JP2012149345A - Amorphous carbon film laminated member and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amorphous carbon film laminated member which has a simple structure, can be manufactured at low cost, does not deteriorate wear resistance, and has high conductivity and high neutralizing property, and a manufacturing method for the same.SOLUTION: The amorphous carbon film laminated member has a discontinuous micro region 20 where conductive carbon fine particles are dispersed and fixed on a conductive substrate and a continuous region 30 where amorphous carbon films are piled up on the region other than the micro region 20 of the conductive substrate, wherein the surface of the micro region 20 consisting of the conductive carbon particles and the surface of the continuous region 30 consisting of the amorphous carbon films are made to be the same plane.

Description

  The present invention relates to an amorphous carbon film laminated member and a method for producing the same, and in particular, an amorphous carbon film laminated member using an amorphous carbon film with improved conductivity as a coating material on a base material and the production thereof. Regarding the method.

  An amorphous carbon film or an amorphous carbon film containing silicon or the like (hereinafter collectively referred to as “amorphous carbon film”) is hard and excellent in wear resistance, has a small friction coefficient, and has an anti-adhesion property. In addition, it is possible to impart high functionality to the surface of the base material, and it has begun to be used in a wide range of industrial fields and applications, mainly for feeders and carriers for small parts, and trays for handling.

The amorphous carbon film depends on film formation conditions such as film thickness, raw material gas and post-treatment, but its volume electric resistivity is about 10 ⁸ to 10 ¹² Ω · cm, which is slightly lower than the insulator. Degree. For this reason, when the amorphous carbon film is used as a coating material such as the above-mentioned feeder for transport and carrier, and a tray for handling, as a general method, the amorphous carbon film is formed thinly on the substrate, By grounding the base material, the static electricity generated when the workpiece comes into contact with the amorphous carbon film is removed through the thin amorphous carbon film and further through the base material. The workpiece was prevented from adhering to the carbonaceous film.
However, the size of the component that contacts and slides on the amorphous carbon film is very small, such as the appearance of chip resistors of 0402 type (vertical width 0.4 mm × width 0.2 mm × thickness 0.2 mm), multilayer ceramic capacitors, etc. As the size of the amorphous carbon film becomes smaller, the static eliminating ability of the conventional amorphous carbon film becomes insufficient, and the phenomenon such as adhesion / remaining on the surface of the amorphous carbon film due to static electricity has been confirmed.
Today, the number of portable electronic devices is increasing, and the components used are becoming increasingly smaller. In such a situation, residue due to sticking of parts in the process of parts transportation, alignment for parts processing, storage, etc. in the production process of micro parts can lead to different performance lots of parts with different performances. And problems such as loss of traceability due to mixing between production lots, causing serious problems in quality control of production processes.

  Also, the amorphous carbon film itself has a slightly higher electrical resistance than the normal amorphous carbon film such as an amorphous carbon film containing silicon, and is used as the base adhesion layer. Alternatively, in order to increase the durability of the amorphous carbon film, there is a current situation that the film is configured to be thicker.

On the other hand, as another anti-wear / adhesion prevention and low-friction surface treatment, the so-called “conductive alumite”, an aluminum or aluminum alloy material, is subjected to a thinner anodic oxidation treatment to reduce the amount of charge. Some have a volume resistivity of about 10 ⁶ Ω · cm suppressed (see Patent Document 1), but such as excellent wear resistance and low friction properties such as an amorphous carbon film. Function cannot be expressed.

JP 2006-291259 A

Electronic components used in small electronic devices such as mobile phones and digital cameras that have appeared since the 1990s are called surface mount types (chip types), and very small components are used. Such chip-like electronic components are called chip resistors, chip LEDs, chip capacitors, etc., and are classified according to size, but at present, the size of the components is further reduced, and 0603 (length 0.6 mm × width) 0.3mm × thickness 0.3mm), 0402 (vertical width 0.4mm × width 0.2mm × thickness 0.2mm), ultra-compact and lightweight parts, that is, transport or storage work of about 0.4 to 0.1 mg Has appeared, the adhesion of the workpiece to the substrate is likely to occur even with weaker static electricity than in the past, and a substrate having a smaller volumetric electrical resistivity has been required.
The requirement for a substrate having such a low volume resistivity is not limited to electronic parts, but extends to machined parts, powders, various other workpieces, and various industrial fields.
In addition, particularly in electronic components, many component failures occur due to accumulation of static electricity. In addition, electrical contact terminals (probes, etc.) used for insulation resistance measurement, capacitance measurement, and other electrical property inspections of electronic components are required to have low electrical resistivity due to their original usage. There are many things.
Therefore, further improvements are needed to improve the electrical conductivity of the amorphous carbon film coated on various substrates.

  The present invention is an amorphous carbon film laminated member that has a simple structure and can be manufactured at low cost, and has high conductivity and charge removal performance without losing wear resistance in transportation, alignment, and storage of microelectronic components and the like. And it aims at providing the manufacturing method.

Therefore, as a result of intensive studies to achieve the above object, the present inventors have established the following means. That is, the amorphous carbon film portion coated on the surface of the conductive base material and the conductive carbon fine particles having a volume electric resistivity lower than 10 ⁶ Ω · cm grounded on the base material are “flying portions”. By providing a portion that exists on the surface in the state, at least a portion of the work such as a small part that is charged with static electricity can take contact with the conductive material, including the movement path of the work, We found that static elimination is possible. In addition, the conductive material disposed in the jump has a low coefficient of friction and an anti-soft metal adhesion prevention property as in the case of the amorphous carbon film, which may impair the original function of the amorphous carbon film. It also turned out not to be.

The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] A discontinuous minute region in which conductive carbon fine particles are dispersed and fixed on a conductive substrate, and a continuous region made of an amorphous carbon film deposited on the conductive substrate other than the region. And an amorphous carbon film laminated member in which the surface of the minute region made of the conductive carbon particles and the surface of the continuous region made of the amorphous carbon film are in the same plane.
[2] The amorphous carbon film laminated member according to [1], wherein the conductive carbon particles are made of carbon graphite or carbon black.
[3] The amorphous carbon film according to [1] or [2], wherein the amorphous carbon film is a component transporting member, a component aligning member, or a component storage member having the amorphous carbon film as an uppermost layer. Laminated member.
[4] (1) A step of dispersing and fixing conductive carbon fine particles only on the minute regions on a conductive base material, and (2) amorphous carbon on the surface of the substrate on which the conductive carbon fine particles are fixed. And (3) the step of planarizing the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane in this order. 3] The method for producing an amorphous carbon film laminated member according to any one of 3).
[5] The step (1) is performed by disposing a mesh or screen plate having a predetermined opening on a conductive substrate and spraying a coating agent containing conductive carbon particles thereon. [4] The method for producing an amorphous carbon film laminated member according to [4] above.
[6] (1 ′) a step of depositing amorphous carbon on a region other than the minute region on the conductive substrate; and (2 ′) the amorphous carbon not deposited on the conductive substrate. A step of fixing conductive carbon fine particles in a minute region; and (3 ′) a step of flattening the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane. The method for producing an amorphous carbon film laminated member according to any one of [1] to [3] above.
[7] In the step (1 ′), a mask having a predetermined opening is disposed on a conductive substrate, and a masking material is applied or sprayed thereon to form a negative pattern on the mask with the masking material. After forming the protective film, the mask is removed, an amorphous carbon film is deposited on the surface of the conductive substrate, and then the protective film portion made of a masking material and the amorphous carbon film formed on the protective film are removed. The method for producing an amorphous carbon film laminated member according to the above [6], which is performed by peeling.

  According to the present invention, a surface that retains static elimination effects of static electricity, does not cause adhesion due to static electricity due to contact of workpieces that generate friction such as being conveyed, aligned, and stored, is hard, has excellent wear resistance, and has a low friction coefficient A state can be formed. For this reason, it is possible to simultaneously impart an antistatic function, wear resistance, and adhesion resistance to a feeder for conveying parts, a carrier, a tray for handling, and the like.

Sectional drawing which described the amorphous carbon film laminated member of this invention typically The top view which described typically the relationship between the amorphous carbon film laminated member of this invention, and the electrode of a microelectronic component The surface of the stainless steel SUS304 2B sprayed with a spray coating agent containing fine particles of graphite was observed at a magnification of 30 times (almost half on the right side: part not covered with the metal mesh, almost half on the left side: with the metal mesh Coated part). Photo at 150x magnification in Fig. 2 (a) CCD magnified photograph (focusing on the surface of the amorphous carbon film, magnification 2000 times) observing the state of the surface portion (for Example 1) where the surface of the stainless steel SUS304 2B was coated with a metal mesh Fig. 3 (a) CCD magnified photo focusing on graphite (2000x magnification) A magnified CCD image at a magnification of 500 times, observing a state in which graphite is formed on the surface of the stainless steel SUS304 2B material not covered with a metal mesh and an amorphous carbon film is formed on the surface. Photo at 2000x magnification in Fig. 4 (a) The surface of stainless steel SUS304 2B is coated with a metal mesh to form graphite, an amorphous carbon film is formed on the surface, and the surface is wiped dry so that the surface is smoothed with valene covered with a nonwoven fabric. CCD photograph of magnification 500 times confirming the surface state of Example 1 of the present invention after Photo at 2000x magnification in Fig. 5 (a) The figure which shows the result of the friction abrasion test of the amorphous carbon film laminated member of the comparative example in which only the amorphous carbon film was formed CCD photograph of the locus of the ball in the frictional wear test of the comparative amorphous carbon film laminated member in which only the amorphous carbon film was formed The figure which shows the result of the friction abrasion test of Example 1 of this invention CCD photograph of ball trajectory of frictional wear test of Example 1 of the present invention CCD magnified photograph of graphite portions scattered on the trajectory of the ball in the frictional wear test of Example 1 of the present invention CCD enlarged photograph observing the surface after spraying the spray coating agent containing fine particles of graphite of Example 3 of the present invention CCD enlarged photograph observing the surface state on which the amorphous carbon film after ultrasonic cleaning of Example 3 of the present invention was formed The figure which shows the outline | summary of the measurement of the electrical resistance by a 4-terminal method in an Example.

Hereinafter, the amorphous carbon film laminated member of this invention is demonstrated using figures.
1A and 1B are diagrams schematically showing an amorphous carbon film laminated member according to the present invention, FIG. 1A is a cross-sectional view thereof, and FIG. 1B is a diagram showing conductivity dispersed with electrodes of a microelectronic component. FIG. 3 is a plan view showing the relationship with conductive carbon fine particles, and shows an exposed surface of a discontinuous minute region in which conductive carbon fine particles are dispersed and fixed in the amorphous carbon film laminated member of the present invention. ing. In the figure, 10 is a conductive substrate, 20 is a discontinuous minute region in which conductive carbon fine particles are dispersed and fixed, 30 is a continuous region made of an amorphous carbon film, and 40 is a multilayer ceramic capacitor. , 40a respectively indicate electrodes formed on both ends of the multilayer ceramic capacitor.

As shown in the sectional view of FIG. 1 (a), the amorphous carbon film laminated member of the present invention is a discontinuous minute region in which conductive carbon fine particles are dispersed and fixed on a conductive substrate (10). (20) and a continuous region (30) made of an amorphous carbon film deposited in addition to the region on the conductive substrate (10), and a micro region (20) made of the conductive carbon fine particles. ) And the surface of the continuous region (30) made of amorphous carbon are in the same plane.
As shown in FIG. 1A, in the amorphous carbon film laminated member of the present invention, the lower side of the fine region (20) of the conductive carbon fine particles is in contact with the conductive base material (10). It is important that the electrical connection is ensured.

Further, the exposed surface of the discontinuous minute region (20) in which the conductive carbon fine particles are dispersed and fixed is formed, for example, on both end sides of the minute electronic component in transportation, alignment, and storage of the minute electronic component. Most preferably, it is interspersed at intervals in the range equal to or narrower than the electrode width. In particular, if the minute regions (20) are scattered at intervals equal to or narrower than the electrode width, a slow earthing circuit can be formed. As a result, static electricity charged in the minute electronic component flows to the ground side, and the static electricity charged in the minute electronic component can be gradually reduced.
FIG. 1B shows an example in which a 0402 type multilayer ceramic capacitor (40) is used as a conveying member. As shown in the figure, the exposed surface of the discontinuous minute region (20) is preferably within a specific surface area within a range of 200 μm so that the wear resistance is not impaired.
Thus, the exposed surface of the discontinuous minute region (20) in the amorphous carbon film laminated member of the present invention can be changed depending on the size of the minute electronic component to be handled. In addition, when sharing a minute electronic component to be handled, it is only necessary to match the size of the smallest electronic component.

In the present invention, the conductive substrate (10) is made of stainless steel (SUS), a metal such as iron, copper, or aluminum, or an alloy thereof, or a metal plating coating on them, or a conductive (antistatic) material. A material such as rubber, resin (rubber or resin mixed with a conductive material), carbon material, or the like is used, and is appropriately selected depending on the application.
In addition, conductive carbon fine particles may be directly fixed on the surface of the conductive substrate, and an amorphous carbon film may be deposited on the conductive substrate. It may have a layer.

  As the conductive carbon fine particles according to one embodiment of the present invention, fine particles such as graphite and carbon black can be used. The conductive carbon fine particles can be arbitrarily selected within a range not contrary to the gist of the present invention. When depositing the amorphous carbon film described below, a part of the conductive carbon fine particles or a part of the aggregate thereof is of a size that can be exposed without being buried in the amorphous carbon film. Preferably, the diameter of the fine particles is 100 nm to 11 μm. Further, the shape of the conductive carbon fine particles is not particularly limited, and is not necessarily granular, and may be a spiral shape such as a carbon nanotube.

An amorphous carbon film (aC: H film) according to an embodiment of the present invention is formed directly on the substrate or via another layer, and includes carbon (c) and It is mainly composed of hydrogen (H). In another embodiment of the present invention, if necessary, by containing each element of silicon (Si), oxygen (O), nitrogen (N) alone or in combination, Functional groups can also be added to the amorphous carbon film.
When Si is contained in the film, the content is generally 1 to 45 atomic%, preferably 4 to 30 atomic%. When oxygen is contained in the film, the content is generally 0.1 to The content is 50 atomic%, preferably 4 to 40 atomic%. When nitrogen is contained in the film, the content is 0.1 to 20 atomic%, preferably 0.5 to 15 atomic%.
The thickness of the aC: H film according to one embodiment of the present invention is not particularly limited, but is preferably at least 50 nm to 10 μm, more preferably 0.5 to 3 μm. When the film is thinner than 50 nm, the continuity of the film is lost, and when the film is thicker than 10 μm, stress peeling of the film occurs. Considering the film formation time and stability, the range of 0.5 to 3 μm is optimal for application of the present invention.

Hereinafter, typical methods for manufacturing the amorphous carbon film laminated member will be described.
The first method includes (1) a step of dispersing and fixing conductive carbon fine particles only on the fine regions on a conductive base material, and (2) non-deposition on the surface of the substrate on which the conductive carbon fine particles are fixed. This is a method comprising a step of depositing crystalline carbon and a step of (3) flattening the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane.

The method for fixing the conductive carbon fine particles only to the minute regions on the conductive base material of (1) is not particularly limited. For example, a mesh or screen plate having a predetermined opening is formed on the substrate. The method of arrange | positioning and spraying the spray coating agent containing an electroconductive carbon particle etc. from there is mentioned.
The size of the opening of the screen or mesh to be used is 10 to 500 μm, and the material of the screen or mesh to be used is a flying opening at a necessary interval according to the shape of the micropart that is a contacted object. It only needs to have a pattern, stainless steel (SUS), Ni, copper, aluminum and other metals and their alloys, emulsion, polyester and other resins, rubber, paper, cellulose, synthetic fibers, inorganic materials, etc. The material is not particularly limited. In order to make the contact between the conductive fine particles and the substrate more reliable at the stage where the coating material is sprayed and the coating material is sufficiently dried and the initial conductive carbon particles are in close contact with the substrate. It is also possible to lightly compress the conductive carbon particles from the upper part toward the base material.

  The method (2) for depositing the amorphous carbon film is not particularly limited, such as a PVD method or a CVD method, but a method using a plasma CVD method of forming a film with a reactive gas is preferable. The plasma CVD method used for the production of the aC: H film of the present invention includes a high frequency plasma CVD method using a high frequency discharge, a direct current plasma CVD method using a direct current discharge, and a microwave plasma using a microwave discharge. Although CVD method etc. are mentioned, any may be sufficient if it is a plasma apparatus using gas as a raw material. Note that conditions such as a substrate temperature, a gas concentration, a pressure, and a time during film formation are appropriately set by a known method according to the composition and film thickness of the amorphous carbon film to be formed.

  Although the step (3) can be performed using a tool, the amorphous carbon film is excellent in wear resistance, but the conductive carbon fine particles are vulnerable to friction, and Since the amorphous carbon film and the conductive carbon fine particles are excellent in adhesion, it is possible to carry out these surfaces by a simple method such as wiping with valene whose surface is covered with a nonwoven fabric or the like. .

  The second method consists of (1 ′) depositing amorphous carbon in a region other than the above-described microregion on the conductive substrate, and (2 ′) depositing amorphous carbon on the conductive substrate. A method comprising: fixing conductive carbon fine particles in an unfinished microscopic area; and (3 ′) flattening the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane. It is.

  The method for depositing amorphous carbon in the region other than the minute region on the conductive substrate (1 ′) is not particularly limited. For example, a mask or mesh is disposed on the conductive substrate, A spraying material such as water-based paint is sprayed to form a protective film with a masking material in a mask or mesh negative pattern, and then the mask or mesh is removed to deposit an amorphous carbon film on the substrate surface Is mentioned. According to this technique, the amorphous carbon film having a pattern similar to that of a mask or mesh is then removed by peeling off the aqueous paint portion and the amorphous carbon film formed on the paint by ultrasonic cleaning or the like. A membrane can be obtained.

In the step (2 ′), spray coating containing conductive carbon particles is applied to the substrate on which the patterned amorphous carbon film has been formed from the top in the same manner as in the step (1). This is performed by fixing the conductive carbon fine particles in a region where the amorphous carbon film is not formed by a method such as spraying an agent.
The subsequent step (3 ′) is the same as the step (3).

  Both the first method and the second method described above are excellent in adhesion between the amorphous carbon film and the conductive carbon fine particles, and the hardness of the amorphous carbon film and the conductive carbon fine particles. (Brittleness) difference, having a discontinuous minute region made of conductive carbon fine particles and a continuous region made of amorphous carbon film on a conductive substrate, This is a method suitable for manufacturing a laminated member having the same plane.

In addition, both the first method and the second method form a desired coating pattern by spraying or the like, and the covering such as a screen, a mask, or a mesh used is completely adhered to the target substrate. Even without the coating, the spray spray material has relatively little wraparound even in the part where the coating floats from the substrate surface, resulting in slight floating between the substrate and the coating as in the coating during the plasma deposition process. There is little need to consider problems such as plasma flowing into the gap to form a film and defects in transfer of the coating pattern. The present invention can also be applied to a substrate with undulations or shallow grooves.
Further, since spray spray does not involve heating during pattern transfer, there is no occurrence of pattern misalignment due to the difference in the coefficient of thermal expansion between the coating and the substrate.
Furthermore, since spray application is performed in an open atmospheric pressure space, not a vacuum process, for example, any surface or part of a substrate having a three-dimensional shape is selectively selected and most suitable for the surface. By covering the pattern, it is possible to sequentially perform surface treatment from an arbitrary direction.

  Furthermore, since the manufacturing method of the present invention is not subjected to patterning in a solution like plating, a substrate that cannot be immersed in a solution, or a plating solution that generally shows acidity or alkalinity. Patterning is easily possible even with a substrate that does not have resistance to the solution. Furthermore, when it is necessary to apply a voltage to the substrate as in the case of electrolytic plating, the substrate needs to have a level of conductivity required for plating, but the conductivity of the substrate is not selected in the spray method. .

Hereinafter, the present invention will be described using examples and comparative examples. However, the present invention is not limited to these examples.
(Examples 1 and 2)
1) Formation of Amorphous Carbon Film on Substrate As a sample, a square plate-like stainless steel (austenite) SUS304 2B material having a width of 20 mm × length of 80 mm and a thickness of 0.6 mm was prepared.
After the sample is placed flat, a # 60 metal mesh (wire diameter 0.12 mm, mesh size 0.3 mm) made of stainless steel SUS is placed on the sample surface so that only half of the sample is covered in the vertical direction. Then, a spray coating agent containing graphite fine particles (manufactured by Autech Co., Ltd., trade name: Black Lube, electric conductivity: 10 ⁻³ Ω · cm) was sprayed. The sample was naturally dried at room temperature for 15 minutes, and then the metal mesh was removed and heated on a hot plate at about 200 ° C. for 10 minutes.

FIG. 2 is a photograph [(a): magnification 30 times, (b): magnification 150 times) of the surface of the obtained sample, and the right side of each photograph is not covered with a metal mesh. The part, the left side is the covered part.
In the portion covered with the metal mesh, it was particularly possible to observe a state where graphite fine particles having a particle diameter of 1 μm or more or secondary particles were scattered on the surface of the sample. Further, it was confirmed that the portion not covered with the metal mesh covered the sample surface as a continuous surface with graphite, and the sample surface was not exposed.
In the sample, a sample portion coated with a metal mesh and interspersed with graphite on the surface was used as a sample for Example 1. Moreover, the part which is not coat | covered with a metal mesh and the graphite has covered the sample surface continuously was made into the sample for the comparative example 1. FIG.
Further, separately, the same sample as that used in the preparation of Example 1 and Comparative Example 1 in a state where no graphite-containing coating agent was sprayed on the surface was prepared, and this was used as a sample for Comparative Example 2.

At the same time, an amorphous carbon film was formed on the sample for Example 1 and the samples for Comparative Examples 1 and 2 under the following conditions to obtain samples of Example 1, Comparative Example 1 and Comparative Example 2.
・ Film forming device: High-pressure DC pulse plasma CVD device ・ Vacuum degree: 7 × 10 ⁻⁴ Pa
・ Raw material gas: Trimethylsilane Flow rate: 30 SCCM Gas pressure: 2 Pa
・ Applied voltage: up to -4 kV ・ Film thickness: 500 nm

  In the case of the plasma CVD method, abnormal discharge frequently occurs due to foreign matters adhering to the base material, and when the predetermined applied voltage is not applied or abnormal power discharge causes a great damage to the power supply circuit. When the amorphous carbon film was formed, abnormal discharge due to graphite sprayed in advance did not occur. This can be estimated because graphite is a good conductor of electricity.

The CCD enlarged photograph of each sample after film-forming is shown below.
First, FIG. 3 shows a CCD enlarged photograph in which the state of the portion covered with the metal mesh of the sample for Example 1 is observed ((a) magnification 500 times, (b) magnification 2000 times). From these photographs, it can be seen that an amorphous carbon film is formed without particularly affecting the periphery of the graphite.
Further, FIG. 4 shows a CCD enlarged photograph in which the state of the portion not covered with the metal mesh of the sample for Comparative Example 1 is observed ((a) magnification 500 times, (b) magnification 2000 times). From FIG. 4, it can be confirmed that a graphite film is present on the entire surface so as to cover the substrate. It can be estimated that an amorphous carbon film was formed thereon.

2) Dry wiping with non-woven fabric valene After the formation of the amorphous carbon film, the surface of the sample for Example 1 and the surface of the sample for Comparative Example 1 were wiped dry using valene that was entirely covered with non-woven fabric. Checked the condition. A black powdery form was observed from the friction surface of the non-woven fabric of valene used for wiping, and it was convex above the surface of the amorphous carbon film (horizontal plane) without being embedded in the formed amorphous carbon film. It was confirmed that the portion of graphite up to the surface of the surface of the amorphous carbon film and the horizontal plane was worn and flattened by valene.
FIG. 5 is a CCD magnified photograph observing the state of the portion covered with the metal mesh of the sample for Example 1 ((a) magnification 500 times, (b) magnification 2000 times).

  As can be seen from the photograph of FIG. 5 which is a sample of Example 1, in the portion covered with the metal mesh, the graphite fixed to the substrate surface layer and protruding above the amorphous carbon film has low hardness. Therefore, it is easily worn away by wiping the non-woven fabric valene, and the graphite is cut to the level of the film plane of the amorphous carbon film. However, for the part rooted in the amorphous carbon film beyond that, since the hard amorphous carbon film around protects the attack from physical friction, the photograph shows the part where graphite was applied. It was not possible to confirm the bare and exposed portion of the base material, and it was confirmed that at least a part of the graphite remained on the base material in a sprayed state.

  From the above, even if an amorphous carbon film close to insulation is formed so as to cover the protrusions of graphite that is applied to ensure conductivity with the base material, Since the graphite particles themselves are soft, the graphite particles are scraped off, and the amorphous carbon film that temporarily covers the surface of the graphite during film formation is destroyed when flattened with the valene or the like, and again becomes a conductive graphite component. Since the graphite itself is exposed to the surface and the graphite is in contact with the base material at the time of application, the contact object of the amorphous carbon film surface layer is electrically connected to the base material through the graphite portion. Turned out to be possible to take.

Next, the electrical resistance of a sample prepared in the same manner as in Example 1 (one in which graphite was scattered and an amorphous carbon film was formed and the surface was rubbed with valene), a width of 20 mm × length of 20 mm, was measured by a four-terminal method. It was measured.
In particular, in order to measure the electrical resistance of a sample interspersed with partially conductive graphite as in Example 1, the metal terminal for measurement does not penetrate through the amorphous carbon film, which is a thin film, to the substrate side. As described above, the electrical resistance measurement contact portion with the sample surface of Example 1 has a conductive rubber (short rubber made by JSR Microtech Co., Ltd., width) on the metal terminal portion surface layer which is the contact portion with the original object to be measured. 10 mm × length 16 mm × thickness 1.35 mm). The outline is shown in FIG.

An object to be measured is a sample prepared under the same conditions as in Example 1 above, a sample having a width of 20 mm and a length of 20 mm on the conductive rubber which is a contact portion located on the lower side of the measuring instrument. Set the “back surface” side on which the sample film is not formed in contact (Example 1 arrangement where the “back surface” side on which the sample film is not formed contacts the lower conductive rubber), and set the upper conductive rubber The measurement was carried out in such a manner that the surface of the object to be measured on which the sample film of Example 1 was formed was sandwiched between the upper conductive rubbers by being lowered by the movable stage.
In this measurement, in addition to the electrical resistance of the object to be measured,
-Contact resistance between conductive rubber and object to be measured-Resistance of conductive rubber-Contact resistance between metal electrode and conductive rubber-Resistance of metal electrode-Contact resistance between lead wire and metal electrode-Resistance of lead wire occurs May affect the measured value. In order to eliminate these effects, the electrical resistance is measured by the 4-terminal method. As a resistance measuring instrument, 34420A manufactured by Agilent was used.
The average resistance value obtained by measuring the electrical resistance of the sample similar to Example 1 by the above method 5 times was 2.92Ω, and it was confirmed that the electrical continuity between the substrate and the amorphous carbon film surface was ensured. did it.

  On the other hand, in the portion that is not covered with the metal mesh of Comparative Example 1, a layer serving as a graphite surface is interposed between the base material and the amorphous carbon film, and the adhesion of the amorphous carbon film is related to the graphite. The soft graphite layer with a Mohs hardness of 1-2, which is in physical contact with the base material only, depends on the frictional force applied through the amorphous carbon film. It was confirmed that it was peeled off from the material.

  From the above, it can be said that it is important that the graphite surface is scattered on the surface of the base material so that the graphite portion is protected by the surrounding amorphous carbon film.

3) Friction and abrasion test In the above description, in order to test whether the structure of the surrounding amorphous carbon film surrounding the graphite part can be industrially implemented, Shinto Kagaku made a friction and abrasion test. A frictional wear test was performed using the equipment Tribogear HHS-2000. As an experimental condition for the frictional wear test, the load was applied by inclined pressurization between two points of 20 g and 100 g. The test atmosphere was air, the indenter moving speed was 5 mm / second, the indenter moving distance was 20 mm, and the sampling rate was up to 25 Hz. Samples and other conditions are described below.

The result of a friction abrasion test is shown.
Two types of samples, the sample of Example 1 and the sample of Comparative Example 2 in which only an amorphous carbon film was formed on a sample of stainless steel SUS, were subjected to a frictional wear test under the above conditions.

FIG. 6A shows the result of the frictional wear test of Comparative Example 2.
The sample of the stainless steel SUS304 of Comparative Example 2 coated with only an amorphous carbon film increases the friction coefficient from about 5 reciprocations to about 0.5μ, but then stabilizes and tends to decrease slightly on the right shoulder. 100 round trips have been completed.
Moreover, according to the CCD photograph (magnification 500 times) of the ball trajectory of the frictional wear test shown in FIG. 6B, the ball trajectory is also discolored, but the surface of the stainless steel SUS as the base material is exposed. Absent.

FIG. 7 (a) shows the result of the friction and wear test of the sample of Example 1 of the present invention.
It can be confirmed that the sample of Example 1 is stable with a friction coefficient equivalent to that of the normal amorphous carbon film formed in the sample of Comparative Example 2 described above.
As a result, the graphite dispersed together with the amorphous carbon film on the base material is wear resistant, which is a characteristic characteristic of the amorphous carbon film in exchange for imparting conductivity even in friction and wear applications. It can be confirmed that it is not at the expense of having the property and the low coefficient of friction.
Further, according to the CCD photograph (500 times magnification) of the ball trajectory of the frictional wear test shown in FIG. 7B, it is found that the surface of the stainless steel SUS as the base material is not exposed. I can confirm.
FIG. 8 shows an enlarged CCD photograph (magnification 5000 times) of the graphite portions scattered on the locus of the ball in the frictional wear test of the sample of Example 1. As for the graphite portion existing on the trajectory of the ball, exfoliation, in particular, the portion where only the graphite portion is detached or exfoliated cannot be observed.

  The amount of graphite added to the surface of the amorphous carbon film changes the interstitial area of the desired graphite, the coating area, etc. by controlling the opening of the masking and the wire diameter of the amorphous carbon film. It is possible.

4) Evaluation of the state of sticking of minute electronic parts due to static electricity In order to confirm the effect of the present invention, a stainless steel (with a round tray) shape having a flange-shaped component conveyance guide (wall) around the inner diameter of the flange (80 mmΦ). (SUS304) A mirror-finished (Ra: 0.05 μm) part-feeding ball feeder workpiece amorphous surface with graphite interspersed by the following method on the workpiece conveyance surface (inside of flange, inner diameter 80 mmφ) A carbon film was created.

As a sample similar to Example 1, first, a stainless steel SUS # 60 metal mesh (wire diameter: 0.12 mm, mesh size: 0.3 mm) was first contacted with the feeder in a form in contact with the upper front surface of the sample. A spray coating agent (manufactured by Autech Co., Ltd., trade name: Black Lub) containing fine graphite particles was sprayed.
The sample was naturally dried at room temperature for 15 minutes, and then the metal mesh was removed and heated on a hot plate at about 170 ° C. for 10 minutes. This is the base material of Example 2.
Next, as a comparative sample similar to Comparative Example 2, a feeder for conveying a mirror finished (Ra: 0.05 μm) part made of stainless steel (SUS304) having the same inner diameter of 80 mm as in Example 2 was prepared. Use wood.

An amorphous carbon film was simultaneously formed on the base materials of Example 2 and Comparative Example 3 under the following conditions.
・ Film forming device: High-pressure DC pulse plasma CVD device ・ Vacuum degree: 7 × 10 ⁻⁴ Pa
・ Raw material gas: Acetylene Flow rate: 30 SCCM Gas pressure: 2 Pa
・ Applied voltage: up to -4 kV ・ Film thickness: 500 nm

After forming the above amorphous carbon film, after rubbing the surface of the base material of Example 2 (feeder in which the amorphous carbon film was formed after being interspersed with graphite fine particles) with valene (Example 2), Example 2 was set in a vibration transfer device that vibrates with a piezoelectric body in an environment of room temperature 25 ° C. and humidity 25%, and the peripheral surface and end surface of the external electrode terminal were finished by Sn plating for mounting a 0402-shaped substrate. 20 multilayer chip ceramic multilayer capacitors were rotated and conveyed at 25 rpm for 10 minutes, then removed and arranged so that the surface of the amorphous carbon film of Example 2 was inclined at 90 ° (vertical), and on the feeder. The number of remaining parts of the 0402-shaped multilayer ceramic capacitor to which static electricity adheres was counted.
As a result, adhesion of the multilayer ceramic capacitor was not recognized on the feeder surface of Example 2.
In Comparative Example 3 (in which an amorphous carbon film was formed) in the same manner as described above, 20 multilayer ceramic capacitors were rotated and conveyed at 25 rpm for 10 minutes, then removed and the surface of the amorphous carbon film was 90 °. The number of the remaining parts of the 0402-shaped multilayer ceramic capacitor adhering to the static electricity on the feeder was counted. The adhesion of 14 parts could be confirmed on the surface of the feeder where only the amorphous carbon film of Comparative Example 3 was applied.
Continuously, 20 0402-shaped multilayer ceramic capacitors (about 0.1 mg) were rotated at 25 rpm, and the state of the feeder surface was observed at 30,000 rpm.
In Example 2, no electrostatic adhesion of the 0402-shaped capacitor and adhesion due to Sn plating (tin oxide) from the multilayer ceramic capacitor electrode were confirmed.
From the above evaluation results, the dispersed graphite part formed together with the amorphous carbon film on the base material has sufficient electrical conductivity and anti-adhesion properties necessary for static electricity removal and prevention of component sticking due to the generation of adhesions. Can be confirmed.

(Example 3)
A photomask is used as a mask having a wire diameter that does not completely accommodate the three-dimensional surface having the largest projected area of a 0402-shaped multilayer ceramic capacitor (vertical width 0.4 mm × width 0.2 mm × thickness 0.2 mm). A mask made of meshed stainless steel SUS304, which was patterned and processed by opening by etching, was prepared with an opening of 200 μm, a wire diameter of 100 μm, and a plate thickness of 50 μm.
On the conveyance surface of the workpiece including the slit of the component conveyance feeder, which is made of an aluminum alloy (A2017) having a rectangular shape of 10 cm in length, 10 cm in width, and 5 mm in thickness, and a concave slit processing is performed in a circular arc shape in part by cutting. The mask was fixed, and the paint was sprayed with an aqueous paint spray (Sunday Paint aqueous spray white made by Dainippon Paint).
When the stainless steel SUS mask was removed after spraying the paint, the paint pattern was confirmed on the feeder surface in the negative pattern of the mask. In addition, a flying paint pattern was confirmed at the bottom of the slit.

After sufficiently drying the coating material, the obtained feeder was put into a high-pressure DC pulse plasma CVD film forming apparatus together with a feeder (base material of Comparative Example 4) made only of aluminum alloy A2017 as a comparative example.
The amorphous carbon film was formed under the following conditions: vacuum, reduced pressure to 1 × 10 ⁻³ Pa, cleaning with argon gas plasma for 5 minutes, amorphous carbon film intermediate layer containing silicon, and acetylene An amorphous carbon film made of a gas raw material was formed at a gas pressure of 2 Pa, a gas flow rate of 40 SCCM, and an applied voltage of −5 Kv for a total of 40 minutes.

After film formation, when the above feeder surface with paint applied in a pattern is confirmed, it is confirmed that the amorphous carbon film is neatly formed so as to fill the gap in the positive pattern part where the paint is not attached. did it.
FIG. 9 shows a CCD magnified photograph observing the surface.

Next, after the surface on which the amorphous carbon film was formed in Example 3 was wiped with a non-woven fabric containing IPA (isopropyl alcohol), IPA was put into an ultrasonic cleaner, and the above-mentioned feeder was ultrasonicated for 15 minutes. After washing, the paint portion and the amorphous carbon film formed on the paint were peeled from the feeder. The same lattice-like amorphous carbon film as that of the stainless steel SUS mask and the bare substrate of the aluminum alloy A2017 feeder were confirmed. Normally, an amorphous carbon film formed on a metal substrate does not peel off from the substrate by ultrasonic cleaning with IPA for about 15 minutes, but the amorphous film formed on the sprayed paint film Since the carbonaceous film is not in direct contact with the metal substrate, it can be easily peeled and removed by wiping or ultrasonic cleaning with IPA. After film formation, it is simpler and more productive than a method in which a part of the film is peeled off to form a part where a substrate without an amorphous carbon film is exposed.
FIG. 10 shows an enlarged CCD photograph of the surface observed. In the figure, the white part is the aluminum alloy of the base material, and the black part is the amorphous carbon film.

Next, a spray coating agent containing the above graphite (manufactured by Autech Co., Ltd., trade name: Black Lub) is applied onto the feeder, and dried at room temperature for 10 minutes, and then 170 ° C. on a hot plate. For 10 minutes.
Confirm that the graphite spray has solidified sufficiently, rub the surface with a non-woven fabric, leave only the graphite sealed in the negative pattern (white part of the photo), and the graphite on the amorphous carbon film (black part of the photo) A composite of an amorphous carbon film and graphite from which carbon was removed was prepared. This is the feeder of Example 3.

Next, the feeder of Example 3 was set in a device that vibrates with a piezoelectric body in an environment of room temperature of 25 ° C. and humidity of 25%. 20 chip-shaped multilayer ceramic capacitors whose peripheral surfaces and end faces of the external electrode terminals are finished by Sn plating for mounting on a 0402-shaped substrate are rotated and conveyed at 20 rpm for 10 minutes on this ball feeder, and then removed and amorphous. The surface of the carbon film was disposed so as to be inclined at 90 ° (perpendicular), and the number of remaining 0402-shaped multilayer ceramic capacitors on the ball feeder was counted.
Similarly, for the feeder of Comparative Example 4 to which only a comparative amorphous carbon film was applied, the number of remaining 0402 multilayer ceramic capacitors adhering to the static electricity on the ball feeder was counted.

As a result, also in Example 3, as in Example 2, adhesion of parts was not recognized on the feeder surface. On the other hand, adhesion of 11 parts was confirmed on the feeder surface of Comparative Example 4 in which only a comparative amorphous carbon film was applied.
In addition, 20 0402 shaped multilayer ceramic capacitors were continuously rotated at 20 rpm, and the state of the feeder surface was observed at 10,000 revolutions. In the feeder of Example 3, the 0402 shaped multilayer ceramic capacitor was observed. There was no adhesion of static electricity or adhesion due to Sn plating (tin oxide).

  From the above evaluation results, the graphite part formed in the base part of the aluminum alloy between the lattice-like amorphous carbon films has sufficient electrical conductivity and anti-adhesion necessary for static electricity removal and prevention of sticking of parts due to the generation of adhesions. It can be confirmed that the prevention property is maintained.

10: Conductive base material 20: Discontinuous minute region in which conductive carbon fine particles are dispersed and fixed 30: Continuous region made of amorphous carbon film 40: Multilayer ceramic capacitor 40a: On both ends of the multilayer ceramic capacitor Formed electrode

Claims (7)

  A non-continuous minute region in which conductive carbon fine particles are dispersed and fixed on a conductive substrate, and a continuous region made of an amorphous carbon film deposited in addition to the region on the conductive substrate, The amorphous carbon film laminated member, wherein the surface of the minute region made of the conductive carbon particles and the surface of the continuous region made of the amorphous carbon film are in the same plane.   The amorphous carbon film laminated member according to claim 1, wherein the conductive carbon particles are made of carbon graphite or carbon black.   3. The amorphous carbon film laminated member according to claim 1, wherein the amorphous carbon film is a component transporting member, a component aligning member, or a component storage member having the amorphous carbon film as an uppermost layer.   (1) a step of dispersing and fixing conductive carbon fine particles only in the minute regions on a conductive base material; and (2) depositing amorphous carbon on the surface of the substrate on which the conductive carbon fine particles are fixed. 4. The method according to claim 1, further comprising: (3) a step of planarizing the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane. The manufacturing method of the amorphous carbon film | membrane laminated member of item.   The step (1) is performed by disposing a mesh or screen plate having a predetermined opening on a conductive substrate and spraying a coating agent containing conductive carbon particles thereon. The method for producing an amorphous carbon film laminated member according to claim 4.   (1 ′) a step of depositing amorphous carbon in a region other than the minute region on the conductive substrate; and (2 ′) a step of depositing amorphous carbon on the conductive substrate on which the amorphous carbon is not deposited. A step of fixing conductive carbon fine particles and a step of (3 ′) flattening the surface of the amorphous carbon film and the surface of the conductive carbon fine particles to be in the same plane are included in this order. Item 4. The method for producing an amorphous carbon film laminated member according to any one of Items 1 to 3. In the step (1 ′), a mask having a predetermined opening is disposed on a conductive substrate, and a masking material is applied or sprayed thereon to form a protective film made of the masking material in the negative pattern of the mask. After forming, remove the mask, deposit an amorphous carbon film on the surface of the conductive substrate, and then peel off the protective film portion made of the masking material and the amorphous carbon film formed on the protective film. The method for producing an amorphous carbon film laminated member according to claim 6, wherein: