JP2018034351A - Metal/fiber reinforced composite structure and manufacturing method of metal/fiber reinforced composite structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal/fiber reinforced resin composite structure excellent in bond strength between a metal member and a fiber reinforced resin member and appearance.SOLUTION: A metal/fiber reinforced resin composite structure 100 is manufactured by binding a metal member 102 and a fiber reinforced resin member 101 which is at least one kind selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member. Surface hardness measured for total 6 linear parts consisting of any 3 linear parts in parallel relationship and any 3 linear parts orthogonal to the 3 linear parts on a bond surface 103 of the metal member 102, according to JIS B0601 (Corresponding International Standard:ISO4287) satisfies following requirements (1) and (2) at same time. (1) it contains 1 or more linear part having negative length rate of roughness curve at cut level of 20% and evaluation length of 4 mm (Rmr) of 30% or less. (2) ten point average roughness (Rz) at evaluation length of 4 mm of all linear parts is over 2 μm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal / fiber reinforced resin composite structure and a method for producing a metal / fiber reinforced resin composite structure.

Fiber reinforced plastic (FRP) products are manufactured by various methods. Among the manufacturing methods of FRP products, sheet-like sheet molding compounds (SMC) obtained by impregnating unsaturated polyester resin compositions into fiber reinforcements such as glass fiber reinforcement and carbon fiber reinforcement are used as raw materials. The method of producing an FRP product by heating and pressing the SMC is suitable for mass production and widely used industrially.
In addition, a bulk bulk molding compound (BMC) obtained by mixing an unsaturated polyester resin composition and a fiber reinforcing material with a kneader or the like as a raw material is used, and an FRP product is formed by heating and pressing the BMC. The manufacturing method is also suitable for mass production and is widely used industrially.

  The main uses of SMC molded articles and BMC molded articles are classified into residential use and automobile use. Among these, automotive applications, particularly SMC molded products for automobile outer plates and BMC molded products are mainly used for outer plates such as hoods, fenders, doors, pillars and spoilers. The characteristics of SMC molded products for automobile outer plates are that they have a beautiful appearance comparable to that of steel plates, that they have high specific strength and specific modulus compared to steel plates, and that they are lightweight, about 1/4 of the specific gravity of steel plates. Recently, attention has been attracted rapidly due to the fact that complex shapes that are difficult to plate with steel sheets can be formed relatively easily, the cost of the product is high, but the cost of the mold is relatively low.

JP 2012-111103 A

  When applying SMC moldings and BMC moldings for automobiles to automobile outer plates, the rigidity and strength of the mounting parts for fixing the SMC moldings and BMC moldings to the vehicle body are very important characteristics. It is necessary to maintain or improve these characteristics while minimizing the cost increase.

  The most common means to ensure the rigidity and strength of the mounting part is to provide a hole in the SCM molded product and BMC molded product, and tighten the bracket with a nut through this hole and fasten it to the vehicle body to integrate it ( Caulking method). However, in this method, the bolt or nut is exposed on the surface of the molded product, and there are cases where it cannot be applied to an automobile outer plate that places importance on the appearance.

  There is also known a method (adhesive method) in which an adhesive is applied to the back side of an SMC molded product and a BMC molded product, and a mounting bracket is attached to the SMC molded product and the BMC molded product. However, with this adhesive method, man-hours are increased by using an adhesive, surface irregularities may occur due to the adhesive treatment and shrinkage of the adhesive, and the adhesive is completely cured to express the desired strength. In order to do this, there is a problem that a heating operation is necessary, or in the case of natural curing, a long time is required (see Patent Document 1).

  From the above, a more economical mounting bracket that does not increase costs, specifically, an SMC molded product in which a mounting bracket with excellent strength and appearance of the mounting portion is joined and fixed without using bolts or adhesives And BMC molded products were strongly demanded by the industry.

  The present invention has been made in view of the above circumstances, and uses a metal member and a fiber reinforced resin member that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member. It is possible to provide a metal / fiber reinforced resin composite structure that can be directly bonded without any problems and has excellent bonding strength and appearance between the metal member and the fiber reinforced resin member.

  The present inventors directly join a metal member and a fiber reinforced resin member, which is at least one selected from SMC members and BMC members, without using an adhesive, and bond strength between the metal member and the fiber reinforced resin member and The design guideline for obtaining a metal / fiber reinforced resin composite structure having an excellent appearance was intensively studied. As a result, the present inventors have found that a measure of the load length ratio (Rmr) of the roughness curve on the surface of the metal member is effective as such a design guideline and reached the present invention.

  That is, according to the present invention, the following metal / fiber reinforced resin composite structure and a method for producing the metal / fiber reinforced resin composite structure are provided.

[1]
A metal / fiber reinforced resin composite structure formed by joining a metal member and a fiber reinforced resin member that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member,
JIS B0601 (corresponding international standard: ISO 4287) for a total of 6 straight line parts consisting of arbitrary 3 straight line parts in parallel relation on the surface of the joint part of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts A metal / fiber reinforced resin composite structure in which the surface roughness measured in accordance with the above satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm [2]
In the metal / fiber reinforced resin composite structure according to the above [1],
JIS B0601 (corresponding international standard: ISO 4287) for a total of 6 straight line parts consisting of arbitrary 3 straight line parts in parallel relation on the surface of the joint part of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts A metal / fiber reinforced resin composite structure in which the surface roughness measured according to the above further satisfies the following requirement (3).
(3) One or more straight line portions having a load length ratio (Rmr) of a roughness curve at a cutting level of 40% and an evaluation length of 4 mm are 60% or less [3]
In the metal / fiber reinforced resin composite structure according to the above [1] or [2],
JIS B0601 (corresponding international standard: ISO 4287) for a total of 6 straight line parts consisting of arbitrary 3 straight line parts in parallel relation on the surface of the joint part of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts A metal / fiber reinforced resin composite structure in which the surface roughness measured in accordance with the above further satisfies the following requirement (4).
(4) The average length (RSm) of the roughness curve elements of all the straight portions is more than 10 μm and less than 300 μm [4]
In the metal / fiber reinforced resin composite structure according to any one of the above [1] to [3],
A metal / fiber reinforced resin composite structure comprising one or more metals selected from aluminum and aluminum alloys as a metal material constituting the metal member.
[5]
In order to produce a metal / fiber reinforced resin composite structure in which a metal member and a fiber reinforced resin member that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member are joined together A manufacturing method of
JIS B0601 (corresponding international standard) for a total of 6 linear parts consisting of arbitrary 3 linear parts in parallel relation on the surface of the joint part with the fiber reinforced resin member and arbitrary 3 linear parts orthogonal to the 3 linear parts A step of preparing the metal member, wherein the surface roughness measured in accordance with ISO 4287) simultaneously satisfies the following requirements (1) and (2):
Stacking the metal member and the fiber reinforced resin member so that at least a part of the joint surface of the metal member and at least a part of the fiber reinforced resin member are in contact with each other, and press-molding under heating;
For producing a metal / fiber reinforced resin composite structure.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm

  According to the present invention, a metal member and a fiber reinforced resin member that is at least one selected from an SMC member and a BMC member can be directly joined without using an adhesive, and the metal member and the fiber reinforced resin member can be joined. It is possible to provide a metal / fiber reinforced resin composite structure excellent in bonding strength and appearance.

It is the perspective view which showed typically an example of the structure of the metal / fiber reinforced resin composite structure of embodiment which concerns on this invention. Explain the measurement points of a total of 6 linear parts composed of arbitrary 3 linear parts in parallel relation and arbitrary 3 linear parts orthogonal to the 3 linear parts on the joint surface of the metal member of the embodiment according to the present invention. It is a schematic diagram for doing.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. Unless otherwise specified, “˜” between numbers in the sentence represents the following.

[Metal / fiber reinforced resin composite structure]
First, the metal / fiber reinforced resin composite structure 100 according to the present embodiment will be described.
FIG. 1 is a perspective view schematically showing an example of the structure of a metal / fiber reinforced resin composite structure 100 according to an embodiment of the present invention. Here, FIG. 1 shows an example in which the metal member 102 is a hook-shaped metal fitting.

The metal / fiber reinforced resin composite structure 100 according to this embodiment includes a metal member 102, and a fiber reinforced resin member 101 that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member. Are joined. Then, JIS B0601 (corresponding international standard) is used for a total of six straight line portions including arbitrary three straight line portions in parallel relation on the joint surface 103 of the metal member 102 and arbitrary three straight line portions orthogonal to the three straight line portions. : Surface roughness measured according to ISO 4287) satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm

  In the metal member 102 according to the present embodiment, a fine uneven structure is formed on the joint surface 103 with the fiber reinforced resin member 101 so as to satisfy the requirements (1) and (2) at the same time. A part of the semi-cured component contained in the fiber reinforced resin member 101 penetrates into such a fine concavo-convex structure and then hardens, whereby the metal member 102 and the fiber reinforced resin member 101 can be joined. By doing so, physical resistance (anchor effect) is effectively developed between the metal member 102 and the fiber reinforced resin member 101, and the metal member 102 and the fiber reinforced resin member 101 are made to use an adhesive. It becomes possible to join firmly. Therefore, in the metal / fiber reinforced resin composite structure 100 according to this embodiment, the metal member 102 and the fiber reinforced resin member 101 are firmly joined without using an adhesive, and further, no bolt or adhesive is used. Therefore, the appearance is also excellent.

  Hereinafter, each member which comprises the metal / fiber reinforced resin composite structure 100 which concerns on this embodiment is demonstrated.

<Fiber-reinforced resin member>
Hereinafter, the fiber reinforced resin member 101 according to the present embodiment will be described.
The fiber reinforced resin member 101 according to the present embodiment is at least one selected from an SMC member and a BMC member.

The SMC member is a member obtained by cutting and processing a later-described SMC sheet into a predetermined shape.
Here, the SMC sheet is a sheet-like semi-cured molding material obtained by impregnating a fiber reinforcing material with an unsaturated polyester resin composition containing an unsaturated polyester resin.
The BMC member is a member obtained by cutting and processing a BMC molded product, which will be described later, into a predetermined shape. Here, the BMC molded product is a semi-cured product obtained by molding a bulk bulk molding compound (BMC) obtained by mixing an unsaturated polyester resin composition and a fiber reinforcing material with a kneader or the like into a predetermined shape. The molding material in a state.
Here, the unsaturated polyester resin composition used for the fiber reinforced resin member 101 is added with various additives such as an inorganic filler, a vinyl monomer, a curing agent, a release agent, and other additives described below, as necessary. An agent may further be included.

Since the unsaturated polyester resin contains a double bond in the molecular structure, it is cured by heat and the physical properties of the resin are improved. The unsaturated polyester resin is not particularly limited, and those generally used for SMC and BMC can be used. For example, iso (iso) resin, ortho resin, tele resin, One kind or two or more kinds selected from a modified bisphenol resin, a bisphenol resin, a vinyl ester resin, and the like can be used.
The content of the unsaturated polyester resin is, for example, 5 to 30% by mass when the entire fiber reinforced resin member 101 is 100% by mass.

The inorganic filler is not particularly limited, and those generally used for SMC and BMC can be used. For example, one kind selected from calcium carbonate, mica, talc, clay, spherical silica, ceramic beads, and the like or Two or more types can be used.
Content of the said inorganic filler is 30-60 mass%, for example, when the whole fiber reinforced resin member 101 is 100 mass%. When the content of the inorganic filler is equal to or less than the upper limit, it is possible to suppress a decrease in physical properties. It is preferable from a viewpoint that manufacturing cost can be reduced as content of the said inorganic filler is more than the said lower limit.

The vinyl monomer and the curing agent are used for the curing reaction of the unsaturated polyester resin composition.
The vinyl monomer is not particularly limited, and those generally used for SMC and BMC can be used. For example, from styrene, methyl methacrylate, divinylbenzene, α-methylstyrene, vinyl acetate, acrylate, etc. One kind or two or more kinds selected can be used.
The content of the vinyl monomer is, for example, 0.1 to 10% by mass when the entire fiber reinforced resin member 101 is 100% by mass.

The curing agent is not particularly limited, and those generally used for SMC and BMC can be used. For example, peroxyester, dialkyl peroxide, alkylaryl peroxide, diaryl peroxide, peroxyketal, ketone One or more selected from peroxides, azo compounds and the like can be used.
Content of the said hardening | curing agent is 0.01-2 mass%, for example, when the fiber reinforced resin member 101 whole is 100 mass%.

  The unsaturated polyester resin composition may contain a release agent in order to improve workability during demolding. The release agent is not particularly limited, and those generally used for SMC and BMC can be used. Examples thereof include zinc stearate and calcium stearate. The content of the release agent is, for example, 0.1 to 5% by mass, preferably 0.5 to 2% by mass, when the entire fiber reinforced resin member 101 is 100% by mass.

The fiber reinforcing material is not particularly limited, and those generally used for SMC and BMC can be used. For example, inorganic fiber reinforcing material such as glass fiber reinforcing material and carbon fiber reinforcing material; polyester fiber reinforcing material, cellulose An organic fiber reinforcing material such as a fiber reinforcing material, a nylon fiber reinforcing material, an aramid fiber reinforcing material, a carbonate fiber reinforcing material, or a polyvinyl alcohol fiber reinforcing material can be used.
The length of the fiber reinforcement is, for example, about 0.5 to 5 mm. When the length of the fiber reinforcing material is equal to or greater than the lower limit, the mechanical properties of the fiber reinforced resin member 101 can be further improved. Moreover, it can suppress more that a crack generate | occur | produces in the fiber reinforced resin member 101 as the length of a fiber reinforcement is below the said upper limit.
Content of the said fiber reinforcement is 20-35 mass, when the whole fiber reinforced resin member 101 is 100 mass%, for example. When the content of the fiber reinforcing material is equal to or higher than the lower limit, the mechanical properties of the fiber reinforced resin member 101 can be further improved. It is preferable from a viewpoint of manufacturing cost that content of the said fiber reinforcement is below the said upper limit.

Other additives can be further mixed into the unsaturated polyester resin composition.
Other additives are not particularly limited, and those generally used for SMC and BMC can be used. For example, pigments, heat stabilizers, UV stabilizers, polymerization reaction inhibitors, low shrinkage agents, butadiene rubbers And thickeners. These additives can be used for fine adjustment of various properties such as mechanical properties, surface appearance, and moldability, although desired physical properties can be obtained even if any of the additives is omitted.

The unsaturated polyester resin composition and the fiber reinforcing material are formed into a sheet-like, semi-cured thermosetting molding material by the SMC method, and the SMC sheet according to the present embodiment is cut into a predetermined shape. Can be obtained. For example, the SMC sheet according to the present embodiment can be obtained by the following procedure.
First, by using a doctor blade or the like, the unsaturated polyester resin composition in paste form is applied onto two release films made of polyolefin such as polyethylene film or polypropylene film, and the unsaturated film is then unsaturated on the release film. Two resin sheets on which a polyester resin layer is formed are produced.
Next, of the obtained two resin sheets, a fiber reinforcing material is spread on the unsaturated polyester resin layer of one resin sheet from above through, for example, a rotating chopper. The other prepared resin sheet is laminated with the surface of the unsaturated polyester resin layer on the inside of the surface of the resin sheet on which the obtained fiber reinforcing material is sprayed. As a result, the fiber reinforcement is sandwiched between the upper and lower unsaturated polyester resin layers.
The fiber reinforcement is impregnated with the unsaturated polyester resin layer by pressurizing, for example, by passing it between a plurality of rolls, and at the same time, the thickness is adjusted. Thereby, the sheet | seat of the three-layer structure which is a release film / fiber reinforced resin layer (= layer which impregnated the unsaturated polyester resin composition in the fiber reinforcement) / release film is created.
Thereafter, the SMC sheet according to the present embodiment can be produced by being semi-cured by being subjected to aging treatment (thickening treatment) as necessary. In the case of performing the aging treatment, the conditions can be appropriately determined in consideration of the moldability of SMC. For example, the heat treatment is performed at a temperature of 40 to 70 ° C. for several hours to several days. Is done.

Further, the unsaturated polyester resin composition and the fiber reinforcing material are formed into a lump-like and semi-cured thermosetting molding material by the BMC method, and the BMC molding according to the present embodiment is molded into a predetermined shape. Goods can be obtained. For example, the BMC molded product according to the present embodiment can be obtained by the following procedure.
First, the unsaturated polyester resin composition and the fiber reinforcing material are mixed with a kneader or the like, and the fiber reinforcing material is impregnated with the unsaturated polyester resin composition to prepare a block BMC.
Thereafter, it is molded into a predetermined shape and subjected to aging treatment (thickening treatment) as necessary to be semi-cured to produce a BMC molded product according to this embodiment. When the aging treatment is performed, the conditions can be appropriately determined in consideration of the moldability of BMC. For example, the heat treatment is performed at a temperature of 40 to 70 ° C. for several hours to several days. Is done.

<Metal member>
Hereinafter, the metal member 102 according to the present embodiment will be described.

Although the metal material which comprises the metal member 102 which concerns on this embodiment is not specifically limited, For example, iron, steel materials, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, titanium, titanium alloy, etc. are mentioned, for example. be able to. These may be used alone or in combination of two or more.
Among these, aluminum (aluminum alone) and an aluminum alloy are preferable, and an aluminum alloy is more preferable from the viewpoint of light weight, low cost, and high strength.
As the aluminum alloy, alloy numbers 1050, 1100, 2014, 2024, 3003, 5052, 7075, etc. defined in JIS H4000 are preferably used.

The shape of the metal member 102 is not particularly limited as long as it can be joined to the fiber reinforced resin member 101. For example, the metal member 102 can have a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, or the like. Moreover, the structure which consists of these combination may be sufficient.
Moreover, the shape of the joint surface 103 joined to the fiber reinforced resin member 101 is not particularly limited, and examples thereof include a flat surface and a curved surface.

  When the use of the metal / fiber reinforced resin composite structure 100 is an automobile outer plate, the metal member 102 joined to the fiber reinforced resin member 101 is usually attached to the inner side of the outer plate, that is, the back surface side of the fiber reinforced resin member 101. The shape of the metal member 102 is not particularly limited as long as it has a function as a metal fitting firmly attached to the vehicle body. Usually, a convex metal fitting, in which the bottom plate portions at both ends are joined to the fiber reinforced resin member 101, is preferably used (see FIG. 1).

  The metal member 102 is roughened, which will be described later, after the metal material is processed into a predetermined shape by a known method such as plastic processing such as cutting, pressing, punching, cutting, polishing, electric discharge processing, or the like. Those that have been treated are preferred. In short, it is preferable to use a material processed into a necessary shape by various processing methods.

From the viewpoint of improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101, any three straight portions in parallel relation on the joint surface 103 of the metal member 102 and any orthogonal to the three straight portions The surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO 4287) for the total of 6 linear parts composed of 3 linear parts simultaneously satisfies the following requirements (1) and (2).
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm

FIG. 2 is a schematic diagram for explaining a total of six straight portions including arbitrary three straight portions in parallel relation on the joint surface 103 of the metal member 102 and arbitrary three straight portions orthogonal to the three straight portions. FIG.
For example, the six straight portions B1 to B6 as shown in FIG. 2 can be selected as the six straight portions. First, a center line B1 passing through the center portion A of the joint surface 103 of the metal member 102 is selected as the reference line. Next, straight lines B2 and B3 that are parallel to the center line B1 are selected. Next, a center line B4 orthogonal to the center line B1 is selected, and straight lines B5 and B6 orthogonal to the center line B1 and parallel to the center line B4 are selected. Here, the vertical distances D1 to D4 between the straight lines are, for example, 2 to 5 mm.
In general, the metal member 102 is subjected to a surface roughening process on the entire metal member 102 as well as the joint surface 103 of the metal member 102 with the fiber reinforced resin member 101. Six straight portions may be selected from locations other than the joint surface 103 on the same surface as or opposite to the joint surface 103 with the fiber reinforced resin member 102.

  The reason why the metal / fiber reinforced resin composite structure 100 having excellent bonding strength between the metal member 102 and the fiber reinforced resin member 101 can be obtained by satisfying the above requirements (1) and (2) is not necessarily clear. It is considered that the joint surface 103 of the metal member 102 with the fiber reinforced resin member 101 has a structure capable of effectively expressing the anchor effect between the metal member 102 and the fiber reinforced resin member 101.

From the viewpoint of further improving the bonding strength between the metal member 102 and the fiber-reinforced resin member 101, any three straight portions in parallel relation on the joint surface 103 of the metal member 102 and the three straight portions are orthogonal to each other. The surface roughness measured according to JIS B0601 (corresponding international standard: ISO4287) for a total of 6 linear parts composed of arbitrary 3 linear parts is one or more of the following requirements (1A) to (1C) Is more preferable, and it is particularly preferable that the requirement (1C) is satisfied. The requirement (1C) is the same as the requirement (3) described above.
(1A) A straight line portion with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm is preferably 30% or less, preferably 2 straight portions or more, more preferably 3 straight portions or more, most preferably (1B) including 6 straight portions, preferably a straight portion having a load level ratio (Rmr) of 20% or less of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm, preferably 1 straight portion or more, more preferably 2 straight lines. More than 3 parts, more preferably 3 straight parts or more, most preferably 6 straight parts (1C) A straight part where the cutting length is 40% and the load length ratio (Rmr) of the roughness curve at an evaluation length of 4 mm is 60% or less Is preferably 1 straight part or more, more preferably 2 straight parts or more, further preferably 3 straight parts or more, and most preferably 6 straight parts

Further, from the viewpoint of further improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101, the measurement is performed in accordance with JIS B0601 (corresponding international standard: ISO 4287) on the bonding portion surface 103 of the metal member 102. The average value of the load length ratio (Rmr) of the roughness curve at a cutting level of 20% and an evaluation length of 4 mm is preferably 0.1% or more and 40% or less, more preferably 0.5% or more and 30% or less. More preferably 1% or more and 20% or less, and most preferably 2% or more and 15% or less.
In addition, what averaged the load length rate (Rmr) of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the said load length rate (Rmr).

The load length ratio (Rmr) of the joint surface 103 of the metal member 102 according to the present embodiment can be controlled by appropriately adjusting the conditions of the roughening treatment on the surface of the metal member.
In the present embodiment, in particular, the type and concentration of the etching agent, the temperature and time of the roughening treatment, the timing of the etching treatment, and the like are listed as factors for controlling the load length ratio (Rmr).

From the viewpoint of further improving the bonding strength between the metal member 102 and the fiber-reinforced resin member 101, any three straight portions in parallel relation on the joint surface 103 of the metal member 102 and the three straight portions are orthogonal to each other. It is preferable that the surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) further satisfies the following requirement (2A) for a total of 6 straight line parts including arbitrary 3 straight line parts.
(2A) The 10-point average roughness (Rz) at an evaluation length of 4 mm of all straight portions is preferably more than 5 μm, more preferably 10 μm or more, and further preferably 15 μm or more.

From the viewpoint of further improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101, the average value of the ten-point average roughness (Rz) on the bonding portion surface 103 of the metal member 102 preferably exceeds 2 μm. It is 50 μm or less, more preferably more than 5 μm and 45 μm or less, further preferably 10 μm or more and 40 μm or less, and particularly preferably 15 μm or more and 30 μm or less.
In addition, what averaged the 10-point average roughness (Rz) of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the said 10-point average roughness (Rz).

From the viewpoint of further improving the bonding strength between the metal member 102 and the fiber-reinforced resin member 101, any three straight portions in parallel relation on the joint surface 103 of the metal member 102 and the three straight portions are orthogonal to each other. It is preferable that the surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) further satisfies the following requirement (4) for a total of six straight line parts composed of arbitrary three straight line parts.
(4) The average length (RSm) of the roughness curve elements of all the linear portions is more than 10 μm and less than 300 μm, more preferably 20 μm or more and 200 μm or less.

From the viewpoint of further improving the joint strength between the metal member 102 and the fiber reinforced resin member 101, the average value of the average length (RSm) of the roughness curve elements on the joint surface 103 of the metal member 102 is preferably 10 μm. And less than 300 μm, more preferably 20 μm or more and 200 μm or less.
In addition, what averaged the average length (RSm) of the roughness curve element of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the average length (RSm) of the said roughness curve element.

The ten-point average roughness (Rz) and the average length (RSm) of the roughness curve element of the joint surface 103 of the metal member 102 according to the present embodiment appropriately adjust the conditions of the roughening treatment on the surface of the metal member. It is possible to control by doing.
In the present embodiment, the temperature and time of the roughening treatment, the etching amount, and the like are particularly cited as factors for controlling the ten-point average roughness (Rz) and the average length (RSm) of the roughness curve elements. .

Next, a method for preparing the metal member 102 that satisfies the load length ratio (Rmr), the ten-point average roughness (Rz), the average length of the roughness curve element (RSm), and the like will be described.
Such a metal member 102 can be formed, for example, by roughening the surface of the metal member using an etching agent.
Here, roughening the surface of the metal member using an etchant itself has been performed in the prior art. However, in this embodiment, factors such as the type and concentration of the etching agent, the temperature and time of the roughening process, the timing of the etching process, and the like are highly controlled. In order to obtain the joint surface 103 of the metal member 102 according to the present embodiment, it is important to highly control these factors.
Hereinafter, an example of a metal member roughening method for obtaining the metal member 102 that satisfies the load length ratio (Rmr), the ten-point average roughness (Rz), the average length of the roughness curve element (RSm), and the like. Show. However, the roughening method of the metal member according to the present embodiment is not limited to the following example.

(1) Pre-treatment step First, it is desirable that the metal member does not have a thick film made of an oxide film, hydroxide, or the like on at least the surface on the joining side with the fiber reinforced resin member 101. In order to remove such a thick film, the surface layer may be polished by mechanical polishing such as sand blasting, shot blasting, grinding, barrel processing, or chemical polishing before the next etching step. Good. In addition, when there is significant contamination such as machine oil on the surface on the joint side with the fiber reinforced resin member 101, it is preferable to perform treatment with an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, or degreasing.

(2) Surface roughening treatment process In this embodiment, as a surface roughening treatment method of a metal member, it is preferable to perform the process by the acid type etching agent mentioned later at a specific timing. Specifically, the treatment with the acid-based etching agent is preferably performed at the final stage of the surface roughening treatment step.

  Examples of the roughening treatment using the acid-based etching agent include treatment methods such as immersion and spraying. The treatment temperature is preferably 20 to 40 ° C., the treatment time is preferably about 5 to 350 seconds, 20 to 300 seconds are more preferred, and 50 to 300 seconds are particularly preferred from the viewpoint that the surface of the metal member can be more uniformly roughened.

  In this embodiment, when the metal member is roughened using the acid-based etchant, the entire surface of the metal member may be roughened, and only the surface to which the fiber reinforced resin member 101 is bonded is used. Partial roughening treatment may be performed.

(3) Post-treatment step In this embodiment, it is usually preferable to perform washing and drying after the surface roughening treatment step. Although there is no restriction | limiting in particular about the method of water washing, It is preferable to wash | clean for predetermined time with immersion or flowing water.

  Furthermore, as a post-treatment step, it is preferable to perform ultrasonic cleaning in order to remove smut and the like generated by the treatment using the acid-based etching agent. The ultrasonic cleaning conditions are not particularly limited as long as the generated smut and the like can be removed, but the solvent used is preferably water, and the treatment time is preferably 1 to 20 minutes.

(Acid etching agent)
In this embodiment, as an etching agent used for the roughening process of the metal member surface, the specific acid type etching agent mentioned later is preferable. By treating with a specific acid-based etching agent, a fine concavo-convex structure suitable for improving adhesion between the fiber reinforced resin member 101 is formed on the surface of the metal member, and the metal member 102 and the fiber reinforced are formed by the anchor effect. It is considered that the bonding strength with the resin member 101 is further improved.

  Hereinafter, the components of the acid-based etching agent that can be used in this embodiment will be described.

  The acid-based etching agent contains at least one of ferric ions and cupric ions and an acid, and may contain manganese ions, various additives, and the like as necessary.

-Ferric ion The said ferric ion is a component which oxidizes a metal member, and this ferric ion can be contained in an acid type etching agent by mix | blending a ferric ion source. Examples of the ferric ion source include ferric nitrate, ferric sulfate, and ferric chloride. Among the ferric ion sources, ferric chloride is preferable because it has excellent solubility and is inexpensive.

  In this embodiment, content of the said ferric ion in an acid type etching agent becomes like this. Preferably it is 0.01-20 mass%, More preferably, it is 0.1-12 mass%, More preferably, it is 0.5-7 % By mass, still more preferably 1-6% by mass, particularly preferably 1-5% by mass. If content of the said ferric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the ferric ion is less than or equal to the above upper limit value, the roughening rate can be maintained appropriately, and thus more suitable for improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101. Uniform roughening becomes possible.

-Cupric ion The said cupric ion is a component which oxidizes a metal member, and can mix | blend this cupric ion in an acid type etching agent by mix | blending a cupric ion source. Examples of the cupric ion source include cupric sulfate, cupric chloride, cupric nitrate, and cupric hydroxide. Of the cupric ion sources, cupric sulfate and cupric chloride are preferred because they are inexpensive.

  In this embodiment, it is preferable that content of the said cupric ion in an acid type etching agent is 0.001-10 mass%, More preferably, it is 0.01-7 mass%, More preferably, it is 0.00. It is 05-1 mass%, More preferably, it is 0.1-0.8 mass%, More preferably, it is 0.15-0.7 mass%, Most preferably, it is 0.15-0.4 mass%. If content of the said cupric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the cupric ion is less than or equal to the above upper limit value, the roughening rate can be maintained appropriately, and thus more suitable for improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101. Uniform roughening becomes possible.

  The acid-based etching agent may contain only one of ferric ion and cupric ion, or may contain both, but both ferric ion and cupric ion It is preferable to contain. By including both the ferric ion and the cupric ion in the acid-based etching agent, a good roughened shape suitable for improving the bonding strength between the metal member 102 and the fiber reinforced resin member 101 can be easily obtained. .

  When the acid-based etching agent contains both ferric ions and cupric ions, the contents of ferric ions and cupric ions are preferably in the above ranges. The total content of ferric ions and cupric ions in the acid-based etching agent is preferably 0.011 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably. Is 0.5 to 10% by mass, particularly preferably 1 to 5% by mass.

Manganese ions The acid-based etching agent may contain manganese ions in order to uniformly roughen the surface of the metal member. Manganese ions can be contained in the acid-based etching agent by blending a manganese ion source. Examples of the manganese ion source include manganese sulfate, manganese chloride, manganese acetate, manganese fluoride, and manganese nitrate. Among the above manganese ion sources, manganese sulfate and manganese chloride are preferable from the viewpoint of being inexpensive.

  In this embodiment, it is preferable that content of the said manganese ion in an acid type etching agent is 0-1 mass%, More preferably, it is 0-0.5 mass%.

-Acid The acid is a component that dissolves a metal oxidized by ferric ions and / or cupric ions. Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, and sulfamic acid, and organic acids such as sulfonic acid and carboxylic acid. Examples of the carboxylic acid include formic acid, acetic acid, citric acid, oxalic acid, malic acid and the like. One or more of these acids can be added to the acid-based etching agent. Of the inorganic acids, sulfuric acid is preferred because it has almost no odor and is inexpensive. Among the organic acids, carboxylic acid is preferable from the viewpoint of uniformity of the roughened shape.

  In the present embodiment, the acid content in the acid-based etching agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 50% by mass, and 1 to 50% by mass. It is still more preferable, it is still more preferable that it is 1-30 mass%, it is still more preferable that it is 1-25 mass%, and it is still more preferable that it is 2-18 mass%. If content of the said acid is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the acid is not more than the above upper limit, workability can be improved because crystal precipitation of the metal salt of the metal member when the liquid temperature is lowered can be prevented.

Other components To the acid-based etching agent that can be used in the present embodiment, a surfactant may be added to prevent unevenness due to surface contaminants such as fingerprints, and other additives may be added as necessary. May be. Other additives include halide ion sources added to form deep irregularities, such as sodium chloride, potassium chloride, sodium bromide, potassium bromide and the like. Alternatively, thio compounds such as thiosulfate ions and thiourea added to increase the roughening treatment speed, azoles such as imidazole, triazole and tetrazole added to obtain a more uniform roughened shape, Examples thereof include a pH adjuster added to control the oxidization reaction. When these other components are added, the total content is preferably about 0.01 to 10% by mass in the acid-based etching agent.

  The acid-based etching agent of this embodiment can be easily prepared by dissolving each of the above components in ion-exchanged water or the like.

[Method for producing metal / fiber reinforced resin composite structure]
Next, a method for manufacturing the metal / fiber reinforced resin composite structure 100 according to the present embodiment will be described. Here, a method for manufacturing the metal / fiber reinforced resin composite structure 100 in which the metal member 102 shown in FIG. 1 is a hook-shaped metal fitting will be described as an example.
The manufacturing method of the metal / fiber reinforced resin composite structure 100 according to the present embodiment includes, for example, the following steps (A) and (B).
(A) JIS B0601 for a total of six straight portions including arbitrary three straight portions in parallel relation on the joint surface 103 with the fiber reinforced resin member 101 and arbitrary three straight portions orthogonal to the three straight portions. (B) a step of preparing a metal member 102 whose surface roughness measured in conformity with (corresponding international standard: ISO 4287) satisfies the requirements (1) and (2) described above at the same time. (B) the joint surface 103 of the metal member 102; A process of stacking the metal member 102 and the fiber reinforced resin member 101 so that at least a part of the fiber reinforced resin member 101 is in contact with each other and press-molding under heating

(Process (A))
First, JIS B0601 (for a total of six straight portions including arbitrary three straight portions in parallel relation on the joint surface 103 with the fiber reinforced resin member 101 and arbitrary three straight portions orthogonal to the three straight portions) Corresponding international standard: A metal member 102 whose surface roughness measured in accordance with ISO 4287) simultaneously satisfies the requirements (1) and (2) described above is prepared.
Here, the metal member 102 can be obtained by performing the above-described roughening process on at least the joint surface 103 to which the fiber reinforced resin member 101 is joined.
Details of the metal member and the roughening treatment are omitted here.

(Process (B))
Next, the metal member 102 and the fiber reinforced resin member 101 are overlapped so that the joint surface 103 of the metal member 102 and at least a part of the fiber reinforced resin member 101 are in contact with each other, and pressure-molded under heating. Thereby, the metal / fiber reinforced resin composite structure 100 is obtained.
As a method of pressure molding under heating, for example, the metal member 102 of the hook-shaped metal fitting 102 is desired on the fiber reinforced resin member 101 in a semi-cured state so that the joint surface 103 is in contact with the fiber reinforced resin member 101. In general, a method in which the fiber reinforced resin member 101 is cured by heat-pressing at least a surface including the joint surface 103 after being disposed at the position is generally employed.
A mold can be arbitrarily used in the heat and pressure molding. When using a metal mold | die, the temperature of an up-and-down metal mold | die is 130-170 degreeC, for example, Preferably it is 140-160 degreeC, and a pressure is 100-2000 MPa, for example, Preferably it is 500-1500 MPa. The pressurization time is, for example, 0.5 to 10 minutes, preferably 1 to 5 minutes.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

DESCRIPTION OF SYMBOLS 100 Metal / fiber reinforced resin composite structure 101 Fiber reinforced resin member 102 Metal member 103 Joint surface

Claims (5)

A metal / fiber reinforced resin composite structure formed by joining a metal member and a fiber reinforced resin member that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member,
JIS B0601 (corresponding international standard: ISO 4287) for a total of six straight lines composed of arbitrary three straight lines in parallel relation on the joint surface of the metal member and arbitrary three straight lines orthogonal to the three straight lines A metal / fiber reinforced resin composite structure in which the surface roughness measured in accordance with the above satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm The metal / fiber reinforced resin composite structure according to claim 1,
JIS B0601 (corresponding international standard: ISO 4287) for a total of six straight lines composed of arbitrary three straight lines in parallel relation on the joint surface of the metal member and arbitrary three straight lines orthogonal to the three straight lines A metal / fiber reinforced resin composite structure in which the surface roughness measured according to the above further satisfies the following requirement (3).
(3) One or more straight line portions having a load length ratio (Rmr) of a roughness curve at a cutting level of 40% and an evaluation length of 4 mm are 60% or less. The metal / fiber reinforced resin composite structure according to claim 1 or 2,
JIS B0601 (corresponding international standard: ISO 4287) for a total of six straight lines composed of arbitrary three straight lines in parallel relation on the joint surface of the metal member and arbitrary three straight lines orthogonal to the three straight lines A metal / fiber reinforced resin composite structure in which the surface roughness measured in accordance with the above further satisfies the following requirement (4).
(4) The average length (RSm) of the roughness curve elements of all the straight portions exceeds 10 μm and is less than 300 μm In the metal / fiber reinforced resin composite structure according to any one of claims 1 to 3,
A metal / fiber reinforced resin composite structure in which the metal material constituting the metal member includes one or more metals selected from aluminum and aluminum alloys. In order to produce a metal / fiber reinforced resin composite structure in which a metal member and a fiber reinforced resin member that is at least one selected from a sheet molding compound (SMC) member and a bulk molding compound (BMC) member are joined together A manufacturing method of
JIS B0601 (corresponding international standard) for a total of 6 straight line parts comprising arbitrary 3 straight line parts in parallel relation on the surface of the joint part with the fiber reinforced resin member and arbitrary 3 straight line parts orthogonal to the 3 straight line parts Preparing the metal member whose surface roughness measured in accordance with ISO 4287) simultaneously satisfies the following requirements (1) and (2):
Stacking the metal member and the fiber reinforced resin member so that at least a part of the joint surface of the metal member and at least a part of the fiber reinforced resin member are in contact with each other;
For producing a metal / fiber reinforced resin composite structure.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm

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