in the case of lamination | stacking, it installed and measured so that the fiber assembly side might become an environmental side of 100 degreeC.

(11) Independence (flexibility)
Samples of 1 mm square, substrate thickness 20 mm + thickness of each face material used in Examples and Comparative Examples were cantilevered, and the amount of deflection was evaluated. Samples with visible deflection were inferior (x), and samples with no clear deflection were considered good (◯).

[Production Example 1 of Resin Molded Body (A-1)]
Polyamide 6 resin (UBE nylon “1022B”, manufactured by Ube Industries, surface tension of 46 mN / m at 20 ° C.) was melted using an extruder, and discharged from a modified extrusion die having a cross-sectional shape shown in FIG. The strand was pelletized with a pelletizer to obtain particles having an average particle diameter of 1.4 mm. When the obtained polyamide resin particles were cut and observed in cross section, they had a concave outer shape in the shape shown in FIG. Ρ ₀ / ρ ₁ was 1.01.
Next, in the in-mold foam molding device, the cavity is a mold of 1 m × 1 m × thickness 30 mm, and the piece on the 1 m × 1 m surface of the movable mold slides in the thickness direction from 30 mm to 15 mm in the cavity direction. As a method of sliding the piece, a die having a structure in which the piece can slide with a 5 MPa hydraulic cylinder was installed. First, the piece was moved using a hydraulic cylinder to a position where the thickness of the molded product of the cavity was 24 mm, and the polyamide resin particles were introduced into the cavity by air pressure. Thereafter, air at 230 ° C. was blown for 30 seconds while pushing the mold piece with a pressure of 2 MPa with a hydraulic cylinder, and when the cavity thickness became 21 mm, the pressure of the hydraulic cylinder of the piece was reduced to 0.1 MPa and then cooled. Then, a polyamide resin molded body A-1 having a 1 m square and a thickness of 20 mm in which the polyamide resin particles were fused to each other was obtained. The porosity of the resin molded body was 67%. From the measured value of ventilation resistance, it was confirmed that there was a continuous void.
The evaluation results of the polyamide resin particles and the resin molded body are shown in Table 1.

[Production Examples 2 to 5 (A-2 to A-5) of resin molded body]
Polyphenylene ether resin (trade name: Zylon TYPES201A, manufactured by Asahi Kasei Corporation, surface tension 40 mN / m at 20 ° C.) 60% by mass, non-halogen flame retardant (bisphenol A-bis (diphenyl phosphate) (BBP)) 18% by mass, impact-resistant polystyrene resin (HIPS) having a rubber concentration of 6% by mass (HIPS) 10% by mass (the rubber component content in the base resin is 0.6% by mass) and general-purpose polystyrene resin (PS) (trade name: GP685 (manufactured by PS Japan Co., Ltd.) was added in an amount of 12% by mass, and the strand discharged from the deformed extrusion die shown in FIG. 3 which was heated and melt-kneaded by an extruder was pelletized with a pelletizer to obtain pellets. An outline of the obtained resin particles is shown in FIG.
3 (b1) is Production Example 2, FIG. 3 (c1) is Production Example 3, FIG. 3 (d1) is Production Example 4, and FIG. Cross-sectional shape.
The obtained resin particles are filled in the mold used in Production Example 1 having the water vapor holes of the in-mold foam molding apparatus, heated with pressurized water vapor of 0.35 MPa, and the resin particles are mutually expanded and fused, In addition, the mold pieces were pressed in the same manner to compress the inside of the cavity, cooled, and taken out from the molding dies to obtain resin moldings A-2 to A-5.
The resin molding obtained from the resin particles of Production Example 2 is A-2, the resin molding obtained from the resin particles of Production Example 3 is A-3, and the resin molding obtained from the resin particles of Production Example 4 The body is A-4, and the resin molded body obtained from the resin particles of Production Example 5 is A-5. In both cases, it was confirmed from the measured values of the airflow resistance that there were continuous voids.
The evaluation results of the resin particles and the resin molded body are shown in Table 1.

[Production Example 6 of Resin Molded Body (A-6)]
100 parts by mass of a polycondensate of ethylene glycol, isophthalic acid and terephthalic acid (isophthalic acid content 2% by mass, surface tension 43 mN / m at 20 ° C.), 0.3 part by mass of pyromellitic dianhydride, sodium carbonate The mixture with 0.03 parts by mass was melted and kneaded at 270 to 290 ° C. while removing the water generated by the reaction while reducing the vent at 650 Torr using an extruder equipped with a vent, as shown in FIG. 3 (f1). After passing through the profile extrusion die, it was immediately cooled in a cooling water tank and cut into small granules using a pelletizer to produce resin particles. The cross section of the obtained resin particle is shown in FIG.
When the cross section of the obtained resin particle was observed, ρ ₀ / ρ ₁ was 1.04. The average particle size was 1.3 mm.
The mold and mold used in Production Example 1 were filled in the mold with a cavity thickness of 23 mm, and the mold was clamped. Steam with a gauge pressure of 0.02 MPa was placed in the mold for 10 seconds, and then steam with a gauge pressure of 0.06 MPa. Was introduced for 20 seconds, heat was maintained for 120 seconds while applying a pressure of 2 MPa to the mold piece, and when the mold cavity became 21 mm, the pressure of the piece was reduced to 0.1 MPa, and the mold cavity was water-cooled, A resin molded body A-6 in which the resin particles were fused was obtained. From the measured value of ventilation resistance, it was confirmed that there was a continuous void.
The evaluation results of the resin particles and the resin molded body are shown in Table 1.

[Production Example 7 of Resin Molded Body (B-1)]
Resin particles and a resin molded body B-1 were obtained under the same conditions as in Production Example 1, except that the modified extrusion die of the extruder was changed to a normal circular section die having no hollow part. It was confirmed that the porosity was 5% and there were almost no continuous voids from the measured value of ventilation resistance.
The evaluation results of the resin particles and the resin molded body are shown in Table 1.

[Method 8 for producing molded resin (B-2)]
The polyamide resin particles obtained in Production Example 7 were put into a 10 ° C. pressure cooker, and 4 MPa of carbon dioxide gas was blown in and absorbed for 3 hours. Next, the carbon dioxide impregnated mini-pellets were transferred to a foaming apparatus, and air at 240 ° C. was blown for 20 seconds to obtain an aggregate of polyamide resin expanded particles. The average particle diameter of the polyamide resin expanded particles contained in the aggregate of the obtained polyamide resin expanded particles was 2.0 mm. When the polyamide resin foam particles were cut and observed, a large number of closed cells were uniformly formed on the entire cut surface of the polyamide resin foam particles. ρ ₀ / ρ ₁ was 3.60. The cross section of the polyamide resin expanded particles had a substantially cylindrical shape with no recess.
The obtained polyamide resin expanded particles were again put in a pressure kettle, and 4 MPa carbon dioxide gas was absorbed at 10 ° C. for 3 hours. Next, using the in-mold foam molding apparatus used in Production Example 1 for the polyamide resin foam particles impregnated with carbon dioxide gas, the mold had a cavity of 1 m × 1 m × thickness and the hydraulic cylinder of the piece was removed, and the piece was inserted when the cavity thickness was 20 mm. Using a fixed mold, polyamide resin foam particles are filled into the mold, air at 230 ° C. is blown for 30 seconds, and the polyamide resin foam particles are fused to each other. Resin molding B-2 was obtained. The porosity of the resin molded body was 4%. In order to confirm the foaming ratio of the resin molded body, the specific gravity of the volume and weight of the resin molded body and the specific gravity of the polyamide resin are compared, and it can be confirmed that this resin molded body is 3 times foamed. As a result of observation, an aggregate of expanded polyamide resin particles having a large number of closed cells having a cell diameter of 200 to 400 μm was formed. From the measured value of the airflow resistance, it was confirmed that there were no voids.
The evaluation results of the polyamide resin particles and the resin molded body are shown in Table 1.

[Production Example 1 (F-1) of Fiber Assembly]
As the nonwoven fabric A, 43 parts by mass of polypropylene meltblown fibers having an average fiber diameter of 3 μm and 57 parts by mass of polypropylene meltblown fibers having an average fiber diameter of 20 μm are spun to create a mixed yarn of both fibers by interlacing. Then, after stacking in a web form on the conveyor net, 43 parts by mass of low melting point polypropylene as a binder is mixed and conveyed with respect to 100 parts by mass of the fiber, and crimped with a thermocompression-bonding roll at 110 ° C., unit area A nonwoven fabric having a weight per unit of 100 g / m ² and a number average average fiber diameter of 3.8 μm was obtained. One nonwoven fabric A was used to form a fiber assembly. The evaluation results of the fiber assembly are shown in Table 2.

[Production Example 2 of fiber assembly (F-2)]
As the nonwoven fabric A, a polypropylene meltblown nonwoven fabric having an average fiber diameter of 3 μm and a weight per unit area of 100 g / m ² is used. On the nonwoven fabric B, an average fiber diameter of 14 μm, a fiber length of 51 mm, and a crimp number of 12 pieces / inch are used. A non-woven fabric made of polyethylene terephthalate having a weight per unit area of 250 g / m ² made of short fibers was stacked and subjected to needle punch lamination to prepare a fiber assembly. The evaluation results of the fiber assembly are shown in Table 2.

[Production Example 3 of Fiber Assembly (F-3)]
The nonwoven fabric B has an average fiber diameter of 17.6 μm, a weight per unit area of 36 g / m ² , and a spunbond nonwoven fabric made of polyethylene terephthalate as a raw material. In addition, a melt-blown nonwoven fabric made of polypropylene resin having a weight per unit area of 16 g / m ² is collected, and an average fiber diameter is 17.6 μm and a basis weight is 36 g / m ² as a nonwoven fabric B ′ thereon. A spunbonded nonwoven fabric made from polyethylene terephthalate was collected and a three-layer fiber assembly integrated by self-bonding was obtained. The evaluation results of the fiber assembly are shown in Table 2.

[Production Example 4 of fiber assembly (F-4)]
Non-woven fabric B is a block copolymer polyester elastomer whose sheath component has hard and soft segments (Toyobo Co., Ltd., Perprene P40B, melting point 180 ° C.), and whose core component is polytrimethylene terephthalate (melting point 223 ° C.) A composite fiber spunbonded nonwoven fabric having an average fiber diameter of 12 μm (weight per unit area is 60 g / m ² ) and nonwoven fabric A are made of Perprene P40B having an average fiber diameter of 2.5 μm and a weight per unit area of 50 g / m ² As a melt blown nonwoven fabric and nonwoven fabric B ′, 30 fusion-bonded fibers having an average fiber diameter of 14 μm, a fiber length of 51 mm, a weight of 200 g / m ² and a thickness of 10 mm consisting of short fibers of 12 crimps / inch are used. Thermally bonded short fiber nonwoven fabric made of polyethylene terephthalate containing mass percent 'Superimposed in this order, a nonwoven fabric B' nonwoven B / nonwoven A / nonwoven B from using 40 fastest needle from side, Togeana density 50 lines / cm ^2, the thickness was performed needle punching lamination processing needle depth 10mm After adjusting the thickness to 2.0 mm, the fibers were integrated by thermal bonding at a temperature 30 ° C. higher than the melting point of the heat-fusible fiber to obtain a fiber assembly. The evaluation results of the fiber assembly are shown in Table 2.

[Production Example 5 (F-5) of fiber assembly]
-Production of nonwoven fabric A-
Polyamide 6 (40 mass%) having a melt viscosity of 212 Pa · s (262 ° C., shear rate of 121.6 sec ⁻¹ ) and a melting point of 220 ° C., a weight average molecular weight of 120,000, a melt viscosity of 30 Pa · s (240 ° C., shear rate of 2432 sec ^{− 1} ) Poly L-lactic acid (60% by mass) having a melting point of 170 ° C. and an optical purity of 99.5% or more is weighed separately, and separately biaxial extrusion kneader (screw shape: in-direction fully meshed double thread screw) : Diameter 37 mm, effective length 1670 mm, L / D = 45.1, kneading part length is 28% of screw effectiveness, kneading part is located on the discharge side from 1/3 of screw effective length, and three backs on the way The polymer alloy chip was obtained by kneading at 220 ° C.
The obtained polymer alloy chip is supplied to a uniaxial extrusion-type melting apparatus for a staple spinning machine, and melt spinning is performed at a melting temperature of 235 ° C., a spinning temperature of 235 ° C. (a base surface temperature of 220 ° C.), and a spinning speed of 1200 m / min. A polymer alloy fiber was obtained. After the yarns were combined, steam drawing was performed to obtain a tow made of a polymer alloy fiber having a single yarn fineness of 3.6 dtex. The tow made of the polymer alloy fiber was crimped (crimp number = 12 / inch) and then cut into 51 mm short fibers. The average fiber diameter was 0.2 μm. The obtained short fibers were opened with a card and then made into a web with a cross wrap weber. This web was needle punched at a punch density of 80 / cm ² to obtain a nonwoven fabric A having a weight per unit area of 30 g / m ² and a thickness of 0.3 mm.
-Production of nonwoven fabric B-
A stable fiber made of polyamide 6 having an average fiber diameter of 20 μm and a fiber length of 51 mm was opened with a card and then made into a web with a cross-wrap weber. This web was needle punched at a punch density of 80 / cm ² to obtain a nonwoven fabric B having a basis weight of 60 g / m ² and a thickness of 0.4 mm.
-Manufacture of fiber assembly-
Each of the two types of nonwoven fabrics obtained above is laminated one by one, and needle punching is performed at a punch density of 40 / cm ² , and the weight per unit area is 90 g / m ² and the thickness is 0.5 mm. C was obtained. By treating the non-woven fabric C with a 1% sodium hydroxide aqueous solution at a temperature of 95 ° C. and a bath ratio of 1:40, 60% by mass of polylactic acid in the non-woven fabric A is seamed, and polyamide 6 nanofibers are obtained. A fiber assembly having a weight per unit area of 72 g / m ² and a thickness of 0.4 mm made of polyamide 6 yarn was obtained. The evaluation results of the fiber assembly are shown in Table 2.

[Examples 1 to 12]
As shown in Table 3, the fiber aggregate described in Table 2 is used as the face material (I), and the resin molded body described in Table 1 is used as the base material (II), so that the fiber aggregate and the resin molded body overlap. Was fixed to the periphery only with a tacker to obtain a laminate. The size of the laminate is the size described in the above test method. The sound absorption characteristics using the face material (I) side of the laminate as a sound source, the thermal energy loss and the self-supporting property (flexibility) using the face material (I) side as the high temperature side were evaluated. The evaluation results are shown in Table 3.
In addition, the stacking order (direction) of the fiber aggregates was a state in which the fiber aggregates were overlapped in the same order (direction) without changing the vertical direction at the time of manufacture. For example, the face material (I) of Example 4 is obtained by superimposing the fiber aggregates so that the nonwoven fabrics are in the order of ABAB from the bottom.

  Also, a sample of only the resin moldings A-1, A-2, a sample in which two fiber assemblies F-2 are laminated, a sample in which eight fiber assemblies F-3 are laminated, and a fiber in the resin molding A-1. Example 2 in which eight aggregates F-3 were laminated, Example 4 in which two fiber aggregates F-2 were laminated on the resin molded body A-2, and fiber aggregates F-3 on the resin molded body A-2 FIG. 4 shows a graph of the frequency and normal incidence sound absorption coefficient of Example 5 in which 8 sheets are stacked. Thus, only the resin foams A-1 and A-2 showed a sound absorption peak at 1500 to 2000 Hz, a sample in which two fiber assemblies F-2 were stacked, and eight fiber assemblies F-3 were stacked. In the sample, the sound absorption performance increases as the frequency increases, and the sound absorption performance at 1000 Hz is low. In Examples 2, 4, and 5, sound absorption is achieved by laminating each fiber assembly on each resin molded body. The peak shifted to 1000-1500 Hz, and the sound absorption rate at 1000 Hz was 0.3 or more.

[Comparative Examples 1 and 2]
In the same manner as in Examples, as shown in Table 3, the fiber aggregate described in Table 2 was used as the face material (I), and the resin molded body described in Table 1 was used as the base material (II). The resin molded body was set so as to overlap, and only the periphery was fixed with a tacker to obtain a laminate. The sound absorption characteristics, thermal energy loss, and self-supporting property (flexibility) of the laminate were evaluated in the same manner as in the examples. The evaluation results are shown in Table 3.

Each of Examples 1 to 12 was excellent in sound absorption characteristics and exhibited a high sound absorption performance with a sound absorption rate at 1,000 Hz of 0.30 or more. Moreover, in the thermal energy loss showing heat insulation performance, all showed the high heat insulation performance of less than 200 W / m < ² > * hr.
On the other hand, in Comparative Example 1, the resin particles are not particles having a concave outer shape portion (foamed particles having a concave shape portion in the outer shape viewed from at least one direction), resulting in few communication voids. The sound absorption performance and the sound absorption rate of 1,000 Hz of the obtained laminate were less than 0.3, which was a bad result. Also, the heat insulation performance was not good as compared with the examples. In Comparative Example 2, since a resin molded body using expanded particles having a concave outer shape portion was used as the resin molded body, the sound absorption coefficient and the heat insulating performance were good results, but the strength was insufficient.

The laminate including the base material and the face material according to the present embodiment is a laminate having high sound absorption performance that has high sound absorption performance even when thin, and also has high heat insulation performance.
Examples of the use of the laminate of the present embodiment include members used for driving noise reduction of automobiles, trains, trains, and other vehicles and aircrafts that are required to be lightweight and quiet, and particularly self-supporting and heat-resistant deformation. It can be particularly preferably used for an engine cover, an engine capsule, an engine room hood, a transmission casing, a sound absorbing cover, a casing for an electric vehicle motor, a sound absorbing cover, and the like in an automobile engine room that requires performance and heat insulation.
Furthermore, the laminate of the present embodiment has various air conditioners such as an air conditioner that is required to be quiet, a refrigerator, a heat pump, etc., a part that forms an air passage such as a duct, a washing machine, a dryer, a refrigerator, and a vacuum cleaner. It can also be used suitably for household electrical appliances, printers, copiers, office automation equipment such as FAX machines, and other building materials such as other wall material cores and flooring cores.

Claims (9)

A laminate including a face material (I) including a fiber assembly and a base material (II) including a resin molded body having a communication gap,
The fiber assembly includes a non-woven fabric A containing ultrafine fibers having an average fiber diameter of 6 μm or less and having a weight per unit area of 10 to 1500 g / m ² .
The resin molded body is a solid resin particle containing a resin, including a resin particle having a concave outer shape portion, the molded resin body fused to each other, and between the fused resin particles Having continuous voids, porosity of 15-80%,
A laminate having a thickness of 5.0 to 80 mm. The face material (I) is a fiber assembly in which the nonwoven fabric A and at least one nonwoven fabric B each having an average fiber diameter of 7 to 40 μm and a weight per unit area of 30 to 2000 g / m ² are laminated. The laminated body according to claim 1, wherein the body is laminated by 1 to 15 sheets.
The laminate according to claim 1.   The laminated body of Claim 1 or 2 whose average particle diameter of the said resin particle is 1.0-4.0 mm.   The laminate according to any one of claims 1 to 3, wherein the resin molded body contains a thermoplastic resin having a surface tension at 20 ° C of 37 to 60 mN / m. The laminate according to any one of claims 1 to 4, wherein the fiber aggregate has an air permeability of 0.1 to 25 cc / (cm ² · sec).   The laminated body as described in any one of Claims 1-5 whose thickness of the said face material (I) is 0.1-6.0 mm.   The said nonwoven fabric B consists of a short fiber, The laminated body as described in any one of Claims 1-6 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 7, which is a self-supporting soundproof material.   A sound-absorbing material comprising the laminate according to any one of claims 1 to 8.

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