JPS589971A - Analog display wristwatch - Google Patents

Abstract

PURPOSE:To provide an analog display wristwatch which can assure hand rotating torque stably for a long period of time by forming an ultrafine porous film and a lubricating film contg. org. metallic compds. on the frictional sliding parts of a time correcting mechanism. CONSTITUTION:In a time correcting mechanism for an analog display wristwatch, an ultrafine porous film 2 is formed by electrodeposition plating or the like on the surface of frictional sliding parts 1 of a center wheel pinion and a center wheel, a cannon pinion and a center wheel pinion, etc. A treating soln. consisting of >=1 kind of org. metallic compds. such as alkoxy compds. of IV sub-group elements, solid lubricating fine particles of (CF)n, etc. and an org. solvent such as isopropyl alcohol is coated thereon and is heated. A lubricating film 3 dispersed with solid lubricating fine particles 4 is thus formed. Stable sliding torque is maintained between the frictional sliding parts by the films formed in such a way effectively for a long period of time.

Description

[Detailed Description of the Invention] In the wood-invented 1 time adjustment mechanism, the 2nd kana and 2 honors, the 2nd kana and the 211th kana, or the entire surface of one of the parts, -14 to F1a. An ultra-fine porous coating is formed in advance only on the parts where the parts slide by friction, and a composite coating II consisting of the 'F1mK organometallic compound and solid lubricating fine particles is formed.
Km is an analog display wristwatch with lubricity added to the engaging parts of the 11th kana and 2nd gear, the #i simple kana and the 2nd kana.

The object of the present invention is to apply a film with high lubricity and wear resistance to a uniform thickness using a simple method.
By forming it on both the number gear, the pedestal or the cylindrical pinion and the second pinion, or on the entire surface of one part, or only on the part where both parts slide by friction, it can be used for a long time without lubrication. Stable sliding torque between the 2nd pinion and the 2nd gear, and between the Fi simple pinion and the 211st pinion, that is, the rotational torque of the glue for adjusting the time (hereinafter referred to as hand times and shift torque)
It is possible to provide the following.

Normally, the time adjustment mechanism of analog display wristwatches is F! .

There is a simple pinion type in which the cylinder pinion and the No. 2 pinion slide by friction when the needle is turned, and an etching type in which the No. 2 pinion and the No. 2 gear slide by friction. The upper limit of the frictional sliding torque between this tube pinion and the 2nd pinion, or between the 2nd pinion and the 21st gear, is about 5 to 15 g-dll from the viewpoint of operability when turning the hands, and the lower limit is for watches. When a certain amount of impact is applied, the 4 cylinder kana, tF
Due to the inertia of the minute hand attached to the No. I2 pinion, it is necessary to provide a tube layer of 2 to 8 g-α to prevent frictional sliding between the tube pinion and the No.2 pinion, and between the Fi No.2 pinion and the No.2 gear.

In addition, from the viewpoint of operability when turning the needle, it is necessary to suppress the desired movement of the frictional sliding torque to ±3 g - degree of damage as much as possible.

In order to ensure such frictional sliding torque, in the design of the Eta type, the side surface of a simple cylinder with a wall thickness of α05~cL15cm is cut by a chisel with a tip diameter of α1~α3cm.
0■ To form a honey-shaped shape within the degree of power, the engaging part of the tube pinion and the second pinion should have a spring-like tightening allowance of α01 to α03mm.In addition, in the Eta type, the plate thickness is α1 to α03mm. 0.
If you cut out the 2 honor gears of 2 cabinets into various shapes, 2
α01-(
It has the choking allowance of LO3sam.

Furthermore, lubricating oil is used for the purpose of providing stable lubricity and wear resistance to the engaging portions between the cylinder pinion and the No. 2 pinion, and between the Fi No. 2 pinion and the No. 2 gear.

However, the use of lubricating oil is difficult because the oil spreads to areas other than the sliding parts, or when used for a long time, chemical changes occur and the lubricating ability decreases, or the space for lubrication is narrow. The amount of lubrication became unstable and stabilized when the special IJ
) There are many problems, such as not having a warranty on the product.

Furthermore, the development of oil-less lubrication processing technology is desired in terms of streamlining the assembly work of watches and eliminating the intermittent lubrication work required in the market.

From this point of view, various solid lubrication treatments have been studied for both this and K.

For example, simple kana and 2nd kana, or 2nd kana and ・2
On the surface of the friction sliding part of the perfume wheel, MO8! , WEl*
.

Solid lubricating fine particles such as 0, BN, (OF)n, FTF]If, etc. are prepared by using an organic binder or an inorganic binder, vapor deposition, sintering, ion blating, etc. Methods of forming a film or forming a film by eutectoid deposition during hard plating have been studied.

However, when both methods are applied to the friction sliding parts of simple pinion □ and 2I pinion, heavy or No. 2 pinion and No. 2 gear, it is difficult to control the coating thickness with the required dimensional accuracy, and the sliding torque There is a problem in that the life of the lubricating film is extremely short under severe usage conditions, such as 2 to 15 g.

Furthermore, the conventional solid lubricant treatment technology and the method using a shaker vacuum device require expensive equipment, require a large amount of man-hours to attach and detach the parts to be treated to a jig, and are difficult to apply in patch treatment. There are cost problems such as difficulty in changing the amount due to the heat, and quality problem C such as the inability to form a coating on the inside of the cylinder of a cylindrical pinion.

Due to the above drawbacks, the conventional solid lubricant treatment technology is
It was difficult to apply and put it into practical use in the zero-friction sliding part of a number pinion, t or second pinion, and two pitched gears.

The present invention completely solves the drawbacks of the prior art, and the surface of the friction sliding portion of the cylinder pinion and the No. 2 pinion, or the No. 2 pinion and the No. 2 gear, is coated in advance with an ultra-fine porous coating. After that, the surface is coated with a treatment liquid in which an organometallic compound and solid lubricating fine particles are dissolved and dispersed in an appropriate organic solvent, and when heated, it becomes stained, resulting in highly variable lubricity and wear resistance. This makes it possible to achieve long-term and stable needle turning torque without lubrication, which was not possible with conventional lubrication treatment. .

To explain the present invention in more detail, the lubrication treatment of the present invention consists of two stages. In the first step, as shown in FIG. 1, a fine porous coating 2 is formed. This film has the effect of improving the wear resistance of the lubricated object M3 formed in the second stage in which the solid lubricating fine particles 4 are dispersed.

1111 of porous coating! Methods include a method in which the surface of the component itself is made porous, and a method in which a porous coating is deposited on the surface of the component. Examples of the former include physical methods such as sandblasting, and chemical etching methods. Examples of the latter include a method in which Ti cape is coated on the decaying surface of the component using a vacuum method and then anodized;
)ii - Snow melting plating method of Co, Or, etc., )J
l-P, Ni-B, lii-Co, 0
There are electroless plating methods such as O-W. Ota. Subject lI#
High hardness is required from the viewpoint of wear resistance.

Picchus hardness is 20 (1 or more is ideal), and both the electrostatic plating film and electroless plating film described above are suitable porous films.The size of the pores is determined by the size of the available lubricating particles. Considering this, 1μ~α01 dust is desirable, 2
Spray a treatment liquid consisting of 1 m or 2 m or more of a sulfur-containing metal compound, 1 wJ body lubricating fine particles, and a suitable organic solvent to form a lubricating film 3Fi in which solid lubricating fine particles 4 are dispersed.

It can be obtained by commonly used IH cloth methods such as dipping and spinner coating, followed by heating. The organometallic compounds to be used include A*A- compounds, alkoxy compounds, acylate compounds, and chelate compounds of each element of subgroup B and group 8, group 3 subgroup a, group 4 subgroup a, group 5 subgroup a. , a thiolate compound, or a mixture or reactant of two or more of them are used. Among these organometallic compounds, jkt(OOaHy)m,
Group 3 alli elements such as In(Oc4He)s, OHsSi(OOHm)m, 81(OOHs)a
, 8n(Oc4'Fb+)4, Pb(OO
Group 4 a subgroup elements such as aHty)a 5b (OO*Hs)
Group 5 subgroup a elements such as s, C5h H@COOTi (
OO4Is)s, Ti(OC@Htt)+, Z
Each alkoxy compound of a group 4 subgroup element such as r(oC4T1e)4 is a metal compound group that can be formed into a film relatively easily. When a metal alkoxy compound forms a film through a thermal decomposition reaction or a combined reaction of a hydrolysis reaction and a thermal decomposition reaction, the metal alkoxy compound undergoes a thermal decomposition reaction.

The hydroxyl group (-0111) present on the surface of the treated area chemically bonds with the adsorbed water, resulting in strong adhesion. However, if the process, combination composition, and concentration/heating conditions of this metal compound are selected, it is possible to apply a soft coating to a hard coating with a uniform thickness. On the other hand, as solid lubricating fine particles dispersed in these films.

Molybdenum disulfide, tungsten disulfide, boron nitride,
Graphite, fluorinated graphite, synthetic resin, red nose oxide, etc.
The zero-dispersion amount of these solid lubricating fine particles used singly or in combination of two or more types if necessary is in the range of 1wt 14 to 9 owt based on the total amount of the organometallic compound. Since these solid lubricating fine particles are used for precision sliding parts, K should have a fine dimensional accuracy and α01jl-15 voice range that is easy to use. Various types of organic solvents can be used. For example, methanol, ethanol, isopropanol, etc.
Ketones such as methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, benzene,
Aromatics such as toluene and xylene, methylene chloride, 1
, 1.1-) rifumylethane, 1', 1.2-) rifuroro, 1.2. ．． Halogenated hydrocarbons such as 2-trifluoroethane are used alone or in combination. A small amount of acids such as hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, etc. may be added to these organic solvents for the purpose of accelerating the film-forming reaction.The composition of the treatment liquid and the negativity of cutting heating may be selected. It can be formed with any thickness from a soft film to a hard film Wlf. Each of these conditions may be arbitrarily adjusted depending on the dimensional accuracy of the material of the part to be treated, the required lubrication performance, etc.

When applied to the 2nd pinion, 2nd gear, platform, or tube pinion of an analog display wristwatch, the porous coating thickness is α1μ to 40J1.
If the film thickness is within the range of α1J-α5-mu, the firing temperature is 60°C to 250°C, and the firing time is 5 minutes to 120 minutes, the dynamic friction coefficient is 0.05 to α50, and the hardness is within the range of 0.05 to α50. A coating of 3H to 911 or higher can be obtained with a grade of lead III, and a sufficient practical lubrication life of the time adjustment mechanism can be ensured.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 A simple kana made of steel (0:1%), which is a time adjustment mechanism part of a cylinder kana type analog display wristwatch, was hardened to a Pickchus hardness of 70.
0 (hereinafter referred to as Hv700) VC heat treatment, and further N1-alloy plating was performed using the following bath composition and electrodeposition conditions.

[Bath IM formation]

Nickel sulfate 1801/1 Cobalt sulfate a OI/1 Cobalt chloride 151/1 Ammonium chloride 251/ boric acid t OIIl [Electrodeposition conditions] Bath temperature 5 rtr.

Current density cliff 2 A/'d, ta" time
The thickness of the 15m1n plating was 2μ, and the surface was confirmed to be porous as shown in No. 21 JK. #Maekana is treated with the following composition of treatment liquid (A) K jl!
The film was immersed for 2 minutes at 6Q°C, and then the solvent was dried at 6Q°C for 1 minute, and the film was fired at 1K and 200°C for 60 minutes.

IM precept for treatment 1w (g) γ-aznopropyltriethoxysilane 3Ir-glycidylpropyltriethoxydisilane 6I tetraethoxysilane III Tetrabutoxytitanium II(OF)n
(Average particle size (103J) 49 isopropylene A = t - A100 mt The coating thickness of the tube pinion treated with the above treatment liquid was about (13J). Also, one treated item was heated to 200 ° C. After that, we immersed it in cold water at 0°C and inspected its appearance after quenching, and it was confirmed that there were no cracks at all and that it had strong adhesion.In order to measure the coefficient of friction of this film, A test piece for a pendulum-type friction tester was subjected to the same treatment as the one with 1/A applied to the front pinnacle, and the friction coefficient was measured with the measuring device.
The value was Fiα15.

Incorporate the processed simple kana into a wristwatch to keep the hand turning torque constant. In addition, the needle rotation durability for 10 years of use phase fraction (1 mark, 1 minute hand, 1 rotation each forward and reverse, 10 years of use, minute hand f forward,
550 WJjr) in reverse.

The relative change in the needle rotation speed at that time with respect to the initial value is set. The results are shown in Figure 5. Figure 3 shows the relative change in needle rotation torque during the needle rotation durability test of a wristwatch that incorporates the lubricated pinion of the present invention.
1 Watch - Epoxy adhesive that shows the relative change in needle rotation torque in a wristwatch needle rotation durability test in which oil for watches (Elsin M56B Swiss Berge Toron Co., Ltd.) was applied to the retaining part of the simple pina and the second pina. The agent is Pinegoo and the MOBt is used as a component.
The 4+ bell diagram in C shows the relative change in the needle rotation torque that is applied to the needle rotation durability test of a wristwatch that incorporates a cylindrical pinion coated on the surface of the surface.

As is clear from FIG. 3, it can be seen that the wristwatch which introduced the simple kana to which the lubricating treatment 1 of the present invention was applied exhibits the best hand-turning durability performance.

In addition, Figure 4 shows the variation in the hand turning torque of each 10-bond wrist watch that has been subjected to the various lubrication treatments described above. As is clear from FIG. 4, it can be seen that the variation in the hand turning torque of the wristwatch containing m number of katakana coated with the lubrication treatment of the present invention is the smallest.

Example 2 A tube pinion similar to that used in Example 1 was immersed in a treatment solution with the following composition for 4 minutes at room temperature, followed by solvent drying at 60°C for 10 minutes, and then immersed in a treatment solution with the following composition. Baking was performed for 100 minutes.

Treatment liquid φ) Os-forming methyltrimethoxysilane 3I Tetraethoxysilane 2.9 Tetrabutoxylead 1011 Tetrabutoxytitanium
11 (CF)n (average particle size αass> 51MO
8, (average grain 4! α2) 1g Aston
50m Isopropyl Alcohol A 50g The coating thickness of the tube pinion treated with the above treatment solution was 145 μt.
It was hot. Moreover, the adhesion was also good, and the coefficient of dynamic friction was α14. The treated cylinder pinion was assembled into a wristwatch, and as in Example 1, the needle was rotated for durability, and the relative change in torque with respect to the initial torque was determined. The results are shown in Figure 5 and 4.
As is clear from the 0 diagram indicated by dK in the figure,
The wristwatch incorporating the tube pinion according to this example is Example 1
It has been confirmed that it has good durability when turning the needle, similar to all wristwatches, and is stable with less wobble.

Example 5 A 211 kana made of carbon steel (1 liter of C), which is an instant correction mechanism part for an Eta-type analog display wristwatch, was heat treated to Hv700, and was further coated with porous chrome plating using the following bath components and conditions. form.

[Chrome plating bath components]

0rbs 50m myos 59k Ba 2000ppm? SOOppm OEsOOOE Small amount [Electrodeposition conditions] Bath temperature -10℃ Current density 1 μm/6 time 5 Q mln When plating was performed under the above conditions, the plating thickness was 15μ, and the plated surface was observed with an electronic microscope. It was confirmed that there were many extremely fine pores.

The No. 2 pinion was treated with the same treatment solution φ) as in Example 2.
After dipping for 1 minute, the solvent is dried at 60° C. for 10 minutes, and the film is further baked at 200° C. for 60 minutes to form a film. The thickness of this coating was Q, 5'Q. Adhesion and dynamic friction coefficient were the same as in Example 2. 2 processed like this
A two-ring wheel is completed using a counter kana, assembled into a wristwatch, and subjected to a needle rotation durability test in the same manner as in Example 1. The relative change in needle rotation torque to the initial value at that time is shown in Fig. 5.
The figure shows the relative change in the hand turning speed of a watch incorporating the No. 2 pinion that has been subjected to the lubricating treatment of the present invention during a turning durability test using 61 watch oil (Elsin MS6B Swiss Beer Gage). The relative change in the needle rotation torque of a wristwatch in which the engagement part between the No. 2 pinion and the No. 2 wheel was lubricated with KsP was measured using the No. 2 pinion whose f1 part surface was sputter-coated with KMo81 to a thickness of 1μ. The graphs of g show the relative changes in the needle turning torque of the two-wheeled #A handheld meter.

As is clear from Figure 5, the wristwatch incorporating the second pinion which has been subjected to the lubrication treatment of the present invention exhibits the best hand turning durability performance.

In addition, FIG. 6 shows a wristwatch in which the various lubrication treatments described above have been applied to 2111 kana, and an OA rack with a hand turning torque of 10 degrees each. As is clear from Figure 6, it can be seen that the variation in the hand turning torque of the wristwatch incorporating the No. 2 pinion which has been subjected to the lubricating treatment of the present invention is the smallest.

In the above embodiment, the simple kana and the cylindrical kana that can be changed to the second kana,
Although the effects have been shown for the No. 2 pinion and the one-side treatment on the No. 2 pinion and the No. 2 gear, it has been confirmed that the treatment on both sides 311 shows an even better effect.

As described above, 1. Applying the lubrication treatment of the present invention to the time adjustment mechanism 0IIlIII sliding member 11 of an analog display wristwatch.
This makes it possible to maintain stable needle turning torque over the long term.

The present invention uses a mechanism that secures slip torque by using spring properties between two movable parts to ensure stable slip torque even in the time adjustment mechanism of analog display taro clocks of watches. To maintain it for a long time,
Take advantage of its effects.

[Brief explanation of the drawing]

Figure 1 of Tuna is a schematic diagram of the lubrication treatment in the present invention. 1. Cross section of the surface of a sliding part 2. Cross section of the porous coating according to the present invention 3. Cross section 4 of the lubricating coating according to the present invention. Figure 2 shows the porosity caused by Ni-Co alloy plating. Figure 11E3 is an electronic photograph of the surface of the coating, with a magnification of 10,000 times.The figure shows the hands of a kana-style analog display wristwatch after applying various lubrication treatments 1 and enduring 10 years of hand rotation. It shows the relative change in turning torque with respect to the initial value. a. Relative, -0.
''' ・], ゛・ ・ C... Parts - 厘、Two-point glue system! Watch hands with adhesive as binder and a pair of tube pinion coated with Mo B＠Ki grain powder □ Relative change in turning torque. d: Relative change in hand turning torque of a wristwatch incorporating a Dutch kana that has been treated according to Example 2 of the present invention. Figure 4 shows the same lubrication treatment as in Figure #3. The range of variation in the needle stitch torque during the needle turning durability of 10 wristwatches with cylindrical pinion applied. The graph shows the relative change in needle rotation torque from the initial value after 10 years of needle rotation durability. d. Relative change in hand rotation torque of a wristwatch. f. Relative change in hand rotation torque of a wristwatch using lubricant on the friction sliding parts of the 21 kana and 211s cars. g. MoB1 sputtered on the surface of the 2nd kana. Relative changes in the hand-turning torque of watches with coated two-ring wheels. Figure 6 shows the variation in the hand-turning torque of 10 wristwatches each with 21 kana subjected to the same lubrication treatment as in Figure 5. Indicates the range. Above is the original person Suwa Seiko Co., Ltd. Kaneshiro Junto Patent attorney Mogami Tsutomuya 1 old sword 7η2 Wainowa T--/ ↓Oda 11 Oniω Sai5r!1 Saigyuzu

Claims (1)

[Claims] The rotational torque applied to the gear passes through the first winding stem, the small iron train (this S model is sometimes omitted), and the minute hand, and the minute hand is attached.21 An analog display wristwatch O11 in which the hour hand is transmitted to the kana or cylindrical kana and the hour wheel where the hour hand is attached! In the F time adjustment mechanism (hereinafter referred to as time adjustment mechanism), the 2nd pinion and 21st gear, the platform or cylinder force, the entire surface of both or one of the parts, or one F1 car item. An ultra-fine porous film is formed on the friction and sliding parts, and an organic metal compound is added on top of it.
1. An analog display wristwatch characterized in that a film is formed by coaching and heating a treatment liquid consisting of a seed or two or more kinds, solid lubricating fine particles, and an organic solvent.