JP2018171820A - Functional laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional laminate having improved sound absorbency, heat insulation performance and vibration-damping performance.SOLUTION: In a functional laminate 10, between a porous surface layer 1 and a resin foam layer 2, a porous intermediate layer 3 with air permeability is laminated. The porous intermediate layer 3 has non-affinity with a foamable resin constituting the resin foam layer 2.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a functional laminate and a method for producing the same.

  2. Description of the Related Art In recent years, many attempts have been made to absorb sound generated by an engine such as a vehicle (for example, an automobile, a truck, a bus, and a train) and an agricultural machine (for example, a mower and a tiller).

  In particular, in the field of automobiles, from the viewpoint of passenger comfort, attempts have been made to absorb engine noise by covering a powertrain member including an engine and a transmission with a sound absorbing material. As the cover material, for example, urethane foam and fiber nonwoven fabric are used alone.

  On the other hand, as an integrated foamed product such as a headrest, seat seat, seat back, and armrest, an integral foam consisting of a latex foam thin layer applied directly to the inner surface of the fabric and a body foam that is directly injected into the inner surface and foamed and cured A product has been reported (Patent Document 1). In such an integrally foamed product, the latex foam thin layer is mechanically bonded so as to embrace the fibers on the inner surface of the fabric in a region close to the fabric to form a bonded region, and the main body foam stock solution is substantially prevented from entering outside. It forms a breathable skin that prevents it.

  In addition, as a foam molded body such as a chair and a cushion, a foam molded body in which a sheet material is integrated on the outer surface of a foam molded body is reported (Patent Document 2). In such a foamed molded article, the sheet material is composed of a laminate of a stretched porous film and a non-woven fabric, and has a property of allowing gas to permeate but not liquid.

International Publication No. 93/03904 JP 2011-148204 A

  The inventor of the present invention has found a new problem that sound absorption is not sufficiently obtained when the technology related to the foamed product or the foamed molded body is applied to, for example, a cover material for a powertrain member.

  Therefore, the inventors of the present invention have found that even if foam molding is performed in a mold, for example, in the presence of a glass fiber nonwoven fabric, sufficient sound absorption is not obtained.

  An object of this invention is to provide the functional laminated body which is excellent by sound-absorbing property.

  Another object of the present invention is to provide a functional laminate that is superior not only in sound absorption but also in heat insulation.

The present invention
Between the porous surface layer and the resin foam layer, a porous intermediate layer having air permeability is laminated,
The said porous intermediate | middle layer is related with the functional laminated body which has non-affinity with respect to the foamable resin which comprises the said resin foam layer.

The functional laminate of the present invention is superior in sound absorption.
The functional laminate of the present invention is also superior in heat insulation.
The functional laminate of the present invention is also superior in vibration damping properties.

The typical sectional view of the functional layered product of the present invention is shown. The shaping | molding die for demonstrating the foam preparation stage of the foam molding process in the manufacturing method of the functional laminated body of this invention, and typical sectional drawing of the inside are shown. The shaping | molding die for demonstrating the foaming step of the foaming molding process in the manufacturing method of the functional laminated body of this invention, and typical sectional drawing of the inside are shown.

[Functional laminate]
The functional laminate of the present invention relates to a laminate having at least sound absorbing properties, and the functionality includes at least one of the properties of sound absorbing properties, heat insulating properties, vibration damping properties, and the like.

  As shown in FIG. 1, the functional laminate 10 of the present invention has a specific porous intermediate layer 3 laminated between a porous surface layer 1 and a resin foam layer 2. The resin foam layer 2 and the porous intermediate layer 3 are bonded and integrated with each other. Since the specific porous intermediate layer 3 has non-affinity for the foamable resin (liquid raw material) constituting the resin foam layer 2 as described later, the resin foam layer 2 is formed due to the non-affinity. Before foaming of the foaming resin (liquid raw material) which comprises, the movement of the said foaming resin to a porous surface layer is inhibited. Specifically, the porous intermediate layer 3 tends to dam the foamable resin before foaming due to the non-affinity, and as a result, it is easy to hold the foamable resin. For this reason, when foaming starts, the foamable resin held in the porous intermediate layer 3 foams while infiltrating into the porous surface layer 1. As a result, the amount of impregnation of the foamable resin into the porous surface layer 1 is moderately reduced, and the foamable resin is sufficiently foamed, so that sound absorption, heat insulation and vibration damping (especially sound absorption) ) Is considered to be sufficiently improved. When the porous intermediate layer is not laminated, excessive movement of the foamable resin to the porous surface layer 1 occurs before foaming, and the foamable resin moves to the porous surface layer in an excessive amount at the time of foaming (impregnation). Therefore, the foamable resin does not foam sufficiently in the porous surface layer. As a result, it is considered that the sound absorbing property, the heat insulating property and the vibration damping property are lowered. FIG. 1 shows a schematic cross-sectional view of the functional laminate of the present invention.

  The foamable resin constituting the resin foam layer 2 is a foamable resin (liquid raw material) used as a raw material for the resin foam layer 2. For example, when the resin foam layer 2 is a polyurethane foam layer, the foamable resin is a mixture of a polyol compound and an isocyanate compound. The foamable resin may contain additives such as a foaming agent and a foam stabilizer.

(Porous intermediate layer)
The porous intermediate layer 3 has air permeability. “Breathability” possessed by the porous intermediate layer 3 is a characteristic that can be rephrased as “liquid permeability”, that is, the porous intermediate layer 3 forms a foamable resin (liquid) inside itself during the production of the functional laminate. It is a characteristic that can be passed through moderately. Since the porous intermediate layer 3 has such air permeability, integration of the porous surface layer 1, the resin foam layer 2, and the porous intermediate layer 3 is achieved. Specifically, the air permeability of the porous intermediate layer 3 is such that the mixed layer portion 11 described later can be formed.

  The porous intermediate layer 3 has non-affinity (hereinafter sometimes simply referred to as “non-affinity”) for the foamable resin constituting the resin foam layer 2. That the porous intermediate layer 3 has the non-affinity means that the surface of the voids of the porous intermediate layer 3 is not easily adapted to the foamable resin or difficult to wet. That is, the contact angle θm of the porous intermediate layer 3 with respect to the foamable resin (hereinafter sometimes simply referred to as “contact angle θm”) is usually 5 ° or more, which inhibits the movement of the foamable resin in the porous intermediate layer. From the viewpoint of easiness and further improvement of sound absorption, heat insulation and vibration damping properties of the functional laminate, it is preferably 10 ° or more, more preferably 10 to 90 °, still more preferably 10 to 50 °, most preferably 11 to 50 °. Since the porous intermediate layer 3 has such non-affinity, the porous intermediate layer 3 tends to inhibit the movement of the foamable resin. For example, the higher the non-affinity of the porous intermediate layer 3 is, the larger the contact angle θm of the porous intermediate layer 3 is. For example, the lower the non-affinity of the porous intermediate layer 3 is, the smaller the contact angle θm of the porous intermediate layer 3 is.

  The contact angle θm of the porous intermediate layer 3 with respect to the expandable resin is a contact angle of the expandable resin on a plane having a surface having the same composition as that of the material constituting the porous intermediate layer.

  The non-affinity of the porous intermediate layer 3 is selected from the viewpoints of easy inhibition of foaming resin movement in the porous intermediate layer and further improvement in sound absorption, heat insulation and vibration damping of the functional laminate. It is preferably higher than the non-affinity of the surface layer 1. That the non-affinity of the porous intermediate layer 3 is higher than the non-affinity of the porous surface layer 1 is that the contact angle θm of the porous intermediate layer 3 to the foamable resin is relative to the foamable resin of the porous surface layer 1. It means that it is larger than the contact angle θs (hereinafter, simply referred to as “contact angle θs”). The contact angle θm (°) of the porous intermediate layer 3 with respect to the foamable resin and the contact angle θs (°) of the porous surface layer 1 with respect to the foamable resin are easy to inhibit the movement of the foamable resin in the porous intermediate layer. From the viewpoint of further improving the sound absorption, heat insulation and vibration damping properties of the functional laminate, it is preferable to satisfy the following relational expression (p1), more preferably to satisfy the following relational expression (p2), It is more preferable to satisfy the following relational expression (p3), and it is most preferable to satisfy the following relational expression (p4).

1 ° ≦ θm−θs (p1)
5 ° ≦ θm−θs ≦ 80 ° (p2)
5 ° ≦ θm−θs ≦ 40 ° (p3)
10 ° ≦ θm−θs ≦ 40 ° (p4)

  The contact angles (θm and θs) of the porous intermediate layer and the porous surface layer with respect to the foamable resin are represented by values measured by the following method. Using a contact angle measuring device G-1.2MG manufactured by Elma Optical Co., Ltd., PGM (propylene glycol monomethyl ether) is dropped onto the test piece, and the contact angle after 30 seconds is measured. As the test piece, a flat plate having a surface having the same composition as the material constituting the porous intermediate layer or the porous surface layer is used.

  The material constituting the porous intermediate layer is not particularly limited as long as it has air permeability and non-affinity as described above, and may be, for example, a fiber nonwoven fabric or a polymer foam. It may be. Hereinafter, specific examples of the nonwoven fabric and the polymer foam having inherently non-affinity without any treatment will be exemplified. When using a porous intermediate layer made of a material that does not inherently have non-affinity, non-affinity treatment is applied to the porous intermediate layer to provide non-affinity. What is necessary is just to use what was made as a porous intermediate | middle layer. In the following, θ shown with a specific example is a contact angle that a predetermined material originally shows without any treatment, and is a contact angle with respect to the foamable resin measured by the method described above. Examples of the non-affinity treatment include treatment using a solution of a fluorine atom-containing resin (for example, a fluorine atom-containing polymer) or a silicone group-containing resin.

  Specific examples of the non-affinity porous intermediate layer nonwoven fabric include polyolefin fibers such as polypropylene (PP) fiber (θ = 20 °), fluorine-containing resin fibers such as PTFE, and silicone-containing resin fibers. One or more organic fiber nonwoven fabrics selected from the group consisting of: The fiber nonwoven fabric of the porous intermediate layer may also be a nonwoven fabric of mixed fibers of organic fibers and inorganic fibers. Examples of the fiber nonwoven fabric of the porous intermediate layer that can be used after non-affinity treatment include the organic fiber and / or inorganic fiber nonwoven fabric described below as an example of the fiber nonwoven fabric of the porous surface layer.

  As the polymer foam of the porous intermediate layer having inherently non-affinity, those having an open cell structure are used. Specific examples of such polymer foams include, for example, a polyolefin foam layer such as a polypropylene foam layer (θ = 20 °); a fluorine-containing resin foam layer (θ = 30 °); a silicone resin foam layer (θ = 30 °). A polymer foam layer selected from the group consisting of: Examples of the polymer foam of the porous intermediate layer that can be used after the non-affinity treatment include the polymer foam described below exemplified as the polymer foam of the porous surface layer.

  The porous intermediate layer is preferably a fiber non-woven fabric, more preferably a non-woven fabric of polyolefin fiber, particularly polypropylene fiber, from the viewpoint of further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate.

  The porous intermediate layer 3 only needs to have the above-mentioned non-affinity at least on the porous surface layer side, but preferably has the above-mentioned non-affinity as a whole.

  The average porosity Rm (%) of the porous intermediate layer and the average porosity Rs (%) of the porous surface layer are as follows from the viewpoint of further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate. The relational expression (x1) is preferably satisfied, the following relational expression (x2) is more preferably satisfied, the following relational expression (x3) is more preferably satisfied, and the following relational expression (x4) is satisfied. Further preferred. When Rm and Rs satisfy the following relational expression, a capillary phenomenon is likely to occur in the porous intermediate layer, and the porous intermediate layer can more easily hold the foamable resin before foaming. For this reason, when foaming starts, the foamable resin held in the porous intermediate layer 3 is further sufficiently foamed while infiltrating into the porous surface layer 1. As a result, it is considered that the sound absorbing property, the heat insulating property, and the vibration damping property (especially the sound absorbing property) are further improved sufficiently. The capillary phenomenon is a physical phenomenon related to the behavior of the foamable resin (liquid) in the voids of the porous intermediate layer 3 and the porous surface layer 1.

1.01 ≦ Rs / Rm (x1)
1.05 ≦ Rs / Rm ≦ 2.0 (x2)
1.10 ≦ Rs / Rm ≦ 1.5 (x3)
1.15 ≦ Rs / Rm ≦ 1.3 (x4)

  The average porosity Rm of the porous intermediate layer is usually from 60 to 95%, the ease of inhibiting the movement of the foamable resin in the porous intermediate layer, and the sound absorbing property, heat insulating property and vibration damping property of the functional laminate. From the viewpoint of further improvement, the content is preferably 65 to 90%.

The average porosity of the porous intermediate layer is the volume ratio of voids formed between fibers when the porous intermediate layer is a fiber nonwoven fabric, that is, the volume ratio of voids between fibers. Expressed as a percentage. The nonwoven fabric of the porous intermediate layer impregnated with the foamable resin is cut out from the functional laminate, and the foamable resin is formed with an organic solvent that dissolves only the foamable resin among the fibers and the foamable resin constituting the nonwoven fabric. Is dissolved to obtain a fiber nonwoven fabric alone. The volume ratio of voids in this fiber nonwoven fabric is calculated, and this value is converted to the volume ratio of voids when the thickness of the fiber nonwoven fabric is the thickness of a porous intermediate layer described later in the functional laminate. The volume ratio of the voids can be calculated from physical properties such as the volume and weight of the fiber nonwoven fabric and the specific gravity of the fiber material. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). Moreover, it can calculate from the volume of the said fiber nonwoven fabric, and the void volume of the said fiber nonwoven fabric measured by methods, such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, a gas adsorption method.
In addition, as a method for measuring the volume ratio of the gap between fibers, the nonwoven fabric of the porous intermediate layer impregnated with the foamable resin is cut out from the functional laminate, and the volume of the nonwoven fabric, the computer tomography method, the liquid After obtaining the void volume of the nonwoven fabric measured by a method such as immersion, water evaporation, suspension method, mercury intrusion method, gas adsorption method, etc., only the fiber material among the fibers and foamable resins constituting the nonwoven fabric The fiber material is dissolved with a solvent that dissolves the resin to obtain a foamable resin alone. The void volume in the foamable resin is measured by the same method as described above, and the void volume of the fiber nonwoven fabric is calculated from the volume of the nonwoven fabric-the void volume of the foamable resin + the void volume of the nonwoven fabric. The volume ratio of the voids in the fiber nonwoven fabric can be calculated from the volume.

  The average porosity of the porous intermediate layer is the volume ratio of bubbles in the polymer inherently possessed by the polymer foam as the porous intermediate layer when the porous intermediate layer is a polymer foam. Expressed as a percentage measured by the method. From the functional laminate, the polymer foam of the porous intermediate layer impregnated with the foamable resin is cut out, and the foamed resin is not foamed in the optical and electron micrographs of the vertical cross section of the sample. The ratio of the area of the bubble to the total area is measured at an arbitrary 100 locations, and the average value is obtained. The area of the bubble is the area of the bubble inherently possessed by the polymer foam as the porous intermediate layer, and the bubble and the bubble due to foaming of the foaming resin are easily affected by the difference in brightness around the bubble. Can be distinguished. In this specification, the parallel cross section when taking an optical microscope or an electron micrograph is a cross section parallel to the outer surface 12, and the vertical cross section is perpendicular to the outer surface 12 of the porous surface layer. It is a cross section.

  The average porosity of the porous intermediate layer uses the value measured from the functional laminate as described above, but even if measured from the material used for manufacturing (foam molding), the equivalent measured value is can get. That is, it can be calculated from physical properties such as the volume and weight of the porous intermediate layer material used for production (foam molding) and the specific gravity of the fiber or polymer of the porous intermediate layer material. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). Further, the volume of the porous interlayer material and the void volume of the porous interlayer material measured by a method such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, a gas adsorption method, etc. Can be calculated. Moreover, in the optical microscope and electron micrograph of the vertical cross section of the said porous intermediate | middle layer material, it can calculate by measuring the ratio of the area of the bubble with respect to the total area in arbitrary 100 places, and calculating | requiring an average value.

  The thickness of the porous intermediate layer is usually 0.1 to 2 mm, and the ease of inhibiting the movement of the foamable resin in the porous intermediate layer and the sound absorbing property, heat insulating property and vibration damping property of the functional laminate are further increased. From a viewpoint of improvement, Preferably it is 0.1-1 mm, Preferably it is 0.2-1 mm.

  The thickness of the porous intermediate layer is such that the interface 32 with the porous surface layer 1 in the porous intermediate layer 3 is a case where the porous intermediate layer is a fiber nonwoven fabric or a polymer foam. To the interface 33 with the resin foam layer 2 and is represented by the thickness measured by the following method. In the optical micrograph of the vertical cross section of the functional laminate, the thickness is measured at an arbitrary 100 points to obtain the average value).

  As for the thickness of the porous intermediate layer, the value measured from the functional laminate as described above is used, but an equivalent measurement value can be obtained even when measured from the material used for production (foam molding). . That is, in the optical micrograph of the vertical cross section of the porous intermediate layer material used for production (foam molding), the thickness is measured at 100 arbitrary positions, and the average value is obtained. Moreover, the thickness of the said porous intermediate | middle layer material is measured with gauges, such as a film thickness meter, a displacement meter, a caliper, and an average value is calculated | required.

  When the porous intermediate layer is a fiber nonwoven fabric, the average fiber diameter and the average fiber length of the fibers constituting the fiber nonwoven fabric are not particularly limited as long as the movement of the foamable resin is inhibited. Average fiber diameter is usually 0.005 to 50 μm, and it is easy to inhibit the movement of the foamable resin in the porous intermediate layer, and the viewpoint of further improving the sound absorption, heat insulation and vibration damping properties of the functional laminate Therefore, it is preferably 0.1 to 20 μm. The average fiber length is usually equal to or greater than the thickness of the porous intermediate layer material, facilitates inhibition of foaming resin movement in the porous intermediate layer, and further enhances sound absorption, heat insulation and vibration damping of the functional laminate. From the viewpoint of improvement, it is preferably 20 mm or more.

  The average fiber diameter of the fiber in the fiber nonwoven fabric of the porous intermediate layer is represented by an average diameter measured by the following method. From the functional laminate, cut out the nonwoven fabric of the porous intermediate layer impregnated with the foamable resin, measure the diameter of any 100 fibers in the optical microscope or electron micrograph of the vertical cross section of the sample, and average Find the value.

  The average fiber length of the fibers in the fiber nonwoven fabric of the porous intermediate layer is represented by an average value measured by the following method. The non-woven fabric of the porous intermediate layer impregnated with the expandable resin is cut out from the functional laminate, and the expandable resin is formed with an organic solvent that dissolves only the expandable resin out of the fibers and the expandable resin constituting the non-woven fabric. Dissolve. The length of arbitrary 100 fibers is measured from the nonwoven fabric in which the foamable resin is dissolved, and the average value is obtained. Moreover, the inside of the nonwoven fabric is three-dimensionally imaged by a method such as CT, and the length of an arbitrary 100 fibers is measured to obtain an average value.

  The average fiber diameter and average fiber length of the fibers of the fiber nonwoven fabric use the values measured from the functional laminate as described above, but they are equivalent even if measured from the material used for manufacturing (foam molding) Is obtained. In other words, the average fiber diameter of the fibers of the fiber nonwoven fabric used for production (foam molding) is determined by measuring the diameter of any 100 fibers in an optical microscope or electron micrograph of a vertical cross section of the nonwoven fabric, and calculating the average value. Ask. The average fiber length of the fibers of the fiber nonwoven fabric used for production (foam molding) is obtained by measuring the length of any 100 fibers and determining the average value. Moreover, the inside of the nonwoven fabric is three-dimensionally imaged by a method such as CT, and the length of an arbitrary 100 fibers is measured to obtain an average value.

When the porous intermediate layer is a fiber nonwoven fabric in particular, the basis weight of the fiber nonwoven fabric is not particularly limited as long as the porous intermediate layer inhibits the movement of the foamable resin, and is usually 5 to 500 g / m ² and porous. From the viewpoint of easily inhibiting the movement of the foamable resin in the quality intermediate layer and further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate, it is preferably 10 to 300 g / m ² .

  The basis weight in the fiber nonwoven fabric of the porous intermediate layer is represented by a value measured by the following method. The nonwoven fabric of the porous intermediate layer impregnated with the foamable resin is cut out from the functional laminate, and the foamable resin is formed with an organic solvent that dissolves only the foamable resin among the fibers and the foamable resin constituting the nonwoven fabric. Is dissolved to obtain a fiber nonwoven fabric alone. The basis weight can be calculated from the area and weight of the nonwoven fabric. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). As another measurement method, the nonwoven fabric of the porous intermediate layer impregnated with the foamable resin is cut out from the functional laminate, and only the fiber material is dissolved out of the fibers and the foamable resin constituting the nonwoven fabric. The fiber material is dissolved with a solvent to obtain a solution of the fiber material. After evaporating the liquid content of the fiber material solution, the weight of the fiber material in the solid content is calculated from the weight of the solid content after evaporation, and the basis weight can be calculated from the area of the nonwoven fabric and the weight of the fiber material.

  As the basis weight of the fiber nonwoven fabric, the value measured from the functional laminate as described above is used. However, even when measured from the material used for production (foam molding), an equivalent measurement value is obtained. That is, the basis weight can be calculated from the area and weight of the fiber nonwoven fabric used for production (foam molding). In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler).

(Porous surface layer)
The material which comprises the porous surface layer 1 is not specifically limited as long as it has porosity, For example, a fiber nonwoven fabric may be sufficient, or a polymer foam may be sufficient.

  Although the porous surface layer 1 may have non-affinity with respect to a foamable resin, it does not need to have it. The porous surface layer 1 preferably has no affinity for the foamable resin rather than the porous intermediate layer from the viewpoint of further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate. . The porous surface layer 1 has less incompatibility than the porous intermediate layer. The contact angle θs with respect to the expandable resin that the porous surface layer 1 has is a foamable resin that the porous intermediate layer has. This means that the contact angle is smaller than θm. From the same viewpoint, the porous surface layer 1 preferably has the above-mentioned “θm−θs” relationship with respect to the porous intermediate layer.

  The contact angle θs with respect to the foamable resin of the porous surface layer 1 is usually 1 ° or more, the ease of inhibiting the movement of the foamable resin in the porous intermediate layer, and the sound absorption, heat insulation and From the viewpoint of further improving the vibration damping properties, it is preferably 1 to 89 °, particularly preferably 1 to 80 °, more preferably 1 to 40 °, still more preferably 1 to 30 °, and most preferably 1 to 20 °. It is. The contact angle θs with respect to the foamable resin of the porous surface layer 1 is a contact angle of the foamable resin on a plane having a surface having the same composition as that of the material constituting the porous surface layer.

  Specific examples of the fiber nonwoven fabric and the polymer foam as materials constituting the porous surface layer 1 are illustrated. When a porous surface layer made of a material that does not inherently have a contact angle θs as described above is used, the porous surface layer is subjected to a surface treatment that increases or decreases the contact angle before and after the treatment. Those having a controlled contact angle may be used as the porous intermediate layer. In the following, θ shown with a specific example is a contact angle that a predetermined material originally shows without any treatment, and is a contact angle with respect to the foamable resin measured by the method described above. Examples of the surface treatment include non-affinity treatment that increases the contact angle by applying a solution of a fluorine atom-containing resin (for example, a fluorine atom-containing polymer) or a silicone group-containing resin.

  As specific examples of the fiber nonwoven fabric of the porous surface layer, for example, from a group consisting of polyolefin fibers such as polypropylene (PP) fibers (θ = 20 °); polyester fibers such as polyethylene terephthalate (PET) fibers (θ = 4 °) Non-woven fabrics of one or more organic fibers selected can be mentioned. The fiber nonwoven fabric of the porous surface layer is also made of one or more inorganic fibers selected from the group consisting of glass fibers (θ = 12 °), silica fibers (θ = 15 °), and alumina fibers (θ = 4 °). It may be a non-woven fabric. It may be a nonwoven fabric of mixed fibers of organic fibers and inorganic fibers. )

  As the polymer foam of the porous surface layer, one having an open cell structure or a closed cell structure is used. Specific examples of such polymer foams include, for example, polyolefin foam layers such as polypropylene foam layers (θ = 20 °); polyurethane foam layers (θ = 4 °); polyesters such as PET foam layers (θ = 4 °) Examples include polymer foam layers selected from the group consisting of foam layers. )

  The porous surface layer is preferably a fiber non-woven fabric, more preferably a non-woven fabric of inorganic fiber or organic fiber, more preferably glass, from the viewpoint of further improving the sound absorption, heat insulation and vibration damping properties of the functional laminate. It is a nonwoven fabric of fiber or polyester fiber (especially PET fiber).

  The average porosity Rs of the porous surface layer is usually from 80 to 99.5%, and it is easy to inhibit the movement of the foamable resin in the porous intermediate layer, and the sound absorption, heat insulation and control of the functional laminate. From the viewpoint of further improving the vibration, it is preferably 90 to 99%.

  The average porosity of the porous surface layer is the volume ratio of the voids formed between the fibers when the porous surface layer is a fiber nonwoven fabric, that is, the volume ratio of the voids between the fibers. Expressed as a percentage. The said nonwoven fabric of the porous surface layer part which is not impregnated with foamable resin is cut out from a functional laminated body. The volume ratio of the voids in the fiber nonwoven fabric is calculated, and this value is converted to the volume ratio of the voids when the thickness is the thickness of the porous surface layer described later in the functional laminate. The volume ratio of the voids can be calculated from physical properties such as the volume, weight, and specific gravity of the fiber nonwoven fabric. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). Moreover, it can calculate from the volume of the said fiber nonwoven fabric, and the void volume of the said fiber nonwoven fabric measured by methods, such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, a gas adsorption method.

  When the porous surface layer is a polymer foam, the average porosity of the porous surface layer is the volume ratio of bubbles in the polymer inherently possessed by the polymer foam as the porous surface layer. Expressed as a percentage measured by the method. From the functional laminate, the polymer foam in the porous surface layer portion not impregnated with the foamable resin is cut out, and in the optical microscope or electron micrograph of the vertical cross section of the sample, bubbles with respect to the entire area at any 100 locations It can be calculated by measuring the ratio of the area and obtaining the average value.

  The average porosity of the porous surface layer uses the value measured from the functional laminate as described above, but even if measured from the material used for manufacturing (foam molding), the equivalent measured value is can get. That is, it can be calculated from physical properties such as the volume and weight of the porous surface layer material used for production (foam molding), the specific gravity of the fiber or polymer of the porous surface layer material. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). Further, the volume of the porous surface layer material and the void volume of the porous surface layer material measured by a method such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, a gas adsorption method, etc. Can be calculated. Moreover, in the optical microscope and electron micrograph of the vertical cross section of the said porous surface layer material, it can calculate by measuring the ratio of the area of the bubble with respect to the whole area in arbitrary 100 places, and calculating | requiring an average value.

  The thickness of the porous surface layer is usually 1 to 50 mm, and it is easy to inhibit the foaming resin movement in the porous intermediate layer and further improve the sound absorption, heat insulation and damping properties of the functional laminate. From the viewpoint, it is preferably 2 to 30 mm.

  The thickness of the porous surface layer is a thickness including a mixed layer portion to be described later, even if the porous surface layer is a fiber nonwoven fabric or a polymer foam. 1 is a thickness from the outer surface 12 to the interface 13 with the porous intermediate layer 3, and is represented by a thickness measured by the following method. In the optical micrograph of the vertical cross section of the functional laminate, the thickness is measured at an arbitrary 100 locations to determine the average value.

  As for the thickness of the porous surface layer, the value measured from the functional laminate as described above is used, but even if measured from the material used for manufacturing (foam molding), the same measured value can be obtained. . That is, in the optical micrograph of the vertical cross section of the porous surface layer material used for production (foam molding), the thickness is measured at arbitrary 100 locations to obtain the average value. Further, the thickness of the porous surface layer material is measured with a gauge such as a film thickness meter, a displacement meter, or a caliper, and an average value is obtained.

  When the porous surface layer is a fiber nonwoven fabric in particular, the average fiber diameter and average fiber length of the fibers constituting the fiber nonwoven fabric are not particularly limited as long as the porous intermediate layer inhibits the movement of the foamable resin. Average fiber diameter is usually 0.005 to 50 μm, and it is easy to inhibit the movement of the foamable resin in the porous intermediate layer, and the viewpoint of further improving the sound absorption, heat insulation and vibration damping properties of the functional laminate Therefore, it is preferably 0.1 to 20 μm, more preferably 1 to 5 μm. The average fiber length is usually 2 mm or more, preferably from the viewpoint of easy inhibition of foaming resin movement in the porous intermediate layer and further improvement of sound absorption, heat insulation and vibration damping of the functional laminate. Is 20 mm or more.

  The average fiber diameter of the fibers in the fiber nonwoven fabric of the porous surface layer is represented by the average diameter measured by the following method. Cut out the nonwoven fabric of the porous surface layer portion not impregnated with the foamable resin from the functional laminate, and measure the diameter of any 100 fibers in the optical microscope and electron micrographs of the vertical cross section of the sample. Find the average value.

  The average fiber length of the fibers in the fiber nonwoven fabric of the porous surface layer is represented by an average value measured by the following method. The said nonwoven fabric of the porous surface layer part which is not impregnated with foamable resin is cut out from a functional laminated body, the length of arbitrary 100 fibers is measured from the said nonwoven fabric, and an average value is calculated | required. Moreover, the inside of the nonwoven fabric is three-dimensionally imaged by a method such as CT, and the length of an arbitrary 100 fibers is measured to obtain an average value.

  The average fiber diameter and average fiber length of the fibers of the fiber nonwoven fabric use the values measured from the functional laminate as described above, but they are equivalent even if measured from the material used for manufacturing (foam molding) Is obtained. In other words, the average fiber diameter of the fibers of the fiber nonwoven fabric used for production (foam molding) is determined by measuring the diameter of any 100 fibers in an optical microscope or electron micrograph of a vertical cross section of the nonwoven fabric, and calculating the average value. Ask. The average fiber length of the fibers of the fiber nonwoven fabric used for production (foam molding) is obtained by measuring the length of any 100 fibers and determining the average value. Moreover, the inside of the said fiber nonwoven fabric is made into a three-dimensional image by methods, such as CT, and the length of arbitrary 100 fibers is measured and an average value is calculated | required.

When the porous surface layer is particularly a fiber nonwoven fabric, the basis weight of the fiber nonwoven fabric is not particularly limited as long as the porous intermediate layer inhibits the movement of the foamable resin, and is usually 50 to 6000 g / m ^2. From the viewpoint of easily inhibiting the movement of the foamable resin in the quality intermediate layer and further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate, it is preferably 100 to 3000 g / m ² .

  The basis weight in the fiber nonwoven fabric of the porous surface layer is represented by a value measured by the following method. The nonwoven fabric of the porous surface layer portion not impregnated with the foamable resin is cut out from the functional laminate, and the basis weight can be calculated from the area and weight of the nonwoven fabric. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler).

  As the basis weight of the fiber nonwoven fabric, the value measured from the functional laminate as described above is used. However, even when measured from the material used for production (foam molding), an equivalent measurement value is obtained. That is, the basis weight can be calculated from the area and weight of the fiber nonwoven fabric used for production (foam molding). In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler).

(Resin foam layer)
The resin foam layer 2 is a polymer foam layer. The polymer constituting the resin foam layer may be any polymer known as a polymer capable of constituting a foam in the plastic field. Specific examples of the resin foam layer include, for example, a polyurethane foam layer; a polyolefin foam layer such as a polyethylene foam layer and a polypropylene foam layer; a polyester foam layer such as a PET foam layer; a silicone foam layer; and a polyvinyl chloride foam layer. Polymer foam layer.

The resin foam layer is preferably a polyurethane foam layer from the viewpoint of further improving the sound absorption, heat insulation and vibration damping properties of the functional laminate.

  The average void diameter Df of the resin foam layer is not particularly limited, and may be, for example, in the range of 0.04 to 800 μm, particularly 10 to 600 μm, depending on the frequency of the sound to be absorbed. The greater the average void diameter Df of the resin foam layer is within the above range, the greater the frequency of the sound that is absorbed. On the other hand, the smaller the average void diameter Df of the resin foam layer is within the above range, the smaller the frequency of the sound that is absorbed.

  For example, when the average void diameter Df of the resin foam layer is 50 to 500 μm, particularly 100 to 300 μm, sound having a frequency of 1000 to 4000 Hz is effectively absorbed. Such sound absorption is suitable when the functional laminate is used for a cover member for a powertrain member of an automobile.

  The average void diameter Df of the resin foam layer is the diameter of bubbles in the polymer, and is represented by the average diameter measured by the following method. A resin foam layer is cut out from the functional laminate, and the diameter of an arbitrary 100 bubbles is measured in an optical microscope or an electron micrograph of a parallel section of the sample, and an average value is obtained.

  The average porosity Rf of the resin foam layer is usually 60 to 98%, and it is easy to inhibit the movement of the foamable resin in the porous intermediate layer, and the sound absorbing property, heat insulating property and vibration damping property of the functional laminate. From the viewpoint of further improvement, it is preferably 80 to 95%.

  The average porosity of the resin foam layer is a volume ratio of bubbles in the polymer, and is expressed by a ratio measured by the following method. A resin foam layer is cut out from the functional laminate, and in the optical microscope and electron micrographs of the vertical cross section of the resin foam material, the ratio of the area of bubbles to the total area is measured at an arbitrary 100 locations, and the average value is obtained. Moreover, it can calculate from physical properties, such as the volume of the said resin foam material, weight, and specific gravity of a polymer. In this specification, the weight was measured using an electronic balance (AE160; manufactured by Mettler). Further, it can be calculated from the volume of the resin foam and the void volume of the resin foam measured by a method such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, a gas adsorption method.

  The thickness of the resin foam layer is usually 1 to 100 mm, and it is easy to inhibit the movement of the foamable resin in the porous intermediate layer, and the viewpoint of further improving the sound absorption, heat insulation and vibration damping of the functional laminate Therefore, it is preferably 2 to 30 mm.

  The thickness of the resin foam layer is a thickness in a direction substantially perpendicular to the outer surface 12 of the porous surface layer 1, and is a thickness up to the interface 22 with the porous intermediate layer 3 in the resin foam layer 2. It is represented by the thickness measured by the method. In the optical micrograph of the vertical cross section of the functional laminate, the thickness is measured at an arbitrary 100 locations to determine the average value.

(Mixed layer)
The functional laminate 10 of the present invention includes a mixed layer portion 11 between the porous intermediate layer 3 and the porous surface layer 1. Specifically, the porous surface layer 1 includes a mixed layer portion 11 on the porous intermediate layer 3 side. More specifically, a part of the porous surface layer 1 on the porous intermediate layer 3 side is converted to the mixed layer part 11, in other words, a part of the porous surface layer 1 on the porous intermediate layer 3 side is mixed. Part 11 is generated. The rigidity of the functional laminate is improved by the mixed layer portion.

  The mixed layer portion is a composite layer of a resin foam layer and a porous surface layer formed between the porous intermediate layer and the porous surface layer. More specifically, the mixed layer portion is a layer formed by infiltrating the foamed resin constituting the resin foam layer into the porous surface layer, foaming and curing, in other words, the constituent material of the porous surface layer and the resin foam. It is a layer where the constituent materials of the layer coexist. In the mixed layer portion, bubbles of the foamable resin are formed in the voids of the porous surface layer before the infiltration of the foamable resin.

  The average gap diameter Dx of the mixed layer portion is not particularly limited, and may be, for example, in the range of 0.04 to 800 μm, particularly 10 to 500 μm, depending on the frequency of the sound to be absorbed. The larger the average gap diameter Dx of the mixed layer portion is within the above range, the greater the frequency of the sound that is absorbed. On the other hand, the smaller the average gap diameter Dx of the mixed layer portion is within the above range, the smaller the frequency of the sound that is absorbed.

  For example, when the average void diameter Dx of the mixed layer portion is 50 to 250 μm, particularly 60 to 200 μm, sound having a frequency of 1000 to 4000 Hz is effectively absorbed. Such sound absorption is suitable when the functional laminate is used for a cover member for a powertrain member of an automobile.

  The average void diameter Dx of the mixed layer portion is the diameter of bubbles in the resin (polymer) formed in the voids of the porous surface layer before the infiltration of the foamable resin, and is measured by the following method. It is represented by In an optical microscope or electron micrograph of a parallel section of the mixed layer portion in the functional laminate, the diameter (longest diameter) of any 100 bubbles is measured, and the average value is obtained. Arbitrary 100 bubbles are arbitrary 100 bubbles formed by foaming of the foamable resin, and the bubbles and the bubbles inherently contained in the polymer foam as the porous surface layer are: It can be easily distinguished by the difference in brightness around the bubble. Moreover, a mixed layer part is cut out from a functional laminated body, the distribution of the diameter of the space | gap in this mixed layer part is measured by methods, such as a mercury intrusion method and a gas adsorption method, and an average diameter can be calculated.

  The average porosity Rx of the mixed layer portion is usually 30 to 95%, and preferably 50 to 90% from the viewpoint of further improving the sound absorbing property, heat insulating property and vibration damping property of the functional laminate.

  The average porosity of the mixed layer portion is a volume ratio of bubbles in the resin (polymer) formed in the void of the porous surface layer before the infiltration of the foamable resin, and is a ratio measured by the following method. expressed. In an optical microscope or electron micrograph of a vertical cross section of the mixed layer portion in the functional laminate, the ratio of the area of bubbles to the total area is measured at an arbitrary 100 locations, and the average value is obtained. The area of the bubbles is the area of bubbles in the resin (polymer) formed by foaming of the foamable resin in the voids of the porous surface layer. When the porous intermediate layer is a polymer foam, the bubbles and The bubbles inherent in the polymer foam can be easily distinguished from each other by the difference in brightness around the bubbles. As another measurement method, the mixed layer portion can be cut out from the functional laminate and calculated from physical properties such as the volume and weight of the mixed layer portion and the specific gravity of the polymer. Further, it can be calculated from the volume of the mixed layer portion and the void volume of the mixed layer portion measured by a method such as a computer tomography method, a liquid immersion method, a water evaporation method, a suspension method, a mercury intrusion method, or a gas adsorption method.

  The thickness of the mixed layer portion is usually 0.05 to 3 mm, which is preferable from the viewpoint of further improving sound absorbing properties, heat insulating properties, and vibration damping properties (particularly sound absorbing properties) in cover member applications for automobile powertrain members. Is 0.1 to 2 mm, more preferably 0.2 to 1.7 mm.

  The thickness of the mixed layer portion is a thickness in a direction substantially perpendicular to the outer surface 12 of the porous surface layer 1, and from the interface 13 with the porous intermediate layer 3 in the porous surface layer 1, the porous surface layer It is the thickness until the foamable resin is not impregnated in 1, and is represented by the thickness measured by the following method. In an optical microscope or electron micrograph of a vertical cross section in the vicinity of the mixed layer portion in the functional laminate, the thickness is measured at an arbitrary 100 locations to obtain an average value. In the optical microscope and the electron micrograph, the fact that the porous surface layer 1 is impregnated with the foamable resin and that the porous surface layer 1 is not impregnated are the presence / absence of the foamable resin in the voids of the porous surface layer 1 / Can be easily distinguished by the absence.

[Method for producing functional laminate]
The functional laminate of the present invention can be produced by a production method including the following lamination base material forming step and foam molding step.

(Lamination substrate forming process)
In this step, the porous surface layer 1 and the porous intermediate layer 3 are superposed to obtain a lamination substrate 40. In order to superimpose, the other layer may simply be placed on one layer, but the porous surface layer 1 and the porous intermediate layer 3 are bonded from the viewpoint of handling of the substrate for lamination. Is preferred.

  The bonding method is not particularly limited as long as the bonding between the porous surface layer 1 and the porous intermediate layer 3 is achieved. For example, a method using an adhesive may be adopted. Adhesion may be achieved on a part of the contact surface between the porous surface layer 1 and the porous intermediate layer 3, or may be achieved on the entire surface. From the standpoint of further improving sound absorption, heat insulation and vibration damping (particularly sound absorption) in the application of a cover member for a powertrain member of an automobile, adhesion is a contact between the porous surface layer 1 and the porous intermediate layer 3. Preferably it is achieved on part of the surface.

  The porous surface layer 1 and the porous intermediate layer 3 can be made of the materials described above, and are available as commercial products. In particular, when the porous surface layer 1 and the porous intermediate layer 3 are fiber nonwoven fabrics, a predetermined fiber is formed by adjusting to a desired physical property by a known molding method such as a hot press molding method or a needle punch molding method (sheet) Shaped material) can be used.

(Foam molding process)
In this step, foam molding is performed in the molding die 50 as shown in FIG. 2A. The mold 50 is usually composed of an upper mold 51 and a lower mold 52. FIG. 2A shows a mold for explaining the foam preparation stage of the foam molding process and a schematic cross-sectional view of the inside thereof.

  Foam molding is performed on the porous intermediate layer 3 side of the substrate for lamination 40 using the foamable resin 20 as a raw material constituting the resin foam layer 2. When foam molding is performed on the porous intermediate layer 3 side of the substrate 40 for lamination, the foamable resin 20 and the laminate are formed so that the resin foam layer 2 is formed on the porous intermediate layer 3 side of the substrate 40 for lamination. This means that the base material 40 is disposed and foam molding is performed. For example, as shown in FIG. 2A, after injecting the foamable resin 20 into the molding surface 520 of the lower mold 52, the base material for lamination 40 is placed on the foamable resin 20, and the porous intermediate layer 3 is the foamable resin. 20 so as to be in contact with 20. (You may arrange the base material 40 for lamination | stacking in the upper mold | type 51 so that the porous intermediate | middle layer 3 may contact the foamable resin 20.) Then, as shown to FIG. 2B, the upper mold | type 51 is closed, When foaming is started, the foamable resin 20 expands, fills the cavity between the upper mold 51 and the lower mold 52, and the resin foam layer 2 is formed. By removing the molded body, a functional laminate in which the porous surface layer 1, the resin foam layer 2, and the porous intermediate layer 3 are integrated is obtained. FIG. 2B shows a mold for explaining the foaming stage of the foam molding process and a schematic cross-sectional view of the inside thereof.

  The foamable resin 20 is a raw material for the resin foam layer. For example, when the resin foam layer is a polyurethane foam layer, the foamable resin 20 is a mixture of a polyol compound and an isocyanate compound. The foamable resin 20 may contain additives such as a foaming agent and a foam stabilizer.

  The foaming conditions are appropriately determined according to the type of the foamable resin 20. For example, the mold 50 may be heated and / or the inside of the mold 50 may be pressurized or depressurized.

[Usage]
The functional laminate 10 of the present invention is useful as a sound absorbing material, a heat insulating material and / or a vibration damping material (especially a sound absorbing material) because it has excellent sound absorbing properties, heat insulating properties and vibration damping properties (especially sound absorbing properties). .
Fields in which the functional laminate 10 of the present invention is useful include, for example, machines equipped with engines such as vehicles (for example, automobiles, trucks, buses and trains) and agricultural machines (for example, mowers and tillers). Fields.

  When the functional laminate 10 of the present invention is used as, for example, a sound-absorbing heat insulating material in a machine equipped with an engine, it is specifically used as a cover member for a powertrain member including an engine and a transmission. More specifically, the functional laminate 10 is used as a cover member that partially or entirely surrounds the powertrain member. The functional laminate 10 is disposed and used such that the resin foam layer 2 side contacts the power train member. Alternatively, it is used such that the porous surface layer 1 side faces the sound source and / or heat source in a non-contact manner, that is, the engine and transmission are arranged on the porous surface layer 1 side.

(Measuring method)
Various physical properties of each layer were measured by the methods described above. In addition, the glass plate of the same composition as the said glass wool was used for the measurement of the contact angle of glass wool. For measurement of the contact angle of PET wool, a PET plate having the same composition as that of the PET wool was used. For the measurement of the contact angle of the PP nonwoven fabric, a PP plate having the same composition as that of the PP nonwoven fabric was used. In particular, for the measurement of the contact angle of “PP nonwoven fabric + fluororesin coat”, which is a PP nonwoven fabric coated with a fluororesin, a fluororesin coat having the same composition as the fluororesin coat is formed on a PP plate having the same composition as the PP nonwoven fabric. A filmed plate was used. The surface roughness of the plates used for measuring the contact angle was commonly Ra of 1.6 μm or less.

(Evaluation method)
Sound absorption coefficient (α):
Normal acoustic absorption coefficient measurement system WinZacMTX, manufactured by Nippon Acoustic Engineering Co., Ltd., and measurement of vertical incident acoustic absorption coefficient using an acoustic tube with an inner diameter of 40 mm in a measurement frequency range of 200 to 4800 Hz (1/3 octave band) (JIS A 1405) -2, ISO 10534-2 compliant), and an average normal incidence sound absorption coefficient of 1000 to 4000 Hz was calculated. As the measurement sample, a functional laminate obtained in each example / comparative example was hollowed out into a columnar shape with a diameter of 40 mm. The functional laminate as a measurement sample was arranged so that sound was incident from the porous surface layer 1 side. It evaluated based on the increase width from the sound absorption rate in the comparative example using the same porous surface layer, without using a porous intermediate | middle layer.
A: 5.0% ≦ increased width; (best)
○: 2.0% ≦ increased width <5.0%; (good)
Δ: 0.5% ≦ increased width <2.0%; (no practical problem)
X: Increase width <0.5%.

Thermal conductivity:
Based on JIS A1412-2 Part 2 heat flow meter method, the thermal conductivity in the thickness direction of the functional laminate is measured at 30 ° C using a steady-state thermal conductivity measuring device HFM436 / 3/1 Lambda manufactured by NETZSCH. Measured.

(Examples 1-3)
-Substrate forming process for lamination Glass wool A having an average fiber diameter of about 7.5 μm was hot press-molded so as to have the average porosity and thickness shown in Table 1 to obtain a porous surface layer 1. A predetermined nonwoven fabric was impregnated with a fluororesin coating agent (FG5030C; manufactured by Fluoro Technology Co., Ltd.) and dried at room temperature to obtain a porous intermediate layer 3 shown in Table 1. The porous intermediate layer 3 was adhered to the porous surface layer 1 to obtain a substrate for lamination 40. Adhesion was achieved with an adhesive at part of the contact surface between the porous surface layer and the porous intermediate layer.

-Foam molding process The raw material of the polyurethane foam of Table 1 was mixed with the mixer as the foamable resin 20, and it inject | poured on the molding surface 520 of the lower mold | type 52, as shown to FIG. 2A. Subsequently, the base material 40 for lamination | stacking was arrange | positioned so that the porous intermediate | middle layer 3 might contact the foamable resin 20 on the said foamable resin 20. FIG. Thereafter, under an environment of 25 ° C. and normal pressure, as shown in FIG. 2B, when the upper mold 51 is closed and foaming is started, the foamable resin 20 expands, and between the upper mold 51 and the lower mold 52 The cavity (size 100 mm × 100 mm × 25 mm) was filled, and the resin foam layer 2 was formed. After cooling, the molded body was demolded to obtain a functional laminate in which the porous surface layer 1, the resin foam layer 2, and the porous intermediate layer 3 were integrated.

Example 4
The same method as in Example 2 except that a glass wool B having an average fiber diameter of about 3.5 μm as the porous surface layer 1 was subjected to hot press molding so as to have the average porosity and thickness described in Table 1. The base material formation process for lamination and the foam molding process were performed.

(Example 5)
The porous surface layer 1 is made of PET fibers having an average fiber length of 51 mm and a fineness of 2.2 denier (average fiber diameter of about 16 μm) with a needle punch and an adhesive so that the average porosity and thickness shown in Table 1 are obtained. In the same manner as in Example 1 except that the PET wool obtained by molding into a shape was used and the porous intermediate layer 3 shown in Table 1 was used, the substrate forming process for lamination and the foam molding process were carried out. went.

(Example 6)
Except for using the porous intermediate layer 3 in Table 1, the substrate forming process for lamination and the foam molding process were performed in the same manner as in Example 1.

(Comparative Example 1)
Without using the porous intermediate layer, the base material forming step and the foam molding step were performed in the same manner as in Example 1 except that the porous surface layer was used alone instead of the base material for stacking. .

(Comparative Example 2)
The base material forming step and the foam molding step were performed in the same manner as in Example 4 except that the porous surface layer was used alone instead of the base material for lamination without using the porous intermediate layer. .

(Comparative Example 3)
Without using the porous intermediate layer, the base material forming step and the foam molding step were performed in the same manner as in Example 5 except that the porous surface layer was used alone instead of the base material for stacking. .

Glass wool A: Glass fiber having an average fiber diameter of about 7.5 μm and an average fiber length of about 50 mm (weight per unit area of porous surface layer 1 by glass wool A Examples 1-3: 960 g / m ² , Example 6: 960 g / m ² , Comparative Example 1: 960 g / m ² )
Glass wool B: Glass fiber having an average fiber diameter of about 3.5 μm and an average fiber length of about 50 mm (weight per unit area of porous surface layer 1 by glass wool B Example 4: 960 g / m ² , Comparative Example 2: 960 g / m ² )
PET wool: PET fiber having an average fiber length of 51 mm and a fineness of 2.2 denier (average fiber diameter of about 16 μm) (weight per unit area of the porous surface layer 1 made of PET wool Example 5: 540 g / m ² , Comparative Example 3: 540 g / m) ² )
PP non-woven fabric A: SP-1040E (manufactured by Maeda Kosen Co., Ltd., basis weight 40 g / m ² )
PP non-woven fabric B: SP-1200E (Maeda Kosen Co., Ltd., basis weight 200 g / m ² )
PP non-woven fabric C: SP-1017E (manufactured by Maeda Kosen Co., Ltd., basis weight 17 g / m ² )
Fluororesin coating: Fluororesin coating agent (FG5030C; manufactured by Fluoro Technology)
Raw material of polyurethane foam A: DK system (Daiichi Kogyo Seiyaku Co., Ltd.)

  The functional laminate of the present invention is a sound-absorbing material and a heat-insulating material in the field of machines including engines such as vehicles (for example, automobiles, trucks, buses, trains, etc.) and agricultural machines (for example, mowers and tillers). And / or useful as a damping material.

1: Porous surface layer 2: Resin foam layer 3: Porous intermediate layer 10: Functional laminate 11: Mixed layer portion 12: Outer surface of porous surface layer 13: Interface of porous surface layer with porous intermediate layer 20: Foamable resin 22: Interface with porous intermediate layer in resin foam layer 32: Interface with porous surface layer in porous intermediate layer 33: Interface with resin foam layer in porous intermediate layer 40: Base for lamination Material 50: Mold 51: Upper mold 52: Lower mold 520: Molding surface of lower mold

Claims (28)

Between the porous surface layer and the resin foam layer, a porous intermediate layer having air permeability is laminated,
The functional laminated body in which the said porous intermediate | middle layer has non-affinity with respect to the foamable resin which comprises the said resin foam layer.   The functional laminate according to claim 1, wherein the non-affinity of the porous intermediate layer is higher than the non-affinity of the porous surface layer.   The functional laminate according to claim 2, wherein a contact angle θm of the porous intermediate layer with respect to the foamable resin is larger than a contact angle θs of the porous surface layer with respect to the foamable resin. The functional laminate according to claim 3, wherein a contact angle θm of the porous intermediate layer with respect to the foamable resin and a contact angle θs of the porous surface layer with respect to the foamable resin satisfy the following relational expression.
5 ° ≦ θm−θs ≦ 40 °   The functional laminate according to claim 1, wherein the porous intermediate layer inhibits the movement of the foamable resin to the porous surface layer due to the non-affinity.   The functional laminate according to claim 1, wherein a contact angle θm of the porous intermediate layer with respect to the foamable resin is 10 to 50 °.   The functional laminate according to any one of claims 1 to 6, wherein the porous intermediate layer has an average porosity of 60 to 95%.   The functional laminate according to any one of claims 1 to 7, wherein the porous intermediate layer has a thickness of 0.1 to 2 mm.   The functional laminated body in any one of Claims 1-8 whose said porous intermediate | middle layer is a fiber nonwoven fabric.   The functional laminate according to claim 1, wherein the porous intermediate layer is an organic fiber nonwoven fabric selected from the group consisting of polyolefin fibers.   The functional laminated body of Claim 9 or 10 in which the fiber which comprises the fiber nonwoven fabric of the said porous intermediate | middle layer has an average fiber diameter of 0.005-50 micrometers. The functional laminate according to claim 1, wherein an average porosity Rm of the porous intermediate layer and an average porosity Rs of the porous surface layer satisfy the following relational expression.
1.10 ≦ Rs / Rm ≦ 1.5   The functional laminate according to claim 1, wherein a contact angle θs of the porous surface layer with respect to the foamable resin is 1 to 40 °.   The functional laminate according to any one of claims 1 to 13, wherein the porous surface layer has an average porosity of 80 to 99.5%.   The functional laminate according to claim 1, wherein the porous surface layer has a thickness of 1 to 50 mm.   The functional laminate according to claim 1, wherein the porous surface layer is a fiber nonwoven fabric.   The functional laminate according to any one of claims 1 to 16, wherein the porous surface layer is a nonwoven fabric of inorganic fibers and / or organic fibers.   The functional laminate according to claim 16 or 17, wherein the fibers constituting the fiber nonwoven fabric of the porous surface layer have an average fiber diameter of 0.005 to 50 µm.   The functional laminate according to claim 1, wherein the resin foam layer has an average void diameter of 0.04 to 800 μm.   20. The resin foam layer according to claim 1, wherein the resin foam layer is a polymer foam layer selected from the group consisting of a polyurethane foam layer, a polyolefin foam layer, a polyester foam layer, a silicone foam layer, and a polyvinyl chloride foam layer. Functional laminate.   The functional laminate according to claim 1, wherein the porous surface layer includes a mixed layer portion of the resin foam layer and the porous surface layer on the porous intermediate layer side.   The functional laminate according to claim 21, wherein the mixed layer portion has a thickness of 0.2 to 1.7 mm.   The functional laminate according to claim 21 or 22, wherein the mixed layer portion has an average void diameter of 60 to 200 µm.   The functional laminate according to any one of claims 21 to 23, wherein the mixed layer portion has an average porosity of 50 to 90%.   The functional laminate according to any one of claims 1 to 24, wherein the functional laminate is used as a sound absorbing material, a heat insulating material and / or a vibration damping material.   The functional laminate is used so that the resin foam layer side is in contact with a heat source and / or a sound source, or the porous surface layer side is arranged so as to face the heat source and / or the sound source without contact. The functional laminate according to claim 1, wherein the functional laminate is used.   The functional laminate according to any one of claims 1 to 26, wherein the functional laminate is used as a cover member for a powertrain member including an automobile engine and a transmission. It is a manufacturing method of the functional layered product according to any one of claims 1 to 27, and
A step of superimposing the porous surface layer and the porous intermediate layer to obtain a base material for lamination; and foam molding of a foamable resin constituting the resin foam layer in a molding die of the base material for lamination A method performed on the porous intermediate layer side.

Images