JP7123605B2 - A substrate at least all or part of the surface of which is made of a metallic material, the substrate having pores on the surface of the metallic material, and a substrate-resin cured product composite comprising the substrate and a cured resin product - Google Patents

Description

The present invention provides a substrate at least all or part of the surface of which is made of a metal material, the surface of the metal material having specific pores, and a substrate-resin containing the substrate and a cured resin. It relates to a composite of cured products.

As one of the methods for joining a metal material and a resin, a method is known in which the surface of the metal material is roughened and then the resin is insert-molded. For example, Patent Document 1 describes as follows.

A metal/resin composite structure formed by bonding a metal member and a resin member made of a thermoplastic resin composition, wherein any three parallel linear portions on the surface of the metal member, and the three For a total of 6 straight sections consisting of arbitrary 3 straight sections orthogonal to the straight section, the surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) The following requirements (1) and (2) at the same time A satisfying metal/resin composite structure.
(1) Including one or more linear sections where the load length ratio (Rmr) of the roughness curve at a cutting level of 20% and an evaluation length of 4 mm is 30% or less (2) Evaluation length of all linear sections Ten-point average roughness (Rz) at 4 mm exceeds 2 μm

JP 2016-27189 A

According to studies by the present inventors, the joint strength of the metal/resin composite structure obtained by the method disclosed in Patent Document 1 was sometimes insufficient.

The present invention solves the above-mentioned problems of the prior art, that is, a substrate having a metal material having specific holes with excellent bonding strength with a resin, and a substrate containing the substrate and a resin cured product-resin cured The purpose is to provide a composite of things.

As a result of intensive studies by the present inventors in order to solve the above problems, the present inventors have found that at least all or part of the surface of a substrate is made of a metal material, and the surface of the metal material has specific pores. The discovery led to the completion of the present invention.
That is, the gist of the present invention is as follows.

[1] A substrate at least all or part of the surface of which is made of a metal material, the surface of the metal material having pores, and satisfying the following requirements (1) and (2).
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at a cutting level of 30% and an evaluation length of 10 μm (2) The average diameter (a) at the entrance of the hole and the average hole depth [2] A substrate-resin composite comprising a substrate and a resin cured product having an aspect ratio (b/a) of 2 or more and 50 or less with respect to the value (b), wherein the substrate is described in [1] and a substrate-resin cured product composite containing a resin cured product in the pores on the surface of the metal material of the substrate.

According to the present invention, there is provided a base material having excellent bonding strength with a resin, at least all or part of the surface of which is made of a metal material, the surface of the metal material having specific holes, and the base material and the base material. A substrate-cured resin composite containing a cured resin can be provided.

It is a schematic diagram for demonstrating the cross-sectional structure of the surface of a base material, and the measuring method of the load length rate of the cross-sectional curve. FIG. 4 is a schematic diagram for explaining the shape of a hole present on the surface of a base material and the positions where the diameter of the hole is measured. FIG. 2 is a schematic diagram of the cross-sectional structure of the base material shown in FIG. 1, and is a schematic diagram for explaining a method of measuring the diameter at the entrance of the hole and the hole depth.

The present invention will be described in detail below.
In this specification, the term "hole" does not mean a through hole, but means something that forms a recess.

<Substrate at least all or part of the surface is made of metal material>
The base material applied to the embodiment of the present invention is not particularly limited as long as at least all or part of the surface is a base material made of a metal material.
Examples of the metal material present on at least all or part of the surface of the substrate include iron, iron alloys, titanium, titanium alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, copper, copper alloys, etc., but particularly Not limited. The base material is not particularly limited, and includes expanded material, extruded material, cast material, and die-cast material. The metal material may be used alone, or two or more metal materials may be used in combination. Among these metal materials, aluminum or an aluminum alloy is preferable from the viewpoint of light weight and high strength. Henceforth, aluminum or an aluminum alloy may be simply called an "aluminum material."

The iron or iron alloy is not particularly limited, and includes industrially used ordinary steel, chromium molybdenum steel, stainless steel, and the like. Specifically, S45C, SCM415, SUS304, SUS316, SUS430, etc., which are standardized in JIS G 4051, JIS G 4053, JIS G4304, etc., can be mentioned.

Titanium or titanium alloys are not particularly limited, and industrially used pure titanium, α-β alloys, β alloys, and the like can be mentioned. Specifically, titanium alloys such as one to four types of pure titanium, Ti-6Al-4V and Ti-22V-4Al, which are standardized in JISH 4600, can be mentioned.

Aluminum or an aluminum alloy is not particularly limited, and any industrially used aluminum material can be applied. An aluminum material refers to a material containing 60% or more of aluminum, and examples of alloy components other than aluminum include magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc. Specific examples include A1050, A2014, A2024, A3003, A5052, A5N01, A6061, A6063, A7075, AC4A, ADC12, etc., which are standardized in JIS H 4000, JIS H 5302 and JIS H 5202.

The magnesium alloy is not particularly limited, and any industrially used magnesium alloy can be applied. Specific examples of magnesium alloys include AZ92, AZ91, AZ80, AZ63, AZ61, AZ31, AM100, AM60, AM50, AM20, AS41, AS21, AE42, and ACM522.

Copper or copper alloy is not particularly limited, and any industrially used copper or copper alloy can be applied. Specific examples of copper or copper alloys include C1020, C1100, C1220, C2801, C4621, C6140, etc., which are standardized in JIS H3100.

The shape of the base material, at least all or part of which is made of a metal material, is not particularly limited as long as it is a shape that can be bonded with resin. may Moreover, the structure which combined these may be used. In addition, all of intermediate products and finished products are included in the category of the substrate according to the embodiment of the present invention. As long as all or part of at least the surface of the base material is made of a metallic material, the other portion may be made of a material other than a metallic material. Of course, the substrate may be composed only of a metal material. Materials other than metal materials include, but are not limited to, metals other than the base material, resins, rubbers, woods, ceramics, composite materials, and the like. A method for joining materials other than the base material is not particularly limited. Moreover, the shape of the surface of the joint portion of the metal material of the substrate, which is joined to the resin, may be a flat surface, a curved surface, or the like, but is not particularly limited.

The base material may be subjected to plastic working, cutting, blasting, polishing, electric discharge machining, drilling, heat treatment (age hardening treatment, solution treatment, etc.). In addition, the base material may be subjected to surface treatment (chemical conversion treatment, plating treatment, anodizing treatment, etc.). is preferably removed.

A substrate according to an embodiment of the present invention, at least all or part of which is made of a metal material, has pores on the surface of the metal material and satisfies the following requirements (1) and (2).
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at a cutting level of 30% and an evaluation length of 10 μm (2) The average diameter (a) at the entrance of the hole and the average hole depth Aspect ratio (b/a) with value (b) is 2 or more and 50 or less

As a result, when the base material having the metal material having the pores is used for the production of a base material-cured resin composite, a composite having excellent bonding strength with the resin can be formed. When the load length ratio of the cross-sectional curve is less than the above lower limit, the above strength is lowered, so that the joint strength with the resin is lowered. The load length ratio of the cross-sectional curve is more preferably 45% or more, and even more preferably 50% or more. There is no particular upper limit for the load length ratio of the cross-sectional curve, but from the viewpoint that if the load length ratio is too high, the percentage of pores present on the metal surface is small, and excellent bonding strength with the resin cannot be obtained. , usually less than 95%.
Moreover, when the aspect ratio is less than 2, the bonding strength with the resin is lowered.
Even if the load length ratio of the cross-sectional curve is at least the above lower limit, if the aspect ratio is less than 2, excellent bonding strength with the resin cannot be obtained. Further, even if the aspect ratio is 2 or more, if the load length ratio of the cross-sectional curve is less than the above lower limit, the above strength is lowered, and excellent bonding strength cannot be obtained.
Therefore, in order to obtain excellent bonding strength with the resin, it is necessary to simultaneously satisfy the above two requirements (1) and (2).

A method for measuring the load length ratio and the aspect ratio of the cross-sectional curve of the metal material having holes according to the embodiment of the present invention will be described below.

(Load length ratio of section curve (Pmr(c)))
The load length ratio (Pmr(c)) of the profile curve represents the ratio of the load length Ml(c) of the profile element at the cutting level c to the evaluation length (ln), as shown in Equation (A). The measurement method is specified in JIS B 0601.
(A) Pmr(c) = Ml(c)/ln
However, it is difficult to accurately measure the shape of the holes according to the embodiment of the present invention with a commercially available surface roughness meter or the like. Therefore, the load length ratio of the cross-sectional curve in the embodiment of the present invention is obtained by observing the cross-sectional structure appearing at the cut end when the base material having the metal material having the holes is cut in the direction perpendicular to the actual surface. Measure from a photograph taken. A method for preparing a sample for observing a cross-sectional structure is not particularly limited, but examples thereof include a mechanical polishing method, a focused ion beam method, an ion milling method, and a microtome method. In short, it suffices if the pore structure can be observed.

In the schematic cross-sectional view of the substrate having a metal material having holes on the surface shown in FIG. Let the distance be Rt. In an embodiment of the present invention, the cutting level c is set at 30%. That is, the height of 30% from the top line with respect to Rt is the cutting level. In an embodiment of the invention, the evaluation length is set to 10 μm. The load length Ml(c) measures the sum of the lengths of the body side of the profile curve elements (Ml ₁ to Ml ₉ in FIG. 1) cut by the cutting level 30% from the photograph taken with an electron microscope. can be obtained by
Therefore, the load length ratio of the cross-sectional curve in the embodiment of the present invention refers to the cross-sectional structure that appears at the cut end when the base material having the metal material having the holes is cut in the direction perpendicular to the actual surface. In the photographs taken, the ratio of the load length Ml(c) at a height of 30% from the top line to the evaluation length of 10 μm is shown. In order to obtain the load length ratio of the cross-sectional curve, it is preferable to use an electron microscope at a magnification of 10,000 times or more.

(aspect ratio)
The aspect ratio according to the embodiment of the present invention is calculated from the ratio (b/a) of the average diameter (a) at the entrance of the holes and the average depth (b) of the holes. An aspect ratio of 2 or more means that there are pores in which the average value of the pore depth in (b) is twice or more than in (a). The average value of the diameter at the entrance of the pores can be measured from a photograph taken with an electron microscope of the surface of the substrate having the metallic material having pores. Circular or elliptical pores are observed on the surface of the metal material of the substrate according to the embodiment of the present invention, as shown in FIG. The average value of the diameter at the entrance of the holes according to the embodiment of the present invention is the average value of the diameter (a in FIG. 2) or the minor axis (b in FIG. 2) of the circular or elliptical openings formed on the surface. Select the top 20% of holes from those with the longest diameter or shortest diameter of the opening, measure their length, integrate all and divide by the number of holes in the top 20% shall be the mean value of the diameter at the entrance of the In order to obtain the diameter of the pores, it is preferable to use an electron microscope at a magnification of 10,000 times or more.

The average value of the diameters at the entrances of the holes is obtained by photographing the cross-sectional structure appearing at the cut end when a large number of holes are cut in the direction perpendicular to the actual surface of the base material. It can also be measured from photographs. In that case, the average value of the diameter at the entrance of the hole is the average value of the opening width of the uppermost part of the formed hole (c in FIG. 3). Measure the length of the holes, add them all up and divide by 10 to get the average diameter at the entrance of the hole. In order to obtain the diameter of the pores, it is preferable to use an electron microscope at a magnification of 10,000 times or more. As for the method for measuring the average value of the diameters at the entrances of the pores, it is more preferable to obtain the average value from a photograph taken with an electron microscope of the surface of the base material having the metallic material having pores.

The average pore depth is measured from a photograph taken by electron microscopic observation of the cross-sectional structure appearing at the cut end when the base material is cut in the direction perpendicular to the actual surface. In order to obtain the pore depth, it is preferable to use an electron microscope at a magnification of 10,000 times or more.
The average value of the hole depth is the average value of the length between the top and the deepest part of the formed holes (d in FIG. 3). The length from the topmost part to the deepest part is measured, and the result obtained by integrating all and dividing by 10 is taken as the average hole depth.

From the viewpoint of further improving the bonding strength between the resin and the base material having the metal material having pores according to the embodiment of the present invention, the diameter of the base material at the entrance is preferably 50 nm or more and 4000 nm or less. more preferably 60 nm or more and 2000 nm or less, and still more preferably 70 nm or more and 1000 nm or less.

From the viewpoint of further improving the bonding strength between the resin and the base material having the metal material having holes according to the embodiment of the present invention, the range of the hole depth of the base material is preferably 100 nm or more and 10 μm or less, It is more preferably 200 nm or more and 9 μm or less, and still more preferably 300 nm or more and 8 μm or less.

The aspect ratio defined in (2) above according to the embodiment of the present invention is 2 or more and 50 or less. From the viewpoint of further improving the bonding strength between the resin and the substrate having the metal material having holes according to the embodiment of the present invention, the aspect ratio range is 2 or more, preferably 3 or more, and further Preferably it is 4 or more. If the aspect ratio exceeds 50, the strength of the metal material itself is reduced.

It is sufficient that one or more of the holes can be confirmed by observing arbitrary 10 points on the surface and cross section of the base material.
More specifically, in an embodiment of the present invention, the number of holes having the aspect ratio in the surface of the metal material is preferably 1 or more, preferably 2, per 1 μm ² of the surface area of the metal material. It is more preferable to have at least
The holes do not need to be present on the entire surface of the base material, and it is sufficient that at least the part to be bonded with the resin described later has the holes.

<Method for Producing Substrate Having Metal Material Having Holes>
Next, a method for manufacturing a base material having a metal material having holes according to an embodiment of the present invention (hereinafter also referred to as a hole forming step) will be described.
In the embodiment of the present invention, the method for producing the base material having the metal material having holes is not particularly limited, and examples thereof include known methods such as imprinting, laser processing, and chemical etching. The imprint method is a method of forming holes by pressing a substrate or roll having a plurality of projections against a base material having a metal material, and includes a transfer method, a press patterning method, and the like. The laser processing method is a method of forming holes by irradiating the surface of a metal material with a laser beam. The chemical etching method is a method in which a substrate having a metal material is brought into contact with a treatment liquid using chemicals to promote corrosion and form holes.
In the hole forming process according to the embodiment of the present invention, the method of forming holes by film formation is excluded. Examples of films include anodized films, chemical conversion films (phosphate-based films, zirconium-based films, chromium-based films, silicate films, lithium-based chemical conversion films), and plated films.

In the embodiment of the present invention, the following chemical etching method is suitable as a method for manufacturing the substrate having the pores. This chemical etching method is particularly suitable for the production of substrates having aluminum material on at least all or part of the surface.
Specifically, as a method for producing the substrate having pores, a surface treatment agent containing a lithium ion source and an alkali source (zinc ions and A second step of contacting an acidic aqueous solution containing an inorganic acid on the surface of the base material contacted with the surface treatment agent. A manufacturing method including steps is preferred.

In the step of forming pores in the surface of the substrate at least all or part of which is made of a metal material, the surface treatment agent of the first step is applied to the surface of the substrate at least all or part of which is made of a metal material. By bringing them into contact, a film containing elemental lithium is formed. At this time, the dissolution reaction of the passivation film including the oxide film on the surface of the base material, at least all or part of which is made of a metal material, is accompanied.
A film containing elemental lithium can be formed using a known method. Examples thereof include boehmite treatment and chemical conversion treatment, but are not limited to these. Here, the film containing the lithium element includes a hydroxide film, an oxide film, a hydrated oxide film, etc. containing a metal derived from the substrate. As the treatment method, for example, the methods described in JP-A-48-89138, JP-A-53-11841, etc. can be used.

The surface treatment agent in the first step contains a lithium ion source and an alkali source as components.

(lithium ion source)
The form of the lithium ion source is not particularly limited, and is suitable from hydroxides, chlorides, carbonates, bicarbonates, nitrates, nitrites, sulfates, persulfates, bromides, bromates, and the like. can be selected one or more.
The treatment liquid used in the first step according to the embodiment of the present invention contains lithium ions of preferably 0.001 mol/L or more and 5.00 mol/L or less, more preferably 0.10 mol/L or more and 4.00 mol/L or less. More preferably, it contains 0.50 mol/L or more and 3.50 mol/L or less. Also, the lithium salt concentration may exceed the saturation solubility.

(Alkaline source)
The first step surface treatment agent contains an alkalinity source. Examples of alkali sources include hydroxides of alkali metals or alkaline earth metals, hydroxides of magnesium, and water-soluble amine compounds.
The alkali metal or alkaline earth metal hydroxide is not particularly limited, and one or more of lithium, sodium, potassium, calcium and the like can be appropriately selected.
The surface treatment agent in the first step contains hydroxide ion as an alkali source, usually 0.001 mol/L or more and 5.00 mol/L or less, more preferably 0.005 mol/L or more and 4.00 mol/L or less, further preferably includes 0.01 mol/L or more and 3.00 mol/L or less. Further, the alkali metal, alkaline earth metal and magnesium hydroxide concentrations may exceed the saturation solubility.

The water-soluble amine compounds include primary amines with alkyl groups of 1 to 12 carbon atoms, secondary amines with alkyl groups of 1 to 12 carbon atoms, and alkyl groups with 1 to 12 carbon atoms. A tertiary amine, a primary amine having a hydroxyalkyl group having 1 to 12 carbon atoms, a secondary amine having a hydroxyalkyl group having 1 to 12 carbon atoms, and a hydroxyalkyl group having 1 to 12 carbon atoms. Any bound tertiary amine can be used, and in addition to these water-soluble amines, aromatic amines in which some or all of the aforementioned alkyl or hydroxyalkyl groups have been substituted with phenol groups.
At least one methylene of the alkyl group having 1 to 12 carbon atoms may be substituted with -NH-.
Specific water-soluble amine compounds are selected from monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, triethylenetetramine, hexamethylenetetramine, ethylenediamine, and ammonia. One type or two or more types can be selected.
The treatment liquid used in the first step according to the embodiment of the present invention contains a water-soluble amine compound of preferably 0.001 mol/L or more and 1.00 mol/L or less, more preferably 0.005 mol/L or more and 0.90 mol/L. The following can be mentioned, more preferably 0.01 mol/L or more and 0.80 mol/L or less.

As the surface treatment agent in the first step, among alkali metal or alkaline earth metal hydroxides, magnesium hydroxides, and water-soluble amine compounds, one component may be used alone, or several components may be used in combination. can also be used as

It is desirable that the surface treatment agent in the first step does not contain zinc ions and silicate ions. In the presence of zinc ions, when using a base material having an aluminum material as the metal material, a zinc substitution film is formed on the surface of the aluminum material, making it impossible to obtain desired pores. Moreover, when silicate ions are present, a film containing silicon is formed on the surface of the aluminum material, making it impossible to obtain desired pores. Furthermore, it is desirable not to contain transition metal ions such as copper, iron, nickel, and tin. Sodium, potassium, magnesium, calcium, etc. supplied from hydroxides of alkali metals, alkaline earth metals, magnesium, and salts thereof may be contained in the coating.

The surface treatment agent in the first step can be easily prepared by dissolving a lithium ion source and an alkali source in ion-exchanged water, industrial water, tap water, or the like. Elements derived from the substrate and water, such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc, may be present in the surface treatment agent.

An organic solvent, a surfactant, and a chelating agent may be added to the surface treatment agent in the first step. When these other components are added, their total content is preferably 50.0% by mass or less with respect to the total amount of the surface treatment agent.

By bringing the substrate into contact with the surface treatment agent in the first step, a coating containing lithium element can be formed on the surface of the base material, at least all or part of which is made of a metal material. The coating amount of the coating is not particularly limited, and the coating may be a continuous film or a discontinuous film.

Examples of the method of contacting the surface treatment agent in the first step with the substrate at least all or part of which is made of a metal material include immersion and spray treatment methods. A film containing lithium element can be formed on the base material by contacting the surface treatment agent, and electrolytic treatment can also be used in combination.
The liquid temperature of the surface treatment agent used in the first step is preferably 20.0°C to 100.0°C. Preferably, the pH is adjusted to 8.0 to 13.0. A contact time of 5 seconds to 1800 seconds is preferred. After the first step, a washing step and a drying step may be performed as necessary.

The acidic aqueous solution in the second step contains an inorganic acid. As the inorganic acid, one or more of appropriate ones can be selected from sulfuric acid, nitric acid, hydrochloric acid, amidosulfuric acid and the like, but the acid is not limited to these. The aqueous solution may contain an organic acid, an inorganic acid salt, an organic acid salt, etc., but preferably does not contain a transition metal.
As the organic acid, one or two or more suitable ones can be selected from formic acid, citric acid, oxalic acid, malic acid, succinic acid, malonic acid, ethylenediaminetetraacetic acid, gluconic acid and the like. It is not limited. As the inorganic acid salt and the organic acid salt, one or two or more suitable ones can be selected from alkali metal salts, alkaline earth metal salts and ammonium salts of the inorganic acid and organic acid. is not limited to The aqueous solution may contain one or more of the above inorganic acids, organic acids, or salts thereof. Although the pores may be formed in an acidic aqueous solution of either the organic acid, the inorganic acid salt, or the organic acid salt alone, from an industrial point of view, the acidic aqueous solution of the inorganic acid alone is preferable.

The total content of the components containing the inorganic acid is preferably 0.1% by mass to 70.0% by mass, more preferably 0.5% by mass to 50.0% by mass, relative to the total amount of the acidic aqueous solution. is more preferable, and 1.0% by mass to 45.0% by mass is even more preferable.

A surfactant, a chelating agent, or the like may be added to the acidic aqueous solution in the second step. When these other components are added, their total content is preferably 10.0% by mass or less with respect to the total amount of the acidic aqueous solution.

The acidic aqueous solution in the second step can be easily prepared by dissolving each of the above components in ion-exchanged water, industrial water, tap water, or the like. Elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the substrate and water may be present in the acidic aqueous solution. In addition, a component associated with dissolution of the film containing lithium element formed in the first step may be mixed.

As the method of bringing the acidic aqueous solution containing the inorganic acid in the second step into contact with the base material at least all or part of the surface of which is made of a metal material, immersion or spraying can be used. Moreover, it is also possible to use electrolytic treatment together.
The acidic aqueous solution used in the second step preferably has a liquid temperature of 10.0°C to 80.0°C. The pH may be acidic, and is preferably adjusted to pH 6.0 or less, for example. The contact time is preferably about 1 to 1800 seconds, more preferably 900 seconds or less. After the second step, a washing step and a drying step are usually performed. In the washing process, ultrasonic waves may be used together. In the drying step, natural drying may be used, or a dryer, air blower, oven, or the like may be used.

In addition, in the manufacturing method (hole forming step) according to the embodiment of the present invention, when the surface of the substrate having the metal material is treated, the entire surface of the substrate having the metal material may be treated, or the substrate may be partially treated. You may In order to obtain excellent bonding strength with the resin, only the portion to be bonded with the resin should be treated.

Other steps may be present in the method of manufacturing a substrate having a metallic material with pores according to an embodiment of the present invention. Examples of other steps include a step of processing the surface of the metal material of the substrate and a step of cleaning it before performing the manufacturing method (hole forming step) according to the embodiment of the present invention. Further, after forming pores in the surface of the metal material of the substrate, a step of forming a coating may be performed before subjecting the substrate to the method for producing a cured resin composite. Each step may be repeated if necessary. Each step will be described in detail below.

(Surface processing process)
The substrate having a metal material used in the substrate manufacturing method according to the embodiment of the present invention is subjected to shot blasting, sandblasting, grinding before the manufacturing method (hole forming step) according to the embodiment of the present invention. Mechanical roughening treatment such as processing, physical roughening treatment such as laser processing and plasma processing, or roughening treatment may be performed in advance by a chemical method. The uneven shape formed after these processes does not matter.

(Surface cleaning process)
The substrate having a metal material, which is used in the substrate manufacturing method according to the embodiment of the present invention, has the surface of the metal material cleaned before the manufacturing method (hole forming step) according to the embodiment of the present invention. Therefore, a pretreatment consisting of a degreasing treatment, an acid treatment with an acid aqueous solution, and/or an alkali treatment with an alkaline solution may be performed.
The method of degreasing treatment is not particularly limited, and for example, a solvent-based, water-based or emulsion-based degreasing agent can be used, and alkali salts, surfactants and the like may be included. As a method for pretreatment by acid treatment, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid and hydrofluoric acid, organic acids such as citric acid and gluconic acid, and mixtures thereof can be used. Moreover, as a method of pretreatment by alkali treatment, an alkali reagent such as sodium hydroxide or potassium hydroxide is prepared, or a mixture thereof can be used.

(Post-treatment process)
A film may be formed on the surface of the metal material having the pores after performing the substrate manufacturing method (pore forming step) according to the embodiment of the present invention. The method of forming the film may be a coating type or a reactive type, and examples of the film to be formed include a natural oxide film, an anodized film, a films), silane coupling agent-cured films, and plated films, but are not limited to these. When forming a film, the film thickness is not particularly limited, but is preferably 100 nm or less. When the thickness of the film is more than 100 nm, the bonding strength with the resin may decrease. The thickness of the coating can be appropriately adjusted according to the shape of the holes.

(Other processing steps)
In addition to the steps described above, other steps may be performed as appropriate. For example, the water washing step may be performed before or after all steps (eg, surface treatment step, surface cleaning step, hole forming step, post-treatment step, etc.). Moreover, a drying step may be appropriately performed after each washing step.

<Method for manufacturing base material-cured resin composite>
The substrate-resin cured product composite according to an embodiment of the present invention is a substrate-resin composite comprising a substrate and a resin cured product, wherein the substrate is the substrate described above, A cured resin is contained in the pores on the surface of the metal material of the substrate.
The base material according to the embodiment of the present invention - the resin cured product in the resin cured product composite includes thermoplastic resins, thermosetting resins, thermoplastic elastomers, resin coatings cured to form coatings, adhesive Any resin, such as a hardened agent, may be used.
A method for producing a substrate-cured resin composite according to an embodiment of the present invention includes a hole forming step, which is a step included in the method for producing a substrate according to an embodiment of the present invention, and forming in the hole forming step and a step of putting the resin into the pores of the surface of the metal material. After the step of introducing the resin into the holes, the resin is cured by cooling, standing, or heating to form a substrate-cured resin composite. The substrate-resin cured product composite may be composed only of the substrate and the resin cured product, or in addition to the substrate having the metal material having the pores and the resin cured product, It may include a mating material that contacts the cured resin. The mating material may be any material including metal, rubber, wood, ceramics, and composite materials, as well as resin materials. Moreover, the shape of the counterpart material is not particularly limited, and may be a plate, bar, band, tube, wire, film, or the like.

As a specific method for producing a substrate-resin cured product composite according to an embodiment of the present invention, an adhesive is applied to the surface or surface of a substrate having a metal material having pores, and then an adhesive is applied to the surface of the substrate. A method of bonding materials by pasting them together, a method of applying resin to the surface or surface of a base material having a metal material having holes, and a method of bonding by thermocompression bonding, a surface or on the surface of a base material having a metal material having holes A method of joining metal and resin by applying resin to melt the resin by laser heating, setting a base material having a metal material with holes in the mold for injection molding A method of joining by insert molding (hereinafter referred to as injection molding joining), the surface or surface of the base material by contacting the resin paint with the surface or surface of the base material having the hole and then curing it Examples include a method of forming a coating film thereon.

The thermoplastic resin can be selected from known thermoplastic resins depending on the application. For example, polyamide-based resin, polycarbonate-based resin, polyvinyl-based resin, polyphenylene sulfide-based resin, polyacrylic-based resin, polyester-based resin, polyacetal-based resin, acrylonitrile-butadiene-styrene copolymer-based resin, polystyrene-based resin, polyimide-based resin, etc. One or two or more suitable ones can be selected from, but are not limited to these.

The thermosetting resin can be selected from known thermosetting resins depending on the application. For example, one or more of suitable resins can be selected from phenol resins, epoxy resins, urea resins, melamine resins, etc., but the resin is not limited to these.

The thermoplastic elastomer can be selected from known thermoplastic elastomers depending on the application. For example, one or more of suitable elastomers can be selected from polyester-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, etc., but the materials are not limited to these.

The resin paint can be selected from known resin paints depending on the application. For example, one or two or more suitable resins can be selected from epoxy resins, acrylic resins, polyester resins, urethane resins, etc., but are not limited to these. The paint may optionally contain ingredients such as pigments, dispersants, plasticizers, solvents, and the like.

Examples of the adhesive include vinyl chloride resin adhesives, vinyl acetate resin adhesives, polyvinyl alcohol adhesives, polyacrylic adhesives, polyamide adhesives, cellulose adhesives, urea resin adhesives, and melamine. Resin adhesives, phenolic resin adhesives, epoxy resin adhesives, silicon resin adhesives, polyester adhesives, polyurethane adhesives, chloroprene rubber adhesives, nitrile rubber adhesives, styrene/butadiene rubber adhesives Suitable adhesives, silicone rubber adhesives, acrylic rubber adhesives, urethane rubber adhesives, hot melt adhesives, etc., may be selected from one or more, but are limited to these. is not.

The thermoplastic resins, thermosetting resins, thermoplastic elastomers, resin paints, and adhesives may contain known fillers. For example, one or more of suitable materials can be selected from glass fiber, carbon fiber, metal fiber, ceramic fiber, glass beads, carbon powder, metal powder, ceramic powder, aluminum oxide powder, and the like. is not limited to The kind, content and shape of the filler are not particularly limited.

Application of composite with substrate having metal material having pores and cured resin according to embodiment of the present invention Composite of substrate having metal material having pores according to embodiment of the present invention and cured resin The body is useful as a material for automobile members, aircraft members, electronic device members, mobile device members, OA device members, home appliance members, and medical device members. The base material having the metal material having the holes can improve not only the bonding strength with the resin but also the adhesiveness of the plating film or the like. The substrate having a metallic material having pores and the substrate-resin cured product composite according to the embodiments of the present invention are not limited to the above applications.

EXAMPLES The present invention and its effects will be specifically described below with reference to examples and comparative examples. The substrates used in the examples and the chemicals used in all treatments were arbitrarily selected from commercially available materials and reagents, and do not limit the actual application of the present invention.

In the production of substrate-resin cured product composites according to Examples 1 to 3 and Comparative Examples 1 to 3, unless otherwise specified, an aluminum material having a width of 20 mm, a length of 45 mm, and a thickness of 1.5 mm was used as the substrate. was used.

<Method for manufacturing base material-cured resin composite>
Unless otherwise specified, the substrate-resin cured product composites according to Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to a surface cleaning process → hole forming process (first process → second process) → injection molding joining. It was manufactured through each step of the process. Each processing of the processing steps will be described below.

(Surface cleaning process)
In the surface cleaning process, after alkaline degreasing {fine cleaner 315E manufactured by Nihon Parkerizing Co., Ltd., 30 g/L (solid content concentration), 70°C, immersion time 1 minute}, alkaline cleaning (sodium hydroxide 1.0 mol/L, 40 °C, immersion time 1 minute), and water washing was carried out after each step.

(Hole forming step)
First Step In the first step, the substrate was immersed in a surface treatment agent containing lithium ions and then washed with water. The pH was adjusted using an aqueous nitric acid solution and an aqueous sodium hydroxide solution.

Second Step In the second step, the substrate was immersed in an acidic aqueous solution containing an inorganic acid, then washed with water and dried.

(Injection molding joining process)
In the injection molding joining step, a polyphenylene sulfide resin (PPS resin) containing 30% glass fiber was injection molded onto the substrate after the hole forming step. For injection molding, an electric servo injection molding machine (Si-50III) manufactured by Toyo Machinery & Metal Co., Ltd. was used. The injection molding conditions were preheat 125° C., molding temperature 320° C., mold temperature 135° C., injection speed 30 mm/sec, injection pressure 1000 kgf, holding pressure 1200 kgf, and cooling time 15 seconds. The dimensions of the molded PPS resin are 10 mm wide×45 mm long×3 mm thick. Also, the bonding area between the substrate and the PPS resin is 10 mm×5 mm.

Based on the base material and treatment steps described above, base material-cured resin composites according to Examples 1 to 3 and Comparative Examples 1 to 3 were produced. The procedures and the like in Examples and Comparative Examples are described below.

[Example 1]
A2017 standardized by JIS H 4000 was used as the base material. As a first step, the substrate was immersed for 300 seconds using the following treatment liquid (1). As a second step, the substrate was immersed for 180 seconds using the following treatment liquid (2). In this manner, a substrate-cured resin composite according to Example 1 was obtained.

The treatment liquid (1) is obtained by adding 3.0 mol/L (mol/L) of lithium chloride and 0.1 mol/L of magnesium nitrate hexahydrate to ion-exchanged water at the target capacity, While measuring the pH with a handy pH meter (portable pH meter HM-30P manufactured by Toa DKK Co., Ltd.) and an electrode for pH measurement (GST-2739C manufactured by the same company), it was adjusted to pH 10.0 using nitric acid and sodium hydroxide. adjusted and adjusted to the target volume. The temperature of the treatment liquid (1) was set at 60°C.

Treatment liquid (2) was added to deionized water so that nitric acid was 6.5 mol/L (mol/L). In this example, no pH adjustment was performed. The temperature of the treatment liquid (2) was set at 50°C.

[Example 2]
A substrate-resin cured product composite of [Example 2] was produced in the same manner as [Example 1] except that the base material was changed to A3003 standardized by JIS H4000.

[Example 3]
A substrate-resin cured product composite of [Example 3] was produced in the same manner as [Example 1] except that the substrate was changed to A5052 standardized by JIS H4000.

[Comparative Example 1]
A2017 standardized by JIS H4000 was used as the base material. A substrate-cured resin composite was produced in the same manner as in [Example 1] except that the processing conditions in the first step and the second step were changed. Specifically, as the first step, the substrate was immersed for 60 seconds using the following treatment liquid (3). As a second step, the substrate was immersed for 300 seconds using the following treatment liquid (4).

The treatment liquid (3) has a target capacity of 4.20 mol/L (mol/L) of sodium hydroxide, 0.66 mol/L of zinc nitrate, and 0.06 mol/L of sodium thiosulfate. and was added to the deionized water to adjust the volume to the target. The temperature of the treatment liquid (3) was set at 35°C.

The treatment liquid (4) has a target volume of sulfuric acid of 0.84 mol/L (mol/L), ferric chloride of 0.96 mol/L, and ferric chloride of 0.03 mol/L. Copper and 0.05 mol/L manganese sulfate monohydrate were added to the ion-exchanged water. In this example, no pH adjustment was performed. The temperature of the treatment liquid (4) was set at 30°C.

[Comparative Example 2]
A substrate-resin cured product composite of [Comparative Example 2] was produced in the same manner as in [Comparative Example 1] except that the substrate was changed to A3003 standardized by JIS H4000.

[Comparative Example 3]
A substrate-resin cured product composite of [Comparative Example 3] was produced in the same manner as in [Comparative Example 1] except that the substrate was changed to A5052 standardized by JIS H4000.

(Load length ratio of section curve)
The load length ratios of the cross-sectional curves of the substrates after the treatment of Examples 1 to 3 and Comparative Examples 1 to 3 were measured by subjecting the substrates after the treatment to a field emission scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S- 4700 Type II), the cross-section was observed at a magnification of 10,000 times, and the obtained cross-section observation photograph was measured using image processing software (ImageJ). A cut level of 30% and a load length ratio of the cross-sectional curve at an evaluation length of 10 μm of 40% or more were evaluated as good (“○”), and cases of less than 40% and calculation impossible were evaluated as bad (“x”). . Table 1 shows the results.

(aspect ratio)
The aspect ratio was calculated from the ratio (b/a) of the average diameter (a) at the pore entrance and the average pore depth (b).
The average value (a) of the diameter at the entrance of the pores was measured from photographs of the surfaces of the treated substrates of Examples 1 to 3 and Comparative Examples 1 to 3 taken with the electron microscope at a magnification of 50,000. Top 10 diameters or minor diameters of the openings of the holes were selected, their lengths were measured, and the result obtained by integrating all and dividing by 10 was taken as the average value of the diameters at the entrance of the holes.
The average value (b) of the pore depth was measured from photographs of cross sections of the substrates after treatment in Examples 1 to 3 and Comparative Examples 1 to 3 taken with the electron microscope at a magnification of 30,000. The top 10 holes with the longest depth were selected, and the length from the top to the deepest part of the holes was measured.
A case where the aspect ratio (b/a) was 2 or more was rated as good (“◯”), and a case where it was less than 2 or could not be calculated was rated as bad (“x”). Table 1 shows the results.

(Tensile shear test)
Bonding strength was evaluated for the substrate-cured resin composites of Examples 1 to 3 and Comparative Examples 1 to 3 by a tensile shear test method standardized in ISO 19095-3. For the tensile shear test, an autograph precision universal testing machine (AG-100kNX) manufactured by Shimadzu Corporation was used. The evaluation was performed under conditions of a room temperature of 25° C. and a tensile speed of 10 mm/min. The tensile shear strength (joint strength: MPa) was calculated as breaking load (N)/joint area (50 mm ² ). After the tensile shear test, the failure mode of the joint between the substrate and the cured resin was visually examined.
Table 1 shows the results. Good ("○") if the cured resin remains in an area of 70% or more of the bonding area on the substrate side, and the cured resin is 10% or more of the bonding area on the substrate side. Bad (“x”) if the broken form remains in an area of less than 70%, and even worse if the broken form remains in an area of less than 10% of the bonding area of the cured resin on the substrate side. (“xx”). When the bonding strength was 30 MPa or more and the failure mode evaluation of the bonding portion was good (“◯”), it was defined that the bonding strength with the resin was excellent.

Claims (1)

A method for producing a substrate, wherein at least all or part of the surface of the substrate is made of a metallic material, the surface of the metallic material has pores, and the following requirements (1) and (2) are satisfied: hand,
a first step of bringing a surface treatment agent containing a lithium ion source and an alkali ion source into contact with the surface of a substrate at least all or part of which is made of a metal material;
A manufacturing method comprising a second step of bringing an acidic aqueous solution containing an inorganic acid into contact with the surface of the substrate that has been brought into contact with the surface treatment agent.
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at a cutting level of 30% and an evaluation length of 10 μm (2) The average diameter (a) at the entrance of the hole and the average hole depth Aspect ratio (b/a) with value (b) is 2 or more and 50 or less

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