JP2006009991A - Sliding member, disc valve and mixing plug using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a disc valve for increasing the adhesive force of a diamond-like hard carbon film to a base forming valve elements, having operating torque less changed in long-time use to prevent the generation of abnormal sounds. <P>SOLUTION: The disc valve comprises the pair of valve elements for sliding each other and the diamond hard carbon film adhered to at least one of the valve elements to form a slide-contact face. The base of one valve element has a liquid phase. On the upper face of the base, an atom-injected atom mixed layer is formed constituting the base. The mixed layer is formed on the base over both crystal particles and the liquid phase. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a disk valve comprising a movable valve body and a fixed valve body constituting a sliding member, in particular a water tap (hot water mixing tap, etc.) including a single lever mixing plug and a thermostud mixing plug, and a mixing plug using the same About.

  Conventionally, a disc valve used for a faucet such as a hot and cold water mixing faucet is relatively slid in a state where two disc-shaped valve bodies (movable valve body and fixed valve body) are in sliding contact with each other, The fluid passage formed in each valve body is opened and closed. Since this type of disc valve is used in a state where the disc valves are constantly rubbed against each other, the valve body constituting the disc valve is made of ceramics having excellent wear resistance and corrosion resistance.

  The disk valve has been used with a lubricant such as grease interposed on the sliding contact surface in order to reduce the operating force between the valve bodies.

  However, in a disc valve using a lubricant, the lubricant on the slidable contact surface flows out in a relatively short period of time due to sliding between the valve bodies, resulting in a non-lubricated state. As it occurred, the lever operating force gradually increased, and finally there was a problem that linking (adhesion) occurred in which the valve bodies stuck together and stopped moving. In addition, depending on the type of lubricant, it may deteriorate during long-term use or adhesion of dust etc. may occur and deteriorate the sliding characteristics, and if the lubricant flows out during water discharge, it may be harmful to the human body. there were.

  Therefore, in recent years, there is a disk valve in which a diamond-like hard carbon film having a self-lubricating property and an excellent wear resistance is attached to a sliding contact surface of at least one of the sliding valve bodies. It has been proposed (see Patent Documents 1 to 4).

  Due to the excellent self-lubricating action of the diamond-like hard carbon film, stable sliding characteristics can be maintained over a long period of time without causing linking even in a non-lubricated state.

  By the way, in recent years, since the internal water pressure of water faucets, hot water and water mixing faucets, etc. rises and there is a possibility that a slight gap may be formed between the sliding contact surfaces, causing water leakage, the sliding contact surface of the valve body is made smooth. In addition, although it is necessary to increase the pressing force between the valve bodies, there is a fear that the diamond-like hard carbon film constituting the sliding contact surface may be peeled off. In particular, in recent years, faucets have been required to have a high sealing performance, and the number of both valve bodies, for example, mirror surfaces having an arithmetic average roughness (Ra) of 0.2 μm or less is increasing. . In particular, there is an increasing number of situations in which a diamond-like hard carbon film has to be deposited on a mirror substrate.

  Therefore, as a result of applying an intermediate layer having a high chemical bonding force to the diamond-like hard carbon film as in Patent Document 2 to increase the adhesion strength, or applying an intermediate layer as in Patent Document 3, the surface of the substrate The method etc. which can be damaged and can improve adhesive force were shown. Furthermore, Patent Document 4 proposes a sliding ceramic material in which a diamond-like hard carbon film is deposited via an intermediate layer made of a WC mixture.

Patent Documents 5 and 6 introduce a sliding component in which a mixed layer of carbon atoms and implanted atoms is formed by ion-implanting the surface of the substrate, and the diamond-like hard carbon film is formed of the mixed layer. It has been shown that by forming, internal stress is relaxed and adhesion is improved.
JP-A-3-223190 Japanese Patent Laid-Open No. 9-292039 JP-A-6-227882 Japanese Patent Laid-Open No. 10-101463 JP-A-7-90553 Japanese Patent Laid-Open No. 5-221691

  However, in Patent Document 2, when an intermediate layer of Ti or Si is formed on the surface of the substrate by PVD, the liquid phase is etched to reach a temperature of about 200 to 300 ° C. As a result, there is a problem that the surface state of the substrate surface becomes slightly rough although it is extremely small.

In the case where the substrate is an alumina sintered body, SiO ₂ , CaO, Na ₂ O, or the like that becomes a liquid phase is selectively eroded to roughen the surface roughness of the substrate surface.

  These etched surfaces affected the surface state after the diamond-like hard carbon film was formed, and the surface was uneven. Specifically, a plurality of spherical protrusions having a mean curvature radius of 10 to 1000 nm and a size of about 0.1 to 0.3 μm were formed.

  These plurality of substantially spherical protrusions contribute to reducing the initial low friction coefficient by reducing the contact area in the initial sliding friction, but when considering long-term use, the above substantially spherical protrusions are It has disappeared, there is a problem that the contact area increases and the operating torque of the lever increases. Particularly in the Japanese domestic market where importance is placed on quality, there is a case where a complaint is made that the operating torque has changed, and it has been a challenge to reduce the operating torque change.

  In addition, when tap water is inserted into the tap water that contains a large amount of metal ions such as Ca and Fe, the voids that have become larger due to etching and the metal components and When calcium or the like adheres and slides the valve bodies, there is a problem that the adhered matter forms a sliding contact surface that deteriorates the low friction property inherent in the diamond-like hard carbon film. In addition, the frictional resistance is increased due to the sliding on the deposit, which causes a problem in that the valve bodies slightly vibrate and abnormal noise is generated.

  In particular, when the fixed valve element has a larger area than the movable valve element and a diamond-like hard carbon film is deposited on the surface of the movable valve element, these phenomena are likely to occur on the surface of the fixed valve element. The edge portion of the movable body moves on the fixed valve body like a car wiper, and metal components, calcium carbonate, and the like easily adhere to and accumulate on the end portion of the movable range of the movable valve body.

  That is, according to the mapping results of the surface analysis of Ca and C (carbon) by the present inventors using X-ray microanalysis (EPMA) of an energy dispersive scanning electron microscope (SEM), It turns out that it is a deposit | attachment, and it is estimated that calcium carbonate precipitated from this.

  By the way, in Patent Document 3, when the intermediate layer is deposited on the surface of the substrate by plasma CVD, ion plating, plasma excitation sputtering, or the like, the surface roughness is roughened. The surface of the obtained diamond-like hard carbon film has a problem that it becomes rough as in Patent Document 2.

  Further, in Patent Document 4, although the substrate is an alumina sintered body, an intermediate layer mainly composed of WC is formed by a PVD method such as a high frequency sputtering method, a magnetron sputtering method, or an ion plating method. In order to form a film on an insulating substrate such as an alumina sintered body, it is necessary to form an intermediate layer with PVD or the like. The phase is etched, and there is a problem that the surface of the diamond-like hard carbon film becomes rough as in Patent Document 2.

  Therefore, as a method of depositing the diamond-like hard carbon film without etching the surface of the substrate, it is proposed to provide a mixed layer on the substrate surface by an ion implantation method by low-temperature treatment. It was technically difficult to perform ion implantation on the insulating substrate.

  For example, in Patent Document 4 in which an ion implantation method is performed, a Si wafer is used as a base. In Patent Document 5, at least one of a metal, a semiconductor, and a carbide thereof is previously formed on the surface of the base. Since the intermediate film is formed, ion implantation is not performed on an insulating substrate such as a ceramic sintered body.

  Accordingly, an object of the present invention is to provide a disk valve in which the adhesion of a diamond-like hard carbon film to a substrate forming a valve body made of a ceramic sintered body is enhanced. In particular, it is to provide a sliding member, particularly a disc valve, and a mixing plug using the same, which have been formed into a film having high adhesion to a mirror surface product of an insulating substrate such as an alumina sintered body.

  It is another object of the present invention to provide a sliding member having a small change in operating torque even after long-term use.

  Furthermore, a sliding member is provided that reduces the occurrence of abnormal noise by reducing the adhesion of metal components, calcium carbonate, etc. to the sliding contact surface, and can maintain smooth sliding even after long-term use. It is to be.

  The sliding member of the present invention for solving the above problems is a sliding member in which a diamond-like hard carbon film is applied to the surface of at least one valve body of a pair of sliding valve bodies to form a sliding contact surface. In the member, the base body of one valve body is a ceramic sintered body provided with a liquid phase, and a mixed layer of atoms and implanted atoms constituting the base body is formed on the top surface of the base body, and the mixed layer comprises: It is formed in both the crystal grains and the liquid phase of the substrate.

  Further, the substrate is an alumina sintered body.

  The alumina sintered body is an alumina sintered body having a purity of 96% or more.

  The mixed layer has a thickness in the range of 50 to 200 nm.

  Further, the implanted atom contains one or more elements of carbon, Si, Ti, Zr, and Hf.

  The arithmetic average roughness of the sliding surface of the sliding member is 0.2 μm or less.

  In the substrate, when the Ca or Si component is confirmed within a range of a depth of 500 nm from the surface of the substrate, it is within a range of ± 10% compared to the composition inside the substrate. .

  Further, the present invention is a disc valve using the sliding member.

  Further, the present invention is a mixing plug using the disk valve.

  As described above, according to the sliding member of the present invention, the sliding member in which the diamond-like hard carbon film is applied to the surface of at least one valve body of the pair of valve bodies that slide with each other to form the sliding contact surface. In the member, the base body of one valve body is a ceramic sintered body provided with a liquid phase, and a mixed layer of atoms and implanted atoms constituting the base body is formed on the top surface of the base body, and the mixed layer comprises: Since it is formed in both the crystal grains and the liquid phase of the base body, it is possible to obtain a sliding member having high adhesion of the diamond-like hard carbon film to the base body forming the valve body. .

  In addition, since the base is an alumina sintered body, a sliding surface having high hardness and high rigidity can be obtained, and an inexpensive sliding member can be obtained.

  Further, since the alumina sintered body is an alumina sintered body having a purity of 96% or more, the corrosion resistance is not impaired, and the substrate surface is etched when the diamond-like hard carbon film is formed. There is nothing.

  Further, since the mixed layer has a thickness in the range of 50 to 200 nm, and the implanted atoms contain one or more elements of carbon, Si, Ti, Zr, and Hf, diamond As a result of forming the film by ion implantation without reducing the adhesion strength of the cylindrical hard carbon film, it is possible to reduce the surface spherical protrusions, provide a sliding member with little change in operating torque, Adhesion can be reduced.

  Furthermore, since the arithmetic mean roughness of the sliding surface of the sliding member is 0.2 μm or less, a sliding member having a smooth surface can be provided.

  Furthermore, in the substrate, when the Ca or Si component is confirmed in a range of a depth of 500 nm from the surface of the substrate, the Ca or Si component is constant within a range of ± 10% or less as compared with the composition inside the substrate. As a feature, it is possible to provide a sliding member in which the surface of the base is not etched, so that the voids of the original base can be kept, and substantially spherical protrusions can be reduced, resulting in a change in operating torque. A small sliding member can be provided.

  Hereinafter, the best mode for carrying out the sliding member of the present invention will be described using a disk valve.

  1A and 1B show an embodiment of a disc valve of the present invention, wherein FIG. 1A shows the entire disc valve, FIG. 1B shows a movable valve body, and FIG. 1C shows a perspective view of a fixed valve body.

  In the disk valve 1 of the present invention, a diamond-like hard carbon film 24 is attached to the surface of a fixed valve body 20 that is at least one of a pair of valve bodies 20 and 30 that slide relative to each other, and a sliding contact surface 21 is formed. The fixed valve body 20 is formed in a disk shape having a fluid passage 22 penetrating the upper and lower surfaces and two fluid discharge ports (for example, a hot water discharge port and a water discharge port), as shown in FIG. Further, the base body 25 of the fixed valve body 20 includes a liquid phase 25 b, and a mixed layer 26 of atoms constituting the base body 25 and implanted atoms is formed on the upper surface of the base body 25. It is formed in both the crystal particles 25a and the liquid phase 25b. A slidable contact surface 21 is formed by depositing a diamond-like hard carbon film 24.

  The movable valve body 30 as the other valve body includes a fluid passage 32 penetrating the upper and lower surfaces, is formed in a disk shape smaller than the one fixed valve body 20, and is in sliding contact with the fixed valve body 20. Is forming.

  Then, as shown in FIG. 3, each of the valve bodies 20 and 30 is brought into close contact with each other in a non-lubricated state, and a lever (not shown) is moved to slide the movable valve body 30. By doing so, the fluid passages 22 and 32 of the valve bodies 20 and 30 are opened and closed to adjust the flow rate of the supply fluid and to adjust the opening of the fluid discharge port.

  At this time, the slidable contact surface 21 of the fixed valve body 20 is coated with a diamond-like hard carbon film 24 having excellent self-lubricating properties and high hardness. The lever 30 can be smoothly slid by reducing the lever operating force without greatly wearing the body 30.

  Since the mixed layer 26 can be processed at a low temperature by ion implantation, the liquid phase 25b on the surface of the substrate 25 is not etched, and the mixed layer 26 can be formed evenly at both the grain boundaries in the substrate 25 and the crystal particles 25a. it can. As a result, the liquid phase 25b component does not decrease near the surface of the base 25, and the surface state of the surface of the base 25 is not impaired. Therefore, it is possible to obtain a surface state that is the same as the surface state of the surface of the base body 25 itself.

In particular, when the substrate 25 is an alumina-based sintered body, SiO ₂ , CaO, Na ₂ O and the like that become the liquid phase 25 _b are easily eroded selectively, but according to the present invention, these components are not etched. I understand that. In order to confirm whether or not these components are etched, it can be confirmed by performing analysis by SIMS (Secondary Ion Mass Spectroscopy). For example, using ADEPT 1010 manufactured by ULVAC-PHI, the primary ion species may be O ₂ ⁺ , the element may be reduced to cations, and analyzed at an acceleration voltage of 3.0 kV and a current of 150 nA.

As confirmed by SIMS, if SiO ₂ , CaO, and Na ₂ O are etched on the surface of the base body 25, the detected components of Si, Ca, and Na rise as they go inside, and finally change in a constant state. I understand. In SIMS, a reference whose composition is known in advance by AES or XPS may be referred to.

  Since the base body 25 is not etched, the surface state after the formation of the diamond-like hard carbon film 24 becomes a smooth surface with few recesses caused by the etching of the liquid phase part 25b. The operating torque of the lever is constant without changing the contact area between the dynamic friction and the later sliding friction. In particular, in the case where the diamond-like hard carbon film 24 was formed on the surface of the etched base 25, the surface condition was affected and the surface was uneven. Specifically, a plurality of spherical protrusions having a mean radius of curvature of 10 to 1000 nm and a size of about 0.1 to 0.3 μm are formed, and the plurality of substantially spherical protrusions make contact in the initial sliding friction. The area can be reduced and the initial low coefficient of friction can be reduced, but when used for a long period of time, the substantially spherical protrusion disappears, the contact area increases, and the lever operating torque increases. However, in the present invention, it is possible to keep the substantially spherical protrusion small, and the lever operating torque is adjusted in its initial state. Therefore, even if the lever is used for a long period of time, the lever operating torque at the initial stage and the latter stage is unlikely to change.

  In addition, even if the tap water is inserted into the tap water that contains a large amount of metal ions such as Ca and Fe, it is a smooth surface with few concave surfaces. It is difficult to adhere, and even if the movable valve bodies 20 and 30 are slid with each other, the frictional resistance is not changed, and no abnormal noise is generated.

  Further, the bases 25 and 35 forming the valve bodies 20 and 30 of the present invention are characterized by being alumina sintered bodies. Further, the alumina sintered body is an alumina sintered body having a purity of 96% or more. More preferably, it is an alumina sintered body having a purity of 99% or more.

  If the fixed valve body 20 is made of resin, the diamond-like hard carbon film 24 cannot be deposited, and if it is made of metal, the hardness is smaller than that of the ceramic sintered body. This is because the diamond-like hard carbon film 24 deposited on the surface may be damaged by the pressing force.

  On the other hand, since the alumina sintered body has high hardness and is not deformed by the pressing force with the movable valve body 30, the diamond-like hard carbon film 24 deposited on the surface thereof is not damaged. Further, since high processing accuracy is obtained, the surface of the fixed valve body 20 is finished to a smooth surface, and the surface of the diamond-like hard carbon film 24 deposited on the surface is smooth and imitating the surface of the fixed valve body 20. It can be a flat surface. Further, it is possible to obtain a disk valve 1 that is inexpensive in price.

  Further, by using an alumina sintered body having a purity of 96% or more, it is possible to provide a base body 25 in which the corrosion resistance is not impaired and the liquid phase 25b is not easily etched when the diamond-like hard carbon film 24 is formed. Become.

  The disc valve 1 of the present invention is preferably characterized in that the thickness of the mixed layer 26 is in the range of 50 to 200 nm.

  By the way, the thickness of the mixed layer 26 is in the range of 50 to 200 nm, and if the thickness is less than 50 nm, the ion-implantation is not sufficiently performed, and the adhesion of the diamond-like hard carbon film 24 cannot be obtained. Moreover, the function as a stress relaxation layer cannot be obtained. On the contrary, when the thickness exceeds 200 nm, stress relaxation by the mixed layer 26 is impaired, and a problem that the diamond-like hard carbon film 24 cannot be sufficiently formed occurs. Therefore, the thickness of the mixed layer 26 is preferably in the range of 50 to 200 nm, and more preferably in the range of 50 to 150 nm.

  By the way, as a method for determining the boundary of the mixed layer 26, it may be determined by using SIMS, and the mixed layer 26 has a range in which the crystal particles 25a, the liquid phase 25b component, and the injected atoms can be detected.

  FIG. 4 shows the result of analysis by SIMS for one embodiment of the disk valve 1 according to the present invention, and FIG. 5 shows the result of analysis by SIMS for one embodiment of a conventional disk valve. It is.

Note that the etching element (primary ion species) at the time of analysis by SIMS is O ₂ ⁺ .

  According to the result of FIG. 4, it can be seen that the components of Al, Ca, Mg, and Si in the substrate 25 are not changed in the surface layer of the substrate 25 and inside, but this is because the liquid phase 25b component of the substrate 25 is etched. This is because no decrease in the detection peak is observed.

  On the other hand, according to the results of FIG. 5, the Al and Mg components are not changed on the surface and inside of the base 25, but the Ca and Si components are reduced on the surface layer compared to the inside of the base 25. I understand. This shows that the Ca and Si components, which are the liquid phase of the substrate 25, were selectively etched because the PVD method was used to deposit the Ti and Si intermediate layer 23. However, regarding Si, since it is also a component of the intermediate layer 23 as seen in the detection peak of Ti, it can be seen that no significant decrease has been confirmed compared to Ca.

  By the way, the boundary portion between the diamond-like hard carbon film 24 and the mixed layer 26 of the present invention may be focused on the peak of the detection element. When the detection peak is observed from the surface layer to the inside, the detection peak of the composition other than carbon is detected. That is, the portion where the rise of the abruptly rises corresponds to this, and the boundary between the substrate 25 and the mixed layer 26 corresponds to the portion where the detection peak of the injected atom is not confirmed.

  For example, in FIG. 4, it can be understood by paying attention to the components of C and Si used as the ion implantation element and C which is a component of the diamond-like hard carbon film 24.

  Similarly, the boundary portion between the conventional diamond-like hard carbon film 24 and the intermediate layer 23 should be focused on the peak of the detection element. When the detection peak is observed from the surface layer to the inside, the detection peak other than carbon is detected. The part where the value rose rapidly corresponds to that.

  Further, the boundary portion between the base 25 and the intermediate layer 23 corresponds to the portion where the detection peak of the element in the intermediate layer is lowered.

  In FIG. 5, it can be understood by paying attention to the components of Ti and Si to be the intermediate layer 23 and C to be a component of the diamond-like hard carbon film 24.

  Then, as a method for judging whether or not the etching is performed, it can be sufficiently judged by confirming a range from the surface of the substrate 25 to a depth of 500 nm, which is within ± 10% compared with the composition inside the substrate 25. It is thought that it is not etched if it is in the range.

  Further, the disk valve 1 of the present invention is preferably characterized in that the implanted atoms 26b include one or more elements of carbon, Si, Ti, Zr, and Hf.

  By including these elements, the adhesion strength of the diamond-like hard carbon film 24 is not impaired, and as a result of being formed by ion implantation, a substantially spherical protrusion on the surface can be reduced, and the disk valve with little change in operating torque 1 can be provided, and as a result, adhesion of foreign matter can be reduced, and an effect of reducing abnormal noise during operation can be obtained.

  Further, the arithmetic average roughness of the sliding contact surfaces 21 and 31 of the disk valve 1 of the present invention is preferably 0.2 μm or less.

  The sliding contact surfaces 21 and 31 of the valve bodies 20 and 30 have a flatness of 1 μm or less and a surface roughness of 0.2 μm or less in terms of arithmetic average roughness (Ra) in order to prevent water leakage. When the arithmetic average roughness (Ra) is 0.2 μm or less, the sealing property can be improved and the friction coefficient can be reduced by the diamond-like hard carbon film 24. Generation | occurrence | production can be prevented effectively and it can be made to slide smoothly over a long period of time. Here, the arithmetic average roughness (Ra) may be measured in accordance with JIS B0601 using a surface roughness measuring device such as Surfcorder SE-2300 manufactured by Kosaka Laboratory.

  Particularly preferably, the sliding contact surfaces 21 and 31 of both valve bodies 20 and 30 have an arithmetic average roughness (Ra) of 0.12 μm or less, more preferably 0.1 μm or less, and a flatness of 1 μm or less. That is good. When the surface state of the sliding contact surfaces 21 and 31 of both valve bodies 20 and 30 becomes rough beyond the above-described range, a large water pressure is applied between the valve bodies 20 and 30 particularly when the water purifier is assembled. This is because water may leak. Here, the flatness may be measured in accordance with JIS B0621 using an optical flat inspection measuring device manufactured by Nikon Corporation. In particular, it is important that the surface of the base body 25 of the movable valve body 20 on which the diamond-like hard carbon film 24 is formed be within the above range, and it is necessary to maintain the surface roughness after the film formation. .

  Furthermore, in the disk valve 1 of the present invention, when the Ca or Si component in the base 25 is confirmed within a depth range of 500 nm from the surface of the base 25, the range is within ± 10% compared to the inside of the base 25. It is characterized by being.

  When the Ca or Si component is decreased, it indicates that the liquid phase 25b component in the substrate 25 has been etched, so that the Ca or Si component is also determined in order to determine that the liquid phase 25b component is not decreased. It is necessary to confirm that it has not decreased, and it can be confirmed by SIMS.

  By the way, the diamond-like hard carbon film 24 is substantially made of carbon and may contain some crystalline material, but basically has an amorphous structure. Crystalline boron nitride (cBN) and hexagonal boron nitride (hBN) have different compositions.

The diamond-like hard carbon film 24 when examined using well Raman spectroscopic analysis apparatus used in the identification of graphite and diamond, and 1333 cm ^-1 is a peak position of the diamond in the vicinity of 1550 cm ^-1 is a peak position of graphite Each has a peak. The diamond-like hard carbon film 24 used in the disk bulb of the present invention may have a peak that is biased to either diamond or graphite, and is preferably biased to the diamond peak position.

  Since such a diamond-like hard carbon film 24 has a very hard Vickers hardness (Hv1.0) of 20 to 50 GPa, it hardly wears even when sliding with the movable valve body 30. .

Furthermore, the diamond-like hard carbon film 24 may contain at least one metal selected from zirconium, tungsten, and titanium and silicon. Thus, by containing at least one metal selected from zirconium, tungsten, and titanium and silicon, the residual stress inside the film can be reduced and the bonding force can be increased. For this reason, the adhesive force with the movable valve body 30 can be made stronger, and a film having a Vickers hardness (Hv1.0) of 55 GPa or higher can be obtained. The diamond-like hard carbon film 24 containing at least one kind of metal of zirconium, tungsten, and titanium and silicon is different from the diamond-like hard carbon film 24 not containing these components, and is measured by a Raman spectroscopic analyzer. Then, it has one peak in the vicinity of 1480 cm ⁻¹ .

  The means for depositing the diamond-like hard carbon film 24 on the fixed valve body 20 is not a method of forming the mixed layer 26 by implanting ions by ion implantation after the diamond-like hard carbon film 24 is formed. After carbon atoms and implanted atoms are implanted on the surface of the substrate 25 to form the mixed layer 26, the diamond-like hard carbon film 24 is formed by a conventional diamond-like hard carbon film 24 deposition method such as CVD or PVD. Alternatively, any method may be used as long as the ion implantation for forming the mixed layer 26 and the diamond-like hard carbon film 24 are simultaneously formed.

  Then, the mixed layer 26 may be formed at a low temperature from room temperature to 200 ° C. using an RF / high voltage pulse superposition method plasma ion implantation film formation (Plasma Based Ion Implantation and Deposition, PBIID) method.

First, sputtering cleaning may be performed with argon gas, and then ion implantation may be performed using a source gas of a mixed gas composed of C and H such as CH ₄ , C ₂ H _{6, and} toluene.

  As a method of performing ion implantation on the surface of the insulating base 25, the movable valve body 20 is held and fixed to a jig capable of embedding the movable valve body 20 made of a conductive metal material such as aluminum, copper, brass, stainless steel or the like. Then, by applying a negative high voltage pulse for performing ion implantation and an RF pulse for generating pulsed plasma using the jig and the substrate 25 simultaneously as a common field, ions can be implanted into the insulating substrate 25. .

  If the diamond-like hard carbon film 24 is formed by an ion plating method or a vacuum deposition method, it is possible to simultaneously perform ion implantation in a high vacuum.

The source gas for forming the diamond-like hard carbon film 24 may be a mixed gas composed of C and H such as CH ₄ , C ₂ H _{6, and} toluene.

  The ceramic sintered body forming each valve body 20, 30 is preferably composed of a ceramic sintered body mainly composed of an alumina sintered body. Since the alumina sintered body has a Young's modulus of 250 to 400 GPa and a Vickers hardness (Hv1.0) larger than 12 GPa, the sliding contact surface 21 can be formed even if the pressing force with the fixed valve body 30 is increased. The disk valve 1 that can be used for a long period of time can be provided because it is not deformed and has excellent chemical resistance. Preferably, if an alumina sintered body having a purity of 96% or more is used, the liquid phase 25b is small and etching is difficult. More preferably, 99% or more alumina sintered body is used.

  These alumina-based sintered bodies are not special and may be any alumina-based sintered body that is generally used as a general structural member.

  In the above embodiment of the present invention, the disk valve 1 in which the diamond-like hard carbon film 24 is attached to the fixed valve body 20 has been described. However, the material of the fixed valve body 20 and the movable valve body 30 is reversed. It goes without saying that the same effect can be obtained even if it is one.

  As described above, according to the disk valve of the present invention, it is possible to provide the disk valve 1 in which the adhesion of the diamond-like hard carbon film 24 to the base body 25 forming the valve body 20 is enhanced. In particular, it is possible to provide a disk valve 1 in which film formation with high adhesion is performed on a mirror surface product of an insulating substrate 25 such as an alumina sintered body.

  In addition, it is possible to provide the disc valve 1 with a small change in operating torque even after long-term use.

  Furthermore, the disc valve 1 that reduces the adhesion of metal components, calcium carbonate, etc. to the sliding contact surface 21, eliminates the generation of abnormal noise, and can maintain smooth sliding even when used for a long period of time. It becomes possible to provide.

  Next, an embodiment of the mixing plug of the present invention will be described with reference to the drawings.

  FIG. 3 is a schematic sectional view showing a mixing plug according to the present invention.

  The mixing 100 stopper is composed of a main body provided with a spout 40a so as to be rotatable, an operation handle 2 for operation disposed at an upper end of the main body, and a valve unit 3 operated by the operation handle 2. is there.

  The valve unit 3 includes a case 4, a valve seat 5 connected to the lower end thereof, a fixed presser plate 6, a movable valve body 30, and a second fixed valve body 20 that are sequentially assembled from the upper end side of the case 4. As provided. The case 4 has a hollow cylindrical shape, and the valve seat 5 is formed with a hot water inflow hole, a water inflow hole, and a mixed water outflow hole. These hot water inflow holes and water inflow holes are connected to hot water supply pipes and water supply pipes (both not shown) piped in the main body 40, and the mixed water outflow holes are connected to a flow path (not shown) to the spout 40a. It is connected. The pressing plate 6, the movable valve body 30, and the fixed valve body 20 are all the disk valves 1 described above, and the pressing plate 6 is an annular body. The movable valve body 30 has a concave portion for mounting an adapter, which will be described later, on the upper surface side, and a concave portion communicating with the fluid passages of the hot water inlet hole, water inlet hole, and mixed water outlet hole of the valve seat 5 on the lower surface side. A flow path is formed. The fixed valve body 20 is formed by opening flow passages 23 communicating with the fluid passages of the hot water inlet hole, water inlet hole and mixed water outlet hole of the valve seat 5, respectively. In addition, a packing for holding the holding plate 6 and the fixed valve body 20 in a watertight manner in the case 4, a packing for preventing water from coming out of the case 4, a packing for sealing the lower surface of the fixed valve body 20, and a valve seat 5 There is a packing that seals the lower end.

  A lever 10 connected to the operation handle 2 is incorporated at the upper end of the case 4. The lever 10 is disposed vertically through a pedestal 11 fixed to the upper end of the case 4 and is held at an intermediate position by a pin 11a.

  On the other hand, the adapter 12 is fixed to the concave portion of the movable valve body 30, and the lower end of the lever 20 is connected to the movable valve body 30 via a pin 12 a mounted on the upper surface thereof.

  As described above, one embodiment of the mixing plug 100 of the present invention has been described with reference to FIG. 3, but is not limited to the shape of FIG. 3. Any type of mixing plug 100 that uses the above-described disk valve 1 can be used to obtain a mixing plug 100 having a small change in operating torque even when used for a long time. Also provided is a mixing plug 100 that reduces the adhesion of metal components, calcium carbonate, etc. to the sliding contact surface, eliminates the generation of abnormal noise, and can maintain smooth sliding even after long-term use. can do.

  Examples of the present invention will be described below.

In order to compare with the disc valve 1 of the present invention, an alumina sintered body having an Al ₂ O ₃ purity of 96% is used for the fixed valve body 20 as a comparative example, and a Ti film and an Si film are arranged in this order on the surface by the PVD method. A material in which a diamond-like hard carbon film 24 was deposited was prepared by the CVD method through the intermediate layer 23 laminated in (1).

  Then, the sliding characteristics of these disc valves 1 were examined.

  The fixed valve body 20 was a substantially disk-shaped body having an outer diameter of 32 mm and a thickness of 5 mm. The movable valve body 30 was a substantially disk-shaped body having an outer diameter of 25 mm and a thickness of 5 mm.

  Then, the sliding contact surfaces 21 and 31 of both valve bodies 20 and 30 were polished so that the flatness was 1 μm or less, and the surface roughness was 0.2 μm or less in terms of arithmetic average roughness (Ra).

  Both valve bodies 20 and 30 formed in this way are set to the faucet while being pressed by the casing with an axial force of 294 N so that the sliding contact surfaces 21 and 31 are in contact with each other. The lever pressing force (torque) required to operate the operation lever was measured with a push-pull gauge under the condition where the pressure was injected at 74 MPa, and the number of sliding times when the torque was increased was measured. Here, the torque increase means when the load when moving up and down the lever of the faucet exceeds 10N.

  In addition, the presence or absence of abnormal noise when slid by 100,000 times was examined. Here, the abnormal noise was defined as a sound in which an unpleasant sound that was heard by a person having normal hearing at a position 30 cm away from the water tap in operation and sounded like a key was confirmed.

  As a result, in the case of using the disk valve 1 of the present invention, even if it was slid more than 250,000 times, there was no noise or torque increase, and smooth sliding characteristics could be obtained over a long period of time. Then, an abnormal noise occurred at the 120,000th time.

FIGS. 1A, 1B and 1C are perspective views showing an embodiment of the disk valve of the present invention. It is an expanded sectional view showing the structure of the fixed valve body concerning the present invention. It is a schematic sectional drawing which shows one Example of the mixing stopper which concerns on this invention. It is the graph analyzed by SIMS with respect to one Example of the disk valve 1 which concerns on this invention. It is the graph analyzed by SIMS with respect to the conventional disk valve | bulb.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Disc valve 2 ... Operation handle 3 ... Valve unit 4 ... Case 5 ... Valve seat 6 ... Holding plate 10 ... Lever 11 ... Base 11a ... Pin 12 ... Adapter 12a ... Pin 20 ... Fixed valve body 30 ... Movable valve body 21, 31 ... Sliding contact surfaces 22, 32 ... fluid passage 23 ... intermediate layer 24 ... diamond-like hard carbon film 25 ... base 26 ... mixing layer 40 ... main body 40a ... spout 100 ... mixing plug

Claims (9)

In a sliding member in which a diamond-like hard carbon film is deposited on the surface of at least one of a pair of valve bodies that slide relative to each other to form a sliding contact surface, the base of one valve body has a liquid phase. It is a ceramic sintered body, and a mixed layer of atoms and implanted atoms constituting the substrate is formed on the upper surface of the substrate, and the mixed layer is formed in both the crystal particles and the liquid phase of the substrate. A sliding member characterized by that. The sliding member according to claim 1, wherein the substrate is an alumina sintered body. The sliding member according to claim 2, wherein the alumina sintered body is an alumina sintered body having a purity of 96% or more. The thickness of the said mixed layer is the range of 50-200 nm, The sliding member in any one of Claims 1-3 characterized by the above-mentioned. The sliding member according to any one of claims 1 to 4, wherein the implanted atom contains at least one element selected from the group consisting of carbon, Si, Ti, Zr, and Hf. The sliding member according to claim 1, wherein an arithmetic average roughness of a sliding surface of the sliding member is 0.2 μm or less. The Ca or Si component in the substrate is characterized by being within a range of ± 10% as compared with the composition inside the substrate when confirmed in a range of a depth of 500 nm from the surface of the substrate. The sliding member in any one of 1-6. A disk valve using the sliding member according to claim 1. A mixing plug using the disk valve according to claim 8.

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