Metal-organic composite materials

Abstract

To provide a metal-organic compound composite material having improved lubricity compared to the prior art.SOLUTION: A metal-organic compound composite material comprises: a metal material 2 containing one or more metals selected from a group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr, in total exceeding 50 mass%; and a plurality of organic compound particles 3, wherein the plurality of organic compound particles are in one or more states selected from a group consisting of a state in which the organic compound particles are attached to a surface of the metal material so as to be peelable with a cellophane adhesive tape, and a state in which the organic compound particles are embedded in the metal material so that at least a part of the metal material is exposed on the surface, and the plurality of organic compound particles include one or more selected from an aliphatic compound containing any two or more selected from a group consisting of hydrogen (H), carbon (C), and oxygen (O) in a unit molecular structure, the aliphatic compound containing one or more amide bonds in the unit molecular structure, and an aromatic compound containing one or more amino groups in the unit molecular structure.SELECTED DRAWING: Figure 1B

Description

[Technical Field]

[0001] The present disclosure relates to metal-organic compound composites. [Background technology]

[0002] Metal materials can be used for sliding members such as machine parts such as bearings, piston rings and cylinders, as well as mold parts used in press working, etc. Sliding members are required to have lubricity (i.e., a low coefficient of friction) because they are subjected to repeated sliding on a daily basis.

[0003] Furthermore, in recent years, with the strengthening of CO2 emission regulations, electric vehicles (EVs) and plug-in hybrid vehicles (PHEVs), which are less dependent on fossil fuels, are on the rise, and the number of components that undergo repeated sliding, such as contact materials, used in EVs and PHEVs is increasing.

[0004] For example, Patent Document 1 discloses that a solid lubricant is brought into contact with a metal material (specifically, the solid lubricant is uniformly dispersed in the metal material), and that talc is preferable as the solid lubricant from the viewpoint of lubricity, etc. Patent Document 2 discloses that an inorganic filler such as talc is brought into contact with a metal material (co-deposited) in order to impart lubricity to the metal material. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 63-118047 [Patent Document 2] Japanese Patent Publication No. 11-241169 Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, in recent years, the number of components that are subjected to repeated sliding has been increasing, and there is a demand for metal materials (or composite materials thereof) with improved lubricity compared to conventional techniques.

[0007] The present invention has been made in view of the above circumstances, and one of its objects is to provide a metal material (or a composite material thereof) having improved lubricity compared to the prior art. [Means for solving the problem]

[0008] Aspect 1 of the present invention is A metal material containing more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr, and a plurality of organic compound particles, The plurality of organic compound particles are A state in which the adhesive tape is attached to the surface of the metal material so as to be peelable with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405), and a state in which the metal material is embedded in the metal material so that at least a portion of the metal material is exposed to the surface, the plurality of organic compound particles include at least one selected from the group consisting of compound A, compound B, and compound C, The compound A is an aliphatic compound containing two or more elements selected from the group consisting of hydrogen (H), carbon (C), and oxygen (O) in a unit molecular structure, The compound B is an aliphatic compound containing one or more amide bonds in a unit molecular structure, The compound C is a metal-organic compound composite, which is an aromatic compound containing one or more amino groups in its unit molecular structure.

[0009] Aspect 2 of the present invention is The metal-organic compound composite according to aspect 1, wherein the plurality of organic compound particles includes the compound A.

[0010] Aspect 3 of the present invention is The metal material contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Sn, Zn, and Cr, The metal-organic compound composite according to aspect 1, wherein the plurality of organic compound particles includes the compound B.

[0011] A fourth aspect of the present invention is The metal material contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, and Cr, The metal-organic compound composite according to aspect 1, wherein the plurality of organic compound particles comprises compound C.

[0012] A fifth aspect of the present invention is The metal-organic compound composite according to any one of Aspects 1 to 4, wherein when the plurality of organic compound particles are subjected to thermogravimetric differential thermal analysis from room temperature to a maximum of 1000°C at a heating rate of 10°C / min, if a melting point is exhibited, the melting point is 100°C or higher, or if no melting point is exhibited.

[0013] A sixth aspect of the present invention is The metal-organic compound composite according to any one of Aspects 1 to 5, wherein when the plurality of organic compound particles are subjected to thermogravimetric differential thermal analysis from room temperature to a maximum of 1000°C at a heating rate of 10°C / min, if a decomposition point is exhibited, the decomposition point is 500°C or less, and if a combustion point is exhibited but no decomposition point is exhibited, the combustion point is 500°C or less.

[0014] A seventh aspect of the present invention is The metal-organic compound composite material according to any one of Aspects 1 to 6, wherein the plurality of organic compound particles does not contain fluorine.

[0015] Aspect 8 of the present invention is A metal-organic compound composite according to any one of Aspects 1 to 7, wherein the plurality of organic compound particles have an average particle size of less than 50 μm.

[0016] A ninth aspect of the present invention is The metal-organic compound composite material according to any one of aspects 1 to 8, wherein the plurality of organic compound particles are attached to the surface of the metal material so as to be peelable with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405).

[0017] A tenth aspect of the present invention is The metal-organic compound composite according to any one of Aspects 1 to 8, wherein the plurality of organic compound particles are embedded in the metal material such that at least a portion of the metal material is exposed on the surface. [Effects of the Invention]

[0018] According to embodiments of the present invention, it is possible to provide a metal composite having improved lubricity compared to the prior art. [Brief explanation of the drawings]

[0019] [Figure 1A] 1 shows a schematic cross-sectional view of an example of a metal-organic compound composite material according to an embodiment of the present invention. [Figure 1B] FIG. 2 is a schematic cross-sectional view of another example of a metal-organic compound composite material according to an embodiment of the present invention. [Figure 2A] 1 shows a photograph of the surface of a metal-organic compound composite material in which polyethylene oxide particles are brought into contact with (adhered to) the surface of the metal material (Ni—P plated layer) produced in Example 1. [Figure 2B] The photograph shows the surface of the metal-organic compound composite material of FIG. 2A after cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) was attached thereto. [Figure 2C] A photograph of Figure 2B after the tape was removed is shown. [Figure 3A] 1 shows a schematic diagram of the surface of a sample subjected to a reciprocating sliding test. [Figure 3B] After a reciprocating sliding test was performed on the metal material in Table 1: Ni-P (no particles), the center of the sliding mark 30 as shown in Figure 3A was measured with a surface roughness meter in a direction perpendicular to the sliding direction. [Figure 4]1 shows a photograph of the surface of a metal-organic compound composite material in which polyethylene oxide particles are brought into contact with (adhered to) the surface of the metal material (Ni—P plated layer) produced in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present inventors conducted extensive research to develop a metal composite with improved lubricity compared to conventional techniques such as those described in Patent Document 1. In such conventional techniques, lubrication is achieved by contacting a metal material with talc or other solid lubricants. Through further research, the present inventors discovered that, unlike talc, which is an inorganic particle with solid lubrication, contacting a specific metal material with specific organic compound particles, which do not necessarily have solid lubricating properties, under specified conditions can reduce the friction coefficient (i.e., improve lubricity) compared to contacting talc. This is believed to be due to the fact that, during sliding between metals, a portion of the specific organic compound decomposes, forming a new reaction film containing carbon and other elements, thereby reducing the friction coefficient near the metal surface and improving lubricity. The reaction film may contain atomic components of the metal material that are thought to diffuse into the film or originate from wear debris. As a result, it has been possible to realize a metal composite material with improved lubricity compared to conventional techniques. Note that the above mechanism does not limit the technical scope of the embodiments of the present invention. The following provides details of each requirement stipulated by the embodiment of the present invention.

[0021] The metal-organic compound composite according to an embodiment of the present invention comprises: The present invention relates to a metal material containing more than 50% by mass of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr, in total, and a plurality of organic compound particles, wherein the plurality of organic compound particles are attached to the surface of the metal material so as to be releasable with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) and / or are embedded in the metal material so that at least a portion of the metal material is exposed on the surface, the plurality of organic compound particles containing one or more selected from the group consisting of Compound A, Compound B, and Compound C, wherein Compound A is an aliphatic compound containing two or more selected from the group consisting of hydrogen (H), carbon (C), and oxygen (O) in its unit molecular structure, Compound B is an aliphatic compound containing one or more amide bonds in its unit molecular structure, and Compound C is an aromatic compound containing one or more amino groups in its unit molecular structure. This makes it possible to improve lubricity compared to the prior art (i.e., metal materials in contact with talc).

[0022] FIG. 1A shows a schematic cross-sectional view of a metal-organic compound composite according to an embodiment of the present invention. In FIG. 1A, the metal-organic compound composite 1 includes a metal material 2 and a plurality of particles 3. The particles 3 are embedded in the metal material 2 such that at least a portion 2a of the metal material 2 is exposed on the surface of the metal-organic compound composite 1 (the particles 3 do not cover the entire surface 2b of the metal material 2). Here, a portion of each particle 3 is embedded in the metal material 2, and the remaining portion is exposed on the surface of the metal-organic compound composite 1. This contact state reduces the friction coefficient near the surface 2b of the metal material 2 and improves lubricity by, for example, decomposing a specific organic compound during sliding of the metal material 2 and forming a new carbon-containing reaction film. Furthermore, by exposing at least a portion 2a of the metal material 2 on the surface of the metal-organic compound composite 1, the initial contact resistance (electrical resistance) before sliding can be reduced when the metal-organic compound composite 1 is used as a contact material. Whether or not at least a portion 2a of the metal material 2 is exposed on the surface can be determined by, for example, visually checking whether or not there is metallic luster.

[0023] In the metal-organic compound composite 1 of FIG. 1A, each particle 3 may be entirely embedded in the metal material 2 before the start of sliding. By performing a sliding treatment so that the particles 3 are exposed, it is possible to reduce the coefficient of friction, similar to the metal-organic compound composite 1. Furthermore, similar to the metal-organic compound composite 1, it is possible to reduce the initial contact resistance. In other words, in this specification, "particle 3 partially embedded in the metal material 2" includes an embodiment in which a single particle 3 is entirely embedded in the metal material 2 before the start of sliding, but partially exposed from the metal material 2 after the start of sliding, with the remaining portion being embedded in the metal material 2.

[0024] FIG. 1B is a schematic cross-sectional view of another example of a metal-organic compound composite according to an embodiment of the present invention. In FIG. 1B, a metal-organic compound composite 11 includes a metal material 2 and a plurality of particles 3, which are attached to a surface 2b of the metal material 2. The particles 3 are attached to the surface 2b with such a weak force that they can be peeled off with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape® No. 405). This contact state allows at least a portion of the particles 3 to be immediately removed from the sliding portion of the metal material 2, resulting in at least a portion of the metal material 2 being exposed on the surface of the metal-organic compound composite 11, similar to the metal-organic compound composite 1. This allows for a reduction in the coefficient of friction near the surface 2b of the metal material 2, similar to the metal-organic compound composite 1. Furthermore, since the metal material 2 can be immediately exposed on the surface of the metal-organic compound composite 11 during contact resistance measurement, the initial contact resistance can be reduced, similar to the metal-organic compound composite 1.

[0025] In Figure 1B, the multiple particles 3 are shown attached to the surface 2b of the metal material 2 so that the metal material 2 is not exposed on the surface of the metal-organic compound composite 1 between the multiple particles 3 (so that the entire surface 2b of the metal material 2 is covered), but this is not limited to this state, and for example, the metal material 2 may be attached to the surface 2b so that a portion of the metal material 2 is exposed on the surface of the metal-organic compound composite 1 between the multiple particles 3.

[0026] As described above, the contact state of the particles 3 with the metal material 2 has been exemplified, but the contact state may be one type or two or more types. For example, in an embodiment of the present invention, a portion of the particles 3 out of all the particles 3 may be attached to the surface of the metal material 2, and the remaining particles 3 may be embedded in the metal material 2. In this case, it is sufficient that at least a portion of the metal material is exposed on the surface of the metal-organic compound composite material on which the particles are attached; even if not exposed, it is sufficient that the particles 3 attached to the surface can be peeled off with cellophane adhesive tape. Furthermore, the embedded state of the particles 3 may also be such that a portion of the particles 3 are exposed from the surface of the metal material 2, and the remaining particles 3 are entirely embedded in the metal material 2.

[0027] The metal material 2 contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr. The metal material 2 preferably contains 75 mass% or more of the metals in total, more preferably 85 mass% or more, and even more preferably 95 mass% or more of the metals in total. The metal material 2 may contain only one of the above metals, or may contain two or more of them.

[0028] The metal material 2 may be a bulk material or may have a surface treatment layer such as a plating layer. There are no particular limitations on the thickness t of the metal material 2. If the metal material 2 has a surface treatment layer such as a plating layer, t may be 0.05 to 100 μm, preferably 0.07 to 50 μm, and more preferably 0.10 to 30 μm.

[0029] With regard to the organic compound particles 3, the term "organic compound" refers to compounds containing carbon, excluding compounds with simple structures such as carbon monoxide, carbon dioxide, carbonates, hydrocyanic acid, cyanates, thiocyanates, BC, and SiC. For example, a silicone resin having a siloxane bond (-Si-O-Si-) in the main chain and organic groups in the side chains is included in the term "organic compound" in this specification.

[0030] Compound A, an organic compound constituting particle 3, is an aliphatic compound containing two or more elements selected from the group consisting of hydrogen (H), carbon (C), and oxygen (O) in its unit molecular structure, and is effective in further reducing the coefficient of friction for all of the above metal types of metal material 2. Therefore, it is preferable that the plurality of particles 3 contain compound A. Examples of compound A include polyolefin resins such as polyethylene and polypropylene, resins obtained by oxidizing these resins (such as polyethylene oxide), and polymethacrylate resins. Note that the term "unit molecular structure" refers to one repeating unit in the case of a polymer, and to individual molecules in the case of a non-polymer.

[0031] Compound B, an organic compound constituting particle 3, is an aliphatic compound containing one or more amide bonds in its unit molecular structure, and is effective in sufficiently reducing the coefficient of friction for all of the above metal species of metal material 2, and further reducing the coefficient of friction for the above metal species except for Ni. Therefore, it is preferable that metal material 2 contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Sn, Zn, and Cr, and that the plurality of particles 3 contain compound B. Examples of compound B include nylon resins such as nylon 66 and nylon 12.

[0032] As an organic compound constituting particle 3, compound C has an amino group (-NR 1 R 2 and R 1 and R 2 is hydrogen or a hydrocarbon group, and R 1 and R 2 (which may be the same or different) and has the effect of sufficiently reducing the coefficient of friction for all of the above metal species of the metal material 2, and further reducing the coefficient of friction for the above metal species except for Zn. That is, it is preferable that the metal material 2 contains more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, and Cr, and that the plurality of particles 3 contain the compound C. Examples of the compound C include melamine cyanurate and sulfanilic acid.

[0033] The particles 3 preferably have a melting point of 100°C or higher or do not exhibit a melting point (i.e., decompose without melting). This prevents the friction coefficient from deteriorating due to melting of the organic compound when the metal-organic compound composites 1 and 11 are heated to high temperatures. More preferably, the particles 3 have a melting point of 110°C or higher or do not exhibit a melting point, and even more preferably have a melting point of 120°C or higher or do not exhibit a melting point. Here, the "melting point" refers to a melting point determined by, for example, performing thermogravimetric differential thermal analysis (TG-DTA) in air at a heating rate of 10°C / min from room temperature to a maximum of 1000°C. Specifically, the melting point can be a temperature within a temperature range in which the mass loss in the TG curve is less than 1%, and is the temperature at the intersection of an extrapolated line from the first inflection point, where the heat flow rate starts to decrease with increasing temperature, to the second inflection point and beyond, where the heat flow rate starts to decrease at a constant slope (i.e., the constant slope line). Furthermore, when the particles 3 do not exhibit a melting point (when the compound decomposes without melting), the decomposition point is preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. Here, the "decomposition point" refers to a decomposition point determined, for example, by performing thermogravimetric differential thermal analysis (TG-DTA) in the atmosphere from room temperature to a maximum of 1000°C at a heating rate of 10°C / min. Specifically, the decomposition point can be a temperature within the temperature range where a mass loss of 1% or more is confirmed in the TG curve, and also a temperature at the intersection of an extrapolated line from the first inflection point, where the heat flow rate starts to decrease with increasing temperature, to the second inflection point and beyond, where the heat flow rate starts to decrease at a constant slope (i.e., the constant slope line).

[0034] From the viewpoint of further reducing the coefficient of friction of the metal-organic compound composites 1 and 11, the decomposition point of the plurality of particles 3 is preferably 500°C or less. More preferably, the decomposition point is 450°C or less, and even more preferably, 400°C or less. When a combustion point is indicated without a decomposition point, the combustion point is preferably 500°C or less, more preferably, 450°C or less, and even more preferably, 400°C or less. Here, the "combustion point" is determined, for example, by performing thermogravimetric differential thermal analysis (TG-DTA) in the atmosphere from room temperature to a maximum of 1000°C at a heating rate of 10°C / min. Specifically, the combustion point can be a temperature within the temperature range in which a mass loss of 1% or more is confirmed in the TG curve, and a temperature at the intersection of an extrapolated line from the first inflection point, where the heat flow rate begins to increase with increasing temperature, to the second inflection point and beyond, where the heat flow rate then begins to increase at a constant slope (i.e., the constant slope line).

[0035] From the viewpoint of cost reduction, it is preferable that the plurality of particles 3 does not contain fluorine.

[0036] The average particle size (average circle equivalent diameter, median diameter (volume basis)) of the plurality of particles 3 is preferably less than 50 μm. This can, for example, further promote the decomposition of a portion of a specific organic compound, with a portion of the decomposition further promoting the reaction of the portion with the vicinity of the surface 2b of the metal material 2. The average particle size of the plurality of particles 3 is more preferably 30 μm or less, and even more preferably 10 μm or less. If the metal material 2 is a surface-treated layer such as a plating layer, the layer surface may become convex if the particle size of the particles 3 is large relative to the layer thickness. If the metal material 2 is a surface-treated layer such as a plating layer, it is preferable that the average particle size of the particles 3 is smaller than the layer thickness, which allows the dispersion density of the particles 3 per volume in the metal material 2 to be improved.

[0037] The plurality of particles 3 are preferably non-conductive, which makes it possible to prevent short circuits at the contacts due to the dropping off of conductive particles when the metal-organic compound composites 1 and 11 are used as contact materials.

[0038] The metal-organic compound composites 1 and 11 according to the embodiments of the present invention may contain other components to achieve the object of the present invention. For example, if the metal material 2 is a surface treatment layer, the metal-organic compound composites 1 and 11 may include a substrate thereof. The substrate material may be a metal (or an alloy thereof) such as copper, iron, aluminum, titanium, or magnesium. The substrate may be in the form of a wrought material such as a plate, strip, bar, profile, or wire, a casting, a sintered material, or a processed part thereof. The metal-organic compound composites 1 and 11 may also contain organic compound particles other than the specific organic compound particles 3 described above, or may contain inorganic particles. In this case, it is preferable that 50% or more by volume of the total particles are the specific organic compound particles 3, more preferably 60% or more by volume, 70% or more by volume, 80% or more by volume, or 90% or more by volume. It is even more preferable that all (100% by volume) are the specific organic compound particles 3.

[0039] The metal-organic compound composite material 11 according to the embodiment of the present invention can be produced by applying a dispersion liquid containing a plurality of organic compound particles 3 to the surface 2 b of the metal material 2 .

[0040] The metal-organic compound composite material 1 according to the embodiment of the present invention is obtained by, for example, dispersing particles 3 in a metal plating solution for a metal material 2 and performing an electroplating process on a substrate while stirring, thereby obtaining a metal-organic compound composite material 1 on the substrate in which a plurality of particles 3 are embedded (co-deposited) in the metal material 2. Note that a surfactant (dispersant) may be used as appropriate to prevent aggregation of the particles 3 in the metal plating solution for the metal material 2 and maintain a stable dispersion state.

[0041] In the process of dispersing the particles 3 in a metal plating solution and conducting electroplating to codeposit the particles 3 into the metal material 2, the following reactions (A) and (B) proceed simultaneously. (A) A reaction in which particles dispersed in liquid are electrostatically or physically adsorbed (contacted) to the surface of a substrate. (B) Reaction in which metal material 2 is deposited (grows) on the substrate surface Particles 3 adsorbed in (A) are incorporated into metal material 2 in (B), resulting in "co-deposition." Under conditions where eutectoid plating proceeds steadily, particles 3 adsorbed in the early stages of the reaction are incorporated into metal material 2, while new particles 3 are simultaneously adsorbed. For this reason, even when the plating process is stopped, particles 3 are often still exposed on the outermost surface. In a typical eutectoid plating process, it is possible to easily produce a metal-organic compound composite 1 containing particles 3 that are partially embedded in metal material 2 and the remaining portions exposed on the surface of metal material 2. Here, the amount of particles 3 co-deposited into the metal material 2 is determined by the balance between the frequency of adsorption of (A) and the plating film growth rate of (B). Therefore, it is possible to change the amount of co-deposition by changing plating conditions, such as the amount of particles 3 dispersed in the plating solution. For example, by using a plating solution that does not contain particles 3 dispersed in the plating solution at the end of the plating process, or by changing the stirring speed of the plating solution to reduce the frequency of adsorption of (A), a layer that does not co-deposit particles 3 can be formed on the outermost surface of the plating, making it possible to produce a metal-organic compound composite in which particles 3 are all embedded in the metal material 2.

[0042] Metal-organic compound composites 1 and 11 according to embodiments of the present invention can improve lubricity (i.e., can reduce the coefficient of friction) compared to conventional techniques. Specifically, metal-organic compound composites 1 and 11 according to embodiments of the present invention can reduce the average value of the coefficient of friction (ratio of horizontal load to vertical load) after each cycle up to 50 cycles in the sliding test described below compared to a metal material in contact with conventional talc instead of particles 3. <Sliding test (reciprocating sliding test)> A mating member, a φ6 mm high carbon chromium bearing steel (SUJ2) ball, is slid for a predetermined number of cycles against the surface of the test metal-organic compound composite 1 or 11, with a normal load of 1 N applied, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm / sec, with one reciprocating movement being defined as one cycle. As the sliding tester, for example, a ball-on-disk testing device (Tribometer manufactured by CSM) can be used.

[0043] The metal-organic compound composites 1 and 11 according to the embodiments of the present invention can have even better wear resistance. Specifically, the metal-organic compound composites 1 and 11 according to the embodiments of the present invention can significantly reduce the amount of wear after 500 cycles of the sliding test compared to when the particles 3 are not in contact (for example, to 1 / 2 or less, preferably to 1 / 5 or less, and more preferably to 1 / 10 or less). [Example]

[0044] The following examples are provided to more specifically describe the embodiments of the present invention. The embodiments of the present invention are not limited to the following examples, and may be modified as appropriate within the scope of the above-described and below-described aims, and all such modifications are within the technical scope of the embodiments of the present invention. [Example]

[0045] Commercially available substrates were Fe plate (thickness t: 0.2 mm), Al plate (thickness t: 0.2 mm), Ti plate (thickness t: 0.2 mm), and Cu plate (thickness t: 0.3 mm) (each metal had a purity of 95% by mass or more). On one surface perpendicular to the thickness direction of the metal, 0.5 ml / cm of a liquid containing various particles shown in Table 1 suspended in alcohol at a rate of 20 mg / ml was applied. 2 The resulting mixture was dried to obtain a metal-organic compound composite in which various particles were in contact with (attached to) the surface of the metal material. Furthermore, using the above-mentioned Cu plate as a substrate, plating layers of Au, Sn, Zn, Ni, Ni-P (Ni content: 85% by mass or more), and Cr were formed by a known method (plating thickness t: 5 μm, purity of each plating layer: 95% by mass or more). Various particles (or particle dispersions) shown in Table 1 were suspended in alcohol at a rate of 20 mg / ml and applied on top of the plating layers at a rate of 0.5 ml / cm. 2The particles were then dripped onto the metal surface and dried to obtain metal-organic compound composites in which various particles contacted (adhered) to the metal surface. Furthermore, thermogravimetric differential thermal analysis (TG-DTA) was performed on the various particles shown in Table 1 using a differential thermobalance (Rigaku Thermoplus EVOII) in air at a heating rate of 10°C / min from room temperature to a maximum of 1000°C, and the melting point, decomposition point, and combustion point of each particle were determined. These results are also shown in Table 1. In Table 1, a "-" in the "Compound Type" column indicates that the compound does not correspond to any of Compounds A to C in the embodiments of the present invention. A "-" in the "Melting Point (°C)," "Decomposition Point (°C)," and "Combustion Point (°C)" columns indicates that the corresponding temperature was not observed in the thermogravimetric differential thermal analysis. A "-" in the "Average Particle Size (μm)" column indicates that the corresponding average particle size was not investigated.

[0046] [Table 1]

[0047] Visual observation of the metal-organic compound composites prepared as described above revealed that in all composites, the particles were in contact with (adhered to) the surface of the metal material without the metal material being exposed between the particles (i.e., the surface of the metal material was covered with the particles). Furthermore, in all of the metal-organic compound composites prepared as described above, the particles in contact with (adhered to) the metal material could be removed by, for example, pressing the adhesive side of cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) with a finger onto the surface of the metal-organic compound composite that had come into contact with the particles, and then peeling it off in a direction perpendicular to the surface. As an example, Figure 2A shows a photograph of the surface of a metal-organic compound composite in which polyethylene oxide particles have been attached to the surface of a metal material (Ni-P plating layer). As shown in Figure 2A, the area where the particles were attached (area surrounded by the dashed line) had no metallic luster, and no exposed metal material was observed. Figure 2B shows a photograph of the metal-organic compound composite shown in Figure 2A after cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) has been applied (the tape is applied in the area surrounded by the dashed-dotted line), and Figure 2C shows a photograph of the metal-organic compound composite after the tape has been peeled off in a direction perpendicular to the surface to which it was applied. In Figure 2B, the cellophane adhesive tape was applied by pressing its adhesive side with a finger against the surface of the metal-organic compound composite that had come into contact with the particles. As shown in Figure 2C, a new metallic luster is observed in the area where the tape had been applied (area surrounded by the dashed-dotted line), indicating that the particles have been removed by the cellophane adhesive tape.

[0048] The metal-organic compound composite materials prepared as described above were subjected to the following lubricity evaluation. The following lubricity evaluation was carried out using a separate sample set in which the cellophane adhesive tape had not been applied or peeled off. <Lubricity evaluation> In a reciprocating sliding test using a ball-on-disk testing device (manufactured by CSM: Tribometer), a counter material, a φ6 mm high carbon chromium bearing steel (SUJ2) ball, was slid against the metal-organic compound composite material under test for 50 cycles, with one reciprocating movement being defined as one cycle, with an applied vertical load of 1 N, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm / sec. To evaluate lubricity, the average friction coefficient (ratio of horizontal load to vertical load) after each cycle was calculated, and those whose average friction coefficient was lower than those when no particles were in contact and when talc was in contact were rated as sufficient (◯); those whose average friction coefficient was not lower than those when no particles were in contact and / or when talc was in contact were rated as insufficient (×); and those whose average friction coefficient was lower by 50% or less than those when no particles were in contact were rated as excellent (◎). The above results are summarized in Table 2.

[0049] [Table 2]

[0050] The results in Table 2 can be interpreted as follows: In Table 2, when the metal material was Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn, or Cr and the particles brought into contact were polyethylene oxide (meeting the requirements of compound A according to an embodiment of the present invention), polypropylene (meeting the requirements of compound A according to an embodiment of the present invention), nylon 12 (meeting the requirements of compound B according to an embodiment of the present invention), or melamine cyanurate (meeting the requirements of compound C according to an embodiment of the present invention), all of the cases satisfied the requirements defined in the embodiments of the present invention, and the friction coefficient was lower than when no particles were brought into contact and when using the prior art (i.e., when talc was brought into contact with the metal material), and the lubricity was improved.

[0051] From the results in Table 2, the following cases (1) to (3) showed lower coefficients of friction and were preferable modes. (1) The metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn, or Cr, and the particles that are in contact with the metal material are Compound A (polyethylene oxide or polypropylene). (2) The metal material is Al, Ti, Cu, Au, Ni-P, Sn, Zn, or Cr, and the particles that are in contact with the metal material are Compound B (Nylon 12). (3) The metal material is Al, Ti, Cu, Au, Ni, Ni-P, Sn, or Cr, and the particles brought into contact with the metal material are compound C (melamine cyanurate).

[0052] On the other hand, when the metal material was Fe and the particles brought into contact were PEEK, the requirements of the embodiment of the present invention were not met, and the coefficient of friction could not be reduced sufficiently.

[0053] Furthermore, the following abrasion resistance evaluation was carried out on some of the above metal-organic compound composite materials. The following abrasion resistance evaluation was carried out by separately preparing a sample set that was not subjected to the above cellophane adhesive tape attachment and peeling, and lubricity evaluation. <Wear resistance evaluation> In a reciprocating sliding test using a ball-on-disk testing device (manufactured by CSM: Tribometer), a counter material, a φ6 mm high carbon chromium bearing steel (SUJ2) ball, was slid against the metal-organic compound composite material under test for 500 cycles, with one reciprocating movement being defined as one cycle, with an applied vertical load of 1 N, a sliding width (sliding stroke) of 10 mm, and an average sliding speed of 30 mm / sec. After the rotational sliding test was completed, a surface profile was obtained using a surface profile measuring device (DEKTAK6M manufactured by ULVAC, Inc.) to calculate the amount of wear.

[0054] FIG. 3A shows a schematic diagram of the surface of a sample that underwent a reciprocating sliding test, and FIG. 3B shows, as an example, the surface profile results obtained by measuring the center of the sliding mark 30 shown in FIG. 3A with a surface roughness meter in a direction perpendicular to the sliding direction after a reciprocating sliding test on the metal material: Ni-P (without particles) in Table 1. Here, the amount of wear (μm 2 ) was calculated by subtracting the area of ​​the protruding portion 31b, which is considered to have protruded upward due to plastic deformation, from the area of ​​the worn portion 31a, which was scraped downward from the average line 32a of the non-sliding portion 32 (other than the sliding portion 31) in the surface profile result of FIG. 3B. The calculated wear amount is shown in Table 3.

[0055] [Table 3]

[0056] The results in Table 3 show that when the requirements of the embodiment of the present invention are met, the amount of wear can be significantly reduced compared to when particles are not in contact with the metal material (when no particles are present). [Example]

[0057] Using the same Cu plate as used in Example 1 as a substrate, a Ni-P plating layer (Ni content: 85% by mass or more) was formed by a known method (plating thickness t: 5 μm, purity of the plating layer: 95% by mass or more), and then 0.5 ml / cm of a liquid in which polyethylene oxide particles shown in Table 1 were suspended in alcohol at a ratio of 2 mg / ml was applied thereon.2 By dropping the mixture and drying it, a metal-organic compound composite was obtained in which polyethylene oxide particles were in contact with (adhered to) the surface of the metal material (Ni-P plating layer).

[0058] Figure 4 shows a photograph of the surface of a metal-organic compound composite in which polyethylene oxidized particles were contacted (adhered) to the surface of the metal material (Ni-P plating layer) prepared as described above. As shown in Figure 4, a metallic luster (e.g., the area surrounded by the dashed line) was observed between the multiple polyethylene oxidized particles, and a portion of the Ni-P plating layer was exposed on the surface of the metal-organic compound composite. Furthermore, since the metal-organic compound composite was prepared (applied) in the same manner as in Example 1, it is believed that the polyethylene oxidized particles could be peeled off using cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405) as in Example 1.

[0059] The metal-organic compound composite, in which polyethylene oxide particles were brought into contact with the metal material (Ni-P plated layer) prepared as described above, was evaluated for lubricity in the same manner as in Example 1. As a result, the average friction coefficient showed an excellent value of 0.17. [Example]

[0060] A pure copper plate with a thickness of 0.3 mm was used as the plating substrate, and the surface was degreased by washing with acetone. Then, a sulfuric acid-based Sn plating solution was used, and organic compound particles (addition amount 30 g / L) shown in Table 4 and a surfactant (AGX Seimi Chemical's Surflon S231, addition amount 5 g / L) were dispersed in the plating solution. While stirring, the Sn plate was used as the counter electrode and the plating was conducted at 1 A / dm 2A current density of 1000 Ω / s was applied for 10 minutes to obtain a metal-organic compound composite in which multiple organic compound particles were co-deposited (embedded) in a 5 μm-thick Sn-plated layer, leaving at least a portion of the metal exposed to the surface. For comparison, a metal material (Sn-plated layer) plated without the dispersion of organic compound particles or surfactant was also prepared. The particles shown in Table 4 were subjected to thermogravimetric differential thermal analysis (TG-DTA) in air at a heating rate of 10 °C / min from room temperature to a maximum of 1000 °C using a differential thermobalance (Rigaku Thermo Plus EVOII). The melting point, decomposition point, and combustion point of the particles were determined. These results are also shown in Table 4. In Table 1, a "-" in the "Melting Point (°C)," "Decomposition Point (°C)," and "Combustion Point (°C)" columns indicates that the corresponding temperature was not observed in the thermogravimetric differential thermal analysis.

[0061] [Table 4]

[0062] The metal-organic compound composite material prepared as above was subjected to a lubricity evaluation and a wear resistance evaluation in the same manner as in Example 1. The results are shown in Tables 5 and 6, respectively.

[0063] [Table 5]

[0064] [Table 6]

[0065] As shown in the results in Table 5, the above metal-organic compound composite was a preferred embodiment in which the metal material was Al, Ti, Cu, Au, Ni, Ni-P, Sn, Zn, or Cr and the particles in contact (embedded) were compound A (crosslinked PMMA), and therefore, compared to the case in which no particles were present, the average friction coefficient was reduced to 50% or less compared to the case in which no particles were present in contact (embedded), which was an excellent result. Furthermore, the results in Table 6 show that when the requirements of the embodiment of the present invention are met, the amount of wear can be significantly reduced compared to when particles are not in contact with the metal material (when no particles are present). [Explanation of symbols]

[0066] 1, 11 Metal-organic compound composites 2 Metal material 2a Part of metal material 2 exposed on the surface 2b Surface of metal material 2 3 Organic compound particles 30 Sliding marks 31 Sliding part 31a Wear area 31b Ridge 32 Non-sliding part 32a Average line

Claims

1. The composite material comprises a metal material containing more than 50 mass% in total of one or more metals selected from the group consisting of Al, Ti, Cu, Au, Ni, Sn, Zn, and Cr, and a plurality of organic compound particles, The plurality of organic compound particles are A state in which the adhesive tape is attached to the surface of the metal material so as to be peelable with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405), and a state in which the metal material is embedded in the metal material so that at least a portion of the metal material is exposed to the surface, the plurality of organic compound particles are made of compound A, The compound A is an aliphatic compound containing, in a unit molecular structure, two or more elements selected from the group consisting of hydrogen (H), carbon (C), and oxygen (O), The metal-organic compound composite material, wherein the plurality of organic compound particles does not contain fluorine.

2. 2. The metal-organic compound composite according to claim 1, wherein, when the plurality of organic compound particles are subjected to thermogravimetric differential thermal analysis from room temperature to a maximum of 1000°C at a heating rate of 10°C / min, if a melting point is exhibited, the melting point is 100°C or higher, or no melting point is exhibited.

3. 2. The metal-organic compound composite according to claim 1, wherein, when the plurality of organic compound particles are subjected to thermogravimetric differential thermal analysis from room temperature to a maximum of 1000°C at a heating rate of 10°C / min, if a decomposition point is exhibited, the decomposition point is 500°C or less, and if a combustion point is exhibited but no decomposition point is exhibited, the combustion point is 500°C or less.

4. 4. The metal-organic compound composite material according to claim 1, wherein the average particle size of the plurality of organic compound particles is less than 50 μm.

5. The metal-organic compound composite material according to any one of claims 1 to 3, wherein the plurality of organic compound particles are attached to the surface of the metal material so as to be peelable with cellophane adhesive tape (manufactured by Nichiban Co., Ltd., product name: Cellotape (registered trademark) No. 405).

6. 4. The metal-organic compound composite material according to claim 1, wherein the plurality of organic compound particles are embedded in the metal material so that at least a portion of the metal material is exposed on the surface.

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