JP2017071106A - Resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate excellent in vibration damping property.SOLUTION: There is provided a resin laminate 1 which comprises a foamed resin layer 4 and a first reinforced resin layer 2 laminated on a main surface 4a of one side of the foamed resin layer 4, wherein the first reinforced resin layer 2 is constituted of a first synthetic resin and a carbon material having a graphene laminated structure, the content of carbon material based on 100 pts.wt. of the first synthetic resin is 5 pts.wt. or more and 150 pts.wt. or less, the foaming ratio of the foamed resin layer 4 is 3 cc/g or more and 30 cc/g or less, a temperature indicating a peak value of tanδ by a dynamic viscoelastic measurement of the foamed resin layer 4 under a condition of a frequency of 10 Hz is in the range of -10°C or more and 30°C or less and the peak value of tanδ is 0.5 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin laminate in which a reinforced resin layer is laminated on at least one side of a foamed resin layer.

  Conventionally, resin laminates that are lightweight and have high rigidity have been widely used in various fields such as architecture, automobiles, aviation, and ships.

  Patent Document 1 below discloses a lightweight and highly rigid sandwich panel made of a polyimide composite material. Patent Document 1 describes that the sandwich panel is formed by sandwiching foamed polyimide as a core material between long fiber reinforced addition type polyimide sheets.

  Patent Document 2 below discloses a structure using a lightweight and highly rigid sandwich panel. Patent Document 2 describes that the sandwich panel is composed of two face plates made of a fiber reinforced synthetic resin material, and a damping material is provided in a part between the face plates.

JP 2008-119974 A Japanese Patent No. 3564034

  When a lightweight and high-rigidity sandwich panel such as Patent Document 1 or Patent Document 2 is used for a panel material of an automobile or the like, the vibration propagated to the panel material is easily transmitted to other members, and the vibration is radiated as sound. There was something to be done. However, in the sandwich panel of Patent Document 2, although a vibration damping material is provided in a part between the face plates, vibration cannot be sufficiently reduced and generation of radiated sound cannot be sufficiently suppressed. It was.

  An object of the present invention is to provide a resin laminate having excellent vibration damping properties.

  The resin laminate according to the present invention includes a foamed resin layer and a first reinforced resin layer laminated on a main surface on one side of the foamed resin layer, and the first reinforced resin layer is The carbon material is composed of a first synthetic resin and a carbon material having a graphene laminated structure, and the content of the carbon material with respect to 100 parts by weight of the first synthetic resin is 5 parts by weight or more and 150 parts by weight or less, When the foaming ratio of the foamed resin layer is 3 cc / g or more and 30 cc / g or less, and the dynamic viscoelasticity measurement of the foamed resin layer is performed under the condition of a frequency of 10 Hz, the temperature showing the peak value of tan δ is − It is in the range of 10 ° C. or more and 30 ° C. or less, and the peak value of tan δ is 0.5 or more.

  In a specific aspect of the resin laminate according to the present invention, the foamed resin layer is laminated on a main surface opposite to the first reinforced resin layer, and a second synthetic resin and graphene laminated structure A second reinforced resin layer made of a carbon material having

  In the resin laminate according to the present invention, preferably, the first and second synthetic resins are each a thermoplastic resin. More preferably, the thermoplastic resin is a polyolefin resin.

  In another specific aspect of the resin laminate according to the present invention, the resin laminate further includes a metal layer laminated on a main surface of the foamed resin layer opposite to the first reinforced resin layer.

  In another specific aspect of the resin laminate according to the present invention, the foamed resin layer includes a third synthetic resin and a resin composition containing a fourth synthetic resin, and the resin composition 100 Content of the said 3rd synthetic resin with respect to a weight part is 20 to 50 weight part.

  In still another specific aspect of the resin laminate according to the present invention, when the dynamic viscoelasticity measurement of the resin composition constituting the foamed resin layer is performed at a frequency of 10 Hz, the peak value of tan δ is The temperature shown is in the range of −10 ° C. or higher and 30 ° C. or lower, and the peak value of tan δ is 0.5 or higher. Preferably, the third synthetic resin is a polyolefin resin.

  In still another specific aspect of the resin laminate according to the present invention, the resin composition constituting the foamed resin layer further includes a fifth synthetic resin.

  In still another specific aspect of the resin laminate according to the present invention, at least one of the fourth and fifth synthetic resins is a copolymer containing an aromatic vinyl block.

  ADVANTAGE OF THE INVENTION According to this invention, the resin laminated body excellent in the damping property can be provided.

It is a typical sectional view showing the resin layered product concerning a 1st embodiment of the present invention. It is typical sectional drawing which shows the resin laminated body which concerns on the 2nd Embodiment of this invention.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing a resin laminate according to the first embodiment of the present invention. As shown in FIG. 1, the resin laminate 1 includes first and second reinforced resin layers 2 and 3 and a foamed resin layer 4. On the first main surface 4a of the foamed resin layer 4, the first reinforced resin layer 2 is provided. On the other hand, the second reinforced resin layer 3 is provided on the second main surface 4 b of the foamed resin layer 4. Therefore, the foamed resin layer 4 is provided so as to be sandwiched between the first and second reinforced resin layers 2 and 3. The resin laminate 1 is a resin laminate having a three-layer structure in which first and second reinforced resin layers 2 and 3 are provided on both surfaces of a foamed resin layer 4. In the present invention, the number of layers in each layer constituting the resin laminate is not particularly limited.

  The first reinforced resin layer 2 is composed of a first synthetic resin and a carbon material having a graphene laminated structure. Content of the said carbon material with respect to 100 weight part of said 1st synthetic resins is 5 to 150 weight part.

  If the content of the carbon material is too small, sufficient rigidity may not be obtained. On the other hand, when there is too much content of the said carbon material, the 1st reinforced resin layer 2 will become weak and a shape may not be maintained.

  The second reinforced resin layer 3 is composed of a second synthetic resin and a carbon material having a graphene laminated structure. In the present embodiment, the second synthetic resin is made of the same resin as the first synthetic resin. Thus, in this invention, the 1st and 2nd reinforced resin layers 2 and 3 may be comprised with the same material, and may be comprised with the other material. In addition, content of the said carbon material with respect to 100 weight part of said 2nd synthetic resins is 5 weight part or more and 150 weight part or less.

  The foamed resin layer 4 is composed of a third synthetic resin and a resin composition containing the fourth synthetic resin. The foamed resin layer 4 has a plurality of bubble cells inside. The expansion ratio of the foamed resin layer 4 is 3 cc / g or more and 30 cc / g or less.

  If the expansion ratio is too small, a sufficient vibration damping effect may not be obtained. On the other hand, if the expansion ratio is too large, the rigidity of the resin laminate 1 may be insufficient.

  In the present invention, the expansion ratio can be measured according to JIS K 7222. Specifically, first, only the foamed resin layer is taken out, and the cross section of the foamed resin layer is cut out vertically. Subsequently, the volume of the cut-out test piece is calculated from the length of the test piece × the width of the test piece × the thickness of the test piece. Next, the calculated volume is divided by the weight of the test piece. Thereby, the expansion ratio is obtained. In the present invention, the expansion ratio was calculated from the average value of 10 test pieces.

  The foamed resin layer 4 has a temperature at which the peak value of tan δ is in the range of −10 ° C. or more and 30 ° C. or less when dynamic viscoelasticity measurement is performed under the condition of a frequency of 10 Hz. Further, the peak value of tan δ is 0.5 or more. Since the temperature and peak value indicating the peak value of tan δ of the foamed resin layer 4 are within the above range, the resin laminate 1 has improved damping properties.

  The temperature indicating the peak value of tan δ and the peak value of tan δ can be determined by measuring in accordance with JIS K 7244-4. Specifically, a test sheet having a width of 5 mm, a length of 24 mm, and a thickness of 0.3 mm is produced. The test sheet thus prepared is obtained by performing temperature dispersion measurement of dynamic viscoelasticity under the conditions of a strain amount of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min. The temperature dispersion measurement of dynamic viscoelasticity can be performed using, for example, a dynamic viscoelasticity measuring apparatus (manufactured by Rheometrics, trade name “RSA”).

  The resin laminate of the present invention such as the resin laminate 1 has improved vibration damping properties because the temperature indicating the peak value of tan δ and the peak value of tan δ of the foamed resin layer are within the above ranges. Moreover, since the reinforced resin layer containing the carbon material which has a graphene laminated structure is laminated | stacked on the foamed resin layer, rigidity is improved. Furthermore, since the reinforced resin layer and the foamed resin layer are formed of resin, the resin laminate is reduced in weight. Therefore, the resin laminate of the present invention can be used in various fields such as architecture, automobiles, aviation, ships and electronic materials.

  Moreover, since the resin laminated body of this invention is excellent in damping property, when it uses for panel materials, such as a motor vehicle, it can suppress the vibration which propagated to the panel materials. Therefore, it is difficult to generate radiated sound. Therefore, the resin laminate of the present invention can be suitably used for panel materials such as automobiles.

  Hereafter, each layer which comprises the resin laminated body of this invention is demonstrated in detail.

(First and second reinforced resin layers)
The first reinforced resin layer is composed of a first synthetic resin and a carbon material having a graphene laminated structure. Further, the second reinforced resin layer is composed of a second synthetic resin and a carbon material having a graphene laminated structure. The first reinforced resin layer and the second reinforced resin layer are preferably made of the same material. Therefore, the first synthetic resin and the second synthetic resin are preferably the same synthetic resin.

Synthetic resin;
Although it does not specifically limit as 1st and 2nd synthetic resin, It is preferable that it is a thermoplastic resin.

  It does not specifically limit as said thermoplastic resin, A well-known thermoplastic resin can be used. Specific examples of the thermoplastic resin include polyolefin, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyester, polyamide, polyurethane, polyethersulfone, polyetherketone, polyimide, polydimethylsiloxane, polycarbonate, or at least two of these. Examples of the copolymer include seeds. A thermoplastic resin may be used independently and multiple may be used together.

  As the thermoplastic resin, a resin having a high elastic modulus is desirable, but a polyolefin that is inexpensive and easy to mold under heating is more preferable.

  It does not specifically limit as said polyolefin, A conventionally well-known polyolefin can be used. Specific examples of polyolefin include ethylene homopolymer polyethylene, ethylene-α-olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-acetic acid. Polyethylene resin such as vinyl copolymer, polypropylene resin as propylene homopolymer, polypropylene resin such as propylene-α-olefin copolymer, polybutene as butene homopolymer, single weight of conjugated dienes such as butadiene and isoprene At least one selected from the group consisting of a polymer or a copolymer can be used. From the viewpoint of further increasing heat resistance and elastic modulus, the polyolefin is preferably a polypropylene resin.

Carbon material with graphene laminated structure:
Although it does not specifically limit as a carbon material which has the said graphene laminated structure, Graphite, a carbon nanotube, exfoliated graphite, a graphene, etc. can be used. Preferably, it is graphite or exfoliated graphite. These carbon materials may be used alone or in combination.

  The exfoliated graphite is obtained by exfoliating the original graphite and refers to a graphene sheet laminate that is thinner than the original graphite. The number of graphene sheets laminated in exfoliated graphite should be less than the original graphite.

  In the carbon material having the above graphene stacked structure, the number of graphene sheets stacked is preferably 1000 layers or more, more preferably 1500 layers or more, and further preferably 2000 layers or more.

  When the number of stacked layers is equal to or more than the above lower limit, the cost of the carbon material having a graphene stacked structure can be suppressed. On the other hand, from the viewpoint of the rigidity reinforcing effect as a filler, the upper limit of the number of graphene sheets stacked is about 3500 layers.

  Note that the number of graphene sheets stacked in graphite can be determined by measuring the thickness of graphite using a scanning electron microscope (SEM) and dividing the graphene by the thickness of the graphene sheet 0.33 nm / layer.

  The number of laminated graphene sheets of exfoliated graphite can be measured using a transmission electron microscope (TEM), and is an arithmetic average of the number of laminated exfoliated graphites.

  Moreover, content of the said carbon material is 5 to 150 weight part with respect to 100 weight part of synthetic resins. If the content of the carbon material is too small, sufficient rigidity may not be obtained. On the other hand, when there is too much content of the said carbon material, a reinforced resin layer will become weak and a shape may not be maintained.

  The content of the carbon material is preferably 8 parts by weight or more and more preferably 100 parts by weight or less with respect to 100 parts by weight of the synthetic resin.

Other additives;
The first and second reinforced resin layers may each contain an inorganic filler different from the carbon material. Examples of such inorganic fillers include talc, mica, glass fiber, cellulose fiber, carbon fiber, carbon nanotube, and carbon nanocoil.

  Various additives may be added to the first and second reinforced resin layers as optional components. Additives include, for example, antioxidants such as phenols, phosphoruss, amines, and sulfurs; ultraviolet absorbers such as benzotriazoles and hydroxyphenyltriazines; metal hazard inhibitors; hexabromobiphenyl ether, decabromo Halogenated flame retardants such as diphenyl ether; flame retardants such as ammonium polyphosphate and trimethyl phosphate; various fillers; antistatic agents; stabilizers; These may be used alone or in combination.

  In the present invention, the carbon material is preferably dispersed in the thermoplastic resin. This is because when the carbon material is dispersed in the thermoplastic resin, the rigidity of the resin laminate can be more effectively increased.

  A method for dispersing the carbon material in the thermoplastic resin is not particularly limited, but the carbon material can be dispersed by kneading the thermoplastic resin and the carbon material.

  The kneading method is not particularly limited. For example, a kneading apparatus such as a twin screw kneader such as a plast mill, a single screw extruder, a twin screw extruder, a Banbury mixer, or a roll is used for kneading under heating. The method of doing is mentioned. Among these, the method of melt kneading using an extruder is preferable.

(Foamed resin layer)
The foamed resin layer has a plurality of bubble cells inside. The expansion ratio of the foamed resin layer is 3 cc / g or more and 30 cc / g or less.

  If the expansion ratio is too small, a sufficient vibration damping effect may not be obtained. On the other hand, if the expansion ratio is too large, the rigidity of the resin laminate may be insufficient.

  The expansion ratio is preferably 5 cc / g or more and 20 cc / g or less.

  The above-mentioned foamed resin layer has a temperature at which the peak value of tan δ is in the range of −10 ° C. or higher and 30 ° C. or lower when dynamic viscoelasticity measurement is performed under conditions of a frequency of 10 Hz. Further, the peak value of tan δ is 0.5 or more. Since the temperature indicating the peak value of tan δ and the peak value of tan δ of the foamed resin layer are within the above ranges, the vibration damping property is enhanced in the resin laminate of the present invention.

  From the viewpoint of further improving the vibration damping properties of the resin laminate, the temperature at which the tan δ peak value of the foamed resin layer is more preferably in the range of −5 ° C. or more and 20 ° C. or less. The peak value of tan δ is preferably 1.0 or more. The peak value of tan δ is preferably as large as possible, but may be set to 2 or less, for example.

  The foamed resin layer is composed of a third synthetic resin and a resin composition containing a fourth synthetic resin. Note that the third synthetic resin and the resin composition are preferably incompatible.

A third synthetic resin;
The third synthetic resin is desirably the same synthetic resin as the first and second synthetic resins. When the third synthetic resin is the same synthetic resin as the first and second synthetic resins, the adhesion between the foamed resin layer and the reinforced resin layer can be further enhanced. Thereby, the rigidity of the resin laminate can be further increased. However, as long as delamination does not occur, the third synthetic resin may not be the same synthetic resin as the first and second synthetic resins.

  Although it does not specifically limit as a 3rd synthetic resin, It is preferable that it is a thermoplastic resin.

  It does not specifically limit as said thermoplastic resin, A well-known thermoplastic resin can be used. Specific examples of the thermoplastic resin include polyolefin, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyester, polyamide, polyurethane, polyethersulfone, polyetherketone, polyimide, polydimethylsiloxane, polycarbonate, or at least two of these. Examples of the copolymer include seeds. A thermoplastic resin may be used independently and multiple may be used together.

  As the thermoplastic resin, a resin having a high elastic modulus is desirable, but a polyolefin that is inexpensive and easy to mold under heating is more preferable.

  It does not specifically limit as said polyolefin, A conventionally well-known polyolefin can be used. Specific examples of polyolefin include ethylene homopolymer polyethylene, ethylene-α-olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-acetic acid. Polyethylene resin such as vinyl copolymer, polypropylene resin as propylene homopolymer, polypropylene resin such as propylene-α-olefin copolymer, polybutene as butene homopolymer, single weight of conjugated dienes such as butadiene and isoprene At least one selected from the group consisting of a polymer or a copolymer can be used. From the viewpoint of further increasing heat resistance and elastic modulus, the polyolefin is preferably a polypropylene resin.

Resin composition;
The above resin composition preferably has a temperature at which the peak value of tan δ is in the range of −10 ° C. or higher and 30 ° C. or lower when dynamic viscoelasticity measurement is performed under the condition of a frequency of 10 Hz. Further, the peak value of tan δ is preferably 0.5 or more.

  If the temperature at which the tan δ peak value of the resin composition is less than the above lower limit or exceeds the above upper limit, a sufficient vibration reducing effect may not be obtained in the operating temperature environment, that is, at room temperature.

  The temperature at which the tan δ peak value of the resin composition is in the range of −5 ° C. or higher and 20 ° C. or lower is more preferable. Further, the peak value of tan δ is more preferably 1.0 or more. The peak value of tan δ is preferably as large as possible, but may be set to 2 or less, for example.

  The temperature indicating the peak value of tan δ and the peak value of tan δ may be expressed by one kind of synthetic resin or may be expressed by mixing two kinds of compatible synthetic resins. That is, the resin composition may include a fifth synthetic resin that is compatible with the fourth synthetic resin. The tan δ measured by dynamic viscoelasticity has two peaks when two or more types of synthetic resins are mixed, but when they are not compatible, This is because it has only one peak corresponding to the blending ratio.

  The fourth and fifth synthetic resins are not particularly limited as long as the resin composition as a whole satisfies the above tan δ range. The fourth and fifth synthetic resins are preferably copolymers having an aromatic vinyl block which is a polymer of an aromatic vinyl monomer. A block copolymer having the aromatic vinyl block and a diene block which is a polymer of a conjugated diene monomer is more preferable.

  The aromatic vinyl monomer is not particularly limited. For example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene. 4-tert-butylstyrene, tert-butoxystyrene, and the like.

  The conjugated diene monomer is not particularly limited, and examples thereof include conjugated diene having 4 to 12 carbon atoms such as butadiene, isoprene, piperylene, dimethylbutadiene and the like.

  Examples of the copolymer having such an aromatic vinyl block include styrene-based elastomers.

  Specific examples of the styrene elastomer include styrene-butadiene copolymer (SB), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene copolymer (SI), and styrene-isoprene-styrene copolymer. (SIS), styrene-ethylene-butylene copolymer (SEB), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene copolymer (SEP), and styrene-ethylene-propylene-styrene. A copolymer such as a copolymer (SEPS) may be mentioned. These copolymers may be block copolymers. Further, it may be a linear type or a radial type. These copolymers may be used alone or in combination of two or more. From the viewpoint of further enhancing the buffering property and shock absorption of the obtained foamed resin layer, the styrene-based elastomer is preferably a styrene-isoprene-styrene block copolymer.

  Although it does not specifically limit as content of the said 3rd synthetic resin, It is preferable that it is 20 weight part or more with respect to 100 weight part of resin compositions, It is more preferable that it is 25 weight part or more, 50 weight Part or less. If the content of the third synthetic resin is too large, sufficient vibration damping properties may not be obtained. On the other hand, if the content of the third synthetic resin is too small, sufficient adhesion between the foamed resin layer and the reinforced resin layer may not be obtained.

Other ingredients;
Moreover, you may use various additives for the said foamed resin layer as an arbitrary component. Additives include, for example, antioxidants such as phenols, phosphoruss, amines, and sulfurs; ultraviolet absorbers such as benzotriazoles and hydroxyphenyltriazines; metal hazard inhibitors; hexabromobiphenyl ether, decabromo Halogenated flame retardants such as diphenyl ether; flame retardants such as ammonium polyphosphate and trimethyl phosphate; various fillers; antistatic agents; stabilizers; These may be used alone or in combination.

(Production method)
Although the manufacturing method of the resin laminated body 1 is not specifically limited, For example, it can manufacture with the following method.

  First, two resin sheets for forming the first and second reinforced resin layers 2 and 3 and a foam sheet for forming the foamed resin layer 4 are prepared.

  Next, the resin sheet, the foamed sheet, and the resin sheet prepared as described above are laminated in this order, and are fused by pressing. Then, the resin laminated body 1 is obtained by pressing at normal temperature.

  In addition, a resin sheet and a foam sheet can be prepared as follows, for example.

Resin sheet;
A composite material is obtained by kneading a synthetic resin and a carbon material having a graphene stacked structure. The kneading method is not particularly limited, and for example, kneading is performed using a kneading apparatus such as a twin screw kneader such as a plast mill, a single screw extruder, a twin screw extruder, a Banbury mixer, or a roll. The method etc. are mentioned.

  Then, the obtained composite material is shape | molded by press work, an extrusion process, calendering etc., and the resin sheet for forming a reinforced resin layer is produced.

Foam sheet;
First, a third synthetic resin, the above resin composition, an additive such as a pyrolytic foaming agent, and other optional components added as necessary, such as a single screw extruder or a twin screw extruder The sheet is supplied to an extruder, melt-kneaded at a temperature lower than the decomposition temperature of the pyrolytic foaming agent, and extruded by extrusion to obtain a sheet-shaped foamable composition.

  Next, the obtained sheet-shaped foamable composition is crosslinked by, for example, electron beam irradiation. Subsequently, the cross-linked sheet-shaped foam composition is heated to a temperature equal to or higher than the decomposition temperature of the thermally decomposable foaming agent and foamed. Thereby, a foam sheet is obtained.

  In addition, it is preferable that the said thermal decomposition type foaming agent is a thermal decomposition type foaming agent which has a decomposition temperature higher than the melting temperature of a synthetic resin, for example. For example, it is preferable to use a chemical foaming agent having a decomposition temperature of 160 to 270 ° C. The chemical foaming agent may be an organic foaming agent or an inorganic foaming agent. The said thermal decomposition type foaming agent may be used independently and may use 2 or more types together.

  Examples of the organic foaming agent include azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (such as barium azodicarboxylate), and azobisisobutyronitrile; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine Hydrazine derivatives such as hydrazodicarbonamide, 4,4′-oxybis (benzenesulfonylhydrazide), toluenesulfonylhydrazide; semicarbazide compounds such as toluenesulfonyl semicarbazide, and the like.

  Examples of the inorganic foaming agent include ammonium acid, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and anhydrous monosodium citrate.

  An azo compound or a nitroso compound is preferable from the viewpoint of forming fine bubbles and improving economic efficiency and safety, and azodicarbonamide, azobisisobutyronitrile or N, N′-dinitrosopentamethylenetetramine is preferable. More preferred is azodicarbonamide.

(Second Embodiment)
FIG. 2 is a schematic cross-sectional view showing a resin laminate according to the second embodiment of the present invention. As shown in FIG. 2, in the resin laminate 21, the metal layer 5 is provided on the second main surface 4 b of the foamed resin layer 4. Therefore, in the resin laminate 21, the second reinforced resin layer is not provided. Other points are the same as in the first embodiment.

  Also in the resin laminate 21, since the temperature indicating the peak value of tan δ and the peak value of tan δ of the foamed resin layer 4 are within the above range, the vibration damping property is enhanced. Moreover, since the 1st reinforced resin layer 2 and the foamed resin layer 4 are formed with resin, the resin laminated body 21 is reduced in weight. Furthermore, since the metal layer 5 is provided instead of the second reinforced resin layer 3, the rigidity of the resin laminate 21 is further enhanced.

  Although it does not specifically limit as a material which comprises the metal layer 5, For example, iron and aluminum can be used. These may be used alone or in combination.

  In addition, the resin laminated body 21 obtained the laminated body in which the 1st reinforcement | strengthening resin layer 2 was provided on the foamed resin layer 4 by the method similar to the resin laminated body 1, and the foamed resin layer in the obtained laminated body 4 can be produced by bonding the metal layer 5 to the second main surface 4b. In addition, a metal layer can be bonded together to the foamed resin layer 4 using an adhesive agent, for example.

  Hereinafter, the effects of the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

Example 1
Production of resin sheet;
100 parts by weight of a synthetic resin (trade name “MA3H” manufactured by Nippon Polypro Co., Ltd.) and 30 parts by weight of scaly graphite (trade name “CNP7” manufactured by Ito Graphite Co., Ltd.) are supplied to a plastmill at a temperature of 200 ° C. Were kneaded and cooled and press-molded at room temperature to obtain two 1 mm thick resin sheets for forming the first and second reinforced resin layers.

Production of foam sheets;
A styrene-vinylisoprene-styrene triblock copolymer containing a styrene block and a vinylisoprene block as a fourth synthetic resin with respect to 100 parts by weight of the foamed resin (trade name “HIBLER 5127”, manufactured by Kuraray Co., Ltd.) Tan δ peak value obtained by dynamic viscoelasticity measurement: 1.07, temperature showing tan δ peak value: 28.0 ° C.) 50 parts by weight, and as a fifth synthetic resin, containing styrene block and vinyl isoprene block Styrene-vinylisoprene-styrene triblock copolymer (manufactured by Kuraray Co., Ltd., trade name “HIBLER 5125”, peak value of tan δ obtained by dynamic viscoelasticity measurement: 1.03, temperature indicating peak value of tan δ: 2 .95 ° C.) 25 parts by weight and random polypropylene as a third synthetic resin Product name “EG8”, melting point: 145 ° C., crystal melting energy: 64.6 mJ / mg) 25 parts by weight, azodicarbonamide (trade name “SO-20”, manufactured by Otsuka Chemical Co., Ltd.) 4.5 weight Parts and 2.0 parts by weight of a phenolic antioxidant (manufactured by Ciba Specialty Chemicals, trade name “Irganox 1010”) are supplied by an extruder and melt-kneaded to obtain a foamable resin sheet. Obtained.

  The foamable resin sheet was crosslinked by irradiating the resulting foamable resin sheet with 3.0 Mrad of an electron beam at an acceleration voltage of 500 keV. Subsequently, the foamable resin sheet was supplied into a foaming furnace and heated at 230 ° C. to obtain a foamed sheet having a thickness of 4.0 mm and a foaming ratio of 10 cc / g.

Production of resin laminates;
The obtained resin sheet, foamed sheet, and resin sheet were laminated in this order, PET films were placed on the top and bottom, and pressed for 10 minutes with a 200 ° C. press. The clearance for the laminate was 5.8 mm. Immediately after pressing for 10 minutes, pressing was performed for 10 minutes with a normal temperature press with a clearance of 5 mm.

In addition, the clearance at the time of a heating was determined by deducting the thickness of PET film from the space | interval of the upper and lower plates of a press. The pressure was 5 kg / cm ² . Moreover, the clearance at the time of cooling at normal temperature was performed using the iron plate of thickness 5mm by which the center part was pulled out so that it might become the outer periphery of a laminated body between upper and lower PET films. This iron plate was also used during heating.

(Example 2)
Example 4 except that the amount of the fourth synthetic resin added was 40 parts by weight, the amount of the fifth synthetic resin added was 40 parts by weight, and the amount of the third synthetic resin added was 20 parts by weight. Thus, a resin laminate was obtained.

(Example 3)
A resin laminate was obtained in the same manner as in Example 1 except that the amount of scale-like graphite added was changed to 60 parts by weight.

Example 4
As a fourth synthetic resin, synthetic resin (manufactured by Asahi Kasei Chemicals, hydrogenated styrene thermoplastic elastomer, trade name “S1605”, tan δ peak value obtained by dynamic viscoelasticity measurement: 1.15, tan δ peak value As a fifth synthetic resin, a synthetic resin (manufactured by Asahi Kasei Co., Ltd., hydrogenated styrene-based thermoplastic elastomer, trade name “S1606”, dynamic viscoelasticity) was used. A resin laminate was obtained in the same manner as in Example 1 except that 25 parts by weight of the tan δ peak value obtained by measurement: 1.01, and the temperature indicating the tan δ peak value: −12.0 ° C. were used. .

(Example 5)
A resin laminate was obtained in the same manner as in Example 4 except that the fifth synthetic resin was not used and the fourth synthetic resin was 75 parts by weight.

(Comparative Example 1)
A resin laminate was obtained in the same manner as in Example 1 except that the fourth and fifth synthetic resins were not used and the third synthetic resin was 100 parts by weight.

(Comparative Example 2)
A resin laminate was obtained in the same manner as in Example 1 except that scaly graphite was not used for the resin sheets for constituting the first and second reinforced resin layers.

(Comparative Example 3)
A resin laminate was obtained in the same manner as in Example 4 except that the addition amounts of the third and fifth synthetic resins were 50 parts by weight, respectively, and the fourth synthetic resin was not used.

(Evaluation)
Dynamic viscoelasticity;
The foamed resin layers (foamed sheets) prepared in Examples and Comparative Examples were cut into a size of 5 mm width × 24 mm length × thickness 0.3 mm to prepare a test sheet. The produced test sheet was subjected to temperature dispersion measurement of dynamic viscoelasticity (−50 ° C. to 50 ° C.) under the conditions of strain amount: 0.1%, frequency: 10 Hz, heating rate: 3 ° C./min, A temperature showing a peak value of tan δ, that is, a peak temperature of tan δ and a peak value of tan δ were obtained. In addition, the temperature dispersion measurement of dynamic viscoelasticity was performed using the dynamic viscoelasticity measuring apparatus (Rheometrics company make, brand name "RSA"). The results are shown in Table 1 below.

Loss factor;
The resin laminates obtained in Examples and Comparative Examples were cut into test pieces having a length of 20 cm and a width of 2.5 cm. The loss factor of the cut-out test piece was measured by a central vibration method at 20 ° C. using a measuring apparatus (manufactured by Rion, product number “SA-01”). The target frequency was 1000 Hz to 5000 Hz. Since the above measurement method is measured at a frequency at which resonance occurs, frequencies of 1000 Hz or less and 2000 Hz or more are also measured, graphed and extrapolated to obtain numerical values of loss coefficients at 1000 Hz and 2000 Hz. . The loss factor is an index indicating the ability to attenuate vibrations, and the higher the value, the better the performance. Moreover, in the object 1000Hz-5000Hz, the thing whose loss coefficient is 0.1 or more was considered as the pass. The results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1,21 ... Resin laminated body 2 ... 1st reinforcement resin layer 3 ... 2nd reinforcement resin layer 4 ... Foam resin layer 4a ... 1st main surface 4b ... 2nd main surface 5 ... Metal layer

Claims (10)

A foamed resin layer;
A first reinforced resin layer laminated on a principal surface on one side of the foamed resin layer;
With
The first reinforced resin layer is composed of a first synthetic resin and a carbon material having a graphene laminated structure,
The content of the carbon material with respect to 100 parts by weight of the first synthetic resin is 5 parts by weight or more and 150 parts by weight or less,
The foaming ratio of the foamed resin layer is 3 cc / g or more and 30 cc / g or less,
When the dynamic viscoelasticity measurement of the foamed resin layer was performed under the condition of a frequency of 10 Hz, the temperature showing the peak value of tan δ was in the range of −10 ° C. or more and 30 ° C. or less, and the peak value of tan δ was 0 A resin laminate that is 5 or more.   A second reinforcing layer which is laminated on a main surface of the foamed resin layer opposite to the first reinforcing resin layer and is made of a carbon material having a second synthetic resin and a graphene laminated structure; The resin laminate according to claim 1, further comprising a resin layer.   The resin laminate according to claim 1 or 2, wherein each of the first and second synthetic resins is a thermoplastic resin.   The resin laminate according to claim 3, wherein the thermoplastic resin is a polyolefin resin.   The resin laminate according to claim 1, further comprising a metal layer laminated on a main surface of the foamed resin layer opposite to the first reinforced resin layer. The foamed resin layer is composed of a third synthetic resin and a resin composition containing a fourth synthetic resin,
The resin laminate according to any one of claims 1 to 5, wherein a content of the third synthetic resin with respect to 100 parts by weight of the resin composition is 20 parts by weight or more and 50 parts by weight or less.   When the dynamic viscoelasticity measurement of the resin composition constituting the foamed resin layer is performed at a frequency of 10 Hz, the temperature showing the peak value of tan δ is in the range of −10 ° C. or higher and 30 ° C. or lower. And the peak value of tan-delta is 0.5 or more, The resin laminated body of Claim 6.   The resin laminate according to claim 6 or 7, wherein the third synthetic resin is a polyolefin resin.   The resin laminate according to any one of claims 6 to 8, wherein the resin composition constituting the foamed resin layer further contains a fifth synthetic resin.   The resin laminate according to claim 9, wherein at least one of the fourth and fifth synthetic resins is a copolymer containing an aromatic vinyl block.

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