JP2017218614A - 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 reduction in a bond strength of a metal member after oxide film formation treatment 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 (1) of roughening at least a joint portion surface 104 of the metal member with the thermoplastic resin member 105, using a roughening treatment aqueous solution (Z) containing a compound (A) having a nitrogen atom in the molecule, and a step (2) of bringing at least the joint portion surface 104 of the metal member into contact with hot water after the step (1).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 Are being studied (for example, Patent Documents 1 to 6).

  Patent Documents 1 to 6 disclose a technique in which, for example, a metal member is immersed in a hydrazine aqueous solution to form a recess on the surface, and then a thermoplastic resin is bonded to the treated surface.

JP 2004-216425 A JP 2009-6721 A International Publication No. 2003/064150 Pamphlet JP 2010-06496 A JP 2012-066383 A JP 2005-119005 A

  According to the study by the present inventors, the metal / resin composite structure obtained by the methods disclosed in Patent Documents 1 to 6 is a metal in order to improve corrosion resistance, wear resistance, scratch resistance, and the like. / It has been clarified that when the treatment for forming an oxide film on the surface of the metal member in the resin composite structure is performed, the bonding strength between the metal member and the resin member decreases.

  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 fall of the joint strength of the metal member and resin member after an oxide film formation process.

  The present inventors diligently studied to obtain a metal member that can suppress a decrease in bonding strength between the metal member and the resin member after the oxide film formation treatment. As a result, after the roughening treatment was performed with the roughening aqueous solution (Z) containing the compound (A) having a nitrogen atom in the molecule, the resulting roughened surface was treated with warm water, thereby forming an oxide film. The present inventors have found that a metal member that can suppress a decrease in the bonding strength between the metal member and the resin member after the formation treatment is obtained, and have reached the present invention.

  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.

（上記式（１）中、Ｒは水素原子または炭素数１以上１０以下の炭化水素基である）

（上記式（２）中、Ｒ^１〜Ｒ^３は、それぞれ独立して水素原子、アルキル基、または１つのヒドロキシ基を有する脂肪族飽和炭化水素基であり、Ｒ^１〜Ｒ^３の少なくとも１つが、１つのヒドロキシ基を有する脂肪族飽和炭化水素基である）
［６］
上記［５］に記載の表面粗化金属部材の製造方法において、
上記モルホリン系化合物がＮ−エチルモルホリン、Ｎ−メチルモルホリンおよびＮ−ｎ−プロピルモルホリンから選択される少なくとも一種を含む表面粗化金属部材の製造方法。
［７］
上記［５］に記載の表面粗化金属部材の製造方法において、
上記アルカノールアミン系化合物がトリエタノールアミンおよびＮ，Ｎ−ジエチルエタノールアミンから選択される少なくとも一種を含む表面粗化金属部材の製造方法。
［８］
上記［１］乃至［４］のいずれか一つに記載の表面粗化金属部材の製造方法において、
上記化合物（Ａ）がアンモニウム塩（Ａ２）を含み、
上記アンモニウム塩（Ａ２）が、アンモニア、塩化アンモニウムおよび硝酸アンモニウムから選択される少なくとも一種を含む表面粗化金属部材の製造方法。
［９］
上記［１］乃至［８］のいずれか一つに記載の表面粗化金属部材の製造方法において、
上記温水が、イオン交換水、純水、または蒸留水である表面粗化金属部材の製造方法。
［１０］
上記［１］乃至［９］のいずれか一つに記載の表面粗化金属部材の製造方法において、
上記温水の温度が４０℃以上９０℃以下である表面粗化金属部材の製造方法。
［１１］
上記［１］乃至［１０］のいずれか一つに記載の表面粗化金属部材の製造方法において、
上記粗化処理水溶液（Ｚ）の２５℃における水素イオン濃度指数（ｐＨ）が９．０以上１１．０以下である表面粗化金属部材の製造方法。
［１２］
上記［１］乃至［１１］のいずれか一つに記載の表面粗化金属部材の製造方法により表面粗化金属部材を作製する工程（Ａ）と、
上記表面粗化金属部材の上記接合部表面に接するように、熱可塑性樹脂または上記熱可塑性樹脂を含む樹脂組成物により構成された熱可塑性樹脂部材を成形し、上記表面粗化金属部材と上記熱可塑性樹脂部材を接合させる工程（Ｂ）と、
を含む金属／樹脂複合構造体の製造方法。
［１３］
上記［１２］に記載の金属／樹脂複合構造体の製造方法において、
上記熱可塑性樹脂が、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリフェニレンサルファイド樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトン樹脂、ポリイミド樹脂、ポリエーテルスルホン樹脂、ポリスチレン樹脂、ポリアクリロニトリル樹脂、スチレン−アクリロニトリル共重合体樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂、（メタ）アクリル系樹脂、およびポリアセタール樹脂から選択される一種または二種以上を含む金属／樹脂複合構造体の製造方法。
［１４］
上記［１２］または［１３］に記載の金属／樹脂複合構造体の製造方法において、
上記工程（Ｂ）の後に、得られた金属／樹脂複合構造体を構成する金属部材の表面に酸化被膜を形成する工程（Ｃ）をさらに含む金属／樹脂複合構造体の製造方法。 [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,
A step (1) of roughening at least a surface of a joint portion of the metal member with the thermoplastic resin member with a roughening aqueous solution (Z) containing a compound (A) having a nitrogen atom in the molecule;
After the step (1), at least the step (2) of bringing the joint surface of the metal member into contact with warm water;
The manufacturing method of the surface roughening metal member containing this.
[2]
In the method for producing a surface roughened metal member according to [1] above,
The manufacturing method of the surface roughening metal member in which the said compound (A) contains 1 type, or 2 or more types selected from the amine (A1) which has an oxygen functional group in a molecule | numerator, ammonium salt (A2), and amine salt (A3).
[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 any one of [1] to [3],
The manufacturing method of the surface roughening metal member which performs the said process (1) after the process (0) which wash | cleans the said junction part surface of the said metal member at least with acidic aqueous solution and / or basic aqueous solution.
[5]
In the method for producing a surface roughened metal member according to any one of [1] to [4],
The compound (A) includes an amine (A1) having an oxygen functional group in the molecule,
Surface roughening wherein the amine (A1) having an oxygen functional group in the molecule contains at least one selected from a morpholine compound represented by the following formula (1) and an alkanolamine compound represented by the following formula (2): A method for producing a metal member.

(In the above formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

(In the above formula (2), R ^{1 to} R ³ are each independently an aliphatic saturated hydrocarbon group having a hydrogen atom, an alkyl group, or one hydroxy group, and at least one of R ^{1 to} R ³ is An aliphatic saturated hydrocarbon group having one hydroxy group)
[6]
In the method for producing a roughened metal member according to [5] above,
A method for producing a surface roughened metal member, wherein the morpholine-based compound contains at least one selected from N-ethylmorpholine, N-methylmorpholine, and Nn-propylmorpholine.
[7]
In the method for producing a roughened metal member according to [5] above,
A method for producing a surface-roughened metal member, wherein the alkanolamine-based compound contains at least one selected from triethanolamine and N, N-diethylethanolamine.
[8]
In the method for producing a surface roughened metal member according to any one of [1] to [4],
The compound (A) includes an ammonium salt (A2),
The manufacturing method of the surface roughening metal member in which the said ammonium salt (A2) contains at least 1 type selected from ammonia, ammonium chloride, and ammonium nitrate.
[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 said warm water is ion-exchange water, a pure water, or distilled water.
[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 temperature of the said warm water is 40 degreeC or more and 90 degrees C or less.
[11]
In the method for producing a roughened metal member according to any one of [1] to [10],
The manufacturing method of the surface roughening metal member whose hydrogen ion concentration index (pH) in 25 degreeC of the said roughening process aqueous solution (Z) is 9.0 or more and 11.0 or less.
[12]
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 [11];
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.
[13]
In the method for producing a metal / resin composite structure according to [12] 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.
[14]
In the method for producing a metal / resin composite structure according to [12] or [13] above,
A method for producing a metal / resin composite structure, further comprising a step (C) of forming an oxide film on the surface of the metal member constituting the obtained metal / resin composite structure after the step (B).

  ADVANTAGE OF THE INVENTION According to this invention, the metal member which can suppress the fall of the joint strength of the metal member and resin member after an oxide film formation process 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 compound (A) which has a nitrogen atom in a molecule | numerator at least in the junction surface 104 with the thermoplastic resin member 105 of a metal member. Step (1) for roughening with the aqueous solution for roughening treatment (Z) contained, and Step (2) for bringing at least the joint surface 104 of the metal member into contact with warm water after Step (1) are included.

By sequentially performing the above steps (1) and (2) on the joint surface 104 of the metal member with the thermoplastic resin member 105, the joint strength between the metal member and the resin member after the oxide film formation treatment is reduced. The reason for obtaining a metal member capable of suppressing the above is not clear, but the following reasons are conceivable.
First, it is considered that the above-described step (1) forms a fine concavo-convex structure capable of effectively expressing the anchor effect between the surface roughened metal member 103 and the thermoplastic resin member 105 on the joint surface 104 of the metal member. It is done. Moreover, it is thought by performing a process (2) that a hydroxyl-containing membrane | film | coat is formed in the fine concavo-convex structure surface formed by the process (1). And, by the synergistic effect of the hydroxyl group-containing film and the fine concavo-convex structure, the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105 in the metal / resin composite structure 106 after the oxide film formation treatment is improved. It is thought that it is possible to do.
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 compound (A) which has a nitrogen atom in a molecule | numerator at least in the junction surface 104 with the thermoplastic resin member 105 of a metal member. Step (1) for roughening with the aqueous solution for roughening treatment (Z) contained, and Step (2) for bringing at least the joint surface 104 of the metal member into contact with warm water after Step (1) are 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.

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 roughening aqueous solution (Z) to be described later, at least the surface of the joint portion of the metal member is pretreated and adhered to the surface of the metal member. It is preferable to remove the oil and fat and 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) Roughening process with roughening aqueous solution (Z) In this embodiment, a roughening process is performed by the roughening aqueous solution (Z) mentioned later. The roughening treatment aqueous solution (Z) in this embodiment is not only a fresh roughening treatment aqueous solution (which may be referred to as virgin liquid in the following description) that has not been immersed in the metal member, but also a metal member. It is defined as a term that also refers to an aqueous solution after being subjected to an immersion treatment (sometimes referred to as a recovered solution in the following description).

In the roughening treatment step (1), a roughening aqueous solution (Z) containing, for example, a compound (A) having a nitrogen atom in the molecule is applied to at least the joint surface 104 of the metal member with the thermoplastic resin member 105. By bringing them into contact with each other, the surface of the joint 104 is roughened.
In the present embodiment, the pH value of the aqueous solution for roughening treatment (Z) shows a high value in the virgin solution, and the pH value tends to gradually decrease as the recovered liquid has a large number of immersions of the metal member by repeating the roughening treatment. .
The hydrogen ion concentration index (pH) at 25 ° C. of the roughened aqueous solution (Z) is 9.0 or more and 11.0 from the viewpoint of further improving the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105. The following range is preferable, and the range of 9.2 to 10.9 is more preferable.

Further, from the viewpoint of more uniformly roughening the surface of the metal member, the content of the compound (A) having a nitrogen atom in the molecule in the roughening aqueous solution (Z) is 0.01% by mass or more and 20% by mass or less. Is preferable, 0.1 mass% or more and 12 mass% or less is more preferable, 0.5 mass% or more and 7 mass% or less is further more preferable, and 1 mass% or more and 6 mass% or less is further more preferable.
If content of the compound (A) which has a nitrogen atom in the said molecule | numerator 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 compound (A) having a nitrogen atom in the molecule is not more than the above upper limit value, the roughening rate can be more appropriately maintained, so that the surface roughened metal member 103 and the thermoplastic resin can be maintained. A suitable uniform roughening can be achieved by improving the bonding strength with the member 105.

Examples of the method for roughening using the aqueous solution for roughening treatment (Z) include treatment methods such as immersion and spraying. From the viewpoint of more uniformly roughening the surface of the metal member, the treatment temperature is usually 20 to 80 ° C., although it depends on the pH value of the roughening aqueous solution (Z) and the roughening treatment time. The treatment time at this time is usually about 1 to 15 minutes, preferably about 2 to 10 minutes.
In this embodiment, when the pH of the roughening aqueous solution (Z) is low, that is, when the concentration of the compound (A) having a nitrogen atom in the molecule in the roughening aqueous solution (Z) is low, the processing temperature is A method such as increasing the treatment time or extending the treatment time is taken. Conversely, when the pH of the aqueous solution (Z) is high, that is, when the concentration of the compound (A) is high, the treatment temperature is lowered or the treatment time is shortened. Is adopted.

By the roughening treatment using the roughening treatment aqueous solution (Z), the surface of the metal member is roughened into a fine concavo-convex structure.
In the present embodiment, when the metal member is roughened using the roughening aqueous solution (Z), the entire surface of the metal member may be roughened, and the thermoplastic resin member 105 is bonded. Only the surface may be partially roughened.

(Compound having a nitrogen atom in the molecule (A))
Hereinafter, the compound (A) having a nitrogen atom in the molecule that can be used in the present embodiment will be described.
As the compound (A) having a nitrogen atom in the molecule, hydrazine and an amine having an oxygen functional group in the molecule (A1) can be formed from the viewpoint of forming a bonding surface 104 that is superior in bonding strength with the thermoplastic resin member 105. ), An ammonium salt (A2) and an amine salt (A3), preferably one or two or more kinds selected from the above, excellent in safety, and excellent in bonding strength with the thermoplastic resin member 105 From the viewpoint of forming 104, it is preferable to include one or more selected from amine (A1), ammonium salt (A2) and amine salt (A3) having an oxygen functional group in the molecule.

・ Amine having oxygen functional group (A1)
The amine (A1) having an oxygen functional group is not particularly limited as long as it is an amine (A1) having an oxygen functional group such as an ether group, a hydroxyl group, an ester group, or a carboxyl group, but is excellent in safety and thermoplastic. From the viewpoint of being able to form a bonding portion surface 104 that is superior in bonding strength with the resin member 105, at least selected from a morpholine compound represented by the following formula (1) and an alkanolamine compound represented by the following formula (2). It is preferable to include one kind. Further, it is possible to obtain a uniform roughening suitable for improving the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105, and to obtain the metal / resin composite structure 106 with less variation in the bonding strength. From the viewpoint of being possible, an alkanolamine compound represented by the following formula (2) is particularly preferable.

（式（１）中、Ｒは水素原子または炭素数１以上１０以下の炭化水素基である）

（式（２）中、Ｒ^１〜Ｒ^３は、それぞれ独立して水素原子、アルキル基、または１つのヒドロキシ基を有する脂肪族飽和炭化水素基であり、Ｒ^１〜Ｒ^３の少なくとも１つが、１つのヒドロキシ基を有する脂肪族飽和炭化水素基である）

(In the formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

(In formula (2), R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group, or an aliphatic saturated hydrocarbon group having one hydroxy group, and at least one of R ^{1 to} R ³ is (It is an aliphatic saturated hydrocarbon group having one hydroxy group)

  Examples of the morpholine compound represented by the above formula (1) include morpholine, N-methylmorpholine, N-ethylmorpholine, Nn-propylmorpholine, N-isopropylmorpholine, Nn-butylmorpholine, N-sec. -Butyl morpholine, N-tert-butyl morpholine, etc. are mentioned. Among these, it is preferable to include at least one selected from N-ethylmorpholine, N-methylmorpholine, and Nn-propylmorpholine from the viewpoint of superior safety and availability.

Examples of the alkanolamine compound represented by the above formula (2) include triethanolamine, propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, N-methylethanolamine, N-methyldiethanolamine, N , N-dimethylethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, 2- (2-aminoethoxy) ethanol Etc.
Among these, triethanol is suitable from the viewpoint of being able to perform uniform roughening more suitable for improving the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105, and being excellent in safety and availability. It is preferable to include one or more selected from amines and N, N-diethylethanolamine.

・ Ammonium salt (A2)
Examples of the ammonium salt (A2) include ammonia, ammonium bicarbonate, ammonium tetraborate, ammonium fluoride, ammonium bromide, ammonium iodide, ammonium chloride, phosphoric acid-diammonium hydrogen phosphate, ammonium dihydrogen phosphate, Ammonium hydrogen sulfate, ammonium tartrate, ammonium sulfate, ammonium nitrate, ammonium thiosulfate, ammonium thiocyanate, ammonium formate, ammonium lactate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium pentanoate, ammonium citrate, ammonium oxalate, ammonium carbonate, five Ammonium borate, ammonium sulfite, ammonium benzoate, ammonium hydrogen oxalate, ammonium hydrogen citrate, methyl sulfate Moniumu, one or more selected from ammonium tetrafluoroborate, and the like. Among these, it is preferable to include at least one selected from ammonia, ammonium chloride, and ammonium nitrate from the viewpoint of superior safety and availability. The ammonium salt (A2) usually contains ammonia, and the ratio of the ammonium salt (A2) and ammonia is such that the hydrogen ion concentration index (pH) at 25 ° C. of the mixture is 9.0 or more and 11.0 or less as described later. It is determined appropriately so as to be within the range.

・ Amine salt (A3)
The amine salt (A3) is selected from, for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, ethanolamine, allylamine, ethanolamine, diethanolamine, triethanolamine, aniline, and other amines. And neutralized salts of one or more water-soluble amines.
Examples of neutralized salts of water-soluble amines include bicarbonate amine salts, tetraborate amine salts, fluorinated amine salts, brominated amine salts, iodinated amine salts, chlorinated amine salts, phosphoric acid-hydrogen diamine salts, Dihydrogen phosphate amine salt, hydrogen sulfate amine salt, tartrate amine salt, sulfate amine salt, nitrate nitrate salt, thiosulfate amine salt, thiocyanate amine salt, formate amine salt, lactate amine salt, acetate amine salt, propionate amine salt , Butyric acid amine salt, pentanoic acid amine salt, citric acid amine salt, oxalic acid amine salt, carbonate amine salt, pentaboric acid amine salt, sulfite amine salt, benzoic acid amine salt, hydrogen oxalate amine salt, hydrogen citrate amine salt , Methylsulfuric acid amine salt, tetrafluoroboric acid amine salt and the like.
Among these, the amine salt (A3) preferably includes an amine chloride salt from the viewpoint of superior safety and availability. The above-mentioned amine salt (A3) usually contains the corresponding naked amine, and the ratio of the amine salt (A3) to the naked amine is such that the hydrogen ion concentration index (pH) at 25 ° C. of the mixture is as described later. It is appropriately determined so as to be in the range of 9.0 to 11.0.

  In the roughening aqueous solution (Z) of the present embodiment, each of the above components is dissolved in ion-exchanged water or the like, the concentration of each component or acid-base is added, and the hydrogen ion concentration index at 25 ° C. is added as necessary. It can be easily prepared by adjusting (pH) to a range of 9.0 or more and 11.0 or less.

(2) Hot water treatment process Subsequently, the hot water treatment of the joint surface 104 is performed by bringing warm water into contact with at least the joint surface 104 of the metal member subjected to the roughening treatment in the step (1).
The temperature of the hot water in the hot water treatment is not particularly limited, but is preferably 40 ° C or higher and 90 ° C or lower, more preferably 50 ° C or higher and 90 ° C or lower, and further preferably 60 ° C or higher and 90 ° C or lower. The treatment time at this time is usually about 5 seconds to 30 minutes, preferably about 10 seconds to 15 minutes.

  The warm water used for the warm water treatment is preferably ion exchange water, pure water, or distilled water. Since such water has a small amount of dissolved ions, a high-quality hydroxyl-containing film can be formed.

Examples of the method for performing the warm water treatment include a treatment method by immersion in warm water, spray of warm water, spray of water vapor, and the like.
By such warm water treatment, a microporous hydroxyl group-containing film having a thickness of about 5 nm to 100 nm is formed on the metal surface. The treatment time can be shortened as the temperature of the warm water is higher, and the treatment time can be lengthened as the temperature of the warm water is lowered so that a desired film thickness can be obtained.
Here, the hydroxyl group-containing film can be formed by subjecting a metal surface to hot water treatment, and can also be referred to as a hydroxide film and / or a hydrated film. For example, a metal hydroxide and / or hydrated oxide can be used. It is a film containing.

  By carrying out this warm water treatment step, the bonding strength with the thermoplastic resin member 105 after the oxide film formation treatment, which was not obtained only by the step (1) of roughening with the roughening aqueous solution (Z), is improved. be able to.

  The present inventors presume this reason as follows. That is, by carrying out the warm water treatment step, a hydroxyl group-containing film is formed on the surface of the fine concavo-convex structure generated on the surface of the metal member in the step (1) of roughening with the roughening aqueous solution (Z). Since such a hydroxyl group-containing film is stable after the oxide film forming process, the bonding strength between the surface roughened metal member 103 and the thermoplastic resin member 105 in the metal / resin composite structure 106 after the oxide film forming process is increased. It is speculated that it can be improved.

  After the hot water treatment step (2), 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.

(Surface roughening treatment of metal members)
[Preparation Example 1]
(Preprocessing)
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.

(Surface roughening treatment with N-ethylmorpholine aqueous solution)
Next, an arbitrary one of the above pretreated aluminum plate materials was selected, and the solution was placed at 40 ° C. in 200 ml of a 3.5% by weight aqueous solution of N-ethylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) so that the plate did not touch the container wall. The surface of the pretreated aluminum plate was etched by rocking while being immersed for 8 minutes. In addition, pH at 25 degreeC of the 3.5 mass% aqueous solution of N-ethylmorpholine was 10.5. Next, ultrasonic cleaning (in water, 1 minute) was performed with running water, and the metal member 1 was obtained by drying. In the following description, the surface roughening treatment following the pretreatment may be referred to as the main treatment.

[Preparation Example 2] (Surface roughening treatment with aqueous triethanolamine solution)
Pretreatment is performed by oscillating one pretreated aluminum sheet prepared in Preparation Example 1 while being immersed in 200 ml of a 2.0 mass% aqueous solution of triethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) at 40 ° C. for 8 minutes. The surface of the aluminum plate was etched. In addition, pH at 25 degreeC of said aqueous solution was 10.5. Next, ultrasonic cleaning (in water, 1 minute) was performed with running water, and the metal member 2 was obtained by drying.

[Example 1]
The metal member 1 was immersed in warm water (ion exchange water) at 70 ° C. for 30 seconds. The obtained metal member is referred to as a metal member 3.
A small dumbbell metal insert mold 102 was attached to J85AD110H manufactured by Nippon Steel Works, and a metal member 3 (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.
Further, the obtained metal / resin composite structure 106 was degreased with alkali, then immersed in a 2.0 mass% sodium hydroxide aqueous solution at 50 ° C for 1 minute, and then neutralized with 6.0 mass% dilute nitric acid ( Room temperature for 30 seconds). Next, chemical polishing was performed at 90 ° C. for 2 minutes in a 90 mass% phosphoric acid / 10 mass% sulfuric acid system, and then desmutted with 6.0 mass% diluted nitric acid. After the anodizing treatment (18% by mass sulfuric acid, 18 ° C., 39 minutes, 1 A / dm ² ), the pre-processed molded body was dyed (Red dye manufactured by Okuno Pharmaceutical Co., Ltd., 50 ° C., 8 minutes), An oxide film was formed on the surface of the metal / resin composite structure 106 by performing Ni sealing (95 ° C., 15 minutes), washing with pure water, and air blowing.
The bonding strength was measured for each of the metal / resin composite structure 106 before forming the oxide film and the metal / resin composite structure 106 after forming the oxide film. Table 1 shows the evaluation results of the obtained bonding strength.

[Example 2]
The metal member 1 was immersed in warm water (ion exchange water) at 70 ° C. for 60 seconds. The obtained metal member is referred to as a metal member 4.
In Example 1, except that the metal member 4 was used instead of the metal member 3, injection molding was performed in the same manner as in Example 1 to obtain a metal / resin composite structure 106. Further, as in Example 1, an oxide film was formed on the surface of the metal / resin composite structure 106.
The bonding strength was measured for each of the metal / resin composite structure 106 before forming the oxide film and the metal / resin composite structure 106 after forming the oxide film. Table 1 shows the evaluation results of the obtained bonding strength.

[Comparative Example 1]
In Example 1, except that the metal member 1 was used instead of the metal member 3, injection molding was performed in the same manner as in Example 1 to obtain a metal / resin composite structure 106. Further, as in Example 1, an oxide film was formed on the surface of the metal / resin composite structure 106.
The bonding strength was measured for each of the metal / resin composite structure 106 before forming the oxide film and the metal / resin composite structure 106 after forming the oxide film. Table 1 shows the evaluation results of the obtained bonding strength.

[Comparative Example 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 3. Further, as in Example 1, an oxide film was formed on the surface of the metal / resin composite structure 106.
The bonding strength was measured for each of the metal / resin composite structure 106 before forming the oxide film and the metal / resin composite structure 106 after forming the oxide film. 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 (14)

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,
A step (1) of roughening at least a surface of a joint portion between the metal member and the thermoplastic resin member with a roughening aqueous solution (Z) containing a compound (A) having a nitrogen atom in the molecule;
After the step (1), at least the step (2) of bringing the surface of the metal member into contact with warm water;
The manufacturing method of the surface roughening metal member containing this. In the manufacturing method of the surface roughening metal member of Claim 1,
The manufacturing method of the surface roughening metal member in which the said compound (A) contains 1 type, or 2 or more types selected from the amine (A1) which has an oxygen functional group in a molecule | numerator, ammonium salt (A2), and amine salt (A3). 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 as described in any one of Claims 1 thru | or 3,
The manufacturing method of the surface roughening metal member which performs the said process (1) after the process (0) which wash | cleans 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 4,
The compound (A) includes an amine (A1) having an oxygen functional group in the molecule,
Surface roughening wherein the amine (A1) having an oxygen functional group in the molecule contains at least one selected from a morpholine compound represented by the following formula (1) and an alkanolamine compound represented by the following formula (2): A method for producing a metal member.

(In the formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)

(In the formula (2), R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group, or an aliphatic saturated hydrocarbon group having one hydroxy group, and at least one of R ^{1 to} R ³ is An aliphatic saturated hydrocarbon group having one hydroxy group) In the manufacturing method of the surface roughening metal member of Claim 5,
A method for producing a surface-roughened metal member, wherein the morpholine-based compound contains at least one selected from N-ethylmorpholine, N-methylmorpholine, and Nn-propylmorpholine. In the manufacturing method of the surface roughening metal member of Claim 5,
The manufacturing method of the surface roughening metal member in which the said alkanolamine type compound contains at least 1 type selected from a triethanolamine and N, N-diethylethanolamine. In the manufacturing method of the surface roughening metal member as described in any one of Claims 1 thru | or 4,
The compound (A) includes an ammonium salt (A2),
The manufacturing method of the surface roughening metal member in which the said ammonium salt (A2) contains at least 1 type selected from ammonia, ammonium chloride, and ammonium nitrate. 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 said warm water is ion-exchange water, a pure water, or distilled water. 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 temperature of the said warm water 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 10,
The manufacturing method of the surface roughening metal member whose hydrogen ion concentration index (pH) in 25 degreeC of the said roughening process aqueous solution (Z) is 9.0 or more and 11.0 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 11,
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 12,
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. In the manufacturing method of the metal / resin composite structure of Claim 12 or 13,
The method for producing a metal / resin composite structure further comprising a step (C) of forming an oxide film on the surface of the metal member constituting the obtained metal / resin composite structure after the step (B).

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