JP2011164078A - Timepiece and method of manufacturing the same - Google Patents

Abstract

Disclosed is a timepiece capable of sufficiently maintaining liquid tightness and airtightness in a harsh environment despite a simple structure, and a timepiece manufacturing method capable of manufacturing such a timepiece efficiently and at low cost. To provide.
A wristwatch (1) includes an exterior part (2) having a sealed structure, and a movement (3) housed in the exterior part (2) and having a watch hand (not shown). Among these, the exterior part 2 has the glass plate 21, the bezel 22, the trunk | drum 23, and the back cover 25, and the connection part of each component was comprised with the plasma polymerization film | membrane which has organosiloxane as a main component. They are connected by bonding films 11, 12 and 13. This improves the airtightness of the sealed structure and eliminates the need for packing at the connecting portion, thereby increasing the degree of freedom in designing the wristwatch 1. A coating 14 made of the plasma polymerization film is also provided on the lower surface of the glass plate 21. Since the coating 14 has hygroscopicity, the antifogging effect of the glass plate 21 is obtained.
[Selection] Figure 1

Description

  The present invention relates to a timepiece and a method for manufacturing a timepiece.

The exterior of the wristwatch has various waterproof (airtight) structures depending on the required level of waterproof or airtight quality. These waterproof (airtight) structures are realized by packing (for example, refer to Patent Document 1).
FIG. 5 is a longitudinal sectional view for explaining a waterproof (airtight) structure of a conventional wristwatch.
The conventional wristwatch 9 includes an exterior portion 92 and a movement 93 that is housed in the exterior portion 92 and has three timepiece hands (pointers) that respectively constitute an hour hand, a minute hand, and a second hand.

Among these, the exterior portion 92 includes a body portion 923, a glass plate (cover glass) 921, a bezel 922 that holds the glass plate 921, and a back cover 925 that is installed on the back side of the body portion 923. . In FIG. 5, the clock hands are omitted.
Further, the glass plate 921 and the bezel 922 are connected via a packing 901. Similarly, the bezel 922 and the body 923 are connected via a packing 902, and the body 923 and the back cover 925 are connected via a packing 903.

  As the packings 901, 902, and 903 used for these connecting portions, elastic packing such as rubber packing and plastic packing is generally used. By compressing these packings 901, 902, and 903 between the respective portions of the connecting portion, the packings 901, 902, and 903 are in close contact with each portion, and the connecting portion is sealed. As a result, it is possible to prevent water and outside air from entering the exterior portion 92.

In recent years, the usage environment of wristwatches is spreading to more severe environments such as the deep sea and outer space.
In such an environment, a large pressure difference is generated between the inside and outside of the exterior portion 92, and thus a very large load is applied to the connection portion. For this reason, it is required to further improve the degree of waterproof or airtight quality at the connecting portion. If water or outside air enters, the movement 93 may be deteriorated.

Special table 2004-514155 gazette

  An object of the present invention is a watch that can sufficiently maintain liquid tightness and air tightness in a harsh environment despite its simple structure, and a watch that can manufacture such a watch efficiently and at low cost. It is to provide a manufacturing method.

The above object is achieved by the present invention described below.
The timepiece of the present invention has at least one pointer, and a movement for rotationally driving the pointer;
Having an airtight structure formed by joining a plurality of components, and an exterior portion for storing the movement in an internal space;
A bonding film provided between the plurality of components and bonding them;
And a coating provided on at least a part of the inner surface of the exterior part,
Each of the bonding film and the coating film is composed of a plasma polymerized film containing organosiloxane as a main component and subjected to activation treatment.
Accordingly, a timepiece that can sufficiently maintain liquid tightness and air tightness in a harsh environment despite a simple structure can be obtained.

In the timepiece of the present invention, the plasma polymerized film includes an atomic structure including a siloxane (Si-O) bond and a leaving group formed of an organic group bonded to the siloxane bond.
It is preferable that a part of the leaving group is detached from the siloxane bond by the activation treatment to develop adhesiveness, and the plurality of parts are bonded using this adhesiveness.
As a result, the bonding film has high bonding strength, chemical resistance, light resistance, and air tightness (liquid tightness), and the exterior part also has mechanical strength, chemical resistance, light resistance, and air tightness (liquid tightness). ) Is high. As a result, it is possible to prevent water and outside air from entering the watch.

In the timepiece of the present invention, in the plasma polymerized film, the content of the leaving group is preferably lower toward the surface side.
Thereby, by evaluating the content distribution of the leaving group in the thickness direction of the plasma polymerized film, it is possible to specify whether or not the plasma polymerized film has been activated.
In the timepiece of the invention, it is preferable that the plasma polymerized film has a hygroscopic property.
Thereby, even if the liquid tightness of an exterior part falls and water infiltrates, the infiltrated water can be absorbed. As a result, it is possible to reliably prevent the movement and the like from being deteriorated by water and the dew condensation in the exterior part.

In the timepiece of the invention, it is preferable that at least a part of the bonding film and at least a part of the coating film are constituted by one continuous plasma polymerized film.
Thus, when forming the bonding film and the coating film, it is not necessary to form a film only in a predetermined region using a mask or the like, and the bonding film and the coating film can be formed at a time. The film ease is improved.

In the timepiece of the present invention, the plurality of parts include an annular body part, an annular bezel provided above the body part, a transparent substrate provided above the bezel and covering the inside of the bezel, A back cover that is provided below the trunk and covers the inside of the trunk;
The coating is preferably provided at least on the lower surface of the transparent substrate.
Thereby, since the anti-fogging effect is given to a transparent substrate, the visibility of the time of a wristwatch can be improved.

The timepiece manufacturing method of the present invention has at least one pointer, and a movement for rotationally driving the pointer;
A method of manufacturing a timepiece having a sealed structure formed by joining a plurality of components, and an exterior portion that houses the movement in an internal space,
A first step of forming a plasma polymerized film using a silane-based gas as a raw material on the joining surfaces of the plurality of parts and at least a part of the inner surface facing the internal space among the plurality of parts;
A second step of activating the plasma polymerized film;
A third step of disposing the movement at a position to be the internal space and joining a plurality of components to each other via the plasma polymerization film.
Thereby, despite the simple structure, it is possible to efficiently and inexpensively manufacture a timepiece that can sufficiently maintain liquid tightness and air tightness in a harsh environment.

In the timepiece manufacturing method of the present invention, it is preferable that the activation process is at least one of a process of exposing the plasma polymerized film to plasma and a process of irradiating the plasma polymerized film with energy rays.
Thereby, it is possible to efficiently activate the plasma polymerization film while preventing deterioration of the base portion of the plasma polymerization film.

It is a longitudinal cross-sectional view which shows embodiment at the time of applying the timepiece of this invention to a wristwatch. It is the elements on larger scale which show the state before the activation process of the joining film | membrane used for the wristwatch shown in FIG. It is the elements on larger scale which show the state after the activation process of the joining film | membrane used for the wristwatch shown in FIG. It is a figure for demonstrating embodiment at the time of applying the manufacturing method of the timepiece of this invention to the manufacturing method of a wristwatch. It is a longitudinal cross-sectional view for demonstrating the waterproof (airtight) structure of the conventional wristwatch.

Hereinafter, a timepiece and a timepiece manufacturing method of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
FIG. 1 is a longitudinal sectional view showing an embodiment when the timepiece of the invention is applied to a wristwatch. In the following, for convenience of explanation, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.
<Watch>
A wristwatch 1 shown in FIG. 1 includes an exterior part (case) 2 and a movement 3 housed in the exterior part 2 and having three clock hands (not shown) that respectively constitute an hour hand, a minute hand and a second hand. And a band (not shown) used when the wristwatch 1 is worn on the arm.

As shown in FIG. 1, the exterior portion 2 includes a body portion 23, a glass plate (transparent substrate) 21, a bezel 22 that holds the glass plate 21, and a back cover 25 that is installed on the back side of the body portion 23. Have.
The movement 3 has a flat shape and is rounded in plan view. This movement 3 is fixed to the inner surface of the exterior part 2. Although it does not specifically limit as a fixing method, For example, engagement, fitting, adhesion | attachment, etc. are mentioned.

In addition, the movement 3 incorporates a drive mechanism (not shown) composed of gears and the like for rotationally driving the timepiece hands described above. The drive system of the drive mechanism may be a mechanical type such as a manual winding type or an automatic winding type, or may be a quartz type.
Further, the movement 3 receives various batteries, a crystal oscillator as a time reference source, a semiconductor element that generates a drive pulse for driving a clock based on the oscillation frequency of the crystal oscillator, and a drive pulse as necessary. It incorporates a step motor that drives the clock hands, an antenna for receiving radio waves, and the like.

In addition to the movement 3, the exterior portion 2 also stores a dial 6 and a frame 7.
The exterior portion 2 has a sealed structure formed by joining four components, and the movement 3 is accommodated in the internal space.
The trunk | drum 23 is the main components of the exterior part 2, and has comprised the annular | circular shape which can arrange | position the movement 3 inside. Examples of the constituent material of the body portion 23 include steel materials such as stainless steel, noble metal materials such as gold, silver, and platinum, non-ferrous metal materials such as brass, white, and titanium, and plastic materials.

An annular bezel 22 is provided above the body portion 23. The constituent material of the bezel 22 is the same as that of the body portion 23.
A disk-shaped glass plate 21 is provided above the bezel 22. The inside of the bezel 22 is covered with the glass plate 21. As the constituent material of the glass plate 21, highly transparent quartz glass, sapphire glass, acrylic glass, or the like is used, and the characters of the dial 6 and the clock hands can be visually recognized from the outside.

A disc-shaped back cover 25 is provided below the trunk portion 23 so as to cover the inside of the trunk portion 23. As a constituent material of the back cover 25, the same material as that of the body portion 23 can be used. A recess is formed in the upper portion of the back cover 25, and the movement 3 is inserted into the recess.
Here, the connection part between the glass plate 21 and the bezel 22, the connection part between the bezel 22 and the body part 23, and the connection part between the body part 23 and the back cover 25 face the joint surfaces of the respective parts, Are provided with bonding films 11, 12, and 13, respectively.

  Specifically, the bonding film 11 is provided between the bonding surface 210 of the glass plate 21 and the bonding surface 220a of the bezel 22, and the bonding film is formed between the bonding surface 220b of the bezel 22 and the bonding surface 230a of the trunk portion 23. 12 is provided, and the bonding film 13 is provided between the bonding surface 230 b of the body portion 23 and the bonding surface 250 of the back cover 25. With these bonding films 11, 12, and 13, each connection portion is connected while maintaining airtightness and liquid tightness. As a result, the exterior portion 2 has a sealed structure, and can prevent water and outside air from entering the internal space.

A coating 14 is formed on the lower surface 211 of the glass plate 21. The coating 14 is formed continuously with the bonding film 11 and is a single film.
Here, each of the bonding films 11, 12, 13 and the coating film 14 is composed of a plasma polymerized film containing organosiloxane as a main component and subjected to activation treatment.
Such a plasma polymerized film has strong adhesiveness. For this reason, each bonding film 11, 12, and 13 uses the adhesiveness to connect each connection portion while maintaining airtightness and liquid tightness.

Hereinafter, the bonding film 11 and the coating film 14 will be described in detail as representatives. The bonding films 12 and 13 have the same configuration as the bonding film 11 described later.
2 is a partially enlarged view showing a state before the activation process of the bonding film used in the wristwatch shown in FIG. 1, and FIG. 3 shows a state after the activation process of the bonding film used in the wristwatch shown in FIG. It is a partial enlarged view.

(Bonding film)
The bonding film 11 is a plasma polymerization film formed on the glass plate 21 and includes a siloxane (Si—O) bond 302 and has a random (or low crystallinity) atomic structure (as shown in FIG. 2). A Si skeleton 301 having an amorphous structure) and a leaving group 303 bonded to the Si skeleton 301. Such a bonding film 11 is a strong film that is not easily deformed by the influence of the Si skeleton 301 including the siloxane bond 302 and having a random atomic structure. This is presumably because the crystallinity of the Si skeleton 301 becomes low (becomes amorphous), so that defects such as dislocations and misalignments at the crystal grain boundaries hardly occur. For this reason, the bonding film 11 itself has high bonding strength, chemical resistance, light resistance, and airtightness (liquid tightness), and the exterior portion 2 also has mechanical strength, chemical resistance, light resistance, and airtightness (liquid tightness). Property) is high.

When the bonding film 11 is activated, the leaving group 303 is desorbed from the Si skeleton 301, and an active hand 304 is generated on the surface and inside of the bonding film 11, as shown in FIG. Thereby, adhesiveness is expressed on the surface of the bonding film 11. When such adhesiveness is developed, the bonding film 11 can be strongly bonded to the glass plate 21 or the bezel 22.
Note that the bond energy between the leaving group 303 and the Si skeleton 301 is often smaller than the bond energy of the siloxane bond 302 in the Si skeleton 301. This is because the bond energy of the siloxane bond 302 is about 430 kJ / mol, which is considerably larger than other bond types. Therefore, when the bonding film 11 is activated, the Si skeleton 301 is destroyed. Without incurring, the bond between the leaving group 303 and the Si skeleton 301 can be selectively cut, and a part of the leaving group 303 can be removed.

Further, such a bonding film 11 has a structure that is relatively close to an inorganic material, and thus becomes a solid that does not have fluidity. For this reason, compared with the conventional packing etc., the thickness and shape of a connection part (bonding film | membrane 11) hardly change. Thereby, the dimensional accuracy of the wristwatch 1 is remarkably higher than that of the prior art.
Further, the crystallinity of the Si skeleton 301 in the bonding film 11 is preferably 45% or less, and more preferably 40% or less. As a result, the Si skeleton 301 includes a sufficiently random atomic structure and exhibits more amorphous characteristics. For this reason, the characteristics of the Si skeleton 301 described above become obvious, and the dimensional accuracy and adhesiveness of the bonding film 11 become more excellent. Moreover, since the mechanical strength and density of the film itself are also improved, the air permeability can be further reduced. Thereby, the hermetic sealing by the bonding film 11 is further enhanced.

Note that the crystallinity of the Si skeleton 301 can be measured by a general crystallinity measurement method, and specifically, a method of measuring based on the intensity of scattered X-rays in a crystal portion (X-ray method). , The method of obtaining from the intensity of the crystallization band of infrared absorption (infrared method), the method of obtaining based on the area under the differential curve of nuclear magnetic resonance absorption (nuclear magnetic resonance absorption method), It can be measured by a chemical method utilizing the difficulty.
Among these, the X-ray method is preferably used from the viewpoint of convenience and the like.

Further, when measuring the degree of crystallinity of the Si skeleton 301, the above-described measurement method may be applied to the bonding film 11. However, it is preferable that the bonding film 11 is subjected to an activation process described later. . By the activation treatment, the leaving group 303 in the bonding film 11 is removed, and the crystallinity of the Si skeleton 301 can be measured more accurately.
Moreover, it is preferable that the bonding film 11 includes a Si—H bond in its structure. This Si-H bond is considered to be generated in the polymer when the silane undergoes a polymerization reaction by the plasma polymerization method, and inhibits the regular formation of siloxane bonds. For this reason, the siloxane bond is formed so as to avoid the Si—H bond, and the regularity of the atomic structure of the Si skeleton 301 is lowered. For this reason, the bonding film 11 including the Si—H bond is a film having a lower crystallinity.

  On the other hand, the greater the Si—H bond content in the bonding film 11, the lower the crystallinity. Specifically, in the infrared absorption spectrum of the bonding film 11, when the intensity of the peak attributed to the siloxane bond is 1, the intensity of the peak attributed to the Si—H bond is 0.001 or more and 0.2. Is preferably about 0.002 or more, more preferably about 0.05 or less, and further preferably about 0.005 or more and 0.02 or less. When the ratio of the Si—H bond to the siloxane bond is within the above range, the atomic structure in the bonding film 11 is relatively random. Therefore, the bonding film 11 is particularly excellent in bonding strength, chemical resistance, and air tightness (liquid tightness).

  By the way, the leaving group 303 bonded to the Si skeleton 301 behaves so as to generate an active hand in the bonding film 11 by detaching from the Si skeleton 301 as described above. Therefore, although the leaving group 303 is relatively easily and uniformly desorbed by the activation treatment, it must be securely bonded to the Si skeleton 301 so that it does not desorb when not activated. There is.

At the time of film formation by the plasma polymerization method, the component of the source gas is polymerized to generate a Si skeleton 301 containing a siloxane bond and a residue bonded thereto. For example, this residue becomes a leaving group 303. obtain.
Examples of the leaving group 303 include an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, an aldehyde group, a ketone group, a carboxyl group, an amino group, an amide group, a nitro group, and a halogen. Alkyl group, mercapto group, sulfonic acid group, cyano group, isocyanate group and the like.

Among these groups, the leaving group 303 is particularly preferably an organic group, and more preferably an alkyl group. Since the organic group and the alkyl group have high chemical stability, the bonding film 11 including the organic group and the alkyl group has excellent weather resistance and chemical resistance.
Here, when the leaving group 303 is a methyl group (—CH ₃ ) in particular, the preferred content is defined as follows from the peak intensity in the infrared light absorption spectrum.

  That is, in the infrared light absorption spectrum of the bonding film 11, when the intensity of the peak attributed to the siloxane bond is 1, the intensity of the peak attributed to the methyl group is about 0.05 to 0.45. Preferably, it is about 0.1 or more and 0.4 or less, more preferably about 0.2 or more and 0.3 or less. Since the ratio of the peak intensity of the methyl group to the peak intensity of the siloxane bond is within the above range, it is necessary and sufficient in the bonding film 11 while preventing the methyl group from inhibiting the generation of the siloxane bond more than necessary. Since a number of active hands are generated, sufficient adhesiveness is generated in the bonding film 11. Further, the bonding film 11 exhibits sufficient weather resistance and chemical resistance due to the methyl group.

Examples of the constituent material of the bonding film 11 having such characteristics include a polymer (polyorganosiloxane) containing a siloxane bond and an organic group that can be a leaving group 303 bonded to the siloxane bond.
Polyorganosiloxane usually exhibits water repellency (non-adhesiveness), but can be easily desorbed by an activation treatment, changes to hydrophilicity, and exhibits adhesiveness. Therefore, it has the advantage that control of this non-adhesiveness and adhesiveness can be performed easily and reliably.

  This water repellency (non-adhesiveness) is mainly an effect of organic groups (for example, alkyl groups) contained in the polyorganosiloxane. Therefore, the bonding film 11 made of polyorganosiloxane has an advantage that the activation process causes the surface to exhibit adhesiveness, and the portion other than the surface can obtain the above-described action / effect by the organic group. . Therefore, such a bonding film 11 has excellent weather resistance and chemical resistance, and maintains the sealed structure of the exterior portion 2 even in an environment where it is exposed to chemicals or the like for a long time. can do.

  Further, among polyorganosiloxanes, those mainly composed of a polymer of octamethyltrisiloxane are preferred. The bonding film 11 mainly composed of a polymer of octamethyltrisiloxane is particularly excellent in adhesiveness. Moreover, since the raw material which has octamethyltrisiloxane as a main component is liquid at normal temperature and has an appropriate viscosity, there is also an advantage that it is easy to handle.

  The average thickness of the bonding film 11 is preferably about 1 nm to 1000 nm, and more preferably about 2 nm to 800 nm. By setting the average thickness of the bonding film 11 within the above range, the glass plate 21 and the bezel 22 can be bonded more firmly while preventing the dimensional accuracy of the wristwatch 1 from being lowered. In particular, compared with the case where conventional packing is used, the exterior portion 2 can be significantly reduced in thickness and the degree of design freedom can be increased.

(Coating)
On the other hand, the coating film 14 is also a plasma polymerization film formed by a plasma polymerization method like the bonding film 11, and includes a siloxane (Si—O) bond 302 and a random (or low crystallinity) atomic structure (amorphous). A Si skeleton 301 having a structure) and a leaving group 303 bonded to the Si skeleton 301.
When the activation process is performed on such a coating 14, the adhesiveness is developed like the bonding film 11. At the same time, the coating film 14 is hygroscopic.

This hygroscopicity is due to the following reasons.
It is considered that when the leaving group 303 is detached from the film 14, a minute gap is generated in the film 14. If the elimination of the leaving group 303 continues, the abundance ratio of siloxane bonds in the coating 14 is relatively increased, so that the coating 14 has a composition close to that of an inorganic material (silica).
That is, it is considered that the coating film 14 subjected to the activation treatment approaches a silica film having a large number of minute voids. Since silica having a large number of voids has almost the same structure as silica gel, it is considered that the coating 14 subjected to the activation treatment exhibits hygroscopicity.

Since the coating 14 is formed on the inner surface of the exterior part 2 as described above, it functions to dehumidify the internal space of the exterior part 2. Thereby, even if the liquid tightness of each connection part of the exterior part 2 falls and water permeates into the internal space, the infiltrated water can be absorbed by the coating 14. As a result, it is possible to reliably prevent the movement 3 and the dial 6 from being deteriorated by water.
Note that the content ratio of the leaving group 303 may be different between the bonding films 11, 12, 13 and the coating 14. For example, the content of the leaving group 303 in the coating 14 is preferably lower than that of the bonding films 11, 12, and 13. Thereby, while the adhesiveness and moisture-proof property in each joining film 11, 12, and 13 are optimized, the hygroscopic property of the film 14 can be improved.

In this way, in order to vary the content of the leaving group 303, the treatment conditions for the activation treatment may be varied. Examples of processing conditions include processing time and processing intensity (energy beam intensity, plasma density, etc.).
In the plasma polymerized film, the leaving group 303 is released from the surface side by the activation treatment, so that the content of the leaving group 303 is lower on the surface side. Therefore, by evaluating the content distribution of the leaving group 303 in the thickness direction of the plasma polymerized film, it can be specified whether or not the plasma polymerized film has been activated.

Further, as described above, the coating 14 is formed on the lower surface of the glass plate 21, and is a single integrated film continuous with the bonding film 11. With such a configuration, when the bonding film 11 and the coating film 14 are formed, it is not necessary to form the film only in a predetermined region using a mask or the like. For example, the bonding film 11 and the coating film 14 are formed on the entire lower surface and side surfaces of the glass plate 21. As long as the film is formed, the bonding film 11 and the coating film 14 can be formed together.
The coating 14 formed on the lower surface of the glass plate 21 also functions as an antifogging film that suppresses condensation on the lower surface of the glass plate 21. As a result, the visibility of the dial 6 and the clock hands can be improved. Especially in the deep sea and outer space, the outside air temperature is often low, so the anti-fogging effect is useful.

<Watch production method>
Next, a method for manufacturing the wristwatch 1 shown in FIG. 1 (a method for manufacturing the timepiece of the present invention) will be described with reference to FIG.
FIG. 4 is a diagram for explaining an embodiment when the timepiece manufacturing method of the present invention is applied to a wristwatch manufacturing method. In the following, for convenience of explanation, the upper side in FIG. 4 is referred to as “upper” and the lower side is referred to as “lower”.

  The method for manufacturing the wristwatch 1 shown in FIG. 1 includes the joining surfaces 210, 220 a, 220 b, 230 a, 230 b, 250 of the glass plate 21, the bezel 22, the body portion 23 and the back cover 25, and the entire lower surface 211 of the glass plate 21. The first step of forming a plasma polymerized film using silane-based gas as a raw material, the second step of applying an activation treatment to the plasma polymerized film, the movement 3 etc. on the upper surface of the back cover 25, and glass Assembling the plate 21, the bezel 22, the body portion 23, and the back cover 25 includes a third step of joining them together. Hereinafter, each process is explained in full detail.

[1] First, a glass plate 21, a bezel 22, a body portion 23, and a back cover 25 are prepared (see FIG. 4A).
Next, prior to the formation of the plasma polymerized film, the bonding surfaces 210, 220 a, 220 b, 230 a, 230 b, 250 of the glass plate 21, the bezel 22, the body portion 23 and the back cover 25, and the entire lower surface 211 of the glass plate 21. In addition, each is subjected to a ground treatment.

Examples of the base treatment include physical surface treatment such as sputtering treatment and blast treatment, plasma treatment using oxygen plasma, nitrogen plasma, etc., corona discharge treatment, etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, ozone Examples include chemical surface treatment such as exposure treatment, or a combination of these.
Note that the base treatment may be performed as necessary.

Next, a plasma polymerized film is formed on each bonding surface 210, 220a, 220b, 230a, 230b, 250 and the entire lower surface 211 of the glass plate 21 (first step).
The plasma polymerized film is a film formed by supplying a mixed gas of a source gas and a carrier gas in a strong electric field, polymerizing molecules in the source gas by the action of plasma, and depositing a polymer on the base. . According to this method, since the underlying portion is activated and cleaned by the action of plasma, a film having high adhesion can be formed regardless of the type of the underlying portion.

Examples of the source gas include organosiloxanes such as methylsiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and methylphenylsiloxane.
On the other hand, for example, helium gas, argon gas, nitrogen gas or the like is used as the carrier gas.

The strong electric field is formed by applying a high frequency voltage to the electrode, and the output density of the high frequency voltage is preferably about 0.01 W / cm ² or more and 100 W / cm ² or less.
Further, the deposition is carried out under reduced pressure, the pressure is preferably about 133.3 × ¹⁰ -5 Pa or more 1333Pa less (1 × ¹⁰ -5 Torr or 10Torr or less), 133.3 × 10 ^- More preferably, it is about ⁴ Pa or more and 133.3 Pa or less (1 × 10 ⁻⁴ Torr or more and 1 Torr or less).
As described above, the bonding films 11, 12, 13 and the coating film 14 are obtained.

The glass plate 21 may be formed on the entire side surface and the entire lower surface. Therefore, if the film is formed from above with the upper surface facing down, it can be easily and efficiently formed without using a mask or the like. Can be membrane. Moreover, even if it forms into a film on the upper surface of the glass plate 21, it does not interfere.
On the other hand, even if the bezel 22, the body 23, and the back cover 25 are formed in regions other than the joint surfaces 220a, 220b, 230a, 230b, 250, the sealing structure of the wristwatch 1 is not affected, and there is no problem. . In addition, since the plasma polymerization film | membrane formed into a film in the surface which faces internal space expresses hygroscopicity by activation process, it contributes to the improvement of the dehumidification capability of internal space.

  [2] Next, the bonding films 11, 12, 13 and the coating film 14 are activated (second step). The activation treatment is not particularly limited as long as it is a treatment that imparts energy to the bonding films 11, 12, 13, and the coating 14. Examples include a treatment to be given, a treatment to be exposed to plasma (giving plasma energy), a treatment to be exposed to ozone gas (giving chemical energy), and the like. Particularly, a treatment to irradiate energy rays and a treatment to be exposed to plasma are preferable.

Examples of energy rays include electromagnetic waves such as ultraviolet rays and X-rays, particle beams such as electron beams and ion beams, and the like.
Among these, it is preferable to irradiate ultraviolet rays having a wavelength of 126 nm to 300 nm. According to such ultraviolet rays, it is possible to develop adhesive properties in a shorter time while preventing the characteristics of the bonding films 11, 12, 13 and the coating 14 from being significantly lowered.

The time for irradiation with ultraviolet rays is not particularly limited, but is preferably 0.5 minutes or more and 30 minutes or less, and more preferably 1 minute or more and 10 minutes or less.
On the other hand, the exposure to plasma is useful in that it can locally activate the vicinity of the surfaces of the bonding films 11, 12, 13 and the coating film 14. That is, there is little possibility that the base portion is deteriorated by the activation process.

Dangling bonds are generated or hydroxyl groups (OH groups) are introduced on the surfaces of the bonding films 11, 12, 13 and the coating film 14 which are energized and activated in this way. In addition, the above-mentioned “activate” means a state where dangling bonds are generated, a state where hydroxyl groups are bonded, or a state where these are mixed.
Note that the bonding films 11, 12, and 13 may be formed on only one of the pair of bonding surfaces facing each other in each connection portion, or may be formed on both.

When the film is formed only on one side, the hydroxyl group exposed on the activated bonding films 11, 12, and 13 and the hydroxyl group exposed on the other bonding surface attract each other by hydrogen bonding, and there is an attractive force between the hydroxyl groups. appear.
In addition, hydroxyl groups that are attracted to each other by hydrogen bonding are dehydrated and condensed depending on temperature conditions and the like. As a result, the hydrogen bond changes to a covalent bond via an oxygen atom, leading to a stronger bond.

In addition, since a hydroxyl group is naturally introduced into the surface of a metal material or the like under the influence of moisture in the air, this can be utilized. Further, since the material can be activated by the base treatment as described above, the base treatment surface can be strongly bonded to the bonding films 11, 12, and 13.
Further, when the bonding films 11, 12, and 13 are formed on both of the pair of bonding surfaces, stronger bonding is possible by the active hands (dangling bonds, hydroxyl groups, etc.) exposed at a higher density.

  [3] Next, the glass plate 21, the bezel 22, the body portion 23, and the back cover 25 are assembled with the movement 3, the dial 6 and the frame 7 arranged on the upper surface of the back cover 25 (FIG. 4B). reference). Specifically, the glass plate 21 and the bezel 22 are bonded via the bonding film 11. Similarly, the bezel 22 and the body portion 23 are bonded via the bonding film 12, and the body portion 23 and the back cover 25 are bonded via the bonding film 13. In this way, the exterior part 2 having the closed structure in which the movement 3 is housed is obtained.

As described above, the wristwatch 1 is obtained. According to this manufacturing method, the exterior portion 2 having a hermetic and liquid-tight sealing structure is manufactured without using a sealing material such as packing. be able to. For this reason, the structure can be simplified and the degree of freedom in design is increased. In particular, the wristwatch 1 can be thinned by omitting packing or the like.
Moreover, compared with a sealed structure using a sealing material such as packing, it is possible to improve the weather resistance against a more severe environment such as deep sea or outer space.

  Furthermore, as long as only one type of plasma polymerized film is formed, the bonding films 11, 12, and 13 for bonding the components constituting the exterior portion 2 and the coating 14 for dehumidifying the internal space of the exterior portion 2, They can be formed simultaneously. Therefore, it is possible to improve the manufacturability of the wristwatch 1, and even if the liquid-tightness of the exterior portion 2 is reduced to allow the ingress of water, the infiltrated water is absorbed by the coating 14 and the movement 3 or the like is deteriorated. Further, fogging of the glass plate 21 can be prevented.

Although the timepiece and the timepiece manufacturing method of the present invention have been described based on the illustrated embodiments, the present invention is not limited to these.
For example, in the timepiece of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits a similar function, and an arbitrary configuration can be added.
Moreover, although the said embodiment demonstrated to the example the case where the exterior part was comprised with four components, if the number of parts which comprise an exterior part is two or more, it will not specifically limit.
Moreover, the timepiece of the present invention is not limited to a wristwatch, and can be similarly applied to other types of timepieces such as a portable timepiece such as a pocket watch, a table clock, and a wall clock.

DESCRIPTION OF SYMBOLS 1 ... Wristwatch (clock) 2 ... Exterior part (case) 21 ... Glass plate (transparent substrate) 22 ... Bezel 23 ... Body part 25 ... Back cover 210, 220a, 220b, 230a, 230b, 250 ... ... Joint surface 211 …… Lower surface 3 ... Movement 303 ... Leaving group 304 ... Active hand 6 ... Dial 7 ... Frame 11, 12, 13 ... Joint film 14 ... Coating 9 ... Watch 92 …… Exterior part 921 …… Glass plate 922 …… Bezel 923 …… Body part 925 …… Back cover 93 …… Movement 901, 902, 903 …… Packing

Claims (8)

A movement having at least one pointer and rotationally driving the pointer;
Having an airtight structure formed by joining a plurality of components, and an exterior portion for storing the movement in an internal space;
A bonding film provided between the plurality of components and bonding them;
And a coating provided on at least a part of the inner surface of the exterior part,
The timepiece characterized in that each of the bonding film and the coating film is composed of a plasma polymerized film containing organosiloxane as a main component and subjected to activation treatment. The plasma polymerized film includes an atomic structure including a siloxane (Si—O) bond and a leaving group formed of an organic group bonded to the siloxane bond,
The part of the leaving group is detached from the siloxane bond by the activation treatment to develop adhesiveness, and the plurality of parts are bonded using the adhesiveness. clock.   3. The timepiece according to claim 1, wherein the content of the leaving group in the plasma polymerized film is lower toward the surface side.   The timepiece according to claim 1, wherein the plasma polymerized film has a hygroscopic property.   The timepiece according to any one of claims 1 to 4, wherein at least a part of the bonding film and at least a part of the coating film are constituted by one continuous plasma polymerized film. The plurality of parts include an annular body, an annular bezel provided above the body, a transparent substrate provided above the bezel and covering the inside of the bezel, and below the body. And a back cover that covers the inside of the body part,
The timepiece according to claim 1, wherein the coating is provided at least on a lower surface of the transparent substrate. A movement having at least one pointer and rotationally driving the pointer;
A method of manufacturing a timepiece having a sealed structure formed by joining a plurality of components, and an exterior portion that houses the movement in an internal space,
A first step of forming a plasma polymerized film using a silane-based gas as a raw material on the joining surfaces of the plurality of parts and at least a part of the inner surface facing the internal space among the plurality of parts;
A second step of activating the plasma polymerized film;
And a third step of arranging the movement at a position to be the internal space and joining a plurality of parts to each other through the plasma polymerization film.   The timepiece manufacturing method according to claim 7, wherein the activation process is at least one of a process of exposing the plasma polymerized film to plasma and a process of irradiating the plasma polymerized film with energy rays.

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