JP7058315B2 - Fiber complex and its manufacturing method - Google Patents

Description

The present invention relates to a fiber complex having excellent strength in a high temperature environment and a method for producing the same.

Since fiber-reinforced synthetic resin reinforced with fiber is lightweight and has high mechanical strength, in recent years, light weight and high mechanical strength in the fields of automobiles, ships, aviation, medical care, etc. have been required. Its use is expanding in the fields where it is used.

As a composite having a fiber-reinforced synthetic resin, a fiber composite is proposed in which a foam is used as the core material and the fiber-reinforced synthetic resin is laminated and integrated on the surface of the core material for the purpose of weight reduction and improvement of heat insulation. (See Patent Documents 1 and 2).
Further, a fiber composite in which the shape of bubbles in the foam of the core material is defined has been proposed (see Patent Documents 3 and 4).

Japanese Patent Application Laid-Open No. 2015-83365 Japanese Unexamined Patent Publication No. 2005-313613 Japanese Unexamined Patent Publication No. 2000-135754 Japanese Unexamined Patent Publication No. 2014-208418

In recent years, there has been an increasing demand for fiber complexes that can withstand use in a higher temperature environment and for shortening the molding cycle thereof.

However, although the fiber composite of Patent Document 1 is composed of a core material having a bubble structure and a surface material made of a thermoplastic resin and carbon fibers, it is not possible to obtain a fiber composite having good rigidity in a high temperature environment such as 100 ° C. difficult.
The composite of Patent Document 2 defines the strength of the reinforcing fibers in the skin material, and although the strength is high in a room temperature environment, it is possible to obtain a fiber composite having good rigidity in a high temperature environment such as 100 ° C. difficult.
The fiber composite of Patent Document 3 can be imparted with impact resistance by defining the shape (aspect ratio) of bubbles in the entire core material of the foam, but when the aspect ratio is reduced, the weight of the fiber composite is reduced. When the aspect ratio is increased, the surface of the foam is easily broken at the interface between the surface of the foam and the skin material containing fiber and resin, and the impact resistance is increased. Is bad.
The fiber composite of Patent Document 4 can further improve the impact resistance by defining the average aspect ratio of the bubbles in the foam core layer and the surface layer, but the foam and the fiber are also in an environment of 100 ° C. And the destruction at the interface with the skin material containing resin is insufficient.

Therefore, an object of the present invention is to provide a fiber composite capable of obtaining rigidity in a high temperature (for example, 100 ° C.) environment, aesthetic appearance, and surface cosmeticity at the time of high temperature molding.

In order to solve the above problems, the present inventors are a fiber composite in which a skin material containing a fiber and a resin is laminated, and the average aspect ratio of bubbles in the core layer of the core material is 0.55 or more and less than 1.00. By using a fiber composite having an average aspect ratio of bubbles in the surface layer of the portion where the surface layer and the skin material are laminated is 0.05 or more and less than 0.45, a high temperature (for example, 100 ° C., etc.) is used. ), We have found that excellent rigidity, aesthetic appearance, and surface cosmeticity during high-temperature molding can be obtained, and have made the present invention.

That is, the present invention is as follows.
(1)
A core material containing a foamed resin having a core layer and a surface layer formed on one or both sides of the core layer, and a fiber in which a fiber and a skin material containing a resin are laminated on at least a part of the surface layer. It is a complex and
The surface layer is from the interface between the skin material and the surface layer to a position 250 μm from the interface in the thickness direction.
In the portion where the surface layer and the skin material are laminated, the average aspect ratio of the bubbles in the surface layer is 0.05 or more and less than 0.45, and the average aspect ratio of the bubbles in the core layer is 0.55. More than 1.00 and less than 1.00
The apparent density of the surface layer is 480 to 800 kg / m ³ .
The apparent density of the core layer is 10 to 690 kg / m ³ .
The foamed resin is a polyamide-based resin, and the polyamide-based resin is a mixture of polyamide-based resins containing an aliphatic polyamide in an amount of more than 50% by mass .
A fiber complex characterized by that.

(2)
The fiber composite according to (1), wherein the content of the resin in the epidermis is 30 to 60% by weight.
(3)
The fiber composite according to (1) or (2), wherein the thermosetting resin is contained in the epidermis and the glass transition temperature of the thermosetting resin is 75 ° C to 140 ° C.
(4)
The fiber complex according to any one of (1) to (3), wherein the epidermis contains an epoxy resin.

The fiber complex of the present invention can provide a fiber complex capable of obtaining rigidity in a high temperature (for example, 100 ° C.) environment, aesthetic appearance, and surface cosmeticity during high temperature molding.

FIG. 1 is a schematic view showing a cross-sectional view of an example of the fiber complex of the present embodiment.

Hereinafter, embodiments for carrying out the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

[Fiber complex]
The fiber composite of the present embodiment has a core material having a core layer and a surface layer formed on one or both sides of the core layer, and a core material containing a foamed resin, and a fiber and a resin on at least a part of the surface layer. It is a fiber composite in which the skin material containing the above-mentioned material is laminated, and the average aspect ratio of the bubbles in the surface layer is 0.05 or more and less than 0.45 in the portion where the surface layer and the skin material are laminated. The average aspect ratio of the bubbles in the core layer is 0.55 or more and less than 1.00.

The entire surface of the core material may be a surface layer, or a part of the core material may be a surface layer.
The fiber composite of the present embodiment is preferably a composite in which a skin material containing fibers and a resin is arranged on at least a part of at least one surface of a core material containing a foamed resin. The skin material may be laminated on the surface layer and provided on both surfaces of the core material, or may be provided on one side. The skin material may be provided on a part of the surface of the core material, or may be provided on the entire surface.

In the fiber composite of the present embodiment, the portion of the surface of the core material on which the skin material is arranged may be appropriately determined according to the shape of the core material, and is, for example, in the case of a sheet (see Examples described later). May be all or part of one side or both sides, may be all or part of the surface that can be seen from a specific direction in a stationary state in the case of a lump, and may be all or part of a surface that can be seen from a specific direction in a stationary state, and in the case of a linear shape, from one end to the extending direction. It may be all or part of the surface for a given length.

The fiber complex of this embodiment will be described with reference to FIG.
The fiber composite 1 of FIG. 1 has a core material 2 in which a surface layer 5 and a surface layer 6 are formed on the entire surfaces of both surfaces of the core layer 7, and a skin material 3 and a skin material 4 on the entire surfaces of the surface layer 5 and the surface layer 6. Is a laminated fiber complex 1. In addition, the core layer and the surface layer in the core material may be laminated with the core layer and the surface layer produced by a different method, or as described in Examples described later, one foaming through a compression step or the like. It may be formed from a laminated body including a body.
The surface layer does not have to be formed on both sides of the core layer 7, and may be formed at least on the surface side of the core material in which the skin material is laminated and integrated. Therefore, when the skin material 3 is laminated and integrated only on the surface layer 5 side of the core material 2, the surface layer 5 is formed on one surface of the core layer 7, and the surface layer 5 is formed on the other surface of the core layer 7. There may be no surface layer. When the surface layer 5 is provided on one surface of the core layer 7, the structure on the other surface side (lower surface side in FIG. 1) of the core layer 7 is not particularly limited, and even a foamed layer is not used. It may be a foamed layer, but it is preferably a foamed layer. When the layer formed on the lower surface of the core layer 7 is a foamed layer, the layer has the same structure as the core layer 7 or the surface layer 5 (for example, average aspect ratio, average major axis, apparent density, etc. of bubbles). May have.

(Core material)
The core material in the fiber composite of the present embodiment contains a foamed resin. The core material may contain a member other than the foamed resin, depending on the purpose and application. However, from the viewpoint that the characteristics of the foamed resin can be easily obtained, it is preferable that the core material is made of only the foamed resin. Further, the core material is preferably a foam containing a foamed resin, and more preferably a foam containing only a foamed resin as a resin component.

-Foam resin-
The foamed resin is preferably a resin having high heat resistance, more preferably a polyester resin, a polyamide resin, a polyphenylene ether resin, a (meth) acrylic resin or the like as a main component, and particularly preferably a polyamide. It is a based resin and a polyphenylene ether based resin. The foamed resin may be used alone or in combination of two or more. Here, "as a main component" means that it contains 50% by mass or more with respect to the total amount (100% by mass) of the foamed resin, and may be 60% by mass or more, or 100% by mass.

As the polyester-based resin, a high-molecular-weight linear polyester obtained as a result of a condensation reaction between a dicarboxylic acid and a dihydric alcohol is preferable. Of these, aromatic polyester resins are preferable.
The polyester resin may be used alone or in combination of two or more.

As the aromatic polyester resin, a polyester containing an aromatic dicarboxylic acid component and a diol component is preferable, and for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like are used. Among them, polyethylene terephthalate is preferable.

In addition to the aromatic dicarboxylic acid component and the diol component, the aromatic polyester resin includes, for example, tricarboxylic acids such as tricarboxylic acids such as trimellitic acid and tetracarboxylic acids such as pyromellitic acid, and trivalent or higher polyvalent carboxylic acids thereof. It may contain an anhydride, a triol such as glycerin, a trivalent or higher polyvalent alcohol such as tetraol such as pentaerythritol, or the like as a constituent component.

When polyethylene terephthalate is used as the polyester resin, it may be crosslinked by a crosslinking agent. As the cross-linking agent, known ones are used, and examples thereof include acid dianhydrides such as pyromellitic anhydride, polyfunctional epoxy compounds, oxazoline compounds, and oxazine compounds. The cross-linking agent may be used alone or in combination of two or more.

Examples of the polyamide-based resin include polyamides, polyamide copolymers, and mixtures thereof.
The polyamide resin may be used alone or in combination of two or more.

Examples of the polyamide include nylon 66, nylon 610, nylon 612, nylon 46, nylon 1212, etc. obtained by polycondensation of diamine and dicarboxylic acid; nylon 6, nylon 12, etc. obtained by ring-opening polymerization of lactam. ; Etc. can be mentioned.
Examples of the polyamide copolymer include nylon 6/66, nylon 66/6, nylon 66/610, nylon 66/612, nylon 66 / 6T (T represents a terephthalic acid component), and nylon 66 / 6I (T). I represents an isophthalic acid component), nylon 6T / 6I, and the like. Of these, aliphatic polyamides are preferable, and nylon 6, nylon 66, nylon 6/66, nylon 66/6 and the like are more preferable.

Examples of the mixture of the polyamide resin include a mixture of nylon 66 and nylon 6, a mixture of nylon 66 and nylon 612, a mixture of nylon 66 and nylon 610, a mixture of nylon 66 and nylon 6I, and nylon 66. Examples thereof include a mixture of nylon 6T and a mixture of nylon 6 and nylon 6I / 6T. Above all, from the viewpoint of increasing the crystallinity of the foamed resin and sufficiently improving the heat resistance and the surface cosmeticity of the composite, the polyamide-based resin in the case of the mixture preferably contains more than 50% by mass of the aliphatic polyamide. , 60% by mass or more is more preferable.

In the molecule of the polyamide resin, such a substituent is used by using a compound or a polymer having a substituent (hereinafter, also referred to as a reactive substituent) that reacts with an amino group or a carboxyl group of the polyamide resin. The degree of cross-linking of the polyamide-based resin may be increased by forming a cross-linking structure via the above.

Examples of the reactive substituent include functional groups such as glycidyl group, carboxyl group, carboxylic acid metal salt, ester group, hydroxyl group, amino group and carbodiimide group, and particularly from the viewpoint of reaction speed. , Glysidyl group and carbodiimide group are preferable.
The above-mentioned reactive substituent may be used alone or in combination of two or more. Further, a compound or a polymer having a reactive substituent may have a plurality of kinds of functional groups in one molecule.
The amount of the reactive substituent introduced into the polyamide-based resin should be such that gelation or the like does not occur in the resin due to cross-linking.

The highly reactive functional groups (amino group and carboxyl group) possessed by the polyamide resin at the ends are changed to low reactive functional groups by adding an end-capping agent in the synthesis of the polyamide resin (polyamide resin). Can be closed).
In this case, the time for adding the end-capping agent includes the time of charging the raw material, the time of starting the polymerization, the middle of the polymerization, and the time of the end of the polymerization.

The terminal encapsulant is not particularly limited as long as it is a monofunctional compound capable of reacting with an amino group or a carboxyl group of a polyamide resin, and is not particularly limited, for example, monocarboxylic acid, monoamine, or acid anhydride. Examples include substances, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like. The terminal encapsulant may be used alone or in combination of two or more.

In particular, when used in a high temperature environment, a heat stabilizer may be used together with the foamed resin, and in particular, the heat stabilizer effectively prevents long-term heat aging in a high temperature environment of 120 ° C. or higher. From the viewpoint, a copper compound is preferable, and a combination of this copper compound and an alkali metal halide compound is also preferable. Here, examples of the alkali metal halide compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, and iodide. Examples include potassium. These may be used alone or in combination of two or more.

［式中、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４は、それぞれ独立して、水素原子；ハロゲン原子；アルキル基；アルコキシ基；フェニル基；ハロゲン原子と一般式（１）中のベンゼン環との間に少なくとも２個の炭素原子を有するハロアルキル基又はハロアルコキシ基で第３α－炭素を含まない基；からなる群から選択される一価の基である。］ The polyphenylene ether (PPE) -based resin refers to a polymer containing a repeating unit represented by the following general formula (1), for example, a homopolymer composed of repeating units represented by the following general formula (1), the following. Examples thereof include a copolymer containing a repeating unit represented by the general formula (1).

[In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atom; halogen atom; alkyl group; alkoxy group; phenyl group; halogen atom and the benzene ring in the general formula (1). It is a monovalent group selected from the group consisting of a haloalkyl group having at least two carbon atoms or a haloalkoxy group containing no 3α-carbon; ]

The polyphenylene ether-based resin is not particularly limited, and is, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-). Methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly ( 2-Ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dibutyl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether 2,6-diphenyl-1,4-diphenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, poly (2-) Methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2-Methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, poly (2) -Chloro-1,4-phenylene) ether, poly (2,6-dibromo-1,4-phenylene) ether and the like can be mentioned. Above all, in particular, in the above general formula (1), R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, and R ₃ and R ₄ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. A polymer containing is preferable.
The polyphenylene ether-based resin may be used alone or in combination of two or more.

The polyphenylene ether-based resin may be used in combination with other resins, and is preferably 40 to 80% by mass, more preferably 40 to 70% by mass, based on 100% by mass of the resin component of the foamed resin. %. When the PPE content is 40% by mass or more, excellent heat resistance can be obtained, and when the PPE content is 80% by mass or less, excellent processability can be obtained.

Examples of other resins used together with the above polyphenylene ether resin include thermoplastic resins and the like, and examples thereof include polyolefin resins such as polyethylene, polypropylene and EVA (ethylene-vinyl acetate copolymer); polyvinyl alcohol; polyvinyl chloride; Polyvinylidene chloride; ABS (acrylonitrile-butadiene-styrene) resin; AS (acrylonitrile-styrene) resin; polystyrene resin; methacrylic resin; polyamide resin; polycarbonate resin; polyimide resin; polyacetal resin; polyester resin; Acrylic resin; Cellulosic resin; Polystyrene-based, Polyvinyl chloride-based, Polyurethane-based, Polyester-based, Polyamide-based, 1,2-Polybutadiene-based, Fluoro-rubber-based thermoplastic elastomer; Polyamide-based, Polyacetal-based, Polyester-based, Fluorine-based thermoplastic engineering plastics; and the like. Further, a modified or crosslinked resin may be used as long as the object of the present invention is not impaired. Of these, polystyrene-based resins are preferable from the viewpoint of compatibility.
The above-mentioned other resins may be used alone or in combination of two or more.

Examples of the polystyrene-based resin in other resins used together with the polyphenylene ether-based resin include homopolymers of styrene or styrene derivatives, copolymers containing styrene and / or styrene derivatives as main components, and the like. Here, "as a main component" means that the amount is 60% by mass or more with respect to the total amount (100% by mass) of the copolymer.
The styrene derivative is not particularly limited, but is, for example, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α-methylstyrene, β-methylstyrene, diphenylethylene, chlorostyrene, bromo. Examples include styrene.
Examples of the homopolymer of styrene or a styrene derivative include polystyrene, polyα-methylstyrene, polychlorostyrene and the like.
Examples of the copolymer containing styrene and / or a styrene derivative as a main component include a styrene-α-olefin copolymer; a styrene-butadiene copolymer; a styrene-acrylonitrile copolymer; a styrene-maleic acid copolymer; Styrene-maleic anhydride copolymer; styrene-maleimide copolymer; styrene-N-phenylmaleimide copolymer; styrene-N-alkylmaleimide copolymer; styrene-N-alkyl substituted phenylmaleimide copolymer; styrene- Acrylic acid copolymer; Styrene-methacrylic acid copolymer; Styrene-methylacrylate copolymer; Styrene-methylmethacrylate copolymer; Styrene-n-alkylacrylate copolymer; Styrene-n-alkylmethacrylate copolymer; Ethylvinylbenzene-divinylbenzene copolymer; ternary copolymer such as ABS, butadiene-acrylonitrile-α-methylbenzene copolymer; styrene graft polyethylene, styrene graft ethylene-vinyl acetate copolymer, (styrene-acrylic acid) ) Graft copolymers such as graft polyethylene and styrene graft polyamide; and the like. These may be used alone or in combination of two or more. Further, the polystyrene-based resin may be used by adding a rubber component such as butadiene, if necessary. The content of the rubber component is preferably 1.0 to 20% by mass, and may be, for example, 6% by mass with respect to 100% by mass of the polystyrene-based resin.

As the polycarbonate-based resin in other resins used together with the above-mentioned polyphenylene ether-based resin, in addition to those obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a molten ester exchange method, a carbonate prepolymer is used as a solid phase. Examples thereof include those polymerized by an ester exchange method and those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. The dihydroxy component used here may be any as long as it is used as the dihydroxy component of aromatic polycarbonate, and may be bisphenols or aliphatic diols.

Examples of bisphenols include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) -1-. Phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t- Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) Propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis ( 4-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy- 3,3'-Didimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3, 3'-Diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2-( 4-Hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane , 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3-adamantane) Diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like can be mentioned.
Examples of the aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethyleneglycol, 1,16-hexadecanediol, and 4,4'-bis (2-). Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethan, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxyethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy)- 3-Isopropyl} propane, 2,2-bis {3-t-butyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2 -Bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2-hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2 , 2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-Cycloxy-4- (2-hydroxyethoxy) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane , 9,9-bis {(2-hydroxyethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} cyclohexane, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclopentane, 4,4'-bis (2-hydroxyethoxy) diphenylether, 4,4'-bis (2-hydroxyethoxy) ) -3,3'-dimethyldiphenyl ether, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantine, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D- Examples thereof include sorbitol (isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol (isoidid) and the like. Among these, aromatic bisphenols are preferable, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene are preferred. Especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyldiphenol and 9,9-bis (4-hydroxy-3-methyl). Phenyl) fluorene is preferred. Of these, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used individually or in combination of 2 or more types. Further, the polycarbonate resin may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound.

Examples of the trifunctional or higher-functional polyfunctional aromatic compound as a branching agent used in such a branched polycarbonate resin include fluoroglucolcin, fluoroglucolside, and 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl). Hepten-2, 2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (1,1,1-tris) 4-Hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4 -{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -Trisphenols such as α and α-dimethylbenzylphenol can be mentioned. Also, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid. Acids and their acid chlorides and the like can be mentioned. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. Hydroxyphenyl) ethane is preferred. Further, regarding the polycarbonate resin, the end may be sealed with phenol or the like.

The (meth) acrylic resin is produced by polymerizing a (meth) acrylic monomer. In addition, (meth) acrylic means either acrylic or methacrylic, or both.

The (meth) acrylic monomer is not particularly limited, and (meth) acrylic acid, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, (meth) lauryl acrylate, (. Examples thereof include 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylamide. Further, the (meth) acrylic resin may contain a monomer component copolymerizable with the (meth) acrylic monomer in addition to the (meth) acrylic monomer. Examples of such a monomer include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, maleic acid amide, maleic acid imide and the like. Furthermore, by conducting a dehydration reaction, a deethanolation reaction, and an amine exchange reaction using heat and, if necessary, a salt, an alkali, or an acid, a glutaric anhydride, a (meth) acrylicimide ring, or a lactone ring can be added to the main chain. By introducing it, heat resistance may be imparted. Particularly preferred examples include a methacrylicimide-based resin, a copolymer resin of maleic anhydride and (meth) acrylic and styrene, and the like.

The foamed resin may further optionally contain other components such as additives, a trace amount of gas, and the like. Other components that may be contained in the foamed resin include stabilizers, impact modifiers, flame retardants, lubricants, pigments, dyes, weather resistance improvers, antistatic agents, impact modifiers, crystal nucleating agents, and glass. Nucleating agents such as beads, inorganic fillers, cross-linking agents, talc and other thermoplastics may be added to the extent that the object of the present invention is not impaired. The content of the other components in the foamed resin may be 30 parts by mass or less, preferably 25 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the foamed resin.

In particular, the stabilizer is not particularly limited, and for example, organic antioxidants such as hindered phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, phosphite compounds, and thioether-based compounds. Agents and heat stabilizers; light stabilizers such as hindered amines, benzophenones and imidazoles; UV absorbers; metal deactivators and the like. These may be used alone or in combination of two or more.

The trace gas that may be contained in the foamed resin is one that is contained in the process of manufacturing the foamed resin (described later). The gas is not particularly limited, and examples thereof include air, carbon dioxide gas, various gases used as a foaming agent, and aliphatic hydrocarbon-based gases. Specific examples of the aliphatic hydrocarbon gas include butane and pentane.

Further, the foamed resin may contain other thermoplastic resins. Examples of other thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, and EVA (ethylene-vinyl acetate copolymer); polyvinyl alcohol; polyvinyl chloride; polyvinylidene chloride; polycarbonate resin; polyimide resin; polyacetal. Resin-based resin; Cellulosic resin; Polyvinyl chloride-based, Polyurethane-based, Polyester-based, 1,2-polybutadiene-based, Fluoro-rubber-based thermoplastic elastomer; Polyacetal-based, Polyester-based, Fluorine-based thermoplastic engineering plastic; Can be mentioned. Further, a modified or crosslinked resin may be used as long as the object of the present invention is not impaired. These may be used alone or in combination of two or more.

-Core layer-
The core material includes a core layer and a surface layer formed on one or both sides of the core layer.

The average aspect ratio of the bubbles contained in the core layer of the core material is 0.55 or more and less than 1.00, preferably 0.55 to 0.90, and more preferably 0.55 to 0.85. The aspect ratio of the bubbles in the center of the core layer is preferably 1.00, but it is preferable that the aspect ratio is low in the portion close to the surface layer because a sudden structural difference from the surface layer is less likely to occur. Therefore, the average of the entire core layer is preferably lower than 1.0. The core layer containing bubbles having an average aspect ratio within the above range absorbs the impact energy while diffusing it toward the surface of the core foam layer when an impact is applied to the fiber complex, especially in a high temperature environment of 100 ° C. It becomes possible to do.
The average aspect ratio of the bubbles in the core layer is the average of the bubbles in the core layer (the core layer on the lower side in the thickness direction of the skin material) in contact with the surface layer in the portion where the surface layer and the skin material are laminated. It may be an aspect ratio.
In the present specification, the average aspect ratio means a value measured by the method described in Examples described later. As the average aspect ratio in the present specification, it is preferable that at least one set of 30 bubbles having an average aspect ratio satisfying a specific range is present, more preferably at least two sets are present, and the average aspect ratio is not satisfied. It is more preferred that there are no 30 bubbles.

The average major axis of the bubbles contained in the core layer is preferably 0.01 to 0.8 mm, more preferably 0.02 to 0.7 mm. When the average major axis of the bubbles is in this range, the core layer can sufficiently absorb the impact energy, which is preferable, especially in a high temperature environment of 100 ° C. Further, since the correlation peeling is less likely to occur in the core layer, the fiber reinforced plastic composite is less likely to be destroyed when a strong impact is applied to the fiber composite, which is preferable.
In the present specification, the average major axis of the bubble means a value measured by the method described in Examples described later. The average major axis in the present specification is preferably 30 bubbles having an average major axis satisfying a specific range, preferably at least one set, more preferably at least two sets, and 30 bubbles not satisfying the specific range. It is more preferable that there are no bubbles.

The apparent density of the core layer is preferably 10 to 700 kg / m ³ , more preferably 20 to 600 kg / m ³ . When the apparent density of the core layer is moderate, stress is applied to the core layer due to buckling of bubbles contained in the core layer when a strong impact is applied to the fiber composite, especially even in a high temperature environment of 100 ° C. Concentrated portions are less likely to occur, and the skin material is less likely to be easily deformed and destroyed, which is preferable. It is also preferable for the purpose of weight reduction.
In the present specification, the apparent density is measured by the method described in Examples described later, which is obtained from the volume and weight measured for the core layer or the surface layer by cutting out only the core layer or the surface layer from the core material. Value.

-Surface layer-
The surface layer is formed on one side or both sides in the thickness direction of the core layer described above. The outermost surface of the surface layer on which the skin material is laminated and integrated may be a joint with the skin material. By interposing a surface layer between the core layer and the skin material in this way and adjusting the foaming aspect ratio of the surface layer to an appropriate state, the adhesion between the surface layer and the skin material is strengthened, and a high temperature environment is achieved. It is possible to reduce the destruction of the laminated structure of the surface layer and the skin material underneath.

The surface layer is preferably from the interface between the skin material and the surface layer to a position 250 μm from the interface in the thickness direction of the core material. Further, in the thickness direction of the core material, the length may be from the interface between the skin material and the surface layer to a position having a length of 14 to 16% with respect to the total thickness of the core material.
Even in a portion where there is no skin material on the surface layer, the skin layer can be formed at a position 250 μm from the surface of the surface layer in the thickness direction of the core material, or from the surface of the surface layer to the total thickness of the core material. It may be up to a position with a length of up to 16%.

The average aspect ratio of bubbles contained in the surface layer in the portion where the surface layer and the skin material are laminated (the interface between the surface layer and the skin material and the portion up to 250 μm in the thickness direction from the interface). Is 0.05 or more and less than 0.45, preferably 0.05 to 0.40, more preferably 0.05 to 0.38, and most preferably 0.05 to 0.35. A surface layer containing bubbles having an average aspect ratio of less than 0.05 is likely to cause delamination between the surface layer and the skin material, and may become a brittle layer. Such a surface layer is not good because the surface layer and the skin material are peeled off and easily destroyed when impact energy is applied to the fiber complex, particularly in a high temperature environment of 100 ° C. Further, in the surface layer containing bubbles having an average aspect ratio of 0.45 or more, the adhesion to the skin material is insufficient, and peeling at the interface with the skin material is likely to occur in a high temperature environment of 100 ° C. When an impact is applied to the fiber composite, the skin material cannot be sufficiently supported, and it is easily deformed and cracked, which is not good.

The average major axis of the bubbles contained in the surface layer is preferably 0.01 to 1.1 mm, more preferably 0.02 to 1.0 mm. When the average major axis of the bubbles is in this range, the adhesion to the skin material is sufficient, and therefore the surface layer is destroyed when a strong impact is applied to the fiber complex, especially in a high temperature environment of 100 ° C. It is preferable because there is little risk. Further, it is preferable that the surface layer is less likely to be peeled off, the epidermis material can be sufficiently supported when an impact is applied to the fiber composite in a high temperature environment, and the epidermis material is not easily cracked.

The apparent density of the surface layer is preferably 40 to 900 kg / m ³ , more preferably 50 to 800 kg / m ³ . When the apparent density is in this range, the hardness is good, and there is little possibility that the skin material is easily deformed and broken when an impact is applied to the fiber composite. Further, it is preferable because the fiber composite is not easily cracked when impact energy is applied, and as a result, the impact resistance of the fiber composite is improved.
Further, it is preferable that the apparent density of the surface layer is smaller than the apparent density of the core layer because the impact is strong and the destruction in the surface layer is suppressed.

(Skin material)
In the skin material containing fibers and resins used in the fiber composite of the present embodiment, for example, a layer made of a fiber reinforced plastic layer forming material obtained by impregnating reinforcing fibers with a reinforcing synthetic resin is heated in a compression step described later. However, it is preferably formed by compression.

The skin material does not need to be laminated and integrated on both surfaces of the core material, as long as the skin material is laminated and integrated on at least one surface of the core material. The lamination of the skin material may be determined according to the use of the fiber composite. Above all, in consideration of the impact resistance of the fiber composite, it is preferable that the skin material is laminated and integrated on each surface layer of the upper and lower surfaces in the thickness direction of the core material. As shown in FIG. 1, such a fiber composite 1 is a core composed of a core layer 7, a surface layer 5 formed as a surface layer on both sides of the core layer 7, and a foam having a surface layer 6. It has a skin material 3 and a skin material 4 which are laminated and integrated with the material 2, the surface layer 5, and the surface layer 6, respectively.

The fibers constituting the skin material are preferably reinforcing fibers. Reinforcing fibers include glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, tyranno fibers, genbuiwa fibers, ceramic fibers and other inorganic fibers; metal fibers such as stainless steel fibers and steel fibers; aramid fibers, polyethylene fibers and polyparaphenylene. Organic fibers such as benzoxador (PBO) fibers; boron fibers and the like can be mentioned. The reinforcing fibers may be used alone or in combination of two or more. Among them, carbon fiber, glass fiber and aramid fiber are preferable, and carbon fiber is more preferable. These reinforcing fibers have excellent mechanical strength in spite of being lightweight.

The reinforcing fiber is preferably used as a reinforcing fiber base material processed into a desired shape. Examples of the reinforcing fiber base material include woven fabrics made of reinforcing fibers, knitted fabrics, non-woven fabrics, and face materials made by binding (sewn) fiber bundles (strands) in which reinforcing fibers are aligned in one direction with threads. .. Examples of the weaving method of the woven fabric include plain weave, twill weave, satin weave and the like. Examples of the thread used for binding the fiber bundle include synthetic resin threads such as polyamide resin threads and polyester resin threads, and stitch threads such as glass fiber threads.

As the fiber-reinforced base material, only one fiber-reinforced base material may be used, or a plurality of fiber-reinforced base materials may be laminated and used as a laminated fiber-reinforced base material. As the laminated fiber reinforced base material, (1) a plurality of laminated fiber reinforced base materials prepared by preparing only one kind of fiber reinforced base material and laminating these fiber reinforced base materials, and (2) a plurality of types of fiber reinforced base materials are laminated. , And (3) a plurality of face materials made by binding (stitching) fiber bundles (strands) in which reinforcing fibers are aligned in one direction with a laminated fiber-reinforced base material in which these fiber-reinforced base materials are laminated. A laminated fiber reinforced base material, etc., prepared by preparing a sheet, stacking these face materials so that the fiber directions of the fiber bundles point in different directions, and integrating (stitching) the overlapped face materials with threads. Is used. Examples of the thread used when integrating the face materials include synthetic resin threads such as polyamide resin threads and polyester resin threads, and stitch threads such as glass fiber threads.

The skin material is preferably a reinforcing fiber impregnated with a reinforcing resin. The impregnated reinforcing resin can bind and integrate the reinforcing fibers. As the reinforcing resin to be impregnated into the reinforcing fibers, either a thermoplastic resin or a thermosetting resin can be used, and a thermosetting resin is preferably used. The reinforcing resin may be used alone or in combination of two or more.
The thermosetting resin is not particularly limited, and is not particularly limited, for example, epoxy resin, unsaturated polyester resin, phenol resin, melamine resin, polyurethane resin, silicon resin, maleimide resin, vinyl ester resin, cyanate ester resin, maleimide resin and cyanide. Examples thereof include a resin prepolymerized with an acid ester resin, and an epoxy resin and a vinyl ester resin are preferable because they are excellent in heat resistance, shock absorption or chemical resistance. The thermosetting resin may contain additives such as a curing agent and a curing accelerator.
The thermoplastic resin is not particularly limited, and examples thereof include an olefin resin, a polyester resin, a thermoplastic epoxy resin, an amide resin, a thermoplastic polyurethane resin, a sulfide resin, an acrylic resin, and the like, and adhesion to a foam. Polyester-based resins and thermoplastic epoxy resins are preferable because they have excellent properties or adhesiveness between the reinforcing fibers constituting the fiber-reinforced plastic layer.

The epoxy resin as the thermoplastic resin includes a polymer or a copolymer of epoxy compounds having a linear structure, an epoxy compound, and a monomer that can be polymerized with the epoxy compound. Examples thereof include a copolymer which is a copolymer and has a linear structure. Specifically, for example, bisphenol A type epoxy resin, bisphenol fluorene type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic type epoxy resin, long chain aliphatic type epoxy resin, glycidyl ester type epoxy. Examples thereof include a resin and a glycidylamine type epoxy resin, and a bisphenol A type epoxy resin and a bisphenol fluorene type epoxy resin are preferable.

Examples of the polyurethane resin as the thermoplastic resin include a polymer having a linear structure obtained by polymerizing a diol and a diisocyanate.
Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, and 1,4-butanediol. The diol may be used alone or in combination of two or more.
Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. The diisocyanate may be used alone or in combination of two or more.

The content of the resin (preferably synthetic resin for reinforcement) in the skin material is preferably 20 to 70% by weight, more preferably 30 to 60% by weight. If the content of the resin (preferably a synthetic resin for reinforcement) is too small, the binding property between the fibers and the adhesiveness between the skin material and the core material become insufficient, and the mechanical strength of the skin material and the fiber composite become insufficient. There is a risk that the impact resistance cannot be sufficiently improved. Further, if the content of the resin is too large, the mechanical strength of the skin material may be lowered, and the impact resistance of the fiber composite may not be sufficiently improved. Further, it is preferable that the heat resistance of the resin is high in order to maintain the rigidity at high temperature, but if it is too high, a high temperature is required for bonding, the molding time becomes long, and the productivity is lowered. The heat resistance can be expressed by the glass transition temperature of the resin, and in the case of a thermosetting resin, it is expressed by the glass transition temperature after curing. The preferred glass transition temperature is 70 to 150 ° C, more preferably 75 ° C to 140 ° C. The glass transition temperature can be measured based on JIS K7121.

The thickness of the skin material is preferably 0.02 to 2 mm, more preferably 0.05 to 1 mm per layer. The skin material having a thickness within the above range is excellent in mechanical strength even though it is lightweight.

The basis weight of the skin material is preferably 50 to 4000 g / m ² , more preferably 100 to 1000 g / m ² . The skin material having a basis weight within the above range is excellent in mechanical strength even though it is lightweight.

[Production method]
(Manufacturing method of foam)
As a method for producing the foam contained in the core material of the present embodiment, a known production method can be used. Specifically, (1) a foamed molded product (foaming) is obtained by filling a mold with foamable resin particles and heating them with steam or the like to foam the resin particles and at the same time heat-sealing the resin particles to each other. (Body) manufacturing method (in-mold foam molding method), (2) Synthetic resin is supplied to the extruder, melt-kneaded in the presence of a foaming agent such as a chemical foaming agent or a physical foaming agent, and extruded and foamed from the extruder. (Extrusion foaming method), (3) Synthetic resin and chemical foaming agent are supplied to the extruder and melt-kneaded at a temperature lower than the decomposition temperature of the chemical foaming agent, and the foamable resin molded product is melted and kneaded from the extruder. , And the foamable resin molded body is foamed to produce a foam. Above all, the in-mold foam molding method has advantages such as easy to freely set the product shape and easy to obtain a foam molded product having a high foaming ratio.

Examples of the resin particles used in the in-mold foam molding method include preliminary foam particles. For example, when producing a polyamide-based resin foam, polyamide-based prefoamed particles can be used.
In addition, in this specification, the preliminary foaming particles refer to resin particles (beads, etc.) having foamability that have not been foamed at the final stage.

The pre-foamed particles can be obtained by impregnating (impregnating) a resin that is a raw material of the foamed resin with a foaming agent to cause foaming. For example, the method of containing (impregnating) the foaming agent in the polyamide resin is not particularly limited, and may be a generally used method.
As a method of impregnating the resin with a foaming agent, a method of impregnating the resin with an aqueous medium in a suspension system such as water (suspension impregnation method) and a method of using a heat-decomposable foaming agent such as sodium bicarbonate (foaming agent decomposition method). ), A method in which the gas is brought into a liquid phase state with an atmosphere above the critical pressure and brought into contact with the resin (liquid phase impregnation method), and a method in which the gas is brought into a gas phase state with an atmosphere below the critical pressure and brought into contact with the resin (gas phase). Impregnation method) and the like. As a method for containing a foaming agent, a vapor phase impregnation method is particularly preferable.

Examples of the foaming agent decomposition method include a method using a thermally decomposable foaming agent such as azodicarbonamide, dinitrosopentamethylenetetramine, hydrazoyldicarbonamide, and sodium bicarbonate. The thermal decomposition type foaming agent may be used alone or in combination of two or more.

In the gas phase impregnation method, the solubility of the gas in the resin is higher and the content of the foaming agent is likely to be higher than in the case of the suspension impregnation method carried out under high temperature conditions. Therefore, in the gas phase impregnation method, it is easy to achieve a high foaming ratio, and the bubble size in the preliminary foamed particles tends to be uniform.

Further, the foaming agent decomposition method is also carried out under high temperature conditions like the suspension impregnation method. Further, in this method, not all of the added pyrolysis foaming agent becomes gas, so that the amount of gas generated tends to be relatively small. Therefore, the gas phase impregnation method has an advantage that the content of the foaming agent can be easily increased. Further, in the gas phase impregnation method, the equipment such as the pressure resistant device and the cooling device tends to be more compact than in the case of the liquid phase impregnation method, and the equipment cost can be easily reduced.

The shape of the resin used in the vapor phase impregnation method is not particularly limited, and examples thereof include beads, pellets, spheres, amorphous pulverized products, and the like, and the size thereof is pre-foaming after foaming. The average diameter is preferably 0.2 to 3 mm from the viewpoint of making the size of the particles appropriate, improving the ease of handling the prefoamed particles, and making the filling at the time of molding more dense.

The conditions of the gas phase impregnation method are not particularly limited, and for example, the atmospheric pressure may be 0.5 to 6.0 MPa from the viewpoint of more efficiently dissolving the gas in the resin. The atmospheric temperature is preferably 5 to 30 ° C.

Here, the foaming agent used in producing the preliminary foamed particles is not particularly limited, and examples thereof include compounds that can be used as air or gas.
Examples of compounds that can be gas are inorganic compounds such as carbon dioxide, nitrogen, oxygen, hydrogen, argon, helium, neon; trichlorofluoromethane (R11), dichlorodifluoromethane (R12), chlorodifluoromethane (R22), tetra. Fluorocarbons such as chlorodifluoroethane (R112), dichlorofluoroethane (R141b), chlorodifluoroethane (R142b), difluoroethane (R152a), HFC-245fa, HFC-236ea, HFC-245ca, HFC-225ca; HFO-1234y, HFO-1234ze Hydrofluoroolefins such as (E); saturated hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane, neopentane; dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, Ethers such as diisopropyl ether, furan, furfural, 2-methylfuran, tetrahydrofuran, tetrahydropyran; chlorinated hydrocarbons such as methyl chloride and ethyl chloride; alcohols such as methanol and ethanol; and the like.
These compounds that can be used as air or gas may be used alone or in combination of two or more.

The foaming agent is preferably one that has little impact on the environment and is not flammable or non-flammable, and from the viewpoint of safety during handling, an inorganic compound that is flammable or non-flammable is more preferable. Carbon dioxide gas (carbon dioxide gas) is particularly preferable from the viewpoint of solubility and ease of handling.

The method for causing foaming in the resin containing (impregnated) the foaming agent (foaming agent impregnated resin) is not particularly limited, but for example, a foaming agent-impregnated resin such as a foaming agent-impregnated polyamide resin is applied from a high pressure atmosphere to a low pressure. A method of expanding the gas as a foaming agent dissolved in the foaming agent-impregnated resin by bringing it into the atmosphere at once to generate foaming, or a method of heating using pressure steam or the like to cause a foaming agent-impregnated resin. A method of expanding the gas inside to cause foaming can be used, and in particular, the advantage of making the size (cell size) of the bubbles inside the molded product, which is the product, uniform, and controlling the foaming ratio. Therefore, it is preferable to use the latter method of heating and foaming because the advantage of facilitating the production of a molded product having a low foaming ratio can be obtained.

Here, when the pre-foamed particles are foamed to a desired foaming ratio, one-step foaming may be performed, or multi-step foaming including secondary foaming and tertiary foaming may be performed. When multi-step foaming is performed, it is easy to prepare pre-foamed particles having a high foaming ratio, and the pre-foamed particles used for molding are up to tertiary foaming from the viewpoint of reducing the amount of resin used per unit volume. It is preferable that the pre-foamed particles have been used.

In particular, in the case of multi-step foaming, it is preferable to pressurize the pre-foamed particles with gas before foaming at each step. The gas used for the pressure treatment is not particularly limited as long as it is inert to the resin, but an inorganic gas or a hydrofluoroolefin having high gas safety and a small global warming potential of the gas is preferable. Examples of the inorganic gas include air, carbon dioxide gas, nitrogen gas, oxygen gas, ammonia gas, hydrogen gas, argon gas, helium gas, neon gas and the like, and examples of the hydrofluoroolefin include HFO-1234y and the like. Examples thereof include HFO-1234ze (E), and air and carbon dioxide gas are particularly preferable from the viewpoint of ease of handling and economy. The method of the pressurizing treatment is not particularly limited, and examples thereof include a method of filling a pressurized tank with preliminary foam particles and supplying gas into the tank.

The foamed resin (particularly a foam) preferably contains the pre-foamed particles, and can be obtained, for example, by molding the pre-foamed particles.

The method for molding the pre-foamed particles is not particularly limited, but for example, the pre-foamed particles are filled in the cavity of the molding die and heated to cause foaming and at the same time heat-melt the pre-foamed particles. After being applied, the product can be solidified and molded by cooling. Here, the method for filling the pre-foamed particles is not particularly limited, but for example, a cracking method for filling the pre-foamed particles with the mold slightly open, or a preparatory pressure-compressed method with the mold closed. Examples thereof include a compression method in which foamed particles are filled, a compression cracking method in which the cracking method is performed after filling a mold with prefoamed particles pressure-compressed.

From the viewpoint of applying a constant gas pressure to the bubbles of the pre-foamed particles to make the size (cell size) of the bubbles inside the particles uniform, before filling the pre-foamed particles into the cavity of the molding mold, It is preferable to pressurize the prefoamed particles with gas. The gas used for the pressure treatment is not particularly limited, and examples thereof include inorganic gas from the viewpoint of flame retardancy, heat resistance, and dimensional stability. The method of the inorganic gas and the pressure treatment is the same as in the case of the pressure treatment with the gas applied to the pre-foamed particles in the case of multi-step foaming.

The heat medium used for molding the prefoamed particles may be a general-purpose heat medium, and is preferably saturated steam or superheated steam from the viewpoint of suppressing oxidative deterioration of the foamed resin, and is uniform with respect to the foamed resin. Saturated steam is more preferred from the viewpoint of enabling heating.

The method for producing the foamed resin is, for example, a filling step of filling the cavity of the mold with the prefoamed particles, and supplying water vapor below the heat fusion temperature of the prefoamed particles into the cavity for 5 to 30 seconds. By a preheating step of preheating the prefoamed particles and by supplying water vapor above the heat fusion temperature of the prefoamed particles into the cavity for 20 to 120 seconds to foam and heat-fuse the prefoamed particles. , A method having a fusion step for obtaining a foamed resin is preferable.
Further, the foamed resin is preferably obtained by heating the prefoamed particles in two steps in the preheating step and the fusion step.
According to this method, in the first step, the pre-foamed particles are pre-heated with steam below the heat fusion temperature of the pre-foamed particles, so that the temperature distribution in the entire aggregate of the pre-foamed particles becomes more uniform. be able to. Then, by the preliminary heating in the first stage, when the preliminary foamed particles are heated with steam having a heat fusion temperature or higher in the second stage, the foaming in the preliminary foamed particles becomes more uniform, and the preliminary foamed particles become more uniform. Is easy to mold into foam.
Further, according to this method, in the obtained foamed resin, the crystallinity size of the resin becomes larger, the crystallinity becomes higher, and a core material having excellent heat resistance can be obtained.

As described above, the temperature at which the pre-foamed particles are heated is preferably close to the heat fusion temperature (Tf) of the pre-foamed particles.
In the present specification, the heat fusion temperature refers to the temperature at which the prefoamed particles are heated in saturated steam and the prefoamed particles are fused to each other. The method for measuring the heat fusion temperature is as described below. In this specification, the heat fusion temperature refers to a value measured by the method described in Examples described later.

The heating temperature in the first stage is preferably lower than Tf (° C.), preferably Tf-20 (° C.) or higher, more preferably Tf-15 (° C.) or higher, and more preferably. It is preferably Tf-2 (° C.) or lower, and more preferably Tf-5 (° C.) or lower.
The heating time of the first step is preferably 2 seconds or more, more preferably 3 seconds or more, more preferably 20 seconds or less, and further preferably 15 seconds or less.

The heating temperature in the second stage is higher than Tf (° C.), preferably Tf + 15 (° C.) or less, more preferably Tf + 10 (° C.) or less, and Tf + 5 (° C.) or less. Especially preferable.
The heating time of the second stage is preferably 10 seconds or more, more preferably 15 seconds or more, preferably 60 seconds or less, and further preferably 45 seconds or less.

If the heating temperature and heating time of the first step and the second step are within the above ranges, the pre-foamed particles can be sufficiently heat-sealed, and the foam in which the crystallization of the resin is further promoted can be obtained. Obtainable.

The density of the foam is preferably 20 kg / m ³ or more from the viewpoint of improving the appearance of the foam resin or the fiber composite by making the strength of the foam resin appropriate and making it difficult for the foam film to break. , 50 kg / m ³ or more, more preferably 800 kg / m ³ or less, and further preferably less than 500 kg / m ³ from the viewpoint of increasing the lightness of the fiber composite.

The closed cell ratio S of the foam is from the viewpoint of improving the strength of the foamed resin and making it difficult for water to be taken into the foam that may occur in the open cell portion, thereby making it difficult to reduce the density of the foam. It is preferably 80% or more, and more preferably 85% or more.
The closed cell ratio S (%) is calculated by the formula represented by the following formula (3).
S (%) = {(Vx-W / ρ) / (Va-W / ρ)} x 100 ... (3)
In the formula, Vx is the true volume of the foam (cm ³ ), Va is the apparent volume of the foam (cm ³ ), W is the weight of the foam (g), and ρ is. , The density of the base resin of the foam (g / cm ³ ).
The closed cell ratio can be measured by cutting the skin material from the fiber complex.

From the viewpoint of suppressing deterioration of physical properties and heat shrinkage in a high temperature environment, the foam has a dimensional change rate of 1.5% or less, more preferably 1.0% or less at 150 ° C. preferable.
The dimensional change rate is a value measured in accordance with the dimensional stability evaluation method B of JIS K6767.

The expansion ratio of the foam is preferably 1.3 to 60 times, more preferably 1.5 to 30 times, and even more preferably 5 to 20 times. The foam having a foaming ratio within the above range has an appropriate heat transfer property, thereby forming a surface foam layer containing bubbles having a desired aspect ratio on the surface portion of the foam in the compression step. Will be easy. In the present invention, the foaming ratio of the foam is a value measured in accordance with JIS K7222.

The fusion rate of the foam is from the viewpoint of increasing the rigidity when stress such as bending strain is applied to the complex and from the viewpoint of suppressing the loss of the preliminary foam particles from the molded body when the foam is cut. , 60% or more, more preferably 70% or more, and most preferably 80% or more.
The method for measuring the fusion rate is as described in the examples.

(Manufacturing method of fiber complex)
As a method for producing the fiber composite of the present embodiment, a known thermoforming method can be used, and examples thereof include a vacuum forming method, a pressure forming method, a compression molding method, and the like. As thermoforming methods applying the vacuum forming method and the pneumatic forming method, for example, a straight forming method, a drape forming method, a plug assist forming method, a plug assist / reverse draw forming method, an air slip forming method, a snapback forming method, and a reverse drawing method. Examples thereof include a molding method, a plug-assisted air slip molding method, a match molding method, and a thermoforming method combining these molding methods.

An example of a procedure for producing a fiber composite by using a thermoforming method will be specifically described. As a method for producing a fiber composite of the present embodiment, a fiber reinforced plastic layer is formed containing reinforcing fibers in which at least a part of at least one surface of a core material (for example, a foam) is impregnated with a reinforcing synthetic resin. The laminate in which the materials are laminated is contained in the core material at a temperature 20 ° C. lower than the glass transition temperature of the reinforcing synthetic resin and 60 ° C. higher than the glass transition temperature of the reinforcing synthetic resin. While heating at a temperature 40 ° C lower than the heat fusion temperature of the foamed resin and 20 ° C higher than the heat fusion temperature of the foamed resin contained in the core material, it is compressed by pressing 0.2 to 1 MPa at the same time. Examples thereof include a method including a compression step for forming.
In the compression step, it is preferable to compress the foam so that the compression deformation rate is 30 to 65%. The heating temperature of the laminated body means the surface temperature of the fiber reinforced plastic layer forming material of the laminated body. When this heating temperature is 20 ° C. lower than the glass transition temperature of the reinforcing synthetic resin and 60 ° C. higher than the glass transition temperature, sufficient curing can be obtained within the curing time, so that the adhesion is improved. However, it is preferable that the rigidity is maintained in a high temperature environment of 100 ° C. Further, the heating temperature is also related to the heat fusion temperature of the foamed resin contained in the core material, and is preferably a temperature 40 ° C. lower than the heat fusion temperature or more and 20 ° C. higher than the heat fusion temperature, which is the condition. It is preferable that the average aspect ratio of the bubbles of the core material and the shape of the bubbles are appropriately maintained, the adhesion of the interface of the laminated body is very high, and the rigidity is maintained in a high temperature environment of 100 ° C. If compression is performed at a temperature higher than 20 ° C. higher than the heat fusion temperature of the foamed resin contained in the core material, the core material melts and air bubbles in the core material burst and disappear, which is not preferable. More preferably, the temperature is 30 ° C. lower than the heat fusion temperature of the foamed resin contained in the core material, and 10 ° C. or higher than the heat fusion temperature of the foamed resin contained in the core material.
The pressing force is preferably 0.2 to 1 MPa, more preferably 0.2 to 0.7 MPa. When the pressing is in this range, the surface appearance of the fiber complex is good, and the average aspect ratio of the bubbles in each layer in the core material is also in the appropriate range. The compression deformation rate indicates the change in thickness in the pressing direction. When a foam having a pressing direction of 5 mm is deformed to 3 mm, this compression deformation rate is 40%. The compression deformation rate is preferably 30 to 65%, and it is possible to make the average aspect ratio of bubbles appropriate while maintaining the weight reduction. The compression deformation rate is preferably 40% or more, more preferably larger than 45%, and preferably 60% or less. In the actual situation of the present invention, it is preferable to carry out the preheating step of the laminated body under the condition that no pressure is applied before the compression step. By carrying out such a preheating step, it is possible to appropriately soften the surface portion of the surface on which the fiber-reinforced plastic layer forming material of the core material is laminated.

Since the core material (preferably foam) contains air bubbles and therefore has low heat transfer properties, it is difficult to heat the central portion of the core material. Therefore, in the compression step, the resin contained in the surface portion of the core material can be appropriately softened by heating the laminate at a predetermined temperature. Further, in the compression step, by heating the laminate at a predetermined temperature, the reinforcing synthetic resin impregnated in the reinforcing fibers can be appropriately softened. Then, by compressing the laminated body while performing such heating, the surface of the core material can be entirely pressed while the skin material is deformed along the surface of the core material. This makes it possible to slightly crush and flatten the bubbles contained in the surface portion of the core material to form a surface layer containing bubbles having a desired average aspect ratio on the surface portion of the core material.

When the reinforcing synthetic resin to be impregnated with the reinforcing fibers contains an uncured thermosetting resin, it is preferable to adjust the heating of the laminate in the compression step to form the fiber-reinforced plastic layer forming material. After keeping the uncured thermosetting resin in a state where the fluidity is maintained without curing and deforming the fiber-reinforced plastic layer forming material along the foam surface, the heating time of the laminate is adjusted. By advancing the curing reaction of the uncured thermosetting resin, the thermosetting resin can be cured and the reinforcing fibers can be bound and integrated, whereby the reinforcing fibers can be bonded and integrated on the core material. Can form a skin material impregnated with. When a thermoplastic resin is used as the reinforcing synthetic resin to be impregnated with the reinforcing fibers, the thermoplastic resin is also cooled and solidified by cooling the laminated body after heating the laminated body in the compression step, whereby the thermoplastic resin is used. Reinforcing fibers can be bound and integrated to form a skin material containing a fiber and a resin obtained by impregnating the reinforcing fiber with a thermoplastic resin on the core material.

In the method of the present invention, it is preferable to use a laminate in which a fiber-reinforced plastic layer forming material containing a reinforcing fiber impregnated with a synthetic resin is laminated on at least one surface of the above-mentioned core material. The surface on which the fiber-reinforced plastic layer forming material is laminated in the core material may be determined according to the use of the obtained fiber composite, and is not particularly limited. Therefore, the fiber reinforced plastic layer forming material may be laminated only on one surface of the core material. Above all, considering the impact resistance of the obtained fiber composite, it is preferable to laminate fiber reinforced plastic layer forming materials on both sides of the core material.

Since the core material of the fiber composite according to the present invention is compressed, it is necessary to adjust the thickness. The thickness can be adjusted by adjusting the degree of pressure applied to the laminate. For example, as a method of adjusting the compression deformation rate of the core material, a method of sandwiching the laminated body by a pressing member in the thickness direction thereof and adjusting the pressing force applied to the laminated body by these pressing members is used. At this time, it is preferable to arrange spacers on the outside of the laminated body, for example, on the outer sides of both ends in the width direction or the length direction of the laminated body. By adjusting the height of the spacer, it is possible to easily adjust the degree of pressure applied to the laminate and the compression deformation rate of the foam.

When a spacer is used, the spacer may be arranged outside the laminated body, for example, at least outside both ends in the width direction or the length direction of the laminated body, and both ends in the width direction of the laminated body. Spacers may be placed on both the outside of the portion and the outside of both ends in the length direction.

As described above, by heating and compressing the laminate in the compression step, a fiber composite is obtained, which is laminated and integrated with the core material on at least one surface of the core material and has a skin material containing fibers and resins. Be done.

By cutting the core material contained in the fiber complex at the central portion in the thickness direction after performing the compression step as described above, the skin material is laminated and integrated only on one surface of the core material. Fiber complexes can also be obtained.

The thickness of the fiber composite of the embodiment of the present invention is not particularly limited, but is preferably 0.5 mm to 1000 mm. The thickness is determined by the thickness of the skin material and the foam that is the core material, but if the desired thickness cannot be obtained when the skin material and the core material are pressure-integrated, the thickness of the core material can be adjusted. It is possible to obtain a desired thickness.

In the fiber composite of the present embodiment, since the core material containing the foamed resin has the above-mentioned core layer and surface layer, the impact resistance is improved while maintaining the rigidity of the skin material in a high temperature environment. Has been done. Therefore, such a fiber complex is not particularly limited, but is suitably used as a housing for components such as aircraft, automobiles, ships, and buildings, and electronic devices.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The method for measuring the physical properties of the foamed resin and the core material (core layer, surface layer) as the core material is shown below.

(A) Density The weight W (kg) of the obtained core material was measured, and then the apparent volume Va (m ³ ) of the core material was measured by a submersion method. Then, the value W / Va (kg / m ³ ) obtained by dividing the weight W by the apparent volume Va was used as the density of the core material.

(B) Closed cell ratio With respect to the core material for which the apparent volume Va was measured in the above-mentioned (A), the true volume (Vx) was measured using an air comparative hydrometer (manufactured by Beckman Co., Ltd.). Then, the closed cell ratio S (%) was calculated according to the formula (3).
S (%) = {(Vx-W / ρ) / (Va-W / ρ)} x 100 ... (3)
In the formula, Vx is the true volume of the core material (cm ³ ), Va is the apparent volume of the core material (cm ³ ), W is the weight of the core material (g), and ρ is. , The density of the base resin of the core material (g / cm ³ ).

(C) Fusing rate A cut line with a depth of 5 mm is made on the surface of a plate-shaped core material with a length of 300 mm, a width of 300 mm, and a thickness of 20 mm so as to divide it into two vertically using a cutter knife. The core material was divided along the line. Regarding the pre-foamed particles appearing on the divided surface, the number (a) in which the pre-foamed particles are broken in the particles (the pre-foamed particles are broken by the divided surface) and along the interface between the pre-foamed particles. The number (b) of those broken (the interface between the preliminary foamed particles is a dividing surface) was measured, and the fusion rate (%) was calculated according to the following formula (4).
Fusion rate (%) = {a / (a + b)} × 100 ... (4)

(D) Thermal fusion temperature The pre-foamed particles of the obtained foamed resin were placed in a state where the pressure inside the bubbles was atmospheric pressure and did not contain a foaming agent such as a hydrocarbon. 10 g of the pre-foamed particles were placed in a metal mesh container so that the pre-foamed particles were in contact with each other, and then heated with saturated steam at a predetermined temperature for 30 seconds. Then, the lowest temperature (° C.) among the temperatures at which the pre-foamed particles were fused by 80% or more as a whole after heating was defined as the thermal fusion temperature (° C.) of the pre-foamed particles.

The evaluation methods (1) to (6) of the fiber complex obtained in Examples and Comparative Examples described later will be described below.

(1) The average aspect ratio of the air bubbles in the core material and (2) the average major axis fiber composite of the air bubbles in the core material were cut in the thickness direction, and the cut surface was photographed at a magnification of 200 using a scanning electron microscope. In addition, a schematic diagram (FIG. 1) of the cut surface of the example will be described. In the photographed image of the obtained cut surface, the skin material is in the thickness direction of the fiber composite composed of the skin material 3, the skin material 4, and the core material 2 (the direction orthogonal to the interface between the core material 2 and the skin material). The portion from the interface between 3 and the core material 2 to the position 250 μm from the interface was designated as the surface layer 5 and the surface layer 6. Further, in the core material 2, the remaining portion excluding the surface layer 5 and the outermost surface 6 was used as the core layer 7.
Next, for the 30 bubbles contained in the core layer 7, the surface layer 4, and the surface layer 5, any two points having the maximum mutual distance on the outer contour line of the bubble cross section were selected, and these 2 points were selected. "Bubble major axis" which is the distance between points, any two points where the straight line orthogonal to the major axis of the bubble and the outer contour line of the bubble cross section intersect, and any two points where the mutual distance is the maximum. It was selected and the "minor axis of the bubble", which is the distance between these two points, was measured.
Then, the arithmetic mean value of the aspect ratio of each bubble obtained by dividing the minor axis of the bubble by the major axis of the bubble was taken as the average aspect ratio of each layer.
Moreover, the arithmetic mean value of the major axis of each bubble was taken as the average major axis of each layer.
When bubbles having an exposed cross section were present on the surface of the core material 2 on the cut surface, such bubbles were excluded from the measurement target of the aspect ratio. For example, when the unfoamed epidermis is cut and removed from the core material, there is a possibility that bubbles having an exposed cross section exist on the surface of the core material. In addition, bubbles existing over the interface between the core layer 7 and the surface layer 5 or the surface layer 6 were also excluded from the aspect ratio measurement targets.
The upper side indicates the upper surface when the horizontal sample is installed in the vertical press machine when integrated with the skin material, and the lower side indicates the lower surface.
The results are shown in Table 1.

(3) Apparent density of core material The core layer and surface layer of the core material of the fiber composite obtained in Examples and Comparative Examples are cut out in a cubic shape, the weight W (kg) is measured, and then a sheet is used with a caliper. Three sides of the shaped fiber composite were measured, and the volume V (m ³ ) thereof was calculated. Then, the ratio of the weight W to the volume V (W / V) (kg / m ³ ) was taken as the apparent density.
The results are shown in Table 1.

(4) Bending strength The bending strength (MPa) of the fiber composites obtained in Examples and Comparative Examples was determined according to JIS K7221. Specifically, 10 test pieces were cut out from the obtained sample in a size of 100 mm in length × 15 mm in width × thickness (obtained sample thickness). As a standard condition, five test pieces that were left to stand in a room controlled at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to adjust the condition were provided for measurement with AUTOGRAPH AG-5000D (manufactured by Shimadzu Corporation) and specified in JIS. The bending strength (in an atmosphere of 23 ° C.) (MPa) was calculated from the formula to be calculated, and the average was calculated. In addition, as a standard state, a test piece which was allowed to stand in a room controlled at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours and then allowed to stand at 100 ° C. for 1 hour in a constant temperature bath was subjected to a state-adjusted test piece at 100 ° C. Five of them were used for the measurement with AUTOGRAPH AG-5000D (manufactured by Shimadzu Corporation) in a constant temperature bath, and the bending strength (under 100 ° C. atmosphere) (MPa) was calculated from the formula specified in JIS, and the average was calculated.
The results are shown in Table 1.

(5) Appearance (5-1) Surface smoothness The fiber composites obtained in Examples and Comparative Examples were brought to a temperature of 23 ° C. and a relative humidity of 50% as standard conditions in the same manner as in (4) Measurement of bending strength. The fiber composite was allowed to stand in a controlled room for 24 hours, and then allowed to stand at 100 ° C. for 1 hour in a constant temperature bath to visually observe the surface of the fiber composite, and the state of adhesion between the skin material and the core material was observed. Was evaluated as follows.
The results are shown in Table 1.
◎ (Excellent): All five test pieces have good surface smoothness and adhesiveness between the skin material and the core material.
◯ (Good): There is no problem in surface smoothness in practical use, but some floating (uki) was observed between the skin material and the core material in any of the five test pieces.
X (inferior): Surface waviness (large unevenness) occurs in any of the five test pieces, and the surface smoothness is not good. Alternatively, in any of the five test pieces, a float is observed between the skin material and the core material, which is a practical problem.

(5-2) Surface cosmeticity The surfaces of the fiber complexes obtained in Examples and Comparative Examples were visually observed, and the state of the surface layer was evaluated as follows.
The results are shown in Table 1.
○ (Good): The resin of the skin material is sufficiently cured, and there is no resin shortage or unevenness on the surface of the fiber complex.
X (inferior): The resin of the skin material penetrates into the core material side, and the fiber is exposed or has an uneven shape on the surface of the fiber composite due to the lack of resin. Shrinkage of the foamed resin occurs, and an uneven shape is formed on the surface.

(6) Thickness The thickness (mm) of the fiber complex obtained in Examples and Comparative Examples was measured using a caliper. In addition, the total thickness (mm) of the skin material laminated on the upper surface layer and the skin material laminated on the lower surface layer was measured using a caliper.
The results are shown in Table 1.

(Example 1)
A cross prepreg having a fiber texture of 200 g / m ² and a carbon fiber content of 60% by mass, which is composed of carbon fibers having a tensile modulus of 250 GPa and an epoxy resin having a glass transition temperature of 90 ° C. after curing. The product name "TR3110" (manufactured by Mitsubishi Rayon Co., Ltd.) was produced, and one front and back surface were prepared as the skin material.
Next, a polyamide-based resin foam as a core material was prepared by the following method.
Nylon 6 as a polyamide resin (trade name: UBE Nylon 1022B, manufactured by Ube Kosan Co., Ltd.) 100 parts by mass, talc as a nuclear agent 0.8 parts by mass, hindered phenolic antioxidant (Irganox1098, manufactured by BASF) 0.3 parts by mass was melt-kneaded under heating conditions with a uniaxial extruder, then extruded into strands, cooled with water in a cold water tank, and cut to prepare a pellet-shaped base resin.
To this, carbon dioxide gas as a foaming agent was contained in the base resin according to the method described in Examples of Japanese Patent Application Laid-Open No. 2011-105879. Then, by heating the base resin containing carbon dioxide gas, foaming was generated, and prefoamed particles having a density of 300 kg / m ³ were obtained.
The obtained prefoamed particles were encapsulated in an autoclave, compressed air was introduced over 1 hour until the pressure in the autoclave reached 0.5 MPa, and then the pressure was maintained at 0.5 MPa for 24 hours. The prefoamed particles were pressure treated.
The cavity dimensions of the mold for in-mold molding in which the pressure-treated prefoamed particles are attached to the in-mold foam molding machine are: length: 300 mm, width: 300 mm, height: 3 mm. After the mold is molded, prefoamed particles are filled, and then saturated steam at 135 ° C. is supplied into the cavity for 10 seconds (first stage heating), and further, saturated steam at 144 ° C. is 30 in the cavity. Pre-foamed particles having a density of 200 kg / m ³ were formed by supplying them for a second (heating in the second step) to foam the pre-foamed particles and then heat-sealing them.
The obtained molded product was cooled by supplying cooling water into the cavity of the mold, and then the mold was opened to take out a polyamide-based resin foam as a core material.
Using the obtained foam as a core material, skin materials are laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body is held at 140 ° C. for 3 minutes without applying pressure, and then the surface pressure is applied. By holding for 20 minutes while pressurizing at 0.5 MPa, the skin material and the core material were simultaneously molded to obtain a fiber composite. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 1 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.
Details of Example 1 are shown in Table 1.

(Example 2)
After obtaining the pre-foamed particles having a density of 200 kg / m ³ in the same manner as in Example 1, the obtained pre-foamed particles are enclosed in an autoclave, and compressed air is charged until the pressure in the autoclave reaches 0.5 MPa. It was introduced over a long period of time, and then a pressure treatment was carried out in which the pressure was maintained at 0.5 MPa for 24 hours, and then by heating at 230 ° C., further foaming was generated, and the density: 120 kg / m. Production and evaluation were carried out in the same manner as in Example 1 except for the point of ³ . Details of Example 2 are shown in Table 1.

(Example 3)
In the same manner as in Example 2, after obtaining the pre-foamed particles having a density of 120 kg / m ³ , the obtained pre-foamed particles are enclosed in an autoclave, and compressed air is introduced until the pressure in the autoclave becomes 0.5 MPa. It was introduced over 1 hour, and then a pressure treatment was carried out in which the pressure was maintained at 0.5 MPa for 24 hours, and then by heating at 230 ° C., further foaming was generated, and the density was 40 kg / kg /. Production and evaluation were carried out in the same manner as in Example ¹ except for the point of m3.
Details of Example 3 are shown in Table 1.

(Example 4)
In Example 1, based on the method described in Examples of JP-A-2011-105879, the base resin of the obtained mini-pellets was placed in a pressure cooker at 10 ° C., and carbon dioxide gas was pressurized at 3 MPa as a foaming agent. After absorption for 3 hours, foamed particles were obtained. The obtained foamed particles were heated by the same in-mold foam molding machine as in Example 1 without re-foaming treatment to obtain a core material having a density of 500 kg / m ³ . Using this core material, production and evaluation were carried out in the same manner as in Example 1.
Details of Example 4 are shown in Table 1.

(Example 5)
The production and evaluation were carried out in the same manner as in Example 1 except that the polyamide-based resin foam as the core material was prepared by the following method.
Nylon 666 (nylon 66/6) as a polyamide resin (trade name: Novamid 2430A, manufactured by DSM Co., Ltd.) 100 parts by mass, 0.8 parts by mass of talc as a nucleating agent, hindered phenol antioxidant (Irganox 1098, 0.3 parts by mass (manufactured by BASF) was melt-kneaded under heating conditions with an extruder, then extruded into strands, cooled with water in a cold water tank, and cut to prepare a pellet-shaped base resin.
To this, carbon dioxide gas as a foaming agent was contained in the base resin according to the method described in Examples of Japanese Patent Application Laid-Open No. 2011-105879. Then, by heating the base resin containing carbon dioxide gas, foaming was generated, and prefoamed particles having a density of 200 kg / m ³ were obtained.
The obtained prefoamed particles were encapsulated in an autoclave, compressed air was introduced over 1 hour until the pressure in the autoclave reached 0.4 MPa, and then the pressure was maintained at 0.4 MPa for 24 hours. The prefoamed particles were pressure treated.
The pressure-treated prefoamed particles were filled in the cavity of the in-mold molding die (cavity dimensions: length: 300 mm, width: 300 mm, height: 3 mm), and then molded. Then, this mold was attached to the in-mold foam molding machine.
Then, saturated steam at 130 ° C. was supplied into the cavity for 40 seconds to foam the pre-foamed particles and heat-fuse them to form the pre-foamed particles.
The obtained molded product was cooled by supplying cooling water into the cavity of the mold, and then the mold was opened to take out a polyamide-based resin foam as a core material.
The obtained foam was used as a core material, and the skin materials used in Example 1 were laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body was laminated at 130 ° C. for 5 minutes without applying pressure. After holding, the skin material and the core material were simultaneously molded to obtain a fiber composite by holding for 20 minutes while pressurizing at 130 ° C. and a surface pressure of 0.5 MPa. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 5 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.
Details of Example 5 are shown in Table 1.

(Example 6)
100 parts by weight of polyethylene terephthalate (PET, trade name "SA-135" manufactured by Mitsui Kagaku Co., Ltd.), a master batch made of polyethylene terephthalate containing talc (polyethylene terephthalate content: 60% by weight, talc content: 40% by weight) A polyethylene terephthalate composition containing 1.8 parts by weight and 0.2 parts by weight of pyromellitic anhydride was melt-kneaded in a single-screw extruder under heating conditions of 290 ° C., and subsequently, normal butane was added from the middle of the extruder. Was press-fitted into a molten polyethylene terephthalate composition so as to be 0.8 parts by weight with respect to 100 parts by weight of polyethylene terephthalate, and uniformly dispersed in the polyethylene terephthalate.
After that, at the front end of the extruder, the molten polyethylene terephthalate composition is cooled to 280 ° C., melt-kneaded under heating conditions in a single-screw extruder, extruded into strands, and cooled in a cold water tank. , Cutting was performed to obtain foamed particles having a pellet-shaped density of 400 kg / m ³ .
The obtained prefoamed particles were encapsulated in an autoclave, compressed air was introduced over 1 hour until the pressure in the autoclave reached 0.5 MPa, and then the pressure was maintained at 0.5 MPa for 24 hours. The prefoamed particles were pressure treated.
The pressure-treated prefoamed particles were filled in the cavity of the in-mold molding die (cavity dimensions: length: 300 mm, width: 300 mm, height: 3 mm), and then molded. Then, this mold was attached to the in-mold foam molding machine.
After that, saturated steam at 135 ° C. is supplied into the cavity for 10 seconds (first stage heating), and then saturated water vapor at 150 ° C. is supplied into the cavity for 30 seconds (heating in the second stage) to prepare the prefoamed particles. Pre-foamed particles were formed by foaming and heat-sealing.
The obtained molded product was cooled by supplying cooling water into the cavity of the mold, and then the mold was opened to take out the PET-based resin foam as the core material.
Using the obtained foam as a core material, skin materials are laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body is held at 140 ° C. for 3 minutes without applying pressure, and then the surface pressure is applied. By holding for 20 minutes while pressurizing at 0.4 MPa, the skin material and the core material were simultaneously molded to obtain a fiber composite. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 6 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.

(Example 7)
70 parts by weight of methyl methacrylate (MMA), 10 parts by weight of styrene (ST), 20 parts by weight of maleic anhydride (MAH), 10 parts by weight of nbutanol as a foaming agent, 0.8 parts by weight of talc, and lauroyl as an initiator. After stirring 0.3 weight of peroxide at room temperature for 10 minutes, place a 15 mm silicone rubber O-packing near the end of the glass plate on a flat surface of a glass plate with a thickness of 500 mm in each of the vertical and horizontal directions, and inside the O-packing. Fill with the previous monomer solution, place another same glass plate on it, sandwich the O packing and the monomer solution with glass, and use multiple clips that can adjust the thickness around the glass. The clips were evenly tightened so that the size was 12 mm. It was immersed in a hot water bath at 60 ° C. for 24 hours. After that, it was taken out and cured in an oven at 130 ° C. for 1 hour, then cooled to room temperature, the clip and the glass plate were removed, and the O packing was cut and deleted to obtain a special acrylic resin plate. This special acrylic resin was pulverized with a pulverizer and classified to obtain 2 mm pulverized particles. The crushed fine particles were placed in an explosion-proof oven at 150 ° C. for 60 minutes, and when n ^- butanol in the crushed fine particles volatilized, the softened crushed fine particles were foamed and taken out. Got
The obtained prefoamed particles were encapsulated in an autoclave, compressed air was introduced over 1 hour until the pressure in the autoclave reached 0.5 MPa, and then the pressure was maintained at 0.5 MPa for 24 hours. The prefoamed particles were pressure treated.
The pressure-treated prefoamed particles were filled in the cavity of the in-mold molding die (cavity dimensions: length: 300 mm, width: 300 mm, height: 3 mm), and then molded. Then, this mold was attached to the in-mold foam molding machine.
After that, saturated steam at 135 ° C. is supplied into the cavity for 10 seconds (first stage heating), and then saturated water vapor at 150 ° C. is supplied into the cavity for 30 seconds (heating in the second stage) to prepare the prefoamed particles. Pre-foamed particles were formed by foaming and heat-sealing.
The obtained molded product was cooled by supplying cooling water into the cavity of the mold, and then the mold was opened to take out an acrylic resin foam as a core material.
The obtained foam was used as a core material, and the skin materials used in Example 1 were laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body was laminated at 120 ° C. for 3 minutes without applying pressure. After holding, the skin material and the core material were simultaneously molded by holding for 20 minutes while pressurizing at a surface pressure of 0.4 MPa to obtain a fiber composite. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 7 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.

(Example 8)
Polyphenylene ether resin (PPE) (manufactured by Asahi Kasei Co., Ltd., S201A) is 60% by mass, non-halogen flame retardant (bisphenol A-bis (diphenyl phosphate) (BBP)) is 18% by mass, and rubber concentration is 6% by mass. Impact-resistant polystyrene resin (HIPS) is used in an amount of 10% by mass (the content of the rubber component in the base resin is 0.6% by mass), and general-purpose polystyrene resin (PS) (manufactured by PS Japan Co., Ltd., GP685) is used in an amount of 12% by mass. These were extruded after heating, melting and kneading with an extruder to prepare a base resin pellet as a core material. According to the method described in Example 1 of JP-A-4-372630, the base resin pellets are housed in a pressure-resistant container, the gas in the container is replaced with dry air, and then carbon dioxide (gas) is used as a foaming agent. The injection was carried out, and the base resin pellets were impregnated with 7% by mass of carbon dioxide over 3 hours under the conditions of a pressure of 3.2 MPa and a temperature of 11 ° C.
Then, the base resin pellets were foamed with pressurized steam while rotating the stirring blades at 77 rpm in the preliminary foaming machine to obtain foamed beads.
The foamed beads were pressurized to 0.5 MPa over 1 hour, then held at 0.5 MPa for 8 hours, and subjected to pressure treatment.
This is filled in an in-mold molding die having steam holes, heated with pressurized steam to expand and fuse the foamed beads with each other, cooled, taken out from the molding die, and foamed bead molded body (foaming). Body) got.
The obtained foam was used as a core material, and the skin materials used in Example 1 were laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body was laminated at 130 ° C. for 3 minutes without applying pressure. After holding, the skin material and the core material were simultaneously molded by holding for 15 minutes while pressurizing at a surface pressure of 0.4 MPa to obtain a fiber composite. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 8 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.

(Example 9)
As a synthetic resin foamed sheet, a rectangular parallelepiped polycarbonate resin (PC) foam having a heat fusion temperature, foamed resin density, closed cell ratio, and fusion ratio, which is shown in Table 1, is a flat surface having a side of 30 cm and a thickness of 3 mm. A fiber composite was obtained in the same manner as in Example 1 except that a sheet was used.
As a method for producing a synthetic resin foam sheet, a polycarbonate resin powder synthesized as follows was used as a raw material. After dissolving 710 parts of 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as "bisphenol A") (bisphenol A solution), 2299 parts of methylene chloride and 112 of 48.5% sodium hydroxide aqueous solution In addition, 354 parts of phosgene was blown at 15 to 25 ° C. over about 90 minutes to carry out a phosgenation reaction. After the completion of phosgenation, 148 parts of methylene chloride solution of p-tet-butylphenol and 88 parts of 48.5% sodium hydroxide aqueous solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes and then stirred. After 5 minutes of emulsification, it was treated with a homomixer (Special Machinery Chemical Industry Co., Ltd.) at a rotation speed of 1200 rpm and a number of passes of 35 times to obtain a highly emulsified dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under no stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, it is poured into a kneader filled with warm water. Methylene chloride was evaporated with stirring to obtain a polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation type dryer to obtain a polycarbonate resin powder.
High molecular weight acrylic resin (manufactured by Mitsubishi Rayon, trade name "Metabrene P-530A", weight average molecular weight 3 million) with respect to 100 parts by weight of the polycarbonate resin powder (glass transition temperature 154 ° C.) thus obtained 1 It contained 0.1 parts by weight and 0.1 parts by weight of the bubble conditioner (polytetrafluoroethylene powder). The temperature of the 50 mmφ T-die twin-screw extruder with L / D of 40 was set to 280 ° C., the raw material was charged from the hopper, liquefied normal butane was pressurized and injected at a pressure of 1 MPa in the middle of the barrel, and the polycarbonate resin was injected at the T-die outlet. Along with foaming, normal butane was vaporized. A foamed sheet was prepared by sandwiching the foamed resin that came out from the top and bottom with stainless seam belts from the outlet. The obtained foam sheet was used as a core material, and the skin materials used in Example 1 were laminated one by one on both the upper and lower surfaces of the core material, and then this laminated body was laminated at 100 ° C. for 3 minutes without applying pressure. After holding, the skin material and the core material were simultaneously molded by holding for 15 minutes while pressurizing at a surface pressure of 0.5 MPa to obtain a fiber composite. The fiber complex had a good flexural modulus and a good appearance in both the standard state and the high temperature environment of 100 ° C.
The fiber composite obtained in Example 9 is a fiber complex in which a skin material is laminated on the entire surface layer of the core material.

(Comparative Example 1)
The foam obtained in Example 1 was used as a core material, and two skin materials used in Example 1 were laminated on both the upper and lower surfaces of the core material, and then the laminate was held at 90 ° C. for 3 minutes. After that, the skin material and the core material were simultaneously molded by holding for 15 minutes while pressurizing at a surface pressure of 0.4 MPa to obtain a fiber composite.

(Comparative Example 2)
The foam obtained in Example 1 was used as a core material, and two skin materials used in Example 1 were laminated on both the upper and lower surfaces of the core material, and then this laminated body was laminated without applying pressure to 165. After holding at ° C. for 3 minutes, the skin material and the core material were simultaneously molded by holding for 20 minutes while pressurizing at a surface pressure of 0.4 MPa to obtain a fiber composite.

(Comparative Example 3)
The foam obtained in Example 1 was used as a core material, and two skin materials used in Example 1 were laminated on both the upper and lower surfaces of the core material, and then this laminated body was laminated without applying pressure to 110. After holding at ° C. for 3 minutes, the mixture was held for 1 minute while being pressurized at a surface pressure of 1.6 MPa. After that, the pressure was released and the mixture was cured in an oven at 80 ° C. for 20 minutes to obtain a fiber composite of a skin material and a core material.
Compared with Examples, Comparative Example 1 had no problem in strength at room temperature because the aspect ratio of bubbles in the surface layer was high, but the bending strength at 100 ° C. was insufficient, resulting in poor results. Further, in Comparative Example 2, the aspect ratio of the bubbles in the surface layer and the core layer is too low, the foaming material does not function as the core material, and the strength is high, but the thickness and surface condition of the molded product are poor. Therefore, the appearance is not good. In Comparative Example 3, since the aspect ratio of the surface layer is too low, the interface between the surface layer and the core layer is weak, and the bending strength at 100 ° C. is insufficient, which is not good. Also, the appearance is not good.

The fiber complex of the present embodiment is excellent in excellent rigidity and aesthetic appearance in a high temperature environment such as 100 ° C., and excellent surface cosmeticity during high temperature molding. The fiber complex of the present invention can be suitably used especially in the field of automobiles.

1 Fiber complex 2 Core material 3 Outer skin material 4 Outer skin material 5 Surface layer 6 Surface layer 7 Core layer

Claims (4)

A core material containing a foamed resin having a core layer and a surface layer formed on one or both sides of the core layer, and a fiber in which a fiber and a skin material containing a resin are laminated on at least a part of the surface layer. It is a complex and
The surface layer is from the interface between the skin material and the surface layer to a position 250 μm from the interface in the thickness direction.
In the portion where the surface layer and the skin material are laminated, the average aspect ratio of the bubbles in the surface layer is 0.05 or more and less than 0.45, and the average aspect ratio of the bubbles in the core layer is 0.55. More than 1.00 and less than 1.00
The apparent density of the surface layer is 480 to 800 kg / m ³ .
The apparent density of the core layer is 10 to 690 kg / m ³ .
The foamed resin is a polyamide-based resin, and the polyamide-based resin is a mixture of polyamide-based resins containing an aliphatic polyamide in an amount of more than 50% by mass .
A fiber complex characterized by that. The fiber composite according to claim 1, wherein the content of the resin in the epidermis is 30 to 60% by weight. The fiber composite according to claim 1 or 2, wherein the thermosetting resin is contained in the epidermis and the glass transition temperature of the thermosetting resin is 75 ° C to 140 ° C. The fiber composite according to any one of claims 1 to 3, wherein the epidermis contains an epoxy resin.

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