JP2024012122A - Articles and methods of manufacturing articles - Google Patents

Abstract

To provide an article which is improved at least in one of in vibration-damping property, acoustic property, and plasticity in articles using FRP.SOLUTION: An article has between a first fiber-reinforced plastic layer and a second fiber-reinforced plastic layer, a layer of a polymer composition having a loss tangent (Tanδ) of 0.2 or more at 20°C in a whole range of a frequency between 100 Hz and 4,000 Hz. A production method of the article includes a step of laminating a first prepreg and a second prepreg via a sheet comprising a polymer composition having a loss tangent (Tanδ) of 0.2 or more at 20°C in a whole range of a frequency between 100 Hz and 4,000 Hz, and heating and compressing the product.SELECTED DRAWING: Figure 1

Description

FIELD OF THE INVENTION The present invention relates to an article having a layer of a polymer composition between layers of fiber-reinforced plastic, and a method of making the article.

Fiber-reinforced plastic (hereinafter referred to as FRP) is lightweight, has high strength, has excellent corrosion resistance, and has a higher degree of freedom in molding than metals, so it is used for bathtubs, tanks, boards, pipes, building materials, industrial materials, and automobiles. It is used in a wide range of products such as parts. In particular, in recent years, FRP using carbon fiber as a reinforcing fiber has been used for products such as aviation parts, sports and leisure goods such as golf shafts and tennis rackets, and industrial materials such as ship parts because of its excellent weight reduction properties. It has begun to be put into practical use as automobile parts, taking advantage of its light weight and strength characteristics.

One of the methods for molding FRP is a press molding method using prepreg such as sheet molding compound (hereinafter referred to as SMC). This method is widely used because it has high productivity and can produce molded products with complex shapes.

In order to satisfy market demands for articles using FRP, techniques for laminating FRP and other materials are known.
For example, in Patent Document 1, an FRP composite structure obtained by placing an elastic body between SMCs, charging them into a mold, and press-molding the object is to provide an FRP molded product with improved impact resistance. things are being proposed.
In addition, Patent Document 2 aims to provide a technology that can obtain an FRP member having a smooth surface without impairing the lightness of FRP. A technique has been proposed in which a high elastic modulus surface layer having a specific tensile elastic modulus range is provided through a low elastic modulus surface layer having a specific tensile elastic modulus.
Patent Document 3 proposes a laminate molded product including a layer made of carbon fiber reinforced plastic and a layer made of thermoplastic elastomer.

Japanese Unexamined Patent Publication No. 127317/1983 Japanese Patent Application Publication No. 2006-51813 Japanese Patent Application Publication No. 2018-154827

Although products using FRP have excellent properties as mentioned above, they are lightweight and have high specific rigidity, so when struck, they produce a harsh high-pitched sound. It has been found that there are cases where high vibration damping performance is required.
Furthermore, there is a trade-off in FRP in that increasing rigidity reduces toughness.

An object of the present invention is to provide an article using FRP in which at least one of vibration damping properties, acoustic properties, and toughness is improved.

[1] Between the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer, the loss tangent (Tan δ) is 0.2 or more at 20°C over the entire frequency range between 100 Hz and 4,000 Hz. An article having a layer of a polymeric composition.

[2] The article according to [1], wherein at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contains a cured thermosetting resin.

[3] The article according to [2], wherein both the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contain a cured thermosetting resin.

[4] The article according to any one of [1] to [3], wherein at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contains discontinuous fibers.

[5] The article according to [4], wherein both the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contain discontinuous fibers.

[6] Any one of [1] to [5], wherein at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contains one or more types of fibers selected from carbon fibers and glass fibers. Articles described in Crab.

[7] The article according to any one of [1] to [6], wherein the polymer composition includes a polymer having a polar group.

[8] The article according to [7], wherein the polymer composition includes acrylonitrile butadiene rubber.

[9] The article according to [7], wherein the polymer composition is a thermoplastic polymer composition containing the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group

[10] The article according to [9], wherein the polyolefin having a polar group includes a maleic anhydride-modified polyolefin.

[11] The article according to any one of [1] to [10], which is a bat.

[12] The article according to any one of [1] to [10], which is an automobile roof panel.

[13] The first prepreg and the second prepreg are made of a sheet made of a polymer composition whose loss tangent (Tan δ) is 0.2 or more at 20°C over the entire frequency range between 100 Hz and 4,000 Hz. A method for manufacturing an article, which includes the steps of laminating the article through a substrate, heating and pressurizing the article.

[14] The method for manufacturing an article according to [13], wherein at least one of the first prepreg and the second prepreg contains a thermosetting resin.

[15] The method for manufacturing an article according to [14], wherein both the first prepreg and the second prepreg contain a thermosetting resin.

[16] The method for producing an article according to any one of [13] to [15], wherein at least one of the first prepreg and the second prepreg contains discontinuous fibers.

[17] The method for producing an article according to [16], wherein both the first prepreg and the second prepreg contain discontinuous fibers.

[18] The article according to any one of [13] to [17], wherein at least one of the first prepreg and the second prepreg contains one or more types of fibers selected from carbon fibers and glass fibers. Production method.

[19] The method for producing an article according to any one of [13] to [18], wherein the polymer composition contains a polymer having a polar group.

[20] The method for producing an article according to [19], wherein the polymer composition contains acrylonitrile butadiene rubber.

[21] The method for producing an article according to [19], wherein the polymer composition is a thermoplastic polymer composition containing the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group

[22] The method for producing an article according to [21], wherein the polyolefin having a polar group includes a maleic anhydride-modified polyolefin.

According to the present invention, it is possible to provide an article using FRP in which at least one, preferably all, of vibration damping properties, acoustic properties, and toughness are improved.

FIG. 1(a) is a chart showing the impulse response results in the evaluation of the vibration damping time of the panel manufactured in Example 1, and FIG. 1(b) is a chart showing the evaluation of the vibration damping time of the panel manufactured in Comparative Example 1. 3 is a chart showing impulse response results in FIG. 2 is a chart showing inertance measurement results in evaluation of vibration damping amount of panels manufactured in Example 1 and Comparative Example 1. FIG. 1 is a schematic diagram showing an example of the configuration of an SMC manufacturing apparatus. FIG. 3 is a schematic diagram showing a flatwise tensile test method in Example 4 and Comparative Examples 5 and 6.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the contents described below, but within the scope in which the effects of the invention can be achieved. can be implemented with arbitrary modifications.
In the present invention, when expressed using "~" with numerical values or physical property values placed before and after it, it is assumed that the values before and after it are included.

[Goods]
The article according to the embodiment has a loss tangent (Tan δ) of 0 at 20°C over the entire frequency range between 100 Hz and 4,000 Hz between the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer. .2 or more (hereinafter sometimes referred to as "polymer composition (A)").

[First fiber reinforced plastic layer]
The first fiber-reinforced plastic layer (hereinafter sometimes referred to as "first FRP layer") consists of fiber reinforcement and a matrix impregnated into the fiber reinforcement. In other words, the fiber reinforcement is impregnated with the matrix.

The matrix is a resin composition, which may be a cured thermosetting resin composition or a thermoplastic resin composition.

If the matrix is a cured thermosetting resin composition, one or more thermosetting resins selected from, but not limited to, unsaturated polyester resins, vinyl ester resins, epoxy resins, polyimide resins, maleimide resins, and phenolic resins. A cured product of resin may be included. Epoxy resins and vinyl ester resins are known to give cured products with good adhesion to carbon fibers.

When the matrix is a thermoplastic resin composition, it may include, but is not limited to, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, ABS resin, acrylic resin, vinyl chloride, polyamide 6, etc. One or more thermoplastic resins selected from polyamide, polycarbonate, polyphenylene ether, polyether sulfone, polysulfone, polyetherimide, polyketone, polyether ketone, polyether ether ketone, and modified products of these resins may be included.

The matrix may contain various additives, fillers, colorants, etc. in addition to the above resin components.

Examples of fibers that the fiber reinforcement may contain include, but are not limited to, inorganic fibers, organic fibers, metal fibers, and natural fibers.

Examples of inorganic fibers include, but are not limited to, carbon fibers, graphite fibers, silicon carbide fibers, alumina fibers, tungsten carbide fibers, boron fibers, and glass fibers. Typical examples of carbon fibers include polyacrylonitrile (PAN) carbon fibers, rayon carbon fibers, and pitch carbon fibers.
Organic fibers include aramid fibers, high density polyethylene fibers, nylon fibers and polyester fibers.
Examples of metal fibers include stainless steel fibers and iron fibers.
Natural fibers include plant-derived fibers such as hemp.
Both fibers can be metal coated if desired.
Among these, glass fiber and carbon fiber are preferable in consideration of mechanical properties such as strength of the first FRP layer. Among these, carbon fiber is particularly preferred from the viewpoint of high specific strength and specific rigidity and excellent weight reduction effect.

The fiber reinforcement material may be composed of only one type of fiber, or may contain two or more types of fiber.

The fiber reinforcement material may include one or both of continuous fibers and short fibers (cut fibers). When the fiber reinforcement material includes continuous fibers, the continuous fibers may be aligned in one direction. The fiber reinforcement may include continuous fibers in the form of a woven fabric. The fiber reinforcement material may be a nonwoven fabric made of continuous fibers, short fibers, or both. The fiber reinforcement material may be a mat made of chopped fibers.

The content of the fiber reinforcing material in the first FRP layer varies depending on the use and required characteristics of the article, and is not particularly limited. When the fiber reinforcement material consists essentially of carbon fibers, the fiber content is preferably 40 to 80% by mass, more preferably 50 to 70% by mass. If the carbon fiber content of the fiber reinforcing material is at least the above lower limit, the reinforcing effect of the fiber reinforcing material will be excellent. If the carbon fiber content of the fiber reinforcing material is below the above upper limit, moldability, surface smoothness, etc. will be excellent.

The thickness of the first FRP layer varies depending on the intended use and required characteristics of the article to be obtained, and is not particularly limited, but is preferably 0.5 to 5.0 mm, more preferably 1.0 to 2.0 mm. . If the thickness of the first FRP layer is at least the above-mentioned lower limit, sufficient mechanical strength can be obtained, and if it is below the above-mentioned upper limit, the article can be made thinner and lighter.

[Second fiber reinforced plastic layer]
Similarly to the first FRP layer, the second fiber-reinforced plastic layer (hereinafter sometimes referred to as "second FRP layer") also includes fiber reinforcement and fiber reinforcement. It consists of an impregnated matrix. In other words, the fiber reinforcement is impregnated with the matrix.
Also in the second FRP layer, as the matrix, fiber reinforcement, etc., the same materials as those described above as the matrix, fiber reinforcement, etc. used in the first FRP layer can be used. The preferred content and thickness of the fiber reinforcing material for the second FRP layer are also the same as those for the first FRP layer.

However, the first FRP layer and the second FRP layer do not need to have the same configuration, and may be different in the type and composition of the matrix, the type and content of the fiber reinforcing material, the thickness, etc.

From the viewpoint of suppressing warping of the obtained article, it is preferable that the first FRP layer and the second FRP layer have the same structure.
On the other hand, by making the first FRP layer and the second FRP layer different in structure, it is possible to obtain an article having different physical properties on the front and back sides.

[Layer of polymer composition (A)]
The article of the present invention has a loss tangent (Tan δ) between the first FRP layer and the second FRP layer of 0.2 or more at 20°C over the entire frequency range between 100 Hz and 4,000 Hz. It has a layer of polymer composition (A).

Generally, the loss tangent (Tan δ) of a polymer composition has a correlation with the vibration damping property of the polymer composition, and the larger the value of the loss tangent, the higher the efficiency of converting vibration energy into thermal energy, and the vibration damping property They tend to be excellent.
Therefore, by creating a structure in which a layer of a polymer composition having a specific dynamic viscoelasticity is arranged between the first FRP layer and the second FRP layer, the vibration damping properties of the FRP article can be improved. can be improved. At this time, a layer of a polymer composition (A) having a loss tangent (Tan δ) of 0.2 or more at 20° C. over the entire frequency range between 100 Hz and 4,000 Hz is arranged as the layer of the polymer composition. As a result, it is possible to absorb vibrations in the solid-borne sound caused by vibrations in the frequency range from around 60 Hz to around 4000 Hz, which is said to be the frequency range of sound that is harsh to humans, and to obtain good acoustic characteristics. A polymer composition having a loss tangent (Tan δ) of less than 0.2 between frequencies of 100 Hz and 4,000 Hz may not have a sufficient vibration absorbing effect and may have poor acoustic properties.

From the viewpoint of obtaining good acoustic properties, the value of loss tangent in the polymer composition (A) is preferably 0.3 or more at 20°C over the entire frequency range between 100 Hz and 4,000 Hz, and 0.3 or more at 20°C. It is more preferably 35 or more, and even more preferably 0.40 or more.

The loss tangent (Tan δ) of the polymer composition between 100 Hz and 4000 Hz at 20° C. can be known from a loss tangent (Tan δ) master curve created based on dynamic viscoelasticity measurements.
The master curve of loss tangent (Tanδ) is obtained by measuring the frequency dispersion of viscoelastic properties at multiple temperatures using a viscoelasticity tester, as shown in JP-A-11-304636 and JP-A-2021-25891. After that, a shift factor is determined using the WLF formula (empirical formula (13) described in JIS K6394), and the frequency dependence curve at each measurement temperature is shifted according to this shift factor.

Specific conditions for dynamic viscoelasticity measurement are as shown in the Examples section below.
As described below, the polymer composition (A) may contain a thermosetting polymer classified as a rubber, but this means that the polymer composition (A) is in a rubber state at room temperature (15 to 30°C). does not mean that it is. Rather, it is preferable that the temperature range in which the polymer composition (A) transitions from a glass state to a rubber state includes a temperature range that includes room temperature.

The thickness of the layer of the polymer composition (A) varies depending on the use of the article, required characteristics, etc., and is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, and preferably It is 2.0 mm or less, more preferably 0.5 mm or less.
When the thickness of the layer of polymer composition (A) is at least the above lower limit, a more preferable improvement effect can be obtained in at least one of vibration damping properties, acoustic properties, and toughness. Furthermore, by interposing the layer of polymer composition (A) between the first FRP layer and the second FRP layer, the surface smoothness of the article is improved compared to the case where this layer is not interposed. obtain.
When the thickness of the layer of polymer composition (A) is below the above upper limit, the mechanical strength of the first FRP layer and the second FRP layer is not impaired, and the article can be made thin and lightweight. Can be done.
From the same point of view, in the laminated portion of the first FRP layer/polymer composition (A) layer/second FRP layer, the ratio of the polymer composition (A) layer to the thickness is 5 to 50. %, particularly preferably 10 to 30%.

The polymer contained in the polymer composition (A) may be thermosetting or thermoplastic.

Specific examples of thermosetting polymers include natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, hydrogenated nitrile rubber, butyl rubber, ethylene propylene rubber, ethylene vinyl acetate rubber, acrylic rubber, polyurethane rubber, and silicone rubber. , fluororubber. These may be used alone or in combination of two or more.
Thermoplastic polymers include polyolefins, polyurethanes, polyesters, and polyamides. These may be used alone or in combination of two or more.

Among these, a polymer with high adhesiveness to the matrix resin of the first FRP layer and the second FRP layer is suitable.
For example, when the matrix resin of the first FRP layer and/or the second FRP layer is thermoplastic, the polymer composition (A ) preferably contains a thermoplastic polymer.

Among the above-mentioned thermosetting polymers, acrylonitrile butadiene rubber is particularly preferred because the loss tangent (Tan δ) can be easily controlled by adjusting the component ratio of acrylonitrile.
When the polymer composition (A) is thermoplastic, it is particularly preferable to contain a polyolefin having a polar group, and particularly preferably to contain the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group

When the matrix resin of the first FRP layer and/or the second FRP layer contains one or more selected from unsaturated polyester resin, vinyl ester resin, epoxy resin, maleimide resin, and phenolic resin, the polymer composition It is preferable that (A) contains a polymer having a polar group.
The polymer having a polar group may be thermosetting or thermoplastic.
Examples of the thermosetting polymer having a polar group include chloroprene rubber, acrylonitrile butadiene rubber, acrylic rubber, and polyurethane rubber.
Thermoplastic polymers having polar groups include polyolefins, polyurethanes, polyesters, and polyamides having heteroatom-containing groups.

In particular, when the matrix resin of the first FRP layer and/or the second FRP layer contains one or more selected from unsaturated polyester resin, vinyl ester resin, epoxy resin, maleimide resin, and phenolic resin, the polymer composition It is preferable that (A) is a thermoplastic polymer composition containing the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group

In the polymer composition (A) containing the above component (a) and component (b), the conjugated diene polymer block (B) of component (a) is isoprene having 3,4 bonds or having 1,2 bonds. By adjusting the content of isoprene, the loss tangent (Tan δ) can be controlled to be 0.2 or more at 20° C. over the entire frequency range between 100 Hz and 4,000 Hz.
Polymer composition (A) containing the above component (a) and component (b) includes the following components (c), component (d), and component (e) in addition to component (a) and component (b). may further include.
Component (c): Hydrogenated block copolymer Component (d): Hydrocarbon softener for rubber Component (e): Olefin polymer

<Component (a)>
Component (a) consists of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) triblock copolymer.

Monomers constituting the vinyl aromatic compound polymer block (A) include styrene, t-butylstyrene, α-methylstyrene, o-, m-, p-methylstyrene, 1,3-dimethylstyrene, vinyl Examples include naphthalene and vinylanthracene, with styrene and α-methylstyrene being particularly preferred.

The lower limit of the content of the vinyl aromatic compound polymer block (A) of component (a) is preferably 10% by mass or more, more preferably 15% by mass or more from the viewpoint of mechanical properties such as tensile strength and heat resistance. . The upper limit of the content of the vinyl aromatic compound polymer block (A) of component (a) is determined by flexibility, rubber elasticity, and bleed when used in combination with the rubber hydrocarbon softener of component (d) described below. From the viewpoint of suppression, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

The monomer constituting the conjugated diene polymer block (B) includes isoprene having 3,4 bonds and/or isoprene having 1,2 bonds, and may contain butadiene.
That is, polyisoprene has four microstructures: cis-1,4 bonds, trans-1,4 bonds, 1,2 bonds, and 3,4 bonds, and among these, isoprene polymers having 1,2 bonds If it is an isoprene polymer block having 3,4 bonds, the double bond will be present in the side chain rather than the main chain of the block copolymer, and this side chain double bond will have 2 carbon atoms. Or, it is thought that the side chain hydrocarbon group of 3 contributes to vibration damping properties.
This vibration damping effect due to the side chain double bond is similarly achieved by the carbon chain even if the double bond becomes a single bond due to hydrogenation.
On the other hand, isoprene with cis-1,4 bonds and trans-1,4 bonds has a double bond incorporated into the main chain and only has side chain hydrocarbon groups with 1 carbon number, so It is presumed that a vibration damping effect as high as that of the side chain hydrocarbon group of No. 3 cannot be obtained.

From the viewpoint of vibration damping properties, the total content of isoprene having 3,4 bonds and isoprene having 1,2 bonds in the conjugated diene polymer block (B) is preferably 40% by mass or more, and 50% by mass or more. It is preferably at least 70% by mass, even more preferably at least 99% by mass.
Note that the content of isoprene having 3,4 bonds and isoprene having 1,2 bonds can be determined by ¹³ C-NMR measurement.

Component (a) may be a hydrogenated block polymer in which some or all of the carbon-carbon double bonds of the conjugated diene polymer block (B) are hydrogenated. When component (a) is a hydrogenated block copolymer, the hydrogenation rate is preferably 50% or more, and 70% or more in hydrogenation rate of carbon-carbon double bonds of conjugated diene polymer block (B). is more preferable, and even more preferably 95% or more. In addition, in component (a), the above-mentioned "hydrogenation rate is 50% or more" and the above-mentioned "at least 50% of the double bonds in the isoprene moiety are saturated by hydrogenation" have the same meaning. be.
Here, the hydrogenation rate can be measured by ¹³ C-NMR. The same applies to the hydrogenation rate of component (c), which will be described later.

The molecular structure of the (A)-(B)-(A) triblock copolymer of component (a) may be linear, branched, radial, or a combination thereof.

The lower limit of the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography for component (a) is determined by flexibility, rubber elasticity, and bleed when used in combination with component (d), a rubber hydrocarbon softener. From the viewpoint of suppression, it is preferably 30,000 or more, more preferably 50,000 or more. The upper limit of the weight average molecular weight of component (a) is preferably 300,000 or less, more preferably 250,000 or less from the viewpoint of fluidity.

Component (a) may be produced by any method as long as the above structure and physical properties can be obtained. For example, the method disclosed in Japanese Patent Publication No. 40-23798, or the method of carrying out block polymerization in an inert solvent in the presence of a lithium catalyst, can be employed. Further, hydrogenation treatment of these block copolymers is described in, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Application Laid-open No. 133203-1983, and Japanese Patent Application Laid-open No. 79005-1989. The published method can be carried out in an inert solvent in the presence of a hydrogenation catalyst.

Examples of commercially available products of component (a) include products such as "Hyblar (registered trademark)" (manufactured by Kuraray Co., Ltd.).

Component (a) may be used alone or in a mixture of two or more types having different block configurations, physical properties, etc.

<Component (b)>
The polyolefin having a polar group, component (b) contained in the polymer composition (A), can be obtained by modifying an unmodified polyolefin with a compound having polarity.

As the polar compound as a modifier, α,β-unsaturated carboxylic acid can be suitably used. Examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. As the modifier, derivatives of these α,β-unsaturated carboxylic acids may be used, and examples of the derivatives include acid anhydrides and esters of these α,β-unsaturated carboxylic acids, and further, Derivatives such as acid halides, amides, and imides may also be used. Among these, maleic acid or its anhydride is particularly preferred. Therefore, it is preferable that the polyolefin having a polar group contains a maleic anhydride-modified polyolefin.

Examples of unmodified polyolefins include, but are not limited to, ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, and 3-methylpentene-1. , 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-1, Dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyl A homopolymer of α-olefins such as octene-1, methylethylheptene-1, diethylhexene-1, dodecene-1 and hexadodecene-1, or any two or more of these α-olefins as a raw material monomer. Examples include copolymers that

Particularly preferred polyolefins have a melt flow rate (MFR) according to JIS K7210: measured at 190°C and a load of 21.2N for polymers whose main component is ethylene, and 230°C for polymers whose main component is propylene. , measured under a load of 21.2N) is 0.01 to 200 g/10 min, preferably 0.1 to 100 g/10 min. Propylene polymers are preferred because they are easy to use. As the propylene polymer, a propylene homopolymer, a propylene/ethylene random copolymer, or a propylene/butene-1 random copolymer is preferable.

It is also possible to use commercially available ethylene polymers and propylene polymers. Commercially available polyethylene includes Novatec (registered trademark) PE from Japan Polyethylene Co., Ltd., LDPE resin from ENEOS NUC, Suntec (registered trademark) from Asahi Kasei, Sumikasen (registered trademark) from Sumitomo Chemical Co., Ltd., and UBE polyethylene from Ube Maruzen Polyethylene Co., Ltd. Examples include.
Commercially available polypropylene includes Novatec (registered trademark) PP from Nippon Polypro, Prime Polypro (registered trademark) from Prime Polymer, Sumitomo Noblen (registered trademark) from Sumitomo Chemical, polypropylene block copolymer from Sunaromer, and Moplen from Lyondell Basell. (registered trademark).

The polyolefin having a polar group used in the present invention is preferably a polyolefin having a modification rate of 0.1 to 20% by mass with α,β-unsaturated carboxylic acid, and this modification rate is 0.2 to 10% by mass. It is more preferable. By setting the modification rate within the above numerical range, it is possible to suppress the incorporation of unreacted substances and by-products and to produce a polymer composition (A) that has sufficient adhesiveness with the first and second FRP layers. Can be done.

In addition, when the polyolefin having a polar group is an α,β-unsaturated carboxylic acid-modified polyolefin, the modification rate with α,β-unsaturated carboxylic acid can be determined by, for example, ¹ H-NMR, infrared absorption spectrum, high-frequency plasma This can be confirmed by ICP emission spectrometry using an emission spectrometer. That is, for example, when the α,β-unsaturated carboxylic acid is maleic acid, the absorption peculiar to maleic acid in a sample press-molded into a sheet with a thickness of about 100 μm, specifically 1900 to 1600 cm ⁻¹ (C It can be determined by measuring the carbonyl characteristic absorption of =O stretching vibration band).
The amount of α,β-unsaturated carboxylic acid in the α,β-unsaturated carboxylic acid-modified polyolefin measured in this way is determined by This is the sum of the amount of α,β-unsaturated carboxylic acid and the α,β-unsaturated carboxylic acid component not grafted to this polyolefin. In the present invention, the sum of the α,β-unsaturated carboxylic acid component grafted to the polyolefin of the modification base material and the ungrafted α,β-unsaturated carboxylic acid component measured by the above measurement method is Unsaturated carboxylic acid amount or modification rate.

The modification method for producing the α,β-unsaturated carboxylic acid-modified polyolefin is not particularly limited, and a solution modification method in which the reaction is performed in an organic solvent or a melt modification method in which the modification is performed in an extruder can be adopted.

Such α,β-unsaturated carboxylic acid-modified polyolefins may be used alone, or α,β-unsaturated carboxylic acids as modifiers, polyolefins as base materials for modification, polyolefins with different modification rates, etc. may be used. Two or more types may be mixed and used.

From the viewpoint of ease of controlling the modification rate, the most preferred α,β-unsaturated carboxylic acid-modified polyolefin used in the present invention as component (b) is a maleic anhydride-modified propylene homopolymer.

<Component (c): Hydrogenated block copolymer>
Component (c) is a hydrogenated product of a block copolymer consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (C), preferably by hydrogenation to It is a hydrogenated block copolymer in which at least 80% of the bonds are saturated (hydrogenation rate of 80% or more) and the weight average molecular weight is 80,000 to 1,000,000.

Examples of vinyl aromatic compounds constituting the vinyl aromatic compound polymer block (A) include styrene, t-butylstyrene, α-methylstyrene, o-, m-, p-methylstyrene, and 1,3-dimethylstyrene. , vinylnaphthalene, vinylanthracene, etc., and styrene and α-methylstyrene are particularly preferred.

The lower limit of the content of the vinyl aromatic compound polymer block (A) of component (c) is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoint of mechanical properties such as tensile strength and heat resistance. , more preferably 20% by mass or more. The upper limit of the content of the vinyl aromatic compound polymer block (A) of component (c) is determined by flexibility and rubber elasticity, and when used in combination with the rubber hydrocarbon softener of component (d) described below. From the viewpoint of suppression, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

The conjugated diene polymer block (C) of component (c) is different from the conjugated diene polymer block (B) of component (a) described above, and is different from the conjugated diene polymer block (C) of component (c). Conjugated diene monomers constituting include, for example, butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4, One or more of 5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc., or a combination of isoprene and one or more of these conjugated diene monomers. Can be mentioned. However, isoprene does not include isoprene having 3,4 bonds and isoprene having 1,2 bonds. Among these, butadiene or a mixture of butadiene/isoprene in a mass ratio of 2/8 to 6/4 is particularly preferred.

Component (c) is not particularly limited as long as it has a structure having a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (C), and may be linear, branched, radial, etc. However, a hydrogenated block copolymer obtained by hydrogenating a block copolymer represented by the following formula (1) or (2) is preferable.

A-(C-A) _m (1)
(A-C) _n (2)
(In the formula, A represents a vinyl aromatic compound polymer block (A), C represents a conjugated diene polymer block (C), m represents an integer of 1 to 5, and n represents an integer of 1 to 5. show.)

In formula (1) or (2), m and n are preferably larger in terms of lowering the order-disorder transition temperature of the rubber-like polymer, but smaller in terms of ease of production and cost. good.

As the hydrogenated block copolymer of component (c), the hydrogenated block copolymer represented by formula (1) is preferable to the hydrogenated block copolymer represented by formula (2) because it has excellent rubber elasticity. A hydrogenated block copolymer represented by the formula (1) in which m is preferably 3 or less, more preferably a hydrogenated block copolymer represented by the formula (1) in which m is 2 or less. is more preferred, and a hydrogenated block copolymer represented by formula (1) where m is 1 is most preferred.

The lower limit of the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography for component (c) is determined by rubber elasticity and mechanical strength, and when used in combination with component (d), a rubber hydrocarbon softener, as described below. From the viewpoint of suppressing bleeding, it is preferably 80,000 or more. From the viewpoint of fluidity, the upper limit of the weight average molecular weight of component (c) is preferably 1,000,000 or less, more preferably 600,000 or less, and even more preferably 400,000 or less.

Component (c) can be produced in the same manner as component (a).

In addition, the hydrogenated block copolymer of component (c) may be a block copolymer in which the polymer molecular chain is extended or branched via a coupling agent residue. Coupling agents used in this case include, for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, 1,2-dibromoethane, 1,4-chloromethylbenzene, Examples include bis(triclosilyl)ethane, epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-benzene triisocyanate.

Commercially available products of component (c) include "TAIPOL (registered trademark)" manufactured by TSRC, "KRATON (registered trademark)-G" manufactured by Kraton Polymer Co., Ltd., "Septon (registered trademark)" manufactured by Kuraray Co., Ltd., and Asahi Kasei Chemicals. An example of this is "Tuftec (registered trademark)".

Component (c) may be used alone or in a mixture of two or more types having different block configurations, physical properties, etc.

<Component (d): Hydrocarbon softener for rubber>
Component (d) is a hydrocarbon softener for rubber (hereinafter sometimes referred to as "hydrocarbon softener for rubber (d)").

As the hydrocarbon softener (d) for rubber, a hydrocarbon having a weight average molecular weight of usually 300 to 2,000, preferably 500 to 1,500 is used, and mineral oil hydrocarbons or synthetic resin hydrocarbons are used. suitable. Here, the weight average molecular weight is a polystyrene equivalent molecular weight measured by gel permeation chromatography.

Generally, mineral oil-based rubber softeners are mixtures of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons. Oils in which the proportion of carbon in aromatic hydrocarbons is 35% by mass or more based on the total carbon content are called aromatic oils, and those in which the proportion of carbon in naphthenic hydrocarbons is 30 to 45% by mass are called naphthenic oils and paraffinic oils. Hydrocarbons with a carbon content of 50% by mass or more are called paraffin oils. In the present invention, paraffin oil is preferably used.

The rubber hydrocarbon softener (d) may be used alone or in combination of two or more.

<Component (e): Olefin polymer>
The polymer composition (A) may contain an olefin polymer to the extent that adhesion is not affected, and heat resistance can be improved by blending the olefin polymer.

The olefin polymer of component (e) (hereinafter sometimes referred to as "olefin polymer (e)") includes ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3 -Methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1 , ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene Homopolymers of α-olefins such as -1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1 and hexadodecene-1, or Copolymers containing any two or more of these α-olefins as raw material monomers can be mentioned. Further, a copolymer of ethylene and an α-olefin or a vinyl monomer such as vinyl acetate or ethylene acrylate can also be used.

Among these olefin polymers (e), propylene polymers having crystallinity are preferred from the viewpoint of heat resistance and compatibility, and propylene homopolymers, propylene block copolymers, and propylene random polymers are preferred. .

The melt flow rate (MFR: measured under the conditions of 230° C. and 21.2 N load according to JIS K7210) of the olefin polymer (e) is preferably 0.01 to 100 g/10 min, more preferably 0.1 ~70g/min. By using a material with an MFR greater than or equal to the above lower limit, it tends to have excellent fluidity and be easily molded, and by using one having an MFR less than the above upper limit, it becomes easier to control the melt viscosity to be desirable for sheet molding.

The olefin polymer (e) may be used alone or in combination of two or more different monomer compositions and physical properties.

<Content of each component>
The polymer composition (A) containing the above component (a) and component (b) may contain component (c), component (d), and component (e) in addition to component (a) and component (b). It preferably contains components (a) to (c), more preferably contains components (a) to (d), and even more preferably contains components (a) to (e).

When the polymer composition (A) containing the above component (a) and component (b) further contains components (c) to (e), component (c) and component The total content of (d) is 30 to 500 parts by mass, the content of component (e) is 3 to 500 parts by mass, and component (c) accounts for 100% by mass in total of component (c) and component (d). ) is preferably 20 to 80% by weight and component (d) is preferably 80 to 20% by weight.

In addition, in the case where component (b) is an α,β-unsaturated carboxylic acid-modified polyolefin, the polymer composition (A) containing the above component (a) and component (b) may be an α,β-unsaturated carboxylic acid-modified polyolefin. Components (a) and (b), as well as optional components (c) to (e ) is preferably blended. By setting the α,β-unsaturated carboxylic acid content in the polymer composition (A) to 0.01 to 10% by mass, sufficient adhesion and adhesion to the first and second FRP layers can be obtained. be able to. The α,β-unsaturated carboxylic acid content of the polymer composition (A) containing the above component (a) and component (b) is more preferably 0.01 to 8% by mass, and even more preferably 0.01 to 8% by mass. 01 to 6% by mass.

<Organic peroxide>
A polymer composition (A) containing components (a) and (b) is prepared by extruding components (a) and (b) together with components (c), (d), and (e) used as necessary. It can be manufactured by heating and mixing using a mixer such as a machine, but at that time, an organic peroxide or a crosslinking aid may be mixed to perform the crosslinking treatment.

Examples of organic peroxides include dimethyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, and 2,5-dimethyl-2,5- Di-(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl -4,4,-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide , t-butylcumyl peroxide, preferably 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(t- butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4, -bis(t-butylperoxy)valerate. These organic peroxides can be used alone or in combination of two or more.

For example, when the organic peroxide contains components (a) to (e), the amount is usually 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, based on a total of 100 parts by mass of all these components. It is used in a range of 2 parts by mass.

During crosslinking treatment with these organic peroxides, sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane - Peroxy crosslinking aids such as -N,N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate Polyfunctional methacrylate monomers such as polyfunctional methacrylate monomers such as vinyl butyrate, polyfunctional vinyl monomers such as vinyl acetate can be blended.

For example, when the above-mentioned crosslinking aid, polyfunctional methacrylate, or polyfunctional vinyl polymer contains all of components (a) to (e), the amount of the crosslinking aid, polyfunctional methacrylate, or polyfunctional vinyl polymer is usually It is used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight.
preferable.

<Other ingredients>
The polymer composition (A) may contain various additives such as stabilizers, lubricants, antioxidants, ultraviolet absorbers, foaming agents, flame retardants, colorants, and fillers, as well as the above component (a), as necessary. , (b), (c), and (e) may be blended with other thermoplastic resins or rubbers.

Among these, it is particularly preferable to contain an antioxidant as a stabilizer. Examples of antioxidants include monophenol-based, bisphenol-based, tri- or higher polyphenol-based, thiobisphenol-based, naphthylamine-based, diphenylamine-based, and phenylenediamine-based antioxidants. Among these, monophenol-based, bisphenol-based, tri- or higher polyphenol-based, and thiobisphenol-based antioxidants are preferred. When blending an antioxidant, when the polymer composition (A) contains all components (a) to (e), the amount added is usually 0 to 100 parts by mass of all components. 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. If the amount added is less than 0.01 parts by mass, it is difficult to obtain the effect of the antioxidant, and if it exceeds 5 parts by mass, an improvement effect commensurate with the amount added cannot be obtained, which is not preferable in terms of cost.

Examples of fillers include glass fibers, hollow glass spheres, carbon fibers, talc, calcium carbonate, mica, potassium titanate fibers, silica, metal soaps, titanium dioxide, and carbon black. These can be used alone or in any combination and ratio of two or more.

Examples of thermoplastic resins other than the above components (a), (b), (c), and (d) include polyphenylene ether resins, polyamide resins such as nylon 6 and nylon 66, polyethylene terephthalate, and polybutylene terephthalate. Examples include polyester resins, polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers, polymethyl methacrylate resins, polystyrene resins, biodegradable resins, and plant-derived resins.
Examples of rubbers include olefin rubbers such as ethylene/propylene copolymer rubber, ethylene/propylene/non-conjugated diene copolymer rubber, polybutadiene rubber, and styrene copolymers other than components (a) and (c). Examples include composite rubber.

<Method for producing polymer composition (A)>
The polymer composition (A) essentially contains at least components (a) and (b), and in addition to these, components (c) to (e) and, if necessary, organic peroxides, crosslinking aids, and various other components. It can be produced by mixing, kneading, or melt-kneading a blend of materials containing additives in a conventional manner using an ordinary extruder, Banbury mixer, mixing roll, roll, Brabender plastograph, kneader Brabender, etc. can. Among these, it is preferable to use an extruder, especially a twin-screw extruder.

When producing the polymer composition (A) by kneading it in an extruder or the like, it is preferable to carry out dynamic heat treatment in which it is melt-kneaded while being heated to usually 80 to 300°C, preferably 100 to 250°C. Note that the treatment time for dynamic heat treatment is not particularly limited, but is usually 0.1 to 30 minutes in consideration of productivity and the like.

This dynamic heat treatment is preferably performed by melt-kneading as described above, and when a twin-screw extruder is used, each component is supplied to the raw material supply port (hopper) of the twin-screw extruder, which has multiple raw material supply ports. It is more preferable to perform dynamic heat treatment.

[Manufacturing method of article]
Although there are no particular limitations on the method for manufacturing the article of the present invention, the article of the present invention may include, for example, a first prepreg forming a first FRP layer and a second prepreg forming a second FRP layer. can be produced by a method that includes the steps of laminating the polymer composition (A) through sheets and heating and pressurizing the polymer composition (A).

The first prepreg and the second prepreg are preferably thermosetting prepregs. Thermoset prepregs are sheets of fiber reinforcement impregnated with an uncured thermoset matrix; examples include UD prepreg, cloth prepreg, tow prepreg, and sheet molding compound (SMC).
A typical method for manufacturing SMC will be described below with reference to FIG. 3.

A continuous fiber bundle 10 is pulled out from the fiber reinforcement package P and sent to a rotary cutter 110.
The number of filaments in the continuous fiber bundle 10 is, for example, 3,000 to 100,000. A continuous fiber bundle having a filament count of 10,000 or more, particularly 15,000 or more, especially 40,000 or more may be partially divided into a plurality of sub-bundles by intermittent slitting before use. The number of filaments in a sub-bundle can be less than 10,000, less than 5,000, less than 3,000, etc., and can be 500 or more, 1,000 or more, etc.

The continuous fiber bundle 10 is cut by a rotary cutter 110 to become a chopped fiber bundle 20.
The fiber length of the chopped fiber bundle 20 is, for example, 5 mm to 10 cm, and may be 1 cm or more and less than 2 cm, 2 cm or more and less than 3 cm, 3 cm or more and less than 4 cm, 4 cm or more and less than 6 cm, etc.

A first matrix layer 41 is formed by applying a matrix paste 40 to the upper surface of a first carrier film 51 running below a rotary cutter 110 using a coating machine 120 equipped with a doctor blade.

The chopped fiber bundles 20 produced by cutting the continuous fiber bundles fall and accumulate on the first matrix layer 41 to form the fiber mat 30.
The basis weight of the fiber mat 30 and the thickness of the first matrix layer 41 and the second matrix layer 42 described below are set in consideration of the fiber content of the SMC to be manufactured.

Following the formation of the fiber mat 30, the second carrier film 52 is bonded to the upper surface side of the first carrier film 51, thereby forming the laminate 60. Before lamination, a second matrix layer 42 is formed on one side of the second carrier film 52 by applying a matrix paste 40 using a coating machine 130 equipped with a doctor blade.
The laminate 60 is formed such that the first matrix layer 41, the fiber mat 30, and the second matrix layer 42 are sandwiched between the first carrier film 51 and the second carrier film 52.

To impregnate the fiber mat 30 with the matrix paste 40, the laminate 60 is pressed in an impregnator 140.
The laminate 60 leaving the impregnation machine 140 is wound onto a bobbin. SMC can be obtained by heating the laminate 60 together with the bobbin and holding it for a certain period of time to sufficiently thicken the matrix paste 40.

The matrix paste for impregnating the above fiber mat includes, in addition to the thermosetting resin mentioned above, an ethylenically unsaturated monomer as a reactive diluent, a thickener, a polymerization initiator, a polymerization inhibitor, a low shrinkage agent, and a filler. It may also contain additives such as agents and colorants.
SMC produced by the above procedure exhibits high fluidity during molding because the fiber reinforcing material is a mat made of short fibers, so molded products with complex shapes such as molded products with ribs and bosses. It can be preferably used when manufacturing.

The prepreg used in the manufacturing method according to the embodiment may be a thermoplastic prepreg such as a stampable sheet.
After cutting the prepreg into an appropriate size, a plurality of prepregs are laminated as necessary and used in the manufacturing method according to the embodiment as the first prepreg and the second prepreg, respectively.

That is, a sheet made of the polymer composition (A) is interposed between the first prepreg and the second prepreg, and the mixture of the first prepreg/sheet made of the polymer composition (A)/second prepreg is separated. The article according to the embodiment can be obtained by forming a laminate, loading it into a mold, and heating and pressurizing it with a press to integrate it.

The heating and pressing conditions when the prepreg is thermosetting vary depending on the type of thermosetting resin contained in the matrix, but the heating temperature is preferably in the range of 130 to 160°C, and 140 to 150°C. More preferred. Further, the press pressure is preferably in the range of 0.5 to 6 MPa, more preferably in the range of 1 to 6 MPa.

The article manufactured in this manner may have a hollow shape.
Further, the sheet made of the polymer composition (A) does not need to have the same stacked size as the prepreg, and may be smaller or larger than the prepreg.
Further, the position where the sheet made of the polymer composition (A) is sandwiched between the first prepreg and the second prepreg does not need to be at the center in the thickness direction, and may be asymmetrically laminated.

The first prepreg and the second prepreg used for manufacturing the article according to the embodiment are made so that the fiber reinforcing material content of the first FRP layer and the second FRP layer in the article according to the embodiment is within a suitable range. Designed to.
The fiber volume content of the first prepreg and the second prepreg is preferably 10 to 85%, more preferably 30 to 85%, and even more preferably 40 to 85%. If the fiber volume content of the prepreg is 10% or more, the strength and elastic modulus of the resulting FRP layer may be sufficient, but if it is 85% or less, the reinforcing fibers will come into contact with each other and rub together, resulting in a decrease in strength. can be restrained from doing so. Here, the fiber volume content of the prepreg is determined in accordance with ASTM D3171.

[Application]
The article according to the embodiment can be applied to a wide range of fields such as various building materials, industrial materials, automobile parts structures, ship parts structures, power parts structures, and building parts structures. Among these, it is suitable for automotive applications where weight reduction is strongly desired, and these applications include, in particular, automotive roof panels and sporting goods such as bats.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, the values of various manufacturing conditions and evaluation results in the following examples have the meaning as preferable upper or lower limits in the embodiments of the present invention, and the preferable ranges are different from the above-mentioned upper or lower limits. , it may be a range defined by the values of the following examples or a combination of values of the examples.

〔raw materials〕
The raw materials used to manufacture the articles of the following Examples and Comparative Examples are as follows.

[Material of fiber reinforced plastic layer]
<SMC-1>
SMC (fiber content: 53% by mass) in which a random mat made of short carbon fibers is impregnated with a resin composition containing vinyl ester resin

<GMC-1>
GMC in which a random mat made of short glass fibers is impregnated with a resin composition containing vinyl ester resin.

[Material of styrenic thermoplastic polymer composition TPS-1]
<Component (a)>
SEPS-1: Hydrogenated product of styrene block/isoprene block/styrene block copolymer (“Hybler (registered trademark) 7125” manufactured by Kuraray Co., Ltd.)
Styrene block content: 20% by mass
Total content of isoprene having 3,4 bonds and isoprene having 1,2 bonds in the isoprene block: approximately 60% by mass
Hydrogenation rate: 98% or more Weight average molecular weight: Approximately 100,000 <Component (b)>
MAH-PP: Maleic anhydride modified polypropylene (propylene homopolymer) (manufactured by Sanyo Chemical Industries, Ltd.)
Maleic anhydride content (modification rate): 2.3% by mass
<Component (c)>
SEBS-1: Hydrogenated product of styrene block/butadiene block/styrene block copolymer (“TAIPOL (registered trademark) 6151” manufactured by TSRC)
Styrene block content: 33% by mass
Hydrogenation rate: 98% or more Weight average molecular weight: Approximately 260,000 <Component (d)>
OIL-1: Softener for paraffin rubber (“Diana (registered trademark) Process Oil PW90” manufactured by Idemitsu Kosan Co., Ltd.)
Molecular weight: 540
Kinematic viscosity at 40°C: 95.5cSt
Pour point: -15℃
Flash point: 272℃
<Component (e)>
PP-1: Propylene homopolymer (manufactured by Nippon Polypro Co., Ltd.)
MFR (230℃, 21.2N load): 5g/10min

<Production of styrenic thermoplastic composition: TPS-1>
Stabilizer for 100 parts by mass of a blend of 50 parts by mass of SEPS-1, 10 parts by mass of MAH-PP, 50 parts by mass of SEBS-1, 50 parts by mass of OIL-1, and 25 parts by mass of PP-1. and 0.1 part by mass of tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane ("Irganox (registered trademark) 1010" manufactured by BASF Japan). The mixture was added and mixed using a Henschel mixer, and extruded using a gravimetric feeder using a Toshiba twin-screw extruder "TEM26" at 200°C and a screw rotation speed of 400 rpm to obtain a styrenic thermoplastic polymer composition. A pellet of TPS-1 was obtained.

[Material of layer of polymer composition]
Polymer composition 1: Styrenic thermoplastic polymer composition: TPS-1
MFR (230℃, 21.2N load): 10g/min Density: 0.9g/cm ³
Duro A hardness: 60
Tensile strength at cutting: 12MPa
Elongation at cutting: 800%
Minimum Tanδ for frequency 100-4000Hz: 0.4
Maximum Tanδ for frequencies 100-4000Hz: 0.7

Polymer composition 2: Acrylonitrile butadiene rubber (NBR)
Tigers Polymer Co., Ltd. NBR (acrylonitrile butane diene rubber) plate (L) <HS70> Product number TNKL7007-HP (thickness 0.5 mm)
Duro A hardness: 70 (catalog value)
Tensile strength at cutting: 12.2MPa (catalog value)
Elongation at cutting: 550% (catalog value)
Minimum Tanδ for frequency 100-4000Hz: 0.5
Maximum Tanδ for frequencies 100-4000Hz: 0.7

Polymer composition 3: Styrenic thermoplastic polymer composition: TPS-2
“Tefa Block (registered trademark) ME5301CS” manufactured by Mitsubishi Chemical Corporation
MFR (230°C, 49N): 7g/min Density: 0.89g/ ^cm3
Duro A hardness: 54
Tensile strength at cutting: 12MPa
Elongation at cutting: 860%
Minimum Tanδ for frequency 100-4000Hz: 0.1
Maximum Tanδ for frequencies 100-4000Hz: 0.1

Polymer composition 4: Olefin thermoplastic polymer composition: TPV-1
“Trexplane (registered trademark) 3655” manufactured by Mitsubishi Chemical Corporation
MFR (230°C, 49N): 10g/min Density: 0.89g/ ^cm3
Duro A hardness: 66
Tensile strength at cutting: 7MPa
Elongation at cutting: 670%
Minimum Tanδ for frequency 100-4000Hz: 0.1
Maximum Tanδ for frequencies 100-4000Hz: 0.1

[Method for evaluating physical properties of polymer composition]
Physical properties of the polymer composition were evaluated using methods (1) to (5) shown below.

(1) Melt flow rate (MFR)
Measurement was carried out at 230°C and under a load of 21.2N or 49N in accordance with ISO1133.

(2) Density Measured in accordance with ISO1183.

(3) Duro A hardness Using an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product number: IS130), each polymer was The composition was injection molded to form a sheet-like test piece with a thickness of 2 mm x width of 120 mm x length of 80 mm, and the hardness (after 15 seconds) was measured in accordance with ISO7619.
However, for an NBR plate made by Tigers Polymer Co., Ltd. with a thickness of 0.5 mm, the catalog value measured within 1 second based on JIS K6253 is shown.

(4) Tensile strength at break/Elongation at break (Tensile test)
Each polymer composition was injection molded using an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product number: IS130) under conditions of an injection pressure of 50 MPa, a cylinder temperature of 220°C, and a mold temperature of 40°C. A sheet with a thickness of 2 mm x width of 120 mm x length of 80 mm was obtained. In accordance with ISO37, a dumbbell-shaped test piece was punched out from the obtained sheet using a test piece punching blade (TYPE 1A), and using this test piece, a test speed: 500 mm/min was carried out in accordance with ISO37. It was measured.
However, for NBR plates made by Tigers Polymer Co., Ltd. with a thickness of 0.5 mm, catalog values based on JIS K6251 are shown.

(5) Minimum Tan δ and maximum Tan δ for frequencies 100 to 4000 Hz
Each polymer composition was injection molded using an in-line screw type injection molding machine (manufactured by Toshiba Machine Co., Ltd., product number: IS130) under conditions of an injection pressure of 50 MPa, a cylinder temperature of 220°C, and a mold temperature of 40°C. A sheet with a thickness of 2 mm x width of 120 mm x length of 80 mm was obtained. From this sheet, a sheet piece having a width of 10 mm and a length of approximately 25 mm was punched out in the MD direction to form a test piece.
However, regarding the NBR plate made by Tigers Polymer Co., Ltd. with a thickness of 0.5 mm, a sheet piece of 10 mm width x approximately 25 mm length was punched out from a sheet of 0.5 mm thickness x 500 mm length x 500 mm width, and this was used as a test piece.
Using the above-prepared test piece, measurements were carried out at -20°C, -10°C, 0°C, 10°C in a nitrogen atmosphere using a measuring device MCR301 type viscoelasticity measuring machine (manufactured by Anton Paar) with the measurement mode set to twist. Storage modulus, loss modulus, and loss tangent (Tan δ) were measured at 20° C., frequency of 0.1 to 25.1 Hz, and strain of 0.1%. Next, in order to expand the frequency range of the temperature-frequency dependence results using the temperature-time conversion rule, the frequency in the measurement is converted based on the Williams-Landel-Ferry equation (WLF equation), and the master value of Tan δ at the reference temperature of 20°C is calculated. Created a curve. From this master curve, the maximum and minimum values of Tan δ in the frequency range of 100 Hz to 4,000 Hz were determined.

[Example/Comparative example]
[Example 1]
A sheet with a width of 280 mm and a thickness of 0.5 mm was produced from the polymer composition 1 at a cylinder temperature of 200° C. using a single-layer T-die molding machine (manufactured by GSI Creos Co., Ltd.).
The sheet was sandwiched between two sheets of SMC-1 and heated and pressed at 140° C. and a pressure of 4 MPa for 5 minutes to form a panel with a thickness of 4 mm. When the cross section of this panel was observed, the thickness of the layer of polymer composition 1 sandwiched between the two FRP layers was 0.5 mm.
The physical properties of the obtained panels were evaluated using methods (1) to (4) described below.

[Example 2]
A panel was molded and evaluated in the same manner as in Example 1, except that a sheet of Polymer Composition 2 was used in place of the sheet of Polymer Composition 1.

[Example 3, Comparative Examples 1 to 4]
In Example 3, a panel was molded in the same manner as in Example 1 except that GMC-1 was used instead of SMC-1.
In Comparative Example 1, a panel was molded in the same manner as in Example 1 except that nothing was sandwiched between two SMC-1 sheets.
In Comparative Example 2, a panel was molded in the same manner as in Example 1, except that a sheet of Polymer Composition 3 was used instead of a sheet of Polymer Composition 1.
In Comparative Example 3, a panel was molded in the same manner as in Example 1, except that a sheet of Polymer Composition 4 was used in place of the sheet of Polymer Composition 1.
In Comparative Example 4, a panel was molded in the same manner as in Example 3, except that nothing was sandwiched between two sheets of GMC-1.
The panels molded in Example 3 and Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1.

[Panel evaluation method]
(1) Vibration damping property Vibration damping property was evaluated by calculating the acceleration/excitation force (inertance) obtained in a hammering test. A hammering test, also called a percussion test, is a test method in which the panel to be tested is vibrated with an impulse hammer and the resulting vibrations are measured using an acceleration sensor.
In this evaluation, the ends of the resulting panels were suspended with strings for free support, and an acceleration sensor was fixed at the center of the panel to measure acceleration. On the other hand, the excitation force is calculated using the value of the excitation force measured by the force sensor when the impulse hammer with a built-in force sensor is used to excite from the opposite side to which the acceleration sensor is fixed after the start of acceleration measurement. It can be measured by

(1)-1 Vibration damping time To measure the vibration damping time, set the trigger so that it is triggered when the impulse hammer is excited, and after starting to capture acceleration every 0.1 seconds, The detection time of acceleration before vibration was approximately 0.16 seconds, and the period after vibration until the end of measurement was approximately 2 seconds. For example, in the panels of Example 1 and Comparative Example 1, impulse response results shown in FIGS. 1(a) and 1(b) were obtained.
The vibration damping time is the time it takes for the inertance to drop to the same level as before the vibration after vibration by the impulse hammer. Specifically, the inertance after vibration by the impulse hammer decreases until the end of the measurement. The vibration damping time was defined as the difference between the first time when the vibration damped to the inertance level before vibration and the damped state was continuously maintained for 0.5 seconds. At this time, as an index of a stable state at the same level as the vibration before excitation, the vibration stability index at X seconds of the following formula 1 was calculated.
In the panels of Examples 1 and 2 and Comparative Examples 1 and 3, the maximum value of the vibration stability index of the state vibration level for about 0.16 seconds before excitation by the impulse hammer was 0.03, so after excitation, When the vibration stability index is within 0.03 for 0.5 seconds continuously, it is considered to be a vibration damping state, and the time immediately after vibration is applied by the impulse hammer is set as 0, and the difference from the first time when a stable state is reached is calculated. The time was calculated as the vibration damping time.
Regarding the panels of Example 3 and Comparative Example 4, the maximum value of the vibration stability index before vibration by the impulse hammer was 0.05, so the vibration stability index continued to be 0.0 for 0.5 seconds after vibration. 05 or less was considered to be a vibration damping state, and the time immediately after vibration was applied by the impulse hammer was set as 0, and the time difference from the initial time when a stable state was reached was calculated as the vibration damping time.
Formula 1:
Vibration stability index = absolute value [(X + 0.1 second acceleration/excitation force) - (X second acceleration/excitation force)]/0.1 (second)
The shorter the vibration damping time, the better the vibration damping performance.

(1)-2 Vibration attenuation The signal obtained by the acceleration sensor was decomposed into each frequency using an FFT analyzer to obtain the inertance (unit: dB) for each frequency.
The amount of inertance attenuation at the peak top of the natural frequency of Examples 1 and 2 and Comparative Examples 2 and 3 was evaluated for the amount of attenuation of the natural frequency with respect to Comparative Example 1.
FIG. 2 shows the measurement results of inertance (unit: dB) obtained by the hammering test of Example 1 and Comparative Example 1. Arrows C-1 to C-7 in FIG. 2 indicate seven natural frequency peaks between 1000 and 4000 Hz in the measurement results of inertance (unit: dB) obtained by the hammering test of Comparative Example 1. With respect to the inertance (dB) of the seven peak tops of Comparative Example 1, the peaks corresponding to the individual natural frequencies of Comparative Example 1 in Examples 1 to 2 and Comparative Examples 2 to 3 are the peaks of Comparative Example 1. In order to shift the frequency slightly to the lower frequency side than the individual peaks, we selected seven peaks (indicated in Figure 2) that appear on the low frequency side, and found the difference in inertance from the peak of Comparative Example 1. , the average value was determined as the peak top attenuation amount.
At this time, for cases where there is no clear peak like Example 1 in Figure 2, a gentle curve on the slightly lower frequency side than the peak of Comparative Example 1, like E-1 to E-7 in Figure 2, is used. The maximum value of the inertance corresponding to the valley and the peak of the valley was defined as the peak top inertance (dB), and the average value of the difference from the inertance of Comparative Example 1 was determined as the attenuation amount.
For example, the peak E-1 of Example 1 was selected for the peak C-1 of Comparative Example 1 in FIG. 2, and the difference in peak top was determined. Similarly, seven differences were determined, such as E-2 for C-2 and E-7 for C-7, and the resulting differences were averaged to calculate the amount of attenuation at the peak top.
Similarly, for Comparative Example 4, six peaks corresponding to the natural frequencies of 1000 to 4000 Hz of Comparative Example 4 were selected, and the differences between the peak tops of each natural frequency of Example 3 were averaged. The amount of attenuation was calculated.
In the frequency range of 1000 to 4000Hz, although vibrations propagate through the air and are converted into sound, they are not reflected directly at the same frequency, but there is a frequency weighting characteristic called A-weighting for measuring noise levels, and with 1000Hz as the standard, Therefore, we selected a frequency range of 1000Hz to 4000Hz that is not affected by the weighting characteristics.
The larger the attenuation value, the better the vibration damping performance.

(2) Acoustic properties The panel used in the hammering test in (1) was struck with the metacarpophalangeal joint of the middle finger on the back of the hand, and the level of sound heard by the human ear was evaluated using the following criteria.
○: When struck, there is no metallic sound, but a low-pitched sound, and there is almost no reverberation. △: When struck, there is a slightly high-pitched metallic sound, and some reverberation remains. ×: When struck, there is a high-pitched metallic sound, and there is reverberation. remains

(3) Toughness The obtained panel was cut into a width of 25 mm using a precision cutting machine, and the bending strength and bending elastic modulus were measured according to ASTM D790, and the maximum bending strain was calculated from the measured values.
The larger the maximum bending strain value, the better the toughness.

(4) Surface smoothness Surface smoothness was evaluated by measuring the arithmetic mean roughness Ra, which is the average value of the distance from the reference line in that section, using the average value of the surface unevenness as a reference line.
The arithmetic mean roughness Ra according to JIS B0601 was measured on the surface of the panel using a surface roughness profile measuring device Surfcom "TOUCH550" manufactured by Tokyo Seimitsu Co., Ltd. The evaluation distance was 5 mm, the measurement speed was 0.6 mm/min, and the cutoff value was 0.8 mm.
The smaller the value of Ra, the better the surface smoothness.

[Example 4, Comparative Examples 5-6]
Using a single-layer T-die molding machine (manufactured by GSI Creos Co., Ltd.) at a cylinder temperature of 200°C, each polymer composition of Polymer Composition 1, Polymer Composition 3, and Polymer Composition 4 was molded into a width. A sheet having a size of 280 mm and a thickness of 0.5 mm was produced.
A sheet of each of the above polymer compositions was sandwiched between two sheets of SMC-1, and heated and pressed at 140° C. and a pressure of 4 MPa for 5 minutes to form a panel with a thickness of 4 mm. When the cross section of this panel was observed, the thickness of the layers of polymer compositions 1, 3, and 4 sandwiched between the two FRP layers was 0.5 mm.
The physical properties of the obtained panel were evaluated using the flatwise adhesion evaluation method described below.

[Flatwise adhesion evaluation method]
A 25 mm square test piece was cut out from the panel. After roughening both main surfaces of this test piece with #120 sandpaper, a film adhesive (FM73 manufactured by Solvay) made of glass nonwoven fabric impregnated with epoxy resin was applied to each of the main surfaces as shown in Fig. 4. An aluminum jig was glued as shown. Before bonding, the adhesive surface of the aluminum jig was also roughened with #120 sandpaper in the same manner as the test piece. The curing condition for film adhesive is 120℃
, for 90 minutes.

As described above, using a test piece with aluminum jigs glued on both sides on both sides, ASTM C297 / 297m "Standard Test Method FOR FOR FOR FLATWISE TENSILE TENSILE TENSILE TENSILE OF SANDWICH CONSTRUCTIO CONSTRUCTIO We performed a flat wise tension test with reference to "NS". A universal testing machine manufactured by Instron was used as the tensile testing machine. The rated capacity of the load cell is 100kN
, the tensile speed was 2 mm/min.
The flatwise tensile strength is the value obtained by dividing the breaking load by the area of the test piece (25 mm x 25 mm).
The test was conducted three times (test piece 1, test piece 2, test piece 3), and the average value of the three measurements was determined.

〔Evaluation results〕
The evaluation results of the panels of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1 below.
Table 2 shows the measurement results of flatwise tensile strength for Example 4 and Comparative Examples 5 and 6.

As shown in Table 1, the panels of Examples 1 to 3 having a layer of polymer composition (A) between the first FRP layer and the second FRP layer had a layer of the polymer composition. Compared with Comparative Examples 1 and 4, which did not have a layer, and Comparative Examples 2 and 3, which had a layer of a polymer composition other than polymer composition (A), the vibration damping properties were higher and the acoustic properties and toughness were also superior. Furthermore, the panels of Examples 1 to 3 had improved surface smoothness compared to Comparative Examples 1 and 4.

As shown in Table 2, the panel of Example 4 having a layer of polymer composition (A) between the first FRP layer and the second FRP layer had a higher flatwise tensile strength than Comparative Examples 4 and 5. It had high strength and high adhesion.

10 continuous fiber bundle 20 chopped fiber bundle 30 fiber mat 40 matrix resin paste 41 first resin layer 42 second resin layer 51 first carrier film 52 second carrier film 60 laminate 110 rotary cutter 120, 130 coating machine 140 impregnation machine

Claims (26)

A polymer having a loss tangent (Tan δ) of 0.2 or more at 20° C. over the entire frequency range between 100 Hz and 4,000 Hz is used between the first fiber reinforced plastic layer and the second fiber reinforced plastic layer. An article having a layer of a composition. The article according to claim 1, wherein at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer includes a cured thermosetting resin. 3. The article of claim 2, wherein both the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer include a cured thermosetting resin. The article according to any one of claims 1 to 3, wherein at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer comprises discontinuous fibers. 5. The article of claim 4, wherein both the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer include discontinuous fibers. According to any one of claims 1 to 3, at least one of the first fiber-reinforced plastic layer and the second fiber-reinforced plastic layer contains one or more types of fibers selected from carbon fibers and glass fibers. goods. An article according to any one of claims 1 to 3, wherein the polymer composition comprises a polymer having polar groups. 7. The article of claim 6, wherein the polymer composition comprises a polymer having polar groups. 8. The article of claim 7, wherein the polymer composition comprises acrylonitrile butadiene rubber. 9. The article of claim 8, wherein the polymer composition comprises acrylonitrile butadiene rubber. 8. The article according to claim 7, wherein the polymer composition is a thermoplastic polymer composition comprising the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group 9. The article of claim 8, wherein the polymer composition is a thermoplastic polymer composition comprising the following components (a) and (b):
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group 12. The article according to claim 11, wherein the polyolefin having polar groups comprises a maleic anhydride modified polyolefin. 13. The article according to claim 12, wherein the polyolefin having polar groups comprises a maleic anhydride modified polyolefin. The article according to any one of claims 1 to 3, which is a bat. Article according to any one of claims 1 to 3, which is an automobile roof panel. The first prepreg and the second prepreg are laminated via a sheet made of a polymer composition having a loss tangent (Tan δ) of 0.2 or more at 20° C. over the entire frequency range between 100 Hz and 4,000 Hz. A method for manufacturing an article, which includes the steps of heating and pressurizing. The method for manufacturing an article according to claim 17, wherein at least one of the first prepreg and the second prepreg contains a thermosetting resin. The method for manufacturing an article according to claim 18, wherein both the first prepreg and the second prepreg contain a thermosetting resin. The method for manufacturing an article according to any one of claims 17 to 19, wherein at least one of the first prepreg and the second prepreg contains discontinuous fibers. 21. The method of manufacturing an article according to claim 20, wherein both the first prepreg and the second prepreg include discontinuous fibers. The method for manufacturing an article according to any one of claims 17 to 19, wherein at least one of the first prepreg and the second prepreg contains one or more types of fibers selected from carbon fibers and glass fibers. The method for producing an article according to any one of claims 17 to 19, wherein the polymer composition contains a polymer having a polar group. 24. The method of making an article according to claim 23, wherein the polymer composition comprises acrylonitrile butadiene rubber. 24. The method for producing an article according to claim 23, wherein the polymer composition is a thermoplastic polymer composition containing the following component (a) and the following component (b).
Component (a): consisting of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) containing isoprene having 3,4 bonds and/or isoprene having 1,2 bonds (A) -(B)-(A) Triblock copolymer and/or hydrogenated component (b) of the triblock copolymer: polyolefin having a polar group 26. The method for producing an article according to claim 25, wherein the polyolefin having a polar group includes a maleic anhydride-modified polyolefin.

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