JPH06101039A - Metal and metallic compound material having surface excellent in bond property and production thereof - Google Patents

Abstract

PURPOSE:To form the surface excellent in adhesion with the adhesive having C-O bond by forming lower oxidizing layer in which the bound energy of oxygen is lower than the standard bound energy of oxygen on the surface layer of metal or metallic compd. CONSTITUTION:The surface of the substrate made of the metal and metallic compd. such as steel, Cu, Al, Si and Zn which can form oxide by reacting with oxygen is irradiated with oxygen ion to form. The bound energy of the inner orbit electron of oxygen atom decreases, and the oxygen atom changes to have more negative charge (negative ionization), and changes from ordinary O<2-> to O<(2+d)-> (but, (d) is >0). An electron is imparted from the oxygene atom to the adhesive having C-O bond, the interaction between the surface of the material and the adhesive increases, and adhesion and wet property are improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal or metal compound material having a surface having excellent adhesiveness and a method for producing the same, more specifically, for example, structural building materials to be adhered or joined, steel plates for automobiles, Si wafers, etc. The present invention relates to a metal or metal compound material having a surface excellent in adhesiveness and a method for producing the material.

[0002]

2. Description of the Related Art A method of adhering the same metal or metal compound to each other using an adhesive or adhering a metal or metal compound to another material is simple and applicable to different materials. Is being started. In order to improve adhesion or bonding (hereinafter collectively referred to as adhesion) properties, the surface of an object to be adhered (hereinafter referred to as substrate) is pretreated. That is, a method is generally used in which the oil and fat that adheres to the surface of the substrate and inhibits adhesion is wiped off with a degreasing solvent or a degreasing agent or removed by mechanical polishing. Further, a method has been proposed in which a natural resin, a synthetic resin or the like is applied to the surface of the substrate to form a smooth hydrophobic film or the like to improve the adhesiveness (Japanese Patent Laid-Open No. 52-96639).

On the other hand, the following ion irradiation and ion implantation techniques have been proposed as a method for modifying the surface of a substrate, although the purpose is not to improve the adhesiveness with an adhesive. That is, by forming a chromium oxide film on the surface of a substrate of a metal material or a ceramic material, and then irradiating the chromium oxide film itself with oxygen ions to form a high-valent chromium oxide, A method for improving the adhesion between chromium oxide and the coating material coated on it has been proposed (JP-A-63-240152).

Further, by using an ion implantation apparatus, nitrogen ions are implanted in the presence of Ti vapor, and Ti ions generated by collision with the nitrogen ions are simultaneously implanted into the substrate, and the nitrogen ions and some of the Ti ions are mutually exchanged. In response to the above, TiN is formed on the surface layer of the substrate, and surface modification is performed to increase the hardness of tools and improve the abrasion resistance (Japanese Patent Laid-Open No. 58-181864).

After implanting ions such as oxygen into the substrate,
A method has been proposed in which the surface is modified by chromate treatment or phosphate treatment to improve the corrosion resistance of the substrate (Japanese Patent Laid-Open No. 1-116072).

[0006]

However, there is a problem that it is difficult to significantly improve the adhesiveness of the adhesive to the substrate by the above-mentioned method of wiping the oil and fat on the substrate or removing it by mechanical polishing. In addition, the method of irradiating oxygen ions after forming chromium oxide on the above-mentioned substrate is less effective in improving the adhesiveness by the adhesive, and since chromium oxide is once formed on the substrate, There was a problem with adhesive strength, not surface modification. Further, the above-mentioned method of simultaneously implanting Ti and nitrogen ions is effective for curing the surface of the substrate, but there is a problem that it is difficult to improve the adhesiveness of the adhesive to the substrate. Further, the above-mentioned technique of implanting ions of oxygen or the like into the substrate has been aimed at forming a base for chemical conversion treatment.

The present invention has been made in view of the above problems, and an object thereof is to provide a metal or metal compound material having a surface having excellent adhesiveness without changing the characteristics of the bulk, and a method for producing the same. There is.

[0008]

In order to achieve the above object, the metal or metal compound material having a surface having excellent adhesiveness according to the present invention is such that the binding energy of oxygen is at least at the surface layer portion more than the standard binding energy of oxygen. It is characterized in that a low oxide layer is formed and it has excellent adhesiveness with an adhesive having a C—O group.

The method for producing a metal or metal compound material having a surface having excellent adhesiveness according to the present invention is characterized in that the surface is irradiated with oxygen ions having an ion energy of 0.5 to 10 KeV.

[0010]

The present inventors have succeeded in forming an oxide by reacting with oxygen, such as steel, copper, aluminum, silicon, zinc, and other metals, and alumina, magnesium oxide, etc., or aluminum nitride, which reacts with oxygen to form an oxide. XPS (Xray) which irradiates oxygen ion on the substrate surface of metal compounds such as
An XPS-O _1S spectrum (hereinafter referred to as an O _1S spectrum) was analyzed and analyzed by using a photoelectron spectroscopy (X-ray photoelectron spectrometer). Also, the O _1S spectra were analyzed for each of the cases where the substrate surface of the metal and the metal compound was not irradiated with oxygen ions, when oxides were formed by thermal oxidation, or when Ar ions were irradiated instead of oxygen ions. A comparative survey was conducted. As a result, the material irradiated with oxygen ions having a predetermined ion energy or higher was not irradiated with oxygen ions, had oxides formed by thermal oxidation, or was irradiated with Ar ions instead of oxygen ions. It was found that the binding energy of the O _1S spectrum was shifted to the low energy side as compared with the one.

Further, for example, an epoxy resin adhesive having a C—O group was applied to each of the above materials, and the adhesiveness or wettability was compared. As a result, the material irradiated with oxygen ions had adhesiveness and wettability. It was found that

Although these reasons have not been fully clarified, it is estimated from the escape depth of photoelectrons (up to 5 nm) that the irradiation of oxygen ions is at least 1 XPS measurement depth.
The binding energy of the core electrons of the oxygen atom at about 3 nm is reduced, so that the oxygen atom has a more negative charge (here, referred to as negative ionization), and the normal O ² to O
^{(2 + d)-} (where d> 0), electrons are donated from the oxygen atom to the adhesive to increase the interaction between the surface of the material and the adhesive, and to improve adhesiveness and wettability. Are expected to improve together.

When the ion energy in oxygen ion irradiation is less than 0.5 KeV or more than 10 KeV, no significant improvement in adhesion or wettability was observed. Further, the ion dose amount is not particularly limited, but if it is 1 × 10 ¹⁶ ions / cm ² or more, the efficiency is enhanced.

According to the metal or metal compound material having a surface having excellent adhesiveness according to the present invention, an oxide layer in which the binding energy of oxygen is lower than the standard binding energy of oxygen is formed at least in the surface layer portion. Oxygen atoms in the oxide layer are negatively ionized, and electrons in the oxygen atoms are donated to the adhesive having a C—O group, so that the interaction between the surface of the material and the adhesive is increased and the material and the adhesive are bonded. The adhesiveness with the agent will be improved.

Further, according to the method for producing a metal or metal compound material having a surface having excellent adhesiveness according to the present invention, the surface is irradiated with oxygen ions having an ion energy of 0.5 to 10 KeV, so that the oxide layer The oxygen atoms of the above are negatively ionized and the electrons at the oxygen atoms are donated to the adhesive having a C—O group, whereby a metal or metal compound material having good adhesiveness with the adhesive can be obtained.

[0016]

EXAMPLES AND COMPARATIVE EXAMPLES Examples of a metal or metal compound material having a surface having excellent adhesiveness and a method for producing the same according to the present invention will be described below with reference to tables and drawings. FIG. 1 is a graph showing changes in the O _1S spectrum before and after the irradiation of oxygen ions on the surface of a silicon dioxide substrate. In this case, the substrate surface temperature of the oxygen ion irradiation is 25
The acceleration voltage of oxygen ions was 5 kV, and Al-Kα (hν = 1486.6 eV) was used as the X-ray source for the measurement of the O _1S spectrum. The vertical axis of the graph shows the photoelectron intensity of the O _1S spectrum, and the horizontal axis shows the binding energy.

As is clear from these results, when the silicon dioxide substrate is irradiated with oxygen ions, the binding energy of oxygen in the oxide is shifted to the low energy side by about 1 eV, and the oxygen amount is changed as compared with the case where the silicon dioxide substrate is not irradiated. It can be seen that has hardly changed.

Further, the substrate temperature is 25 on the surface of the metallic copper substrate.
When the binding energy of the O _1S spectrum of Cu ₂ O formed by irradiating oxygen ions under the condition that the accelerating voltage of oxygen ions is 10 kV at ℃, the Cu formed by thermal oxidation of metallic copper was examined as in FIG. It was found that the energy shifts to the low energy side as compared with the binding energy of the O _1S spectrum in ₂ O.

Next, an aluminum plate, a cold-rolled steel plate, a hot-dip galvanized steel plate, a chrome-plated steel plate, a copper-plated steel plate, or a tin-plated steel plate is selected as the substrate, and the width is 25 mm x 150 mm x length.
Each sample was molded into a 0.8 mm thick piece, and the surfaces of these samples were first subjected to a degreasing treatment with acetone. Further subjected to irradiation of the ion energy of 0.1~20KeV oxygen ions to these sample surface under conditions of the sample surface temperature 25 ° C., O before irradiation the binding energy of the _1S spectrum of conventional O _1S spectrum Lower than the binding energy. C- is formed on the surface of each material produced in this way.
A commercially available epoxy adhesive having an O group was applied and adhered two by two, and two materials were pulled in opposite directions as shown in FIG. 2 to perform a peeling test. Table 1 shows the results of the peeling test. In the table, ○ marks indicate cohesive failure of the adhesive (breakage in the adhesive), Δ marks indicate interface peeling of a part of the adhesive surface, and × marks indicate the entire surface. Indicates that the interface is peeled off. As a comparative example, the case where oxygen ions are not irradiated is shown at the bottom.

[0020]

[Table 1]

As is clear from this table, an aluminum plate, a cold rolled steel plate, a hot dip galvanized steel plate, a chrome plated steel plate,
Ion energy of copper-plated steel and tin-plated steel is 0.
Irradiation with oxygen ions of 5 to 10 KeV can improve the adhesiveness with the adhesive.

As the substrate, alumina, magnesium oxide, silicon dioxide, silicon wafer, aluminum nitride,
Select titanium plate or titanium nitride, 8mm width x 25mm length x 1
Each sample was molded to a thickness of mm, and the surfaces of these samples were first degreased with acetone. Further subjected to irradiation of the ion energy of 0.1~20KeV oxygen ions to these sample surface under conditions of the sample surface temperature 25 ° C., O before irradiation the binding energy of the _1S spectrum of conventional O _1S spectrum Lower than the binding energy. A commercially available epoxy adhesive having a C—O group was applied to the surface of each material thus produced, and the wettability thereof was investigated. The reason the peeling test was not performed is that these materials are brittle and difficult to pull,
Therefore, it was decided to determine the adhesiveness based on whether or not the wettability was good. Table 2 shows the results of the investigation of wettability. In the table, ◯ indicates that the entire surface is well wetted, Δ indicates that the entire surface is wet, and x indicates that the surface is not wet at all. Also, as a comparative example, the case where oxygen ions are not irradiated is shown at the bottom.

[0023]

[Table 2]

As is clear from this table, when alumina, magnesium oxide, silicon dioxide, silicon wafer, and aluminum nitride are irradiated with oxygen ions having an ion energy of 0.5 to 10 KeV, the wettability with the adhesive can be improved. That is, it is possible to improve the adhesiveness with the adhesive.

As is clear from these results, metals capable of forming oxides on the surface (aluminum, cold-rolled steel sheet, hot-dip galvanized steel sheet, chrome-plated steel sheet, copper-plated steel sheet, tin-plated steel sheet, silicon wafer, copper, titanium plate) and metal compounds (aluminum nitride, alumina, magnesium oxide, silicon dioxide, ordinary O _1S spectrum before binding energy of O _1S spectrum when irradiated irradiation ion energy in the titanium nitride) is oxygen ions 0.5~10KeV The binding energy is lower than that of (3), and the adhesiveness with the adhesive having a C—O group can be improved.

[0026]

As described in detail above, in the metal or metal compound having a surface having excellent adhesiveness according to the present invention, an oxide having a binding energy of oxygen lower than the standard binding energy of oxygen at least in the surface layer portion. As the layer is formed, the oxygen atoms of the oxide layer are negatively ionized and the electrons at the oxygen atoms are donated to the adhesive having C—O groups, enhancing the interaction between the material surface and the adhesive. The adhesiveness of the material with the adhesive can be improved.

Further, in the method for producing a metal or metal compound material having a surface having excellent adhesiveness according to the present invention,
Since the surface is irradiated with oxygen ions having an ion energy of 0.5 to 10 KeV, the oxygen atoms of the oxide layer are negatively ionized and the electrons in the oxygen atoms are donated to the adhesive having a C—O group, and the material surface The interaction between the adhesive and the adhesive is enhanced, and a metal or metal compound material having excellent adhesiveness with the adhesive can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing changes in O _1S spectra before and after irradiation of oxygen ions on a silicon dioxide substrate.

FIG. 2 is a schematic cross-sectional view showing a peel test method for evaluating the adhesiveness of a metal or metal compound material having a surface having excellent adhesiveness according to an example of the present invention.

Claims (2)

[Claims] 1. An adhesion characterized in that an oxide layer having a binding energy of oxygen lower than the standard binding energy of oxygen is formed at least in the surface layer portion, and has excellent adhesiveness with an adhesive having a C—O group. A metal or metal compound material having a surface with excellent properties. 2. Ion energy on the surface is 0.5 to 10
A method for producing a metal or metal compound material having a surface excellent in adhesiveness, which comprises irradiating with KeV oxygen ions.