WO2010016485A1 - Composite d'alliage métallique avec composition de résine polyamide et son procédé de fabrication - Google Patents

Composite d'alliage métallique avec composition de résine polyamide et son procédé de fabrication Download PDF

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Publication number
WO2010016485A1
WO2010016485A1 PCT/JP2009/063801 JP2009063801W WO2010016485A1 WO 2010016485 A1 WO2010016485 A1 WO 2010016485A1 JP 2009063801 W JP2009063801 W JP 2009063801W WO 2010016485 A1 WO2010016485 A1 WO 2010016485A1
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Prior art keywords
resin composition
polyamide resin
metal alloy
alloy
polyamide
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PCT/JP2009/063801
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English (en)
Japanese (ja)
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正徳 成富
直樹 安藤
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大成プラス株式会社
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Priority to JP2010523861A priority Critical patent/JP5302315B2/ja
Publication of WO2010016485A1 publication Critical patent/WO2010016485A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14795—Porous or permeable material, e.g. foam
    • B29C2045/14803—Porous or permeable material, e.g. foam the injected material entering minute pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts

Definitions

  • the present invention relates to a composite body that is used for a housing of an electronic device, a housing of a household electrical appliance, a machine part, and the like, and in particular, various metal alloys and a polyamide resin composition that are strongly joined, and a manufacturing method thereof. More specifically, a composite of a metal alloy and a polyamide resin composition obtained by surface-treating a metal alloy and injection-molding a thermoplastic resin composition containing a polyamide resin as a main resin component on the surface, and production thereof Regarding the method.
  • Patent Document 1 discloses a technique for injection-bonding polybutylene terephthalate resin (hereinafter referred to as “PBT”) to an aluminum alloy
  • Patent Document 2 discloses a polyphenylene sulfide resin (hereinafter referred to as “PPS”) for an aluminum alloy.
  • PBT polybutylene terephthalate resin
  • PPS polyphenylene sulfide resin
  • the aluminum alloy is immersed in a dilute aqueous solution of a water-soluble amine compound, and the aluminum alloy is finely etched due to the weak basicity of the aqueous solution, and at the same time, the adsorption of amine compound molecules on the aluminum alloy surface is caused.
  • the aluminum alloy thus treated is inserted into an injection mold, and the molten thermoplastic resin is injected at a high pressure.
  • thermoplastic resin is rapidly cooled in contact with an aluminum alloy maintained at a mold temperature lower than the melting temperature of the thermoplastic resin.
  • the resin that is to be solidified while crystallizing is kept in a molten state due to heat generation, and the solidification is delayed, so that the resin enters into the ultra-fine recess on the aluminum alloy surface formed by the etching.
  • the cooled resin fits into the recesses on the surface of the aluminum alloy and solidifies, so that the resin is difficult to peel off from the surface of the aluminum alloy, and the aluminum alloy and the thermoplastic resin are firmly bonded.
  • Patent Document 3 As a technique for bonding a metal and a resin, in addition to the above, there is also disclosed a bonding technique in which a large hole is formed in an anodized film of an aluminum material, and a synthetic resin body is bitten into the hole and bonded (for example, Patent Document 3). See).
  • Patent Document 4 a technique is known in which the surface of a metal part is chemically etched in advance, and then the metal part is inserted into a mold of an injection molding machine and injection molded using a thermoplastic resin material. See). Differences between the technique of Patent Document 4 and the inventions of Patent Documents 1 and 2 by the present inventors will be described later.
  • Patent Documents 1 and 2 described above have a very large effect in an aluminum alloy or the like, but are not effective in injection joining to a metal other than an aluminum alloy.
  • the inventors of the present invention have developed a new technology in the process of developing and improving the injection joining of a hard resin to an aluminum alloy. That is, the conditions under which injection joining can be performed without chemisorption of the amine compound on the metal surface without obtaining assistance of a special exothermic reaction or any specific chemical reaction have been established.
  • the condition on the resin side for enabling the injection joining is to use a hard highly crystalline resin, that is, to use PPS, PBT and aromatic polyamide resin. And it is making these the resin composition improved according to injection joining.
  • the condition on the metal alloy side is that the surface of the metal part to be inserted into the mold has an ultra-fine uneven shape into which the resin can enter, and the surface layer is hard.
  • the magnesium alloy that is covered with the natural oxide layer has low corrosion resistance, so this is subjected to chemical conversion treatment or electrolytic oxidation treatment to form a surface layer of metal oxide or metal carbonate.
  • a metal phosphorous oxide by using a metal phosphorous oxide, a high hardness ceramic surface layer can be obtained.
  • the magnesium alloy having a surface layer subjected to these treatments has a surface hardness that matches the conditions on the metal alloy side.
  • the mold and the inserted magnesium alloy are maintained at a temperature of several hundreds of degrees Celsius or lower than the melting point of the resin to be injected, the injected resin is rapidly cooled as soon as it enters the flow path in the mold, and becomes a magnesium alloy. There is a high possibility that the temperature is below the melting point of the resin when approaching.
  • any crystalline resin is rapidly cooled from the molten state to below the melting point, it does not crystallize and solidify in zero hours, but it is in a molten state below the melting point for a short time, that is, supercooled. There is a state time.
  • the resin can enter the recess within a limited time during which microcrystals are generated from overcooling.
  • the resin can penetrate if the concave portion has a large diameter of several hundred nm. This is because the size of a microcrystal having a shape when an alignment state is generated from a molecular chain that has moved irregularly to the molecular chain is estimated to be several nm to 10 nm when estimated from a molecular model.
  • microcrystals can easily enter ultrafine recesses with a diameter of 20 to 30 nm, but it is determined that recesses with a diameter of about several hundred nm can enter.
  • countless microcrystals are generated simultaneously.
  • the temperature of the resin flow suddenly rises because there is a temperature drop at the tip of the injection resin or at the location in contact with the metal mold surface. Therefore, in the case of a recess having a diameter of about 100 nm, it may not be possible to penetrate to the bottom of the recess.
  • the crystallization proceeds and solidifies considerably after entering the interior, a corresponding bonding force is generated.
  • the surface of the magnesium alloy is a hard and strong surface layer such as a ceramic crystallite group such as a metal oxide or an amorphous layer, and as described above, an ultrafine uneven shape having a diameter of nm order (preferably 100 nm or more). If so, the resin is strongly caught in the recess, and the solidified resin is difficult to escape from the recess, so that the bonding force is improved.
  • the above-described conditions on the resin side that is, improvement of the resin composition to be injected into a hard highly crystalline resin is a very important factor.
  • the resin composition is injection-molded, it is rapidly cooled from the molten state to a temperature below the melting point to crystallize and solidify, but if the resin composition has a slow crystallization rate, it penetrates deep into the recess. Because it is easy, it can produce a stronger bonding force.
  • Patent Document 5 A technology has been proposed (Patent Document 5). This proves that injection bonding is possible even without chemisorption of the amine compound, that is, when no heat is generated due to the encounter between the thermoplastic resin and the amine compound molecule. That is, it shows that injection bonding can be performed using PBT and PPS improved for injection bonding by setting the same surface shape and physical properties of various metal alloys.
  • Patent Document 4 Inserts a chemically etched copper wire into an injection mold, injects PPS, etc., and creates a battery lid with lead wires in the shape of several copper wires penetrating through the center of a PPS disk. Describes the method. It is described that the surface roughness (roughness) of the copper wire by chemical etching ensures airtightness at the interface between the lead wire and the resin, and gas does not leak from the periphery of the lead wire even if the internal pressure of the battery rises. Yes.
  • Patent Document 4 is not an injection joining technique claimed by the present inventors, but is a technique on an extension line of normal injection molding.
  • the relationship between the metal linear expansion coefficient and the resin molding shrinkage ratio is simply shown. It is the technology used.
  • the metal rod-shaped object is clamped from the resin-molded product portion when the molded product is released from the mold and allowed to cool. This is due to the following reason.
  • the coefficient of linear expansion of the metal is 1.7 to 2.5 ⁇ 10 ⁇ 5 ° C.
  • the wire The expansion rate is about 100 ° C., and the degree of shrinkage is only 0.2 to 0.3%.
  • one of the resins has a molding shrinkage of about 1% for PPS and 0.5% for PPS with glass fiber, and even a resin with increased filler shrinks more than the metal after injection molding. It is.
  • a shape product with a metal part in the center and its periphery covered with a resin part that is, a shape part in which the metal part penetrates the resin part
  • the resin part is tightened by molding shrinkage. Due to the effect, it is possible to manufacture an integrated product in which the metal part is difficult to come off from the resin portion.
  • Such a manufacturing method of a clamped metal and resin integrated product is a conventionally known method, and there is a handle of an oil stove as a similar molded product. This handle is manufactured by inserting a thick iron wire having a diameter of about 2 mm into an injection mold and injecting a heat resistant resin or the like into the mold.
  • the wire is provided with jagged scratches (for example, knurling) so that the resin does not move.
  • Patent Document 4 the uneven processing of the metal surface is changed from the conventional physical processing method to the chemical processing method, the unevenness is made slightly fine, and a resin that is hard and crystalline on the resin side is frequently used. It is a feature that improved the gripping effect.
  • the series of injection joining techniques disclosed by the present inventors do not require any resin hugging effect.
  • the force required for breaking was several tens of MPa, indicating a very strong joining force.
  • the inventors of the present invention clarified the conditions for injection-bonding a thermoplastic resin composition to a magnesium alloy and the composite exhibiting a shear rupture force and a tensile rupture force of several tens of MPa (Patent Document 5). Furthermore, the conditions were applied to a copper alloy (Patent Document 6), a titanium alloy (Patent Document 7), and stainless steel (Patent Document 8), and the effectiveness was verified.
  • the present inventors refer to the joining theory relating to the aluminum alloy as “NMT” theory, and the injection theory relating to metal alloys in general as the “new NMT” theory.
  • NMT joining theory relating to the aluminum alloy
  • new NMT injection theory relating to metal alloys in general as the “new NMT” theory.
  • the theory of “new NMT” that can be used more widely will be described in detail below. That is, in order to perform injection joining that exhibits extremely strong joining force, there are conditions on both the metal alloy side and the injection resin side. First, the following three conditions are necessary on the metal alloy side.
  • the first condition is that the surface of the metal alloy is uneven with a period of 1 to 10 ⁇ m by a chemical etching technique, and the uneven height difference is about half of the period, that is, a rough rough surface of 0.5 to 5 ⁇ m. That is.
  • a chemical reaction that is not constant.
  • it when viewed with a roughness meter, it is in the range of 0.2 to 20 ⁇ m. It is necessary to be able to draw a roughness curve having irregularities with a regular cycle and a maximum height difference of 0.2 to 5 ⁇ m.
  • the roughness surface has an RSm of 0.8 to 10 ⁇ m and an Rz of 0.2 to 5 ⁇ m, the aforementioned roughness is used.
  • the degree condition is substantially satisfied.
  • RSm is the average length of contour curve elements defined in Japanese Industrial Standard (JIS B 0601: 2001, ISO 4287: 1997)
  • Rz is Japanese Industrial Standard (JIS B 0601: 2001, ISO 4287: 1997).
  • the inventors of the present invention called the “surface having a roughness on the order of microns” as an easy-to-understand word because the ideal rough surface irregularity period is approximately 1 to 10 ⁇ m as described above.
  • the second condition is that ultrafine irregularities with a period of 5 nm or more are further formed on the surface of the metal alloy having a roughness on the order of microns. In other words, it needs to be rough when viewed with microscopic eyes.
  • fine etching is performed on the surface of the metal alloy, and the inner wall surface of the recess having the above-mentioned micron-order roughness is 5 to 500 nm, preferably 10 to 300 nm, more preferably 30 to 100 nm (optimum). A value of 50 to 70 nm) is formed.
  • the irregularity period is 10 nm or less, it is clearly difficult to enter the resin component. Further, in this case, since the unevenness height difference is usually small, the surface becomes smooth as viewed from the resin side. As a result, it no longer serves as a spike. If the period is about 300 to 500 nm or longer (in that case, the diameter and period of the concave part having a micron order roughness is estimated to be close to 10 ⁇ m), the spike in the micron order concave part Because the number of slashes, the effect becomes difficult to work. Therefore, in principle, it is necessary that the period of the ultra fine irregularities is in the range of 10 to 300 nm.
  • the resin may enter between them even with a period of 5 nm to 10 nm.
  • this is the case when 5 to 10 nm diameter rod-shaped crystals are complex.
  • the shape of the ultra-fine irregularities may easily cause an anchor effect.
  • this corresponds to a shape like a pearlite structure in which steps having a height and depth of several hundred to 500 nm and a width of several hundred to several thousand nm are infinitely continuous. Including such a case, the required period of ultrafine irregularities was specified to be 5 nm to 500 nm.
  • the RSm range is defined as 1 to 10 ⁇ m and the Rz range is defined as 0.5 to 5 ⁇ m, but the RSm is 0.8 to 1 ⁇ m and the Rz is 0.2 to 0.2 ⁇ m.
  • the bonding force can be maintained high if the irregular period of the ultra-fine irregularities is in a particularly preferable range (approximately 30 to 100 nm). Therefore, we decided to expand the range of RSm slightly to a smaller one. That is, RSm was in the range of 0.8 to 10 ⁇ m and Rz was in the range of 0.2 to 5 ⁇ m.
  • the third condition is that the surface layer of the metal alloy is ceramic.
  • the surface layer needs to be a metal oxide layer having a thickness equal to or greater than that of the natural oxide layer, and the metal alloy type having relatively low corrosion resistance (
  • the third condition is that the surface layer is a thin layer of metal oxide or metal phosphorous oxide generated by chemical conversion treatment or the like.
  • the NMT theory for aluminum alloys is not limited to those having the first to third conditions. Instead of these first to third conditions, the aluminum alloy surface is covered with ultra-fine irregularities with a period of 20 to 80 nm, and the amine compound is chemisorbed on the surface. What satisfy
  • filled conditions may be sufficient.
  • the resin composition that can be injection-bonded with a strong force to the surfaces of the various metal alloys subjected to the surface treatment includes a resin composition improved by compounding different polymers with PBT and PPS, as described above, and an aromatic It is a resin composition of a polyamide resin mixture containing a group polyamide (Patent Documents 5 to 8). Further, in order to stably maintain the bonding state between the metal alloy and the thermoplastic resin for a long period of time, it is necessary that the linear expansion coefficients of both are close.
  • the linear expansion coefficient of the thermoplastic resin composition can be considerably lowered by containing a large amount of reinforcing fibers such as glass fibers and carbon fibers, that is, a filler, and the limit is (2-3) ⁇ 10 ⁇ 5. ° C -1 .
  • Metals close to this value near room temperature are aluminum, magnesium, copper, and silver, and steel materials and titanium alloys have a smaller linear expansion coefficient. Nevertheless, since reducing the linear expansion coefficient on the resin side is effective in reducing the difference in linear expansion coefficient between the two and maintaining the bonding force for a long period of time, addition of a filler is important.
  • the present inventors have already disclosed a system of a polyamide resin mixture containing PBT and PPS and an aromatic polyamide as described above as a resin usable for injection joining with a metal alloy.
  • the polyamide resin itself is not necessarily suitable as the resin used for injection joining with the metal alloy.
  • Inexpensive and versatile polyamide resins such as polyamide 6 (hereinafter referred to as “PA6”), polyamide 66 (hereinafter referred to as “PA66”), an aliphatic polyamide resin (so-called nylon resin) that is easy to handle as an engineering plastic, are described above. This is because the injection bonding is once performed on the aluminum alloy, but the bonding force is weak.
  • the composite obtained by injection molding an aliphatic polyamide resin suitable as an engineering plastic into a metal alloy exhibits a strong bonding force and can maintain the bonding force, the versatility of the aliphatic polyamide resin described above, It can be applied to a wide range of technical fields due to its cost.
  • An object of the present invention is to provide a composite in which a polyamide resin composition containing an aliphatic polyamide resin as a main resin component and a metal alloy are firmly integrated by injection molding, and a manufacturing technique thereof.
  • an aliphatic polyamide resin that does not contain any aromatic polyamide resin that easily absorbs ultraviolet rays can be halogen-free even when a flame retardant is used, and its adjustment is easy.
  • the use of aliphatic polyamide resin which is quick and easy to use for screwing bosses, meets the demands of the demand side.
  • the aliphatic polyamide resin is flexible, when a screw boss is used, a normal wood screw type screw can be tightened even if it contains a little filler.
  • An object of the present invention is to provide a polyamide resin composition which is strongly bonded by injection molding to a metal alloy and whose resin content is all aliphatic polyamide resin, and the polyamide resin composition and the metal alloy It is in providing the composite_body
  • a polyamide 610 resin (hereinafter referred to as “PA610”) was selected as the aliphatic polyamide resin, and a polyamide resin composition containing this as a resin component was used as an injection molding resin. Thereby, the strong injection joining with the metal alloy was attained.
  • PA610 polyamide 610 resin
  • the bonding strength was maximized when PA610 contained 45% by mass of resin and PA66 or PA6 contained 55% by mass.
  • PA610 is suitable for injection molding with a metal alloy among aliphatic polyamide resins.
  • PA610 is obtained by a copolycondensation reaction of hexamethylenediamine having 6 carbon atoms and sebacic acid having 10 carbon atoms.
  • the density of peptide bonds is clearly lower than that of PA6 and PA66, it is a peptide bond having a strong influence on the periphery, so it cannot be assumed that the crystallization rate at equilibrium is greatly reduced by PA610.
  • PA6 is obtained by a polycondensation reaction of ⁇ -caprolactam (carbon number 6)
  • PA66 is obtained by a co-condensation polymerization reaction of hexamethylenediamine (carbon number 6) + adipic acid (carbon number 6), that is, carbon as a unit.
  • the numbers are the same.
  • PA610 is obtained by a copolycondensation reaction of hexamethylenediamine having 6 carbon atoms and sebacic acid having 10 carbon atoms. That is, the carbon numbers of both are greatly different. Therefore, it can be expected that when the PA 610 cools from the molten state and tries to align (crystallize), it will take more time than the PA 6 and PA 66.
  • PA610 since it can be estimated that the crystallization speed of PA610 during quenching is significantly slower than that of PA6 and PA66, it has physical properties suitable for injection joining alone. This is thought to be confirmed by an injection joining experiment in which a polyamide composed of hexamethylenediamine and a terminal dicarboxylic acid having 9 or 11 carbon atoms is synthesized.
  • the injection joining of the present invention is different from the injection joining that the present inventors have performed so far.
  • PA610 has lower hardness (softer) than PA6, PA66, nylon 6I (condensation polymer of hexamethylenediamine and isophthalic acid), nylon 6T (condensation polymer of hexamethylenediamine and terephthalic acid), and the like.
  • nylon 6I condensation polymer of hexamethylenediamine and isophthalic acid
  • nylon 6T condensation polymer of hexamethylenediamine and terephthalic acid
  • the inventors estimated that the crystallization rate of PA610 is high and has sufficient hardness or quickness to ensure injection joining. However, the hardness is still softer than that of PPS and PBT crystals, and if a force in the peeling direction is applied with a strong force, it may be deformed and dropped out without being cut from the recess on the metal alloy surface. Estimated.
  • the above-mentioned aliphatic polyamide resins such as PA6 and PA66 are not only weakly bonded to the metal alloy when injection molded, but also once bonded to the metal alloy due to expansion and contraction due to high hygroscopicity. Even so, there was a problem that it was easily destroyed in an actual environment.
  • the bonding strength with the metal alloy can be improved by using a mixed compound of polyamide resins in which an aromatic polyamide resin is mixed with the above aliphatic polyamide resin, but the hygroscopicity and water absorption are still higher than those of PBT and PPS. Therefore, it is difficult to maintain the bonding force.
  • PA610 has lower hygroscopicity than other aliphatic polyamide resins, and is quick and slightly soft. Therefore, this quickness increases the internal strain even during moisture absorption. It is considered that it suppresses and contributes to maintaining the bonding force with the metal alloy.
  • the present invention takes the following means in order to achieve the object.
  • the average length (RSm) of the contour curve element is 0 on the surface of the metal alloy when analyzed by (1) scanning probe microscope observation. A roughness of the order of micron with a maximum height (Rz) of 0.2 to 5 ⁇ m was generated (2), and the surface having the roughness was observed with a 100,000 times electron microscope. At this time, ultra-fine irregularities with a period of 5 to 500 nm are formed, and (3) surface treatment is performed to make the surface layer a thin layer of metal oxide or metal phosphate. This surface-treated metal alloy is inserted into an injection mold.
  • a polyamide resin composition containing 10 to 100% by mass of polyamide 610 on the surface of the inserted metal alloy is injected.
  • the injected polyamide resin composition is solidified after entering the ultra-fine irregularities, whereby the metal alloy and the molded article of the polyamide resin composition are joined.
  • the metal alloy used here is selected from, but not limited to, an aluminum alloy, a magnesium alloy, a copper alloy, a titanium alloy, stainless steel, and a steel material.
  • the polyamide resin composition may be entirely aliphatic polyamide resin.
  • Polyamide 610 accounted for 20 to 70% by mass of the resin content, and the balance exhibited a strong bonding force when a polyamide resin such as polyamide 66 or polyamide 6 was used.
  • Polyamide 610 accounted for 30 to 50% by mass of the resin content, and the balance exhibited particularly strong bonding strength when a polyamide resin such as polyamide 66 or polyamide 6 was used.
  • These polyamide resin compositions contain at least one selected from carbon fiber, glass fiber, boron fiber, calcium carbonate, dolomite, talc, glass powder, and clay as fillers in an amount of 30 to 50% by mass based on the total resin composition. It is preferable to include.
  • polyamide resin composition in which the resin content is entirely an aliphatic polyamide resin and the polyamide 610 accounts for 80 to 100% by mass of the resin content.
  • a polyamide resin composition in which polyamide 610 accounts for 80 to 100% by mass of the resin, and the balance is polyamide 66 or polyamide 6.
  • a polyamide resin composition in which polyamide 610 occupies 100% by mass of the resin can be used.
  • These polyamide resin compositions contain at least one selected from carbon fiber, glass fiber, boron fiber, calcium carbonate, dolomite, talc, glass powder, and clay as fillers in an amount of 0 to 20% by mass based on the total resin composition. It is preferable to include.
  • each element constituting the present invention will be described.
  • Metal alloy The type of metal alloy in the present invention, that is, a metal alloy having a surface structure based on the above-mentioned “new NMT” is not particularly limited in theory. However, “new NMT” can be applied to hard and practical metal alloys. The present inventors have exemplified metal alloy species mainly composed of aluminum, magnesium, copper, titanium, and iron as metal alloy species to which “new NMT” can be applied. Hereinafter, these will be described. However, since “new NMT” aims to improve the adhesive force by the anchor effect, it is not limited to at least the following metal alloy types. Patent Documents 1 and 2 described aluminum alloys. Patent Document 5 describes a magnesium alloy. Patent Document 6 describes a copper alloy. Patent Document 7 describes a titanium alloy. Patent Document 8 describes stainless steel. These various metal alloys will be described in detail.
  • A1000 series to 7000 series corrosion-resistant aluminum alloy, high-strength aluminum alloy, heat-resistant aluminum alloy, etc.
  • JIS Japanese Industrial Standard
  • Any one of ADC 1 to 12 types can be used.
  • Magnetic alloy For example, a magnesium alloy for extension (for example, A31B) and a magnesium alloy for casting (for example, AZ91D) defined by the International Organization for Standardization (ISO), Japanese Industrial Standards (JIS), American Society for Testing and Materials (ASTM), or the like can be used.
  • ISO International Organization for Standardization
  • JIS Japanese Industrial Standards
  • ASTM American Society for Testing and Materials
  • the copper alloy used in the present invention refers to copper, brass, phosphor bronze, Western night, aluminum bronze and the like. All copper, including pure copper alloys such as C1020 and C1100, C2600 brass alloys, C5600 copper white alloys and other iron-based copper alloys for connectors as defined in Japanese Industrial Standards (JIS H 3000 series) Alloys are the target.
  • Titanium alloys used in the present invention are pure titanium alloys, ⁇ -type titanium alloys, ⁇ -type titanium alloys, ⁇ - ⁇ -type titanium alloys, etc. defined by the International Organization for Standardization (ISO), Japanese Industrial Standards (JIS), etc. All titanium alloys are targeted.
  • ISO International Organization for Standardization
  • JIS Japanese Industrial Standards
  • the stainless steel referred to in the present invention is a Cr-based stainless steel obtained by adding chromium (Cr) to iron, a Cr-Ni-based stainless steel added by combining nickel (Ni) with chromium (Cr), A known corrosion-resistant iron alloy called stainless steel is the object.
  • the steel materials used in the present invention refer to steel materials such as carbon steels (so-called general steel materials) such as general structural rolled steel materials, high-tensile steels (high-tension steels), low-temperature steels, and reactor steel plates.
  • general steel materials such as carbon steels (so-called general steel materials) such as general structural rolled steel materials, high-tensile steels (high-tension steels), low-temperature steels, and reactor steel plates.
  • SPCC cold rolled steel
  • SPHC hot rolled steel
  • SAPH hot rolled steel sheet for automobile structure
  • Structural steel materials such as hot-rolled high-tensile steel plate materials for automobile processing (hereinafter referred to as “SPFH”) and steel materials mainly used for machining (hereinafter referred to as “SS material”) are included.
  • the steel materials referred to in the present invention are not limited to the above steel materials, and include all steel materials standardized by Japanese Industrial Standards (JIS), International Organization for Standardization (ISO), and the like.
  • the purpose of the chemical etching in the present invention is to generate a roughness on the order of microns on the surface of the metal alloy.
  • corrosion such as general corrosion, pitting corrosion, and fatigue corrosion, but it is possible to select an appropriate etching agent by selecting a chemical species that causes general corrosion for the metal alloy and performing trial and error.
  • the metal alloys that are actually sold in the market such as pure copper-based copper alloys and pure titanium-based titanium alloys, have a purity of 99.9% or more and are hardly called alloys. Included in the alloy. Most of the metal alloys that are actually used are mixed with a wide variety of elements in order to obtain characteristic physical properties, and there are few pure metal materials, and they are substantially alloys.
  • the metal alloy After shaping the metal alloy into a predetermined shape, the metal alloy is degreased by immersing it in an aqueous solution in which a degreasing agent for the metal alloy is dissolved and washed with water.
  • This process is a process for removing most of the machine oil and finger grease adhering in the process of shaping the metal alloy, and it is preferably always performed.
  • it is preferably immersed in a thinly diluted acid / base aqueous solution and washed with water. This is a process that the present inventors have referred to as preliminary acid cleaning and preliminary base cleaning.
  • the purpose of fine etching in the present invention is to form ultra-fine irregularities on the surface of a metal alloy.
  • the surface hardening process in this invention aims at making the surface layer of a metal alloy into a thin layer of a metal oxide or a metal phosphate.
  • nano-order fine etching may be performed at the same time by performing the chemical etching, and ultra-fine irregularities may be formed.
  • the natural oxide layer on the surface may be thicker than the original and the surface hardening process may be completed.
  • a pure titanium-based titanium alloy is only subjected to chemical etching, so that the surface has a roughness on the order of microns and ultra-fine irregularities are also formed. That is, fine etching is performed together with chemical etching.
  • fine etching is performed together with chemical etching.
  • the present inventors have generally confirmed that when the film (chemical conversion film) formed on the surface of the metal alloy by chemical conversion treatment is thick, the adhesive force often decreases. A strong adhesive force can be obtained when the thin layer is such that the diffraction line is not detected by XRD, such as the thin layer of manganese oxide adhered to the magnesium alloy.
  • XRD X-ray diffraction
  • the fracture surface is mostly between the chemical conversion film and the metal alloy layer.
  • the bonding force between the thick chemical conversion film and the cured adhesive was always stronger than the bonding force between the chemical conversion film and the metal alloy.
  • the adhesive strength does not decrease for a long period of time if the chemical conversion treatment time is further increased to increase the thickness of the chemical conversion treatment layer.
  • the chemical conversion film is thickened, the adhesive strength itself is lowered. Therefore, the degree of balance depends on the purpose of use and application.
  • the surface treatment method of various metal alloys will be described in detail.
  • the processing method is different between an alloy containing a relatively large amount of silicon in an aluminum alloy and an alloy containing a small amount of these components.
  • a method for treating an aluminum alloy having a low silicon content will be described. That is, the following treatment methods are preferred for aluminum alloys for drawing such as A1050, A1100, A2014, A2024, A3003, A5052, and A7075. That is, it is preferable that the aluminum alloy is immersed in an acidic aqueous solution for a short time and washed with water, and the acid component is adsorbed on the surface layer of the aluminum alloy in order to proceed the next chemical etching with good reproducibility.
  • This treatment is called a preliminary pickling step, and a dilute aqueous solution having a concentration of 1% to several percent of an inexpensive mineral acid such as nitric acid, hydrochloric acid, sulfuric acid or the like can be used.
  • an inexpensive mineral acid such as nitric acid, hydrochloric acid, sulfuric acid or the like
  • an inexpensive mineral acid such as nitric acid, hydrochloric acid, sulfuric acid or the like
  • This chemical etching removes oil and dirt remaining on the surface of the aluminum alloy together with the surface layer of the aluminum alloy. Simultaneously with this peeling, the surface has a roughness on the order of microns. That is, the uneven surface has an RSm of 0.8 to 10 ⁇ m and an Rz of 0.2 to 5.0 ⁇ m.
  • it is preferable to remove sodium ions by immersing again in an acidic aqueous solution and washing with water.
  • the inventors refer to this as a neutralization step.
  • this acidic aqueous solution a nitric acid aqueous solution having a concentration of several percent is particularly preferable.
  • the fine etching that is the final treatment is performed on the aluminum alloy that has undergone the neutralization process.
  • the aluminum alloy is immersed in an aqueous solution containing one or more of hydrated hydrazine, ammonia, and a water-soluble amine compound. Thereafter, it is preferably washed with water and dried at 70 ° C. or lower. This is also a measure for reviving the rough surface with respect to the fact that the surface is slightly changed by the sodium removal ion treatment performed in the neutralization step and the roughness is maintained, but the surface becomes slightly smooth.
  • Fine etching is performed by dipping in a weakly basic aqueous solution such as a hydrated hydrazine aqueous solution for a short time. It is particularly preferable to form a large number of ultrafine irregularities with a period of 40 to 50 nm on the inner wall surface of the recesses having a roughness on the order of microns.
  • the drying temperature after washing with water is set to a high temperature of, for example, 100 ° C. or higher, if the inside of the dryer is sealed, a hydroxylation reaction occurs between boiling water and aluminum, and the surface changes to form a boehmite layer.
  • the This is not preferable because it cannot be said to be a strong surface layer.
  • it is preferable to dry with hot air at 90 ° C. or lower, preferably 70 ° C. or lower. When dried at 70 ° C.
  • XPS analysis can detect elements existing at a depth of 1 to 2 nm from the surface of the metal. From this result, it was immersed in an aqueous solution of hydrated hydrazine or an amine compound, and then washed with water and dried with warm air to obtain aluminum. It was confirmed that the original natural oxide layer (a thin aluminum oxide layer having a thickness of about 1 nm) that the alloy had became thicker by fine etching. Unlike at least the natural oxide layer, it was confirmed that the thickness was 2 nm or more.
  • the above process is a process for satisfying the first condition to the third condition in the “new NMT”.
  • the surface of the aluminum alloy is covered with ultrafine irregularities with a period of 20 to 80 nm, And what satisfy
  • the chemical etching is not an essential process, and only the fine etching may be performed.
  • chemical etching has the effect of further improving the bonding strength with the thermoplastic resin composition. In particular, it is effective for aluminum alloys other than 1000 series aluminum alloy (pure aluminum alloy type).
  • degreasing treatment In the surface treatment of the magnesium alloy, first, degreasing treatment is performed. Specifically, a commercially available aqueous solution of a degreasing material for magnesium alloy is used. In a general commercial product, the concentration is 5 to 10%, the liquid temperature is 50 to 80 ° C., and the magnesium alloy is immersed in this for 5 to 10 minutes.
  • chemical etching is performed in which the magnesium alloy is immersed in an acidic aqueous solution for a short time, followed by washing with water.
  • the surface layer of the magnesium alloy including the dirt that cannot be removed in the degreasing process is peeled off, and at the same time, a roughness on the order of microns is generated. That is, when scanning with a scanning probe microscope, irregularities with RSm of 0.8 to 10 ⁇ m and Rz of 0.2 to 5 ⁇ m are detected.
  • an aqueous solution for chemical etching an aqueous solution of carboxylic acid or mineral acid having a concentration of 1% to several percent can be used.
  • aqueous solutions of citric acid, malonic acid, acetic acid, nitric acid and the like are particularly preferred.
  • aluminum and zinc contained in a magnesium alloy usually do not dissolve and remain on the surface of the magnesium alloy as a black smut. Then, the aluminum smut is removed by soaking in a weakly basic aqueous solution. It is preferable to dissolve the zinc smut by immersing it in a strong base aqueous solution.
  • magnesium alloy from which the smut has been dissolved and removed in this way is subjected to chemical conversion treatment. That is, since magnesium is a metal with a very high ionization tendency, the oxidation rate due to moisture and oxygen in air is faster than other metals. Magnesium alloys have a natural oxide film, but are not strong enough from the viewpoint of corrosion resistance, and oxidative corrosion easily proceeds even in a normal environment. Therefore, in general, magnesium alloys are soaked in an aqueous solution such as chromic acid or potassium dichromate to cover the entire surface with a thin layer of chromium oxide (called chromate treatment), or a manganese salt containing phosphoric acid. A treatment for covering the entire surface with a manganese phosphate compound is performed by dipping in an aqueous solution of the above, and a corrosion prevention treatment is performed. These treatments are called chemical treatments in the magnesium industry.
  • the chemical conversion treatment performed on the magnesium alloy is a treatment in which the magnesium alloy is immersed in an aqueous solution containing a metal salt and the surface thereof is covered with a thin layer of metal oxide and / or metal phosphate.
  • the chromate type chemical conversion treatment using a hexavalent chromium compound is avoided from the viewpoint of environmental pollution, and the chemical conversion treatment using a metal salt other than chromium, which is called non-chromate treatment, Manganese phosphate chemical conversion treatment or silicon chemical conversion treatment is performed.
  • a weakly acidic aqueous solution of potassium permanganate as an aqueous solution for chemical conversion treatment.
  • a coating covering the surface is manganese dioxide.
  • a magnesium alloy excluding smut is dipped in a very dilute acidic aqueous solution for a short time, and then washed with water to remove the surface basic components.
  • the method of immersing in the aqueous solution for chemical conversion treatment after that, washing with water, and drying is preferable.
  • a dilute acidic aqueous solution a citric acid or malonic acid aqueous solution having a concentration of 0.1 to 0.3% is used. It is preferable to immerse in this aqueous solution at around room temperature for about 1 minute.
  • an aqueous solution containing potassium permanganate 1.5 to 3%, acetic acid around 1% and sodium acetate around 0.5% is preferably used at a temperature of 40 to 50 ° C.
  • the immersion time is preferably about 1 minute.
  • FIG. 5 is a 100,000 times electron micrograph of the magnesium alloy surface subjected to the above treatment. Although it is difficult to express these ultra-fine concavo-convex shapes with sentences, daringly speaking, this ultra-fine concavo-convex shape has innumerable rod-like or spherical protrusions having a diameter of 5 to 20 nm and a length of 10 to 30 nm. It can be said that spherical objects having a diameter of 80 to 120 nm are irregularly stacked.
  • the rod-like (needle-like) substance having a diameter of about 10 nm can be said to be completely crystalline from the result of observation with an electron microscope, but the diffraction line seen in manganese oxide by analysis with an X-ray diffractometer (XRD). Was not recognized.
  • X-ray diffractometer cannot detect if the amount of crystals is small, it cannot be judged at present whether these are crystals. At least, these are too amorphous to be amorphous (non-crystalline), so it is determined that they are not amorphous. From XPS analysis, large peaks of manganese (which is an ion and not zero-valent manganese) and oxygen are recognized, and there is no doubt that the surface layer is a manganese oxide. This surface has a dark color tone and is a manganese oxide mainly composed of manganese dioxide.
  • degreasing treatment is first performed. Specifically, a commercially available aqueous solution of a degreasing material for copper alloy is used. Commercially available degreasing agents for iron, stainless steel, or aluminum alloy can also be used. Further, an aqueous solution in which a neutral detergent for industrial use or general household is dissolved can be used. Usually, a commercially available degreasing agent or neutral detergent is dissolved in water to a concentration of several to 5%, the temperature of this aqueous solution is 50 to 70 ° C., and the copper alloy is immersed in this for 5 to 10 minutes and washed with water. .
  • preliminary base washing in which the copper alloy is immersed in a caustic soda solution having a concentration of several percent maintained at around 40 ° C. and then washed with water.
  • chemical etching is performed by immersing the copper alloy in an aqueous solution containing hydrogen peroxide and sulfuric acid, followed by washing with water.
  • This chemical etching is preferably performed using an aqueous solution containing several percent of both sulfuric acid and hydrogen peroxide at 20 ° C. to around room temperature.
  • the immersion time at this time is several minutes to 20 minutes, although it varies depending on the alloy type.
  • a roughness on the order of microns is obtained with most copper alloys. That is, when analyzed with a scanning probe microscope, RSm is 0.8 to 10 ⁇ m and Rz is 0.2 to 5 ⁇ m.
  • surface hardening treatment is performed to oxidize the surface of the copper alloy that has undergone the chemical etching step.
  • blackening treatment a method called blackening treatment is known in the electronic component industry
  • the surface effect treatment carried out in the present invention is different from the blackening treatment in its purpose and degree of oxidation, but the content of the treatment itself is the same. It is.
  • the surface layer of the copper alloy is oxidized with an oxidizing agent under strong basicity. When copper atoms are ionized with an oxidizing agent, if the surroundings are strongly basic, they are not dissolved in an aqueous solution and become black cupric oxide.
  • the surface is blackened to improve the efficiency of heat radiation and heat absorption.
  • This processing is called blackening processing in the electronic component industry using copper.
  • This blackening treatment can also be used for the surface hardening treatment of the present invention.
  • the purpose of the surface hardening treatment in the present invention is to form nano-order ultra-fine irregularities on the surface of the copper alloy having a certain roughness and harden the surface layer (that is, fine etching and surface hardening treatment).
  • the immersion time in the present invention is extremely short compared to the blackening treatment in the electronic component industry.
  • the surface hardening treatment was performed with different immersion times, and the surface of the copper alloy after each surface hardening treatment was observed with an electron microscope to identify a suitable immersion time.
  • the immersion time is 0.5-1.0 minutes. The degree is preferred.
  • the surface When the surface is observed with an electron microscope, it has a roughness on the order of microns, and a circular hole with a diameter of 10 to 150 nm and an elliptic hole with a major axis or minor axis of 10 to 150 nm are formed on the surface. .
  • the circular holes and the elliptical holes have an ultra-fine uneven shape that exists on the entire surface with a period of 30 to 300 nm.
  • both ultra-fine irregularities and a surface hardened layer can be obtained simultaneously.
  • the immersion time in the treatment liquid was set to 2 to 3 minutes, the adhesive strength with the adherend was lowered. From this, it was confirmed that performing the surface curing treatment for a long time weakens the adhesive strength, and is not preferable.
  • the rough surface obtained as a result of the above-described chemical etching often has an RSm exceeding 10 ⁇ m.
  • the RSm was clearly larger than copper alloys other than pure copper.
  • Rz is obviously small for a large RSm (for example, RSm is 8 ⁇ m, Rz is 0.4 ⁇ m, etc.).
  • the metal crystal grain size is large, such as C1020 (oxygen-free copper) having a high copper content, the RSm is clearly increased as described above, and the irregularity period and the metal crystal grain size are large. Was estimated to have a direct correlation.
  • the present inventors once again performed chemical etching and re-cured the surface of the pure copper-based copper alloy that had been subjected to the surface-curing treatment, for which it was determined that Rz was relatively small.
  • the second chemical etching may be performed in a shorter time than the first chemical etching.
  • RSm was 10 ⁇ m or less
  • Rz was several ⁇ or more.
  • the ultra-fine irregularities are the same as when the repeated treatment is not performed.
  • titanium alloy surface treatment In the surface treatment of the titanium alloy, first, degreasing treatment is performed. There is no need for special ones. Specifically, general degreasing agents such as commercially available iron degreasing agents, stainless steel degreasing agents, aluminum alloy degreasing materials, magnesium alloy degreasing agents and the like can be used. Moreover, the aqueous solution which melt
  • general degreasing agents such as commercially available iron degreasing agents, stainless steel degreasing agents, aluminum alloy degreasing materials, magnesium alloy de
  • hydrofluoric acid can be used as the reducing acid that can corrode the titanium alloy.
  • hydrofluoric acid has the highest etching rate. Therefore, hydrofluoric acid is used when efficiency is important.
  • hydrofluoric acid can invade human skin and lead to bones, which can last for several days. In short, there are problems different from hydrochloric acid and the like, and it is preferable to avoid the use of hydrofluoric acid from the viewpoint of the working environment.
  • ammonium difluoride which is a half-neutralized product of hydrofluoric acid that can be handled much more safely than hydrofluoric acid.
  • a treatment method is preferred in which an aqueous solution of about 1% ammonium difluoride and hydrogen is immersed in this solution for several minutes at a temperature of 50 to 60 ° C. and then washed with water. Chemical etching with 1 hydrogen di-ammonium difluoride aqueous solution was performed to obtain micron-order roughness.
  • the surface of the titanium alloy is washed and dried after chemical etching. It turned out that it became a mysterious shape of ultra fine irregularities, and the surface was covered with a thin layer of titanium oxide. In short, separate fine etching and surface hardening treatment were unnecessary.
  • FIG. 7 An analysis example of a titanium alloy etched with an aqueous solution of ammonium difluoride and washed with water and then dried is shown.
  • a scanning analysis result by a scanning probe microscope was obtained.
  • RSm was 1.8 ⁇ m
  • Rz was 0.9 ⁇ m.
  • FIG. 7 an example of a 10,000 times and 100,000 times electron micrograph of the same processed material is shown in FIG. 7 (upper 10,000 times, lower: 100,000 times).
  • XPS analysis revealed that large oxygen and titanium peaks were obtained, and that the surface compound was clearly titanium oxide.
  • the surface color tone was dark brown, and it was seen as a thin film of titanium (trivalent) oxide or a mixed oxide of titanium (trivalent) and titanium (tetravalent). That is, the surface was a metal color before etching, and this surface was a natural oxidation layer of titanium, but after etching with an aqueous hydrogen bifluoride solution, it changed to a dark titanium oxide layer that was not a natural oxidation layer.
  • This titanium oxide layer was etched by 10 to several tens of nm with an argon ion beam, and the etched surface was analyzed by XPS.
  • This XPS analysis revealed the thickness of the titanium oxide layer, which is clearly thicker than the natural oxide layer, and when pure titanium-based titanium alloy was etched with an aqueous solution of 1 hydrogen difluoride ammonium. It was considered to be 50 nm or more.
  • the valence of titanium ions decreases from the surface to the inside, the divalence increases from the tetravalent or trivalent and tetravalent mixed state of the surface toward the inside, and further the divalent decreases to zero. It turns out that it leads to metal.
  • the oxide film that is titanium oxide is not a simple titanium oxide layer, but a continuously changing layer in which the titanium valence continuously decreases from the surface and reaches zero. As it penetrated from the surface, the surface was a continuously changing layer that became darker and thinner toward the inside. Since there is no clear boundary between such a metal oxide film and a metal alloy, the bonding force between the oxide film layer and the metal alloy layer is extremely strong. Therefore, it can be said that it has sufficient resistance to the force to peel off both.
  • the specific treatment method for titanium alloys other than pure titanium-based titanium alloys is the same as the treatment method described above, but is included as a small amount of additive by the nascent hydrogen gas generated during etching with a reducing strong acid aqueous solution.
  • other metals may be reduced to produce insoluble matter, so-called smut.
  • Most of the smut can be dissolved and removed by immersing in a nitric acid aqueous solution having a concentration of several percent. However, depending on the alloy, smut that does not dissolve in the aqueous nitric acid solution may be generated. In that case, it is preferable to wash by applying ultrasonic waves during washing with water.
  • the surface shape of an alloy other than a pure titanium-based titanium alloy etched with ammonium monohydrogen difluoride and smut-removed is a surface shape that is difficult to express in a language as compared to the above-mentioned photograph of FIG. become.
  • An example of an ⁇ - ⁇ type titanium alloy containing aluminum is shown in the photograph of FIG. 8 (top: 10,000 times, bottom: 100,000 times).
  • a smooth dome-like part without ultra-fine irregularities (similar to FIG. 7), which looks like a titanium alloy, was observed, but a mysterious shape like a dead leaf of a plant was observed.
  • the entire surface is not covered with ultrafine irregularities with a period of 10 to 300 nm, which is preferable as the second condition described above, but with a longer period (referred to as “fine irregularities”) is observed.
  • the unevenness itself was smooth.
  • the dead leaf shape portion is thin and curved, and if it has hardness, it becomes a strong spike shape.
  • the surface of the ⁇ - ⁇ type titanium alloy is mostly the part that does not meet the second condition (ultra-fine irregularities with a period of 5 nm to 500 nm) in the new NMT described above. It is thought that it can play the role of unevenness. Since the spike shape of the surface is large, it is rather related to the micron-order roughness (surface roughness) required under the first condition required by the new NMT.
  • Stainless steel surface treatment In the surface treatment of stainless steel, first degreasing treatment is performed. A special degreasing agent is not necessary, and a commercially available general degreasing agent for stainless steel, a degreasing agent for iron, a degreasing agent for aluminum alloy, or a commercially available neutral detergent can be used. Usually, a commercially available degreasing agent or neutral detergent is dissolved in water to a concentration of several percent, the temperature of this aqueous solution is 40 to 70 ° C., stainless steel is immersed in this for 5 to 10 minutes, and then washed with water.
  • Stainless steel is totally corroded by aqueous solutions of hydrohalic acid such as hydrochloric acid, sulfurous acid, sulfuric acid, and metal halides.
  • hydrohalic acid such as hydrochloric acid, sulfurous acid, sulfuric acid, and metal halides.
  • the immersion conditions may be changed depending on the type of stainless steel.
  • the hardness is lowered by annealing or the like to structurally increase the metal crystal grain size, the crystal grain boundaries are reduced, and it is difficult to obtain a micron-order roughness by corroding the entire surface.
  • chemical etching is performed so as to obtain a surface in which a portion having a roughness on the order of microns is predominant.
  • SUS304 it is preferable to immerse a sulfuric acid aqueous solution having a concentration of about 10% at a temperature of 60 to 70 ° C. for several minutes, and this treatment method can obtain the micron order roughness required in the present invention.
  • SUS316 it is preferable to immerse an aqueous sulfuric acid solution having a concentration of about 10% at a temperature of 60 to 70 ° C. for 5 to 10 minutes.
  • Hydrohalic acid such as aqueous hydrochloric acid, is also suitable for chemical etching, but if this aqueous solution is heated to high temperatures, part of the acid may volatilize and corrode surrounding iron structures. Some processing is required for the gas.
  • an aqueous sulfuric acid solution is preferable in terms of cost.
  • the progress of overall corrosion may be too slow with an aqueous solution of sulfuric acid alone.
  • fine etching is achieved at the same time by performing chemical etching.
  • an oxidizing acid such as nitric acid such as nitric acid, ie nitric acid, hydrogen peroxide, potassium permanganate, sodium chlorate, etc.
  • nitric acid such as nitric acid, ie nitric acid, hydrogen peroxide, potassium permanganate, sodium chlorate, etc.
  • FIG. 9 An example of chemical etching of stainless steel with sulfuric acid aqueous solution is shown in FIG. A micron-order roughness is formed on the surface by appropriate etching. When the surface is observed with an electron microscope, it can be seen that the surface is covered with ultrafine irregularities. In short, in stainless steel, fine etching is achieved at the same time by chemical etching alone.
  • FIG. 9 a shape in which particles having a diameter of 20 to 70 nm, irregular polygonal shapes, etc. are stacked is recognized, and this 10,000 times photograph (FIG. 9 (top)) and 100,000 times photograph (FIG. 9 (bottom)). Both of them were very similar to the lava field on the slope of the lava plateau formed by lava flowing around the volcano.
  • the surface is an oxide of a metal having exactly the same composition as that of ordinary stainless steel, and is covered with a similar corrosion resistant surface.
  • degreasing treatment In the surface treatment of the steel material, first, degreasing treatment is performed.
  • steel materials that are commercially available such as SPCC, SPHC, SAPH, SPFH, SS material, etc.
  • degreasing agents that are commercially available for these steel materials, degreasing agents for stainless steel, degreasing agents for aluminum alloys, or commercially available
  • a general-purpose neutral detergent can be used.
  • a commercially available degreasing agent or neutral detergent is dissolved in water to a concentration of several percent, the temperature of this aqueous solution is set to 40 to 70 ° C., the steel material is immersed in this for 5 to 10 minutes, and then washed with water.
  • a dilute caustic soda aqueous solution for a short time, it is preferably washed with water. This is because the preliminary chemical cleaning improves the reproducibility of the next chemical etching.
  • ⁇ Surface treatment method I Chemical etching only> After the chemical etching described above, it is washed with water, dried, and observed with an electron micrograph. Ultra-fine irregularities with a height and depth of 50 to 500 nm and a width of several hundred to several thousand nm followed by infinite steps. Often, the shape covers almost the entire surface. This seems to have exposed the pearlite structure that steel materials generally have. Specifically, when an aqueous sulfuric acid solution is used under appropriate conditions in the chemical etching step, an uneven surface having a roughness on the order of microns can be obtained, and at the same time, stepped ultrafine unevenness can be formed simultaneously. Many.
  • ⁇ Surface treatment method II Adsorption of amine-based molecules> After the chemical etching described above, the substrate is washed with water, immersed in an aqueous solution of ammonia, hydrazine, or a water-soluble amine compound, washed with water, and dried. And broad amine-type substances, such as ammonia, remain in steel materials. When the steel material after drying is analyzed by XPS, nitrogen atoms are confirmed. Therefore, it was estimated that amines in a broad sense including ammonia and hydrazine were chemisorbed on the steel material surface. According to the result of observation with a 100,000 times electron microscope, a thin film-like foreign substance is adhered to the surface, so that an amine complex of iron may be formed.
  • aqueous ammonia hydrazine aqueous solution, or aqueous solution of water-soluble amine
  • the effect can be obtained by using an aqueous solution having a concentration of 0.5 to several percent at room temperature, immersing for 0.5 to several minutes, washing with water and drying.
  • ammonia water having a concentration of about 1% which is slightly odorous but inexpensive, or an aqueous solution of 1% to several percent of hydrated hydrazine having a small odor and a stable effect is preferable.
  • ⁇ Surface treatment method III chemical conversion treatment>
  • the steel material that has undergone chemical etching or the steel material that has been subjected to chemical etching and adsorption of the amine-based molecules is washed with water, and then immersed in an aqueous solution containing a hexavalent chromium compound, a permanganate, or a zinc phosphate-based compound. Wash with water.
  • the steel material surface is covered with a metal oxide such as chromium oxide, manganese oxide, zinc phosphorous oxide, or metal phosphorous oxide, thereby improving the corrosion resistance. This is a well-known method for improving the corrosion resistance of steel materials.
  • the purpose of the chemical conversion treatment in the present invention is not to ensure complete corrosion resistance but to have at least sufficient corrosion resistance until injection joining is performed, and it is difficult to cause trouble over time in the joined portion even after bonding. That is.
  • the chemical conversion film is thickened, it is preferable from the viewpoint of corrosion resistance, but not preferable from the viewpoint of bonding strength.
  • a chemical conversion film is necessary, since it has a property of being hard but brittle, if it is too thick, the bonding force is weakened.
  • chromium (III) oxide When a steel material is immersed in a dilute aqueous solution of chromium trioxide, washed with water and dried, the surface is covered with chromium (III) oxide. The surface was not covered with a uniform film-like object, and protrusions having a diameter of 10 to 30 nm and an equivalent height were generated at a distance of about 100 nm. Further, an aqueous solution of potassium permanganate having a concentration of several percent adjusted to weak acidity could be preferably used. In order to obtain a high adhesive force on the surface of the steel material, it is necessary to make the chemical conversion film thin.
  • an aqueous solution having a concentration of several percent is brought to a temperature of 45 to 60 ° C., and the steel material is immersed in this for 0.5 to several minutes. there were.
  • Polyamide resin composition for injection joining As the polyamide resin composition used in the present invention, two kinds of resins will be described as specific examples. These are properly used depending on the application. One is a resin composition having a high injection bonding strength, and the other is a soft resin molded product having a low injection bonding strength. This is suitable for characteristic uses such as snap fit.
  • PA66 or PA6 accounts for 90 to 30% by mass and PA610 accounts for 10 to 70% by mass in the resin component. Of these, PA66 or PA6 accounts for 80 to 30% by mass and PA610 accounts for 20 to 70% by mass in the resin content. Furthermore, PA66 or PA6 accounts for 70-50% by mass (optimum value is 55% by mass) and PA610 accounts for 30-50% by mass (optimum value is 45% by mass) in the resin content. .
  • This resin composition preferably contains an inorganic filler such as glass fiber in an amount of 30 to 50% by mass based on the entire resin composition.
  • This resin composition is a resin composition having increased hardness, bonding strength, and the like.
  • PA66 containing glass fibers PA610 not containing glass fibers
  • PA66 containing glass fibers compared to those using compound pellets in which separately added glass fibers are well dispersed and mixed with each other are used as the resin composition.
  • PA610 which does not contain glass fiber showed higher injection joining force. This is a unique phenomenon in terms of polymer physics, and the reasoning for explaining the event is described in the experimental examples.
  • the latter resin composition is such that PA610 accounts for 80 to 100% by mass and other polyamide resins account for 0 to 20% by mass in the resin content.
  • This resin composition preferably contains an inorganic filler such as glass fiber in an amount of 0 to 20% by mass based on the entire resin composition.
  • the latter is somewhat soft and has a bonding strength that is less than that of the former resin composition. However, it can be used sufficiently for purposes other than applications that require extremely high bonding strength.
  • the filler used can be glass fiber, carbon fiber, boron fiber, other reinforcing fiber group, and / or calcium carbonate, dolomite, talc, glass powder, clay, and other inorganic powders.
  • the filling of the filler is effective for increasing the bonding strength and adjusting the softness.
  • FIG. 1 and 2 are views relating to injection joining of a thermoplastic resin
  • FIG. 1 is a cross-sectional view schematically showing a cross section of an injection mold used in an experimental example.
  • FIG. 1 shows a state in which the mold is closed and injection molding is performed.
  • FIG. 2 is an external view showing the appearance of a composite 7 of a metal alloy piece and a polyamide resin composition (solidified product) injection-bonded using an injection mold.
  • This injection mold is composed of a movable side mold plate 2 and a fixed side mold plate 3, and a resin injection part composed of a pinpoint gate 5, a runner and the like is formed on the fixed side mold plate 3 side.
  • the composite 7 is molded as follows.
  • the movable mold plate 2 is opened, and the metal alloy piece 1 is inserted into a cavity formed between the movable mold plate 2 and the fixed mold plate 3.
  • the movable side template 2 is closed to the state before injection in FIG.
  • the molten polyamide resin composition is injected into the inserted cavity of the metal alloy piece 1 through the pinpoint gate 5.
  • the polyamide resin composition is molded while filling the cavity while being joined to the metal alloy piece 1, and a composite 7 in which the metal alloy piece 1 and the polyamide resin composition (solidified product) 4 are integrated is obtained.
  • the composite 7 has a joint surface 6 between the metal alloy piece 1 and the polyamide resin composition 4, and the area of the joint surface 6 is 5 mm ⁇ 10 mm. That is, the area of the joining face 6 is 0.5 cm 2.
  • the present invention it is possible to obtain a composite in which a polyamide resin composition containing an aliphatic polyamide resin suitable as an engineering plastic as a main resin component and a metal alloy are firmly integrated by injection molding.
  • the composite of the present invention is obtained by strongly joining and integrating a metal alloy and a polyamide resin composition containing PA610.
  • a metal alloy is used as a chassis of an electronic device, it is possible to injection-mold a polyamide resin composition therein, and to firmly bond the boss or rib that is the molded product to the chassis.
  • the polyamide resin composition and metal alloy which does not contain any aromatic polyamide resin that easily absorbs ultraviolet rays, and the resin component is all aliphatic polyamide resin, by injection molding, A completely halogen-free composite can be produced, contributing to environmental measures.
  • the aliphatic polyamide resin is flexible, when it is used as a screw boss, even if it contains some filler, it can meet the demands of the customer, such as a normal wood screw type screw can be tightened.
  • PA610 has a low hygroscopicity as compared with other aliphatic polyamide resins, and has a quickness and is slightly soft, this quickness suppresses the expansion of internal strain including the time of moisture absorption, Contributes to maintaining the bonding strength with metal alloys.
  • PA610 which is 100% by mass of PA610 and does not contain an inorganic filler, exhibited a shear breaking force of 20 MPa under dry conditions. That is, there is no need to mix with other resins, and a high bonding force is exhibited without using a filler, which greatly contributes to shortening the manufacturing process and reducing the cost.
  • the composite made of a metal alloy shaped article and an aliphatic polyamide resin molded product obtained by the present invention is particularly suitable for use in mobile electronic devices, home appliances, mechanical parts, etc., and is a halogen-free composite.
  • FIG. 1 is a cross-sectional view of an injection mold used in the experimental example.
  • FIG. 2 is an external view showing an external appearance of a composite of a metal alloy piece and a polyamide resin composition obtained by injection joining.
  • FIG. 3 is an electron micrograph (upper 10,000 times, middle: 50,000 times, lower: 100,000 times) of a surface obtained by chemically etching an A5052 aluminum alloy with a caustic soda aqueous solution and finely etching with a hydrated hydrazine aqueous solution.
  • FIG. 1 is a cross-sectional view of an injection mold used in the experimental example.
  • FIG. 2 is an external view showing an external appearance of a composite of a metal alloy piece and a polyamide resin composition obtained by injection joining.
  • FIG. 3 is an electron micrograph (upper 10,000 times, middle: 50,000 times, lower: 100,000 times) of a surface obtained by chemically etching an A5052 aluminum alloy with a caustic soda aqueous solution and finely etching with
  • FIG. 4 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching an A7075 aluminum alloy with a caustic soda aqueous solution and finely etching with a hydrated hydrazine aqueous solution.
  • FIG. 5 is a 100,000 times electron micrograph of a surface obtained by chemically etching an AZ31B magnesium alloy with a citric acid aqueous solution and chemical conversion treatment with a potassium permanganate aqueous solution.
  • FIG. 6 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching a KFC copper alloy with sulfuric acid / hydrogen peroxide aqueous solution and surface hardening treatment with sodium chlorite aqueous solution.
  • FIG. 7 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching a KS40 pure titanium-based titanium alloy with an aqueous solution of 1 hydrogen difluoride ammonium.
  • FIG. 8 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching KSTi-9 ( ⁇ - ⁇ titanium alloy) with an aqueous solution of 1 hydrogen ammonium difluoride.
  • FIG. 9 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching SUS304 stainless steel with a sulfuric acid aqueous solution.
  • FIG. 10 is an electron micrograph (upper 10,000 times, lower: 100,000 times) of a surface obtained by chemically etching SPCC cold-rolled steel with a sulfuric acid aqueous solution and chemical conversion treatment with a potassium permanganate aqueous solution.
  • Example 1 (Surface treatment of aluminum alloy) A commercially available 1.6 mm thick A5052 aluminum alloy sheet was obtained and cut to produce a large number of 45 mm ⁇ 18 mm rectangular pieces. “NE-6 (Meltex Co., Ltd., Tokyo, Japan)”, a commercially available degreasing agent for A5052 aluminum alloy, was added to the first tank together with water, and an aqueous solution having a concentration of 7.5% at 60 ° C. It was. The A5052 aluminum alloy sheet was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution having a temperature of 40 ° C.
  • an aqueous solution containing 3.5% monohydric hydrazine at 60 ° C. was prepared in another fifth tank, and the A5052 aluminum alloy sheet was immersed in it for 2 minutes and washed with water. Subsequently, it put into the warm air dryer which was 67 degreeC for 15 minutes, and dried. After drying, the A5052 aluminum alloy sheet was wrapped together with aluminum foil, which was then sealed in a plastic bag. Four days later, the surface of the single A5052 aluminum alloy sheet was observed with an electron microscope and found to be covered with a recess having a diameter of 30 to 100 nm. The photograph regarding this is shown in FIG.
  • Example 2 (Surface treatment of aluminum alloy) A commercially available A7075 aluminum alloy sheet having a thickness of 3 mm was obtained and cut to produce a large number of 45 mm ⁇ 18 mm rectangular pieces. “NE-6”, a commercially available degreasing agent for A7075 aluminum alloy, was added to the first tank together with water to form an aqueous solution at 60 ° C. and a concentration of 7.5%. The A7075 aluminum alloy sheet was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution having a temperature of 40 ° C. was prepared in another second tank, and the A7075 aluminum alloy sheet was immersed in it for 1 minute and washed with water.
  • NE-6 a commercially available degreasing agent for A7075 aluminum alloy
  • a 1.5% strength aqueous caustic soda solution at 40 ° C. was prepared in another third tank, and the A7075 aluminum alloy sheet was immersed for 4 minutes and washed with water.
  • a 3% nitric acid aqueous solution adjusted to 40 ° C. was prepared in another fourth tank, and the A7075 aluminum alloy sheet was immersed in it for 1 minute and washed with water.
  • an aqueous solution containing 3.5% monohydric hydrazine at 60 ° C. was prepared in another fifth tank, and the A7075 aluminum alloy sheet was immersed in it for 2 minutes and washed with water.
  • the A7075 aluminum alloy sheet was immersed in a 5% hydrogen peroxide aqueous solution at 40 ° C. for 5 minutes and washed with water.
  • it put into the warm air dryer which was 67 degreeC for 15 minutes, and dried.
  • the A7075 aluminum alloy sheet was wrapped together with aluminum foil, which was then sealed in a plastic bag.
  • one A7075 aluminum alloy sheet was observed with an electron microscope, it was found to be covered with a recess having a diameter of 40 to 100 nm. The photograph regarding this is shown in FIG.
  • another A7075 aluminum alloy sheet was subjected to a scanning probe microscope to obtain roughness data. According to this, the surface had RSm of 3 to 4 ⁇ m and Rz of 1 to 2 ⁇ m.
  • Example 3 (Surface treatment of magnesium alloy) A commercially available AZ31B magnesium alloy sheet having a thickness of 1 mm was obtained and cut to prepare a large number of 45 mm ⁇ 18 mm rectangular pieces. “Cleaner 160 (manufactured by Meltex Co., Ltd.)”, which is a commercially available degreasing agent for magnesium alloys, was added to the first tank together with water to obtain an aqueous solution at 65 ° C. and a concentration of 7.5%. The AZ31B magnesium alloy sheet was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% strength aqueous hydrated citric acid solution at 40 ° C.
  • an aqueous solution containing 20% of “CB-5002 (MEC Co., Ltd., Hyogo, Japan)”, which is an etching material for copper alloy at 25 ° C., and 18% of 30% hydrogen peroxide was prepared.
  • the KFC plate material which is a copper alloy piece was immersed for 8 minutes and washed with water.
  • an aqueous solution containing 10% caustic soda at 65 ° C. and 5% sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the KFC plate was immersed for 1 minute and washed with water.
  • the surface was a mixture of small particle diameters with a diameter of 10 to 20 nm and large indefinite polygons with a diameter of 50 to 150 nm, in other words, the shape of a lava plateau sloped glass field.
  • the entire surface was covered with an ultra-fine uneven shape. A photograph of the relationship is shown in FIG.
  • Example 5 (Surface treatment of titanium alloy) A commercially available pure titanium type titanium alloy JIS type 1 “KS40 (manufactured by Kobe Steel, Ltd.)” 1 mm thick plate material was obtained and cut to produce a large number of 45 mm ⁇ 18 mm rectangular pieces. An aqueous solution containing 7.5% of “NE-6” which is a commercially available aluminum alloy degreasing agent in a tank was made 60 ° C. to obtain a degreasing aqueous solution. KS40, which is the titanium alloy plate material, was immersed in the aqueous solution for 5 minutes for degreasing and thoroughly washed with water.
  • KA-3 manufactured by Metallurgy Engineering Laboratory, Tokyo, Japan
  • a universal etching material containing 40% ammonium difluoride at 60 ° C An aqueous solution was prepared, and the KS40 was immersed in the solution for 3 minutes and washed thoroughly with ion-exchanged water. Subsequently, it was immersed in a 3% nitric acid aqueous solution for 1 minute and washed with water. It put into the warm air dryer which was 90 degreeC for 15 minutes, and dried.
  • the above KS40 was wrapped together with aluminum foil, which was then stored in a plastic bag.
  • one KS40 was cut and observed with an electron microscope and a scanning probe microscope. From observation with an electron microscope, the surface has a height or width of 10 to 300 nm and a length of 10 nm or more of ridges or mountain ranges (mountain-like) convex portions having a period of 10 to 350 nm and existing on the entire surface. A unique ultra-fine irregular shape was shown. A photograph related to this is shown in FIG.
  • the surface when observed with a scanning probe microscope, the surface had an RSm of 3 to 4 ⁇ m and an Rz of 1 to 2 ⁇ m, and the difference in height between individual irregularities was mostly 0.5 to 1.5 ⁇ m. Further, from the analysis by XPS, a large amount of oxygen and titanium were observed on the surface, and a small amount of carbon was observed. From these, it was found that the surface layer was mainly composed of titanium oxide, and because it was dark, it was presumed to be a trivalent titanium oxide.
  • Example 7 (Stainless steel surface treatment) A commercially available 1 mm thick stainless steel SUS304 plate was obtained and cut to produce a large number of 45 mm ⁇ 18 mm rectangular pieces. An aqueous solution containing 7.5% of “NE-6” which is a commercially available aluminum alloy degreasing agent in a tank was made 60 ° C. to obtain a degreasing aqueous solution. The stainless steel SUS304 plate was immersed in the aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Subsequently, an aqueous solution containing 10% of 98% sulfuric acid at 60 ° C.
  • one stainless steel SUS304 plate was cut and observed with an electron microscope and a scanning probe microscope. From the observation with an electron microscope, the surface is covered with an ultrafine irregular shape of a laminar plate slope galley field, that is, a shape in which particles with a diameter of 20 to 70 nm and indefinite polygonal shapes are stacked, and the coverage is about 90%. The related photograph is shown in FIG. At the same time, by scanning analysis with a scanning probe microscope, the surface was 2-6 ⁇ m in the interval between peaks and valleys, and RSm was around 4 ⁇ m. The height difference was 0.2 to 1 ⁇ m. Yet another stainless steel SUS304 plate was subjected to XPS analysis.
  • the various resin compositions were produced in the same manner by changing the mixing ratio (number of parts by mass) of “Amilan CM3001G45” and “Amilan 2001”.
  • PA66 accounted for 91% by mass and PA610 accounted for 9% by mass as the resin component composition, and a resin composition (2) containing 43% by mass of glass fibers was obtained.
  • PA66 accounted for 83 mass% and PA610 accounted for 17 mass% as a resin component composition, and the resin composition (3) which contains 41 mass% of glass fibers as a whole was obtained.
  • PA66 accounted for 56 mass% and PA610 accounted for 44 mass% as a resin part composition, and the resin composition (5) which contains 36 mass% of the whole glass fiber was obtained.
  • PA66 accounted for 46 mass% and PA610 accounted for 54 mass% as a resin component composition, and the resin composition (6) which contains 36 mass% of glass fibers as a whole was obtained. Further, PA66 accounted for 27% by mass and PA610 accounted for 73% by mass as the resin component composition, and a resin composition (8) containing 36% by mass of glass fibers was obtained.
  • Table 1 shows the composition ratio (PA66: PA610) in the resin text of these resin compositions (1) to (8) and the mass ratio of the glass fiber as the filler to the entire resin composition.
  • Example 11 (Injection joining force of PA66 / PA610 resin) An A5052 aluminum alloy sheet material prepared in Experimental Example 1 was inserted into an injection mold heated to 140 ° C., and the resin composition prepared in Experimental Example 9 was injected at an injection temperature of 280 ° C., and an integrated product having the shape shown in FIG. Got. These were placed in a hot air drier at 150 ° C. for 1 hour, aged and allowed to cool, and the internal distortion of the joint surface due to injection joining was removed. Three days later, the sample was broken with a tensile tester, and the shear breaking strength was measured. Table 3 shows the average of three measurements for each.
  • the A5052 aluminum alloy sheet material prepared in Experimental Example 1 was inserted into an injection mold heated to 140 ° C., and various resin compositions prepared in Experimental Example 10 were injected at an injection temperature of 280 ° C., and the shape shown in FIG. An integrated product was obtained. These were placed in a hot air drier at 150 ° C. for 1 hour, aged and allowed to cool, and the internal distortion of the joint surface due to injection joining was removed. Three days later, the sample was broken with a tensile tester, and the shear breaking strength was measured. Each of the three measurements was shown in Table 2.
  • the resin composition (5) had the highest shear breaking strength (29.8 MPa), but the resin composition as a whole was a dry blend (1 ) Occupied the highest value (35.8 MPa).
  • Resin compositions (1) and (5) have the same resin composition, and the glass fiber ratio is not significantly different. However, a difference of 6 MPa occurred in the shear breaking force. This phenomenon has been reproduced in subsequent tests, and the physical properties of the resin composition change due to the uniformity of the distribution density of the filler added to the thermoplastic resin, in other words, the distribution pattern of the filler density. It is shown that.
  • the molded product from the dry blend has one kind of sea-island structure. That is, a kind of hard segment part (island part) where harder PA66 and glass fiber are gathered at high concentrations, and other part (sea part) where PA66, PA610 and glass fiber are mixed are somewhat low in hardness. ) Is assumed. More simply, the existence density of the glass fibers is not completely uniform as a whole, and it can be considered that the hardness is low relative to the glass fiber addition rate as a whole, and this has been effective in improving the speed.
  • the rate of addition of fillers such as reinforcing fibers and inorganic powders is directly related to the hardness, strength, linear expansion rate, and molding shrinkage rate of the thermoplastic resin.
  • the filler distribution is not completely uniform dispersion but sea-island type uniform dispersion where the density of the filler existing density is an island, the degree of influence of the filler addition rate on various polymer properties can be expected to change. If the island part has a high density of reinforcing fibers, the hardness, tensile modulus, and flexural modulus will probably decrease, and the linear expansion rate, molding shrinkage rate, and water absorption rate will have a relatively small effect. We can infer that it will improve.
  • Example 13 (Injection bonding strength of PA610 resin)
  • the A5052 aluminum alloy sheet produced in Experimental Example 1 was inserted into an injection mold heated to 140 ° C., and PA610 resin “Amilan 2001” containing no glass fiber was used as it was for injection joining.
  • the injection temperature was 280 ° C. These were placed in a hot air drier at 150 ° C. for 1 hour and aged, and after 3 days, they were broken with a tensile tester and the shear breaking strength was measured. Six measurements were 16-22 MPa, and the average was 19.5 MPa.
  • the shear breaking force between the A7075 aluminum alloy and the resin composition (1) was measured in Experimental Example 14, the shear breaking force between the AZ31B magnesium alloy and the resin composition (1) was measured in Experimental Example 15, and the KFC copper alloy The shear breaking force with the resin composition (1) was measured in Experimental Example 16, the shear breaking force between the KS40 titanium alloy and the resin composition (1) was measured in Experimental Example 17, and the KSTi-9 titanium alloy and the resin composition were measured.
  • the shear breaking force with the product (1) was measured in Experimental Example 18, the shear breaking force between SUS304 stainless steel and the resin composition (1) was measured in Experimental Example 19, and the SPCC cold-rolled steel material and the resin composition ( The shear breaking strength with 1) was measured in Experimental Example 20.
  • the average values are shown in Table 3 together with the test results of Experimental Example 11 (shear breaking force between the A5052 aluminum alloy and the resin composition (1)).
  • the surface treatment method of various metal alloys is not limited to the method shown in the above experimental example. All the methods shown in the surface treatment examples of the various metal alloys described above can be naturally applied, and even if the above-mentioned PA66 / PA610 resin is injection-molded to the metal alloys subjected to these surface treatments, the same shearing is possible. This is considered to indicate the breaking force.
  • any metal alloy type was firmly bonded to the resin composition (1).
  • the A5052 aluminum alloy showed an extremely high shear breaking force of 35.8 MPa and the A7075 aluminum alloy showed an extremely high shear breaking force of 26.3 MPa. This indicates that it can be used for applications requiring extremely high reliability.
  • KFC copper alloy, KS40 titanium alloy, KSTi-9 titanium alloy, and SUS304 stainless steel also show a high shear fracture strength of around 20 MPa, and can be used for applications requiring high reliability.
  • other AZ31B magnesium alloys and SPCC cold rolled steel materials the bonding strength that can be sufficiently used in general applications was shown.
  • the present invention relates to a technique for joining a metal alloy and a polyamide resin composition.
  • the polyamide resin composition is injection-molded inside the chassis of the electronic device, and the boss or rib that is the molded product can be firmly bonded to the chassis.
  • the housing of electronic devices it can be used for housings of household electrical appliances, machine parts, and the like.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention porte sur : un composite obtenu par liaison tenace d'un alliage métallique à un article moulé d'une résine polyamide aliphatique ; et un procédé pour la production du composite. (1) Une surface d'un alliage de métal est amenée à avoir une rugosité de l'ordre du micromètre dans laquelle les éléments de courbe de contour ont une longueur moyenne (RSm) de 0,8-10 µm et une hauteur maximale (Rz) de 0,2-5 µm. (2) Dans la surface ayant la rugosité, des irrégularités microfines ayant une période de 5-500 nm sont formées. (3) Une couche de surface est convertie en une couche mince d'un oxyde métallique ou d'un phosphate de métal. Cet alliage métallique est introduit à l'intérieur d'un moule d'injection. Une composition de résine polyamide composée d'un ingrédient de résine comprenant 56 % en masse de PA66 et 44 % en masse de PA610 et des fibres de verre avec lesquelles l'ingrédient de résine est chargé, est injectée de façon à être disposée sur la surface de l'alliage. La composition de résine polyamide injectée vient à l'intérieur des irrégularités microfines puis se solidifie. Ensuite, l'alliage métallique est lié de façon tenace à l'article moulé résultant de la composition de résine polyamide.
PCT/JP2009/063801 2008-08-06 2009-08-04 Composite d'alliage métallique avec composition de résine polyamide et son procédé de fabrication WO2010016485A1 (fr)

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JP2011156764A (ja) * 2010-02-01 2011-08-18 Taisei Plas Co Ltd 金属とポリアミド樹脂組成物の複合体及びその製造方法
EP2500156A1 (fr) * 2011-03-14 2012-09-19 Hong Fu Jin Precision Industry (ShenZhen) Co. Ltd. Composite en acier inoxydable et résine et procédé de fabrication associé
WO2012132639A1 (fr) * 2011-03-25 2012-10-04 宇部興産株式会社 Composite de métal et de résine thermoplastique
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CN106903839A (zh) * 2013-07-18 2017-06-30 三井化学株式会社 金属/树脂复合结构体、金属构件以及应用
JP2018506449A (ja) * 2014-12-25 2018-03-08 ビーワイディー カンパニー リミテッド 金属−樹脂の複合体およびその製造方法、並びに電子製品のシェル
JPWO2020059128A1 (ja) * 2018-09-21 2021-08-30 三井化学株式会社 金属／樹脂複合構造体、金属／樹脂複合構造体の製造方法および冷却装置
CN113906161A (zh) * 2019-06-11 2022-01-07 三菱瓦斯化学株式会社 水性组合物、使用了其的不锈钢表面的粗糙化处理方法、以及经过粗糙化处理的不锈钢及其制造方法

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JP2011156764A (ja) * 2010-02-01 2011-08-18 Taisei Plas Co Ltd 金属とポリアミド樹脂組成物の複合体及びその製造方法
EP2500156A1 (fr) * 2011-03-14 2012-09-19 Hong Fu Jin Precision Industry (ShenZhen) Co. Ltd. Composite en acier inoxydable et résine et procédé de fabrication associé
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JPWO2012132639A1 (ja) * 2011-03-25 2014-07-24 宇部興産株式会社 金属と熱可塑性樹脂の複合体
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JP2016525032A (ja) * 2013-07-16 2016-08-22 イルグァンポリマー カンパニー リミテッド 金属合金とセラミック樹脂の複合体及びその製造方法
CN106903839A (zh) * 2013-07-18 2017-06-30 三井化学株式会社 金属/树脂复合结构体、金属构件以及应用
CN106903839B (zh) * 2013-07-18 2019-01-04 三井化学株式会社 金属/树脂复合结构体、金属构件以及应用
JP2018506449A (ja) * 2014-12-25 2018-03-08 ビーワイディー カンパニー リミテッド 金属−樹脂の複合体およびその製造方法、並びに電子製品のシェル
EP3243651A4 (fr) * 2014-12-25 2018-08-08 BYD Company Limited Composite métal-résine et son procédé de préparation et boîtier de produit électronique
JPWO2020059128A1 (ja) * 2018-09-21 2021-08-30 三井化学株式会社 金属／樹脂複合構造体、金属／樹脂複合構造体の製造方法および冷却装置
JP7074868B2 (ja) 2018-09-21 2022-05-24 三井化学株式会社 冷却装置
CN113906161A (zh) * 2019-06-11 2022-01-07 三菱瓦斯化学株式会社 水性组合物、使用了其的不锈钢表面的粗糙化处理方法、以及经过粗糙化处理的不锈钢及其制造方法

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