JP2021123571A - Member having amorphous carbon film, and method of producing the same - Google Patents

Abstract

To provide a member having an amorphous carbon film having sufficient antibacterial property, and a high percentage of a sp3 hybrid carbon atom.SOLUTION: The member is provided, comprising: a substrate; and a film formed on the substrate, and including amorphous carbon and metal which are dispersed in the amorphous carbon, the atomic concentration of the metal in the film is 1 atom%-6 atom%, the amorphous carbon includes a carbon atom forming a bond by a sp2 hybrid orbital, and a carbon atom forming a bond by a sp3 hybrid orbital, and the percentage of the number of the carbon atoms forming a bond by the sp3 hybrid orbital to a total of the number of the carbon atom forming a bond by the sp2 hybrid orbital and the number of the carbon atom forming a bond by the sp3 hybrid orbital is 57 atom% or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a member having an amorphous carbon film and a method for producing the same.

Diamond-like carbon (DLC, amorphous carbon), which is a kind of amorphous carbon, is attracting attention as a surface coating material in various fields. In addition, silver (Ag) is known to have antibacterial properties. Non-Patent Document 1 describes that a mixed film of Ag particles and DLC (Ag-DLC film) exhibits antibacterial properties.

Further, Patent Document 1 also discloses an antibacterial DLC film coating member. In Patent Document 1, the DLC film is a vapor deposition film of an amorphous carbon / hydrogen solid having a composition of C: 85-60 at% and H: 15-40 at%, and has an antibacterial action in this film. It contains 1 to 30 at% of metal fine particles.

P. Pisarik et al. , "Antibacterial, mechanical and surface products of Ag-DLC films prepared by dual PLD for medical applications" Materials Science Science

Japanese Unexamined Patent Publication No. 2015-81370

According to the first aspect, it is a member including a base material and a film formed on the base material and containing amorphous carbon and a metal dispersed in the amorphous carbon, and the atomic concentration of the metal in the film. Is 1 atomic% to 6 atomic%, and the amorphous carbon contains a carbon atom forming a bond by ^{an sp 2 hybrid orbital and a carbon atom forming a bond by an sp 3} hybrid orbital, and the sp ² hybrid is formed. The number of carbon atoms forming a bond in the sp ³ hybrid orbital relative to the total number of carbon atoms forming a bond in the sp ³ hybrid orbital and the number of carbon atoms forming a bond in the sp 3 hybrid orbital. A member having a proportion of 57 atomic% or more is provided.

According to the second aspect, amorphous carbon and the amorphous carbon formed by simultaneously or alternately irradiating the base material with carbon ions and metal ions by a filtered Casodec vacuum arc method. A member comprising a film containing a metal dispersed therein is provided.

According to the third aspect, it is a member including a base material and a film formed on the base material and containing amorphous carbon and a metal dispersed in the amorphous carbon, and the atomic concentration of the metal in the film. Provided is a member in which the atomic concentration of hydrogen is 7 atomic% to 30 atomic% and the atomic concentration of hydrogen in the membrane is 6 atomic% or less.

According to the fourth aspect, it is a manufacturing method for manufacturing the members of the first, second or third aspect, and carbon ions and the metal ions are formed on the base material by a filtered cascade vacuum arc method. A production method comprising forming the film by irradiating the film simultaneously or alternately is provided.

It is the schematic sectional drawing of the member which concerns on 1st and 2nd Embodiment. It is a schematic block diagram of a film forming apparatus. It is a figure which shows the relationship between the Ag concentration and ^{the ratio of sp 3 mixed carbon atom.} It is a graph which shows the result of the hardness measurement of the film of a sample. It is a graph which shows the result of the antibacterial property test using Escherichia coli. It is a graph which shows the result of the antibacterial property test using MRSA. It is a graph which shows the result of the antibacterial property test using Pseudomonas aeruginosa. It is a graph which shows the result of the antibacterial persistence test. It is a graph which shows the result of the cytotoxicity test (LDH assay). It is a graph which shows the result of the cytotoxicity test (simultaneous staining of live cells and dead cells). It is a graph which shows the result of the blood compatibility test (blood coagulation test). 12 (a) to 12 (c) are electron microscope (SEM) photographs of the sample surface after the blood coagulation test. FIG. 12 (d) is an enlarged photograph of the region e of FIG. 12 (c). It is a graph which shows the result of the blood compatibility test (hemolytic test).

[First Embodiment]
<Member with membrane>
Hereinafter, embodiments of the members will be described with reference to the drawings. As shown in FIG. 1, the member 100 has a base material 40 and a film 50 formed on the base material 40.

(1) Base material 40
The base material 40 may have various shapes depending on the use of the member 100, and may be made of various materials. For example, it may be composed of resin, silicon, titanium, stainless steel, or the like.

(2) Membrane 50
The film 50 covers at least a part of the surface of the base material 40. The film 50 is a film having antibacterial properties, and contains amorphous carbon 60 and a metal 70 dispersed in the amorphous carbon 60.

The metal 70 having antibacterial activity is not particularly limited, and examples thereof include silver, mercury, platinum, copper, cadmium, gold, cobalt, nickel, and lead, or alloys containing these, and silver is preferable.

The film 50 of the present embodiment is formed by simultaneously or alternately irradiating the base material 40 with carbon ions and metal ions by a filtered cascade vacuum arc method (FCVA method). When an amorphous carbon film containing a metal is formed by using a conventional film forming method different from the FCVA method, for example, the pulse laser deposition method (PLD method) used in Non-Patent Document 1, sp ^{3 in the film} The proportion of hybrid carbon atoms is low. However, film 50 was deposited by FCVA method, also contain a metal 70, it can increase the proportion of sp ³ hybridized carbon atoms in the film 50 as compared with the conventional film-forming methods.

Film 50 of the present embodiment, the antimicrobial property can be obtained by including a metal 70, further, by increasing the proportion of sp ³ hybridized carbon atoms, good high hardness, high sliding properties, such as high durability Mechanical characteristics can be obtained. It is also possible ^{to increase the proportion of sp 3} mixed carbon atoms in the membrane 50 and control the value to a specific range with high blood compatibility. High blood compatibility means that hemolysis and blood coagulation are suppressed when the surface 50b of the membrane 50 is brought into contact with blood. By enhancing blood compatibility, it becomes possible to apply it to medical devices (for example, artificial joints, blood bags, etc.) that come into contact with blood, which need to suppress hemolysis and blood coagulation. As described above, the membrane 50 of the present embodiment can have antibacterial properties, good mechanical properties, high blood compatibility, and the like.

Film 50 formed by FCVA method, a high proportion mechanisms sp ³ hybridized carbon atoms in the film 50 also contain metal 70, the FCVA method, ducts 23a having a bent structure (double bend structure), by 23b, This is because the impurities (neutral particles) generated in the arc plasma generation units 10a and 10b are removed before entering the film forming chamber unit 30 and are difficult to be mixed in the 50 (see FIG. 2). Details of the FCVA method will be described later.

In the present specification, the FCVA method means a method (film formation method) in which impurities generated in the arc plasma generation unit are removed by a double vent mechanism so that only ions can reach the substrate. Therefore, in addition to the method generally called the FCVA method, as a method belonging to the above-defined category, for example, a filtered arc deposition method (FAD) method, a filtered arc ion plating method, and the like can be mentioned. The film 50 of the present embodiment can also be formed by using these methods.

The atomic concentration of the metal 70 in the film 50 is 1 atomic% to 6 atomic%. When the atomic concentration of the metal 70 is at least the lower limit of the above range, the precipitation of the metal 70 on the surface 50b of the film 50 is promoted, and the film 50 can have high antibacterial properties. On the other hand, if the atomic concentration of the metal 70 is not more than the upper limit of the above range, the film 50 can have high biocompatibility. High biocompatibility means, for example, low cytotoxicity and no adverse effect on cells in the living body. In general, a film having a low atomic concentration of the metal 70 and a low antibacterial property tends to have a high biocompatibility, and a film having a high atomic concentration of the metal 70 and a high antibacterial property tends to have a low biocompatibility. However, the film 50 of the present embodiment can achieve both high antibacterial properties and high biocompatibility by setting the atomic concentration of the metal 70 in the film 50 within the above range.

Although the atomic concentration of the metal 70 will be described in detail later, it can be adjusted by adjusting the film forming conditions of the film 50. Further, the atomic concentration of the metal 70 can be analyzed by, for example, Rutherford Backscattering Spectroscopy (RBS) measurement.

Amorphous carbon 60 contained in the film 50, sp ² form a bond by hybrid orbital to have carbon atoms (sp ² hybridized carbon atoms) and sp ³ carbon atoms forming the bond by hybrid orbitals (sp ³ hybridized carbon atoms )including. The proportion α of the sp ³ hybridized carbon atoms in the amorphous carbon 60 is defined as the following equation (1). The ratio α forms a bond due to the sp ³ hybrid orbital to the sum of the number of carbon atoms forming the bond ^{due to the sp 2 hybrid orbital and the number of carbon atoms forming the bond due to the sp 3} hybrid orbital. It is the ratio of the number of carbon atoms.

α (atomic%) = ( ^{number of sp 3} mixed carbon atoms) / {(number of sp ² mixed carbon atoms) + (number of sp ³ mixed carbon atoms)} × 100 ... (1)

In the membrane 50, the ratio α of the sp ³ hybridized carbon atoms as defined in formula (1) is at 57 atom% or more, preferably, 57 atomic% to 77 atomic%. By setting the ratio α to 57 atomic% or more, good mechanical properties such as high hardness, high slidability, and high durability, and high blood compatibility can be obtained. Further, by making the proportion of sp ³ hybridized carbon atom α with 77 atomic% or less, the stress is relaxed, the possibility of film separation is reduced.

The ratio α of the sp ³ hybridized carbon atoms as defined in formula (1), details of which will be described later, it can be adjusted by adjusting the film formation conditions of films 50. Further, the ratio α of the sp ³ hybridized carbon atoms as defined in formula (1), for example, can be analyzed by X-ray photoelectron spectroscopy (XPS).

The film 50 may be composed of only the amorphous carbon (carbon) 60 and the metal 70, or may contain other elements as long as the effects of the present embodiment are not impaired. For example, the membrane 50 may contain hydrogen. The stress of the film 50 can be relaxed by containing hydrogen.

Further, the membrane 50 may not contain hydrogen, or the atomic concentration of hydrogen in the membrane 50 may be 6 atomic% or less. That is, the atomic concentration of hydrogen contained in the film 50 may be 0 to 6 atomic%. If the atomic concentration of hydrogen contained in the film 50 is a 6 atomic% or less, a carbon - to increase the proportion of sp ³ hybridized carbon atoms that are involved in carbon bonds. As a result, the film 50 has a dense structure, and the hardness of the film 50 can be further increased. By forming the film 50 by the FCVA method, it becomes easy to reduce the atomic concentration of hydrogen contained in the film 50 to 6 atomic% or less. Thereby, the hardness of the film 50 can be easily increased. The atomic concentration of hydrogen contained in the film 50 can be measured by, for example, RBS / HFS (Rutherford backscattering analysis / hydrogen forward scattering analysis). When a conventional film forming method different from the FCVA method is used, it is difficult to obtain a high-hardness amorphous carbon film having an atomic concentration of hydrogen in the film of 6 atomic% or less. For example, although the atomic concentration of hydrogen can be below 6 atomic% in the sputtering method, sp ³ high hardness of the film for the ratio is less than 50 atomic% of carbon difficult to obtain. Further, it is known that an amorphous carbon film formed by chemical vapor deposition (CVD method) usually contains 20 atomic% or more of hydrogen, and it is difficult to obtain an amorphous carbon film having high hardness.

The hardness of the film 50 is, for example, preferably 20 GPa or more, and more preferably 30 GPa. The upper limit of the hardness of the film 50 is not particularly limited, but from a practical point of view, it may be 50 GPa or less, or 40 GPa or less. The hardness of the film 50 can be measured, for example, by using the nanoindentation method under the measurement conditions described in Examples described later.

Further, the film 50 may have at least one of a hydroxyl group, a carboxyl group and an amino group on its surface 50b. When the surface 50b of the membrane 50 has a hydroxyl group, a carboxyl group or an amino group, the contact angle of pure water decreases. The degree of decrease in the contact angle of pure water varies depending on the amount of functional groups formed. For example, the contact angle of pure water on the surface 50b of the membrane 50 is 10 ° or less, 5 ° or less, or 4 ° or less. Can be adjusted. As disclosed in International Patent Publication No. WO / 2018/193779, the protein adsorption and cell adhesion of the amorphous carbon membrane can be enhanced by setting the contact angle of pure water of the amorphous carbon membrane to 10 ° or less. ..

The method for forming a functional group on the surface 50b of the film 50 is not particularly limited, and the method disclosed in International Patent Publication No. WO / 2018/193779 may be used. For example, the surface 50b of the film 50 is irradiated with ultraviolet rays. The wavelength of the ultraviolet rays and the irradiation amount of the ultraviolet rays can be appropriately adjusted, and examples thereof include conditions for irradiating light containing ultraviolet rays having a wavelength of 185 nm for about 20 minutes. At this time, for example, the irradiated light may include ultraviolet rays having a wavelength of 254 nm.

Even if a functional group such as a hydroxyl group, a carboxyl group, or an amino group is formed on the surface of the membrane 50, the contact angle may change after a certain period of time, but the functional group is formed even if the contact angle changes. As long as it is, the protein adsorption and cell adhesion of the membrane are maintained. For example, the contact angle of pure water measured immediately after the treatment of forming a functional group on the surface of the amorphous carbon film, that is, the treatment of lowering the contact angle may be 10 ° or less. Here, immediately after the treatment means, for example, within 2 minutes after the treatment.

The film thickness of the film 50 can be appropriately determined according to the use of the member 100. For example, the film thickness of the film 50 can be 1 nm to 500 nm or 1 to 300 nm. The film thickness of the film 50 can be adjusted by adjusting the film formation conditions of the film 50 such as the film formation time.

Film 50 described above, by being formed by FCVA method, also contain a metal 70, it can increase the proportion of sp ³ hybridized carbon atoms in the film 50 as compared with the conventional film-forming methods. As a result, the membrane 50 can have antibacterial properties, good mechanical properties, high blood compatibility, and the like. Further, the film 50 of the present embodiment, the atomic concentration of the metal 70 is 1 atomic% to 6 atomic%, and is formula (1) defined in the sp ³ ratio of hybridized carbon atoms α is 57 atomic% or more Is preferable. By satisfying this condition, the membrane 50 can have both high antibacterial property and high biocompatibility, and further has higher mechanical properties, blood compatibility and the like.

Further, the membrane 50 of the present embodiment is exposed on the surface of the member 100 as shown in FIG. 1 in order to impart antibacterial properties, biocompatibility, blood compatibility, good mechanical properties and the like to the member 100. .. That is, no other layer is laminated on the surface 50b of the film 50, and the surface 50b is exposed to the outside. Immediately after the film formation, the atomic concentration of the metal 70 is substantially uniform in the film 50, and the atomic concentration of the metal 70 on the surface 50b is equal to the atomic concentration of the metal 70 in the film 50 described above. The proportion of sp ³ hybridized carbon atoms as defined in formula (1) alpha is substantially uniform in film 50, the proportion of sp ³ hybridized carbon atoms as defined in formula (1) at the surface 50b alpha, described above equal to the ratio α of the sp ³ hybridized carbon atoms as defined in formula (1) in the film 50.

Further, the membrane 50 of the embodiment has high antibacterial property and low biocompatibility by balancing antibacterial property and biocompatibility, and has low antibacterial property and high biocompatibility with the passage of time. The characteristics can also be changed to the state. For example, by adjusting the precipitation amount and the precipitation rate of the metal 70 deposited on the surface 50b of the film 50, the metal 70 can be changed from a state in which the surface 50b has a large amount of precipitation of the metal 70 and has high antibacterial activity and low biocompatibility. It can be changed to a state in which the amount of precipitation is small (or does not precipitate), the antibacterial property is low, and the biocompatibility is high. The member 100 provided with the membrane 50 having such characteristics is expected to be applied to, for example, an artificial joint, an artificial organ, or the like to be transplanted in a living body. In transplant surgery for artificial joints and the like, it is preferable that the artificial joint (member 100) has high antibacterial properties immediately after surgery having a high risk of bacterial infection. When the risk of bacterial infection decreases over time after surgery, the artificial joint (member 100) preferably has high biocompatibility.

The member 100 according to the present embodiment may be used, for example, in medical instruments, medical materials, housing building materials, biological culture-related devices, and daily necessities. The film 50 may be arbitrarily arranged depending on the use of the member 100. The film 50 may be formed so as to cover the entire surface of the base material 40, or may be formed only partially on the surface of the base material 40. When the member 100 is used in a medical device, the membrane 50 may be provided in a region of the member 100 that may be exposed to bacteria. Since the membrane 50 has an antibacterial effect, the growth of bacteria can be suppressed. The member 100 may be used alone or in combination of a plurality of members 100.

The term "medical instrument" includes all things that can be generally called medical instruments, and specifically, artificial joints, artificial bones, artificial teeth, artificial tooth roots, artificial hearts, artificial heart valves, artificial blood vessels, and artificial ones. Anal, artificial urinary tract, artificial pleural membrane, artificial prosthesis, stent (including vascular stent, bronchial stent), guide wire, catheter, indwelling catheter, pacemaker electrode, pacemaker lead wire, contact lens, artificial crystalline body, electric scalpel, high frequency scalpel , Injection needles, blood bags, blood collection tubes, scalpels, endoscopes, filters such as blood filters, channels such as blood circuits, tubes such as blood supply tubes, forceps, artificial lungs, artificial heart-lung machines, dialysis devices , Orthopedic instruments, scalpels, artificial scalpels, artificial vocal bands, cannulas, cerebral artery treatment coils, artificial pancreas, acupuncture and moxibustion treatment instruments, electrodes, sutures, wound covering materials, wound protection materials, effluent tubes, orthopedic implants, pacemakers Etc. are included. Since the member 100 has high blood compatibility, it can be used as an instrument that comes into contact with blood (for example, a medical instrument such as an artificial joint or a blood bag). Further, since the member 100 has high biocompatibility, it can be used as an instrument (for example, a medical instrument such as an artificial joint) that comes into contact with a living body. In addition, "biological culture-related equipment" includes all equipment generally used in the biological culture process, and specifically used for cell and bacterial culture equipment, cell and bacterial observation equipment, microscopes, and cell and bacterial manipulation. Includes equipment to be used.

<Manufacturing method of parts>
A method of manufacturing the member 100 will be described. The method for manufacturing the member 100 is to form a film 50 containing the amorphous carbon 60 and the metal 70 dispersed in the amorphous carbon 60 on the base material 40 by a filtered cascade vacuum arc method (FCVA method). include. In the present embodiment, the film 50 is formed by simultaneously or alternately irradiating the base material 40 with carbon ions and metal ions by the FCVA method. The FCVA method has an advantage that the base material 40 having a complicated shape can be uniformly coated and a film 50 having a high adhesive force with the base material 40 can be formed even at room temperature.

The FCVA film forming apparatus 1 shown in FIG. 2 mainly includes a first arc plasma generating section 10a, a second arc plasma generating section 10b, a first filter section 20a, a second filter section 20b, and a film forming chamber section. It is composed of 30. The first arc plasma generating section 10a and the second arc plasma generating section 10b are connected to the film forming chamber section 30 by the duct-shaped first filter section 20a and the second filter section 20b, respectively, and are formed by a vacuum device (not shown). The pressure of the membrane chamber portion 30 is set to a degree of vacuum of about ^10-5 to ^{10-7 [Torr].}

The first arc plasma generation unit 10a is provided with a first target 11a as a cathode and an anode (striker) (not shown). When the striker is brought into contact with the first target 11a and immediately released, an arc discharge is generated, thereby generating an arc plasma. Neutral particles and charged particles generated from the first target 11a by the arc plasma fly through the first filter unit 20a toward the film forming chamber unit 30.

The first filter unit 20a is provided with a first duct 23a around which the first electromagnet coil 21a is wound and a coil 25a for the first ion scan. The first duct 23a is bent twice in two orthogonal directions between the first arc plasma generation unit 10a and the film forming chamber portion 30, and the first electromagnet coil 21a is wound around the outer periphery thereof. Since the first duct 23a has such a bent structure (double bend structure), the neutral particles in the first duct 23a are removed by colliding with the inner wall surface and accumulating. By passing an electric current through the first electromagnet coil 21a, a Lorentz force acts on the charged particles inside the first duct 23a, and the charged particles are concentrated in the central region of the duct cross section and fly along the bending of the duct to form a film. It is guided to the chamber portion 30. That is, the first electromagnet coil 21a and the first duct 23a form a narrow-band electromagnetic spatial filter through which only charged particles pass with high efficiency.

Similarly, the second arc plasma generation unit 10b is provided with a second target 11b as a cathode and an anode (striker) (not shown). Further, the second filter unit 20b is provided with a second duct 23b around which the second electromagnet coil 21b is wound and a second ion scan coil 25b, and the second electromagnet coil 21b and the second duct 23b are charged. It constitutes a narrow-band electromagnetic spatial filter that allows only particles to pass through with high efficiency.

The first ion scan coil 25a and the second ion scan coil 25b scan the beams of charged particles that pass through the first duct 23a and the second duct 23b and enter the film forming chamber portion 30, respectively, as described above. A holder 31 is provided in the film forming chamber portion 30, and the base material 40 is set on the surface of the holder 31. The holder 31 rotates on its axis by the motor 35. An arbitrary bias voltage can be applied to the holder 31 by the power supply 37. A beam of particles scanned by the first ion scanning coil 25a and a beam of particles scanned by the second ion scanning coil 25b are incident on the surface of the base material 40 held by the holder 31 and are mounted on the base material 40. These particles are uniformly deposited on the surface.

In this embodiment, a graphite target is used as the first target 11a and a metal target is used as the second target 11b. As the metal, as described above, silver, mercury, platinum, copper, cadmium, gold, cobalt, nickel, lead, or an alloy containing these is used, but silver is preferably used. Using these targets, the base material 40 is simultaneously or alternately irradiated with carbon ions and metal ions. A negative bias voltage is applied to the holder 31 by the power supply 37. As a result, the charged particles incident on the base material 40 are accelerated. The accelerated charged particles are deposited on the base material 40, and a dense amorphous carbon film 50 containing a metal is uniformly formed on the base material 40 to obtain a member 100.

First and second arc plasma generator 10a, in 10b, since the neutral particles produced with charged particles can not control the incident energy by the substrate bias reaches the substrate 40, bonding by sp ³ hybrid orbital of the carbon atom Inhibit. In the FCVA method, the neutral particles generated in the arc plasma generating portions 10a and 10b are removed by the ducts 23a and 23b having a bent structure (double bend structure) before entering the film forming chamber portion 30, and are mixed in the film 50. It's hard to do. Therefore, the film 50 was formed by FCVA method, a high proportion of sp ³ hybridized carbon atoms in the film 50 also contain metal 70.

The proportion of metal deposited on the base material 40 (atomic concentration of metal) can be controlled, for example, by changing the currents (filter currents) of the first electromagnet coil 21a and the second electromagnet coil 21b. Application ratio of sp ³ hybridized carbon atoms in the amorphous carbon 60, i.e., the proportion of sp ³ hybridized carbon atoms as defined in formula (1) may, for example, a metal concentration in the amorphous carbon 60, and the holder 31 by a power supply 37 It can be controlled by adjusting the bias voltage to be applied.

The film 50 may be formed only on a part of the base material 40. In this case, after covering the region of the base material 40 that does not form the film 50 with a mask, the base material 40 may be set in the holder 31 to form the film 50.

[Second Embodiment]
The present embodiment relates to the member 200 shown in FIG. The member 200 has the same configuration as the member 100 of the first embodiment except that the composition of the film 150 is different from that of the film 50 of the first embodiment. Therefore, in the present embodiment, the description of the structure of the member 200 other than the film 150 will be omitted.

The film 150 covers at least a part of the surface of the base material 40. The film 150 contains an amorphous carbon 60 and a metal 70 dispersed in the amorphous carbon 60. As the metal 70, the same metal as in the first embodiment may be used. Further, the film 150 is formed by the FCVA method as in the first embodiment.

The atomic concentration of the metal 70 in the film 150 is 7 atomic% to 30 atomic%, preferably 12 atomic% to 30 atomic%. As described above, the film 50 of the first embodiment can achieve both high antibacterial properties and high biocompatibility by setting the atomic concentration of the metal 70 to 1 atomic% to 6 atomic%. On the other hand, the atomic concentration of the metal 70 of the film 150 of the present embodiment is higher than the atomic concentration of the metal 70 of the film 50 of the first embodiment. The membrane 150 of the present embodiment, which has a high atomic concentration of the metal 70, has higher antibacterial properties and cytotoxicity. That is, the membrane 150 of the present embodiment is an antibiotic (antibiotic membrane, antibiotic amorphous carbon membrane) having a property of inhibiting cell proliferation and function or killing cells. Here, the "antibiotic (antibiotic membrane, antibiotic amorphous carbon membrane)" is a substance (membrane) having a property of inhibiting the growth or function of not only bacteria but also cells. means. When the atomic concentration of the metal 70 in the membrane 150 is 7 atomic% or more, the membrane 150 can sufficiently kill cells. Further, when the atomic concentration of the metal 70 in the film 150 is 30 atomic% or less, the hardness is 10 GPa or more, which can be equal to or higher than that of a general hydrogenated amorphous carbon film.

The film 150 may be composed of only the amorphous carbon (carbon) 60 and the metal 70, or may contain other elements as long as the effects of the present embodiment are not impaired. For example, the membrane 150 may contain hydrogen. The stress of the film 50 can be relaxed by containing hydrogen.

Further, the film 150 does not have to contain hydrogen, and the atomic concentration of hydrogen in the film 150 is 6 atomic% or less. That is, the atomic concentration of hydrogen contained in the film 150 is 0 to 6 atomic%. When the atomic concentration of hydrogen contained in the membrane 150 is 6 atomic% or less, the membrane 150 can have mechanical properties such as appropriate hardness and durability, and the range of use as an antibiotic is widened.

Further, the hardness of the film 150 may be, for example, 10 GPa or more. When the hardness of the membrane 150 is 10 GPa or more, the membrane 150 can have mechanical properties such as appropriate hardness and durability, and the range of use as an antibiotic is widened. The upper limit of the hardness of the film 150 is not particularly limited, but from a practical point of view, it may be 30 GPa or less, or 20 GPa or less.

The amorphous carbon 60 contained in the film 150 may contain sp ² mixed carbon atoms and sp ³ mixed carbon atoms. In the membrane 150, the ratio α of the sp ³ hybridized carbon atoms that is defined by the aforementioned formula (1), for example, be 20 atomic percent or more. By the sp ³ ratio of hybridized carbon atoms α to 20 atomic% or more, the film 150 may have mechanical properties such as appropriate hardness and durability, spreads range of use as antibiotics.

Similar to the membrane 50 of the first embodiment, the membrane 150 may have at least one hydroxyl group, carboxyl group and amino group on the surface 150b, and the contact angle of pure water on the surface 50b of the membrane 150 may be different. It may be 10 ° or less, 5 ° or less, or 4 ° or less. Further, the film thickness of the film 150 can be appropriately determined according to the use of the member 200. For example, the film thickness of the film 150 can be 1 nm to 500 nm or 1 to 300 nm. Further, the film 150 can be formed by the FCVA method in the same manner as the film 50 of the first embodiment.

The member 200 of the present embodiment may be used, for example, in the medical device, medical material, housing building material, biological culture-related device, and daily necessities described in the first embodiment. For example, the member 200 can be applied to an intraocular lens used for cataract treatment. In the eye where an intraocular lens is provided by surgery for cataract treatment, a large amount of cells such as lens epithelial cells proliferate in the posterior capsule and become cloudy, causing a problem of developing late-onset cataract. Since the membrane 150 of the present embodiment has a property of killing cells (cytotoxicity), the proliferation of cells can be suppressed by using the member 200 as an intraocular lens. This can be expected to suppress the occurrence of late-onset cataracts.

Hereinafter, a member having an antibacterial film and a method for producing the same will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

1. Preparation of sample (1) Samples q to t
Amorphous carbon films (films 50 and 150) were formed on the base material 40 using the FCVA film forming apparatus 1 (see FIG. 2) to prepare a sample q (member 100) (see FIG. 1). As the base material 40, plate-shaped stainless steel (JIS symbol: SUS316L, 30 mm × 30 mm × 0.03 mm) was used. SUS316L is a commonly used medical stainless steel.

The base material 40 was alternately irradiated with carbon ions and silver ions by the FCVA method. A sintered graphite target was used as the first target 11a of the FCVA film forming apparatus 1, and a silver target was used as the second target 11b. The sintered graphite target used was dehydrated. The film forming conditions were adjusted so that the atomic concentration (Ag concentration) of silver with respect to the total amount of silver and carbon deposited was 1 atomic% and the film thickness was about 100 nm. The film forming conditions are as follows. The arc current of the arc power supply (cathode side power supply) in the first arc plasma generation unit 10a: 80A, the arc current of the arc power supply in the second arc plasma generation unit 10b: 120A, and the current of the first electromagnet coil 21a in the first filter unit 20a. (First filter current): 14A, current of the second electromagnet coil 21b in the second filter section 20b (second filter current): 5A, current of the anode side power supply in the first arc plasma generation section 10a (first anode current). : 6A, current of power supply on the anode side in the second arc plasma generation unit 10b (second anode current): 6A, substrate bias: -66V, film formation time: 650 seconds. The base material was not heated, and the temperature of the base material during film formation was about 25 to 30 ° C. The ultimate pressure of the film forming chamber portion 30 was 2 × 10 ^-4 Pa or less. X-ray photoelectron spectroscopy by (XPS), was determined the ratio α of the sp ³ hybridized carbon atoms are the in the amorphous carbon 60 defined by the formula (1), was 65 atom%. Sample q was obtained by the method described above.

Each sample r to t (members 100 and 200) was prepared by the same production method as that of sample q. However, in the samples r to t, the atomic concentration (Ag concentration) of silver in the amorphous carbon film was set to the value shown in Table 1 by adjusting the second filter current value to control the silver film formation rate. In the amorphous carbon film of each sample R～t, by X-ray photoelectron spectroscopy (XPS), was determined the ratio α of the sp ³ hybridized carbon atoms are the in the amorphous carbon 60 defined by the formula (1). The results are also shown in Table 1.

(2) References 1 to 3
References 1 to 3 were prepared as references used for the evaluation of the sample described below. Reference 1 (Ref. 1) was a base material (plate-shaped stainless steel, JIS symbol: SUS316L) on which no film was formed. References 2 and 3 (Ref. 2 and 3) are samples in which 100 nm of amorphous carbon containing no Ag is formed on a base material (plate-shaped stainless steel, JIS symbol: SUS316L) by the FCVA method, and the above formula (Ref. 2 and 3) is used. ^{The ratio of sp 3} mixed carbon atoms in the amorphous carbon defined in 1) was 78 atomic% in Reference 2 and 63 atomic% in Reference 3. References 2 and 3 have been confirmed to have high biocompatibility, reference 2 has ^{a composition characterized by a relatively high proportion of sp 3} mixed carbon atoms, and reference 3 has relatively high blood compatibility. It is a composition characterized by that.

The evaluation described below was performed using the sample described above, but in some evaluations, a sample in which the size and / or material of the base material of the sample and the thickness of the amorphous carbon film were changed was used. Since the characteristics of the amorphous carbon film are not affected even if the base material and the like are different, the samples having the amorphous carbon film having the same composition are given the same sample number.

2. Evaluation The following evaluations were performed on the prepared samples q to t.

(1) Relationship between Ag concentration and sp ³ mixed carbon atom ratio α In the graph of FIG. 3, the Ag concentration (atomic%) of the film in the samples q to t and reference 2 and sp defined by the formula (1). The relationship with the ratio α of the ^{three mixed carbon atoms is shown.} For comparison, the amorphous carbon film formed by using a PLD method disclosed in Non references 1, together the relationship between the Ag concentration (atom%) sp ³ ratio of hybridized carbon atoms α Figure It is shown in the graph of 3.

As shown in FIG. 3, in both samples q~t and non references 1 of the amorphous carbon film, as the Ag concentration increases, the proportion of sp ³ hybridized carbon atom α is decreased. However, the sample q~t, compared with the amorphous carbon film of the non-cited document 1, the degree of reduction in the proportion α of the sp ³ hybridized carbon atoms is small. Amorphous carbon film formed by FCVA method of sample q~t also contain a metal 70, as compared with the deposited amorphous carbon film by using a PLD method of non references 1, sp ³ hybridized carbon It was confirmed that the proportion of atoms could be increased.

(2) Measurement of film hardness Sample q (Ag concentration: 1 atomic%), Sample r (Ag concentration: 6 atomic%), Sample t (Ag concentration: 30 atomic%) and Reference 2 (Ag concentration: 0 atomic%) The hardness of the film was measured by the nanoindentation method. For the hardness measurement, a Si wafer was used as the base material 40, and a sample in which an amorphous carbon film was formed on the Si wafer at 300 nm was used. Further, the hardness of the film was measured with the pressing depth of 20 to 35 nm. The results are shown in the graph of FIG.

As shown in FIG. 4, the higher the Ag concentration, the lower the hardness of the film. However, if the hardness of the film is 20 GPa or more, it is sufficiently high (hard). It was confirmed that when the Ag concentration of the film was 1 atomic% to 6 atomic%, a sufficient hardness of 30 GPa or more could be obtained. Further, the film hardness of the sample t (Ag concentration: 30 atomic%) is 10 GPa or more, and the lower the Ag concentration, the higher the film hardness. Therefore, if the Ag concentration of the film is 30 atomic% or less, It was confirmed that a film hardness of 10 GPa or more could be obtained. When the hardness of the film is 10 GPa or more, the hardness is equal to or higher than that of a general amorphous carbon film.

(3) Antibacterial property test (film adhesion method)
Three types of bacteria were prepared: Escherichia coli, methicillin-resistant Staphylococcus aureus (MRSA), and Pseudomonas aeruginosa. An aqueous solution of each bacterium was prepared by using a normal bouillon medium diluted to 1/50 with distilled water as the culturing solution of the bacterium. Usually, in the antibacterial property test using the film adhesion method specified in JIS Z 2801: 2012, a normal bouillon medium diluted to 1/500 with distilled water is used. For the purpose of evaluating the antibacterial properties and antibacterial effects on daily products, for example, it reproduces the environment in which a substance that nourishes the bacteria on the desk exists, and because the dilution ratio of the medium is high, it grows for the bacteria. It will be a difficult situation. On the other hand, according to a preliminary study, it was found that when each bacterial growth was evaluated by the film adhesion method using a normal bouillon medium diluted to 1/500 on the base material and SUS316L used for reference 1, the bacteria decreased without growing. confirmed. The decrease in the number of bacteria indicates that the bacterial growth, which is a problem in medical devices, cannot be reproduced. Therefore, the dilution rate of the normal bouillon medium in which the number of bacteria grows even on SUS316L is searched, and if the normal bouillon medium is diluted to 1/50 with distilled water, each bacterium grows on SUS316L. Ordinary bouillon medium was used. It was also confirmed that each bacterium grows on titanium, which is also known as a medical metal like SUS316L, if it is a normal bouillon medium diluted 1/50 with distilled water. Compared to the dilution rate of 1/500, the dilution rate of 1/50 makes it easier for bacteria to grow. Therefore, the sample to be evaluated is evaluated in a harsher environment than JIS Z 2801: 2012. , Decreasing the number of bacteria indicates that it has stronger antibacterial properties.

Based on the above, an aqueous solution of each bacterium (bacterial concentration: about) prepared using a normal bouillon medium diluted 1/50 with distilled water on the membranes of samples q to t and on reference 1 (stainless substrate). 1 × 10 ⁴ CFU / mL) 0.1 mL was added dropwise. Further, a polyethylene film (20 mm × 20 mm) was placed on the film, and the bacterial aqueous solution was spread on the film.

Next, the samples q to t and the reference 1 were left to stand in an environment having a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more for about 24 hours to culture the bacteria. After culturing, samples q to t and Reference 1 were immersed in 10 mL of SCDLP liquid medium and shaken to recover the cultured bacteria, and 10 mL of a recovered solution was obtained. The culture medium of agarose, diluted samples q to t and the recovery solution of Reference 1 were mixed, and the bacteria were cultured in an environment of a temperature of 35 ± 1 ° C. for about 48 hours. After culturing, by counting the number of bacteria on the culture medium, the number of bacteria per ^{unit area (cm 2) existing on the samples q to t and the reference 1 was calculated for each of the samples q to t and the reference 1.} bottom.

The graphs of FIGS. 5 to 7 show the number of bacteria (relative value) per ^{unit area (cm 2) of the samples q to t.} FIG. 5 shows the results using Escherichia coli, FIG. 6 shows the results using MRSA, and FIG. 7 shows the results using Pseudomonas aeruginosa. The number of bacteria per ^{unit area (cm 2} ) of the samples q to t shown in the graphs of FIGS. 5 to 7 is a relative value with the number of bacteria per ^{unit area (cm 2) of Reference 1 as 100.} The number of bacteria (relative value) shown in the graphs of FIGS. 5 to 7 is less than 100, and the lower the number, the smaller the number of bacteria as compared with Reference 1.

As shown in FIGS. 5 to 7, the numbers of bacteria in the samples q to t are significantly reduced as compared with the reference 1 (stainless steel substrate), and the amorphous carbon film having the film composition used in the samples q to t is made of stainless steel. It was shown that high antibacterial properties can be imparted by forming a film on the substrate.

(4) Antibacterial Sustainability Test An antibacterial persistence test was conducted on sample q (Ag concentration: 1 atomic%) and sample t (Ag concentration: 30 atomic%) by the method described below. Samples q and t immersed in normal human umbilical vein endothelial cells so that the sample unit cm ² per 1 mL (HUVEC) medium (EGM (TM) -2BulletKit (TM)), 3 hours after the start of immersion, Immersion was continued after 1 day, 6 days, 13 days and 20 days while exchanging the medium, and the sample was taken out from the medium after 1 month (28 days). The taken-out sample was washed with phosphate buffered saline (PBS) and pure water, dried, and then the antibacterial property was evaluated by the same method as the above-mentioned antibacterial property test (film adhesion method).

The graph of FIG. 8 shows the number of bacteria (relative value) per ^{unit area (cm 2} ) of the samples q and t after immersion in the medium (1 month later). For comparison, the results of the antibacterial test of the same samples q and t when stored in the air for one month (28 days) are also shown in FIG. ^{The number of bacteria per unit area (cm 2} ) of the samples q and t shown in the graph of FIG. 8 is a relative value with the number of bacteria per ^{unit area (cm 2} ) of Reference 1 as 100, as in FIGS. 5 to 7. Is. The number of bacteria (relative value) shown in the graph of FIG. 8 was less than 100, and the lower the number, the lower the number of bacteria as compared with Reference 1, and antibacterial properties could be imparted to the stainless steel base material. It is shown that.

As shown in FIG. 8, the antibacterial property of sample q after immersion in the medium for 1 month was lower than that of sample q stored in the air, but the number of bacteria was smaller than that of reference 1, and the medium for 1 month. It was confirmed that even after immersion, it showed sufficient antibacterial properties. The sample t showed the same antibacterial property as the sample t stored in the air even after being immersed in the medium for one month.

(5) Cytotoxicity test A test container was prepared by placing a cylindrical member (resin tube) upright on each of the amorphous carbon film of samples q to t and the amorphous carbon film of reference 2 (on a Si wafer). .. The prepared test container has a well having an amorphous carbon film on the bottom surface and a cylindrical member on the side surface. 0.5 mL of culture solution for human normal umbilical vein endothelial cells (HUVEC) and about 50,000 human umbilical vein endothelial cells (HUVEC) were injected into the wells of the test container in an environment of _{37 ° C. and 5% CO 2.} It was allowed to stand for one day (about 24 hours). After standing, evaluations 1 and 2 described below were performed.

(A) Evaluation 1 (LDH assay)
The amount of lactate dehydrogenase (LDH) released from the cell into the culture medium was measured, and the degree of non-cell injury was determined based on the measured amount of LDH. LDH is an enzyme present in the cytoplasm that normally remains in the cytoplasm but is released into the culture medium when the cell membrane is damaged. That is, the larger the amount of LDH released into the culture medium, the more damaged the cells, and the smaller the amount of LDH, the less damaged the cells. In this evaluation, the degree to which the cells were not damaged (non-cell damage degree) was determined based on the measured amount of LDH.

The graph of FIG. 9 shows the degree of non-cytotoxicity (relative value) of samples q to t. The non-cytotoxicity of samples q to t shown in the graph of FIG. 9 is a relative value with the non-cytotoxicity of Reference 2 as 100. Reference 2 (Amorphous carbon without Ag) has been confirmed to be non-cytotoxic. Therefore, in FIG. 9, the closer the non-cytotoxicity (relative value) of the samples a to t is to 100, the less the cytotoxicity is.

(B) Evaluation 2 (simultaneous staining of live and dead cells)
The cells attached to each of the amorphous carbon film of Samples q to t and the amorphous carbon film of Reference 2 were stained with a fluorescent dye (Hoechst 33258, Calcein-AM, EthD-III) (cell nucleus: blue, living cell: green, Dead cells: red), total cells and the number of dead cells were counted using a fluorescence microscope, respectively. In addition, the state of living cells was observed from green fluorescence.

The graph of FIG. 10 shows the number of living cells and the number of dead cells (relative values) of samples q to t. The number of living cells is calculated by subtracting the number of dead cells from the total number of cells. The total number of cells, which is the sum of the number of living cells and the number of dead cells of the samples q to t shown in the graph of FIG. 10, is a relative value with the total number of cells of Reference 2 as 100.

As shown in FIG. 9, the samples q to t have a non-cellular injury degree in the samples q and r (Ag concentration: 1 to 6 atomic%) having a low Ag concentration in the amorphous carbon film in the evaluation 1 (LDH assay). The (relative value) was 90% or more, suggesting that the adverse effect on cells was very small or absent. On the other hand, the degree of non-cytotoxicity (relative value) was significantly reduced in the samples s and t (Ag concentration: 12 to 30 atomic%) having a high Ag concentration in the amorphous carbon film. Further, as shown in FIG. 10, in evaluation 2 (simultaneous staining of cell nuclei, living cells, and dead cells), all of the samples q and r (Ag concentration: 1 to 6 atomic%) having a low Ag concentration in the amorphous carbon film. The number of cells was not significantly different from that of Reference 2, and the proportion of dead cells was also very small, suggesting that the adverse effects on cells were very small or absent. On the other hand, in the samples s and t (Ag concentration: 12 to 30 atomic%) having a high Ag concentration in the amorphous carbon film, the proportion of dead cells increased significantly, and all cells adhering to the amorphous carbon film due to cell death. The number has decreased significantly. From this result, it was confirmed that the samples q and r (Ag concentration: 1 to 6 atomic%) having a low Ag concentration have almost no cytotoxicity and can be applied to a field where high biocompatibility is required. On the other hand, the samples s and t (Ag concentration: 12 to 30 atomic%) having a high Ag concentration have properties as antibiotics (antibiotic membrane, antibiotic amorphous carbon membrane) and have the property of killing cells (cytotoxicity). ) Was confirmed to be applicable to the required fields.

(6) Blood compatibility test A blood compatibility test was performed using samples q, t and Reference 3. At this time, a plate-shaped stainless steel (JIS symbol: SUS316L, 10 mm × 10 mm × 0.3 mm) was used as the base material 40. Specifically, human blood was brought into contact with the sample to evaluate coagulation (blood coagulation due to a foreign body reaction) and hemolytic property (disintegration of erythrocytes).

(A) Blood coagulation test Human blood (heparin 1 U / mL) was brought into contact with each sample q, t and reference 3, and shaken at 37 ° C. for 4 hours. After shaking, the amount (concentration) of three types of proteins, specifically, thrombin-antithrombin complex (TAT) in blood, which is an index of blood coagulation, and β-thromboglobulin (β-TG), which is an index of platelet activity. ) And SC5b-9, which is an index of inflammatory response, and their respective concentrations were measured. In addition, electron microscope (SEM) observation of the surfaces of each sample q, t and reference 3 after the blood coagulation test was also performed.

The graph of FIG. 11 shows the measured three types of protein amounts (relative values). The amount of protein shown in the graph of FIG. 11 is the result (protein amount) when a similar blood compatibility test was performed on a human blood sample at the same timing using a commercially available blood bag (Terumo Corporation: Terumo Separation Bag). It is a relative value set to 100. The lower the amount of protein (relative value) shown in the graph of FIG. 11, the higher the blood compatibility. If the amount of protein (relative value) is less than 100, each blood bag is compared with a commercially available blood bag. The item indicates high blood compatibility.

As shown in FIG. 11, all of the samples q and t and the reference 3 had a low TAT concentration (relative value) and a low blood coagulation property. The concentrations of β-TG, which is an index of platelet activity, and SC5b-9, which is an index of inflammatory response, were equivalent to those of commercially available blood bags.

12 (a) to 12 (c) show SEM photographs of the film surfaces of Reference 3, Samples q and t, respectively. When blood coagulation occurred, a large amount of blood cell lines such as fibrin chains and erythrocytes were observed on the membrane, but these were hardly observed on the membrane surface of any of the samples. However, in the samples t (Ag concentration: 30 atomic%) shown in FIGS. 12 (c) and 12 (d), spiny erythrocytes were observed. From this result, there is a possibility that hemolysis has occurred in the sample t, and the hemolytic test described below was performed.

(B) Hemolyticity test The hemolytic rate of blood was determined by the two methods described below. At this time, a plate-shaped stainless steel (JIS symbol: SUS316L, 20 mm × 20 mm × 0.03 mm) was used as the base material 40.

(Bi) Indirect contact method Each sample q, t and reference 3 were immersed in phosphate buffered saline (PBS) and left at 37 ° C. for 72 hours to obtain an extract. The obtained extract was mixed with human blood (non-coagulated with sodium citrate) at a predetermined volume ratio (PBS: human blood = 7: 1) and shaken at 37 ° C. for 3 hours. Then, the hemolysis rate was measured from the absorbance of the mixed solution.

(B-ii) Direct contact method Each sample q, t and reference 3 are immersed in phosphate buffered saline (PBS), and further, human blood (non-coagulated with sodium citrate) and a predetermined volume ratio ( The mixture was mixed with PBS: human blood = 7: 1), the blood was brought into direct contact with each sample, and the mixture was shaken at 37 ° C. for 3 hours. Then, the hemolysis rate was measured from the absorbance of the mixed solution brought into contact with each sample.

The graph of FIG. 13 shows the hemolysis rate of each sample obtained by the (bi) indirect contact method and the (bi) direct contact method. In addition, the hemolysis rate of the negative control material and the positive control material is also shown in the graph of FIG. A high-density polyethylene film was used as the "negative control material", and a 1.5% nonionic surfactant-containing polyvinyl chloride pellet was used as the "positive control material".

As shown in FIG. 13, a sample q (Ag concentration: 1 atom) having a low Ag concentration in the amorphous carbon film was used in both the (bi) direct contact method and the (bi) indirect contact method. %) And the hemolysis rate of Reference 3 were as low as the hemolysis rate of the negative target material. On the other hand, the sample t (Ag concentration: 30 atomic%) having a high Ag concentration in the amorphous carbon film had a high hemolysis rate. As described above, although it could not be confirmed by the blood coagulation test, in the samples s and t (Ag concentration: 12 to 30 atomic%) having a high Ag concentration in the amorphous carbon membrane as the result of the cytotoxicity test by the hemolytic test. It was suggested that the adverse effects on cells may be high. From the results of these blood compatibility tests and cytotoxicity tests, for example, a sample with a low Ag concentration of about 1 to 6 atomic% can be applied to fields where biocompatibility and high blood compatibility are required. Guessed.

(7) Measurement of atomic concentration of hydrogen contained in the membrane As a new evaluation sample, the sample u in which the atomic concentration of silver in the membrane (Ag concentration) is 4 atomic%, and the atomic concentration of silver in the membrane (Ag concentration) are Sample v, which is 9 atomic%, was prepared by the same method as sample q and sample t. Hydrogen contained in the membranes of sample q (Ag concentration: 1 atomic%), sample u (Ag concentration: 4 atomic%), sample v (Ag concentration: 9 atomic%) and sample t (Ag concentration: 30 atomic%). Atomic concentration was measured by RBS / HFS (Razaford Backscattering Analysis / Hydrogen Forward Scattering Analysis). The measurement results are shown in Table 2.

As shown in Table 2, it was confirmed that the atomic concentration of hydrogen contained in the films of the samples q, u, v and t formed by the FCVA method was low and was 6 atomic% or less. It is known that an amorphous carbon film formed by a conventional film forming method different from the FCVA method, for example, a chemical vapor deposition (CVD method), usually contains 20 atomic% or more of hydrogen. There is.

The member 100 having the membrane 50 of the present embodiment has sufficient antibacterial properties, and can have properties such as good mechanical properties, high blood compatibility, and high biocompatibility according to the use of the member 100. .. The member 100 of the present embodiment can be used, for example, for medical instruments, medical materials, biological culture-related devices, housing building materials, and daily necessities.

1 Film deposition equipment 40 Base material 50 Film 50b Surface 60 Amorphous carbon 70 Metal 100 Member

Claims (15)

With the base material
A member formed on the base material and provided with amorphous carbon and a film containing a metal dispersed in the amorphous carbon.
The atomic concentration of the metal in the film is 1 atomic% to 6 atomic%.
The amorphous carbon contains a carbon atom forming a bond by ^{an sp 2} hybrid orbital and a carbon atom forming a bond by an ^{sp 3 hybrid orbital.}
The carbon forming the bond by the sp ³ hybrid orbital with respect to the total number of carbon atoms forming the bond ^{by the sp 2} hybrid orbital and the number of carbon atoms forming the bond by the ^{sp 3 hybrid orbital.} A member having a ratio of the number of atoms of 57 atomic% or more. With the base material
A member including amorphous carbon and a film containing a metal dispersed in the amorphous carbon, which is formed by simultaneously or alternately irradiating the base material with carbon ions and metal ions by a filtered Casodec vacuum arc method. .. The member according to claim 2, wherein the atomic concentration of the metal in the film is 1 atomic% to 6 atomic%. The amorphous carbon contains a carbon atom forming a bond by ^{an sp 2} hybrid orbital and a carbon atom forming a bond by an ^{sp 3 hybrid orbital.}
The carbon forming the bond by the sp ³ hybrid orbital with respect to the total number of carbon atoms forming the bond ^{by the sp 2} hybrid orbital and the number of carbon atoms forming the bond by the ^{sp 3 hybrid orbital.} The member according to claim 2 or 3, wherein the ratio of the number of atoms is 57 atomic% or more. The member according to any one of claims 1 to 4, wherein the hardness of the film is 20 GPa or more. The member according to any one of claims 1 to 5, wherein the atomic concentration of hydrogen in the film is 6 atomic% or less. The carbon forming the bond by the sp ³ hybrid orbital with respect to the total number of carbon atoms forming the bond ^{by the sp 2} hybrid orbital and the number of carbon atoms forming the bond by the ^{sp 3 hybrid orbital.} The member according to claim 1 or 4, wherein the ratio of the number of atoms is 57 atomic% to 77 atomic%. With the base material
A member formed on the base material and provided with amorphous carbon and a film containing a metal dispersed in the amorphous carbon.
The atomic concentration of the metal in the film is 7 atomic% to 30 atomic%.
A member having an atomic concentration of hydrogen in the membrane of 6 atomic% or less. The member according to claim 8, wherein the atomic concentration of the metal in the film is 12 atomic% to 30 atomic%. The member according to claim 8 or 9, wherein the hardness of the film is 10 GPa or more. The amorphous carbon contains a carbon atom forming a bond by ^{an sp 2} hybrid orbital and a carbon atom forming a bond by an ^{sp 3 hybrid orbital.}
The carbon forming the bond by the sp ³ hybrid orbital with respect to the total number of carbon atoms forming the bond ^{by the sp 2} hybrid orbital and the number of carbon atoms forming the bond by the ^{sp 3 hybrid orbital.} The member according to any one of claims 8 to 10, wherein the ratio of the number of atoms is 20 atomic% or more. The member according to any one of claims 1 to 11, wherein the metal is at least one selected from the group consisting of silver, mercury, platinum, copper, cadmium, gold, cobalt, nickel, and lead. The member according to claim 12, wherein the metal is silver. The member according to any one of claims 1 to 13, wherein the film has at least one of a hydroxyl group, a carboxyl group and an amino group on its surface. A manufacturing method for manufacturing the member according to any one of claims 1 to 14.
A production method comprising forming the film by simultaneously or alternately irradiating the base material with carbon ions and the metal ions by a filtered Casodec vacuum arc method.

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