JP2016210027A - Fiber-reinforced composite material and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber-reinforced composite material having a reinforced fiber as a reinforcement material, where the fiber-reinforced composite material excels in vibration-damping performance, impact resistance, and surface appearance.SOLUTION: A fiber-reinforced composite material comprises a reinforced fiber bundle and a thermoplastic elastomer component.SELECTED DRAWING: None

Description

  The present invention relates to a fiber-reinforced composite material containing a thermoplastic elastomer component reinforced by a reinforcing fiber bundle and a molded body thereof.

The fiber reinforced plastic is a fiber reinforced composite material including a base resin and reinforced fibers such as carbon fibers and glass fibers, and the base resin is reinforced by the reinforced fibers.
Fiber reinforced plastics are used in a wide range of applications such as automobile members, building materials, interior materials, precision equipment, and electronic equipment because of their high elasticity and strength.

Conventionally, thermosetting resins (for example, unsaturated polyester resins, epoxy resins, phenol resins, etc.) have been used as base resins for fiber reinforced plastics.
In addition, there are examples in which a hard thermoplastic resin [for example, a polyester resin (for example, polybutylene terephthalate resin, etc.), a polypropylene resin, a polyphenylene sulfide resin, nylon, or the like] or the like is used as the base resin (Patent Documents 1 to 6). ).

JP 2014-227610 A JP 2007-182065 A JP 2011-006578 A JP 2002-321215 A JP 2014-077209 A Japanese Patent No. 5279121

  However, the conventional fiber reinforced plastic using a thermoplastic resin or a thermosetting resin as the base resin has a problem that vibration damping characteristics (damping property) and impact resistance are not sufficient.

An object of the present invention is to obtain a fiber-reinforced composite material having excellent vibration damping properties.
Another object of the present invention is to obtain a fiber reinforced composite material excellent in impact resistance.
Furthermore, another object of the present invention is to obtain a fiber reinforced composite material having an excellent surface appearance.
Furthermore, another object of the present invention is to obtain a composite molded body using these fiber-reinforced composite materials as a reinforcing material for a non-thermoplastic resin molded body.

  Since fiber reinforced plastic is generally used as a substitute for metal, a hard resin such as a thermosetting resin or a hard thermoplastic resin has been used as the base resin. The present inventors have surprisingly conceived of using a thermoplastic elastomer having elasticity as a base resin.

As a result of further diligent research to solve the above problems, the present inventors have combined a thermoplastic elastomer component (particularly, a component containing a polyester block copolymer and a polyvinyl alcohol resin) with a reinforcing fiber bundle. As a result, it was found that a fiber-reinforced composite material excellent in vibration damping, impact resistance and surface appearance was obtained, and the present invention was completed.
That is, the present invention relates to the following fiber reinforced composite materials and the like.
[1] A fiber reinforced composite material composed of a continuous fiber reinforced fiber bundle and a thermoplastic elastomer component.
[2] The fiber-reinforced composite material according to [1], wherein the thermoplastic elastomer component is a yarn.
[3] The fiber-reinforced composite material according to [1], wherein an aqueous dispersion or powder of a thermoplastic elastomer component is combined with a reinforcing fiber bundle.
[4] A polyester block copolymer in which the thermoplastic elastomer component contains as constituent components a hard segment (a) containing an aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit. The fiber-reinforced composite material according to any one of [1] to [3], which contains 60% by mass or more of the polymer (A).
[5] The fiber-reinforced composite material according to any one of [1] to [4], wherein the thermoplastic elastomer component further contains a polyvinyl alcohol resin (B).
[6] The above-mentioned [1], wherein the melt viscosity of the thermoplastic elastomer component measured at a temperature 60 ° C. higher than the melting point of the thermoplastic elastomer component is 50 to 10,000 Pa · sec at a shear rate of 100 / sec. ] The fiber reinforced composite material in any one of [5].
[7] The thermoplastic elastomer component contains a hard segment (a) containing a crystalline aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit as constituent units, A polyester block copolymer (A) having a melting point of less than 210 ° C., a polyvinyl alcohol resin (B), a silane coupling agent (C), and an antioxidant (D). 66 to 98.98% by mass, 1 to 30% by mass of the polyvinyl alcohol resin (B), 0.01 to 5.0% by mass of the silane coupling agent (C), and the antioxidant (D ) In an amount of 0.01 to 5.0% by mass. The fiber-reinforced composite material according to any one of the above [1] to [6].
[8] The thermoplastic elastomer as a constituent unit includes a hard segment (a) containing a crystalline aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit. A polyester block copolymer (A) having a melting point of less than 210 ° C., a polyvinyl alcohol resin (B), a silane coupling agent (C), an antioxidant (D) and a polyester random copolymer (E), 46-98.98% by mass of the polyester block copolymer (A), 1-30% by mass of the polyvinyl alcohol resin (B), and 0.01-5.0% by mass of the silane coupling agent (C). , 0.01 to 5.0% by mass of the antioxidant (D) and 1 to 25% by mass of the polyester random copolymer (E). Above, wherein the [1] to fiber-reinforced composite material according to any one of [7].
[9] A composite molded body obtained by bonding the fiber-reinforced composite material according to any one of [1] to [8] and a non-thermoplastic resin molded body.
[10] The composite molded body according to [9], wherein the fiber-reinforced composite material and the non-thermoplastic resin molded body are thermally fused without using an adhesive.
[11] The composite molded body according to [9] or [10], wherein the non-thermoplastic resin molded body is a metal, glass, concrete, or wood.

According to the present invention, it is possible to obtain a fiber-reinforced composite material excellent in vibration damping properties and impact resistance and a molded body thereof.
Moreover, according to this invention, the fiber reinforced composite material excellent in the surface external appearance and its molded object can be obtained.
Moreover, according to this invention, the fiber reinforced composite material excellent in the adhesiveness of a reinforced fiber and base resin, and its molded object can be obtained.
The fiber-reinforced composite material of the present invention can be used as a reinforcing material for a non-thermoplastic resin molded body.
Furthermore, the fiber-reinforced composite material of the present invention can be joined to a non-thermoplastic resin molded body without using an adhesive.

  Further, when a thermoplastic resin such as a polyester resin is used as the base resin, there is a problem that the base resin is easily hydrolyzed, but the fiber reinforced composite material of the present invention is difficult to hydrolyze.

  In addition, when a thermosetting resin is used as the base resin, a cross-linking reaction is required. Therefore, the processing time for combining with the reinforcing fiber was several hours (for example, 1 to 3 hours). In the reinforced composite material, since the thermoplastic elastomer is used, the processing time for combining with the reinforcing fiber is as short as several minutes (for example, 1 to 30 minutes), and the production efficiency of the composite material can be improved. .

It is a figure which shows the vibration damping characteristic measuring method of an Example and a comparative example. It is a figure which shows the sound pressure measuring method of an Example and a comparative example. It is a figure which shows the falling ball test method of an Example and a comparative example.

Hereinafter, the present invention will be specifically described.
The fiber-reinforced composite material of the present invention is composed of a reinforcing fiber bundle and a thermoplastic elastomer component.

[Reinforced fiber bundle]
In the present invention, the reinforcing fiber bundle is usually a fiber bundle in which a plurality of reinforcing fibers are arranged in one direction. The reinforcing fiber bundle is preferably a fiber bundle of continuous fibers.
Although it does not specifically limit as a reinforced fiber, For example, an inorganic fiber, an organic fiber, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the inorganic fiber include carbon fiber, glass fiber, silicon carbide fiber, and metal fiber. Examples of the metal fibers include metals such as stainless steel, aluminum, nickel, and iron, or fibers of these alloys.

  Examples of the organic fibers include synthetic fibers (for example, aramid fibers, polyamide fibers, polyester fibers, polyethylene fibers, acrylic fibers, etc.).

  The reinforcing fiber bundle used in the present invention is at least one or more reinforcing materials selected from carbon fiber, glass fiber and aramid fiber from the viewpoints of high strength, high elastic modulus, high heat resistance, corrosion resistance, lightness and the like. A reinforcing fiber bundle composed of fibers is preferred.

Examples of the carbon fiber include PAN (polyacrylonitrile) -based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and the like.
Examples of the glass fiber include glass fibers such as E glass, C glass, S glass, and D glass.
Examples of the aramid fiber include para-aramid fiber (for example, polyparaphenylene terephthalamide fiber), meta-aramid fiber (for example, polymetaphenylene isophthalamide fiber), and the like.

  Moreover, the manufacturing method of the reinforcing fiber and reinforcing fiber bundle used in the present invention is not particularly limited, and may be a conventionally known method.

The reinforcing fiber bundle may contain components other than the reinforcing fibers. For example, a sizing agent may be applied to the surface of the reinforcing fibers.
The sizing agent is not particularly limited, and examples thereof include epoxy resins (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolac type epoxy resin, etc.), polyethylene glycol, polyurethane, polyester and the like. Can be mentioned. These can be used alone or in combination of two or more.

  Although the application quantity of a sizing agent is not specifically limited, For example, it is 0.01-10 mass% with respect to the mass of a reinforced fiber, Preferably it is 0.05-5 mass%.

  The length of the reinforcing fiber bundle is not particularly limited, but is different depending on the use application from the viewpoint of the reinforcing effect and the like, but is 10 mm or more, preferably 20 mm or more, more preferably 30 mm, from the viewpoint of vibration control or impact resistance. That's it.

  The fiber diameter of the reinforcing fiber bundle is not particularly limited, but is, for example, 1 to 30 μm, preferably 3 to 20 μm from the viewpoint of the reinforcing effect and the like.

  In the present invention, the reinforcing fiber bundle may remain in the form of a fiber bundle in which a plurality of reinforcing fibers are arranged in one direction (that is, in the form of a thread), or a processed product of the fiber bundle [for example, a fiber bundle Woven fabric obtained by using yarn as a woven yarn, fiber bundle non-woven fabric, UD (Unidirectional) tape or sheet obtained by aligning and converging fibers in one direction, fiber bundle knitting (for example, orthogonal) And a prepreg (for example, a prepreg obtained by impregnating a cloth of reinforcing fiber bundles with a thermosetting resin containing a curing agent)]. In addition, the manufacturing method of these woven fabric, nonwoven fabric, UD tape or sheet, knitted fabric, and prepreg is not particularly limited, and may be a conventionally known method.

The basis weight of the processed product of the reinforcing fiber bundle is preferably 50 to 1000 g / m ² , more preferably 100 to 500 g / m ² . Moreover, the thickness of the processed product of the reinforcing fiber bundle is preferably 0.01 to 2 mm, more preferably 0.04 to 1.5 mm. In this case, the bondability between the reinforcing fiber bundle and the thermoplastic elastomer component is good, and the reinforcing fiber bundle is difficult to peel off, which is preferable. Further, in this case, the strength and impact absorbability of the fiber reinforced composite material are excellent, which is preferable.
The processed product of the reinforcing fiber bundle may be used singly or may be used by superposing two or more.

[Thermoplastic elastomer component]
In the present invention, the thermoplastic elastomer (hereinafter also referred to as TPE) component may be a thermoplastic elastomer alone or may contain components other than the thermoplastic elastomer.
Examples of the thermoplastic elastomer include polyester-based TPE (for example, a polyester block copolymer including a hard segment including a polyester unit and a soft segment including a polyether and / or a polyester unit as constituent units), polystyrene-based TPE ( For example, a hard block containing a polystyrene unit and a polystyrene block copolymer containing as a constituent unit a soft segment containing a polybutadiene unit and / or a polyisoprene unit), a polyolefin TPE (for example, a hard segment containing a polypropylene unit, and a polyolefin A polyolefin block copolymer containing a soft segment containing a unit as a constituent unit), polyurethane-based TPE (for example, a hard segment containing a polyurethane unit, Polyurethane block copolymer containing as a constituent unit a soft segment containing a steal unit and / or a polyether unit), a polyamide TPE (for example, a hard segment containing a nylon unit and a soft containing a polyester unit and / or a polyether unit) And a polyamide block copolymer containing a segment as a constituent unit). These can be used alone or in combination of two or more.
Among these thermoplastic elastomers, polyester-based TPE is more preferable from the viewpoints of adhesion to reinforcing fibers, vibration control, and the like.

  The polyester-based TPE preferably comprises mainly (crystalline) aromatic polyester units (eg 50-100 mol%, preferably 70-100 mol%, more preferably 90-100 mol% in the hard segment). Hard segment (a) and mainly aliphatic polyether units and / or aliphatic polyesters (eg 50-100 mol%, preferably 70-100 mol%, more preferably 90-100 mol% in soft segment) It is a polyester block copolymer (A) which contains the soft segment (b) containing a unit as a structural unit.

  The hard segment (a) includes an aromatic dicarboxylic acid and / or an ester-forming derivative thereof (hereinafter, simply referred to as “aromatic dicarboxylic acid component”, hereinafter the same in the same expression), a diol and / or Or it is preferable that it is an aromatic polyester unit formed from the ester-forming derivative (diol component).

Specific examples of the aromatic dicarboxylic acid are not particularly limited. For example, C _8-20 aromatic dicarboxylic acid [for example, benzenedicarboxylic acid (for example, terephthalic acid, isophthalic acid, phthalic acid, 5-sulfoisophthalic acid, 3 -Sodium sulfoisophthalate etc.), naphthalene dicarboxylic acid (eg naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid etc.), anthracene dicarboxylic acid (eg anthracene dicarboxylic acid etc.), biphenyl dicarboxylic acid ( For example, diphenyl-4,4′-dicarboxylic acid and the like), diphenoxyethane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid and the like] and the like.

Furthermore, examples of ester-forming derivatives of aromatic dicarboxylic acids include aromatic dicarboxylic acid lower alkyl esters (for example, aromatic dicarboxylic acid C _1-4 alkyl esters), aromatic dicarboxylic acid aryl esters (for example, aromatic dicarboxylic acid). Dicarboxylic acid C _6-10 aryl ester, etc.), aromatic dicarboxylic acid halides (for example, aromatic dicarboxylic acid chloride) and the like.
The aromatic dicarboxylic acid or ester-forming derivative thereof can be used alone or in combination of two or more.

In the present invention, a part of the aromatic dicarboxylic acid component (for example, 0.1 to 50 mol% of the total amount of the aromatic dicarboxylic acid component) is converted into an alicyclic dicarboxylic acid [for example, C _6-20 fat. Cyclic dicarboxylic acids (eg, 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid, etc.)], aliphatic dicarboxylic acids [eg, C _2-20 aliphatic dicarboxylic acids (eg, Adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, etc.)], dimer acid and other dicarboxylic acids and / or ester-forming derivatives thereof (the derivatives exemplified above, such as lower alkyl esters, etc.) May be.
The other dicarboxylic acids or ester-forming derivatives thereof can be used alone or in combination of two or more.

  In the present invention, it is preferable to use two or more of the aromatic dicarboxylic acid component or the aromatic dicarboxylic acid component and other dicarboxylic acid components. For example, terephthalic acid component and isophthalic acid component, terephthalic acid component and dodecane are used. Preferred examples include a diacid component, a combination of a terephthalic acid component and a dimer acid component, and the like. By using two or more dicarboxylic acid components, the crystallinity of the hard segment (a) can be lowered, flexibility can be imparted, and thermal adhesiveness with reinforcing fibers, non-thermoplastic resin molding The thermal adhesiveness with the body is also improved.

  Further, the content of the structural unit derived from the aromatic dicarboxylic acid component in the polyester unit in the hard segment (a) is the total structural unit derived from the aromatic dicarboxylic acid component and the other dicarboxylic acid component (that is, the total dicarboxylic acid component). For example, 50 to 100 mol%, preferably 70 to 100 mol%, and more preferably 90 to 100 mol%.

Next, the diol which forms aromatic polyester with the said aromatic dicarboxylic acid etc. is demonstrated.
Specific examples of the diol used in the present invention include diols having a molecular weight of 400 or less, such as aliphatic diols [for example, alkanediols (for example, 1,4-butanediol, ethylene glycol, trimethylene glycol, propylene glycol, pentamethylene). Glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, etc.), alicyclic diol [eg, cycloalkanediol (eg, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, etc.), aromatic diol {eg, , Xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) P) sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quarterphenyl, etc.} preferable.
Such diols can also be used in the form of ester-forming derivatives (for example, acetyl compounds, alkali metal salts, etc.). These diol components and derivatives thereof may be used alone or in combination of two or more.

The hard segment (a) preferably contains a terephthalic acid component and / or an isophthalic acid component and a diol component as a dicarboxylic acid component.
The hard segment (a) is preferably a polybutylene terephthalate unit formed from a terephthalic acid component and a 1,4-butanediol component, and a polybutylene isoform formed from an isophthalic acid component and a 1,4-butanediol component. Phthalate units, and copolymers thereof (block copolymer or random copolymer), and the like, particularly preferably, a polybutylene terephthalate unit formed from a terephthalic acid component and a 1,4-butanediol component; A copolymer (block copolymer or random copolymer) having a polybutylene isophthalate unit formed from an isophthalic acid component and a 1,4-butanediol component.

The soft segment (b) of the polyester block copolymer (A) is preferably an aliphatic polyether unit and / or an aliphatic polyester unit.
Examples of the aliphatic polyether include poly C _2-6 alkylene glycol {or poly (C _2-6 alkylene oxide) glycol} [for example, poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide). ) Glycol, poly (hexamethylene oxide) glycol, etc.], C _2-6 alkylene oxide copolymer [eg, copolymer of ethylene oxide and propylene oxide, poly (C _2-6 alkylene oxide) glycol C _2-6 alkylene oxide addition polymer {e.g., poly (propylene oxide) ethylene oxide addition polymers of glycol}, C _2-6 copolymer glycols of alkylene oxides (e.g., a copolymer glycol of ethylene oxide and tetrahydrofuran ], And the like.
Examples of the aliphatic polyester include polymers having an aliphatic hydroxycarboxylic acid as a polymerization component [for example, poly (ε-caprolactone), polyenantlactone, polycaprylolactone, etc.], aliphatic dicarboxylic acids and aliphatics. Examples include polymers containing dialcohol as a polymerization component (for example, polybutylene adipate, polyethylene adipate, etc.).
These can be used individually by 1 type or in combination of 2 or more types.

  These soft segments (b) include poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adducts, ethylene oxide and the like from the viewpoint of excellent elasticity characteristics of the resulting polyester block copolymer (A). And a copolymer of ethylene and tetrahydrofuran, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate, and the like are preferable. Among these, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, ethylene oxide and A copolymer glycol of tetrahydrofuran is preferred.

  Moreover, as a number average molecular weight of these soft segments (b), it is preferable that it is about 300-6000.

  In the polyester block copolymer (A) used in the present invention, the copolymerization ratio of the hard segment (a) and the soft segment (b) is usually 5 to 80% by mass of the hard segment (a) and the soft segment (b). ) Is 20 to 95% by mass, preferably 10 to 75% by mass of hard segment (a) and 25 to 90% by mass of soft segment (b).

  The polyester block copolymer (A) used in the present invention preferably has a melting point of less than 210 ° C. In the present invention, the melting point of the polyester block copolymer (A) is usually measured by a differential scanning calorimeter (DSC), which means that the measured melting point is below 210 ° C. When the polyester block copolymer (A) having a melting point of less than 210 ° C. is used, the polyvinyl alcohol resin (B) described later is not coarsely dispersed in the polyester block copolymer (A), and the fiber reinforced composite material Bonding strength with the non-thermoplastic resin molding can be increased.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. Specific examples thereof include an ester-forming derivative such as an aromatic dicarboxylic acid lower alkyl diester, an excess amount of diol (low molecular weight glycol), and a soft segment (b) component, which are obtained by transesterification in the presence of a catalyst. Any of a method of polycondensing a reaction product, a method of esterifying an aromatic dicarboxylic acid, an excess amount of a diol and a soft segment (b) component in the presence of a catalyst, and polycondensing the resulting reaction product, etc. You may take a method.

  In the thermoplastic elastomer component used in the present invention, the blending amount of the polyester block copolymer (A) is usually 46% by mass to 98.98% by mass, preferably 66% by mass to 98.98% by mass, and more preferably. Is 70% by mass to 98.98% by mass, more preferably 76% by mass to 98.98% by mass. If it is 46% by mass or more, the thermoplastic elastomer component obtained is excellent in mechanical properties and molding processability, and if it is 98.98% by mass or less, the bonding strength between the fiber-reinforced composite material and the non-thermoplastic resin molding is improved. .

The thermoplastic elastomer component used in the present invention preferably contains a polyvinyl alcohol resin (B) from the viewpoint of improving the bonding strength with the non-thermoplastic resin molding.
Examples of the polyvinyl alcohol resin (B) used in the present invention include polyvinyl acetal resins such as polyvinyl butyral resin.
The polyvinyl alcohol resin (B) to be used is not particularly limited, and commercially available products can be used. For example, S-flex BL-1, BL-2, BX-L, BM- manufactured by Sekisui Chemical Co., Ltd. S, KS-3, etc., Denka Butyral 3000-1, 3000-2, 3000-4, 4000-2, etc., manufactured by Denki Kagaku Kogyo Co., Ltd. may be mentioned, but are not limited thereto.

  In the thermoplastic elastomer component used in the present invention, the amount of the polyvinyl alcohol resin (B) is preferably 0.5 to 40 parts by mass, particularly preferably 1 to 100 parts by mass of the thermoplastic elastomer. Part by mass to 30 parts by mass. If it is 0.5 parts by mass or more, the bonding strength between the fiber reinforced composite material and the non-thermoplastic resin molded article is high, and if it is 40 parts by mass or less, the mechanical strength of the obtained thermoplastic elastomer component is high, and the molding processability is improved. Is also preferable.

  In the thermoplastic elastomer component used in the present invention, the amount of the polyvinyl alcohol-based resin (B) is preferably 1% by mass to 30% by mass, particularly preferably 3% by mass to the total amount of the thermoplastic elastomer component. 20% by mass. If it is 1% by mass or more, the bonding strength between the fiber reinforced composite material and the non-thermoplastic resin molded article is high, and if it is 30% by mass or less, the mechanical strength of the obtained thermoplastic elastomer component is high and the molding processability is also excellent. Therefore, it is preferable.

The thermoplastic elastomer component used in the present invention may contain a silane coupling agent (C).
Although it does not restrict | limit especially as a silane coupling agent (C) used for this invention, Preferably, functional groups (reactivity), such as an amino group, an epoxy group, a vinyl group, an allyl group, a (meth) acryl group, a sulfide group In particular, a silane coupling agent having an epoxy group is preferably used.
Specific examples of the silane coupling agent (C) include amino group-containing alkoxysilanes [for example, 3-aminopropyltrimethoxysilane, 3-aminopropylethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxy. Silane, 3- (2-aminoethyl) aminopropylmethyl dimethosysilane, 3-phenylaminopropyltrimethoxysilane, etc.], epoxy group-containing alkoxysilane [for example, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.], sulfide group-containing alkoxysilane [ For example, (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, etc.], vinyl group-containing alkoxysilane (for example, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane) Etc.), allyl group-containing alkoxysilane (eg, allyltrimethoxysilane), (meth) acryl group-containing alkoxysilane (eg, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane), mercapto Group-containing alkoxysilanes (for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.) and the like are preferable, and epoxy group-containing alkoxysilanes are preferable. Or it can be used in combination and use of two or more.

  In the thermoplastic elastomer component used in the present invention, the amount of the silane coupling agent (C) is preferably 0.01 parts by mass to 6 parts by mass, particularly preferably 0 with respect to 100 parts by mass of the thermoplastic elastomer. 0.05 parts by mass to 3 parts by mass. If it is 0.01 parts by mass or more, the bonding strength between the fiber-reinforced composite material and the non-thermoplastic resin molded article is high, and if it is 6 parts by mass or less, blooming can be prevented or thermal stability can be improved. Therefore, it is preferable.

  In the thermoplastic elastomer component used in the present invention, the amount of the silane coupling agent (C) is, for example, 0.01% by mass to 5% by mass, preferably 0.05% by mass with respect to the total amount of the thermoplastic elastomer component. % To 3% by mass, more preferably 0.1% to 1.5% by mass. If the amount of the silane coupling agent (C) is 0.01% by mass or more, the bonding strength between the fiber-reinforced composite material and the non-thermoplastic resin molded article is high, and if it is 5% by mass or less, blooming occurs. Can be prevented and thermal stability is improved.

The thermoplastic elastomer component used in the present invention may contain an antioxidant (D).
The antioxidant (D) used in the present invention is one selected from the group consisting of aromatic amine antioxidants, hindered phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants. Or 2 or more types can be mentioned, among which aromatic amine-based antioxidants are preferably used.

Specific examples of the aromatic amine antioxidant include phenylnaphthylamine, 4,4′-dimethoxydiphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, and 4-isopropoxydiphenylamine. However, among these, the use of diphenylamine compounds is preferred.
Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy Methyl-2,6-di-t-butylphenol, 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4 ′ -Bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t- Monobutylphenol), 4,4′-methylene-bis (6-tert-butyl-o-cresol), 4,4′-methylene-bis (2,6-di-tert-butylphenol), 2,2′-methylene -Bis (4-methyl-6-cycl Rohexylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), bis (3-methyl-) 4-hydroxy-5-t-butylbenzyl) sulfide, 4,4′-thiobis (6-tert-butyl-o-cresol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2 , 6-Bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) -4-methylphenol, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzenesulfonic acid, 2 , 2′-dihydroxy-3,3′-di (α-methylcyclohexyl) -5,5′-dimethyl-diphenylmethane, α-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxy Phenyl Propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β- (3,5-di -T-butyl-4-hydroxyphenol) propionate], N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), 2,2-thio [diethyl- Bis-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], dioctadecyl ester of 3,5-di-tert-butyl-4-hydroxybenzenephosphonic acid, tetrakis [methylene-3 (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) 4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) ) Isocyanurate, tris [β- (3,5-di-t-butyl-4hydroxyphenyl) propionyl-oxyethyl] isocyanurate, and the like. Among these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

The sulfur-based antioxidant is a compound containing sulfur such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. Among these, the use of a thiodipropion ester-based compound is particularly preferable.
Phosphorous antioxidants are compounds containing phosphorus such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite. . Among these, it is preferable to use a compound having a sulfur atom in the molecule and a compound having two or more phosphorus atoms in the molecule.

  In the thermoplastic elastomer component used in the present invention, the blending amount of the antioxidant (D) is preferably 0.01 parts by mass to 5 parts by mass, particularly preferably 0.000 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. It is 05 mass parts-3 mass parts. The amount of 0.01 parts by mass or more is preferable because the thermoplastic elastomer component has excellent heat resistance, particularly long-term heat aging resistance, and can prevent occurrence of copper damage when bonded to a metal. Moreover, if it is 5 mass parts or less, since generation | occurrence | production of blooming can be prevented or the mechanical strength of a thermoplastic elastomer component improves, it is preferable.

  In the thermoplastic elastomer component used in the present invention, the blending amount of these antioxidants (D) is, for example, 0.01% by mass to 5% by mass, preferably 0.05%, based on the total amount of the thermoplastic elastomer component. The content is from 3% by mass to 3% by mass, and more preferably from 0.1% by mass to 1.5% by mass. If the total blending amount of the antioxidant (D) is 0.01% by mass or more, the heat resistance of the thermoplastic elastomer component, particularly the long-term heat aging resistance is excellent, and the occurrence of copper damage when joining with a metal is prevented. This is preferable. Moreover, if it is 5 mass% or less, since blooming generation | occurrence | production can be prevented or the mechanical strength of a thermoplastic elastomer component improves, it is preferable.

The thermoplastic elastomer component used in the present invention may contain a resin that does not belong to the category of thermoplastic elastomers.
As resin which does not belong to the category of a thermoplastic elastomer, it is a polyester random copolymer (E), for example.
As a polyester random copolymer (E), unless the effect of this invention is inhibited, it does not specifically limit, A commercial item can also be used. Examples of commercially available products include “Chemit” (registered trademark) manufactured by Toray Fine Chemical Co., Ltd., “Byron” (registered trademark) manufactured by Toyobo Co., Ltd., “Eritel” (registered trademark) manufactured by Unitika, and the like. Chemit R1159, R-228, R-248, R-283, Q-1500, R-273, R-50, R-98, R-99, R-92, K-1294, K-1089 (above, Toray Fine Chemical Co., Ltd.), Byron 200, 220, 240, 103, 300, 500 (above, manufactured by Toyobo Co., Ltd.), Elitel UE3220, UE3221, UE3230, UE3231, UE3400, UE350 (above, manufactured by Unitika Ltd.) .

  The polyester random copolymer (E) is preferable from the viewpoints of adjusting the melt viscosity of the thermoplastic elastomer component and improving the bonding strength between the reinforcing fiber bundle and the non-thermoplastic resin molding.

  In the thermoplastic elastomer component used in the present invention, the blending amount of these polyester random copolymers (E) is, for example, 1 part by mass to 25 parts by mass, preferably 2 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. Part to 20 parts by weight, more preferably 3 parts to 15 parts by weight. If the total blending amount of the polyester random copolymer (E) is 1 part by mass or more, the adjustment of the melt viscosity is facilitated, and the effect of improving the bonding strength with the reinforcing fiber bundle and the non-thermoplastic resin molding is obtained. Moreover, if it is 25 mass parts or less, since there is little concern that the mechanical strength of a thermoplastic elastomer component falls, it is preferable.

  In the thermoplastic elastomer component used in the present invention, the blending amount of these polyester random copolymers (E) is, for example, 1% by mass to 25% by mass, preferably 2% by mass with respect to the total amount of the thermoplastic elastomer component. -20% by mass, more preferably 3% by mass to 15% by mass. If the total blending amount of the polyester random copolymer (E) is 1% by mass or more, the adjustment of the melt viscosity becomes easy, and the effect of improving the bonding strength with the reinforcing fiber bundle and the non-thermoplastic resin molded product is obtained. Moreover, if it is 25 mass% or less, since there is little concern that the mechanical strength of a thermoplastic elastomer component falls, it is preferable.

Furthermore, various additives can be added to the thermoplastic elastomer component used in the present invention as long as the object of the present invention is not impaired.
Examples of the additives include molding aids (for example, known crystal nucleating agents and lubricants), light resistance agents (for example, ultraviolet absorbers, hindered amine compounds, etc.), hydrolysis resistance improvers, and colorants (for example, pigments). , Dyes, etc.), antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, mold release agents and the like.
Although the compounding quantity of these additives is not specifically limited, It is 0.01 mass part-10 mass parts with respect to 100 mass parts of thermoplastic elastomers, Preferably it is 0.05 mass part-5 mass parts.

The thermoplastic elastomer component used in the present invention preferably comprises a hard segment (a) containing an aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit. It is preferable that the polyester block copolymer (A), polyvinyl alcohol resin (B), silane coupling agent (C), and antioxidant (D) having a melting point of less than 210 ° C. are included.
More preferably, the thermoplastic elastomer component further includes a polyester random copolymer (E).

  The thermoplastic elastomer component is a polyester block copolymer (A) of 66 to 98.98% by mass, a polyvinyl alcohol resin (B) of 1 to 30% by mass, and a silane coupling agent (C) of 0.01. It is preferable that -5.0 mass% and 0.01-5.0 mass% of antioxidant (D) are included. Furthermore, the polyester block copolymer (A) is 46 to 98.98% by mass, the polyvinyl alcohol resin (B) is 1 to 30% by mass, and the silane coupling agent (C) is 0.01 to 5.0% by mass. More preferably, the antioxidant (D) contains 0.01 to 5.0% by mass and the polyester random copolymer (E) contains 1 to 25% by mass.

  The melting point (or softening point) of the thermoplastic elastomer component used in the present invention is, for example, 100 to 230 ° C, preferably 100 to 200 ° C, more preferably 100 to 170 ° C. Melting | fusing point can be measured by the method according to the below-mentioned Example.

The melt viscosity of the thermoplastic elastomer component used in the present invention is, for example, 50 to 50 at a shear rate of 100 / sec measured at a temperature 60 ° C. higher than the melting point (or softening point) of the thermoplastic elastomer component. It is 10,000 Pa · sec, preferably 100 to 5000 Pa · sec, and more preferably 500 to 2000 Pa · sec.
If it is such a range, it is preferable from viewpoints, such as being easy to impregnate a reinforcing fiber bundle and improving joint strength with a reinforcing fiber bundle. Melt viscosity can be measured by the method according to the below-mentioned Example.

  Although the manufacturing method of the thermoplastic elastomer component used for this invention is not specifically limited, For example, a polyester block copolymer (A), a polyvinyl alcohol-type resin (B), a silane coupling agent (C) A method of supplying a raw material blended with an antioxidant (D) and, if necessary, a polyester random copolymer (E) to a screw type extruder and melt-kneading can be employed. The thermoplastic elastomer component obtained by the above method can be pelletized and used for subsequent molding.

[Fiber-reinforced composite materials]

  The fiber-reinforced composite material of the present invention may be in a form in which the thermoplastic elastomer component covers the reinforcing fiber bundle, and the surface appearance is that the surface of the fiber-reinforced composite material is a layer of only the thermoplastic elastomer component. It is preferable because it is excellent.

The manufacturing method of the fiber reinforced composite material of the present invention is not particularly limited as long as it is manufactured including a reinforcing fiber bundle and a thermoplastic elastomer (TPE) component.
In the fiber-reinforced composite material of the present invention, for example, the TPE component is bonded to a fiber bundle (reinforced fiber bundle) of reinforcing fibers aligned in one direction or a processed product thereof, and the TPE component and the reinforcing fiber bundle are combined. It can be manufactured by a method. The joining can be performed, for example, by impregnating a reinforcing fiber bundle or a processed product thereof with a TPE component. The impregnation is preferably performed by heating and melting the TPE component.
In this method, the shape (form) of the TPE component is not particularly limited, and examples thereof include a thread (fiber), a sheet, a film, a nonwoven fabric, a powder, and a pellet. The method for forming the TPE component into a yarn, sheet, film, nonwoven fabric, powder, or pellet is not particularly limited, and may be a conventionally known method.
In this method, the processed product of the reinforcing fiber bundle is not particularly limited.

The heating and melting method is not particularly limited, and may be a conventionally known method, for example, using a hot press or a mold.
The heating and melting temperature is not particularly limited and is, for example, 100 to 300 ° C.
The heating and melting time is not particularly limited, and is, for example, 10 seconds to 5 minutes.
Although the load in the case of heat-melting is not specifically limited, For example, it is 0.1-10 MPa.
After heating and melting, using a press adjusted to a temperature of 20 to 40 ° C. or the like, a load (for example, 0.1 to 10 MPa or the like) may be applied (for example, 10 seconds to 5 minutes or the like) for cooling and solidification.

Prior to the heating and melting, the TPE component may be applied to the reinforcing fiber bundle or a processed product thereof.
In this case, the TPE component is preferably an aqueous dispersion of the TPE component, a powder of the TPE component, or the like.
The powder of the TPE component can be obtained by freeze-pulverizing the TPE component. The average particle diameter of the TPE component powder is, for example, 1 to 20 μm.
When an aqueous dispersion is used, a fiber reinforced composite material can be obtained by drying the reinforcing fiber bundle coated with the aqueous dispersion or a processed product thereof, removing moisture, and then applying the heat melting. By using the aqueous dispersion, the TPE component is easily impregnated into the reinforcing fiber bundle, and the bonding strength with the reinforcing fiber is also increased.

When using a TPE component sheet and a processed product of a reinforcing fiber bundle, for example, after alternately stacking a TPE component sheet and a processed product of a reinforcing fiber bundle, the above-mentioned heat-melting is performed, whereby a fiber reinforced composite A material can be obtained.
In this invention, it is preferable to laminate | stack so that all the outermost layers after a lamination | stacking may become a layer of a TPE component from the surface improvement of the fiber reinforced composite material obtained.

  Also, when using a prepreg as a processed product of reinforcing fiber bundles, as described above, sheets of TPE components and processed products of reinforcing fiber bundles may be alternately laminated and then heated and melted. After laminating 1 sheet or several sheets (for example, 2 to 5 sheets), the temperature of the thermosetting resin when the prepreg is formed by laminating a TPE component sheet or nonwoven fabric on both or one side of the outermost layer The TPE component may be heated and melted (for example, 130 to 200 ° C.), and the TPE component may be bonded to the reinforcing fiber bundle together with the thermosetting resin impregnated in the prepreg.

  In addition, the fiber reinforced composite material of the present invention forms a woven fabric using TPE component yarns and reinforcing fiber bundles (yarns) as weaving yarns (for example, one yarn as warp and the other as weft). Can also be obtained. The method for producing the woven fabric is not particularly limited, and can be performed by using a thread of the TPE component in a conventionally known method for producing a woven fabric of reinforcing fiber bundles.

The fiber reinforced composite material may be molded as necessary.
The method of molding fiber reinforced composite material is not particularly limited, but for example, hand lay-up molding, spray-up molding, SMC (Sheet Molding Compound) molding, RTM (Resin Transfer Molding) molding, BMC (Bulk Molding Compound) molding is used. can do. These molding methods may follow conventionally known methods.

[Composite molded body]
By bonding the fiber-reinforced composite material of the present invention to a non-thermoplastic resin molded body (non-thermoplastic resin material), a fiber-reinforced composite material composite molded body can be obtained. In this invention, joining with a non-thermoplastic resin molded object can be performed without interposing an adhesive agent.
The non-thermoplastic resin molded body is not particularly limited, and examples thereof include metals such as aluminum alloys, copper alloys, various steel materials, magnesium alloys, and metals subjected to surface treatment such as alumite and chromium, epoxy resins, and phenol resins. And thermosetting resins such as melamine resin, urea resin and polyurethane resin, wood such as straw, straw and cedar, various glasses, concrete, mortar and asphalt.

Moreover, joining with a non-thermoplastic resin molding can be performed by heating and melting.
The heating and melting method is not particularly limited, and may be a conventionally known method. For example, a hot pressing machine, an electromagnetic induction heating machine, a laser welding machine, or the like can be used.

The above-described fiber-reinforced composite material and composite molded body thereof according to the present invention can be used for a part that joins a fiber-reinforced composite material and a metal part or a glass part. For example, a housing part, a housing material, a sport It can be used for applications such as goods, automobile parts, and exterior parts of motorcycles.
Further, the fiber reinforced composite material of the present invention and the composite molded body thereof are used for reinforcing a structure formed of concrete, steel, or the like by joining with concrete, steel, or the like (for example, bridges, overpasses, buildings, etc. It can also be used for reinforcing materials.
The fiber-reinforced composite material of the present invention and the composite molded body thereof can be directly joined to parts previously joined with an adhesive or the like by heating and melting a thermoplastic elastomer component without using an adhesive or the like. It becomes possible.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples. The present invention can be implemented with appropriate modifications within the scope of the gist of the present invention. In the following examples, “parts” and “%” indicate mass units unless otherwise specified.

[Thermoplastic elastomer component]
Hytrel 4057N (melting point: 162 ° C.) manufactured by Toray DuPont Co., Ltd. as the polyester block copolymer (A), S-LEC BL-1 manufactured by Sekisui Chemical Co., Ltd., silane coupling agent (polyvinyl alcohol resin (B)) C) as Toray Dow Corning Co., Ltd. Z-6040, Shiraishi Calcium Co., Ltd. Naugard 445 (aromatic amine antioxidant) as the antioxidant (D), Polyester random copolymer (E) as Toray Chemit R-99 manufactured by Fine Chemical Co., Ltd. was dry blended at the compounding ratio shown in Table 1, and melt-kneaded at a temperature setting of 220 ° C. using a twin screw extruder having a 45 mmφ screw, then pelletized, and thermoplastic. Elastomer components (Y-1), (Y-2), (Y-3), (Y-4), and (Y-5) were obtained.

[Measurement of melting point of thermoplastic elastomer component]
DSC Q100 manufactured by TA Instruments Inc. was used, and the melting point was measured by heating from room temperature to 240 ° C. at a rate of temperature increase of 10 ° C./min.

[Measurement of melt viscosity of thermoplastic elastomer components]
Using a Capillograph C1 manufactured by Toyo Seiki Seisakusho, the relationship between shear rate and melt viscosity was measured under the conditions of a measurement temperature of 202 ° C., an orifice length of 10 mm, and an orifice diameter of 1.0 mm, and the shear rate was 100 / sec. The melt viscosity was read.

[Create film]
For each thermoplastic elastomer component, a film having a thickness of 50 μm and a width of 300 mm × length of 300 mm was formed. Further, a film having a film thickness of 50 μm and a width of 300 mm × length of 300 mm using polybutylene terephthalate (Toraycon 1401 manufactured by Toray Industries, Inc.) was formed.

[Creation of non-woven fabric]
For each thermoplastic elastomer component, a nonwoven fabric having a basis weight of 100 g / m ² , a width of 300 mm × a length of 300 mm was prepared by melt blowing. Further, a nonwoven fabric having a basis weight of 100 g / m ² , width 300 mm × length 300 mm using polybutylene terephthalate (Toraycon 1401 manufactured by Toray Industries, Inc.) was prepared by melt blowing.

[Vibration damping characteristics]
A test piece having a width of 10 mm and a length of 170 mm was cut out from the obtained fiber reinforced composite material, and the upper 20 mm was fixed with a clamp using the apparatus shown in FIG. The loss factor and resonance frequency were measured as damping characteristics at the resonance point.

[Sound pressure measurement]
A test piece having a width of 100 mm and a length of 100 mm was cut out from the obtained fiber-reinforced composite material, and the test piece was placed on an iron pedestal using the apparatus shown in FIG. The maximum acceleration of the iron pedestal when a steel ball of 5 cm to 28 g was freely dropped and the maximum sound pressure level of 10 cm from the center and 14 cm in height were measured.

[Joint strength test]
The obtained fiber reinforced composite material is cut into a width of 20 mm and a length of 100 mm, and laminated with an aluminum (A1100) plate having a thickness of 1 mm, a width of 20 mm, and a length of 50 mm so that the length of the overlapping portion is 20 mm. Using a hot press set at 220 ° C., the thermoplastic elastomer component portion of the composite material was heated and melted, and the fiber-reinforced composite material was heat-sealed to an aluminum plate to prepare a joining test piece. The end of the fiber reinforced composite material and the end of the aluminum plate of the obtained joint test piece were sandwiched with a chuck, and the tensile shear peel strength was measured at a strain rate of 200 mm / min using INSTRON 5565 manufactured by Instron Japan.

[Falling ball test of composite molded body]
The obtained fiber reinforced composite material was cut into a width of 20 mm and a length of 200 mm, and a 200 ° C. iron was used for a test piece using a thermoplastic elastomer component on one side of a brazing material having a film thickness of 6 mm, a width of 20 mm and a length of 200 mm. In the test piece using polybutylene terephthalate, a 230 ° C. iron was pressed and melted by heating to prepare a composite molded body. As shown in FIG. 3, the brazing material was fixed on the upper side so that the steel ball hits the brazing material at a distance between supporting points of 100 mm as shown in FIG. 3, and a steel ball with a load of 250 g was fixed from a height of 50 cm. The fiber reinforced composite was dropped to the side of the brazing material, and the damaged state of the brazing material and the fiber reinforced composite material as a composite molded body was visually confirmed. A composite material that retained its shape was marked with ◎, a brace material that was broken but the reinforcing fibers were not broken, and a crushed material and a fiber-reinforced composite material that were broken.

[Example 1]
The thermoplastic elastomer component (Y-1) film and Toray Co., Ltd. TORAYCA CROSS UT70-20G unidirectional material are each cut into a width of about 100 mm and a length of 250 mm, and each of the outermost layers has a TPE component (Y-1). With the film in place, 3 TPE component films and 2 TORAYCA cloths are alternately laminated, Teflon film is inserted as a release film on both surfaces, and 1 MPa with hot press and mold adjusted to a temperature of 200 ° C. Was applied for 30 seconds to melt the TPE component and impregnate the carbon fiber. Immediately thereafter, a 1 MPa load was applied for 30 seconds with a press adjusted to a temperature of 30 ° C. for cooling and solidification to obtain a fiber-reinforced composite material. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 2]
A fiber-reinforced composite material was obtained in the same manner as in Example 1 except that the thermoplastic elastomer component (Y-2) nonwoven fabric was used. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 3]
Each of the thermoplastic elastomer component (Y-2) film and the aramid sheet (Fibra sheet AK-20 / 20) manufactured by Fivebex Co., Ltd. is cut into a width of about 100 mm and a length of about 250 mm, and each of the outermost layers has a TPE component. (Y-2) A hot press in which three TPE component films and two aramid sheets are alternately laminated in a state having a film, a Teflon film is inserted as a release film on both surfaces, and the temperature is adjusted to 200 ° C. A 1 MPa load was applied for 30 seconds in the mold to melt the TPE component and impregnate the carbon fiber. Immediately thereafter, a 1 MPa load was applied for 30 seconds with a press adjusted to a temperature of 30 ° C. for cooling and solidification to obtain a fiber-reinforced composite material. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 4]
A fiber-reinforced composite material was obtained in the same manner as in Example 3 except that the thermoplastic elastomer component (Y-3) film was used. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 5]
A fiber-reinforced composite material was obtained in the same manner as in Example 3 except that the thermoplastic elastomer component (Y-4) film was used. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 6]
Carbon fiber prepreg trading card manufactured by Toray Industries, Inc. (3252S-10 using matrix resin 2592) is cut at a width of about 250 mm and a length of 250 mm, and the four cut pieces are laminated so that the fiber direction is shifted by 90 degrees. A thermoplastic elastomer component (Y-1) non-woven fabric is laminated on both sides. Then, after covering the periphery with a Teflon film as a release film, it was molded using a hot press at a temperature of 160 ° C. and a load of 1 MPa for 30 minutes, and then cooled and solidified for 5 minutes at a load of 1 MPa with a cooling press set at 30 ° C. A carbon fiber reinforced composite material having a TPE component layer on the outermost surface was obtained. The obtained fiber reinforced composite material had a good surface appearance in which no pinholes were visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Example 7]
A fiber-reinforced composite material was obtained in the same manner as in Example 1 except that the thermoplastic elastomer component (Y-5) non-woven fabric was used. A layer of the TPE component was present on the surface of the fiber reinforced composite material, and a good surface appearance was obtained in which no pinhole was visually confirmed. Table 2 shows measurement results of various tests of the obtained fiber reinforced composite material and a molded body obtained using the composite material.

[Comparative Example 1]
A fiber-reinforced thermoplastic resin composite was obtained in the same manner as in Example 1 except that a film formed of polybutylene terephthalate was used instead of the thermoplastic elastomer component (Y-1). A thermoplastic resin layer was present on the surface of the fiber reinforced thermoplastic resin composite material, and a good surface appearance was obtained in which no pinholes were observed visually. Table 2 shows the measurement results of various tests of the obtained fiber-reinforced thermoplastic resin composite and the molded body obtained using the composite.

[Comparative Example 2]
A carbon fiber reinforced thermosetting resin composite was obtained in the same manner as in Example 6 except that the carbon fiber prepreg used in Example 6 was used and the TPE component was not laminated on the outermost surface. Several pinholes were found on the surface of the fiber reinforced composite. In addition, a carbon fiber reinforced thermosetting resin composite is cut into a width of 20 mm and a length of 100 mm for a bonding strength test, and overlaps with an end portion of an aluminum (A1100) plate having a thickness of 1 mm, a width of 20 mm, and a length of 50 mm. After applying an epoxy resin (Bond E2500S manufactured by Konishi Co., Ltd.) so that the film thickness becomes 0.1 mm, the epoxy resin is cured by leaving it at a temperature of 30 ° C. and a load of 0.1 MPa for 24 hours. A composite molded body of carbon fiber reinforced thermosetting resin composite material was obtained.
Furthermore, the carbon fiber reinforced thermosetting resin composite was cut into a width of 20 mm and a length of 200 mm for a ball drop test of the molded body, and an epoxy resin ( After applying a bond E2500S manufactured by Konishi Co., Ltd. so that the film thickness becomes 0.1 mm, the epoxy resin is cured by leaving it at a temperature of 30 ° C. and a load of 0.1 MPa for 24 hours to heat the carbon fiber reinforced heat. A composite molded body of a curable resin composite material was obtained. Table 2 shows the measurement results of various tests of the obtained carbon fiber reinforced thermosetting resin composite and composite molded body.

[Comparative Example 3]
Four reinforcing fibers obtained by cutting an aramid sheet (Fibra sheet “AK-20 / 20) manufactured by Fivex Co., Ltd. into a width of 250 mm and a length of 250 mm are used, and an epoxy resin (manufactured by Konishi Co., Ltd.) is used for each aramid sheet. After laminating 4 sheets coated with Bond E2500S so that the film thickness becomes 0.1 mm, and covering with a Teflon film as a release film, it was left at a temperature of 30 ° C. and a load of 0.1 MPa for 24 hours. The epoxy resin was cured to obtain a fiber reinforced thermosetting resin composite, and several pinholes were confirmed on the surface of the fiber reinforced composite.
In addition, for bonding strength test, the aramid sheet was cut into four sheets having a width of 20 mm and a length of 100 mm, and an epoxy resin (overlapping with the end portion 20 mm of an aluminum (A1100) plate having a thickness of 1 mm, a width of 20 mm, and a length of 50 mm was obtained. After laminating an aramid sheet coated with Bond E2500S manufactured by Konishi Co., Ltd., the epoxy resin was cured to a thickness of 0.1 mm by leaving it at a temperature of 30 ° C., a load of 0.1 MPa for 24 hours. A composite molded body of a fiber reinforced thermosetting resin composite material was obtained.
Further, for the ball drop test of the composite molded body, the aramid sheet was cut into a width of 20 mm and a length of 200 mm, and an epoxy resin (manufactured by Konishi Co., Ltd.) was placed on one side of a brazing material having a thickness of 6 mm, a width of 20 mm and a length of 200 mm. After laminating an aramid sheet coated with a bond E2500S so that the film thickness becomes 0.1 mm, the epoxy resin is cured at a temperature of 30 ° C. and a load of 0.1 MPa for 24 hours to cure the fiber reinforced thermosetting resin. A composite molded body of the composite material was obtained. Table 2 shows the measurement results of various tests of the obtained fiber-reinforced thermosetting resin composite material and composite molded body.

The fiber reinforced composite materials of Examples 1 to 7 using the thermoplastic elastomer components (Y-1), (Y-2), (Y-3), (Y-4), and (Y-5) are vibration-damping. It has excellent characteristics and sound pressure, and has a good surface appearance with no surface defects such as pinholes.
In the joint strength of the composite molded body heat-welded with aluminum, Examples 1 to 3, 6 and 7 showed particularly high values. In any of Examples 1 to 7, the fiber reinforced composite material was used on the fracture surface. The deposits derived from the TPE component were adhered to both the aluminum side and the aluminum side, and the TPE component layer serving as the adhesive layer was broken.

  Even in the falling ball test of the composite molded body heat-welded with the brazing material, the thermoplastic elastomer is flexible, so Examples 1 to 7 are excellent in impact absorbing effect, and in Examples 1 to 3 and 7 having particularly high bonding strength, Sufficient reinforcement effect was shown without damaging the material. In Examples 4 to 6, although the brazing material was destroyed, the fiber-reinforced composite material was not destroyed.

In Comparative Examples 1 to 3 using a polybutylene terephthalate resin or an epoxy resin which is a hard resin, the vibration damping property of the composite material was inferior and a high value was also shown in sound pressure measurement.
As a result of the bonding strength and the falling ball test as a composite molded body, in Comparative Example 1, the polybutylene terephthalate resin does not bond with aluminum, and the bonding with the brazing material is weak and the impact of the falling ball causes a fiber reinforced thermoplastic resin. The composite material peeled off and was damaged.
In Comparative Examples 2 and 3, it took a long time to obtain sufficient bonding strength by bonding with an epoxy resin, but both aluminum and brazing material showed relatively high bonding strength. However, in the falling ball test, it was confirmed that the hard epoxy resin was destroyed by the high impact energy received by the wood, and the carbon fiber and the aramid fiber were also damaged by that energy, which was insufficient for reinforcing the composite molded body. there were.

  From the above, by combining the thermoplastic elastomer component and the reinforcing fiber bundle, the fiber reinforced composite material can be compared with the combination of the conventional thermoplastic resin and the reinforcing fiber bundle or the combination of the thermosetting resin and the reinforcing fiber bundle. It was confirmed that the vibration and shock resistance were excellent.

The fiber-reinforced composite material of the present invention is excellent in vibration damping and impact resistance characteristics by using a thermoplastic elastomer component, and also has excellent surface appearance by making the surface a layer of a thermoplastic elastomer component. Applicable to exterior parts.
Furthermore, by using a specific thermoplastic elastomer component, heat fusion to metal, glass, wood, concrete, etc. becomes more suitable, application to a composite molded body with improved vibration damping and impact resistance, It can be used as a reinforcing material for metals, glass, wood, concrete and the like.

1. 1. Fiber reinforced composite material Clamp 3. Iron pedestal 4. Steel ball 5. Sound level meter 6. Wood material wrecking ball

Claims (11)

  A fiber-reinforced composite material composed of a continuous fiber reinforced fiber bundle and a thermoplastic elastomer component.   The fiber-reinforced composite material according to claim 1, wherein the thermoplastic elastomer component is a thread.   The fiber-reinforced composite material according to claim 1, wherein an aqueous dispersion or powder of the thermoplastic elastomer component is combined with a reinforcing fiber bundle.   Polyester block copolymer in which the thermoplastic elastomer component includes a hard segment (a) containing an aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit as constituent components ( The fiber-reinforced composite material according to any one of claims 1 to 3, which contains 60% by mass or more of A).   The fiber-reinforced composite material according to any one of claims 1 to 4, wherein the thermoplastic elastomer component further contains a polyvinyl alcohol resin (B).   The melt viscosity of the thermoplastic elastomer component measured at a temperature 60 ° C. higher than the melting point of the thermoplastic elastomer component is 50 to 10,000 Pa · sec at a shear rate of 100 / sec. The fiber reinforced composite material according to any one of the above.   The thermoplastic elastomer component contains a hard segment (a) containing an aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit as constituent units, and the melting point is less than 210 ° C. Polyester block copolymer (A), polyvinyl alcohol resin (B), silane coupling agent (C) and antioxidant (D), and the polyester block copolymer (A) is 66 to 98. 98% by mass, 1-30% by mass of the polyvinyl alcohol resin (B), 0.01-5.0% by mass of the silane coupling agent (C), and 0.01% of the antioxidant (D). The fiber-reinforced composite material according to any one of claims 1 to 6, comprising -5.0% by mass.   The thermoplastic elastomer component contains a hard segment (a) containing an aromatic polyester unit and a soft segment (b) containing an aliphatic polyether unit and / or an aliphatic polyester unit as constituent units, and the melting point is less than 210 ° C. Polyester block copolymer (A), polyvinyl alcohol resin (B), silane coupling agent (C), antioxidant (D) and polyester random copolymer (E). A) is 46 to 98.98% by mass, the polyvinyl alcohol-based resin (B) is 1 to 30% by mass, the silane coupling agent (C) is 0.01 to 5.0% by mass, and the antioxidant ( D) is 0.01 to 5.0% by mass, and the polyester random copolymer (E) is 1 to 25% by mass. Fiber-reinforced composite material according to any of Motomeko 1-7.   The composite molded object which the fiber reinforced composite material in any one of Claims 1-8, and the non-thermoplastic resin molded object joined.   The composite molded body according to claim 9, wherein the fiber reinforced composite material and the non-thermoplastic resin molded body are heat-sealed without an adhesive.   The composite molded article according to claim 9 or 10, wherein the non-thermoplastic resin molded article is a metal, glass, concrete, or wood.