JP2018115279A - Lubrication treating agent for timepiece band, timepiece band, timepiece and method for manufacturing timepiece - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubrication treating agent for a timepiece band, which can suppress occurrence of stains even if time passes when the lubrication treating agent is used at a locked part of a clasp of the timepiece band.SOLUTION: The lubrication treating agent for a timepiece band of the present invention comprises neutral phosphate ester (A1) having a melting point of 80°C or more and/or neutral phosphite ester (A2) having a melting point of 80°C or more, and neutral phosphoric acid ester (B1) having a melting point of 10°C or less and having in a molecule two or more groups represented by general formula (b1-1) in Formula 1 below and/or neutral phosphite (B2) having a melting point of 10°C or less and having in a molecule two or more groups represented by general formula (b2-1) in Formula 1 below. In Formula 1, R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a lubricant for a watch band, a watch band, a watch, and a method for manufacturing a watch.

  As the watch band of the wristwatch, a metal middle end that is a part for connecting the 6 o'clock side band and the 12 o'clock side band is used. The middle ring has a locking portion for attaching a wrist watch to the wrist.

  Moreover, the process which makes a lubricating composition adhere with respect to the latching | locking part of the produced middle ends is performed. As a lubricating composition, for example, a lubricating composition (Patent Document 1) containing hydrocarbon and / or ether, neutral phosphate ester and / or neutral phosphite ester, and paraffin is used.

JP 2010-1333 A

  However, when the lubricating composition is attached to the latching portion of the produced middle ends, stains may occur over time.

  Accordingly, an object of the present invention is to provide a lubricant for a watch band that can suppress the occurrence of stains when used in a locking portion of a middle part of a watch band.

  The watchband lubricant according to the embodiment of the present invention includes a neutral phosphate (A1) having a melting point of 80 ° C. or higher and / or a neutral phosphite (A2) having a melting point of 80 ° C. or higher, a melting point Is 10 ° C. or lower, neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or melting point of 10 ° C. or lower, A neutral phosphite (B2) having two or more groups represented by the formula (b2-1), and the neutral phosphate (A1) and the neutral phosphite (A2) The neutral phosphate ester (B1) and the neutral phosphite ester (B2) are included in a total amount of 100 parts by mass or more and 200 parts by mass or less with respect to a total of 100 parts by mass.

  (In formulas (b1-1) and (b2-1), R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.)

  When the lubricant for a watch band according to the present invention is used for a middle end of a watch band, the occurrence of stains is suppressed.

FIG. 1 is a perspective view of a middle end. FIG. 2 is a perspective view of the middle distillate in a disassembled state.

  DESCRIPTION OF EMBODIMENTS Embodiments (embodiments) for carrying out the present invention will be described in detail with reference to the drawings. The present invention is not limited by the contents described in the following embodiments. The constituent elements described below include those that can be easily assumed by those skilled in the art and those that are substantially the same. Furthermore, the structures described below can be combined as appropriate. Various omissions, substitutions and / or modifications of the configuration can be made without departing from the scope of the present invention.

Embodiment
<Lubricant for watch band>
The watch band lubricant of the embodiment includes a neutral phosphate (A1) having a melting point of 80 ° C. or higher and / or a neutral phosphite (A2) having a melting point of 80 ° C. or higher, and a melting point of 10 ° C. or lower. A neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or a melting point of 10 ° C. or lower, and the following general formula (b2- And neutral phosphite (B2) having two or more groups represented by 1).

  In formula (b1-1) and formula (b2-1), each R independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms. The aliphatic hydrocarbon group having 10 to 16 carbon atoms may be a linear, branched, or cyclic aliphatic hydrocarbon group, or a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group having 10 to 16 carbon atoms include linear alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group (cetyl group). Groups are preferably used.

  In the watch band lubricant treatment of the embodiment, one or more neutral phosphates (A1) may be used, and one or more neutral phosphates (A2) may be used. You may use, and 1 type, or 2 or more types of neutral phosphoric acid ester (A1) and 1 type, or 2 or more types of neutral phosphorous acid ester (A2) may be mixed and used. Moreover, in the lubricant for watch bands of the embodiment, one or more neutral phosphates (B1) may be used, or one or more neutral phosphites (B2). ), Or one or more neutral phosphates (B1) and one or more neutral phosphites (B2) may be used in combination. In the present specification, the neutral phosphate ester (A1) and the neutral phosphite ester (A2) are collectively referred to as neutral (phosphite) ester (A), and neutral phosphate ester (B1 ) And neutral phosphite (B2) are also referred to as neutral (phosphite) ester (B).

  The watch band lubricant treatment of the embodiment includes a solid neutral (sub) phosphate (A) and a liquid neutral (sub) phosphate (B) at room temperature (20 ° C.). It is usually pasty.

  Since the middle ring used for a watch band of a wristwatch is usually manufactured by an ion plating method, a sputtering method, or the like, the surface of the produced middle ring is very clean. For this reason, there are cases where the frictional force is so great that the locking portion cannot be locked and released. Therefore, the wristwatch may not be attached or detached.

  Then, the process which makes a lubricating composition adhere with respect to the produced middle distill is performed. As a lubricating composition, for example, a lubricating composition containing hydrocarbons and / or ethers, neutral phosphates and / or neutral phosphites and paraffins is used. This process enables the locking portion to function.

  The locking portion is in a portion exposed on the front surface of the middle ring, that is, a portion that can be visually recognized when the timepiece is removed. In order to lubricate the locking portion, the above-mentioned lubricating composition was adhered thereto, the excess lubricating composition was wiped off, and an attempt was made to prevent the occurrence of stains. However, the adhered lubricating composition is difficult to dry sufficiently, and may flow out over time and spread around the locking portion. Further, the neutral phosphate ester and / or the neutral phosphite ester may separate and spread around the locking portion. Moreover, the said lubricating composition adhering to the metal surface becomes easy to be visually recognized by the spot shape with progress of time. Therefore, a stain may occur in the locking portion and its surroundings. In the timepiece manufacturing process, if a stain occurred, a wiping operation was performed.

  On the other hand, in the watch band lubricant treatment of the embodiment, the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) are both excellent in lubricity, and thus manufactured. When attached to the middle ends, the locking portion can function. In particular, the neutral (sub) phosphate (B) has two or more groups represented by the above formula (b1-1) in one molecule, or the above formula (b2-1) in one molecule. Since it has two or more groups represented by the formula, that is, it is bifunctional, it is more excellent in lubricity.

  Moreover, when the watch band lubricant treatment agent of the embodiment is used, it is possible to lubricate the locking portion of the middle ring for a long period of time. This is because the watch band lubricant treatment of the embodiment is usually in a paste form, and thus tends to stay at the place where it is adhered. In particular, the bifunctional neutral (sub) phosphate (B) is easily adsorbed on the metal surface, and tends to stay in the place where it is attached.

  Furthermore, when the lubricant for a watch band of the embodiment is used, it is difficult to look like a stain even if time passes. This is presumably because a stable paste was formed by using the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B). As described above, the watch band lubricant treatment agent of the embodiment is suitably used for a portion that is easily visually recognized, such as a retaining portion of a middle ring.

  The neutral (sub) phosphate (A) has a melting point of 80 ° C. or higher. When the melting point is within this range, a stable paste can be formed. That is, it is possible to prevent the components from separating and flowing out when attached to the latching portion of the middle distillate.

  Among such neutral (sub) phosphate esters (A), as the neutral phosphate ester (A1), tris (2,4-di-t-butylphenyl) phosphate, hydrogenated bisphenol A / penta An erythritol phosphate polymer is mentioned. Examples of the neutral phosphite (A2) include tris (2,4-di-tert-butylphenyl) phosphite and hydrogenated bisphenol A / pentaerythritol phosphite polymer.

  The neutral (sub) phosphate (B) has a melting point of 10 ° C. or lower. When the melting point is within this range, a stable paste can be formed together with the neutral (phosphite) phosphate (A). That is, it is possible to prevent the components from separating and flowing out when attached to the latching portion of the middle distillate.

  Among the neutral (sub) phosphate esters (B), as the neutral phosphate ester (B1), a neutral phosphate ester (b1) represented by the following general formula (b1) is preferably used. According to the neutral phosphate ester (b1), it is possible to lubricate the locking portion of the middle end for a long period of time and to suppress the occurrence of stains.

In formula (b1), R ^{b11 to} R ^b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.

  The aliphatic hydrocarbon group having 10 to 16 carbon atoms may be a linear, branched, or cyclic aliphatic hydrocarbon group, or a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group having 10 to 16 carbon atoms include linear alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group (cetyl group). Groups are preferably used.

R ^{b15 to} R ^b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

  Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec- Examples include a butyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, a neopentyl group, and an isohexyl group.

Since the neutral phosphate ester (b1) has a specific substituent in R ^{b15 to} R ^b18 , the film of the lubricant for watch band of the embodiment can be strengthened and the lubricity can be improved.

In particular, R ^b15 and R ^b17 are linear alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and R ^b16 and R ^b18 are those having 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms. When it is a branched alkyl group, the lubricity can be further improved.

R ^b191 and R ^b192 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

  Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, sec-butyl group, and isobutyl group. , T-butyl group, isopentyl group, t-pentyl group, and neopentyl group.

However, the total number of carbon atoms of R ^b191 and R ^b192 is 1 to 5. Thus, for example, when R ^b191 is a hydrogen atom, R ^b192 is a linear or branched alkyl group having 1 to 5 carbon atoms, and when R ^b191 is a methyl group, R ^b192 is 1 carbon atom. When R ^b191 is an ethyl group, R ^b192 is a linear or branched alkyl group having 2 to 3 carbon atoms.

In particular, since the film of the lubricant for a watch band of the embodiment becomes stronger, R ^b191 is a hydrogen atom, and R ^b192 is a linear or branched alkyl group having 1 to 5 carbon atoms. Is more preferable.

  Among the neutral (phosphite) esters (B), the neutral phosphite ester (B2) represented by the following general formula (b2) is preferable as the neutral phosphite ester (B2). Used for. According to the neutral phosphite ester (b2), it is possible to lubricate the locking portion of the middle end for a long period of time and to suppress the occurrence of stains.

In formula (b2), R ^{b21 to} R ^b24 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.

  The aliphatic hydrocarbon group having 10 to 16 carbon atoms may be a linear, branched, or cyclic aliphatic hydrocarbon group, or a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group having 10 to 16 carbon atoms include linear alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group (cetyl group). Groups are preferably used.

R ^b25 to R ^b28 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

  Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec- Examples include a butyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, a neopentyl group, and an isohexyl group.

Neutral phosphite (b2), since it has a specific substituent in R ^b25 to R ^b28, can membranes watchband lubricating treatment agent embodiments firmly, thereby improving the lubricity.

In particular, R ^b25 and R ^b27 are 1 to 6 carbon atoms, preferably 1 to 3 straight chain alkyl group, R ^b26 and R ^b28 are 3 to 6 carbon atoms, preferably min 3-4 When it is a branched alkyl group, the lubricity can be further improved.

R ^b291 and R ^b292 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

  Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, sec-butyl group, and isobutyl group. , T-butyl group, isopentyl group, t-pentyl group, and neopentyl group.

However, the total number of carbon atoms of R ^b291 and R ^b292 is 1 to 5. Thus, for example, when R ^b291 is a hydrogen atom, R ^b292 is a linear or branched alkyl group having 1 to 5 carbon atoms, and when R ^b291 is a methyl group, R ^b292 is 1 carbon atom. When R ^b291 is an ethyl group, R ^b292 is a linear or branched alkyl group having 2 to 3 carbon atoms.

In particular, since the film of the lubricant for watch band of the embodiment becomes stronger, R ^b291 is a hydrogen atom, and R ^b292 is a linear or branched alkyl group having 1 to 5 carbon atoms. Is more preferable.

  Since structural stability is considered to be higher when used in the watch band lubricant of the embodiment, the neutral phosphite (A2) and the neutral phosphite (B2) are more preferably used. .

  In the embodiment, the watch band lubricant treatment agent comprises neutral phosphate ester (B1) and neutral phosphate ester, with respect to 100 parts by mass of neutral phosphate ester (A1) and neutral phosphite ester (A2). It is preferable that the phosphate ester (B2) is included in an amount of 100 parts by mass or more and 200 parts by mass or less in total and 150 parts by mass or more and 170 parts by mass or less. When each component is used in this amount, a solid neutral (sub-) phosphate (A) and liquid neutral (sub-) phosphate (B) are contained in a stable state. When the neutral (phosphite) ester (A) having a melting point of 80 ° C. or higher is used in this amount, the paste state can be maintained even if it is left at a high temperature (for example, 40 ° C. or higher), and it is difficult to flow out. Also, such a watchband lubricant is easy to apply and handle. On the other hand, if the amount of the neutral (sub) phosphate (A) is too large, even if mixed with the neutral (sub) phosphate (B), the paste cannot be prepared as a tatter and applied to the locking portion. There are cases where it is not possible. Also, if the amount of the neutral (sub) phosphate (B) is too large, it may spread greatly when applied to the locking part, and the excess treatment agent may not be wiped off. Can occur.

The watch band lubricant treatment of the embodiment is usually in the form of a paste and has the following characteristics.
At 25 ° C., 0.03 g of a watch band lubricant treatment agent is applied in a circle (diameter 2 mm) on the stainless steel plate, and the stainless steel plate is set up vertically. Usually, even if it is kept vertical for 5 minutes, the applied watch band lubricant treatment agent remains in the circle. In particular, with respect to a total of 100 parts by weight of the neutral (sub) phosphate ester (A), when the total amount of the neutral (sub) phosphate ester (B) is 150 parts by weight or more and 170 parts by weight or less, Usually, even if kept vertical for 30 minutes, the applied watchband lubricant treatment agent remains in the circle. When the above characteristics are within this range, the latch portion of the middle ring can be lubricated for a long period of time by the watchband lubricant treatment of the embodiment, and the occurrence of stains can be suppressed.

  The lubricant for a watch band of the embodiment includes a neutral (sub) phosphate (A) and a neutral (sub) phosphate (B), but preferably does not include a solvent. ) Only the phosphate ester (A) and the neutral (sub) phosphate ester (B) may be contained. In this case, since the watchband lubricant treatment agent of the embodiment contains only the components necessary for lubrication, the latching portion of the middle end can be lubricated for a longer period of time, and the occurrence of stains can be further suppressed. In addition, the other component may be contained in the range which does not inhibit the effect of the lubricating agent for watch bands of embodiment. In addition, when other components are included, for example, in an amount of 3 parts by mass or less with respect to a total of 100 parts by mass of the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B). included.

  The method for preparing the lubricant for watch band of the embodiment is not particularly limited as long as a composition containing neutral (sub) phosphate (A) and neutral (sub) phosphate (B) is obtained. For example, when an agate mortar is mixed with a solid neutral (sub) phosphate (A) and a liquid neutral (sub) phosphate (B), the watch band of the embodiment that is in the form of a paste A lubricating treatment agent can be prepared. Normally, it becomes white and paste-like as it is mixed. In addition, you may mix by a 3 roll mill. In the preparation of the lubricant for the watch band, the amount ratio of the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) in the treating agent is the same as the above-mentioned band lubricant. It is desirable to be in a preferred range for the treatment agent.

<Watch bands and watches>
The watch band of the embodiment has a metal clasp. First, the structure of Nakadome will be described more specifically with reference to the drawings. FIG. 1 is a perspective view of a middle end. FIG. 2 is a perspective view of the middle distillate in a disassembled state.

  As shown in FIG. 1, the middle ring 6 is made of metal and is connected to the 6 o'clock side band 1 and the 12 o'clock side band 2. A watch body is finally connected to the 6 o'clock side band 1 and the 12 o'clock side band 2 to form a wristwatch. The middle end 6 is constituted by a middle folding member 5 and a middle end main body 6a. The middle folding member 5 includes a middle plate 3 and a frame-shaped outer plate 4 that is rotatably connected to an end portion of the middle plate 3. Engaging claws 9 are planted on the front side of the intermediate plate 3. The engaging claw 9 has an umbrella portion 9b formed at the end of the shaft portion 9a.

  As shown in FIGS. 1 and 2, the middle retaining body 6 a is composed of a middle retaining frame 16, a push button holding member 17, a slide plate 18, and push buttons 19 and 20.

  The slide plate 18 includes a plate main body 35, and an opening 36 is formed in the plate main body 35. A plurality of ratchet teeth 37 constituting engagement tooth portions are formed on both side edges of the opening 36 in the longitudinal direction of the band. In this case, the ratchet teeth 37 are formed with their locking side portions 37a facing the 12 o'clock side band 2 side. The push buttons 19, 20 have a button main body 38, and a notch 39 is formed on one side of the tip of the button main body 38. An arcuate engagement portion 40 is formed on the front side of the notch 39, and an engagement protrusion 41 is formed on the original side of the notch 39. The push buttons 19 and 20 are locked to the push button holding member 17, and the slide plate 18 is locked between the middle frame 16 and the push button holding member 17. The locking portion includes an engaging claw 9 having a shaft portion 9a and an umbrella portion 9b, and an engaging portion 40.

  Next, the mounting operation and the detaching operation (in other words, the locking operation of the locking portion and the releasing operation thereof) of the timepiece having the middle ring 6 that has undergone the lubrication process will be described. In the mounting operation, after passing the wrist through the watch, the intermediate plate 3 is folded to the outer plate 4 side, and the engaging claws 9 provided on the intermediate plate 3 are engaged with the engaging portion 40. Specifically, the shaft portion 9 a is locked to the engaging portion 40. In this way, the watch band is attached to the wrist. On the other hand, in the detaching operation, the button main body 38 of the push buttons 19 and 20 is pushed from both sides, the engaging portion 40 is pushed and widened to release the engaging claw 9, the middle plate 3 is opened outside, and the wrist is pulled out. .

  In the watch band of the embodiment, the watch band lubricant treatment agent of the embodiment is attached to the middle ring 6, specifically to the engaging portion. More specifically, the watch band lubricant treatment agent of the embodiment adheres to the engaging claw 9 having the shaft portion 9a and the umbrella portion 9b, particularly the umbrella portion 9b. Here, it can be confirmed by liquid chromatography mass spectrometry (LC / MS) that the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) are attached. In addition, the clasp which the timepiece band of the embodiment has only needs to have a locking portion, and is not limited to the clasp 6 having the above-described structure. Furthermore, the locking portion is not limited to the locking portion having the above-described structure, as long as a wrist watch can be attached to the wrist.

  The watch of the embodiment has the watch band. In such a watch band and a watch, the retaining portion of the middle ring can be lubricated for a long period of time, and the occurrence of stains can be suppressed. The watch band and the watch can be manufactured by, for example, a watch manufacturing method described later.

<Watch manufacturing method>
The watch manufacturing method according to the embodiment includes a watch band lubrication treatment process in which a watch band lubricant treatment agent is attached to the center of the watch band, and a watch for assembling a watch using the watch band treated in the lubrication treatment process. Assembly process. As a result, a watch in which the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) are attached to the middle distillate is obtained. Such a watch is excellent in the lubricity of the middle distiller and suppresses the occurrence of stains in the middle distiller.

(Lubrication process)
In the lubricating treatment step, the middle dot 6 which is usually produced by an ion plating method, a sputtering method or the like and has a very clean surface and having the above-described structure is used. This middle end 6 is in a state where the frictional force is too large and the locking portion does not function.

  In the lubricating treatment step, the above-described watch band 6 is applied to the inner ring 6 (specifically, the engaging claw 9 (particularly the umbrella portion 9b) and the engaging portion 40 having the shaft portion 9a and the umbrella portion 9b). Apply lubricant. Specifically, a watch band lubricant treatment agent is applied to the umbrella portion 9b so as to become white with a toothpick or a cotton swab. The locking operation of the locking portion and the releasing operation thereof are repeated several times to apply pressure to the umbrella portion 9b, and on the surface of the umbrella portion 9b, neutral (sub) phosphate (A) and neutral (sub) phosphate Ester (B) is attached. By repeating the locking operation and the releasing operation of the locking portion, the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) are also attached to the engaging portion 40. Next, the excessively adhered watchband lubricant is wiped off. Thus, the surface of the umbrella part 9b and the engaging part 40 can be processed, and neutral (sub) phosphate (A) and neutral (sub) are formed on the surface of the umbrella part 9b and the engaging part 40. A film of phosphate ester (B) is formed.

  Alternatively, the umbrella portion 9b coated with the watchband lubricant to such an extent that it becomes white with a toothpick or cotton swab is heated to 80 ° C. or more toward the heater. Heating is finished when the watchband lubricant becomes transparent. After reaching room temperature, wipe off any excess watch band lubricant that has become white. Next, the neutral (sub) phosphate (A) and the neutral (sub) phosphate (B) are also attached to the engaging portion 40 by repeating the locking operation and the releasing operation of the locking portion. Thus, the surface of the umbrella part 9b and the engaging part 40 can be processed, and neutral (sub) phosphate (A) and neutral (sub) are formed on the surface of the umbrella part 9b and the engaging part 40. A film of phosphate ester (B) is formed.

  By this lubrication processing step, the above-described timepiece mounting operation and detaching operation (in other words, the locking portion locking operation and the releasing operation thereof) are possible. That is, the locking portion can exhibit its function. Moreover, according to this lubrication treatment process, the generation of stains is suppressed. In the conventional lubricating composition (for example, a lubricating composition containing hydrocarbon and / or ether, neutral phosphate ester and / or neutral phosphite ester, and paraffin), the middle distillate in the lubricating composition is used. It was necessary to perform lubricating treatment by boiling 6. On the other hand, according to the watch band lubrication treatment agent of the embodiment, the lubrication treatment can be performed in a simple process, such as repetition of the engagement operation of the engagement portion and the release operation thereof, or heating toward the heater. Yes.

(Assembly process)
In the assembling process, a timepiece is assembled using the middle ring 6 processed in the lubricating process. Specifically, it can be performed by a known method using a known component.

  The middle ring used in the method for manufacturing the timepiece of the embodiment is not limited to the middle ring 6 having the above-described structure as long as it has a locking portion. Furthermore, the locking portion is not limited to the locking portion having the above-described structure, as long as a wrist watch can be attached to the wrist. Moreover, you may assemble the 6 o'clock side band 1 and the 12 o'clock side band 2 and the middle ring 6 in the assembly process after the lubrication treatment process.

  As described above, the present invention relates to the following.

  [1] Neutral phosphate ester (A1) having a melting point of 80 ° C. or higher and / or neutral phosphite ester (A2) having a melting point of 80 ° C. or higher and a melting point of 10 ° C. or less, A neutral phosphate ester (B1) having two or more groups represented by the general formula (b1-1) and / or a melting point of 10 ° C. or less, and a group represented by the following general formula (b2-1) Neutral phosphite ester (B2) having two or more, and the neutral phosphorous ester (A1) and the neutral phosphite ester (A2) with respect to 100 parts by mass in total. A lubricant for a watch band, comprising the acid ester (B1) and the neutral phosphite ester (B2) in a total amount of 100 parts by mass or more and 200 parts by mass or less.

(In formulas (b1-1) and (b2-1), R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.)

  According to the watch band lubricant treating agent described in [1] above, it is possible to improve the lubricity of the middle ring and to suppress the occurrence of stains.

[2] The neutral phosphate ester (B1) is represented by the following general formula (b1), and the neutral phosphite ester (B2) is represented by the following general formula (b2). The watch band lubricant treatment according to [1].

(In the formula (b1), R ^b11 ~R ^b14 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b15 to R ^b18 are each independently, 1 to 6 carbon atoms R ^b191 and R ^b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^b192 The total number of carbon atoms in ^b192 is 1-5.)

(In the formula (b2), R ^b21 ~R ^b24 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b25 to R ^b28 are each independently, 1 to 6 carbon atoms R ^b291 and R ^b292 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^b291 and R ^b292 The total number of carbon atoms of ^b292 is 1 to 5.)

  Since the watchband lubricant treating agent according to the above [2] is superior in stability, it can further improve the lubricity of the middle distillate and further suppress the occurrence of stains.

[3] The neutral phosphate ester (B1) and the neutral phosphite ester (B) and the neutral phosphite ester (A2) and the neutral phosphite ester (A2) in a total of 100 parts by mass. The lubricant for watch bands according to [1] or [2], wherein B2) is contained in a total amount of 150 parts by mass or more and 170 parts by mass or less.

  Since the lubricant for watch bands described in [3] above is further excellent in stability, it can further improve the lubricity of the middle end and further suppress the occurrence of stains.

[4] In the formula (b1), R ^b15 and R ^b17 are each independently a linear alkyl group having 1 to 6 carbon atoms, and R ^b16 and R ^b18 are each independently 3 carbon atoms. A branched alkyl group having ^˜6 , R ^b191 is a hydrogen atom, and R ^b192 is a linear or branched alkyl group having 1 to 5 carbon atoms, in the formula (b2) , R ^b25 and R ^b27 are each independently a straight chain alkyl group having 1 to 6 carbon atoms, R ^b26 and R ^b28 are each independently a branched alkyl group having 3 to 6 carbon atoms The clock according to [2] or [3], wherein R ^b291 is a hydrogen atom, and R ^b292 is a linear or branched alkyl group having 1 to 5 carbon atoms. Lubricant for bands.

  According to the watch band lubricant treating agent according to the above [4], since a strong lubricating film can be formed, the lubricity of the middle end can be further improved.

[5] A watch band having a middle ring, wherein the watch band lubricant treatment agent according to any one of [1] to [4] is adhered to the middle ring.

[6] A timepiece having the timepiece band according to [5].

  The watch band described in the above [5] and the watch described in the above [6] are excellent in the lubricity of the middle ends and suppress the occurrence of stains.

[7] A watchband lubrication process for attaching a watchband lubricant to the center of the watchband, and a watch assembly process for assembling a watch using the watchband processed in the lubrication process. The watchband lubricant is a neutral phosphate ester (A1) having a melting point of 80 ° C. or higher and / or a neutral phosphite ester (A2) having a melting point of 80 ° C. or higher, and a melting point of 10 ° C. or lower. Yes, neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or melting point is 10 ° C. or lower, and the following general formula (b2-1) ) And a neutral phosphite ester (B2) having two or more groups represented by the formula (1), and a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). In contrast, the neutral phosphate ester Ether (B1) and a manufacturing method of the watch, which comprises the neutral phosphite (B2) in an amount of up to 200 parts by weight 100 parts by mass or more in total.

(In formulas (b1-1) and (b2-1), R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.)

  According to the method for manufacturing a timepiece described in [7], a timepiece having excellent middle-lubricating lubricity and suppressing the occurrence of stains can be obtained.

[8] The neutral phosphate ester (B1) is represented by the following general formula (b1), and the neutral phosphite ester (B2) is represented by the following general formula (b2). The method for manufacturing a timepiece according to [7].

(In the formula (b1), R ^b11 ~R ^b14 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b15 to R ^b18 are each independently, 1 to 6 carbon atoms R ^b191 and R ^b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^b192 The total number of carbon atoms in ^b192 is 1-5.)

(In the formula (b2), R ^b21 ~R ^b24 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b25 to R ^b28 are each independently, 1 to 6 carbon atoms R ^b291 and R ^b292 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^b291 and R ^b292 The total number of carbon atoms of ^b292 is 1 to 5.)

  According to the method for manufacturing a timepiece described in [8] above, it is possible to obtain a timepiece that is more excellent in the lubricity of the middle distiller and in which the occurrence of stains is further suppressed.

[Example]
[Example 1-1]
As neutral phosphate ester (A1), 100 parts by mass of tris (2,4-di-t-butylphenyl) phosphate (melting point: 181 to 184 ° C.) and neutral phosphate ester (B1) (neutral phosphorus as esters (b1)), 4,4'-butylidene bis (3-methyl -6-t-butylphenyl ditridecyl phosphate) (R ^b11 ~R ^b14 = tridecyl radical, R ^b15, R ^b17 = methyl radical, R 150 parts by mass of ^b16 , ^Rb18 = t-butyl group, ^Rb191 = hydrogen atom, ^Rb192 = n-propyl group (melting point: 10 ° C. or less) are put in an agate mortar and mixed to obtain a paste-like watch band A lubricating treatment agent was obtained.

[Example 1-2]
Other than using 100 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-3]
Other than using 130 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-4]
Other than using 170 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-5]
Other than using 200 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-6]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral hypophosphorus As acid ester (B2) (neutral phosphite ester (b2)), 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) (R ^{b21 to} R ^b24 = tridecyl group, R ^b25, R ^b27 = methyl, R ^b26, R ^b28 = t- butyl ^group, R b291 = hydrogen atom, R ^B292 = n-propyl) (mp 10 ° C. or below) except for using the example 1 In the same manner as in No. 1, a pasty lubricant for a watch band was obtained.

[Example 1-7]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 100 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-6.

[Example 1-8]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 130 parts by mass of 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-6.

[Example 1-9]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 170 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-6.

[Example 1-10]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 200 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-6.

[Example 1-11]
As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) instead of 150 parts by mass, As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate), and neutral Other than using 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) as phosphite (B2) (neutral phosphite (b2)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-12]
As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) instead of 150 parts by mass, As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 85 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate), and neutral Other than using 85 parts by mass of 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphite) as phosphite (B2) (neutral phosphite (b2)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-13]
As neutral phosphate ester (A1), 100 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphate polymer (melting point: about 202 ° C.) and neutral phosphate ester (B1) (neutral phosphate ester (b1)) 150 parts by mass of 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) in an agate mortar and mixed to obtain a paste-like lubricant for watch bands It was.

[Example 1-14]
Other than using 100 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-13, a pasty watch band lubricant treatment agent was obtained.

[Example 1-15]
Other than using 130 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-13, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-16]
Other than using 170 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-13, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-17]
Other than using 200 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-13, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-18]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral hypophosphorus Example 1 except that 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used as the acid ester (B2) (neutral phosphite (b2)). In the same manner as in No. 13, a pasty lubricant for a watch band was obtained.

[Example 1-19]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 100 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-18.

[Example 1-20]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 130 parts by mass of 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-18.

[Example 1-21]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 170 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-18.

[Example 1-22]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), 200 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used. Otherwise, a paste-like lubricant for watch band was obtained in the same manner as in Example 1-18.

[Example 1-23]
As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) instead of 150 parts by mass, As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate), and neutral Other than using 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) as phosphite (B2) (neutral phosphite (b2)) In the same manner as in Example 1-13, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-24]
As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) instead of 150 parts by mass, As neutral phosphate ester (B1) (neutral phosphate ester (b1)), 85 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate), and neutral Other than using 85 parts by mass of 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphite) as phosphite (B2) (neutral phosphite (b2)) In the same manner as in Example 1-13, a paste-like watch band lubricant treatment agent was obtained.

[Example 1-25]
Instead of 100 parts by mass of tris (2,4-di-t-butylphenyl) phosphate as neutral phosphate (A1), tris (2,4-di- -T-Butylphenyl) phosphate and watch band lubrication in the same manner as in Example 1-1 except that 50 parts by mass of hydrogenated bisphenol A.pentaerythritol phosphate polymer was used. A treating agent was obtained.

[Example 1-26]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral hypophosphorus Example 1 except that 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used as the acid ester (B2) (neutral phosphite (b2)). In the same manner as in No. 25, a pasty lubricant for watch band was obtained.

[Example 1-27]
Instead of 100 parts by mass of tris (2,4-di-t-butylphenyl) phosphate as neutral phosphate (A1), tris (2,4-di- -T-butylphenyl) phosphate is used in an amount of 50 parts by mass, and hydrogenated bisphenol A-pentaerythritol phosphate polymer is used in an amount of 50 parts by mass; as neutral phosphate ester (B1) (neutral phosphate ester (b1)), Instead of 150 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) and neutral phosphite Example 4 except that 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used as ter (B2) (neutral phosphite (b2)) A paste-like lubricant for a watch band was obtained in the same manner as in 1-1.

[Example 1-28]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = decyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1 except that 10 ° C. or lower) was used.

[Example 1-29]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = hexadecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1 except that 10 ° C. or lower) was used.

[Example 1-30]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = n- propyl group, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) A paste-like lubricant for watch band was obtained in the same manner as in Example 1-1 except that (melting point: 10 ° C. or lower) was used.

[Example 1-31]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = isopropyl, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp 10 ° C. Except for the following, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-32]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- pentyl) (mp A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1 except that 10 ° C. or lower) was used.

[Example 1-33]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = ^ethyl, R b192 = n- propyl group) (mp A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1 except that 10 ° C. or lower) was used.

[Example 1-34]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = decyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 1-6 to obtain a pasty watchband lubricant.

[Example 1-35]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = hexadecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 1-6 to obtain a pasty watchband lubricant.

[Example 1-36]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = n- propyl group, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- A paste-like lubricant for watch band was obtained in the same manner as in Example 1-6 except that (propyl group) (melting point: 10 ° C. or less) was used.

[Example 1-37]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = isopropyl, R ^B191 = hydrogen ^atom, R b192 = n- propyl) ( A pasty watchband lubricant was obtained in the same manner as in Example 1-6 except that the melting point was 10 ° C. or lower.

[Example 1-38]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- pentyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 1-6 to obtain a pasty watchband lubricant.

[Example 1-39]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = ^ethyl, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 1-6 to obtain a pasty watchband lubricant.

[Examples 2-1 to 2-12]
In Examples 2-1 to 2-12, as neutral phosphate ester (A1), instead of tris (2,4-di-t-butylphenyl) phosphate, neutral phosphate ester (A2) And tris (2,4-di-t-butylphenyl) phosphite (melting point 185 ° C.) in the same manner as in Examples 1-1 to 1-12, respectively, An agent was obtained.

[Examples 2-13 to 2-24]
In Examples 2-13 to 2-24, as the neutral phosphate ester (A1), hydrogenated bisphenol A was used as the neutral phosphite ester (A2) instead of hydrogenated bisphenol A / pentaerythritol phosphate polymer. Except for using pentaerythritol phosphite polymer (melting point: 202 ° C.), a paste-like lubricant for watch band was obtained in the same manner as in Examples 1-13-1-24.

[Example 2-25]
As neutral phosphite ester (A2), tris (2,4-di-t-butylphenyl) phosphite was used as neutral phosphite ester (A2) instead of 100 parts by mass as tris (2,4 -Di-t-butylphenyl) phosphite and 50 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphite polymer in the same manner as in Example 2-1, except that a paste-like watch band was used. A lubricating treatment agent was obtained.

[Example 2-26]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral hypophosphorus Example 4 except that 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used as the acid ester (B2) (neutral phosphite (b2)) In the same manner as in No. 25, a pasty lubricant for watch band was obtained.

[Example 2-27]
As neutral phosphite ester (A2), tris (2,4-di-t-butylphenyl) phosphite was used as neutral phosphite ester (A2) instead of 100 parts by mass as tris (2,4 -Di-t-butylphenyl) phosphite and 50 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphite polymer; neutral phosphate ester (B1) (neutral phosphate ester (b1)) As a substitute for 150 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate), neutral phosphate ester (B1) (neutral phosphate ester (b1)) 4,4'-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral parts, and Example 75 except that 75 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite) was used as ester (B2) (neutral phosphite (b2)) In the same manner as in 2-1, a pasty watch band lubricant treatment agent was obtained.

[Example 2-28]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = decyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp Except for using 10 ° C. or lower), a paste-like lubricant for watch band was obtained in the same manner as in Example 2-1.

[Example 2-29]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = hexadecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp Except for using 10 ° C. or lower), a paste-like lubricant for watch band was obtained in the same manner as in Example 2-1.

[Example 2-30]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = n- propyl group, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) A pasty watchband lubricant was obtained in the same manner as in Example 2-1, except that the melting point was 10 ° C. or lower.

[Example 2-31]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = isopropyl, R ^B191 = hydrogen ^atom, R b192 = n- propyl group) (mp 10 ° C. Except for the following, a pasty lubricant for watch band was obtained in the same manner as in Example 2-1.

[Example 2-32]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- pentyl) (mp Except for using 10 ° C. or lower), a paste-like lubricant for watch band was obtained in the same manner as in Example 2-1.

[Example 2-33]
In place of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as neutral phosphate ester (B1) (neutral phosphate ester (b1)), neutral phosphate ester ^{(b1) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = ^ethyl, R b192 = n- propyl group) (mp Except for using 10 ° C. or lower), a paste-like lubricant for watch band was obtained in the same manner as in Example 2-1.

[Example 2-34]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = decyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 2-6 to obtain a paste watchband lubricant.

[Example 2-35]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = hexadecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 2-6 to obtain a paste watchband lubricant.

[Example 2-36]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = n- propyl group, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- Except for using (propyl group) (melting point: 10 ° C. or lower), a paste-like lubricant for watch band was obtained in the same manner as in Example 2-6.

[Example 2-37]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = isopropyl, R ^B191 = hydrogen ^atom, R b192 = n- propyl) ( A pasty watchband lubricant was obtained in the same manner as in Example 2-6 except that the melting point was 10 ° C. or lower.

[Example 2-38]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = hydrogen ^atom, R b192 = n- pentyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 2-6 to obtain a paste watchband lubricant.

[Example 2-39]
As neutral phosphite ester (B2) (neutral phosphite ester (b2)), instead of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphite), neutral phosphite ^{(b2) (R b11 ~R b14} = tridecyl, R ^b15, R ^b17 = methyl, R ^b16, R ^b18 = t- butyl group, R ^B191 = ^ethyl, R b192 = n- propyl ) (Melting point: 10 ° C. or lower) was used in the same manner as in Example 2-6 to obtain a paste watchband lubricant.

[Comparative Example 1]
Example 1-1 except that tristearyl phosphite (melting point: 42 ° C.) was used as the neutral phosphate ester (A1) instead of tris (2,4-di-t-butylphenyl) phosphate. Similarly, a paste-like watch band lubricant treatment agent was obtained.

[Comparative Example 2]
Other than using 250 parts by mass of 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) In the same manner as in Example 1-1, a paste-like watch band lubricant treatment agent was obtained.

<Evaluation method and evaluation results>
Using the prepared watchband lubrication treatment agent, the locking portion of the middle ring 6 shown in FIGS. 1 and 2 was treated (lubrication treatment step). The middle ring 6 was still manufactured, and the locking portion was not functioning. Specifically, a watchband lubricant was applied to the umbrella portion 9b so as to become white with a cotton swab. The locking operation of the locking portion and the releasing operation thereof are repeated several times to apply pressure to the umbrella portion 9b, and on the surface of the umbrella portion 9b, neutral (sub) phosphate (A) and neutral (sub) phosphate Ester (B) was attached. The neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B) were also attached to the engaging portion 40 by repeating the locking operation and the releasing operation of the locking portion. Subsequently, the excessively attached lubricant for the watch band was wiped off. Thus, the surface of the umbrella part 9b and the engaging part 40 was processed. By this process, the locking part came to function. In addition, after the said process, in the latching | locking part using the lubricating agent for watch bands of an Example, all did not have a stain.

For the middle 6 subjected to the lubrication treatment step, the locking operation of the locking portion and the releasing operation thereof were repeated 1000 times (locking / release operation repeated test). The lubricity of the locking portion after the locking / release operation repeated test, that is, whether the locking / release operation can be performed smoothly was investigated. Moreover, it was investigated whether the latching | locking part had generate | occur | produced. The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 4.
Lubricity A: The lock / release operation can be performed smoothly B: The occurrence of the stain where the lock / release operation cannot be performed smoothly A: The stain was not generated
B: Blemish occurred

In addition, a heating test was conducted for 1 hour at a temperature of 80 ° C. on the middle distillate 6 that had undergone the lubricating treatment step. The lubricity of the locking part after the heating test, that is, whether the locking / releasing operation can be performed smoothly was investigated. Moreover, it was investigated whether the latching | locking part had generate | occur | produced. The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 4.
Lubricity A: The lock / release operation can be performed smoothly B: The occurrence of the stain where the lock / release operation cannot be performed smoothly A: The stain was not generated
B: Blemish occurred

  Further, the following characteristics of the lubricant for watch bands of the example were examined. At 25 ° C., 0.03 g of a watchband lubricant was applied in a circle (diameter 2 mm) on the stainless steel plate, and the stainless steel plate was set up vertically. It was observed whether the applied watch band lubricant was changed when held vertically for 5 minutes and 30 minutes.

  A watch including neutral (sub) phosphate (B) in a total amount of 100, 130 and 200 parts by mass with respect to a total of 100 parts by mass of neutral (sub) phosphate (A). As for the band lubricant, the applied watch band lubricant remained in the circle after being held for 5 minutes. However, after holding for 30 minutes, the applied lubricant for watchband spread out of the circle. On the other hand, a watch band including neutral (sub) phosphate (B) in a total amount of 150 parts by mass and 170 parts by mass with respect to a total of 100 parts by mass of neutral (sub) phosphate (A). As for the lubricant for a watch, the applied lubricant for a watch band remained in the circle both after being held for 5 minutes and after being held for 30 minutes.

DESCRIPTION OF SYMBOLS 1 6 o'clock side band 2 12 o'clock side band 3 Middle plate 4 Outer plate 5 Middle folding member 6 Middle retainer 6a Middle retainer main body 9 Engaging claw 9a Shaft portion 9b Umbrella portion 16 Middle retainer frame 17 Push button holding member 18 Slide plate 19 , 20 Push button 35 Plate body 36 Opening portion 37 Ratchet teeth 37a Locking side portion 38 Button body 39 Notch portion 40 Engagement portion 41 Engagement protrusion

Claims (8)

A neutral phosphate (A1) having a melting point of 80 ° C. or higher and / or a neutral phosphite (A2) having a melting point of 80 ° C. or higher;
Melting point is 10 ° C. or less, neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or melting point is 10 ° C. or less, A neutral phosphite (B2) having two or more groups represented by the general formula (b2-1),
The neutral phosphate ester (B1) and the neutral phosphite ester (B2) are added to 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). A lubricant for watch bands, comprising a total amount of 100 parts by mass or more and 200 parts by mass or less.

(In formulas (b1-1) and (b2-1), R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.) The neutral phosphate ester (B1) is represented by the following general formula (b1), and the neutral phosphite ester (B2) is represented by the following general formula (b2). 2. A lubricant for a watch band according to 1.

(In the formula (b1), R ^b11 ~R ^b14 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b15 to R ^b18 are each independently, 1 to 6 carbon atoms R ^b191 and R ^b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^b192 The total number of carbon atoms in ^b192 is 1-5.)

(In the formula (b2), R ^b21 ~R ^b24 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b25 to R ^b28 are each independently, 1 to 6 carbon atoms R ^b291 and R ^b292 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^b291 and R ^b292 The total number of carbon atoms of ^b292 is 1 to 5.)   The neutral phosphate ester (B1) and the neutral phosphite ester (B2) are added to 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). 3. The watch band lubricant treatment agent according to claim 1, comprising a total amount of 150 parts by mass or more and 170 parts by mass or less. In the formula (b1), R ^b15 and R ^b17 are each independently a linear alkyl group having 1 to 6 carbon atoms, and R ^b16 and R ^b18 are each independently having 3 to 6 carbon atoms. A branched alkyl group, R ^b191 is a hydrogen atom, and R ^b192 is a linear or branched alkyl group having 1 to 5 carbon atoms;
In the formula (b2), R ^b25 and R ^b27 are each independently a linear alkyl group having 1 to 6 carbon atoms, R ^b26 and R ^b28 are each independently a 3-6 carbon atoms The branched alkyl group, R ^b291 is a hydrogen atom, and R ^b292 is a linear or branched alkyl group having 1 to 5 carbon atoms. Lubricant for watch band as described in 1.   A watch band having a center ring, wherein the watch band lubricant treatment agent according to any one of claims 1 to 4 is attached to the center ring.   A timepiece having the timepiece band according to claim 5. A watch band lubrication process in which a watch band lubricant treatment agent is attached to the watch band middle ring,
A watch assembling step for assembling a watch using the watch band treated in the lubrication treatment step,
The watchband lubricant is a neutral phosphate ester (A1) having a melting point of 80 ° C. or higher and / or a neutral phosphite ester (A2) having a melting point of 80 ° C. or higher,
Melting point is 10 ° C. or less, neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or melting point is 10 ° C. or less, A neutral phosphite (B2) having two or more groups represented by the general formula (b2-1),
The neutral phosphate ester (B1) and the neutral phosphite ester (B2) are added to 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). A method for manufacturing a timepiece, comprising a total amount of 100 parts by mass or more and 200 parts by mass or less.

(In formulas (b1-1) and (b2-1), R each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.) The neutral phosphate ester (B1) is represented by the following general formula (b1), and the neutral phosphite ester (B2) is represented by the following general formula (b2). A method for manufacturing the timepiece according to claim 7.

(In the formula (b1), R ^b11 ~R ^b14 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b15 to R ^b18 are each independently, 1 to 6 carbon atoms R ^b191 and R ^b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^b192 The total number of carbon atoms in ^b192 is 1-5.)

(In the formula (b2), R ^b21 ~R ^b24 each independently represents an aliphatic hydrocarbon group having a carbon number of 10 to 16, R ^b25 to R ^b28 are each independently, 1 to 6 carbon atoms R ^b291 and R ^b292 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^b291 and R ^b292 The total number of carbon atoms of ^b292 is 1 to 5.)

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