JP2017218616A - Method for producing surface roughened metal member and method for producing metal/resin composite structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for obtaining a metal member capable of suppressing variation in a bond strength of a metal member and a resin member.SOLUTION: A method for producing a surface roughened metal member 103 is for producing the surface roughened metal member 103 used for bonding to a thermoplastic resin member 105 composed of a thermoplastic resin (P1) or a resin composition (P2) containing the thermoplastic resin (P1) and includes a step of roughening at least a joint portion surface 104 of the metal member with the thermoplastic resin member 105 with a metal hydroxide aqueous solution.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a surface roughened metal member and a method for producing a metal / resin composite structure.

  Resin is used as a substitute for metal from the viewpoint of weight reduction of various parts. However, it is often difficult to replace all metal parts with resin. In such a case, it is conceivable to manufacture a new composite part by joining and integrating the metal molded body and the resin molded body. However, a technique capable of joining and integrating a metal molded body and a resin molded body with an industrially advantageous method with high bonding strength has not been put into practical use.

  In recent years, as a technology for joining and integrating metal moldings and resin moldings, engineering plastics with polar groups that have affinity with the metal member are joined to the metal member surface with fine irregularities Has been studied (for example, Patent Document 1).

  In Patent Document 1, hot water treatment is performed on a metal surface, a microporous hydroxyl group-containing film is formed on the surface, and a thermoplastic resin is injected onto the metal surface on which the microporous hydroxyl group-containing film is formed. Also disclosed is a method for producing a composite of metal and resin, wherein the metal and the thermoplastic resin are integrated through the film.

JP 2008-162115 A

  According to the study by the present inventors, even if the metal / resin composite structure obtained by the method disclosed in Patent Document 1 is manufactured under the same conditions, the bonding strength between the metal member and the resin member It became clear that there would be variations.

  This invention is made | formed in view of the said situation, and provides the manufacturing method for obtaining the metal member which can suppress the dispersion | variation in the joining strength of a metal member and a resin member.

  The inventors of the present invention diligently studied to obtain a metal member that can suppress the variation in bonding strength between the metal member and the resin member. As a result, the metal member that can suppress variation in the bonding strength between the metal member and the resin member by bringing the surface of the joint portion of the metal member with the thermoplastic resin member into contact with the metal hydroxide aqueous solution and performing a roughening treatment. Was obtained, and the present invention was achieved.

  That is, according to this invention, the manufacturing method of the surface roughening metal member shown below and the manufacturing method of a metal / resin composite structure are provided.

[1]
A production method for producing a surface-roughened metal member used for joining with a thermoplastic resin or a thermoplastic resin member composed of a resin composition containing the thermoplastic resin,
The manufacturing method of the surface roughening metal member including the process of roughening the joining surface with the said thermoplastic resin member of a metal member at least by the metal hydroxide aqueous solution.
[2]
In the method for producing a surface roughened metal member according to [1] above,
The manufacturing method of the surface roughening metal member whose metal element which comprises the said metal member, and the metal element which comprises the said metal hydroxide aqueous solution are the same metal elements.
[3]
In the method for producing a roughened metal member according to [1] or [2] above,
The surface roughened metal member is one or two selected from iron, steel, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, zinc, zinc alloy, tin, tin alloy, titanium and titanium alloy. The manufacturing method of the surface roughening metal member which is comprised with the metal material more than a seed | species.
[4]
In the method for producing a roughened metal member according to [1] or [2] above,
The method for producing a surface roughened metal member, wherein the surface roughened metal member is composed of at least one metal material selected from aluminum and an aluminum alloy.
[5]
In the method for producing a roughened metal member according to [4] above,
The manufacturing method of the surface roughening metal member whose said metal hydroxide aqueous solution is aluminum hydroxide aqueous solution.
[6]
In the method for producing a roughened metal member according to any one of [1] to [5],
When the saturation concentration of the metal hydroxide aqueous solution is Z mol / L,
The manufacturing method of the surface roughening metal member whose density | concentration of the said metal hydroxide aqueous solution is (0.1 * Z) mol / L or more and (1.0 * Z) mol / L or less.
[7]
In the method for producing a roughened metal member according to any one of [1] to [6],
The manufacturing method of the surface roughening metal member which performs the process roughened with the said metal hydroxide aqueous solution after the process of wash | cleaning the said junction part surface of the said metal member at least with acidic aqueous solution and / or basic aqueous solution.
[8]
In the method for producing a roughened metal member according to any one of [1] to [7],
A method for producing a surface-roughened metal member, wherein the aqueous metal hydroxide solution is an aqueous solution obtained by dissolving a metal hydroxide in water selected from ion-exchanged water, pure water, or distilled water.
[9]
In the method for producing a roughened metal member according to any one of [1] to [8] above,
The manufacturing method of the surface roughening metal member whose temperature of the said metal hydroxide aqueous solution in the process roughened by the said metal hydroxide aqueous solution is 40 to 90 degreeC.
[10]
In the method for producing a roughened metal member according to any one of [1] to [9],
The manufacturing method of the surface roughening metal member whose hydrogen ion concentration index (pH) in 25 degreeC of the said metal hydroxide aqueous solution is 6.0 or more and 8.0 or less.
[11]
A step (A) of producing a surface roughened metal member by the method for producing a surface roughened metal member according to any one of [1] to [10];
A thermoplastic resin member made of a thermoplastic resin or a resin composition containing the thermoplastic resin is molded so as to contact the surface of the joint portion of the surface roughened metal member, and the surface roughened metal member and the heat A step (B) of joining the plastic resin member;
The manufacturing method of the metal / resin composite structure containing this.
[12]
In the method for producing a metal / resin composite structure according to [11] above,
The above thermoplastic resin is polyolefin resin, polyester resin, polyamide resin, polyphenylene sulfide resin, polycarbonate resin, polyether ether ketone resin, polyether ketone resin, polyimide resin, polyether sulfone resin, polystyrene resin, polyacrylonitrile resin. , A styrene-acrylonitrile copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, a (meth) acrylic resin, and a metal / resin composite structure containing one or more selected from polyacetal resins.

  ADVANTAGE OF THE INVENTION According to this invention, the metal member which can suppress the dispersion | variation in the joint strength of a metal member and a resin member can be provided.

It is the external view which showed typically an example of the structure of the metal / resin composite structure which concerns on this embodiment. It is the block diagram which showed typically an example of the process which manufactures the metal / resin composite structure which concerns on this embodiment.

  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. In addition, "A-B" which shows the numerical range in a sentence represents A or more and B or less unless there is particular notice.

FIG. 1 is an external view schematically showing an example of the structure of the metal / resin composite structure 106 according to the present embodiment.
The method of manufacturing the surface roughened metal member 103 according to the present embodiment includes joining the thermoplastic resin member 105 composed of the thermoplastic resin (P1) or the resin composition (P2) containing the thermoplastic resin (P1). It is a manufacturing method for manufacturing the surface roughening metal member 103 used for this, Comprising: The process of roughening at least the junction surface 104 with the thermoplastic resin member 105 of a metal member with a metal hydroxide aqueous solution is included. .

By roughening the joint surface 104 of the metal member with the thermoplastic resin member 105 in contact with the metal hydroxide aqueous solution, a metal member that can suppress variation in the joint strength between the metal member and the resin member is obtained. The reason is not clear, but the following reasons are possible.
First, by performing a metal hydroxide aqueous solution treatment, the surface of the metal member is dissolved, and then the hydroxide is precipitated and the surface roughened metal member 103 and the thermoplastic resin member 105 are formed on the joint surface 104 of the metal member. A fine concavo-convex structure constituted by a hydroxyl group-containing film capable of effectively expressing the anchor effect between the two is formed. Here, since the metal hydroxide is dissolved in the metal hydroxide aqueous solution, when the metal hydroxide aqueous solution is used as the roughening treatment solution, the dissolution of the surface of the metal member and the water are higher than when warm water is used. It is considered that the formation of the fine concavo-convex structure occurs more uniformly and with good reproducibility because the oxide precipitates earlier. As a result, it is considered that variation in bonding strength between the metal member and the resin member can be suppressed.

  Hereinafter, the thermoplastic resin member 105, the method of manufacturing the surface roughened metal member 103, and the method of manufacturing the metal / resin composite structure 106 will be described in this order.

[Thermoplastic resin member]
Hereinafter, the thermoplastic resin member 105 according to the present embodiment will be described.
The thermoplastic resin member 105 is made of a thermoplastic resin (P1) or a resin composition (P2) containing a thermoplastic resin (P1). The resin composition (P2) includes a thermoplastic resin (P1) as a resin component and, if necessary, a filler (B). Furthermore, the resin composition (P2) contains other compounding agents as necessary.

(Thermoplastic resin (P1))
Although it does not specifically limit as a thermoplastic resin (P1), For example, (meth) acrylic-type resin, such as polyolefin resin and poly (meth) acrylic acid methyl resin, polystyrene resin, polyvinyl alcohol-polyvinyl chloride copolymer resin, Aromatic polyethers such as polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl formal resin, polymethylpentene resin, maleic anhydride-styrene copolymer resin, polycarbonate resin, polyphenylene ether resin, polyether ether ketone resin, polyether ketone resin Ketone, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, polyetherimide resin, styrene elastomer, polyolefin elastomer, polyurethane elastomer, poly Steal elastomer, polyamide elastomer, ionomer, aminopolyacrylamide resin, isobutylene maleic anhydride copolymer, ABS, ACS, AES, AS, ASA, MBS, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate Vinyl chloride graft polymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, carboxyvinyl polymer, ketone resin, amorphous copolyester resin, norbornene resin, fluoroplastic, polytetra Fluoroethylene resin, fluorinated ethylene polypropylene resin, PFA, polychlorofluoroethylene resin, ethylenetetrafluoroethylene copolymer, polyfluoride Vinylidene resin, polyvinyl fluoride resin, tetrafluoroethylene-perfluoroalkyl vinyl ether resin, polyarylate resin, thermoplastic polyimide resin, polyvinylidene chloride resin, polyvinyl chloride resin, polyvinyl acetate resin, polysulfone resin, polyparamethylstyrene resin , Polyallylamine resin, polyvinyl ether resin, polyphenylene oxide resin, polyphenylene sulfide (PPS) resin, polymethylpentene resin, oligoester acrylate, xylene resin, maleic acid resin, polyhydroxybutyrate resin, polysulfone resin, polylactic acid resin, poly Glutamic acid resin, polycaprolactone resin, polyethersulfone resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer resin, polyaceter Resin. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more types.

  Among these, as the thermoplastic resin (P1), from the viewpoint that the effect of improving the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105 can be obtained more effectively, a polyolefin resin or a polyester resin. , Polyamide resin, polyphenylene sulfide resin, polycarbonate resin, polyether ether ketone resin, polyether ketone resin, polyimide resin, polyether sulfone resin, polystyrene resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene- One or two or more thermoplastic resins selected from styrene copolymer resins, (meth) acrylic resins, and polyacetal resins are preferably used.

As the polyolefin-based resin, a polymer obtained by polymerizing olefin can be used without any particular limitation.
Examples of the olefin constituting the polyolefin-based resin include ethylene, α-olefin, and cyclic olefin.

  Examples of the α-olefin include linear or branched α-olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. More specifically, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-octene, Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like can be mentioned.

  As said cyclic olefin, a C3-C30 cyclic olefin is mentioned, Preferably it is C3-C20. More specifically, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene and the like.

  As the olefin constituting the polyolefin resin, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1- Examples include pentene. Of these, ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene are more preferable, and ethylene or propylene is more preferable.

  The polyolefin resin may be obtained by polymerizing the above-mentioned olefin alone, or may be obtained by random copolymerization, block copolymerization, or graft copolymerization in combination of two or more. .

  The polyolefin resin may be a linear resin or a resin having a branched structure.

  Examples of the polyester resin include aliphatic polyesters such as polylactic acid, polyglycolic acid, polycaprolactone, and polyethylene succinate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT), and polycyclohexylenedimethylene terephthalate (PCT). ) And the like.

  Examples of the polyamide resins include ring-opening polymerization aliphatic polyamides such as PA6 and PA12; polycondensation polyamides such as PA66, PA46, PA610, PA612, and PA11; MXD6, PA6T, PA9T, PA6T / 66, PA6T / 6. Semi-aromatic polyamides such as amorphous PA; polyaromatic polyamides such as poly (p-phenylene terephthalamide), poly (m-phenylene terephthalamide), poly (m-phenylene isophthalamide), amide elastomers, etc. It is done.

(Filler (B))
The resin composition (P2) is used from the viewpoints of adjusting the difference in coefficient of linear expansion between the surface roughened metal member 103 and the thermoplastic resin member 105, improving the mechanical strength of the thermoplastic resin member 105, and improving heat cycle characteristics. The filler (B) may further be included.

  As the filler (B), for example, organic fibers such as glass fibers, carbon fibers, metal fibers, and aramid fibers, carbon particles, clay, talc, silica, minerals, calcium carbonate, magnesium carbonate, and cellulose fibers are used. Or you can choose two or more. Among these, Preferably, they are 1 type, or 2 or more types selected from glass fiber, carbon fiber, talc, and a mineral.

  The shape of the filler (B) is not particularly limited, and may be any shape such as a fiber shape, a particle shape, or a plate shape.

  When the thermoplastic resin member 105 contains the filler (B), the content is usually 5% by mass or more and 95% by mass or less, preferably 10% by mass or more when the entire thermoplastic resin member 105 is 100% by mass. It is 90 mass% or less, More preferably, it is 20 mass% or more and 80 mass% or less.

  The filler (B) has an effect of controlling the linear expansion coefficient of the thermoplastic resin member 105 in addition to the effect of increasing the rigidity of the thermoplastic resin member 105. In particular, in the case of the composite of the surface roughened metal member 103 and the thermoplastic resin member 105 of the present embodiment, the temperature dependence of the shape stability differs greatly between the surface roughened metal member 103 and the thermoplastic resin member 105. In many cases, the composite is likely to be distorted when a large temperature change occurs. When the thermoplastic resin member 105 contains the filler (B), this distortion can be reduced. Moreover, when content of the said filler (B) exists in the said range, reduction of toughness can be suppressed.

In the present embodiment, the filler (B) is preferably a fibrous filler, more preferably glass fiber and carbon fiber, and particularly preferably glass fiber.
Thereby, since shrinkage | contraction of the thermoplastic resin member 105 after shaping | molding can be suppressed, joining of the surface roughening metal member 103 and the thermoplastic resin member 105 can be made stronger.

(Other ingredients)
The resin composition (P2) may contain other compounding agents for the purpose of imparting individual functions.
Examples of the compounding agents include heat stabilizers, antioxidants, pigments, weathering agents, flame retardants, plasticizers, dispersants, lubricants, mold release agents, antistatic agents, and impact modifiers.

(Production method of resin composition (P2))
The manufacturing method of a resin composition (P2) is not specifically limited, Generally, it can manufacture by a well-known method. For example, the following method is mentioned. First, the thermoplastic resin (P1), the filler (B) as necessary, and the other compounding agents as needed, a Banbury mixer, a single screw extruder, a twin screw extruder, a high speed The resin composition (P2) is obtained by mixing or melt-mixing using a mixing device such as a twin-screw extruder.

[Production Method of Surface Roughened Metal Member]
Next, a method for manufacturing the surface roughened metal member 103 will be described.
Hereinafter, an example of the manufacturing method of the surface roughening metal member 103 is shown. However, the manufacturing method of the surface roughening metal member 103 which concerns on this embodiment is not limited to the following examples.

  The method of manufacturing the surface roughened metal member 103 according to the present embodiment includes joining the thermoplastic resin member 105 composed of the thermoplastic resin (P1) or the resin composition (P2) containing the thermoplastic resin (P1). It is a manufacturing method for manufacturing the surface roughening metal member 103 used for this, Comprising: The process of roughening at least the junction surface 104 with the thermoplastic resin member 105 of a metal member with a metal hydroxide aqueous solution is included. .

Although the metal material which comprises the surface roughening metal member 103 is not specifically limited, For example, iron, steel materials, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, zinc, zinc alloy, tin, tin alloy And titanium and titanium alloys. Among these, aluminum, aluminum alloy, magnesium, magnesium alloy, zinc, zinc alloy, tin and tin alloy are preferable. These may be used alone or in combination of two or more.
Among these, aluminum (aluminum simple substance) and aluminum alloy are preferable from the viewpoint of light weight and high strength, and aluminum alloy is more preferable.
Examples of the aluminum alloy include alloy alloys 1050, 1100, 2014, 2024, 3003, 5052, 6061, 6063, and 7075 as defined in JIS H4000, casting alloys such as AC5A and AC4C, and die castings such as ADC12. Alloys are preferably used.

Moreover, it is preferable that the metal element which comprises a metal member, and the metal element which comprises a metal hydroxide aqueous solution are the same metal elements. By doing so, it is possible to suppress the entry of different kinds of metal elements into the fine concavo-convex structure. As a result, a finer fine concavo-convex structure is formed, and the surface roughened metal member 103 in the metal / resin composite structure 106 The joining force with the thermoplastic resin member 105 can be improved.
That is, when at least one metal material selected from aluminum (aluminum alone) and an aluminum alloy is used as the metal material constituting the surface roughened metal member 103, an aluminum hydroxide aqueous solution is used as the metal hydroxide aqueous solution. It is preferable.

The shape of the surface roughened metal member 103 is not particularly limited as long as it can be joined to the thermoplastic resin member 105. For example, the surface roughened metal member 103 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.
Further, the shape of the joint surface 104 to be joined to the thermoplastic resin member 105 is not particularly limited, and examples thereof include a flat surface and a curved surface.

  The surface roughened metal member 103 is processed into a predetermined shape as described above by metal removal such as cutting, plastic working with a press, punching, cutting, polishing, electric discharge machining, etc. Those made of are preferred. In short, it is preferable to use a material processed into a necessary shape by various processing methods.

(0) Pretreatment step First, before the step (1) of roughening with a metal hydroxide aqueous solution to be described later, at least the joint surface of the metal member is pretreated, and the oil and fat adhered to the surface of the metal member It is also preferable to remove the oxide film.
Examples of such pretreatment include physical treatment such as blast treatment and knurling; laser treatment such as laser scanning; cleaning treatment with an erodible aqueous solution or an erodible suspension. Among these methods, a washing treatment using an acidic aqueous solution and / or a basic aqueous solution as the erodible aqueous solution is preferably employed.

The washing treatment with the acidic aqueous solution and / or the basic aqueous solution can be performed, for example, by the following procedure.
First, a metal member is immersed in a commercially available aqueous solution of a degreasing agent for metal members, for example, at 30 to 80 ° C. for 1 to 10 minutes, and then the metal member is washed with water.
Subsequently, the metal member is immersed in an acidic aqueous solution having a concentration of 0.1 to 5% by mass, for example, at 30 to 80 ° C. for 0.1 to 10 minutes, and then the metal member is washed with water. The purpose of using the acidic aqueous solution is mainly to remove the oxide film. The aqueous solution is not particularly limited as long as it is an acidic aqueous solution suitable for this purpose.
Next, the metal member is immersed in a basic aqueous solution having a concentration of 0.1 to 3% by mass, for example, at 30 to 80 ° C. for 1 to 10 minutes, and then the metal member is washed with water. Bases used in the basic aqueous solution include hydroxides of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and soda ash (Na ₂ CO ₃ , anhydrous sodium carbonate) which is an inexpensive material containing these hydroxides. Etc. Further, alkaline earth metal hydroxides (Ca, Sr, Ba, Ra) can also be used. By immersing in the basic aqueous solution, the surface of the metal member dissolves as ions while releasing hydrogen, and the surface of the metal member becomes a fine etched surface.
Next, the metal member is immersed in an acidic aqueous solution having a concentration of 0.1 to 5% by mass, for example, at 30 to 80 ° C. for 0.1 to 10 minutes, and then the metal member is washed with water. The purpose of using an acidic aqueous solution is for smut removal and neutralization. If the base remains on the surface of the metal member, the pH adjustment of the treatment liquid in the roughening treatment step subsequent to this step may be complicated, and thus neutralization is necessary. Also, if the metal dissolved in the metal member is not completely dissolved in the previous step of the basic aqueous solution and is present in the vicinity of the surface as a hydroxide or other composition, it should be immersed in an acidic aqueous solution. You can also remove them. There is no particular limitation as long as it is an acidic aqueous solution suitable for this purpose, and examples thereof include nitric acid, hydrochloric acid, sulfuric acid, and hydrofluoric acid.

(1) Step of roughening with aqueous metal hydroxide solution Next, the joint surface 104 is roughened by bringing at least the joint surface 104 of the metal member into contact with the aqueous metal hydroxide solution. By bringing the metal member into contact with the aqueous metal hydroxide solution, the surface of the metal member is dissolved, and then the hydroxide is precipitated and the surface of the metal member is roughened into a fine concavo-convex structure.
In this embodiment, when the metal member is roughened using the metal hydroxide aqueous solution, the entire surface of the metal member may be roughened, and only the surface to which the thermoplastic resin member 105 is bonded is used. Partial roughening treatment may be performed.

Although the temperature of metal hydroxide aqueous solution is not specifically limited, It is preferable that it is 40 to 90 degreeC, 50 to 90 degreeC is more preferable, 60 to 90 degreeC is further more preferable.
The treatment time with the metal hydroxide aqueous solution is usually 5 seconds to 60 minutes, preferably 10 seconds to 30 minutes, more preferably 1 to 15 minutes.

  The water used for the metal hydroxide aqueous solution is preferably ion exchange water, pure water, or distilled water. Since such water has a small amount of dissolved ions, it is possible to prevent foreign metal elements from entering the fine uneven structure formed. As a result, when an aqueous solution obtained by dissolving a metal hydroxide in such water is used, a higher-quality hydroxyl group-containing film can be formed. Thereby, the joining strength between the metal member and the resin member can be further improved.

  In addition, the hydrogen ion concentration index (pH) at 25 ° C. of the aqueous metal hydroxide solution is preferably in the range of 6.0 or more and 8.0 or less, and 6.50 or more and 7 or less, from the viewpoint of forming a higher-quality hydroxyl group-containing film. A range of .5 or less is more preferable.

  The concentration of the aqueous metal hydroxide solution is (0. 0 when the saturation concentration of the aqueous metal hydroxide solution is Z mol / L from the viewpoint of further suppressing variation in the bonding strength between the metal member and the resin member. 1 × Z) mol / L or more (1.0 × Z) mol / L or less is preferable, and (0.5 × Z) mol / L or more (1.0 × Z) mol / L or less. Is more preferable, and (0.8 × Z) mol / L or more and (1.0 × Z) mol / L or less is more preferable.

As a method of roughening the metal member with the metal hydroxide aqueous solution, a method of immersing the metal member in the metal hydroxide aqueous solution, a method of spraying the metal hydroxide aqueous solution onto the metal member, a metal hydroxide aqueous solution The method etc. which spray vapor | steam on a metal member are mentioned.
By roughening the metal member with a metal hydroxide aqueous solution, a microporous hydroxyl group-containing film having a thickness of about 5 nm to 100 nm is formed on the surface of the metal. The treatment time can be shortened as the temperature of the metal hydroxide aqueous solution is higher, and the treatment time can be lengthened as the temperature of the metal hydroxide aqueous solution is lowered so as to obtain a desired film thickness.
Here, the hydroxyl group-containing film can be formed by subjecting a metal surface to a metal hydroxide aqueous solution treatment, and can also be referred to as a hydroxide film and / or a hydrated film, for example, a metal hydroxide and / or water. It is a film containing a hydrated oxide.

  After the metal hydroxide aqueous solution treatment step (1), drying is performed as necessary.

[Method for producing metal / resin composite structure]
Next, a method for manufacturing the metal / resin composite structure 106 according to this embodiment will be described.
Although the manufacturing method of the metal / resin composite structure 106 is not particularly limited, it preferably includes at least the following steps (A) and (B), and includes the following step (C) as necessary.
(A) The process of producing the surface roughening metal member 103 by the manufacturing method of the surface roughening metal member 103 which concerns on this embodiment mentioned above (B) A step of molding the thermoplastic resin member 105 made of the resin composition (P2) containing the plastic resin (P1) or the thermoplastic resin (P1), and bonding the surface roughened metal member 103 and the thermoplastic resin member 105. C) Step of forming an oxide film on the surface of the metal member constituting the obtained metal / resin composite structure 106 after the step (B). That is, the thermoplastic resin (P1) is applied to the surface roughened metal member 103. ) Or the resin composition (P2) while being molded so as to have a desired shape of the thermoplastic resin member 105, the metal / resin composite structure 106 according to the present embodiment is obtained. It is. The step (A) has been described in the method for manufacturing the roughened metal member 103 according to the above-described embodiment, and thus the description thereof is omitted here.

  The molding method of the thermoplastic resin member 105 includes injection molding, extrusion molding, heat press molding, compression molding, transfer molding, casting molding, laser welding molding, reaction injection molding (RIM molding), and rim molding (LIM molding). A resin molding method such as thermal spray molding can be employed.

  Moreover, when manufacturing the composite body which consists of a metal member-thermoplastic resin film which coat | covered the thermoplastic resin (P1) or the resin composition (P2) film | membrane to the surface roughening metal member 103, a thermoplastic resin (P1) or A coating method in which the resin varnish is prepared by dissolving or dispersing the resin composition (P2) in a solvent and the resin varnish is applied to the surface roughened metal member 103, and other various coating methods can be employed. Examples of other coating methods include baking coating, electrodeposition coating, electrostatic coating, powder coating, and ultraviolet curable coating.

Among these, as a molding method of the thermoplastic resin member 105, an injection molding method is preferable. Specifically, the surface-roughened metal member 103 is inserted into the cavity portion of the injection mold, and the thermoplastic resin (P1). Or it is preferable to manufacture by the injection molding method which injects a resin composition (P2) to a metal mold | die. Specifically, a method including the following steps (i) to (iii) is preferable.
(I) Step of preparing thermoplastic resin (P1) or step of manufacturing resin composition (P2) (ii) Step of placing surface roughened metal member 103 in a mold for injection molding (iii) Heat A step of injection-molding the thermoplastic resin (P1) or the resin composition (P2) into the mold so as to be in contact with at least a part of the surface roughened metal member 103, and molding the thermoplastic resin member 105. The process will be described.

  (I) About the process of manufacturing resin composition (P2), it is as the manufacturing method of the above-mentioned resin composition (P2).

  Next, an injection molding method according to steps (ii) and (iii) will be described.

  First, a mold for injection molding is prepared, the mold is opened, and the surface roughened metal member 103 is installed in the cavity (space). Thereafter, the mold is closed and the thermoplastic resin (P1) or resin is placed in the mold so that at least a part of the resin composition (P2) is in contact with the surface of the surface roughened metal member 103 on which the fine uneven structure is formed. The composition (P2) is injected and solidified. Thereafter, the metal / resin composite structure 106 can be obtained by opening the mold and releasing the mold.

Further, in combination with the injection molding by the above steps (ii) to (iii), injection foam molding or high-speed heat cycle molding (RHCM, heat & cool molding) for rapidly heating and cooling the mold may be used in combination. .
Injection foaming methods include adding a chemical foaming agent to the resin, injecting nitrogen gas or carbon dioxide directly into the cylinder of the injection molding machine, or injecting nitrogen gas or carbon dioxide in a supercritical state. Although there is a MuCell injection foam molding method in which it is injected into a cylinder part of a molding machine, the metal / resin composite structure 106 in which the resin member is a foam can be obtained by any method. In any method, a counter pressure can be used as a mold control method, or a core back can be used depending on the shape of a molded product.
High-speed heat cycle molding can be carried out by connecting a rapid heating / cooling device to a mold. The rapid heating / cooling apparatus may be a generally used system. As a heating method, any one of a steam type, a pressurized hot water type, a hot water type, a hot oil type, an electric heater type, an electromagnetic induction overheating type, or a combination of them may be used.
As a cooling method, any one of a cold water type and a cold oil type or a combination thereof may be used. As conditions for the high-speed heat cycle molding method, for example, the injection mold is heated to a temperature of 100 ° C. or more and 250 ° C. or less, and after the injection of the thermoplastic resin (P1) or the resin composition (P2) is completed, It is desirable to cool the injection mold.
The temperature at which the mold is heated varies depending on the thermoplastic resin (P1) constituting the thermoplastic resin (P1) or the resin composition (P2), and is a crystalline resin having a melting point of less than 200 ° C. 100 ° C. or higher and 150 ° C. or lower is preferable, and 140 ° C. or higher and 250 ° C. or lower is desirable for a crystalline resin having a melting point of 200 ° C. About an amorphous resin, 50 to 250 degreeC is desirable and 100 to 180 degreeC is more desirable.

Next, a method for forming a coating film on the surface roughened metal member 103 will be described.
As a method of forming a coating film on the surface roughened metal member 103, a conventionally used coating film forming method can be used without limitation.

  For example, the coating can be performed by applying the various coating materials to the surface of the surface roughened metal member 103 by a method such as spray coating such as air spray or airless spray, dip coating, brush coating, roller coating, or coater coating.

  In the metal / resin composite structure 106 according to this embodiment, the thermoplastic resin (P1) or the resin composition (P2) constituting the thermoplastic resin member 105 is formed on the surface 110 of the surface roughened metal member 103. It is obtained by entering the fine concavo-convex structure and joining the surface roughened metal member 103 and the thermoplastic resin member 105 to form a metal-resin interface.

That is, since the surface 110 of the surface roughened metal member 103 has a fine uneven structure suitable for improving the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105, an adhesive is used. Without this, it becomes possible to ensure the bondability between the surface roughened metal member 103 and the thermoplastic resin member 105.
Specifically, when the thermoplastic resin (P1) or the resin composition (P2) enters the fine concavo-convex structure on the surface 110 of the surface roughened metal member 103, the surface roughened metal member 103 and the thermoplastic resin. A physical resistance force (anchor effect) is effectively expressed between the member 105 and the surface roughened metal member 103, which is usually difficult to join, and the thermoplastic resin (P1) or the resin composition (P2). It is considered that the thermoplastic resin member 105 thus configured can be firmly bonded.

  The thus obtained metal / resin composite structure 106 can also prevent moisture and moisture from entering the interface between the surface roughened metal member 103 and the thermoplastic resin member 105. That is, the air tightness and water tightness at the adhesion interface of the metal / resin composite structure 106 can be improved.

In the manufacturing method of the metal / resin composite structure 106 according to the present embodiment, a step of forming an oxide film on the surface of the metal member constituting the obtained metal / resin composite structure 106 is further performed after the step (B). You may do it. In this case, an oxide film is formed on the surface of the roughened metal member 103 other than the joint portion with the thermoplastic resin member 105. Thereby, the corrosion resistance, wear resistance, scratch resistance and the like of the metal / resin composite structure 106 can be improved.
Although it does not specifically limit as a method of forming an oxide film, For example, anodic oxide film processing, such as alumite processing, is mentioned. As an anodic oxidation solution used in the anodic oxide film treatment, for example, sulfuric acid, oxalic acid, boric acid, chromic acid, or the like can be used.

[Use of metal / resin composite structure]
Since the metal / resin composite structure 106 according to the present embodiment has high productivity and high degree of freedom in shape control, it can be developed for various applications.
Furthermore, since the metal / resin composite structure 106 according to the present embodiment exhibits high airtightness and watertightness, it is preferably used for applications according to these characteristics.

  For example, use for household goods such as structural parts for vehicles, on-vehicle equipment, housing for electronic equipment, housing for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, furniture, kitchenware, etc. , Medical equipment, building material parts, other structural parts and exterior parts.

  More specifically, the following parts are designed so that the metal supports a portion where the strength is insufficient with the resin alone. For vehicles, instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, radiators, oil pans, steering wheels, An ECU box, an electrical component, etc. are mentioned. Examples of building materials and furniture include glass window frames, handrails, curtain rails, chests, drawers, closets, bookcases, desks, chairs, and the like. Examples of precision electronic components include connectors, relays, and gears. Moreover, a transport container, a suitcase, a trunk, etc. are mentioned as a transport container.

  In addition, a combination of the high thermal conductivity of the surface roughened metal member 103 and the adiabatic property of the thermoplastic resin member 105 is used for parts used in equipment for optimally designing heat management, for example, various home appliances. be able to. Specifically, household appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, personal computers, mobile phones, smartphones, digital cameras, tablets Electronic information devices such as type PCs, portable music players, portable game machines, chargers, and batteries.

  For these, since the surface area is increased by roughening the surface of the metal member, the contact area between the surface roughened metal member 103 and the thermoplastic resin member 105 is increased, and the thermal resistance of the contact interface is reduced. It comes from being able to.

  Other applications include toys, sports equipment, shoes, sandals, bags, forks and knives, spoons, dishes such as dishes, ballpoint pens and mechanical pencils, files, binders and other stationery, frying pans and pans, kettles, frying, Examples include a ladle, a hole insulator, a whisk, a cooking tool such as a tongue, a lithium ion secondary battery component, a robot, and the like.

  As mentioned above, although the use of the metal / resin composite structure of this invention was described, these are the illustrations of the use of this invention, and can also be used for various uses other than the above.

  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.

  Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.

Note that FIGS. 1 and 2 are used as a common view of each embodiment.
FIG. 1 is an external view schematically showing an example of the structure of the metal / resin composite structure 106 of the surface roughened metal member 103 and the thermoplastic resin member 105.
FIG. 2 is a configuration diagram schematically showing an example of a process of manufacturing the metal / resin composite structure 106 of the surface roughened metal member 103 and the thermoplastic resin member 105. Specifically, a surface roughened metal member 103 which is processed into a predetermined shape and has a surface (surface treatment region) 104 having a fine concavo-convex structure formed on the surface is placed in an injection mold 102 and injected. The molding machine 101 injects the thermoplastic resin (P1) or the resin composition (P2) through the gate / runner 107, and the surface roughened metal member 103 and the thermoplastic resin member 105 on which the fine uneven structure is formed are integrated. The process for manufacturing the metal / resin composite structure 106 is schematically shown.

(Evaluation method of bonding strength)
Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, a dedicated jig is attached to the tensile tester, and at room temperature (23 ° C.), the distance between chucks is 60 mm and the tensile speed is 10 mm / min And measured. The joint strength (MPa) was obtained by dividing the breaking load (N) by the area of the metal / resin joint.

(Pretreatment of metal parts)
[Preparation Example 1]
An aluminum plate material (thickness: 1.6 mm) of alloy number 6063 defined in JIS H4000 was cut into a shape having a length of 45 mm and a width of 18 mm. Next, any 20 aluminum sheets were subjected to a surface treatment in accordance with the method described in Experimental Example 1 of JP2012-066383A.
That is, a commercially available aluminum alloy degreasing agent NE-6 (manufactured by Meltex Co.) and water were charged into a first 1 L beaker, and 600 ml of an aqueous solution having a degreasing agent concentration of 7.5% by mass at 60 ° C. did. 20 aluminum plate members were immersed in this for 7 minutes so as not to overlap. After soaking, it was washed thoroughly with water.
Subsequently, 600 ml of a 1 mass% hydrochloric acid aqueous solution adjusted to 40 ° C. was prepared in a second 1 L beaker and immersed in the aluminum plate for 20 minutes so as not to overlap. After soaking, it was washed thoroughly with water. Next, 600 ml of a 1.5% strength by weight sodium hydroxide aqueous solution adjusted to 40 ° C. was prepared in a third 1 L beaker, and the 20 washed aluminum plates were immersed for 4 minutes so as not to overlap. After soaking, it was washed thoroughly with water. Next, 600 ml of a 3 mass% nitric acid aqueous solution adjusted to 40 ° C. was prepared in a fourth 1 L beaker, and 20 aluminum sheets were immersed in the beaker for 1 minute so as not to overlap. After soaking, it was washed thoroughly with water. A pretreated aluminum sheet was obtained by the above procedure.

[Example 1]
The pretreated aluminum plate material prepared in Preparation Example 1 was placed in a 70 ° C. aqueous aluminum hydroxide solution (solvent: ion-exchanged water, pH: 6.9, aluminum hydroxide concentration: 3.8 × 10 ⁻⁶ mol / L) for 4 minutes. Soaked. The obtained metal member is referred to as metal member 1.
A small dumbbell metal insert mold 102 was mounted on J85AD110H manufactured by Nippon Steel Works, and metal member 1 (103) was installed in the mold 102. Next, as a thermoplastic resin (P1) in the mold 102, a commercially available PBT resin (manufactured by Changchun Co., Ltd.) is used. Injection molding was performed under conditions of a time of 10 seconds to obtain a metal / resin composite structure 106.
A total of four metal / resin composite structures 106 were produced by the same method.
The bonding strength of each of the obtained metal / resin composite structures 106 was measured. Table 1 shows the evaluation results of the obtained bonding strength.

[Example 2]
The pretreated aluminum plate material prepared in Preparation Example 1 was placed in a 60 ° C. aqueous aluminum hydroxide solution (solvent: ion-exchanged water, pH: 6.8, aluminum hydroxide concentration: 3.8 × 10 ⁻⁶ mol / L) for 6 minutes. Soaked. The obtained metal member is referred to as metal member 2.
In Example 1, a metal / resin composite structure 106 was obtained by performing injection molding in the same manner as in Example 1 except that the metal member 2 was used instead of the metal member 1. Further, a total of four metal / resin composite structures 106 were produced by the same method.
The bonding strength of each of the obtained metal / resin composite structures 106 was measured. Table 1 shows the evaluation results of the obtained bonding strength.

[Comparative Example 1]
The pretreated aluminum plate material prepared in Preparation Example 1 was immersed in ion exchange water at 70 ° C. for 4 minutes. The obtained metal member is referred to as a metal member 3.
In Example 1, a metal / resin composite structure 106 was obtained by performing injection molding in the same manner as in Example 1 except that the metal member 3 was used instead of the metal member 1. Further, a total of four metal / resin composite structures 106 were produced by the same method.
The bonding strength of each of the obtained metal / resin composite structures 106 was measured. Table 1 shows the evaluation results of the obtained bonding strength.

[Comparative Example 2]
The pretreated aluminum plate material prepared in Preparation Example 1 was immersed in ion exchange water at 60 ° C. for 6 minutes. The obtained metal member is referred to as a metal member 4.
In Example 1, a metal / resin composite structure 106 was obtained by performing injection molding in the same manner as in Example 1 except that the metal member 4 was used instead of the metal member 1. Further, a total of four metal / resin composite structures 106 were produced by the same method.
The bonding strength of each of the obtained metal / resin composite structures 106 was measured. Table 1 shows the evaluation results of the obtained bonding strength.

101 Injection Molding Machine 102 Mold 103 Surface Roughened Metal Member 104 Joint Surface 105 Thermoplastic Resin Member 106 Metal / Resin Composite Structure 107 Gate / Runner 110 Surface of Surface Roughened Metal Member

Claims (12)

A production method for producing a surface roughened metal member used for joining with a thermoplastic resin or a thermoplastic resin member constituted by a resin composition containing the thermoplastic resin,
The manufacturing method of the surface roughening metal member including the process of roughening the joining part surface with the said thermoplastic resin member of a metal member at least by the metal hydroxide aqueous solution. In the manufacturing method of the surface roughening metal member of Claim 1,
The manufacturing method of the surface roughening metal member whose metal element which comprises the said metal member, and the metal element which comprises the said metal hydroxide aqueous solution are the same metal elements. In the manufacturing method of the surface roughening metal member of Claim 1 or 2,
The surface roughened metal member is one or two selected from iron, steel, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, zinc, zinc alloy, tin, tin alloy, titanium and titanium alloy. The manufacturing method of the surface roughening metal member which is comprised with the metal material more than a seed | species. In the manufacturing method of the surface roughening metal member of Claim 1 or 2,
The method for producing a surface roughened metal member, wherein the surface roughened metal member is composed of at least one metal material selected from aluminum and an aluminum alloy. In the manufacturing method of the surface roughening metal member of Claim 4,
The manufacturing method of the surface roughening metal member whose said metal hydroxide aqueous solution is aluminum hydroxide aqueous solution. In the manufacturing method of the surface roughening metal member as described in any one of Claims 1 thru | or 5,
When the saturation concentration of the aqueous metal hydroxide solution is Z mol / L,
The manufacturing method of the surface roughening metal member whose density | concentration of the said metal hydroxide aqueous solution is (0.1 * Z) mol / L or more and (1.0 * Z) mol / L or less. In the manufacturing method of the surface roughening metal member as described in any one of Claims 1 thru | or 6,
The manufacturing method of the surface roughening metal member which performs the process roughened by the said metal hydroxide aqueous solution after the process of wash | cleaning the said junction part surface of the said metal member at least with acidic aqueous solution and / or basic aqueous solution. In the manufacturing method of the surface roughening metal member as described in any one of Claims 1 thru | or 7,
A method for producing a surface-roughened metal member, wherein the aqueous metal hydroxide solution is an aqueous solution obtained by dissolving a metal hydroxide in water selected from ion-exchanged water, pure water, or distilled water. In the manufacturing method of the surface roughening metal member according to any one of claims 1 to 8,
The manufacturing method of the surface roughening metal member whose temperature of the said metal hydroxide aqueous solution in the process roughened by the said metal hydroxide aqueous solution is 40 degreeC or more and 90 degrees C or less. In the manufacturing method of the surface roughening metal member according to any one of claims 1 to 9,
The manufacturing method of the surface roughening metal member whose hydrogen ion concentration index (pH) in 25 degreeC of the said metal hydroxide aqueous solution is 6.0 or more and 8.0 or less. A step (A) of producing a surface roughened metal member by the method for producing a surface roughened metal member according to any one of claims 1 to 10,
A thermoplastic resin member composed of a thermoplastic resin or a resin composition containing the thermoplastic resin is molded so as to contact the surface of the joint portion of the surface roughened metal member, and the surface roughened metal member and the heat A step (B) of joining the plastic resin member;
The manufacturing method of the metal / resin composite structure containing this. In the manufacturing method of the metal / resin composite structure of Claim 11,
The thermoplastic resin is polyolefin resin, polyester resin, polyamide resin, polyphenylene sulfide resin, polycarbonate resin, polyether ether ketone resin, polyether ketone resin, polyimide resin, polyether sulfone resin, polystyrene resin, polyacrylonitrile resin. , A styrene-acrylonitrile copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, a (meth) acrylic resin, and a metal / resin composite structure containing one or more selected from polyacetal resins.

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