JP2017032321A - Timepiece component and timepiece component manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a timepiece component having high resistance to impact from the outside.SOLUTION: A timepiece component 108 includes: a silicon base body 301 formed of silicon; and a covering part 302 which is formed of nanofibers 302a and which covers at least one face of an outer surface of the silicon base body 301. The nanofibers 302a which constitute the timepiece component 108 configurating a drive mechanism of a timepiece and which form the covering part 302 prevent impact from the outside from directly acting on the main body (silicon base body 301) of the timepiece component 108, so as to ensure high resistance to the impact from the outside.SELECTED DRAWING: Figure 3A

Description

  The present invention relates to a timepiece part constituting a mechanical part in a timepiece and a method for manufacturing the timepiece part.

  The drive mechanism (movement) of the mechanical timepiece includes a speed control mechanism (a balance) constituted by a hairspring, a balance wheel, and the like, and an escapement constituted by an escape wheel and an ankle. Conventionally, a hairspring has been widely formed by processing metal, but due to variations in processing accuracy and the influence of internal stress of the metal, the shape as designed may not be obtained. . Moreover, the metal hairspring may be deformed by repeated expansion and contraction for a long time.

  A timepiece constructed using such a hairspring is inferior in timekeeping accuracy. For this reason, conventionally, instead of a metal material, a material having a crystal structure such as crystal or silicon is etched to manufacture a hairspring having higher accuracy than a metal hairspring and suppressing variations in processing accuracy. There was technology.

  Since a material having a crystal structure such as crystal or silicon has less deformation with respect to environmental temperature than a metal, a balance spring formed using a material having a crystal structure such as crystal or silicon is made of metal. Better temperature characteristics. On the other hand, since materials having a crystal structure such as quartz and silicon are brittle materials, the balance spring using a material having a crystal structure such as quartz and silicon is more resistant to impact than metal balance springs. Inferior to

As a related technique, specifically, for example, the outer surface of a silicon micromechanical component conventionally used for a movement component or the like is formed by a film formed of an amorphous material such as silicon oxide (SiO ₂ ). There has been a technique for coating (see, for example, Patent Document 1 below). Patent Document 1 below describes that at least a part of an amorphous material is further covered with a film made of a material such as diamond-like carbon or carbon nanotube.

  Further, as a related technique, specifically, there has been conventionally a technique in which, for example, a hairspring is integrally formed using carbon nanofibers (see, for example, Patent Document 2 below). In addition, as a related technique, specifically, conventionally, for example, a weaving method of carbon fiber or glass fiber such as plain weave, twill weave, satin weave, etc. in an arbitrary pattern such as a watch case has an arbitrary thickness. There is a technique in which a resin is impregnated in the woven fabric after being laminated (see, for example, Patent Document 3 below).

Special table 2008-544290 Japanese Patent Laid-Open No. 2002-341054 JP 60-89346 A

However, the conventional technique described in Patent Document 1 described above has a problem that the film is missing when an impact is applied from the outside because SiO ₂ forming the film covering the watch part is a fragile material. . A timepiece component such as a hairspring in which a film covering the timepiece component is missing is inferior in impact resistance.

Further, since the conventional technique described in Patent Document 1 described above is based on the premise that the outer surface of a silicon micromechanical component is coated with an amorphous material such as SiO ₂ , Even if at least a portion is covered with a film made of a material such as diamond-like carbon or carbon nanotube, the problem that the amorphous material under the film is lost due to an external impact is not solved.

  In addition, the conventional technique described in Patent Document 2 described above has a problem in that it is damaged when an impact is applied from the outside because the timepiece part is formed using carbon having high rigidity. In addition, since the conventional technique described in Patent Document 3 described above uses a woven fabric previously woven into an arbitrary pattern according to the timepiece part, it is suitable for manufacturing a small timepiece part that constitutes the driving mechanism of the mechanical timepiece. There was no problem.

  An object of the present invention is to provide a timepiece component and a timepiece component manufacturing method having high resistance to an external impact in order to solve the above-described problems caused by the prior art.

  In order to solve the above-described problems and achieve the object, a timepiece component according to the present invention is a timepiece component that constitutes a timepiece drive mechanism, and is formed of a silicon base portion formed of silicon and nanofibers. And a covering portion covering at least one surface of the outer surface of the silicon base portion.

  In the timepiece component according to the present invention as set forth in the invention described above, the nanofiber is formed of a material harder than silicon.

  In the timepiece component according to the present invention as set forth in the invention described above, the nanofiber is at least one of alumina nanofiber or carbon nanofiber.

  The timepiece component according to the present invention is the timepiece according to the present invention described above, wherein at least one of the escape wheel and ankle constituting the escapement, the balance spring and the balance wheel constituting the speed control mechanism, and the gear constituting the train wheel. It is characterized by being.

  In addition, the method for manufacturing a timepiece component according to the present invention is based on the shape of the timepiece component constituting the timepiece drive mechanism on the active layer or the silicon single crystal substrate laminated on at least one surface side of the support layer via an oxide film. A mask forming step of forming a mask having a predetermined pattern, and an etching step of performing an etching process on the active layer or the silicon single crystal substrate to remove the remaining part of the mask formed in the mask forming step; A coating step of forming a coating portion by coating at least one surface of the active layer or the outer surface of the silicon single crystal substrate with a drug containing nanofibers after the etching step.

  In the method for manufacturing a watch part according to the present invention, in the above-described invention, the active layer or the silicon single crystal substrate in which at least one outer surface is coated with the chemical in the coating step is heated. And a heating step for removing the liquid component contained in.

  Further, in the method of manufacturing a watch part according to the present invention, in the above invention, the coating step is performed by applying the agent to at least one surface of the active layer or the outer surface of the silicon single crystal substrate. Alternatively, at least one surface of the outer surface of the silicon single crystal substrate is covered with the drug.

  According to the timepiece component and the method for manufacturing the timepiece component according to the present invention, there is an effect that it is possible to provide a timepiece component having high resistance to an external impact.

It is explanatory drawing which shows the drive mechanism of the mechanical timepiece manufactured by the manufacturing method of embodiment concerning this invention in which the timepiece components of embodiment concerning this invention are integrated. It is explanatory drawing which shows the structure of a hairspring. It is explanatory drawing which shows the cross section which cut | disconnected some hairsprings. It is explanatory drawing (the 1) which shows the position of the coating | coated part with respect to a silicon base part. It is explanatory drawing (the 2) which shows the position of the coating | coated part with respect to a silicon base part. It is explanatory drawing (the 3) which shows the position of the coating | coated part with respect to a silicon base part. It is explanatory drawing (the 1) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 2) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 3) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 4) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 5) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 6) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 7) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 8) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 9) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 10) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing (the 11) which shows the manufacturing method of the hairspring of embodiment concerning this invention. It is explanatory drawing which shows an example of an etching pattern. It is explanatory drawing which shows the result of having compared the performance of the hairspring manufactured by the manufacturing method of embodiment concerning this invention. It is explanatory drawing which shows the Young's modulus of a silicon | silicone, an alumina nanofiber film | membrane, and an alumina.

  Exemplary embodiments of a timepiece component and a method for manufacturing the timepiece component according to the present invention will be explained below in detail with reference to the accompanying drawings.

  First, a drive mechanism for a mechanical timepiece will be described as a drive mechanism for a timepiece manufactured by the manufacturing method according to the embodiment of the present invention and incorporating the timepiece component according to the embodiment of the present invention. FIG. 1 is an explanatory view showing a drive mechanism of a mechanical timepiece manufactured by the manufacturing method according to the embodiment of the present invention and incorporating the timepiece component according to the embodiment of the present invention.

  In FIG. 1, a drive mechanism 101 of a mechanical timepiece in which a timepiece part manufactured by the manufacturing method according to the embodiment of the present invention is incorporated includes an barrel 102, an escapement 103, a speed control mechanism (balance) 104, a train wheel 105 or the like. The barrel 102 houses a power mainspring (not shown) inside a thin cylindrical box. A gear wheel called a barrel wheel on the outer periphery of the barrel 102 is provided and meshes with a number wheel constituting the train wheel 105.

  The power spring is a long thin metal plate in a wound state and is accommodated in the barrel 102. The center end of the power spring (the end located on the inner peripheral side in the wound state) is attached to the center axis of the barrel 102 (barrel true). The outer end of the power spring (the end located on the outer peripheral side in the wound state) is attached to the inner surface of the barrel 102.

  The escapement 103 includes a escape wheel 106 and an ankle 107. The escape wheel 106 is a gear provided with key-shaped teeth, and the teeth of the escape wheel 106 mesh with the ankle 107. The ankle 107 converts the rotational movement of the escape wheel 106 into a reciprocating motion by meshing with the teeth of the escape wheel 106.

  The balance with hairspring 104 includes a hairspring 108, a balance wheel 109, and the like. The hairspring 108 is a long member in a wound state, and has a spiral shape. The hairspring 108 is designed to exhibit excellent isochronism in a state in which the drive mechanism 101 is configured by being incorporated in a mechanical timepiece.

  The balance with hairspring 104 can regularly reciprocate by the expansion and contraction of the hairspring 108 by the spring force. The balance wheel 109 has a ring shape, and adjusts and controls the repetitive motion from the ankle 107 to maintain a constant speed of vibration. The balance wheel 109 includes an arm extending radially from the center (balance) 109 a of the balance wheel 109 inside the ring shape formed by the balance wheel 109.

  The train wheel 105 is provided between the barrel 102 and the escape wheel 106 and is constituted by a plurality of gears engaged with each other. Specifically, the train wheel 105 includes a second wheel 110, a third wheel 111, a fourth wheel 112, and the like. The barrel of the barrel 102 is engaged with the second wheel 110. A second hand 113 is attached to the fourth wheel & pinion 112, and a minute hand 114 is attached to the second wheel & pinion 110. In FIG. 1, illustration of the hour hand and the ground plate for supporting each gear is omitted.

  In the drive mechanism 101, the center of the power spring is fixed to the center of the barrel 102 (barrel true) so that it cannot reversely rotate, and the outer end of the power spring is fixed to the inner peripheral surface of the barrel. When the power spring wound around the center of the barrel 102 (the barrel barrel true) tries to return to its original position, it is urged by the outer end of the power spring to be unwound in the same direction as the rolled-up direction, and the barrel 102 is rolled up. Rotates in the same direction as the mainspring unwinding. The rotation of the barrel 102 is sequentially transmitted to the second wheel 110, the third wheel 111, and the fourth wheel 112, and is transmitted from the fourth wheel 112 to the escape wheel 106.

  Since the escape wheel 107 meshes with the escape wheel 106, when the escape wheel 106 rotates, the teeth (impact surface) of the escape wheel 106 push up the claws of the ankle 107, thereby the balance in the ankle 107. The tip on the 104 side rotates the balance with hairspring 104. When the balance with hairspring 104 is rotated, the claw of the ankle 107 immediately stops the escape wheel 106. When the balance with hairspring 104 reversely rotates with the force of the hairspring 108, the nail of the ankle 107 is released, and the escape wheel 106 rotates again.

  In this way, the speed governor causes the balance 104 to repeat regular reciprocating rotational movement by the expansion and contraction of the isochronous hairspring 108, and the escapement 103 gives the balance 104 a force for reciprocating movement. At the same time, the gears in the train wheel 105 are rotated at a constant speed by regular vibration from the balance with hairspring 104. The escape wheel 106, the ankle 107, and the balance 104 constitute a speed control mechanism that converts the reciprocating motion of the balance 104 into a rotational motion.

(Structure of the hairspring 108)
FIG. 2 is an explanatory view showing the structure of the hairspring 108. FIG. 2 shows a plan view of the hairspring 108 viewed from the direction of the arrow X in FIG. 1 and a cross section taken along the line AA in the plan view. In FIG. 2, the hairspring 108 includes a mainspring portion 201 having a thin coil shape. Further, the hairspring 108 includes a hairball 202 provided at an end portion on the inner peripheral side of the mainspring portion 201 having a thin coil shape.

  The mainspring portion 201 and the whisker ball 202 are connected by a connecting portion 202a. The mainspring portion 201 has a coil shape in which the beard ball 202 is wound around the beard ball 202 via the connection portion 202a. Further, the hairspring 108 is provided with a hairspring 203 provided at an outer peripheral end portion of the mainspring portion 201 having a thin coil shape. The beard holder 203 is fixed to a balance (not shown) that supports the balance 104.

  In FIG. 2, the symbol t indicates the thickness dimension of the hairspring 108. The thickness dimension of the hairspring 108 is determined according to the thickness dimension of the Si layer in a laminated substrate (SOI substrate) described later or the dimension in the thickness direction formed from the silicon single crystal substrate. In FIG. 2, a symbol w indicates a width dimension of the hairspring 108 in a plan view.

  The width dimension of the hairspring 108 may be varied depending on the position of the hairspring 108. That is, the width dimension of a part of the mainspring portion 201 in the hairspring 108 may be set as w, and the width dimension of another part may be set as a dimension larger than w. Specifically, for example, the width dimension at a specific position may be selectively varied in the length direction of the hairspring (the direction from the whistle ball 202 to the outer whiskers 203 along the spiral). . Thereby, intensity | strength can be raised effectively, without reducing the softness | flexibility or elastic property of the hairspring 108. FIG.

(Cross section of hairspring 108)
FIG. 3A is an explanatory view showing a cross section of a part of the hairspring 108. In FIG. 3A, the B part in FIG. 2 is enlarged and shown. In FIG. 3A, the hairspring 108 includes a silicon base portion 301 and a covering portion 302. The silicon base portion 301 is made of silicon and constitutes the basic shape of the hairspring 108.

  The covering portion 302 is formed by a minute fiber-like member (nanofiber 302a). The covering portion 302 can be formed, for example, by stacking a plurality of nanofibers 302a on the outer surface of the silicon base portion 301. The covering portion 302 is formed by nanofibers 302a that are irregularly stacked. Although the nanofiber 302a is made of a material harder than silicon, the nanofiber 302a also has elasticity because it is in a stacked state.

  Specifically, the coating portion 302 can be formed of, for example, a metal oxide nanofiber, specifically, an alumina nanofiber as the nanofiber 302a. Alumina nanofibers that have been researched and developed by, for example, the New Energy and Industrial Technology Development Organization can be used. The alumina nanofiber is a material obtained by molding alumina, which is an oxide of aluminum (aluminum oxide), into a fiber having a diameter of 4 to 6 nm and a length of 1000 to 5000 nm (the maximum length is about 5000 nm). It is known that alumina forming nanofibers has a high hardness (Mohs's hardness).

  Moreover, specifically, the coating | coated part 302 can be formed as a nanofiber 302a with a carbon nanofiber instead of an alumina nanofiber, for example. Carbon nanofiber is a fibrous material made by carbonizing acrylic fiber or pitch (by-products such as petroleum, coal, coal tar, etc.) at a high temperature as a raw material, and a predetermined ratio of the total mass (for example, 90%) or more is composed of carbon.

  Or, specifically, the covering portion 302 may be formed of carbon nanotubes as the nanofibers 302a, for example, instead of alumina nanofibers. A carbon nanotube is a material in which a sheet-like member (graphene sheet) in which carbon atoms are bonded so as to have a hexagonal lattice structure is formed into a single-layer or multilayer coaxial tube, and its application has been widely studied in recent years. . Furthermore, the coating | coated part 302 may be formed by mixing two or more nanofibers among various nanofibers, such as an alumina nanofiber, a carbon nanofiber, and a carbon nanotube, as the nanofiber 302a.

  In FIG. 3A, the hairspring 108 in which the entire outer surface of the silicon base portion 301 is covered with the covering portion 302 has been described. However, the covering portion 302 is not limited to covering the entire silicon base portion 301. The covering portion 302 only needs to cover at least a part of the silicon base portion 301 as shown in FIGS. 3B, 3C, and 3D, for example.

  3B, 3 </ b> C, and 3 </ b> D are explanatory views showing the position of the covering portion 302 with respect to the silicon base portion 301. 3B, FIG. 3C, and FIG. 3D show a cross section of the hairspring 108 having a covering portion 302 that covers a part of the silicon base portion 301 in place of the covering portion 302 that covers the entire silicon base portion 301. .

  Specifically, FIG. 3B and FIG. 3C show a cross section of the hairspring 108 including a covering portion 302 that covers only a surface parallel to the width direction of the silicon base portion 301, that is, an end surface in the thickness direction. The end face in the thickness direction is orthogonal to the direction (axial direction) passing through the center of the silicon substrate 301 that is spiraling. When providing the covering portion 302 only on the end face in the thickness direction, as shown in FIG. 3C, the covering portion 302 may be provided only on one of the end faces, as shown in FIG. 3B, on both end faces in the thickness direction. A covering portion 302 may be provided.

  In addition, specifically, in FIG. 3D, instead of the covering portion 302 that covers the entire silicon base portion 301, the covering portion 302 that covers the curved surface portion (side surface) that is curved by winding the silicon base portion 301 in a vortex. 2 shows a cross section of a hairspring 108 having In this case, as shown in FIG. 3D, the covering portion 302 can be provided on both the inner (inner peripheral side) surface and the outer (outer peripheral side) surface of the side surface of the silicon base portion 301. In this case, the covering portion 302 may be provided only on the inner surface of the both side surfaces of the silicon base portion 301, or may be provided only on the outer surface (both are not shown). ).

  Further, the covering portion 302 is provided, for example, such that either one of both end surfaces in the thickness direction and only the inner side surface (or only the outer side surface) of both side surfaces of the silicon base portion 301 are provided. (Not shown). Alternatively, the covering portion 302 may be provided on, for example, both end surfaces in the thickness direction and only one of the side surfaces of the silicon base portion 301 (not shown).

(Watch parts manufacturing method)
Next, a method for manufacturing a timepiece component constituting the drive mechanism 101 of the mechanical timepiece according to the embodiment of the present invention will be described. In the embodiment, a method for manufacturing the hairspring 108 as a timepiece component constituting the drive mechanism 101 of the mechanical timepiece will be described. 4-15 is explanatory drawing which shows the manufacturing method of the hairspring 108 which comprises the drive mechanism 101 of the mechanical type timepiece of embodiment concerning this invention.

  When manufacturing the hairspring 108 by the manufacturing method according to the embodiment of the present invention, first, the laminated substrate (SOI substrate) 314 shown in FIG. 4 is formed. As shown in FIG. 4, the multilayer substrate 314 includes three layers: a support layer 311, an oxide film (Box layer) 312, and an active layer (Si layer) 313. In the laminated substrate 314, the support layer 311, the oxide film 312 and the active layer 313 are sequentially laminated along the thickness direction. In the multilayer substrate 314, the oxide film 312 is sandwiched between the support layer 311 and the active layer 313.

In forming the multilayer substrate 314, first, an oxide film 312 is formed on one surface side of the support layer 311. The support layer 311 is made of silicon (Si). The oxide film 312 is made of silicon dioxide (SiO ₂ ). The oxide film 312 functions as a stopper when performing the etching process by the deep RIE technique in the subsequent processes. The oxide film 312 can be formed using various known film formation techniques or various known oxidation techniques. Description of the method for forming the oxide film 312 is omitted.

  In this embodiment, hereinafter, the surface of the support layer 311 on which the oxide film 312 is formed will be described as the “front surface” of the support layer 311, and the surface of the support layer 311 opposite to the front surface will be supported. The “back side” of the layer 311 will be described. In this embodiment, hereinafter, the surface of the oxide film 312 opposite to the support layer 311 will be described as the “front surface” of the oxide film 312, and the surface of the oxide film 312 on the support layer 311 side will be described as an oxide film. The “back side surface” 312 will be described.

  Although the illustration of the method for forming the multilayer substrate 314 is omitted, when forming the multilayer substrate 314, first, the oxide film 312 is formed on the front side surface of the support layer 311, and then the active surface is formed on the front side surface of the oxide film 312. Layer 313 is formed. As a result, the support layer 311, the oxide film 312 and the active layer 313 are sequentially stacked along the thickness direction, and the stacked substrate (SOI substrate) in which the oxide film 312 is sandwiched between the support layer 311 and the active layer 313. ) 314 is formed. In this embodiment, hereinafter, the surface of the active layer 313 opposite to the oxide film 312 will be described as the “front side surface” of the active layer 313, and the surface of the active layer 313 on the oxide film 312 side of the active layer 313 will be described. It will be described as “back side”.

  The active layer 313 can be formed using various known film formation techniques. Description of the method for forming the active layer 313 is omitted. With the manufacturing method according to the present invention, a timepiece part manufactured using the multilayer substrate 314 is formed on the active layer 313. That is, the hairspring 108 according to the embodiment of the present invention is realized by a part of the active layer 313 by being manufactured by a manufacturing method described later.

  Next, as shown in FIG. 5, a mask 501 based on the shape of the hairspring 108 is formed on the front side surface of the active layer 313. In forming the mask 501, first, a photoresist is applied to the front side surface of the active layer 313 in the multilayer substrate 314. For example, the photoresist is applied over the entire surface (entire surface) of the active layer 313.

  The mask 501 is obtained by exposing the multilayer substrate 314 coated with the photoresist as described above to a pattern based on the shape of the hairspring 108 from the front side surface of the active layer 313 and performing exposure. By processing 314 with a developing solution to remove unnecessary photoresist, the active layer 313 can be formed on the front side surface side. In this way, the mask 501 based on the shape of the hairspring 108 can be formed on the front side surface side of the active layer 313. Here, the mask forming step in the timepiece part manufacturing method according to the present invention can be realized by the step of forming the mask 501.

  The photoresist used for forming the mask 501 is a photosensitive substance whose physical properties such as solubility in a developer change when exposed to light (or electron beam). For example, the photoresist is developed by being exposed to light. A positive photoresist whose solubility in the liquid is increased can be used. Alternatively, in forming the mask 501, a negative type photoresist whose solubility in a developing solution is lowered by exposure may be used instead of the positive type photoresist.

  The exposure pattern differs depending on whether a positive photoresist or a negative photoresist is used. The exposure pattern in the case of using a positive photoresist and the exposure pattern in the case of using a negative photoresist have a relationship in which the exposure position is reversed. Since a series of processes related to the formation of the mask 501 can be easily realized by using a known technique, description thereof is omitted. By using the photolithography technique as described above, the mask 501 can be formed with high accuracy.

  Next, as shown in FIG. 6, the active layer 313 on which the mask 501 is formed is etched using the mask 501 to remove the active layer 313 in the range indicated by reference numeral 601 in FIG. Then, a portion of the active layer 313 that is not covered with the mask 501 is removed by etching using the mask 501.

  By etching using the mask 501 for the active layer 313, as shown in FIG. 6, the remaining part of the active layer 313 except the mask 501 part is removed, and a part of the active layer 313 is formed in the shape of the mask 501. It is processed into a shape according to. Here, an etching process can be realized by a process of performing an etching process on the active layer 313 using the mask 501.

  The etching process for the active layer 313 can be realized by a dry etching process in which a material is etched by a reactive gas such as an etching gas, ions, radicals, or the like. As described above, the active layer 313 can be processed with high accuracy according to the shape of the hairspring 108 by performing etching using the mask 501 formed with high accuracy using the photolithography technique.

The etching process for the active layer 313 is preferably reactive ion etching (RIE), which is one of dry etching processes, and more preferably realized by a dry etching process using deep RIE technology. By realizing the etching process on the active layer 313 by the dry etching process using the deep RIE technique, it is possible to perform a fine process with high accuracy. Specifically, in the method for manufacturing a watch part of this embodiment, for example, a mixed gas of SF ₆ (sulfur hexafluoride) and C ₄ F ₈ (cyclobutane octafluoride) (SF ₆ + C ₄ F _8). ), The active layer 313 is deep-digged and dry-etched by the RIE technique.

  Reactive ion etching is one of the microfabrication technologies classified as dry etching. In the reaction chamber, an electromagnetic wave is applied to the etching gas to turn it into plasma, and a high frequency voltage is applied to the cathode on which the sample is placed. The self-bias potential is generated between the sample and the plasma by this, and the ion species and radical species in the plasma are accelerated and collided in the direction of the sample by the self-bias potential, so that the ion sputtering and the chemical reaction of the etching gas are simultaneously performed. The sample is processed by generating. Deep RIE (Deep Reactive Ion Etching) is one type of reactive ion etching (RIE), and can perform a narrow and deep etching process, that is, an etching process with a high aspect ratio.

  After etching the active layer 313, the mask 501 formed on the active layer 313 is removed (peeled) as shown in FIG. Since the mask 501 can be easily removed by various known methods, description of the removal method and the removal procedure of the mask 501 will be omitted. In manufacturing the hairspring 108, after removing the mask 501, a mask 801 is formed on the back side of the support layer 311 as shown in FIG. The mask 801 has a position and shape that avoids a portion constituting the hairspring 108.

  That is, the mask 801 is formed on the active layer 313 in the support layer 311 when viewed from the support layer 311 side along the thickness direction of the multilayer substrate 314 as indicated by an arrow 800 in FIG. The pattern is formed so as to be a pattern that opens a position that overlaps with the portion constituting the hairspring 108 and a predetermined range (the range indicated by reference numeral 802 in FIG. 8) including the overlapping position.

  As a result, as shown in FIG. 8, the support layer 311 at the positions included in the range 802 is not covered with the mask 801 and is exposed to the outside. The mask 801 can be formed in a manner similar to the mask 501 described above. Since a series of processes for forming the mask 801 can be easily realized by using a known technique, description thereof is omitted. By using the photolithography technique as described above, the mask 801 can be formed with high accuracy.

  Next, as shown in FIG. 9, etching is performed using the mask 801 on the support layer 311 on which the mask 801 is formed, and the remaining part of the support layer 311 that is covered with the mask 801 is left. Remove the part. By etching the support layer 311 using the mask 801, the support layer 311 is located at a position included in a range (a range indicated by reference numeral 901 in FIG. 9) that is exposed to the outside without being covered by the mask 801. The support layer 311 is removed.

  Further, when the laminated substrate 314 is viewed from the support layer 311 side along the thickness direction of the laminated substrate 314 by the etching process on the support layer 311 as indicated by an arrow 900 in FIG. , A portion included in the range 901 is exposed to the outside. The etching process for the support layer 311 using the mask 801 can be performed in the same manner as the etching process for the active layer 313 described above. Further, the removal of the mask 801 can be performed in the same manner as the removal of the mask 501 formed on the active layer 313 described above.

  Next, as shown in FIG. 10, the mask 801 is removed from the support layer 311 subjected to the etching process. By removing the mask 801, in the laminated substrate 314, a portion of the support layer 311 covered with the mask 801 is exposed to the outside, and the oxide film 312 is exposed to the outside in the range 802. .

  Next, as shown in FIG. 11, wet etching is performed to remove (peel) a portion of the oxide film 312 other than the portion sandwiched between the support layer 311 and the active layer 313. Specifically, the oxide film 312 can be removed by performing wet etching using, for example, hydrofluoric acid with the support layer 311 and the active layer 313 as the mask 501. As a result, the support layer 311 and the oxide film 312 that overlap with the portion constituting the hairspring 108 in the active layer 313 are removed, and only the portion constituting the hairspring 108 is brought into a hollow state, and the external layer 313 Exposed. The portion of the active layer 313 that is in a hollow state implements the silicon base portion 301 in the hairspring 108.

  In this embodiment, as described above, the removing step in the method for manufacturing a watch part according to the present invention can be realized by the step of etching the support layer 311 and the step of etching the oxide film 312. it can. Note that, in the active layer 313 from which the oxide film 312 is removed, the back side surface is flat and is in a so-called mirror surface state.

  Next, as shown in FIG. 12, the outer surface of the active layer 313 is covered with a drug 381 containing nanofibers 302a. Specifically, for example, the outer surface of the active layer 313 can be coated by applying a drug 381 including nanofibers 302a on the outer surface of the active layer 313. Here, the coating step in the method for manufacturing a watch part according to the present invention can be realized by the step of applying the medicine 381 including the nanofiber 302a to the outer surface of the active layer 313.

  The application of the medicine 381 may be performed over the entire laminated substrate 314 as an application range, or an area limited to a pattern portion where the hairspring 108 to be manufactured is formed may be performed as an application range. When the area limited to the pattern portion where the hairspring 108 is formed is set as the application range of the drug 381, for example, the area where the drug 381 is applied can be limited to a desired pattern by performing silk screen printing.

  When the area limited to the pattern portion where the hairspring 108 is formed is set as the application range of the medicine 381, for example, the area limited to the pattern portion obtained by inverting the pattern of the mask 801 can be set as the application range. In this case, the medicine 381 is applied not only to the part where the hairspring 108 is formed but also to the entire range 802 in FIG. 8 described above.

  In general, since the watch parts such as the hairspring 108 are small, the pattern portion of the mask 801 is reversed rather than the area limited to the pattern portion completely matching the pattern of these watch parts. The effect of applying the drug 381 to a uniform thickness over the entire timepiece part (hairsprings) can be expected when the limited area is the application range.

  In addition, the medicine 381 may be applied only to the front side surface of the laminated substrate 314 or may be applied to the front side surface and the back side surface of the laminated substrate 314. In the actual laminated substrate 314, the thickness of the support layer 311 and the oxide film 312 (dimension in the thickness direction of the laminated substrate 314) is very thin. For this reason, even if the drug 381 is applied to the back side surface of the multilayer substrate 314, the drug 381 can be satisfactorily applied to the back side surface of the active layer 313.

  The drug 381 can be realized as the nanofiber 302a by, for example, a metal oxide nanofiber, specifically, a liquid in which alumina nanofiber is dispersed in a predetermined solution or dispersion medium. As the liquid (dispersion medium) in which the alumina nanofibers are dispersed, for example, only water (pure water) or a liquid mainly containing water and containing an additive such as a predetermined dispersant can be used. Moreover, the medicine 381 may be realized as the nanofiber 302a, for example, by a liquid in which carbon nanofibers are dispersed in a predetermined solution or dispersion medium. Alternatively, the drug 381 may be realized by a liquid in which carbon nanotubes are dispersed in a predetermined solution or dispersion medium.

  Next, as shown in FIG. 13, the laminated substrate 314 in which the outer surface of the active layer 313 is coated with the medicine 381 containing the nanofiber 302a is heated. In this embodiment, for example, the laminated substrate 314 whose outer surface of the active layer 313 is coated with the drug 381 containing the nanofiber 302a is heated at 100 ° C. for 30 to 60 minutes as shown in FIG. Here, the heating step in the timepiece component manufacturing method according to the present invention can be realized by the step of heating the laminated substrate 314 whose outer surface of the active layer 313 is coated with the medicine 381 including the nanofiber 302a.

  The heating temperature and time may be any temperature and time that can remove the liquid component (moisture) contained in the medicine 381, and the heating temperature is not limited to 100 ° C., and the heating time is 30 to 60 minutes. It is not limited to. Specifically, for example, the heating temperature may be lower than 100 ° C., and the heating time at the lower temperature may be longer than 60 minutes. Alternatively, specifically, for example, the heating temperature may be higher than 100 ° C., and the heating time at the increased temperature may be shorter than 30 minutes.

  Further, the production of the hairspring 108 is not limited to the method of removing the liquid component (water) by heating. Specifically, for example, the liquid component (moisture) may be removed by leaving it in an environment maintained at a predetermined humidity or lower for a predetermined time. Alternatively, specifically, for example, the liquid component (moisture) may be removed by leaving it for a predetermined time in a space decompressed by a vacuum pump or the like.

  When manufacturing the hairspring 108, when the laminated substrate 314 whose outer surface of the active layer 313 is coated with the drug 381 including the nanofiber 302a is heated, the liquid component (water) contained in the drug 381 is removed, and the active layer 313 On the outer surface, a covering portion 302 formed by the nanofiber 302a is provided. Here, of the active layer 313 provided with the covering portion 302 formed by the nanofibers 302a on the outer surface, the active layer 313 constituting the watch part (hairspring 108) forms the silicon base portion 301 according to the present invention. Realized.

  Finally, as shown in FIG. 14, a portion constituting the hairspring 108 is peeled off from the laminated substrate 314 on which the covering portion 302 is formed by removing the liquid component contained in the medicine 381 by heating, and the hairspring. The part which becomes 108 is removed. The portion constituting the hairspring 108 can be removed using, for example, a tool such as tweezers 1401.

  Since the portion constituting the hairspring 108 is connected only to the tip portion of the hairspring 203 with respect to the laminated substrate 314, the portion constituting the hairspring 108 is simply held by the tweezers 1401 and pulled. It can be easily scraped off. Through the series of manufacturing steps as described above, the hairspring 108 including the silicon base portion 301 and the covering portion 302 that covers the silicon base portion 301 is formed as shown in the cross section of FIG. Can be manufactured.

(Example of etching pattern)
FIG. 15 is an explanatory diagram showing an example of an etching pattern. FIG. 15 shows the laminated substrate 314 after the support layer 311 and the oxide film 312 are removed by etching during the production of the hairspring 108 by the production method described above.

  The laminated substrate 314 after the support layer 311 and the oxide film 312 are removed by etching is a component etched into the shape of the hairspring 108 when viewed from either the support layer 311 side or the active layer 313 side. The portion 1501 is left, and the surrounding portion 1502 is removed to form a space. The laminated substrate 314 after the support layer 311 and the oxide film 312 are removed by etching is formed with a part 1501 and a frame part 1503 surrounding the space part 1502 around the part 1501.

  The component unit 1501 is connected to the frame unit 1503 via a component connection unit 1504. Thereby, when manufacturing the hairspring 108, a plurality of component parts 1501 can be formed on one laminated substrate 314, and a plurality of component parts 1501 can be handled at a time. As a result, it is possible to improve the handleability of the part 1501 when the hairspring 108 is manufactured, that is, the hairspring 108.

  The component connecting portion 1504 connects the portion of the hairspring 203 of the hairspring 108 and the frame portion 1503 in the component portion 1501. The frame portion 1503 forms a space 1505 that allows insertion of tweezers or the like for tearing off the component portion 1501 around the component connection portion 1504. The part 1501 can be satisfactorily and reliably removed from the frame part 1503 by bringing the part sandwiched by tweezers or the like when peeling the part part 1501 from the frame part 1503 close to the part to which a pulling force is applied when being peeled off. .

  The hairspring 108 is fixed to the balance with the balance 104 that supports the balance with hairspring 203. For this reason, the portion of the beard 203 has high strength (resistance) against the force for gripping the beard 203. In this embodiment, since the whisker 203 and the frame part 1503 are connected by the component connecting part 1504, when the part 1501 is peeled off from the frame part 1503, the part of the beard 203 is sandwiched by tweezers or the like. In addition, it is possible to prevent the portion of the beard 203, that is, the hairspring 108 from being damaged.

  In the multilayer substrate 314 after the support layer 311 and the oxide film 312 are removed by etching, the pattern formed by the component portion 1501, the space portion 1502, the frame portion 1503, and the component connection portion 1504 indicates that the multilayer substrate 314 is viewed from the support layer 311 side. The pattern is reversed between when viewed and when viewed from the active layer 313 side. The space portion 1502 penetrates from the front side surface to the back side surface of the multilayer substrate 314.

(Performance comparison example)
Next, the performance of the hairspring 108 manufactured by the manufacturing method according to the embodiment of the present invention will be described. FIG. 16 is an explanatory view showing the result of comparing the performance of the hairspring manufactured by the manufacturing method according to the embodiment of the present invention. In FIG. 16, as an example of the impact resistance of the hairspring, each sample of the hairspring is dropped twice from the specified height (take1, take2) and dropped from each height. The results of an impact test comparing impact resistance according to the presence or absence of damage such as cracking or chipping are shown. “◯” in the table shown in FIG. 16 indicates that there is no damage in which no crack or chipping occurs, and “X” indicates that damage such as cracking or chipping occurs.

  In FIG. 16, the “untreated” column indicates the result of the impact test of the hairspring made of only silicon (only the silicon base portion 301). As can be seen from FIG. 16, the drop height, which is a measure of the impact resistance of the untreated hairspring, was 60 cm at the maximum.

  On the other hand, the hairspring 108 in which the silicon substrate portion 301 is covered with the “alumina nanofiber film” as in the covering portion 302 shown in FIG. 3 is more resistant to the “untreated” hairspring. It was found that good impact resistance was obtained without damage even when the drop height, which is a measure of impact, exceeded 110 cm.

  FIG. 17 is an explanatory diagram showing the Young's modulus of an alumina nanofiber film and alumina. In FIG. 17, the “untreated” column indicates the balance spring composed of only the silicon base portion 301, that is, the Young's modulus of silicon. In FIG. 17, based on the Young's modulus of silicon, a substance having a Young's modulus higher than the Young's modulus is evaluated as “hard”, and a substance having a Young's modulus lower than the Young's modulus is evaluated as “soft”. Show.

  As shown in FIG. 17, the alumina nanofiber membrane is elastic because its raw material, alumina itself, is higher than the Young's modulus of silicon and is a hard material despite being a hard material. As a result, the Young's modulus is lower than the Young's modulus of silicon, and it is "softer" than silicon. Therefore, as shown in the above-described results shown in FIGS. 16 and 17, by covering the silicon base portion 301 with the covering portion 302 formed of alumina nanofibers, productivity can be ensured and an external impact can be prevented. It is possible to obtain the hairspring 108 (timepiece component) capable of preventing a direct action on the main part of the component (silicon base portion 301) and ensuring high resistance to external impact.

  In the above-described embodiment, the outer surface of the active layer 313 is coated on the outer surface of the active layer 313 with the drug 381 including the nanofiber 302a by applying the drug 381 including the nanofiber 302a. The method of coating the outer surface of the active layer 313 with the drug is not limited to application. For example, instead of the application method, a spraying method, a method by electrodeposition (electroplating), or a method by electrospinning (electrospinning method) may be used. Further, instead of the above method, by immersing the laminated substrate 314 after removing the oxide film 312 in the medicine 381 containing the nanofibers 302a, the outer surface of the active layer 313 is coated with the medicine 381 containing the nanofibers 302a. You may make it coat | cover.

  In the above-described embodiment, the support layer 311 and the oxide film 312 are removed by etching, and then the outer surface of the active layer 313 is covered with the drug 381 including the nanofiber 302a. The timing at which the outer surface is coated with the medicine 381 including the nanofiber 302a is not limited to this. For example, instead of the above timing, after removing the mask 501 formed on the active layer 313 and before forming the mask 801 on the back side surface of the support layer 311, the outer surface of the active layer 313 is formed on the nanofiber 302 a. You may make it coat | cover with the chemical | medical agent 381 containing.

  In this case, the back side surface of the active layer 313 is not covered with the drug 381, but a film formed of the nanofibers 302a can be formed on the front side surface of the active layer 313 or on the front side surface and the side surface. The strength of watch parts can be ensured.

  Further, the method for manufacturing a timepiece part according to the embodiment of the present invention is not limited to the one including the step of promoting the removal of the liquid component (moisture) contained in the medicine 381 by heating, decompression, or the like. It does not include a step of promoting the removal of the liquid component (moisture) contained in the drug 381 such as heating or decompression, and is left for a predetermined time after the outer surface of the active layer 313 is coated with the drug 381 including the nanofiber 302a, The covering portion 302 may be formed by naturally removing the liquid component (water) (gas-liquid equilibrium or the like).

  In the above-described embodiment, the example in which the timepiece part is manufactured using the laminated substrate 314 including the support layer 311, the oxide film 312, and the active layer 313 has been described, but the present invention is not limited to this. Instead of the laminated substrate 314, a watch part may be manufactured using a silicon single crystal substrate.

  As described above, the hairspring 108 which is a timepiece component according to the embodiment of the present invention is a timepiece component constituting a timepiece driving mechanism, and includes a silicon base portion 301 formed of silicon and a nanofiber 302a. And a covering portion 302 that covers at least one part (a part) of the outer surface of the silicon base portion 301.

  According to the hairspring 108 of the embodiment of the present invention, the impact from the outside is reduced by the nanofibers 302a forming the covering portion 302 provided on at least one surface of the active layer 313 that is the silicon base portion 301. Direct action on the main body (silicon substrate 301) can be prevented, and high resistance to external impact can be ensured.

  Although the technique described in Patent Document 1 described above describes that at least a part of an amorphous material is further covered with a coating made of a material such as diamond-like carbon or carbon nanotube, the coating is tribology. (Anti-friction) is a means to counteract and is a technology that utilizes the rigidity of diamond-like carbon or carbon nanotubes, so even if it is covered with the coating, the amorphous material under the coating is affected by an external impact. The problem of lacking is not solved.

  On the other hand, the nanofibers 302a forming the covering portion 302 in this embodiment are each a minute member independent of the nanofibers 302a, and the covering portion 302 is entangled (overlapped) with the minute nanofibers 302a. Layered. For this reason, the covering portion 302 formed by the nanofibers 302a hardly cracks even when an external force is applied, and can stably cover the timepiece component.

  In addition, the covering portion 302 is made of, for example, a main body (silicon substrate) of a watch component by a polymer or the like in which a plurality of monomers are combined (polymerized) and integrated to uniformly cover the main body (silicon substrate portion 301) of the watch component. It is more flexible than covering the part 301). For this reason, even when the timepiece part is deformed due to, for example, an external impact or expansion or contraction due to a change in ambient temperature, the covering portion 302 can flexibly follow the change, and the timepiece part is covered. Can do. Thereby, the high tolerance with respect to the impact from the outside can be exhibited continuously.

  Further, the hairspring 108 of the embodiment according to the present invention is characterized in that the nanofiber 302a is formed of a material harder than silicon. According to the watch part of the embodiment of the present invention, a watch part having excellent durability is manufactured by covering the main part (silicon base part 301) of the watch part with the nanofiber 302a made of a material harder than silicon. can do.

  Further, the nanofibers 302a, which are independent minute members, are stacked and configured in a cotton shape, thereby suppressing the influence of external impacts on the main body (silicon base body 301) of the watch part, and high While ensuring flexibility, high resistance to external impact can be ensured. Thereby, for example, it is possible to secure a high resistance against an external impact while securing the original function of a part that exhibits a function by being deformed like the hairspring 108.

  Further, the hairspring 108 of the embodiment according to the present invention is characterized in that the nanofiber 302a is at least one of alumina nanofiber or carbon nanofiber. According to the hairspring 108 of the embodiment of the present invention, the use of alumina nanofibers or carbon nanofibers that are widely used in the market and have a stable quality makes it possible to have a high resistance against external impacts. The stability of the quality of the mainspring 108 can be ensured.

  Further, the balance spring 108 according to the embodiment of the present invention includes a escape wheel and ankle constituting an escapement, a balance spring 108 and a balance wheel 109 constituting a speed control mechanism, and a train wheel 105 (110, 111, 112) and the like.

  According to the hairspring 108 of the embodiment of the present invention, at least one of the timepiece components driven for timing in the mechanical timepiece is attached to the nanofiber 302a on at least one surface of the active layer 313 that is the silicon base portion 301. A timepiece component such as the hairspring 108 having the covering portion 302 formed by the above method can be manufactured. Accordingly, a mechanical timepiece can be configured using each timepiece component provided with the covering portion 302 as appropriate according to the application, and high resistance to external impact can be ensured in the entire mechanical timepiece.

  In addition, in the method of manufacturing the hairspring 108 which is the timepiece component according to the embodiment of the present invention, the timepiece constituting the timepiece driving mechanism is formed on the active layer 313 laminated on at least one surface side of the support layer via the oxide film. A mask having a predetermined pattern based on the shape of the part is formed. Then, etching is performed on the active layer 313 to remove the residue while leaving the mask portion, and then cover at least one surface of the active layer 313 with the drug 381 including the nanofiber 302a. A feature is that the covering portion 302 is formed.

  According to the method of manufacturing the hairspring 108 that is the timepiece component according to the embodiment of the present invention, the hairspring having the covering portion 302 formed of the nanofibers 302a on at least one surface of the active layer 313 that is the silicon base portion 301. 108 can be manufactured. Accordingly, it is possible to prevent a shock from the outside from directly acting on the main body portion (silicon base portion 301) of the hairspring 108, and to manufacture a timepiece component such as the hairspring 108 having high resistance to the impact from the outside. Can do.

  In addition, the method of manufacturing the hairspring 108 that is the timepiece component according to the embodiment of the present invention includes the active layer 313 in which at least one outer surface is coated with the drug 381 in the coating step, that is, the active layer 313. A feature is that the liquid component contained in the drug 381 is removed by heating the multilayer substrate 314.

  According to the method of manufacturing the hairspring 108 according to the embodiment of the present invention, the liquid component contained in the drug 381 is forcibly removed by heating, thereby evaporating the dispersion medium that disperses the nanofibers 302a in the drug 381 ( Even when the volatility is low, the covering portion 302 can be reliably formed. As a result, it is possible to manufacture a timepiece component having high resistance to external impact.

  Further, in the method for manufacturing the hairspring 108 according to the embodiment of the present invention, the covering portion 302 is applied to at least one outer surface of the active layer 313 by applying the drug 381 to at least one outer surface of the active layer 313. It is characterized by forming. According to the method for manufacturing the hairspring 108 of the embodiment according to the present invention, the covering portion 302 can be formed easily and reliably.

  As described above, the timepiece part and the method for manufacturing the timepiece part according to the present invention are useful for the timepiece part and the method for manufacturing the timepiece part constituting the mechanical part in the timepiece, and in particular, the drive mechanism of the mechanical timepiece. Suitable for timepiece parts and methods for producing timepiece parts.

101 Drive mechanism 102 Barrel 103 Escapement machine 104 Speed control mechanism
105 wheel train 106 escape wheel 107 ankle 108 hairspring 109 balance wheel 110 second wheel 111 third wheel 112 fourth wheel 301 silicon base portion 302 covering portion 302a nanofiber 311 support layer 312 oxide film 313 active layer 314 laminated substrate 381 drugs

Claims (7)

A timepiece component constituting a timepiece drive mechanism,
A silicon substrate formed by silicon;
A coating formed by nanofibers and covering at least one surface of the outer surface of the silicon substrate,
A watch part characterized by comprising:   The timepiece component according to claim 1, wherein the nanofiber is made of a material harder than silicon.   The timepiece component according to claim 1, wherein the nanofiber is at least one of alumina nanofiber and carbon nanofiber.   4. The escape wheel and ankle constituting the escapement, the hairspring and balance wheel constituting the speed control mechanism, and the gear constituting the train wheel. One watch part. A mask forming step of forming a mask having a predetermined pattern based on the shape of a watch component constituting a watch driving mechanism on an active layer or a silicon single crystal substrate laminated at least on one surface side of the support layer via an oxide film;
An etching step of performing an etching process on the active layer or the silicon single crystal substrate to remove a residue while leaving a mask portion formed in the mask forming step;
A coating step of forming a coating portion by coating at least one surface of the active layer or the outer surface of the silicon single crystal substrate with a drug containing nanofibers after the etching step;
A method for manufacturing a watch part, comprising:   The heating step of removing the liquid component contained in the drug by heating the active layer or the silicon single crystal substrate in which at least one outer surface is coated with the drug in the coating step. Item 6. A method for manufacturing a timepiece part according to Item 5.   In the covering step, at least one surface of the active layer or the silicon single crystal substrate is coated with at least one surface of the active layer or the silicon single crystal substrate, thereby covering at least one surface of the active layer or the silicon single crystal substrate with the agent. The method for manufacturing a timepiece part according to claim 5 or 6,

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