JP6779142B2 - Lubricating agents for watch bands, watch bands, watches and how to manufacture watches - Google Patents

Description

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

A metal clasp, which is a component connecting the 6 o'clock side band and the 12 o'clock side band, is used for the watch band of the wristwatch. This Nakadome has a locking portion for wearing a wristwatch on the wrist.

Further, a treatment is performed in which the lubricating composition is adhered to the locking portion of the manufactured middle distillate. As the lubricating composition, for example, a lubricating composition containing a hydrocarbon and / or ether, a neutral phosphate ester and / or a neutral phosphite ester, and paraffin is used (Patent Document 1).

Japanese Unexamined Patent Publication No. 2010-1333

However, when the lubricating composition is adhered to the locking portion of the manufactured intermediate distillate, stains may occur over time.

Therefore, an object of the present invention is to provide a lubricating agent for a watch band, which suppresses the occurrence of stains when used for a locking portion of a clasp of a watch band.

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

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

When the lubricating agent for a watch band of the present invention is used for retaining the watch band, the generation of stains is suppressed.

FIG. 1 is a perspective view of Nakadome. FIG. 2 is a perspective view of the disassembled state of Nakadome.

An embodiment (embodiment) for carrying out the present invention will be described in detail with reference to the drawings. The present invention is not limited to the contents described in the following embodiments. In addition, the components described below include those that can be easily assumed by those skilled in the art and those that are substantially the same. Further, the configurations described below can be combined as appropriate. In addition, various omissions, substitutions and / or changes of the configuration can be made without departing from the gist of the present invention.

[Embodiment]
<Lubricating agent for watch bands>
The watch band lubricant of the embodiment includes 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. A neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or having a melting point of 10 ° C. or less and the following general formula (b2-). Includes a neutral phosphite (B2) having two or more groups represented by 1).

In formulas (b1-1) and (b2-1), 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 may be 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). The group is preferably used.

In the watch band lubricant of the embodiment, one or more neutral phosphate esters (A1) may be used, and one or more neutral phosphite esters (A2) may be used. It may be used, and one or more neutral phosphate esters (A1) and one or more neutral phosphite esters (A2) may be mixed and used. Further, in the lubricant for the watch band of the embodiment, one or more kinds of neutral phosphate esters (B1) may be used, and one or more kinds of neutral phosphite esters (B2) may be used. ) May be used, or one or more neutral phosphate esters (B1) and one or more neutral phosphite esters (B2) may be mixed and used. In the present specification, the neutral phosphate ester (A1) and the neutral phosphite ester (A2) are collectively referred to as a neutral (phasphite) phosphate ester (A), and a neutral phosphate ester (B1). ) And the neutral phosphite ester (B2) are also referred to as a neutral (phasphite) ester (B).

The watch band lubricant of the embodiment contains a solid neutral (phasphite) ester (A) and a liquid neutral (phasphite) ester (B) at room temperature (20 ° C.). It is usually in the form of a paste.

Since the clasp used for the watch band of a wristwatch is usually manufactured by an ion plating method, a sputtering method, or the like, the surface of the manufactured clasp is very clean. Therefore, the frictional force may be too large to lock and release the locking portion. Therefore, it may not be possible to put on or take off the watch.

Therefore, a treatment is performed in which the lubricating composition is adhered to the produced medium distillate. As the lubricating composition, for example, a lubricating composition containing a hydrocarbon and / or ether, a neutral phosphate ester and / or a neutral phosphite ester, and paraffin is used. This process allows the locking portion to function.

The locking portion is in a portion exposed on the surface of the clasp, that is, a portion that can be visually recognized when the watch is removed. In order to lubricate the locking portion, the above-mentioned lubricating composition was adhered to the locking portion, and excess lubricating composition was wiped off to prevent the generation of stains. However, the adhered lubricating composition is difficult to dry sufficiently, and may flow out over time and spread around the locking portion. In addition, the neutral phosphate ester and / or the neutral phosphite ester may separate and spread around the locking portion. In addition, the lubricating composition adhering to the metal surface becomes easily visible as a stain over time. Therefore, stains may occur in and around the locking portion. Even in the manufacturing process of watches, when stains occur, wiping work is performed.

On the other hand, in the lubrication agent for the watch band of the embodiment, the neutral (phasphite) phosphate ester (A) and the neutral (phasphite) phosphate ester (B) are both excellent in lubricity and are therefore produced. When attached to the clasp, the locking portion can function. In particular, the neutral (sub) phosphate ester (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, that is, it is bifunctional, it is more excellent in lubricity.

Further, by using the watch band lubrication agent of the embodiment, the locking portion of the clasp can be lubricated for a long period of time. This is because the watch band lubricant of the embodiment is usually in the form of a paste, so that it easily stays in the place where it is attached. In particular, the bifunctional neutral (sub) phosphate ester (B) is easily adsorbed on the metal surface and easily stays at the place where it is attached.

Further, when the watch band lubricating agent of the embodiment is used, it is difficult to look like a stain over time. It is considered that this is because a stable paste is formed by using the neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B). As described above, the lubrication agent for the watch band of the embodiment is preferably used for a portion that is easily visible, such as a locking portion of a clasp.

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

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

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

Among the above-mentioned neutral (sub) phosphoric acid esters (B), as the neutral phosphoric acid ester (B1), the neutral phosphoric acid ester (b1) represented by the following general formula (b1) is preferably used. According to the neutral phosphoric acid ester (b1), the locking portion of the intermediate distillate can be lubricated for a long period of time, and the generation of stains can be suppressed.

In the formula (b1), R ^{b11 to} R ^b14 independently represent 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 may be 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). The group is preferably used.

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

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

Since the neutral phosphate ester (b1) has a specific substituent on R ^{b15 to} R ^b18 , the film of the watch band lubricant according to 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, and R ^b16 and R ^b18 have 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.

Linear or branched alkyl groups 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, neopentyl group and the like.

However, the total number of carbon atoms of R ^b191 and R ^b192 is 1 to 5. Therefore, 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 has 1 carbon atom. ~ 4 is a linear or branched alkyl group, and when R ^b191 is an ethyl group, R ^b192 is a linear or branched alkyl group having 2 to 3 carbon atoms.

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

Further, among the above-mentioned neutral (sub) phosphate esters (B), as the neutral phosphite ester (B2), the neutral phosphite ester (b2) represented by the following general formula (b2) is preferable. Used for. According to the neutral phosphite ester (b2), the locking portion of the intermediate distillate can be lubricated for a long period of time, and the generation of stains can be suppressed.

In formula (b2), R ^{b21 to} R ^b24 each independently represent 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 may be 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). The group is preferably used.

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

As linear or branched alkyl groups having 1 to 6 carbon atoms, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec- Examples thereof include butyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, neopentyl group and 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 independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

Linear or branched alkyl groups 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, neopentyl group and the like.

However, the total number of carbon atoms of R ^b291 and R ^b292 is 1 to 5. Therefore, 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 has 1 carbon atom. ~ 4 is a linear or branched alkyl group, and 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 the 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.

Neutral phosphite ester (A2) and neutral phosphite ester (B2) are more preferably used because they are considered to have higher structural stability when used in the watch band lubricant of the embodiment. ..

In the watch band lubricant of the embodiment, the neutral phosphate ester (B1) and the neutral phosphite ester (B1) and the neutral phosphite ester (B1) are added to a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). It is preferable that the phosphoric acid ester (B2) is contained in a total amount of 100 parts by mass or more and 200 parts by mass or less, and 150 parts by mass or more and 170 parts by mass or less. When each component is used in this amount, a paste containing a solid neutral (sub) phosphate ester (A) and a liquid neutral (sub) phosphate ester (B) in a stable state is obtained. When a neutral (phasphite) 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 for it to flow out. Further, such a lubricant for a watch band is easy to apply and easy to handle. On the other hand, if the amount of the neutral (sub) phosphate ester (A) is too large, the paste cannot be prepared even if it is mixed with the neutral (sub) phosphate ester (B), and it is applied to the locking portion. It may not be possible. In addition, if the amount of neutral (sub) phosphate ester (B) is too large, it may spread widely when applied to the locking portion, and excess treatment agent may not be wiped off, resulting in stains on the locking portion later. Can occur.

The watch band lubricator of the embodiment is usually in the form of a paste and has the following characteristics.
At 25 ° C., a 0.03 g amount of a watch band lubricant is applied to a circle (diameter 2 mm) on a stainless steel plate, and the stainless steel plate is erected vertically. Normally, even if the watch band is held vertically for 5 minutes, the applied watch band lubricant remains in the circle. In particular, when the neutral (phasphite) ester (B) is contained in a total amount of 150 parts by mass or more and 170 parts by mass or less with respect to a total of 100 parts by mass of the neutral (sub) phosphate ester (A), Normally, even if the watch band is held vertically for 30 minutes, the applied watch band lubricant stays in the circle. When the above characteristics are in this range, the locking portion of the clasp can be lubricated for a long period of time by the watch band lubricating agent of the embodiment, and the occurrence of stains can be suppressed.

The watch band lubricant of the embodiment contains a neutral (spha) phosphate ester (A) and a neutral (suba) phosphate ester (B), but preferably contains no solvent and is neutral (suba). ) Phosphite ester (A) and neutral (sub) phosphate ester (B) may be contained only. In this case, since the watch band lubrication agent of the embodiment contains only the components necessary for lubrication, the locking portion of the clasp can be lubricated for a longer period of time, and the occurrence of stains can be further suppressed. In addition, other components may be contained as long as the effect of the watch band lubrication agent of the embodiment is not impaired. When other components are contained, 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 ester (A) and the neutral (sub) phosphate ester (B). included.

The method for preparing the lubricating agent for the watch band of the embodiment is not particularly limited as long as a composition containing a neutral (sub) phosphoric acid ester (A) and a neutral (sub) phosphate ester (B) can be obtained. For example, a watch band of an embodiment in which a solid neutral (phasphite) ester (A) and a liquid neutral (phasphite) ester (B) are mixed in an agate mortar to form a paste. Lubricating agent can be prepared. It usually becomes whiter and paste-like as it is mixed. In addition, you may mix by 3 roll mills and the like. In the preparation of the watch band lubricant treatment agent, the amount ratio of the neutral (phasphite) phosphate ester (A) and the neutral (sub) phosphate ester (B) in the treatment agent is the band lubrication described above. It is desirable to make it within a preferable range in the treatment agent.

<Watch band and watch>
The watch band of the embodiment has a metal clasp. First, the structure of Nakadome will be described more concretely with reference to figures. FIG. 1 is a perspective view of Nakadome. FIG. 2 is a perspective view of the disassembled state of Nakadome.

As shown in FIG. 1, the clasp 6 is made of metal and is connected to the 6 o'clock side band 1 and the 12 o'clock side band 2. The 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 center retainer 6 is composed of a center folding member 5 and a center retainer main body 6a. The center-folding member 5 is composed of a middle plate 3 and a frame-shaped outer plate 4 rotatably connected to an end portion of the middle plate 3. Engagement claws 9 are planted on the front side of the middle 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 retaining body 6a is composed of a retaining frame 16, a push button holding member 17, a slide plate 18, and push buttons 19 and 20.

Further, the slide plate 18 includes a plate body 35, and an opening 36 is formed in the plate body 35. A plurality of ratchet teeth 37 forming an engaging tooth portion are formed on both side edges of the opening 36 in the longitudinal direction of the band. In this case, the ratchet tooth 37 is formed with its locking side portion 37a facing the 12 o'clock side band 2 side. The push buttons 19 and 20 have a button body 38, and a notch 39 is formed on one side of the tip of the button body 38. An arc-shaped engaging portion 40 is formed on the tip side of the notch portion 39, and an engaging protrusion 41 is formed on the original side of the notch portion 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 retaining frame 16 and the push button holding member 17. The locking portion is composed of an engaging claw 9 having a shaft portion 9a and an umbrella portion 9b, and an engaging portion 40.

Next, a mounting operation and a removing operation (in other words, a locking operation of the locking portion and an unlocking operation thereof) of the clock having the clasp 6 that has undergone the lubrication treatment step will be described. In the mounting operation, after passing the wrist through the watch, the middle plate 3 is folded toward the outer plate 4, and the engaging claw 9 provided on the middle plate 3 is engaged with the engaging portion 40. Specifically, the shaft portion 9a is locked to the engaging portion 40. In this way, the watch band is worn on the wrist. On the other hand, in the removal operation, the button bodies 38 of the push buttons 19 and 20 are pushed from both sides, the engaging portion 40 is expanded to disengage the engaging claws 9, the middle plate 3 is opened outward, and the wrist is pulled out. ..

In the watch band of the embodiment, the lubrication agent for the watch band of the embodiment is attached to the clasp 6, specifically, to the locking portion. More specifically, the lubricating agent for the watch band of the embodiment is attached 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) or the like that the neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B) are attached. The watch band of the embodiment may have a locking portion, and is not limited to the middle clasp 6 having the above-mentioned structure. Further, the locking portion is not limited to the locking portion having the above-mentioned structure, as long as the wristwatch can be worn on the wrist.

Further, the watch of the embodiment has the above-mentioned watch band. In such a watch band and a watch, the locking portion of the clasp 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, the method for manufacturing a watch described later.

<Watch manufacturing method>
The method for manufacturing a watch according to the embodiment is a watch band lubrication step of adhering a watch band lubrication agent to the clasp of the watch band, and a watch assembling the watch using the watch band treated in the above lubrication step. Including the assembly process of. As a result, a clock in which the neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B) are attached to the middle distillate can be obtained. Such a watch has excellent lubricity of the clasp, and the occurrence of stains on the clasp is suppressed.

(Lubrication process)
In the lubrication treatment step, a clasp 6 which is usually manufactured by an ion plating method, a sputtering method or the like and has a very clean surface and has the above-mentioned structure is used. The clasp 6 is in a state where the frictional force is too large and the locking portion is not functioning.

In the lubrication treatment step, the clasp 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) is attached to the above-mentioned clock band. Apply a lubricant. Specifically, the umbrella portion 9b is coated with a lubricant for a watch band to the extent that it becomes white with a toothpick or a cotton swab. The locking operation and the unlocking operation of the locking portion are repeated several times to apply pressure to the umbrella portion 9b, and the neutral (phasphite) ester (A) and the neutral (sub) phosphoric acid are applied to the surface of the umbrella portion 9b. The ester (B) is attached. By repeating the locking operation and the releasing operation of the locking portion, the neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B) are also attached to the engaging portion 40. Then, the excess adhesive for the watch band is wiped off. In this way, the surfaces of the umbrella portion 9b and the engaging portion 40 can be treated, and the surfaces of the umbrella portion 9b and the engaging portion 40 are coated with the neutral (sub) phosphate ester (A) and the neutral (sub). A film of phosphate ester (B) is formed.

Alternatively, the umbrella portion 9b coated with the watch band lubricant to the extent that it becomes white with a toothpick or a cotton swab is heated to 80 ° C. or higher toward the heater. When the watch band lubricant becomes transparent, heating is finished. After room temperature, wipe off any excess whitened watch band lubricant. Next, the neutral (sub) phosphate ester (A) and the neutral (sub) phosphate ester (B) are also attached to the engaging portion 40 by repeating the locking operation of the locking portion and the releasing operation thereof. In this way, the surfaces of the umbrella portion 9b and the engaging portion 40 can be treated, and the surfaces of the umbrella portion 9b and the engaging portion 40 are coated with the neutral (sub) phosphate ester (A) and the neutral (sub). A film of phosphate ester (B) is formed.

This lubrication process enables the above-mentioned mounting operation and removal operation of the watch (in other words, the locking operation of the locking portion and the releasing operation thereof). That is, the locking portion can exert its function. Further, according to this lubrication treatment step, the generation of stains can be suppressed. In the conventional lubricating composition (for example, a lubricating composition containing a hydrocarbon and / or ether, a neutral phosphoric acid ester and / or a neutral phosphite ester, and paraffin), the medium is retained in the lubricating composition. It was necessary to boil 6 and perform lubrication treatment. On the other hand, according to the watch band lubrication agent of the embodiment, the lubrication treatment can be performed in a simple process such as repeating the locking operation and the releasing operation of the locking portion or heating toward the heater. You can.

(Assembly process)
In the assembling step, the watch is assembled using the middle clasp 6 processed in the lubrication treatment step. Specifically, it can be carried out by a known method using known parts.

The clasp used in the method for manufacturing a timepiece of the embodiment may have a locking portion, and is not limited to the clasp 6 having the above-mentioned structure. Further, the locking portion is not limited to the locking portion having the above-mentioned structure, as long as the wristwatch can be worn on the wrist. Further, after the lubrication treatment step, the 6 o'clock side band 1, the 12 o'clock side band 2 and the middle clasp 6 may be assembled in the assembling step.

Based on the above, the present invention relates to the following.

[1] 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 are described below in one molecule. A neutral phosphate ester (B1) having two or more groups represented by the general formula (b1-1) and / or a group having a melting point of 10 ° C. or lower and represented by the following general formula (b2-1). The above-mentioned neutral phosphorus is contained with respect to a total of 100 parts by mass of the above-mentioned neutral phosphoric acid ester (A1) and the above-mentioned neutral phosphite ester (A2), including two or more neutral phosphite esters (B2). A lubricant for a watch band, which comprises an acid ester (B1) and the neutral phosphite (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 independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.)

According to the watch band lubrication agent according to the above [1], the lubricity of the clasp can be improved and the occurrence of stains can be suppressed.

[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 lubricating agent 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 It represents a linear or branched alkyl group, R ^B191 and R ^{B 192} each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B191 and R 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 It represents a linear or branched alkyl group, R ^B291 and R ^B292 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B291 and R The total number of carbon atoms in ^b292 is 1-5.)

Since the watch band lubricator according to the above [2] is more excellent in stability, the lubricity of the clasp can be further improved and the occurrence of stains can be further suppressed.

[3] The neutral phosphoric acid ester (B1) and the neutral phosphite ester (B1) with respect to a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). The lubricant for a watch band according to [1] or [2], which contains B2) in a total amount of 150 parts by mass or more and 170 parts by mass or less.

Since the watch band lubricator according to the above [3] is more excellent in stability, the lubricity of the clasp can be further improved and the occurrence of stains can be further suppressed.

[4] In the above formula (b1), R ^b15 and R ^b17 are independently linear alkyl groups having 1 to 6 carbon atoms, and R ^b16 and R ^b18 are independently having 3 carbon atoms. ~ 6 is 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 above 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. Lubricating agent for bands.

According to the watch band lubrication agent described in [4] above, a strong lubricating film can be formed, so that the lubricity of the clasp can be further improved.

[5] A watch band having a clasp, wherein the watch band lubricant according to any one of [1] to [4] is attached to the clasp.

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

The watch band according to the above [5] and the watch according to the above [6] are excellent in lubricity of the clasp and suppress the occurrence of stains.

[7] Includes a watch band lubrication process in which a watch band lubricant is adhered to the clasp of the watch band, and a watch assembly step in which the watch is assembled using the watch band processed in the lubrication process. The above-mentioned lubricant for the watch band 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, a neutral phosphate ester (B1) having two or more groups represented by the following general formula (b1-1) in one molecule and / or having a melting point of 10 ° C. or less and the following general formula (b2-1) ) Is included in the neutral phosphite ester (B2) having two or more groups, and the total amount of the neutral phosphate ester (A1) and the neutral phosphite ester (A2) is 100 parts by mass. On the other hand, a method for producing a clock, which comprises the neutral phosphate 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 independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.)

According to the method for manufacturing a timepiece according to the above [7], a timepiece having excellent lubricity of a clasp 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 watch 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 It represents a linear or branched alkyl group, R ^B191 and R ^{B 192} each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B191 and R 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 It represents a linear or branched alkyl group, R ^B291 and R ^B292 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B291 and R The total number of carbon atoms in ^b292 is 1-5.)

According to the method for manufacturing a timepiece according to the above [8], it is possible to obtain a timepiece which is more excellent in lubricity of the clasp and has less stains.

[Example]
[Example 1-1]
As the neutral phosphate ester (A1), 100 parts by mass of tris (2,4-di-t-butylphenyl) phosphate (melting point 181 to 184 ° C.) and the 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 , R ^b18 = t-butyl group, R ^b191 = hydrogen atom, R ^b192 = n-propyl group (melting point 10 ° C or less) are mixed in a ^{Menou dairy pot} , and a paste-like watch band is used. Lubricating agent for use was obtained.

[Example 1-2]
Other than using 100 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) , A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-3]
Other than using 130 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-4]
170 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-5]
Other than using 200 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-6]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), neutral subphosphorus As an acid ester (B2) (neutral phosphite ester (b2)), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) (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 paste-like lubricant for a watch band was obtained.

[Example 1-7]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 100 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-6.

[Example 1-8]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 130 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-6.

[Example 1-9]
170 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used as the neutral phosphite ester (B2) (neutral phosphite ester (b2)). Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-6.

[Example 1-10]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 200 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-6.

[Example 1-11]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used instead of 150 parts by mass. As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) and neutral Other than using 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) as the phosphite (B2) (neutral phosphite (b2)). , A paste-like lubricating agent for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-12]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used 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-t-butylphenylditridecyl phosphate) and neutral As the phosphite (B2) (neutral phosphite (b2)), 85 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. , A paste-like lubricating agent for a watch band was obtained in the same manner as in Example 1-1.

[Example 1-13]
As the neutral phosphate ester (A1), 100 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphate polymer (melting point of about 202 ° C.) and the neutral phosphate ester (B1) (neutral phosphate ester (b1)) As a whole, 150 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was put into a Menou dairy pot and mixed to obtain a paste-like lubricant for a watch band. It was.

[Example 1-14]
Other than using 100 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)) , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-15]
Other than using 130 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-16]
170 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-17]
Other than using 200 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-18]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), neutral subphosphorus Example 1-Except that 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used as the acid ester (B2) (neutral phosphite ester (b2)). In the same manner as in No. 13, a paste-like lubricating agent for a watch band was obtained.

[Example 1-19]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 100 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-18.

[Example 1-20]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 130 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-18.

[Example 1-21]
170 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used as the neutral phosphite ester (B2) (neutral phosphite ester (b2)). Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-18.

[Example 1-22]
As the neutral phosphite ester (B2) (neutral phosphite ester (b2)), 200 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Other than that, a paste-like lubricant for a watch band was obtained in the same manner as in Example 1-18.

[Example 1-23]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used instead of 150 parts by mass. As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) and neutral Other than using 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) as the phosphite (B2) (neutral phosphite (b2)). , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-24]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) was used 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-t-butylphenylditridecyl phosphate) and neutral As the phosphite (B2) (neutral phosphite (b2)), 85 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. , A paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-13.

[Example 1-25]
Tris (2,4-di-t-butylphenyl) phosphate as neutral phosphate (A1) instead of 100 parts by weight Tris (2,4-di) as neutral phosphate (A1) Lubricating for a paste-like watch band in the same manner as in Example 1-1, except that 50 parts by mass of -t-butylphenyl) phosphate and 50 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphate polymer were used. Obtained a treatment agent.

[Example 1-26]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), neutral subphosphorus Example 1-Except that 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used as the acid ester (B2) (neutral phosphite ester (b2)). A paste-like lubricant for a watch band was obtained in the same manner as in No. 25.

[Example 1-27]
Tris (2,4-di-t-butylphenyl) phosphate as a neutral phosphate (A1) instead of 100 parts by mass, as a neutral phosphate (A1), Tris (2,4-di) Using 50 parts by mass of -t-butylphenyl) phosphate and 50 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphate polymer; as neutral phosphate ester (B1) (neutral phosphate ester (b1)). As neutral phosphate ester (B1) (neutral phosphate ester (b1)) instead of 150 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) As 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) and as neutral phosphite (B2) (neutral phosphite (b2)). A paste-like lubricant for a watch band, in the same manner as in Example 1-1, except that 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used. Got

[Example 1-28]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 the temperature was 10 ° C. or lower.

[Example 1-29]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 the temperature was 10 ° C. or lower.

[Example 1-30]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 a 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]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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. A paste-like lubricating agent for a watch band was obtained in the same manner as in Example 1-1 except that the following) was used.

[Example 1-32]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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]
As neutral phosphate (B1) (neutral phosphate (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 lubricating agent 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]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Mixing point of 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-6.

[Example 1-35]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Mixing point of 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-6.

[Example 1-36]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 a 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]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-6 except that the melting point was 10 ° C. or lower.

[Example 1-38]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Melity 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-6.

[Example 1-39]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Melity 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Examples 1-6.

[Examples 2-1 to 2-12]
In Examples 2-1 to 2-12, as the neutral phosphate ester (A1), instead of tris (2,4-di-t-butylphenyl) phosphate, as the neutral phosphite ester (A2). , Tris (2,4-di-t-butylphenyl) phosphite (melting point 185 ° C.), and the same as in Examples 1-1 to 1-12, respectively, for a paste-like lubrication treatment for a watch band. I got the agent.

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

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

[Example 2-26]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), neutral subphosphorus Example 2-Except that 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used as the acid ester (B2) (neutral phosphite (b2)). A paste-like lubricant for a watch band was obtained in the same manner as in No. 25.

[Example 2-27]
Tris (2,4-di-t-butylphenyl) phosphite as neutral phosphite (A2) instead of 100 parts by mass as tris (2,4) as neutral phosphite (A2) 50 parts by mass of −di-t-butylphenyl) phosphite and 50 parts by mass of hydrogenated bisphenol A / pentaerythritol phosphite polymer; neutral phosphate (B1) (neutral phosphate (b1)) As, instead of 150 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), neutral phosphate (B1) (neutral phosphate (b1)) As a result, 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), and neutral phosphite (B2) (neutral phosphite (b2)) As in the case of Example 2-1 except that 75 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) was used, the paste-like lubrication for the watch band was used. Obtained a treatment agent.

[Example 2-28]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 lubricating agent for a watch band was obtained in the same manner as in Example 2-1 except that (10 ° C. or lower) was used.

[Example 2-29]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 lubricating agent for a watch band was obtained in the same manner as in Example 2-1 except that (10 ° C. or lower) was used.

[Example 2-30]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 a watch band was obtained in the same manner as in Example 2-1 except that (melting point: 10 ° C. or lower) was used.

[Example 2-31]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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. A paste-like lubricating agent for a watch band was obtained in the same manner as in Example 2-1 except that the following) was used.

[Example 2-32]
As a neutral phosphate ester (B1) (neutral phosphate ester (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 2-1 except that the temperature was 10 ° C. or lower.

[Example 2-33]
As neutral phosphate (B1) (neutral phosphate (b1)), instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate), 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 lubricating agent for a watch band was obtained in the same manner as in Example 2-1 except that (10 ° C. or lower) was used.

[Example 2-34]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Mixing point of 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Example 2-6.

[Example 2-35]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Mixing point of 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Example 2-6.

[Example 2-36]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 lubricating agent for a watch band was obtained in the same manner as in Example 2-6 except that a propyl group (with a melting point of 10 ° C. or less) was used.

[Example 2-37]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 paste-like lubricant for a watch band was obtained in the same manner as in Example 2-6 except that the melting point was 10 ° C. or lower.

[Example 2-38]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Melity 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Example 2-6.

[Example 2-39]
Neutral as a neutral phosphite ester (B2) (neutral phosphite ester (b2)) instead of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) 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 ) (Melity 10 ° C. or lower) was used, and a paste-like lubricating agent for a watch band was obtained in the same manner as in Example 2-6.

[Comparative Example 1]
As the neutral phosphate ester (A1), Tristearyl phosphite (melting point 42 ° C.) was used instead of tris (2,4-di-t-butylphenyl) phosphate. In the same manner, a paste-like lubricant for the watch band was obtained.

[Comparative Example 2]
Other than using 250 parts by mass of 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl phosphate) as the neutral phosphate ester (B1) (neutral phosphate ester (b1)). , A paste-like lubricant for a watch band was obtained in the same manner as in Example 1-1.

<Evaluation method and evaluation result>
The locked portion of the clasp 6 shown in FIGS. 1 and 2 was treated with the prepared lubrication agent for a watch band (lubrication treatment step). The clasp 6 was still manufactured and the locking portion was not functioning. Specifically, the umbrella portion 9b was coated with a lubricant for a watch band to the extent that it became white with a cotton swab. The locking operation and the unlocking operation of the locking portion are repeated several times to apply pressure to the umbrella portion 9b, and the neutral (phasphite) ester (A) and the neutral (sub) phosphoric acid are applied to the surface of the umbrella portion 9b. The ester (B) was attached. By repeating the locking operation of the locking portion and the releasing operation thereof, the neutral (phasphite) phosphate ester (A) and the neutral (phasphite) phosphate ester (B) were also adhered to the engaging portion 40. Then, the excess adhesive for the watch band was wiped off. In this way, the surfaces of the umbrella portion 9b and the engaging portion 40 were treated. By this process, the locking portion came to function. In addition, after the above treatment, no stain was generated in any of the locking portions using the watch band lubricating agent of the example.

For the intermediate clasp 6 that had undergone the lubrication treatment step, the locking operation of the locking portion and the releasing operation thereof were repeated 1000 times (locking / releasing operation repeated test). The lubricity of the locking portion after the locking / releasing operation repeated test, that is, whether the locking / releasing operation can be performed smoothly was investigated. In addition, it was investigated whether or not stains were generated in the locking portion. The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 4.
Lubricity A: Locking / releasing operation was performed smoothly B: Locking / releasing operation was not performed smoothly Generation of stains A: No stains were generated
B: There was a stain

In addition, a heating test was conducted on the middle distillate 6 that had undergone the lubrication treatment step at a temperature of 80 ° C. for 1 hour. The lubricity of the locking portion after the heating test, that is, whether the locking / releasing operation can be performed smoothly was investigated. In addition, it was investigated whether or not stains were generated in the locking portion. The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 4.
Lubricity A: Locking / releasing operation was performed smoothly B: Locking / releasing operation was not performed smoothly Generation of stains A: No stains were generated
B: There was a stain

Furthermore, the following characteristics were investigated for the watch band lubricant in the examples. At 25 ° C., a 0.03 g amount of a watch band lubricant was applied to a circle (diameter 2 mm) on a stainless steel plate, and the stainless steel plate was erected vertically. It was observed whether the applied watch band lubricant changed when the watch band was held vertically for 5 minutes and 30 minutes.

A clock containing 100 parts by mass, 130 parts by mass, and 200 parts by mass of neutral (sub) phosphate ester (B) in total with respect to 100 parts by mass of neutral (phasphite) ester (A). As for the band lubricant, after holding for 5 minutes, the applied watch band lubricant remained in the circle. However, after holding for 30 minutes, the applied lubricant for the watch band spread out from the inside of the circle. On the other hand, a clock band containing a total of 150 parts by mass and 170 parts by mass of the neutral (sub) phosphate ester (B) with respect to a total of 100 parts by mass of the neutral (sub) phosphate ester (A). As for the lubricant for watch band, the applied lubricant for watch band remained in the circle after holding for 5 minutes and after holding for 30 minutes.

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

Claims (8)

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.
A neutral phosphate ester (B1) having a melting point of 10 ° C. or lower and 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, which is described below. It contains a neutral phosphite ester (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 a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). A lubricant for a watch band, which comprises 100 parts by mass or more and 200 parts by mass or less in total.

(In formulas (b1-1) and (b2-1), R independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.) The claim is characterized in that 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 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 It represents a linear or branched alkyl group, R ^B191 and R ^{B 192} each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B191 and R 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 It represents a linear or branched alkyl group, R ^B291 and R ^B292 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B291 and R The total number of carbon atoms in ^b292 is 1-5.) The neutral phosphate ester (B1) and the neutral phosphite ester (B2) are added to a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). The lubricant for a watch band according to claim 1 or 2, wherein the total amount is 150 parts by mass or more and 170 parts by mass or less. In the above formula (b1), R ^b15 and R ^b17 are independently linear alkyl groups having 1 to 6 carbon atoms, and R ^b16 and R ^b18 are independently having 3 to 6 carbon atoms, respectively. It is 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 Claim 2 or 3 which is a 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. Lubricants for watch bands as described in. A watch band having a clasp, wherein the watch band lubricating agent according to any one of claims 1 to 4 is attached to the clasp. A watch having the watch band according to claim 5. A watch band lubrication process that attaches a watch band lubrication agent to the watch band clasp,
The watch assembly step of assembling the watch using the watch band treated in the lubrication treatment step is included.
The clock band lubricant is composed of 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.
A neutral phosphate ester (B1) having a melting point of 10 ° C. or lower and 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, which is described below. It contains a neutral phosphite ester (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 a total of 100 parts by mass of the neutral phosphate ester (A1) and the neutral phosphite ester (A2). A method for manufacturing a watch, which comprises an amount of 100 parts by mass or more and 200 parts by mass or less in total.

(In formulas (b1-1) and (b2-1), R independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.) The claim is characterized in that 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). 7. The method for manufacturing a watch 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 represents a straight-chain or branched alkyl group, R ^B191 and R ^{B 192} each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms, R ^B191 and R 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 It represents a linear or branched alkyl group, R ^B291 and R ^B292 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ^B291 and R The total number of carbon atoms in ^b292 is 1-5.)

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