JP2017177704A - Resin composite, automobile, windmill for wind power generation, robot, and medical instrument - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have a resin composite body exert excellent strength while suppressing excessive mass increase.SOLUTION: A resin composite includes: a fiber-reinforced resin material A1 provided with a sheet-like fiber substrate, and a resin impregnated in the fiber substrate; and a core material A2 composed of a resin foam, so as to coat the surface of the core material with the fiber-reinforced resin material, where a substrate gap part having a wider distance between the surface of the core material and the fiber substrate than that of circumferences is formed, the core material has a corner part, the substrate gap part is formed at least at a part of a region along the corner part, and a resin pool storing a resin of the fiber-reinforced resin material is formed between the surface of the core material and the fiber substrate in the substrate gap part.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a resin composite, an automobile, a wind turbine for wind power generation, a robot, and a medical device.

Conventionally, an impregnated polyester resin or the like is impregnated into a sheet-like fiber base material such as a woven fabric obtained by plain weaving continuous fibers for reinforcement, a face material in which continuous fibers are aligned in one direction, or a mat with random short fibers. The fiber reinforced resin material is widely used under the name of FRP (Fiber Reinforced Plastics).
Since the FRP has high mechanical strength, demands are increasing in various fields such as the automobile field, the ship field, the aircraft field, the medical field, the power generation field, the industrial field, and the home appliance field.
In these fields, there is a strong demand for the structural members to be lightweight and have high strength.

  For this reason, in recent years, the use of a resin composite in which a fiber reinforced resin material is laminated and integrated on the surface of a core material made of a resin foam such as a foam sheet or a bead foam molded body has been studied (the following patents). Reference 1).

JP 2008-080749 A

In the resin composite, a fiber reinforced resin layer with excellent strength is formed on the surface layer portion with a fiber reinforced resin material and an excellent lightness is exhibited by the core material. It is considered useful as an automobile exterior member such as a cover and a trunk lid.
The resin composite is also considered to be suitable as a constituent member for wind turbines for wind power generation, robots, medical equipment, and the like.

In addition to such applications, resin composites are required to have further improved strength.
However, simply increasing the thickness of the fiber-reinforced resin layer for the purpose of improving the strength may cause a problem that the light weight of the resin composite is impaired.
This invention is made | formed in view of such a condition, Comprising: It makes it the subject to exhibit the intensity | strength excellent in the resin composite, suppressing the mass increase excessively.

  The present inventor has intensively studied to solve the above problems, finds that reinforcing the corner portion of the core material is important for exerting excellent strength in the resin composite, and completes the present invention. Has been reached.

That is, in order to solve the above problems, the present invention has a sheet-like fiber base material and a fiber reinforced resin material provided with a resin impregnated in the fiber base material, and a core material made of a resin foam, A resin composite in which a surface of a core material is coated with the fiber reinforced resin material, and a base material separation portion is formed in which a distance from the core material surface to the fiber base material is wider than the surroundings, and the core material is a corner. And the base material separation part is formed in at least a part of the region along the corner part, and the base material separation part has a fiber reinforced resin between the surface of the core material and the fiber base material. Provided is a resin composite in which a resin reservoir in which a resin of a material is stored is formed.
In addition, the present invention provides an automobile, a wind turbine for wind power generation, a robot, and a medical device in which the resin composite as described above is adopted as a constituent member.

  Since the resin composite of the present invention has the above-described configuration, it has excellent mechanical strength. According to the present invention, an automobile, a wind turbine for wind power generation, a robot, and a medical device can be excellent in strength and light in weight.

The schematic perspective view of the resin composite of one Embodiment. II-II arrow directional cross-sectional view of FIG. The schematic perspective view of the resin complex of other embodiment. FIG. 4 is a schematic front view of the resin composite of FIG. 3. FIG. 5 is a cross-sectional view taken along line VV in FIG. 4. FIG. 6 is a cross-sectional view taken along line VI-VI in FIG. 4. The schematic sectional drawing of the resin composite_body | complex which concerns on other embodiment. 2 is a corner cross-sectional photograph of the resin composite of Example 1. FIG.

Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic perspective view showing an example of a resin composite. A resin composite A according to this embodiment includes a rectangular plate-shaped substrate portion 11 and a flat quadrangular frustum shape at the center portion of the substrate portion 11. And a raised portion 12 that is raised.
As shown in FIGS. 1 and 2, the resin composite A of the present embodiment includes a fiber reinforced resin material A1 and a core material A2 made of a resin foam, and the fiber reinforced laminated on the core material A2. A fiber reinforced resin layer A10 is provided by the resin material A1.
The fiber-reinforced resin material A1 of the present embodiment is a sheet body including a sheet-like fiber base material and a resin impregnated in the fiber base material, although not shown.

In the resin composite A of the present embodiment, the core material A2 is formed of a flat plate-like resin foam A20.
The resin foam A20 constituting the core material A2 has a square frustum shape that is slightly smaller than the raised portion 12 to be precise.
As shown in FIG. 2, the resin composite A of the present embodiment has a sandwich structure in which the resin foam A20 is sandwiched from above and below by two fiber reinforced resin materials A11 and A12 that are slightly larger than the resin foam A20. The two fiber reinforced resin materials A11 and A12 overlap each other on the outside of the resin foam and are directly bonded to each other.
The two fiber reinforced resin materials A11 and A12 have almost all the regions other than the directly bonded regions adhered to the surface of the resin foam.
That is, the resin composite A of the present embodiment has an outer peripheral portion that is thinner than the central portion, and there is no difference in height between the outer peripheral portion and the central portion on the lower surface side. Only in the case, the step is formed with a middle height compared to the surrounding area.

As described above, the resin composite A of the present embodiment has the quadrangular pyramid-shaped core material A <b> 2 that is slightly smaller than the raised portion 12.
That is, the core A2 extends outwardly from a rectangular top surface in a plan view, a rectangular bottom surface that is slightly larger than the top surface, and four sides that define the outer edge of the top surface to four sides that define the outer edge of the bottom surface. And a trapezoidal side surface that is four inclined surfaces.
In the resin composite A of the present embodiment, the core material A2 has a first corner portion A2a between the bottom surface and the side surface, and has a second corner portion A2b between the top surface and the side surface, and is adjacent to each other. A third corner portion A2c is provided between the side surfaces.
These corners A2a, A2b, A2c are rounded and have a radius of curvature (R) of 0.5 mm or more.
Further, in the corner portions A2a, A2b, A2c, the distance from the surface of the core material to the fiber base material (not shown) is larger than the portion adjacent to the corner portions A2a, A2b, A2c.
That is, in the resin composite A of the present embodiment, a base material separation portion in which the distance from the core surface to the fiber base material is wider than the surroundings is formed, and the base material separation portion is formed in a region along the corner portion. Has been.
In the base material separation portion, a resin reservoir A3 in which the resin of the fiber reinforced resin material A1 is stored is formed between the surface of the core material A2 and the fiber base material.

The resin reservoir A3 is provided along the corners A2a, A2b, A2c of the core material A2, and connects the outer edge of the top surface, the outer edge of the bottom surface, and the corners of the bottom surface and the top surface of the core material A2. A frame structure is formed along the ridgeline.
That is, the resin reservoir A3 forms a frame structure having a quadrangular pyramid shape as a whole, and makes the resin composite A exhibit high strength.

The core material A2 is advantageous in forming a large resin reservoir A3 when the corner portion has a larger radius of curvature (R), and the core material itself is also missing when the corner portion has a larger radius of curvature (R). It becomes difficult to occur.
In this respect, in this embodiment, the curvature radius (R) of the corner portion is set to 0.5 mm or more as described above.
The radius of curvature (R) of the corner portion is preferably 0.5 mm or more and 30 mm or less, and more preferably 0.5 mm or more and 10 mm or less.

In the sense of reinforcing the corner portion, it is preferable that the resin of the fiber reinforced resin material A1 penetrates into the core material at the corner portion.
In the core material, the resin is preferably permeated in the base material separation portion, and the resin is preferably continuous with the resin reservoir A3.

Here, as the resin foam constituting the core material, one produced as follows can be adopted.
(1) Filling the mold with resin foam particles, heating and foaming the resin foam particles with a heat medium such as hot water or water vapor, and fusing and integrating the foam particles with the foam pressure of the resin foam particles A method for producing a foam having a desired shape (in-mold foam molding method).
(2) The resin is supplied to the extruder together with the air conditioner and melt-kneaded in the presence of a foaming agent such as a chemical foaming agent or a physical foaming agent, and the melt-kneaded product is extruded and foamed from the extruder to obtain a foam. Manufacturing method (extrusion foaming method).
(3) A method for producing a foam by producing a massive foamable resin molded body containing a chemical foaming agent and foaming the foamable resin molded body in a mold.

In addition, the following methods can be employ | adopted as a manufacturing method of the resin foam particle used by the said in-mold foam molding method of said (1).
(1a) A resin is supplied into an extruder, melted and kneaded in the presence of a physical foaming agent, and melted and kneaded material is cut from a nozzle mold attached to the extruder while being extruded and foamed, and then cooled to obtain resin foam particles. How to manufacture.
(1b) A resin is supplied into an extruder, melted and kneaded in the presence of a physical foaming agent, and extruded and foamed from a nozzle mold attached to the extruder to produce a strand-like extrudate. A method of producing resin foam particles by cutting at intervals.
(1c) Supplying resin into an extruder, melt-kneading in the presence of a physical foaming agent, extrusion-foaming from a circular die or T-die attached to the extruder to produce a foamed sheet, and cutting the foamed sheet A method for producing resin foam particles.

  When the core material is a foam molded body (bead foam molded body) obtained by in-mold foam molding of resin foam particles, the resin preferably penetrates into at least one of the foam particles and between the foam particles. It is preferable that it penetrates both inside the foamed particles and between the foamed particles.

Further, the other manufacturing method of the core material is not particularly limited. For example, the core material is extruded from a die attached to the tip of the extruder after being supplied to the extruder and melt-kneaded in the presence of a foaming agent. There is a method of producing an extruded foam sheet by foaming.
In addition, as said die | dye, what is utilized in extrusion foaming can be used, For example, T die, a circular die, etc. are mentioned.

In the said manufacturing method, when T-die is used as die | dye, a foamed sheet can be manufactured by carrying out extrusion foaming to a sheet form from an extruder.
On the other hand, when a circular die is used as a die, a cylindrical body is produced by extrusion foaming from a circular die into a cylindrical shape, and the cylindrical body is gradually expanded in diameter and then supplied to a cooling mandrel for cooling. After that, the foamed sheet can be manufactured by cutting the cylindrical body continuously between the inner and outer peripheral surfaces in the direction of extrusion, and cutting and opening the cylindrical body.
At that time, in order to cool the entire front and back surfaces of the foam sheet substantially uniformly, a cooling means having an air ring can be used.
As the structure of the air ring, known materials can be used, but those capable of uniformly discharging the air volume described later are preferable.
If it does so, expansion | swelling of a bubble will be suppressed and a non-foaming layer can be obtained on the surface.
Thus, a thick thermoplastic resin foam sheet in which physical properties such as surface density, surface hardness, and surface smoothness are constant in the width direction can be continuously produced.
The blown gas and the air volume may be appropriately adjusted according to the type of thermoplastic resin, the temperature during extrusion, and the like.

Examples of the chemical foaming agent include azodicarbonamide, dinitrosopentamethylenetetramine, hydrazoyl dicarbonamide, sodium bicarbonate, and the like.
In addition, a chemical foaming agent may be used independently or 2 or more types may be used together.

Examples of the physical blowing agent include saturated aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane and hexane, ethers such as dimethyl ether, methyl chloride, halogenated hydrocarbons, carbon dioxide and nitrogen. Can be mentioned.
The physical foaming agent is preferably dimethyl ether, propane, normal butane, isobutane or carbon dioxide, more preferably propane, normal butane or isobutane, and particularly preferably any of normal butane or isobutane. .
In addition, a physical foaming agent may be used independently or 2 or more types may be used together.

Examples of the air conditioner include talc, mica, silica, diatomaceous earth, aluminum oxide, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, magnesium carbonate, Examples include inorganic compound particles such as potassium sulfate, barium sulfate and glass beads, and organic compound particles such as polytetrafluoroethylene.
Furthermore, azodicarbonamide, sodium hydrogen carbonate, a mixture of sodium hydrogen carbonate and citric acid, which also functions as a thermal decomposition type foaming agent, and the like can also be used as the bubble regulator.

  The foamed molded article has one or more selected from the group consisting of an acrylic resin, a polyester resin, and a polystyrene resin in that it is excellent in strength and relatively easy to foam in a good foamed state. Those containing a resin are preferred.

When an acrylic resin foam is employed as the core material, the acrylic resin forming the acrylic resin foam may be a polymer composed of one or more acrylic monomers, or one or more acrylic monomers. And a copolymer of at least one aromatic vinyl monomer.
In order to exhibit excellent strength in the acrylic resin foam, the acrylic resin is preferably a copolymer of an acrylic monomer and an aromatic vinyl monomer.
Examples of the acrylic monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and (meth) acrylic acid 2- Ethylhexyl, cyclohexyl (meth) acrylate, (meth) acrylamide, benzyl (meth) acrylate, maleic anhydride, maleic acid, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, maleic amide, maleic imide, etc. Can be mentioned.
Examples of the aromatic vinyl monomer include styrene and methylstyrene.

Among them, the acrylic resin contains methyl methacrylate, (meth) acrylic acid, and styrene as monomer units, and optionally contains one or both of maleic anhydride and methacrylamide as the monomer units, and The monomer units are preferably contained in the following proportions.
(A) Methyl methacrylate: 35 to 70% by mass
(B) (Meth) acrylic acid: 14 to 45% by mass
(C) Styrene: 10 to 20% by mass
(D) Maleic anhydride: 0 to 10% by mass
(E) Methacrylamide: 0 to 10% by mass

The acrylic resin foam can be obtained, for example, by foaming, with a foaming agent, a polymer obtained by polymerizing a polymerizable solution containing the monomer in the above proportion with a polymerization initiator.
In this specification, the term “(meth) acryl” is used to mean both “acryl” and “methacryl”.
Therefore, the above “(meth) acrylic acid: 14 to 45% by mass” means “when both the acrylic acid and methacrylic acid are included and the total content thereof is 14 to 45% by mass”, “methacrylic acid”. 3 cases, including the case where the acrylic acid content is 14 to 45% by mass and the case where the acrylic acid content is not included and the content of methacrylic acid is 14 to 45% by mass. It is.

  When a polyester resin foam is employed as the core material, the polyester resin forming the polyester resin foam may be an aromatic polyester resin or an aliphatic polyester resin.

  The aromatic polyester resin is a polyester containing an aromatic dicarboxylic acid component and a diol component, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. As the aromatic polyester resin constituting the core material, polyethylene terephthalate is preferable. In addition, an aromatic polyester resin may be used independently or 2 or more types may be used together.

  In addition to the aromatic dicarboxylic acid component and the diol component, the aromatic polyester resin includes, for example, a tricarboxylic acid such as trimellitic acid such as trimellitic acid, a tetracarboxylic acid such as pyromellitic acid, or a polyvalent carboxylic acid such as tricarboxylic acid or its anhydride. Products, triols such as glycerin, and trihydric or higher polyhydric alcohols such as tetraols such as pentaerythritol may be contained as constituent components.

  As the aromatic polyester resin, a recycled material recovered and recycled from a used plastic bottle or the like can be used.

  Polyethylene terephthalate may be crosslinked by a crosslinking agent. Known crosslinking agents are used, and examples thereof include acid dianhydrides such as pyromellitic anhydride, polyfunctional epoxy compounds, oxazoline compounds, and oxazine compounds. In addition, a crosslinking agent may be used independently or 2 or more types may be used together.

  When polyethylene terephthalate is crosslinked with a crosslinking agent, the crosslinking agent may be supplied to the extruder together with the polyethylene terephthalate. If the amount of the cross-linking agent supplied to the extruder is too small, the melt viscosity at the time of melting of the polyethylene terephthalate may become too small, and bubbles may be broken, and if it is too much, the melt viscosity at the time of melting of the polyethylene terephthalate. When the foam is produced by extrusion foaming, extrusion foaming may be difficult. Therefore, the amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of polyethylene terephthalate. It is more preferable to set it as 1-1 mass parts.

Examples of the aliphatic polyester resin include a polylactic acid resin.
As the polylactic acid-based resin, a resin in which lactic acid is polymerized by an ester bond can be used. From the viewpoint of commercial availability and imparting foamability to the polylactic acid-based resin expanded particles, D-lactic acid (D-form) 1 or 2 selected from the group consisting of a copolymer of L-lactic acid (L-form), a homopolymer of either D-lactic acid or L-lactic acid, D-lactide, L-lactide and DL-lactide The above lactide ring-opening polymer is preferred. In addition, polylactic acid-type resin may be used independently, or 2 or more types may be used together.

  Polylactic acid-based resins include, as monomer components other than lactic acid, for example, aliphatic hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and hydroxyheptanoic acid; succinic acid, adipic acid, and suberic acid Aliphatic polycarboxylic acids such as sebacic acid, dodecanedicarboxylic acid, succinic anhydride, adipic anhydride, trimesic acid, propanetricarboxylic acid, pyromellitic acid, pyromellitic anhydride; ethylene glycol, 1,4-butanediol, It may contain an aliphatic polyhydric alcohol such as 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

  The polylactic acid resin may contain other functional groups such as an alkyl group, a vinyl group, a carbonyl group, an aromatic group, an ester group, an ether group, an aldehyde group, an amino group, a nitrile group, and a nitro group. The polylactic acid-based resin may be crosslinked by an isocyanate-based crosslinking agent or the like, or may be bonded by a bond other than an ester bond.

When a polystyrene resin foam is employed as the core material, the polystyrene resin forming the polystyrene resin foam is not particularly limited. For example, styrene, methyl styrene, ethyl styrene, i-propyl styrene, dimethyl styrene A homopolymer or copolymer containing a styrene monomer such as chlorostyrene or bromostyrene as a monomer unit, a styrene monomer, and one or more vinyl monomers copolymerizable with the styrene monomer as a monomer unit And the like.
As the polystyrene resin, a copolymer containing, as a monomer unit, a styrene monomer and one or more vinyl monomers copolymerizable with the styrene monomer is preferable, methacrylic acid and / or methyl methacrylate, A copolymer containing a styrene monomer as a monomer unit is more preferable.
In addition, polystyrene type resin may be used individually by 1 type for formation of a core material, or 2 or more types may be used together.

When the core material is composed of a resin foam other than the above, examples of the resin constituting the resin foam include a polycarbonate resin, a polyphenylene ether resin, a polymethacrylimide resin, a polyolefin resin, and a polyamide resin. It is done.
In addition, the foam does not need to be comprised with single type of resin, and may be comprised with the mixed resin containing 2 or more types of resin.

The core material generally has a thickness of preferably 1 to 30 mm, more preferably 1 to 20 mm, and particularly preferably 1 to 10 mm.
The core material of this embodiment has a corner part.
The shape of the corner portion preferably has a certain degree of roundness in order to suppress stress concentration, and preferably has a roundness of “R = 0.5 mm” or more even at a location where the radius of curvature is the smallest.
In addition, one of the surfaces of the core material that are adjacent to each other via the corner portion and the other surface have an angle formed by these surfaces of less than 90 ° when they are extended toward the corner portion. Is preferred. By doing in this way, when an external force is added, it can suppress that a corner part becomes a fracture start part.

The apparent density of the resin foam which constitutes the core is preferably 0.05~1.2g / cm ^3, more preferably 0.08~0.9g / cm ^3.
The density of the resin foam refers to a value measured according to JIS K7222: 1999 “Foamed plastics and rubbers—Measurement of apparent density”. The apparent density of the core material in the resin composite is measured on the core material after the fiber reinforced resin layer is peeled from the resin composite.

When the core material is formed of a foamed sheet, the apparent density of the foamed sheet is preferably set to the above value.
If the apparent density of the foamed sheet is too low, the resin composite may not exhibit sufficiently good mechanical strength due to thinning due to molding pressure during thermoforming or excessive flattening of bubbles. . If the apparent density of the foamed sheet is too high, the thermoformability is lowered, and there is a possibility that a resin composite having a desired shape cannot be easily obtained.

A fiber reinforced resin material for forming a fiber reinforced resin layer on such a core material contains a resin and a fiber base material. In this embodiment, the sheet-like fiber base material is impregnated with the resin. Is used.
Examples of reinforcing fibers constituting the fiber substrate include glass fibers, carbon fibers, silicon carbide fibers, alumina fibers, tyrano fibers, basalt fibers, ceramic fibers, and other inorganic fibers; stainless fibers, steel fibers, and other metal fibers; Examples thereof include organic fibers such as fibers, polyethylene fibers, and polyparaphenylene benzoxador (PBO) fibers; boron fibers and the like.
Reinforcing fibers may be used alone or in combination of two or more.
Among these, carbon fiber, glass fiber, and aramid fiber are preferable, and carbon fiber is more preferable.
These reinforcing fibers have excellent mechanical properties despite being lightweight.
It is preferable that 90 mass% or more of the fiber reinforced resin material is carbon fiber.

Examples of the fiber base material include woven fabrics and knitted fabrics in which reinforcing fibers are used in the form of continuous fibers, and UD (Unidirectional Fabric) that is aligned in one direction.
Examples of the weaving method include plain weave, twill weave and satin weave.
Examples of the fiber base material include a nonwoven fabric using reinforcing fibers in a short fiber state.

The fiber base material may be used without laminating only one fiber base material, or may be used by laminating a plurality of fiber base materials.
Examples of the fiber substrate in which a plurality of sheets are laminated (hereinafter also referred to as “laminated fiber substrate”) include the following embodiments.
(1) A laminated fiber base material prepared by laminating only one kind of fiber base material and laminating them.
(2) A laminated fiber base material prepared by laminating a plurality of types of fiber base materials.
(3) A plurality of fiber base materials such as UD are prepared, these fiber base materials are overlapped so that the directions of the fibers are different from each other, and the overlapped fiber base materials are integrated by stitching. Laminated fiber substrate.

As the resin to be impregnated into the fiber base material, either a thermoplastic resin or a thermosetting resin can be used.
The thermosetting resin 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 include a resin obtained by prepolymerization with an acid ester resin, and an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin are preferable because they are excellent in heat resistance, shock absorption, or chemical resistance.
That is, in order to more remarkably exert the effect of reinforcing the corner portion by the resin reservoir, the resin impregnated into the fiber base is one or more selected from the group consisting of epoxy resins, unsaturated polyester resins, and vinyl ester resins. It is preferable that the thermosetting resin is included.
It is preferable that 90% by mass or more of the resin contained in the fiber reinforcing material is the thermosetting resin.
The fiber reinforcement may contain a curing agent or a curing accelerator for curing the thermosetting resin, or may contain other additives.
In addition, a thermosetting resin may be used independently or 2 or more types may be used together.

The epoxy resin is a polymer or copolymer of epoxy compounds and having a linear structure, or a copolymer of an epoxy compound and a monomer that can be polymerized with this epoxy compound. Examples include a copolymer having a chain structure.
Specifically, as the epoxy resin, 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 resin, glycidyl amine type epoxy resin and the like, and bisphenol A type epoxy resin and bisphenol fluorene type epoxy resin are preferable.
In addition, an epoxy resin may be used independently or 2 or more types may be used together.

Examples of the thermoplastic resin include, but are not limited to, olefin resins, polyester resins, polyamide resins, thermoplastic polyurethane resins, sulfide resins, acrylic resins, and the like. Polyester resins are preferred because they are excellent in adhesion between reinforcing fibers constituting the resin layer.
In addition, a thermoplastic resin may be used independently or 2 or more types may be used together.

Examples of the thermoplastic polyurethane resin include a polymer having a linear structure obtained by polymerizing diol and diisocyanate. Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and the like.
Diols may be used alone or in combination of two or more.
Examples of the diisocyanate include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Diisocyanate may be used independently or 2 or more types may be used together.
In addition, a thermoplastic polyurethane resin may be used independently or 2 or more types may be used together.

The resin content in the fiber reinforced resin layer is preferably 20 to 70 mass%, more preferably 30 to 60 mass%.
If the resin content is too low, the binding properties between the reinforcing fibers and the adhesion between the fiber reinforced resin layer and the core material will be insufficient, and the mechanical properties of the fiber reinforced resin layer and the surface hardness or bending of the resin composite will be insufficient. There is a possibility that the elastic modulus cannot be sufficiently improved.
Moreover, when there is too much content of resin, there exists a possibility that the mechanical physical property of a fiber reinforced resin layer may fall and the surface hardness or bending elastic modulus of a resin composite body cannot fully be improved.

The thickness of the fiber reinforced resin layer is preferably 0.02 to 2 mm, and more preferably 0.05 to 1 mm.
The fiber reinforced resin layer having a thickness within the above range is excellent in mechanical properties despite being lightweight.

Basis weight of the fiber-reinforced resin layer is preferably ^{50~4000g / m 2, 100~1000g / m} 2 is more preferable.
The fiber reinforced resin layer having a basis weight of the fiber reinforced resin layer within the above range is excellent in mechanical properties despite being lightweight.

In the present embodiment, the resin reservoir is formed by the resin leached from the fiber reinforced resin material as described above toward the corner portion of the core material.
As a result, it is possible to suppress a sudden change in strength at the boundary between the fiber reinforced resin layer and the corner portion, so that the location is unlikely to become a starting point of breakage due to deformation, and as a result, the resin composite can have high strength. .

As described above, in the resin composite of this embodiment, it is preferable that the resin penetrates the core material.
In the first corner portion A2a in which the thickness of the core material sandwiched between the two fiber reinforced resin layers is tapered, the area ratio in the entire region where the resin permeates is 0.5 to 30%. Preferably, it is 1 to 25%, more preferably 5 to 25%.
Further, the permeating resin preferably has a reach distance from the surface of the core material of 0.05 to 3 mm, and more preferably 0.1 to 2 mm.

The method for observing the region where the resin exists can be, for example, the method shown below.
The resin composite is cut along a plane orthogonal to the direction in which the corner portion extends, and the cut surface is magnified 100 to 200 times using an electron microscope to obtain an enlarged photograph.
In addition, as an electron microscope, the electron microscope marketed with the brand name "digital microscope VHX-1000" from Keyence Corporation can be used, for example.
Next, with respect to the range of 10 mm radius from the apex of the corner portion in the direction in which the thickness of the core material tapers, the cross-sectional area of the core material and the area of the region where the resin infiltrates in the cross-sectional area are determined. Measure using image processing software.
In addition, as image processing software used for calculating the area, a product name “AutoCAD LT 2015” from AutoDesk can be used.
The determination of each region (presence / absence of resin) can be made based on the following measurement (microscopic FT-IR analysis) inside and outside the region identified by the microscope.
For epoxy ^resins, 3100 cm -1, can confirm the presence by absorption peak near 3600 cm ^-1 is observed.

apparatus:
Perkin Elmer Fourier transform infrared spectrophotometer Spectrum One
High-speed IR imaging system Spectrum Spotlight 300
Measurement mode: spot / ATR method Resolution: 4 cm ⁻¹
Number of scans: 32 times Background number: 32 times aperture: 100 × 100 μm
Detector: Duet (trade name) Detector (MCT detector)
Furthermore, X-CT or the like can be used in combination with the above method, and the region between the resin and the resin foam can be clarified by a staining method in combination with the above method.
A high strength improvement effect can be obtained while suppressing an increase in the mass of the resin composite due to the penetration of the resin in such a form.

The resin composite is produced by preparing a preform with a fiber reinforced resin material temporarily attached to the surface of the resin foam, and pressurizing the preform under a heating condition in which the resin of the fiber reinforced resin material is sufficiently softened. The fiber reinforced resin material and the resin foam can be manufactured by bonding and integration.
In this case, a resin composite having a shape different from that of the preform can be produced by pressurization under heating conditions.
Moreover, pressurization and heating of the preform can be carried out using a mold.
And when producing a resin complex, the resin pool can be formed in a corner part by making the pressure added in the part used as a corner part slightly lower than the site | part adjacent to a corner part.
Moreover, resin can be penetrate | infiltrated into a core material by setting the pressure at this time more than fixed.
In addition, you may make it provide the base material spacing part whose space | interval from a core material surface to a fiber base material is wider than the circumference | surroundings only in a part of area | region along a corner part.
Moreover, you may form a base material separation part other than a corner part.
When using a plate-like core material as in the present embodiment, for example, when the core material is laid flat, the fiber base material is separated from a part of the top surface on the upper side and the bottom surface on the lower side. May be bulged outwardly to form one or a plurality of dot-like substrate spacing portions on one or both sides of the resin composite to reinforce the resin composite.
Moreover, the base material separation part formed in the single side | surface or both surfaces of a plate-shaped resin composite_body | complex may be rib shape.
The ribs in which the resin reservoir is contained may be arranged in one direction or arranged radially.

A known method can be used as thermoforming for imparting a three-dimensional shape such as a raised portion to the preform.
Examples of the thermoforming include vacuum forming, pressure forming, and compression forming.
Examples of thermoforming methods that apply vacuum forming, pressure forming, and compression forming include straight forming, drape forming, plug assist forming, plug assist reverse draw forming, air slip forming, and snapback. Examples thereof include a molding method, a reverse draw molding method, a plug assist / air slip molding method, a match molding method, a press molding method, an SMC molding method, and a thermoforming method combining these molding methods.
A resin composite with good appearance can be obtained even if a fiber reinforced resin material having poor moldability is used. Among these methods, the resin composite can be produced by press molding, match molding, or the like. The method is preferred. Moreover, as a method for producing the resin composite, a method for producing by a autoclave method or a hand layup method is also preferable.

The resin composite obtained in this way is excellent in mechanical strength and lightness such as compressive strength and bending strength, so it is in the transportation equipment field such as automobile, aircraft, railway vehicle or ship, home appliance field, information terminal field. It can be used for a wide range of applications such as wind power components, industrial machinery, medical equipment, furniture, etc., especially automotive parts (ceiling panels, bonnets, undercovers, floor panels, door panels, etc.), home appliances It can be suitably used as a component for a product (such as a casing).
The resin composite can also be used for wind turbine blades for wind power generation, robot bodies and arms.
An automobile, a windmill for wind power generation, a robot, and a medical device can exhibit light weight by adopting the resin composite of the present embodiment as a constituent member.

In this wind turbine for wind power generation, the resin composite can be applied in the form of a blade as shown in FIGS. 3 to 6 and FIG. 7, for example.
The wind turbine blade 100 according to the present embodiment is a plurality of blades that are attached to the rotating shaft of the wind turbine. As shown in FIGS. 3 and 4, the mounting portion 110 is attached to the rotating shaft of the wind turbine, and extends from the attaching portion 110. And a blade portion 120.
The blade portion 120 is a plate-like body that extends long in the extending direction, and has a streamlined cross-sectional shape that is pointed on one side in the width direction of the blade portion 120.
The blade portion 120 has a shape obtained by twisting the plate-like body, and has a shape in which the plate-like body is twisted while maintaining a streamlined cross-sectional shape from the distal end 120c to the base end 120d. (See FIGS. 5 and 6, for example).

Further, as shown in the figure, the blade portion 120 increases in thickness from the center in the longitudinal direction toward the base end 120d, and in the vicinity of the attachment portion 110, the width and thickness of the blade portion 120 progresses toward the attachment portion 110 side. Is formed to decrease.
In other words, the blade portion 120 of the present embodiment is formed with a throttle portion 130 that is narrowed so that the width and thickness of the blade portion 120 decrease as proceeding toward the attachment portion 110 side.
The attachment portion 110 is formed with three through holes 190, 190, 190 for attachment to the rotating shaft of the windmill.

As shown in FIGS. 5 and 6, the windmill blade 100 includes an outer skin 150.
In the blade portion 120 and the attachment portion 110, an internal space S is formed inside the outer skin 150, and the internal space S is formed by connecting the internal space of the blade portion 120 and the internal space of the attachment portion 110.
The outer skin 150 is formed of the fiber reinforced resin material A10 as described above.
That is, the outer skin 150 is formed of a fiber-reinforced resin material including a sheet-like fiber base material and a resin impregnated in the fiber base material.

A core body 180 is disposed in the internal space S surrounded by the outer skin 150 of the attachment portion 110, and the core body 180 is made of a fiber reinforced resin material having a higher tensile strength than the fiber reinforced resin material of the outer skin 150.
That is, the fiber reinforced resin material constituting the core body 180 has a higher mass ratio of the fiber than the fiber reinforced resin material constituting the outer skin 150, the fiber itself has a higher tensile strength, or a synthetic impregnated into the fiber. Either the tensile strength of the resin is high.

  Thus, by arranging the core body 180 made of a fiber reinforced resin material having a higher tensile strength than the fiber reinforced resin material of the outer skin, the attachment strength of the attachment portion 110 can be increased.

A core material 160 composed of a plurality of resin foams A20 is disposed in the internal space S of the outer skin 150 in the blade portion 120.
The core member 160 includes a rod-like beam body that extends from the attachment portion 11 to the tip of the blade portion through the central portion in the width direction of the blade portion 12, and rod-shaped members disposed on both sides of the beam body. .
That is, the core material 160 of the present embodiment is a structure in which three rod-shaped bodies are in contact with each other and are arranged side by side.
The girder includes a girder core 160a that is slightly thinner than the girder, and a girder skin 160b that covers the girder core 160a.
More specifically, the outer skin 150 has two inner wall surfaces 120 a and 120 a that face each other in the thickness direction of the blade portion 12.
The girder contacts both the inner wall surfaces 120a and 120a and connects the inner wall surfaces 120a and 120a (see FIG. 6).
The girder is arranged along the longitudinal direction of the blade 120 from the tip 120c of the blade 120 to the base 120d of the blade 120).
The rod-shaped member 160c that constitutes the core member 160 together with the girders is a resin foam A20, which is filled in a space other than the girders in the internal space S and adheres to the inner wall surfaces 12a and 12a of the outer skin 150. ing.
The core body 180 of the mounting portion 110 is in contact with the beam body. The core body 180 and the beam body are continuously arranged along the longitudinal direction of the blade 100.

Here, the spar core 160a is formed of a resin foam A20, and the spar outer shell 160b is formed of a fiber reinforced resin material that is the same as or different from the outer shell 150 of the blade 100.
The girder outer skin 160b is preferably formed of a fiber reinforced resin material having a fiber density (mass ratio) higher than that of the outer skin 150.
The foamed resin constituting the girder core 160a is preferably a hard foam. Examples of the hard foam include acrylic resin foam, polyurethane resin foam, polystyrene resin foam, phenol resin foam, poly Examples thereof include a vinyl chloride resin foam.
The girder core 160a of the present embodiment is formed of an acrylic resin foam.
The resin foam A20 forming the girder core 160a has a square bar shape whose cross-sectional shape is a quadrangle (trapezoid), and is provided with a slightly rounded corner portion A2x at locations corresponding to the four corners of the cross section. Between the part A2x and the girder outer skin 160b or the outer skin 150, there is formed a base material separation portion where the distance from the core material surface to the fiber base material is wider than the surroundings, and the base material separation portion serves as a resin reservoir A3.
The resin reservoir A3 extends along the four corners of the girder core 160a and extends from the attachment portion 110 toward the tip of the blade portion 120.

The rod-shaped member 160c that forms the core member 160 together with the girders is an acrylic resin foam.
That is, a part of the core material 160 of the present embodiment is formed of a fiber reinforced resin material (girder skin), and the remaining part is formed of an acrylic resin foam.
The bar-shaped member 160c and the girder core 160a are in contact with the inner wall surface of the outer skin 150 as shown in the figure.
The two rod-shaped members 160c arranged with the girder sandwiched therebetween have a cross-sectional shape that is generally triangular with a thickness decreasing toward both ends in the width direction of the blade portion 120.
That is, when the direction in which the blade portion 120 faces the wind is the front end side in the width direction, and the direction in which the wind flows is the end end in the width direction, the resin foam A20 disposed on the front end side of the girder is directed toward the front end. The thickness is thin.
Similarly, the resin foam A20 disposed on the end side with respect to the girder is thinner toward the end.
The resin foam A20 on both sides of the girders is also provided with corners A2y by being rounded at locations corresponding to the three corners in the cross-sectional shape.
Between the corner portion A2y and the girder outer skin 160b and the outer skin 150, a base material separation portion is formed in which the distance from the core surface to the fiber base material is wider than the surroundings, and the base material separation portion becomes a resin reservoir A3. ing.
The resin reservoir A3 extends along the three corners of the foam 160c, and extends from the attachment portion 110 toward the tip of the blade portion 120.
That is, the blade 100 of this embodiment is not only simply integrated with the outer skin 150 and the core material 160 but also reinforced by the resin reservoir A3.
As a result, the blade 100 of this embodiment exhibits excellent strength.

Such an effect can also be exhibited in a wind turbine blade 100 ′ as shown in FIG.
FIG. 7 is a schematic cross-sectional view corresponding to FIG. 5, and is a cross-sectional view relating to a cross section crossing the blade portion of the wind turbine blade.
In the wind turbine blade 100 ′ shown in FIG. 7, a core material 160 ′ is formed of a resin foam A20 that fills the inside of the outer skin 150 ′.
The resin foam A20 constituting the core material 160 ′ has a spindle-shaped cross-sectional shape in which the width direction end side extends longer than the tip end side, and has corner portions A2z at both ends in the width direction.
Also in the corner portion A2z, a base material separation portion having a wider distance to the fiber base material than the surroundings is formed, and the base material separation portion serves as a resin reservoir A3.
Thus, since the resin reservoir A3 is formed in the portion where the thickness of the core material 160 ′ is reduced, the blade 100 ′ of the present embodiment exhibits excellent strength.
That is, the resin composite according to the present embodiment is suitable as a constituent material for a wind turbine blade.

In addition, the shape and application of the resin composite according to the present embodiment are not particularly limited.
The resin composite according to the present embodiment has various shapes such as a square, other polygons, a circle, an ellipse, a semicircle, a crescent, an indeterminate form, etc. It can be.
Moreover, the resin composite which concerns on this embodiment is not limited to the said illustration in the formation material and the manufacturing method.
That is, the resin composite of this embodiment is not limited to the above examples.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1
An expansion ratio of 10 times, manufactured by Sekisui Plastics Kogyo Co., Ltd., a product name “Formac HR # 1000 grade” (acrylic resin foam) was prepared by cutting as a bonnet-shaped core material having a flat portion thickness of 5 mm.
A corner portion was formed on the outer periphery of the “formac” so that the tip angle was 40 °.
Next, a face material (trade name “Pyrofil Prepreg TR3523-395GMP”, manufactured by Mitsubishi Rayon Co., Ltd., impregnated with 200 g / m ²⁾ , thickness: 0. 23 mm) was laminated on each of the front and back of “Formac” to obtain a preform.

This preform is set in an autoclave (Tandelion DL-2010 manufactured by Hanyuda Iron Works), the preform is molded under conditions of 130 ° C., 0.3 MPa, 60 minutes, and a resin composite having a bonnet shape Got.
The resin composite was prepared so that a resin reservoir was formed between the fiber base material and the core material at the corner portion.

(Examples 2 to 7)
The core material was changed as described in Table 1 to obtain a resin composite.
“Polyester type” in Table 1 is an extruded foam sheet (thickness 3 mm) produced by polyethylene terephthalate (PET, trade name “CH-611” manufactured by Toyobo Co., Ltd.).

(Resin pool, resin penetration area)
A cross-sectional photograph was taken of the corner portion of the resin composite of Example 1.
As a result, as shown in FIG. 8, a resin reservoir X was formed between the fiber base material at the corner and a portion Y into which the resin had permeated was observed.
The formation length of the resin reservoir (FIG. 8 “L”) was 0.6 mm.
The area ratio (ratio to the cross-sectional area of the core material in the circle) of the resin-infiltrated portion Y and the resin reservoir X was determined within a circle having a radius of 10 mm at the corner portion ("Z" in FIG. 8).
The results are shown in Table 1.

(Bonnet end bending strength)
From the bonnet structure of each example, the strip-shaped sample (15 mm × 130 mm (vertical center direction from the end)) was collected and measured by the following method.
The bending strength of the resin composite was measured using a small tabletop tester (trade name “FGS-1000TV / 1000N + FGP-100” manufactured by Nidec Symposium) and software “FGS-TV Ver2” for a small tabletop tester.
The jig used was “FGTT-531” manufactured by Nidec Sympos.
A strip-shaped sample was cut out from the boundary portion and placed on a support stand, and the maximum point load was measured under the conditions of a load cell 1000N, a test speed of 5 mm / min, a tip jig 5R of the support stand, and an opening width of 100 mm.
The results are shown in Table 1.

  From the above, it can be seen that according to the present invention, the resin composite can exhibit excellent strength while suppressing an excessive increase in mass.

A resin composite A1 fiber reinforced resin material A2 core material A3 resin reservoir A2a (first) corner portion A2b (second) corner portion A2c (third) corner portion

Claims (7)

A fiber-reinforced resin material comprising a sheet-like fiber substrate and a resin impregnated in the fiber substrate;
Having a core made of resin foam,
A resin composite in which the fiber reinforced resin material is coated on the surface of the core material,
A base material separation portion in which the distance from the core surface to the fiber base material is wider than the surroundings is formed,
The core material has a corner portion, and the base material separation portion is formed in at least a part of a region along the corner portion,
In the base material separation portion, a resin composite in which a resin pool in which a resin of a fiber reinforced resin material is stored is formed between the surface of the core material and the fiber base material. The resin impregnated in the fiber base material includes one or more thermosetting resins selected from the group consisting of epoxy resins, unsaturated polyester resins, and vinyl ester resins, and the resin foam is an acrylic resin The resin composite according to claim 1, comprising at least one resin selected from the group consisting of a resin, a polyester-based resin, and a polystyrene-based resin.   The resin composite according to claim 2, wherein the thermosetting resin is infiltrated into the core material in the base material separation portion.   An automobile in which the resin composite according to any one of claims 1 to 3 is adopted as a constituent member.   A wind turbine for wind power generation in which the resin composite according to any one of claims 1 to 3 is adopted as a constituent member.   A robot in which the resin composite according to any one of claims 1 to 3 is adopted as a constituent member.   A medical device in which the resin composite according to any one of claims 1 to 3 is adopted as a constituent member.