WO2020100430A1 - Watch band lubrication composition, watch band manufacturing method, and watch band - Google Patents

Abstract

A watch band lubrication composition comprising a lubricating agent (A), an anti-wear agent (B), and a solvent, wherein: the lubricating agent (A) either includes a paraffin wax (A-1), or includes at least one selected from aliphatic saturated hydrocarbons (A-2) having a melting point of at least 45°C and 23 to 38 carbon atoms, inclusive; the anti-wear agent (B) includes at least one selected from the neutral phosphoric acid ester (B-1) represented by formula (b-1) and the neutral phosphorous acid ester (B-2) represented by formula (b-2); and the total concentration of the lubricating agent (A) and the anti-wear agent (B) in the watch band lubrication composition is at least 0.0025 mass% but less than 0.1 mass%.

Description

Lubricating composition for watch band, method for manufacturing watch band, and watch band

The present invention relates to a watch band lubricating composition, a watch band manufacturing method, and a watch band.

A wristwatch has a head that has the function of displaying the time and a watch band that is used to wear the wristwatch on the wrist. In the case of a metal watch band, it is usually manufactured by connecting a plurality of small metal parts called pieces. Here, a lubricating component is attached to the metal pins, and the pins are inserted into the pin insertion portions of the pieces to connect the pieces to each other. In the manufactured timepiece band, the component for lubrication acts between the pin insertion portion and the pin of the piece, so that the connecting portion between the pieces moves smoothly. Therefore, the squeak of the watch band can be suppressed when the wristwatch is worn.

Patent Document 1 describes a watch band lubricating composition for supplying a lubricating component between a pin insertion portion and a pin of a piece. The watch band lubricating composition includes a hydrocarbon and / or an ether, a neutral phosphoric acid ester and / or a neutral phosphorous acid ester, and a paraffin wax. Specific examples of the neutral phosphate and / or the neutral phosphite include trioleyl phosphite, trioctyl phosphite, trimethylol propane phosphite, tetraphenyl dipropylene glycol diphosphite, and tristearyl phosphite. , Tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate, triphenyl phosphate, tristearyl phosphate and the like are used.

JP, 2010-1333, A

However, in the timepiece band produced using the lubricating composition for a timepiece band of Patent Document 1, the component for lubrication exudes from between the pin insertion portion and the pin of the bridge while the timepiece band is used. There was a problem. If the exuded lubricant component forms a stain on the outer surface of the bridge, it will impair the aesthetic appearance of the watch band.

Therefore, an object of the present invention is to provide a lubricating composition for a watch band in which a lubricating component is less likely to seep out between a pin insertion portion and a pin of a piece when used in a watch band.

A watch band lubricating composition according to the present invention is a watch band lubricating composition containing a lubricant (A), an antiwear agent (B) and a solvent, wherein the lubricant (A) is paraffin wax ( A-1) or at least one selected from the group consisting of saturated aliphatic hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less. ) Is selected from a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B-2) represented by the following general formula (b-2). The concentration of the lubricant (A) and the antiwear agent (B) in the lubricating composition for a watch band containing at least one kind is 0.0025 mass% or more and less than 0.1 mass% in total.

(In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)

(In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)

When the watch band lubricating composition of the present invention is used in a watch band, it is difficult for the lubricating component to seep out between the pin insertion portion of the bridge and the pin.

The mode (embodiment) for carrying out the present invention will be described in detail. The present invention is not limited to the contents described in the embodiments below. Further, the constituent elements described below include those that can be easily conceived by those skilled in the art and those that are substantially the same. Furthermore, the configurations described below can be appropriately combined. In addition, various omissions, substitutions, or changes in the configuration can be made without departing from the scope of the present invention.

[Embodiment 1]
<Lubricant composition for watch band>
The lubricating composition for a watch band of Embodiment 1 is used for supplying a lubricating component between the pin insertion portion and the pin of the bridge when the metal watch band is manufactured. The pins and bridges are made of, for example, stainless steel, titanium, titanium alloy, copper, copper alloy, tungsten, nickel alloy.

The lubricating composition for a watch band of Embodiment 1 contains a lubricant (A), an antiwear agent (B), and a solvent. The lubricant (A) contains paraffin wax (A-1), or at least one selected from aliphatic saturated hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less. Including seeds. The antiwear agent (B) contains at least one selected from a neutral phosphoric acid ester (B-1) and a neutral phosphorous acid ester (B-2) described later.

Here, the lubricant (A) and the antiwear agent (B) function as the above-mentioned components for lubrication. In the production of a watch band, usually, the lubricating composition for a watch band of Embodiment 1 is attached to a pin, the solvent therein is removed, and then the pin is inserted into the pin insertion portion of the bridge. In other words, the pin is inserted into the pin insertion portion of the bridge with the lubricant (A) and the antiwear agent (B) attached. When the lubricating composition for a watch band of Embodiment 1 is used, the lubricant (A) and the antiwear agent (B) are less likely to seep out between the pin insertion portion and the pin of the bridge in the manufactured watch band. It is also possible to suppress the exudation of lubricating components from forming stains on the outer surface of the bridge, so that the aesthetics of the watch band can be maintained for a long time. This is due to the characteristics of the molecular structure of the antiwear agent (B), and the interaction between the molecules of the antiwear agent (B) and the metal constituting the pin or the like becomes stronger, and This is probably because the exudation is suppressed.

Further, when the lubricating composition for a watch band of Embodiment 1 is used, it is possible to lubricate the connecting portion of the bridge for a long period in the manufactured watch band. This is because a lubricant (A) and an antiwear agent (B) are suppressed from seeping out, and a specific lubricant (A) having excellent slidability and a specific antiwear agent (excellent in abrasion resistance ( B) is used in combination. It is considered that the excellent wear resistance of the antiwear agent (B) is due to the alkyl group contained in the molecule of the antiwear agent (B).

By the way, when the conventional watch band lubricating composition is used, the lubricating component is more likely to seep out between the pin insertion portion and the pin of the bridge than the watch band lubricating composition of the first embodiment. During use of the watch band, the lubricating component exuded may form a stain on the outer surface of the bridge. For this reason, after connecting the pieces to each other to manufacture the watch band, it is necessary to provide a processing step in order to prevent exudation during use of the watch band. The processing steps are performed, for example, before shipping the watch band. In the processing step, the watch band is heated to intentionally exude excess lubricating components, and the exuded lubricating components are wiped off. This treatment step may be repeated a plurality of times until the exudation of the lubricating component due to heating is stopped. On the other hand, according to the timepiece band lubricating composition of Embodiment 1, the lubricant (A) and the antiwear agent (B) are less likely to seep out, so that the above-mentioned treatment step can be omitted. In addition, the aesthetics can be maintained for a long time.

[Lubricant (A)]
The lubricant (A) contains paraffin wax (A-1), or at least one selected from aliphatic saturated hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less. Including seeds. The paraffin wax (A-1) may be used alone or in combination of two or more. The aliphatic saturated hydrocarbon (A-2) may be used alone or in combination of two or more.

Paraffin wax (A-1) preferably has a melting point of 45 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 75 ° C. or lower. When the melting point is in this range, exudation from between the pin insertion portion of the piece and the pin can be suitably suppressed. Examples of the paraffin wax (A-1) include unrefined paraffin wax (slack wax, scale wax, etc., separated by a dewaxing method for petroleum vacuum distillation distillate oil, vacuum distillation residue oil, heavy distillate oil, etc. ) And purified paraffin wax obtained by decolorizing and purifying these unpurified paraffin waxes. As the paraffin wax (A-1), specifically, a commercially available product can be used. Commercial products are usually distinguished by their melting points (Fahrenheit), and any of the eight types specified in JIS K 2235 may be used. That is, as the paraffin wax (A-1), eight kinds from 120P (48.9 ° C. or more and less than 51.7 ° C.) to 155P (68.3 ° C. or more and less than 71.0 ° C.) are used.

The aliphatic saturated hydrocarbon (A-2) has a melting point of 45 ° C or higher. The saturated aliphatic hydrocarbon (A-2) preferably has a melting point of 80 ° C. or lower. The aliphatic saturated hydrocarbon (A-2) is preferably a linear aliphatic saturated hydrocarbon having 23 to 38 carbon atoms. Such an aliphatic saturated hydrocarbon (A-2) can preferably suppress exudation from between the pin insertion portion and the pin of the bridge. Examples of the saturated aliphatic hydrocarbon (A-2) include tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane. , Hexatriacontane, heptatriacontane, octatriacontane, and the like. These are commercially available as high-purity chemicals. For example, the saturated aliphatic hydrocarbon (A-2) has a purity of 95% by mass or more.

▽ Aliphatic saturated hydrocarbon (A-2) has a narrower melting point than paraffin wax (A-1) and is less sticky. Therefore, the saturated aliphatic hydrocarbon (A-2) can more appropriately suppress the exudation from between the pin insertion portion and the pin of the bridge, as compared with the paraffin wax (A-1). Octacosan, nonacosan, triacontane, hentriacontane, and dotriacontane are preferably used because the film of the lubricating component interposed between the pin insertion portion of the bridge and the pin can be made stronger and exudation can be further suppressed. .. Further, octacosan is more preferably used from the viewpoint of compatibility with the antiwear agent (B).

[Abrasive agent (B)]
The antiwear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B- represented by the following general formula (b-2). At least one selected from 2) is included. The neutral phosphoric acid ester (B-1) and the neutral phosphorous acid ester (B-2) may be used alone or in combination of two or more kinds. You may use combining 1 type, or 2 or more types of neutral phosphoric acid ester (B-1), and 1 type, or 2 or more types of neutral phosphorous acid ester (B-2).

In formula (b-1), R ^b11 to R ^b14 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 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 decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group (cetyl group). Groups are preferably used.

R ^b15 to R ^b18 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 thereof 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 (B-1) has a specific substituent in R ^b15 to R ^b18, it exhibits excellent wear resistance and can lubricate the connecting portion of the bridge for a long period of time. It is considered that this is because if R ^b15 to R ^b18 have a specific substituent, the film of the component for lubrication interposed between the pin insertion portion of the bridge and the pin becomes strong.

Particularly, 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 have 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms. A branched alkyl group has more excellent abrasion resistance.

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, neopentyl group.

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 atoms. ^Is a straight-chain or branched alkyl group having 4 to 4 carbon atoms, and when R ^b191 is an ethyl group, R ^b192 is a straight-chain or branched alkyl group having 2 to 3 carbon atoms. In particular, it is more preferable that R ^b191 is a hydrogen atom and R ^b192 is a linear or branched alkyl group having 1 to 5 carbon atoms because the film of the component for lubrication becomes stronger.

In formula (b-2), 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 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 decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and hexadecyl group (cetyl group). Groups are preferably used.

R ^b25 ~ 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 thereof 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 (B-2), because it has a specific substituent in R ^b25 ~ R ^b28, it lubricates the connecting portion of the piece and exhibits an excellent wear resistance, a long term. This is because, if has a specific substituent in R ^b25 ~ R ^b28, film components for lubrication is considered to become firmly interposed between the pin insert and the pin of the frame.

In particular, R ^b25 and R ^b27 are ~ 1 -C 6, preferably straight-chain alkyl group of 1 to 3, the number R ^b26 and R ^b28 are 3 to 6 carbon atoms, preferably 3-4 min A branched alkyl group has more excellent abrasion resistance.

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, neopentyl group.

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 atoms. ^Is a straight-chain or branched alkyl group having 4 to 4 carbon atoms, and when R ^b291 is an ethyl group, R ^b292 is a straight-chain or branched alkyl group having 2 to 3 carbon atoms. In particular, it is more preferable that R ^b291 is a hydrogen atom and R ^b292 is a linear or branched alkyl group having 1 to 5 carbon atoms because the film of the component for lubrication becomes stronger.

When used in the above-mentioned lubricant composition for a watch band, it is considered that the structural stability is higher, the exudation can be suppressed for a longer period, and the lubricity can be maintained for a longer period. The phosphoric acid ester (B-2) is more preferably used.

〔solvent〕
The solvent is not particularly limited as long as it can dissolve the lubricant (A) and the antiwear agent (B). Specific examples of the solvent include hexane, nonane, toluene, tetrahydrofuran (THF), diethyl ether, chloroform, cyclohexane, heptane, methylcyclohexane, and methanol. From the viewpoint of safety, hexane and nonane are preferably used. Be done. The solvent may be used alone or in combination of two or more.

In the lubricating composition for a watch band of Embodiment 1, the concentrations of the lubricant (A) and the antiwear agent (B) are 0.0025% by mass or more and less than 0.1% by mass, preferably 0.0025% by mass. It is at least mass% and less than 0.02 mass%. The solvent is appropriately used so as to have the above concentration.

In the watch band lubricating composition of Embodiment 1, the contents of the lubricant (A) and the antiwear agent (B) are small as in the above range. For this reason, in the watch band, the amounts of the lubricant (A) and the antiwear agent (B) attached to the pin insertion portion or the pin of the bridge are also reduced. However, according to the lubricating composition for a watch band of the first embodiment, the connecting portion of the bridge can be lubricated for a long period of time. This is due to the excellent wear resistance of the antiwear agent (B). Further, since the amounts of the lubricant (A) and the antiwear agent (B) present between the pin insertion portion of the bridge and the pins are small, the seepage of the lubricant (A) and the antiwear agent (B) can be further suppressed. ..

If the concentration is lower than the above range, it may not be possible to properly lubricate the connecting parts of the bridge. On the other hand, if the concentration is higher than the above range, the lubricant (A) and the antiwear agent (B) may ooze out between the pin insertion portion and the pin of the bridge.

Since the antiwear agent (B) can be easily attached to the pins, the lubricant (A) in the lubricating composition for a watch band of the first embodiment has a larger amount or the same amount (parts by mass) as the antiwear agent (B). ) Is preferred. That is, it is preferable that the lubricant (A) is contained in an amount (parts by mass) equal to or more than the amount of the antiwear agent (B). For example, in the watch band lubricating composition of Embodiment 1, the concentration of the lubricant (A) is 0.0012 mass% or more and 0.06 mass% or less, and the concentration of the antiwear agent (B) is 0.0008 mass%. % Or more and 0.045 mass% or less, and it is more preferable that the concentration of the lubricant (A) is equal to or higher than the concentration of the antiwear agent (B). Due to the excellent wear resistance of the anti-wear agent (B), even a small amount can lubricate the connecting portion of the bridge for a long time.

[Antioxidant (C)]
The watch band lubricating composition of Embodiment 1 may further contain a hindered amine compound (C-1) described later as an antioxidant (C).

When the lubricating composition for a watch band of Embodiment 1 contains the hindered amine compound (C-1), the pin is used as a lubricant (A), an antiwear agent (B) and a hindered amine during the manufacture of the watch band. The compound (C-1) is attached to the pin insertion portion of the bridge while being attached. In this case, even if the contents of the lubricant (A) and the antiwear agent (B) are smaller, the connecting portion of the bridge can be lubricated for a long period of time. This is considered to be due to the following reasons. While the watch band is being used, pressure may be applied to the anti-wear agent (B) between the pin insertion portion of the bridge and the pin, and the molecule may be broken to generate radicals. Since the hindered amine compound (C-1) can trap this radical, it is considered that the chain destruction of the molecules of the antiwear agent (B) can be stopped.

Also, in order to adjust the length of the watch band, etc., the pin may be slid at high pressure between the pin insertion part and the pin insertion part by removing or inserting the pin. In this case, a high pressure is applied to the wear resistant agent (B) between the pin insertion portion of the piece and the pin. It is considered that if the hindered amine compound (C-1) is interposed between the pin insertion portion of the piece and the pin, radicals generated by breaking the molecules of the antiwear agent (B) can be trapped. Therefore, when adjusting the length of the band, it is not necessary to newly treat the pin with the lubricating composition for a watch band to further attach the lubricating component to the pin. According to the lubricating composition for a watch band of the first embodiment, normally, the lubricity of the connecting portion of the bridge can be maintained even if the pin is inserted into and removed from the pin insertion portion a plurality of times.

The antioxidant (C) contains a hindered amine compound (C-1) represented by the following general formula (c-1). The antioxidant (C) may be used alone or in combination of two or more.

In formula (c-1), R ^c21 and R ^c22 each independently represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms. The aliphatic hydrocarbon group having 1 to 10 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 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, heptyl group and octyl group. Linear or branched such as nonyl group, nonyl group, decyl group, isopropyl group, sec-butyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, 2-ethylhexyl group An alkyl group is preferably used. Of these, a linear or branched alkyl group having 5 to 10 carbon atoms is more preferable from the viewpoint of improving durability.

R ^c23 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1 , 6-hexylene group, 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 3-methyl-1,5-pentylene group, etc. A chain or branched alkylene group is preferably used. Of these, a divalent linear or branched alkylene group having 5 to 10 carbon atoms is more preferable from the viewpoint of improving durability.

In particular, from the viewpoint of improving durability, it is more preferable that the sum of the number of carbon atoms of R ^c21 , R ^c22 and R ^c23 is 16 to 30 among the above.

In the watch band lubricating composition of Embodiment 1, the concentration of the antioxidant (C) is preferably 0.00025 mass% or more and 0.0025 mass% or less. The solvent is appropriately used so as to have the above concentration.

[Fluorescent agent (D)]
The lubricating composition for a watch band of Embodiment 1 may further contain at least one selected from coumarin and coumarin derivatives as the fluorescent agent (D). The lubricating composition for a watch band according to the first embodiment may not include the fluorescent agent (D). Coumarin and coumarin derivatives may be used alone or in combination of two or more. In the present specification, “coumarin and coumarin derivatives” are collectively referred to as “coumarin and the like”.

When manufacturing a watch band, as described above, usually, the watch band lubricating composition is attached to the pin, the solvent therein is removed, and then the pin is inserted into the pin insertion portion of the piece. When the lubricating composition for a watch band of the first embodiment contains coumarin and the like, it is inspected whether the lubricant (A) and the antiwear agent (B) are properly attached before removing the solvent. it can. In the state before removing the solvent, coumarin and the like are attached to the pins together with the lubricant (A) and the antiwear agent (B). Further, since coumarin and the like can be uniformly mixed in the watch band lubricating composition of Embodiment 1, the coumarin and the like are evenly mixed and attached to the pin together with the lubricant (A) and the antiwear agent (B). It is thought that Therefore, by irradiating the pin with light having a wavelength emitted by coumarin or the like and checking the presence or absence of the light emission, it is possible to properly inspect whether the lubricant (A) and the antiwear agent (B) are attached.

Also, when manufacturing a watch band, usually, attach the watch band lubricating composition to the pin, remove the solvent in it, and then insert the pin into the pin insertion part of the piece. At this time, coumarin and the like can be easily removed together with the solvent. This is because coumarin and the like have sublimation properties.

Further, even when a small amount of coumarin or the like remains on the pin during the production of the watch band, even if the coumarin or the like does not contain a sulfur atom, a nitrogen atom or a phosphorus atom, even if it is inserted into the pin insertion portion of the piece, It does not adversely affect the metal forming the pins and the like. That is, the lubricity of the connecting portion of the bridge is not adversely affected. Further, since coumarin and the like are solid at room temperature to about 60 ° C., it is difficult for the coumarin or the like to exude from between the insert portion of the piece and the pin. Even if it oozes out, it is difficult to see coumarin and the like, and it is difficult to spoil the aesthetic appearance of the watch band.

The coumarin derivative preferably has a molecular weight larger than that of coumarin (molecular weight 146.14) and 300 or less. Further, the coumarin derivative preferably has a substituent introduced at the 4-position and the 7-position. Moreover, it is preferable that the substituent does not include a sulfur atom and a phosphorus atom. That is, the substituent is preferably a substituent containing a carbon atom and a hydrogen atom, or a substituent containing a carbon atom, an oxygen atom and a hydrogen atom. These substituents may be a substituent further containing a nitrogen atom. More specifically, it is more preferable that the 4-position has an alkyl group having 1 to 3 carbon atoms. As the fluorescent agent (D), such a coumarin derivative and coumarin are particularly preferably used from the viewpoint of sublimability. It is considered that the coumarin derivative containing a nitrogen atom has high solubility but low sublimation property, but if the molecular weight is in the above range, it does not affect the sublimation property and is preferably used.

In the watch band lubricating composition of Embodiment 1, the concentration of the fluorescent agent (D) is preferably 0.0006 mass% or more and 0.03 mass% or less. The solvent is appropriately used so as to have the above concentration.

[Other ingredients]
The watch band lubricating composition of Embodiment 1 may further contain other components. If the lubricating composition for a watch band of Embodiment 1 contains other components, the lubricant (A), the antiwear agent (B) and other components adhere to the pins during the manufacture of the watch band. It is inserted in the pin insertion part of the piece in the state.

Other ingredients include rust preventives. If a rust preventive agent is used, the connecting portion of the bridge can be lubricated for a longer period of time. As the rust preventive agent, from the viewpoint of the stability of the metal constituting the pin, etc., an ester rust preventive agent, a partial ester (ASA) rust preventive agent of isodecyl succinic acid and ethylene oxide, a straight chain fatty acid The rust preventive agent is preferably used.

The total concentration of other components in the lubricating composition for a watch band of Embodiment 1 is preferably 0.00025 mass% or more and 0.0025 mass% or less. The solvent is appropriately used so as to have the above concentration.

The watch band lubricating composition of Embodiment 1 is obtained by mixing the above-mentioned components. When mixing, ultrasonic agitation may be performed. In this composition, the lubricant (A) and the antiwear agent (B) are usually dissolved in a solvent.

<Method for manufacturing watch band and watch band>
The method of manufacturing the timepiece band according to the first embodiment is a method of manufacturing a timepiece band that includes a pin and a piece having a pin insertion portion. The pins and bridges are made of, for example, stainless steel, titanium, titanium alloy, copper, copper alloy, tungsten, nickel alloy. Specifically, in the method of manufacturing the watch band of the first embodiment, the watch band lubricating composition containing the lubricant (A), the antiwear agent (B) and the solvent is attached to the pin, and then the solvent is added. A step of evaporating and attaching a lubricant (A) and an antiwear agent (B) to the pin (component adhering step), and a pin having the lubricant (A) and antiwear agent (B) attached to the pin insertion portion. And a step of fixing the piece with a pin (piece fixing step). The above-mentioned lubricating composition for watch bands is used as the lubricating composition for watch bands.

In the component attaching step, first, a watch band lubricating composition containing a lubricant (A), an antiwear agent (B) and a solvent is attached to the pin. Specifically, a pin is dipped in the above watch band lubricating composition to adhere the composition to the pin surface. In order to treat the entire surface of the pin evenly, it is preferable to immerse the pin while shaking or applying ultrasonic waves. The immersion time is usually 10 seconds to 5 minutes.

Next, the solvent is removed (evaporated), and the lubricant (A) and antiwear agent (B) are attached to the pins. Specifically, the pin is taken out from the above watch band lubricating composition and dried to evaporate the solvent. Dry at room temperature (15 to 25 ° C.), preferably room temperature air drying. Alternatively, hot air drying may be performed. Considering safety, the temperature of hot air is preferably 120 to 150 ° C. As a result, a pin having the surface on which the lubricant (A) and the antiwear agent (B) are adhered can be obtained.

In the piece fixing process, insert the pin obtained in the component attaching process into the pin insertion part. As a result, the pieces are connected to each other and the pieces are fixed.

In this way, a watch band including a pin and a piece having a pin insertion portion can be manufactured. Here, the pin is inserted into the pin insertion portion, the piece is fixed by the pin, and the lubricant (A) and the antiwear agent (B) are interposed between the pin and the piece. In the method of manufacturing the watch band of the first embodiment, since the above-described lubricating composition for watch band is used, the lubricant (A) and the wear resistant agent (B) are exuded from between the pin insertion portion and the pin of the bridge. Difficult to maintain aesthetics. Moreover, the connecting portion of the bridge can be lubricated for a long period of time. These effects are due to the fact that the specific wear agent (B) is adopted and the contents of the lubricant (A) and the antiwear agent (B) are small, as described above.

In the above watch band, the amount of lubricant (A) and antiwear agent (B) interposed between the pin and the bridge is small. Specifically, the amount of the lubricating composition for a watch band used in the watch band is such that it becomes colorless and transparent when one drop is deposited on an aluminum foil with a dispenser and the solvent is evaporated. In the above watch band, it is considered that the same amount as this is interposed between the pin and the piece.

The method of manufacturing the watch band of the first embodiment may further include a step of laminating a colored coating film on the surface of the piece after the piece fixing step (coating layer laminating step). For example, the color of the colored film may be gold (pink, yellow), gray, or black. Specifically, a film containing a metal, a film containing a reaction compound of a metal element and a non-metal element, a film containing diamond-like carbon, and the like are stacked by a sputtering method, a CVD method, or an ion plating method. The watch band on which the colored film is formed becomes a colored watch band corresponding to the color of the colored film.

By the way, the watch band is usually degreased before performing the sputtering method. At the time of this degreasing, when a conventional watch band lubricating composition is used, the lubricating component is more likely to seep out between the pin insertion portion and the pin of the bridge than the above watch band lubricating composition. In a colored watch band, a stain formed by exuding a lubricating component is particularly noticeable due to its color. This greatly impairs the aesthetics. Therefore, after the laminating step, it is necessary to provide the wiping step for wiping off the stains already formed and the above-mentioned treatment step for preventing the exudation during use of the watch band. That is, this is a treatment step in which the colored watch band is heated to intentionally exude excess lubricating components, and the exuded lubricating components are wiped off. This treatment step is often repeated several times until the exudation of the lubricating component due to heating stops. On the other hand, even in the case of a colored watch band, when the above-mentioned lubricating composition for a watch band is used, the lubricant (A) and the antiwear agent (B) are less likely to exude, so that the wiping step may be omitted or the The number of processing steps can be reduced. Also, the aesthetics can be maintained for a long time.

Further, in the case of including a coating layer laminating step, a step of additionally adhering the watch band lubricating composition between the pin insertion part and the pin after performing the wiping step or the treating step (additional adhering step) You may go. As a result, the lubricating component exuded by degreasing can be supplemented. Also in this case, by using the above-mentioned lubricating composition for a watch band, the lubricant (A) and the antiwear agent (B) are less likely to exude from between the pin insertion portion and the pin of the bridge, and the appearance can be maintained.

Further, when a watch band lubricating composition containing an antioxidant (C) or other components is used, in the component adhering step, the pins together with the lubricant (A), the antiwear agent (B) and the solvent are used. Then, a watch band lubricating composition containing an antioxidant (C) or other components is applied. Then, the solvent is evaporated to deposit the antioxidant (C) or other components on the pin together with the lubricant (A) and the antiwear agent (B). Further, in the piece fixing step, a pin to which the antioxidant (C) or other component is attached together with the lubricant (A) and the antiwear agent (B) is inserted into the pin insertion portion, and the piece is fixed by the pin. To do. In this way, a watch band including a pin and a piece having a pin insertion portion can be manufactured. Here, a pin is inserted into the pin insertion portion, and the piece is fixed by the pin. Between the pin and the piece, together with the lubricant (A) and the antiwear agent (B), an antioxidant (C) or other Is intervened. According to such a method of manufacturing a watch band, the effects described in the description of the antioxidant (C) or other components are exhibited.

Further, in the case of using the watch band lubricating composition containing the fluorescent agent (D), the fluorescent agent (D) together with the lubricant (A), the antiwear agent (B) and the solvent is applied to the pin in the component attaching step. A lubricating composition for watch bands containing Next, in the state before removing the solvent, it is inspected whether the lubricant (A) and the antiwear agent (B) are properly attached. Specifically, the pin is irradiated with light having a wavelength emitted by the fluorescent agent (D), and the presence or absence of the emission is checked. Then, if the lubricant (A) and the antiwear agent (B) are properly attached, the solvent and the fluorescent agent (D) are removed, and the lubricant (A) and the antiwear agent (B) are attached to the pins. To adhere. Further, in the piece fixing step, the pin to which the lubricant (A) and the antiwear agent (B) are attached is inserted into the pin insertion portion, and the piece is fixed by the pin. It is preferable to remove the solvent and the fluorescent agent (D) at 80 to 200 ° C. Here, the pin is inserted into the pin insertion portion, the piece is fixed by the pin, and the lubricant (A) and the antiwear agent (B) are interposed between the pin and the piece. According to such a method of manufacturing the watch band, the effects described in the description of the fluorescent agent (D) are exhibited.

In the above watch band lubricating composition and watch band manufacturing method, the case where the watch band lubricating composition is attached to the pin and the lubricant (A) and the antiwear agent (B) are attached to the pin will be described. However, it is not limited to this. Alternatively, the watch band lubricating composition may be attached to the pin insertion portion, and the lubricant (A) and the antiwear agent (B) may be attached to the pin insertion portion. That is, as a method of manufacturing a watch band, a watch band lubricating composition containing a lubricant (A), an antiwear agent (B), and a solvent is attached to a pin insertion portion, and then the solvent is evaporated, Inserting the pin into the step of attaching the lubricant (A) and the antiwear agent (B) to the pin insertion section (component attachment step) and the pin insertion section where the lubricant (A) and the antiwear agent (B) are attached However, a step of fixing the piece with a pin (piece fixing step) may be included. In this case as well, the watch band described above can be obtained.

[Embodiment 2]
The watch band lubricating composition of Embodiment 2 is a watch band lubricating composition containing a lubricant (A), an antiwear agent (B), a fluorescent agent (D), and a solvent. Contains paraffin wax (A-1) or at least one selected from saturated aliphatic hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less. The wear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B-2) represented by the following general formula (b-2). ), The fluorescent agent (D) contains at least one selected from coumarin and coumarin derivatives, and the lubricant (A), fluorescent agent (D) and The concentration of the antiwear agent (B) is 0.0025% by mass or more and less than 0.1% by mass in total, and the total amount of the lubricant (A) and the fluorescent agent (D) is less than that of the antiwear agent (B). It is contained in an amount (parts by mass) greater than or equal to the amount.

Wherein ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 ~ 6 represents a straight-chain or branched alkyl group, R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^b191 The total number of carbon atoms of R ^b192 is 1 to 5.

Wherein ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 ~ 6 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, and R ^b291 and R ^b291 The total number of carbon atoms of R ^b292 is 1 to 5.

The lubricating composition for a watch band of Embodiment 2 contains a fluorescent agent (D). Since the anti-wear agent (B) can be easily attached to the pin, the lubricant (A) and the fluorescent agent (D) in the lubricating composition for the watch band of the second embodiment are more than the anti-wear agent (B) in total. Is included in a large amount or the same amount (part by mass). That is, the total amount of the lubricant (A) and the fluorescent agent (D) is equal to or more than the amount of the antiwear agent (B) (parts by mass). For example, in the watch band lubricating composition of Embodiment 2, the total concentration of the lubricant (A) and the fluorescent agent (D) is 0.0012 mass% or more and 0.06 mass% or less, and the wear resistance agent (B ) Is 0.0008 mass% or more and 0.045 mass% or less, and the total concentration of the lubricant (A) and the fluorescent agent (D) is not less than the concentration of the antiwear agent (B). Is preferred. Further, the concentration of the fluorescent agent (D) is more preferably equal to or lower than the concentration of the lubricant (A). Due to the excellent wear resistance of the anti-wear agent (B), even a small amount can lubricate the connecting portion of the bridge for a long time. Further, it is considered that the fluorescent agent (D) can play a role of uniformly adhering the antiwear agent (B) on the pins together with the lubricant (A). Therefore, a part of the lubricant (A) can be replaced with the fluorescent agent (D) as described above.

The other aspects of the watch band lubricating composition of Embodiment 2 are the same as those of the watch band lubricating composition of Embodiment 1. Further, regarding the method of manufacturing a watch band using the lubricating composition for a watch band of Embodiment 2, and the resulting watch band, the method of manufacturing the watch band of Embodiment 1 and the watch band (manufacturing of the watch band of Embodiment 1 are also described. Method, watch band of Embodiment 1).

From the above, the present invention relates to the following.
[1] A lubricating composition for a watch band, comprising a lubricant (A), an antiwear agent (B) and a solvent, wherein the lubricant (A) contains a paraffin wax (A-1), or The antiwear agent (B) contains at least one selected from saturated aliphatic hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less. The watch band containing at least one selected from the neutral phosphoric acid ester (B-1) represented by 1) and the neutral phosphorous acid ester (B-2) represented by the following general formula (b-2). The lubricating composition for a watch band, wherein the total concentration of the lubricant (A) and the antiwear agent (B) in the lubricating composition is 0.0025 mass% or more and less than 0.1 mass%.

(In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)

(In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
When the above-mentioned lubricating composition for a watch band is used for a watch band, it is difficult for a lubricating component to seep out from between the pin insertion portion of the bridge and the pin.

[2] The lubricating composition for watch bands according to [1] above, wherein the lubricant (A) is octacosane.
The above-mentioned lubricating composition for a watch band is preferable in that it can further strengthen the film of the component for lubrication, can further suppress exudation, and has good compatibility with the antiwear agent (B).

[3] The lubricating composition for watch bands according to [1] or [2], further containing a hindered amine compound (C-1) represented by the following general formula (c-1) as an antioxidant (C). object.

(In the formula (c-1), R ^c21 and R ^c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ^c23 is a divalent fatty acid having 1 to 10 carbon atoms. Represents a group hydrocarbon group.)
The above-mentioned lubricating composition for a watch band can lubricate the connecting portion of the bridge for a long period of time even if the content of the lubricant (A) and the antiwear agent (B) is smaller.

[4] The lubricating composition for watch bands according to any one of the above [1] to [3], further containing at least one selected from coumarin and coumarin derivatives as the fluorescent agent (D).
The above-mentioned lubricating composition for a watch band can be inspected for proper adhesion of the lubricant (A) and the antiwear agent (B).

[5] The watch band according to any one of the above [1] to [4], wherein the lubricant (A) is contained in an amount (parts by mass) that is equal to or more than the amount of the antiwear agent (B). Lubricating composition.
The above-mentioned lubricating composition for a watch band easily attaches the antiwear agent (B) to the pin.

[6] A method for manufacturing a watch band including a pin and a piece having a pin insertion part, the watch band lubricating composition comprising a lubricant (A), an antiwear agent (B) and a solvent in the pin. And then removing the solvent to attach the lubricant (A) and the antiwear agent (B) to the pin, and the pin insertion portion to the lubricant (A) and the anti-wear agent. Inserting the pin to which the wear agent (B) adheres and fixing the bridge with the pin, wherein the lubricant (A) contains paraffin wax (A-1) or has a melting point of 45. The antiwear agent (B) contains at least one selected from aliphatic saturated hydrocarbons (A-2) having a carbon number of 23 or more and 38 or less at a temperature of not less than 0 ° C., and the antiwear agent (B) has the following general formula (b-1) The lubricating composition for a watch band, which contains at least one selected from the group consisting of the neutral phosphoric acid ester (B-1) represented and the neutral phosphorous acid ester (B-2) represented by the following general formula (b-2). In the product, the concentration of the lubricant (A) and the antiwear agent (B) is 0.0025 mass% or more and less than 0.1 mass% in total, and a method for manufacturing a watch band.

(In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)

(In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)

[7] A watch band including a pin and a piece having a pin insertion portion, wherein the pin is inserted into the pin insertion portion and the piece is fixed by the pin, and the pin and the piece are lubricated. The agent (A) and the antiwear agent (B) are interposed, and the lubricant (A) contains paraffin wax (A-1) or has a melting point of 45 ° C. or higher and a carbon atom number of 23 or more. The antiwear agent (B) contains at least one selected from aliphatic saturated hydrocarbons (A-2) of 38 or less, and the antiwear agent (B) is a neutral phosphate (B- A watch band containing at least one selected from 1) and a neutral phosphite (B-2) represented by the following general formula (b-2).

(In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)

(In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
According to the method of manufacturing the timepiece band and the timepiece band, the lubricant (A) and the antiwear agent (B) are less likely to exude from between the pin insertion portion and the pin of the bridge, and the appearance can be maintained. Moreover, the connecting portion of the bridge can be lubricated for a long period of time.

[8] A lubricating composition for watch bands, comprising a lubricant (A), an antiwear agent (B), a fluorescent agent (D) and a solvent, wherein the lubricant (A) is paraffin wax (A-1). Or containing at least one selected from the group consisting of aliphatic saturated hydrocarbons (A-2) having a melting point of 45 ° C. or higher and a carbon atom number of 23 or more and 38 or less, and the antiwear agent (B) is At least one selected from a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B-2) represented by the following general formula (b-2) And the fluorescent agent (D) contains at least one selected from coumarin and coumarin derivatives. In the lubricating composition for watch band, the lubricant (A), the fluorescent agent (D), and the abrasion resistance are included. The total concentration of the agent (B) is 0.0025% by mass or more and less than 0.1% by mass, and the total amount of the lubricant (A) and the fluorescent agent (D) is the antiwear agent (B). The lubricating composition for a watch band, which is contained in an amount (parts by mass) or more of

(In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)

(In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
When the above-mentioned lubricating composition for a watch band is used for a watch band, it is difficult for a lubricating component to seep out from between the pin insertion portion of the bridge and the pin.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example 1-1]
Octacosane (purity 98% or more, melting point 60 to 63 ° C.) as the aliphatic saturated hydrocarbon (A-2) and 4,4′-butylidene bis (3-methyl-6) as the neutral phosphite (B-2) in -t- butylphenyl ditridecyl phosphite) (formula ^{(b-2), R b21} ~ R b24 = tridecyl, R ^b25, R ^b27 = methyl, R ^b26, R ^b28 = t- butyl ^group, R b291 = Hydrogen atom, R ^b292 = n-propyl group), and hexane as a solvent.
Octacosane and 4,4′-butylidene bis (3-methyl-6-t-butylphenylditridecyl phosphite) were added to hexane, and the mixture was stirred by ultrasonic waves to obtain a watch band lubricating composition. The saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) quickly dissolved in the solvent.
Here, the concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was adjusted to be 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.005% by mass, and the concentration of the neutral phosphite (B-2) was 0.005% by mass.

[Example 1-2]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0075% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00375% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00375% by mass.

[Example 1-3]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.005% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) is , 0.0025% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.0025% by mass.

[Example 1-4]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0025% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00125% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00125% by mass.

[Example 1-5]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.02% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 1-1, except that the concentration was adjusted to 01% by mass and the concentration of the neutral phosphite (B-2) was 0.01% by mass. Obtained.

[Example 1-6]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.05% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 1-1, except that the concentration of the neutral phosphite (B-2) was adjusted to 0.025% by mass. Obtained.

[Example 1-7]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.09% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 1-1, except that the concentration of the neutral phosphite (B-2) was 045% by mass and the concentration was 0.045% by mass. Obtained.

[Example 1-8]
Octacosane (purity of 98% or more) as the saturated aliphatic hydrocarbon (A-2) and 4,4′-butylidene bis (3-methyl-6-t-butylphenylditril) as the neutral phosphite (B-2) in decyl phosphite) (formula ^{(b-2), R b21} ~ R b24 = tridecyl, R ^b25, R ^b27 = methyl, R ^b26, R ^b28 = t- butyl ^group, R b291 = hydrogen atom, R ^B292 = N-propyl group), and hexane as a solvent.
Octacosane and 4,4′-butylidene bis (3-methyl-6-t-butylphenylditridecyl phosphite) were added to hexane, and the mixture was stirred by ultrasonic waves to obtain a watch band lubricating composition. The saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) quickly dissolved in the solvent.
Here, the concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was adjusted to be 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.0067% by mass, and the concentration of the neutral phosphite (B-2) was 0.0033% by mass.

[Example 1-9]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-8 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0075% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.005% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.0025% by mass.

[Example 1-10]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-8 to prepare a lubricating composition for watch bands.
Here, the total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.005% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) is , 0.0033% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.0017% by mass.

[Example 1-11]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-8 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0025% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00167% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00083% by mass.

[Example 1-12]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.02% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A lubricating composition for watch bands was prepared in the same manner as in Example 1-8, except that the concentration of the neutral phosphite (B-2) was adjusted to 0.0067% by mass. Obtained.

[Example 1-13]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.05% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 1-8, except that the concentration of the neutral phosphite (B-2) was 033% by mass, and the concentration was 0.017% by mass. Obtained.

[Example 1-14]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.09% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 1-8, except that the concentration of the neutral phosphite (B-2) was adjusted to 0.03% by mass. Obtained.

[Comparative Example 1-1]
Hexane was further added to the lubricating composition for watch bands obtained in Example 1-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.002% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.001% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.001% by mass.

[Example 2-1]
Except for using octanosane (purity 98% or higher), dotriacontane (purity 96% or higher, melting point 69 to 72 ° C.) as the aliphatic saturated hydrocarbon (A-2), and prolonging the ultrasonic stirring time. A lubricating composition for watch bands was obtained in the same manner as in Example 1-1. By increasing the stirring time by ultrasonic waves, the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) could be dissolved in the solvent.
That is, the concentrations of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) were adjusted to 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.005% by mass, and the concentration of the neutral phosphite (B-2) was 0.005% by mass.

[Example 2-2]
Hexane was further added to the watch band lubricating composition obtained in Example 2-1 to prepare a watch band lubricating composition.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0025% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00125% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00125% by mass.

[Example 2-3]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.02% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 2-1, except that the concentration was adjusted to 01% by mass and the concentration of the neutral phosphite (B-2) was 0.01% by mass. Obtained.

[Example 2-4]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.09% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 2-1, except that the concentration of the neutral phosphite (B-2) was 045% by mass and the concentration was 0.045% by mass. Obtained.

[Example 2-5]
Example 1-8 except that as the aliphatic saturated hydrocarbon (A-2), octatriacan (purity of 98% or higher) was replaced by dotriacontane (purity of 96% or higher), and the stirring time by ultrasonic waves was lengthened. A lubricating composition for a watch band was obtained in the same manner as in. By increasing the stirring time by ultrasonic waves, the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) could be dissolved in the solvent.
That is, the concentrations of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) were adjusted to 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.0067% by mass, and the concentration of the neutral phosphite (B-2) was 0.0033% by mass.

[Example 2-6]
Hexane was further added to the lubricating composition for a watch band obtained in Example 2-5 to prepare a lubricating composition for a watch band.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0025% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00167% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00083% by mass.

[Example 2-7]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.02% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A lubricating composition for a watch band was prepared in the same manner as in Example 2-5, except that the concentration of the neutral phosphite (B-2) was 0133% by mass, and the concentration was 0.0067% by mass. Obtained.

[Example 2-8]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.09% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 2-5, except that the concentration was adjusted to 06% by mass and the concentration of the neutral phosphite (B-2) was 0.03% by mass. Obtained.

[Example 3-1]
Example 1-1, except that tetracosane (purity 99% or higher, melting point 50 to 53 ° C) was used as the aliphatic saturated hydrocarbon (A-2) instead of octacosane (purity 98% or higher). A lubricating composition for a watch band was obtained.
That is, the concentrations of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) were adjusted to 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.005% by mass, and the concentration of the neutral phosphite (B-2) was 0.005% by mass.

[Example 3-2]
Hexane was further added to the lubricating composition for watch bands obtained in Example 3-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of the aliphatic saturated hydrocarbon (A-2) and the neutral phosphite (B-2) is 0.0025% by mass, and the concentration of the aliphatic saturated hydrocarbon (A-2) is , 0.00125% by mass, and the concentration of the neutral phosphite (B-2) was adjusted to 0.00125% by mass.

[Example 3-3]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.02% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 3-1, except that the concentration of the neutral phosphite (B-2) was adjusted to be 0.01% by mass and 0.01% by mass. Obtained.

[Example 3-4]
The total concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was 0.09% by mass, and the concentration of the saturated aliphatic hydrocarbon (A-2) was 0. A watch band lubricating composition was prepared in the same manner as in Example 3-1, except that the concentration of the neutral phosphite (B-2) was 045% by mass and the concentration was 0.045% by mass. Obtained.

[Example 4-1]
Paraffin wax 130 ° F (melting point 46.1 to 68.3 ° C, typical melting point) as paraffin wax (A-1) instead of octacosane (purity 98% or more) as aliphatic saturated hydrocarbon (A-2) A lubricating composition for a watch band was obtained in the same manner as in Example 1-1, except that the temperature was 54.4 ° C. and it contained a liquid oil component.).
That is, the paraffin wax (A-1) and the neutral phosphite (B-2) were prepared so that the total concentration was 0.01% by mass. Further, the paraffin wax (A-1) was prepared to have a concentration of 0.005% by mass, and the neutral phosphite (B-2) was prepared to have a concentration of 0.005% by mass.

[Example 4-2]
Hexane was further added to the lubricating composition for watch bands obtained in Example 4-1 to prepare a lubricating composition for watch bands.
Here, the total concentration of paraffin wax (A-1) and neutral phosphite (B-2) is 0.0025% by mass, and the concentration of paraffin wax (A-1) is 0.00125% by mass. The concentration of the neutral phosphite (B-2) was adjusted to 0.00125% by mass.

[Example 4-3]
The total concentration of the paraffin wax (A-1) and the neutral phosphite (B-2) is 0.02% by mass, the concentration of the paraffin wax (A-1) is 0.01% by mass, neutral A lubricating composition for a watch band was obtained in the same manner as in Example 4-1, except that the concentration of the phosphite (B-2) was adjusted to 0.01% by mass.

[Example 4-4]
The total concentration of paraffin wax (A-1) and neutral phosphite (B-2) is 0.09% by mass, the concentration of paraffin wax (A-1) is 0.045% by mass, neutral A lubricating composition for a watch band was obtained in the same manner as in Example 4-1, except that the concentration of the phosphite (B-2) was adjusted to 0.045% by mass.

[Examples 5-1 to 5-6]
As the neutral phosphite (B-2), 4,4′-butylidenebis (3-methyl-6-t-butylphenylditridecylphosphite) (in the formula (b-2), R ^b21 to R ^b24 = tridecyl group, R ^b25, R ^b27 = methyl, R ^b26, R ^b28 = t- butyl ^group, R b291 = hydrogen atom, instead of R ^B292 = n-compound is a propyl group), with a compound of Table 5 A lubricating composition for watch bands was obtained in the same manner as in Example 1-1 except for the above. In Table ^{5, R b21 ~ R b24,} R b25, R b27, R b26, R b28, R b291 and R ^B292 represents a substituent in formula (b-2).
That is, the concentration of the saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) was adjusted to 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) was 0.005% by mass, and the concentration of the neutral phosphite (B-2) was 0.005% by mass.

[Example 6-1]
Octacosane (purity of 98% or more) as the saturated aliphatic hydrocarbon (A-2) and 4,4′-butylidenebis (3-methyl-6-t-butylphenylditril) as the neutral phosphite (B-2) in decyl phosphite) (formula ^{(b-2), R b21} ~ R b24 = tridecyl, R ^b25, R ^b27 = methyl, R ^b26, R ^b28 = t- butyl ^group, R b291 = hydrogen atom, R ^B292 = Compound of n-propyl group), a coumarin derivative as a fluorescent agent (D) (molecular weight 231, a derivative having substituents introduced at the 4th and 7th positions, and the substituent at the 4th position has 1 to 2 carbon atoms). And hexane as a solvent.
Octacosane, 4,4′-butylidene bis (3-methyl-6-t-butylphenylditridecyl phosphite) and coumarin derivative were added to hexane, and the mixture was stirred by ultrasonic waves to obtain a watch band lubricating composition. .. The saturated aliphatic hydrocarbon (A-2) and the neutral phosphite (B-2) quickly dissolved in the solvent.
Here, the concentration of the saturated aliphatic hydrocarbon (A-2), the fluorescent agent (D) and the neutral phosphite (B-2) was adjusted to 0.01% by mass in total. The concentration of the saturated aliphatic hydrocarbon (A-2) is 0.0025% by mass, the concentration of the fluorescent agent (D) is 0.0025% by mass, the concentration of the neutral phosphite (B-2). Was prepared to be 0.005% by mass.

[Example 6-2]
The total concentration of the saturated aliphatic hydrocarbon (A-2), the fluorescent agent (D) and the neutral phosphite (B-2) is 0.02% by mass, the saturated aliphatic hydrocarbon (A-2) Of 0.005% by mass, the concentration of the fluorescent agent (D) is 0.005% by mass, and the concentration of the neutral phosphite (B-2) is 0.01% by mass. A lubricating composition for a watch band was obtained in the same manner as in Example 6-1 except for the above.

[Example 6-3]
The total concentration of the aliphatic saturated hydrocarbon (A-2), the fluorescent agent (D) and the neutral phosphite (B-2) is 0.0075% by mass, the aliphatic saturated hydrocarbon (A-2) Of 0.0025% by mass, the concentration of the fluorescent agent (D) is 0.0025% by mass, and the concentration of the neutral phosphite (B-2) is 0.0025% by mass. A lubricating composition for a watch band was obtained in the same manner as in Example 6-1 except for the above.

[Comparative Example 2-1]
100 parts by mass of hexane, 0.1 part by mass of trioleyl phosphite and 0.1 part by mass of 130 ° paraffin were mixed to obtain a lubricating composition for a watch band. At this time, trioleyl phosphite and paraffin were dissolved in the solvent.

<Evaluation method and evaluation criteria>
The following evaluation methods 1 and 2 were performed.
(Evaluation 1)
The watch band lubricating compositions of Examples 1-1 to 5-6 and Comparative Examples 1-1 and 2-1 were subjected to the following procedure. The lubricating composition for a watch band was placed on an Inconel pin placed in a small plate, dried at room temperature, and the solvent was evaporated. A watch band was assembled using a pin to which a lubricating component was attached and a stainless steel piece.
The watch band lubricating compositions of Examples 6-1 to 6-3 were subjected to the following procedure. The lubricating composition for watch bands was placed on a pin made of Inconel placed in a small plate and dried at 100 ° C. to evaporate or sublimate the solvent and the fluorescent agent (D). A watch band was assembled using a pin to which a lubricating component was attached and a stainless steel piece.
The assembled watch band was kept at 100 ° C. in the atmosphere for 1 hour. Then, it was examined whether or not the lubricating component exudes from between the pin insertion portion of the bridge and the pin.
The evaluation criteria are as follows. It should be noted that, if A to C, it is a level at which the aesthetic appearance can be maintained for a long time when the watch band is used.
A: No oozing out of the lubricating component is observed.
B: Lubricating component slightly exudes.
C: Lubricating component slightly exudes (the amount is larger than B).
D: Lubricating component is oozing out (larger amount than C).
The evaluation results are shown in the table below.

(Evaluation 2)
The lubricating compositions for watch bands of Examples 1-1 to 5-6 and Comparative Examples 1-1 and 2-1 were subjected to the following procedure. An Inconel pin was inserted into the pin insertion portion of the stainless steel piece, and the watch band was assembled first. Then, the watch band lubricating composition was placed between the pin insertion portion of the bridge and the pin, dried at room temperature, and the solvent was evaporated.
In this way, the lubricating component was attached between the pin insertion portion of the piece and the pin.
The assembled watch band was kept at 100 ° C. in the atmosphere for 1 hour. Then, it was examined whether or not the lubricating component exudes from between the pin insertion portion of the bridge and the pin.
The evaluation criteria are as follows. It should be noted that, if A to C, it is a level at which the aesthetic appearance can be maintained for a long time when the watch band is used.
A: No oozing out of the lubricating component is observed.
B: Lubricating component slightly exudes.
C: Lubricating component slightly exudes (the amount is larger than B).
D: Lubricating component is oozing out (larger amount than C).
The evaluation results are shown in the table below.

In Comparative Example 1-1, the evaluation results of Evaluations 1 and 2 were A, but it was difficult to remove the pin from the piece. Also, the squeak of the watch band was seen. In Comparative Example 2-1, the evaluation results of Evaluations 1 and 2 were D.

As described above, in the method of manufacturing a watch band, when the film laminating step is included, the lubricating composition for a watch band is provided between the pin insertion part and the pin after performing the wiping step or the treating step. You may perform the process (additional adhesion process) of making additional adhesion. The excellent evaluation result of Evaluation 2 corresponds to that the lubricating component is less likely to exude from between the pin insertion portion and the pin of the bridge and the aesthetic appearance can be maintained even when the additional attachment step is performed. That is, according to the lubricating composition for a watch band of the example, it is understood that the lubricating component is less likely to exude and the aesthetic appearance can be maintained even when the additional adhesion step is performed.

Claims (8)

1. A lubricating composition for a watch band, comprising a lubricant (A), an antiwear agent (B) and a solvent,
   The lubricant (A) contains at least paraffin wax (A-1) or has a melting point of 45 ° C. or higher and is selected from at least aliphatic saturated hydrocarbons (A-2) having 23 to 38 carbon atoms. Including one
   The antiwear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B-1) represented by the following general formula (b-2). -2) containing at least one selected from
   In the lubricating composition for a watch band, the concentrations of the lubricant (A) and the antiwear agent (B) are 0.0025 mass% or more and less than 0.1 mass% in total.
   Lubricating composition for watch band.
   

   

   (In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 And R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms, and R ^b191 and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)
   

   

   (In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
2. The lubricant (A) is octacosane,
   The lubricating composition for watch bands according to claim 1.
3. Further, as the antioxidant (C), a hindered amine compound (C-1) represented by the following general formula (c-1) is included:
   The lubricating composition for watch bands according to claim 1 or 2.
   

   

   (In the formula (c-1), R ^c21 and R ^c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ^c23 is a divalent fatty acid having 1 to 10 carbon atoms. Represents a group hydrocarbon group.)
4. Furthermore, the fluorescent agent (D) contains at least one selected from coumarin and coumarin derivatives,
   The lubricating composition for watch bands according to any one of claims 1 to 3.
5. The lubricant (A) is contained in an amount (parts by mass) greater than or equal to the amount of the antiwear agent (B).
   The lubricating composition for watch bands according to any one of claims 1 to 4.
6. A method of manufacturing a watch band including a piece having a pin and a pin insertion part
   A lubricating composition for a watch band containing a lubricant (A), an antiwear agent (B) and a solvent is adhered to the pin, then the solvent is removed, and the lubricant (A) and Depositing the antiwear agent (B),
   Inserting the pin to which the lubricant (A) and the anti-wear agent (B) adhere to the pin insertion portion, and fixing the bridge by the pin,
   The lubricant (A) contains at least paraffin wax (A-1) or has a melting point of 45 ° C. or higher and is selected from at least aliphatic saturated hydrocarbons (A-2) having 23 to 38 carbon atoms. Including one
   The antiwear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B) represented by the following general formula (b-2). -2) including at least one selected from
   In the lubricating composition for watch bands, the concentration of the lubricant (A) and the antiwear agent (B) is 0.0025 mass% or more and less than 0.1 mass% in total.
   Manufacturing method of watch band.
   

   

   (In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)
   

   

   (In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
7. A watch band including a piece having a pin and a pin insertion portion, wherein the pin is inserted into the pin insertion portion, and the piece is fixed by the pin,
   A lubricant (A) and an antiwear agent (B) are interposed between the pin and the bridge,
   The lubricant (A) contains at least paraffin wax (A-1) or has a melting point of 45 ° C. or higher and is selected from at least aliphatic saturated hydrocarbons (A-2) having 23 to 38 carbon atoms. Including one
   The antiwear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B) represented by the following general formula (b-2). -2) containing at least one selected from
   Watch band.
   

   

   (In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)
   

   

   (In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)
8. A lubricating composition for a watch band, comprising a lubricant (A), an antiwear agent (B), a fluorescent agent (D) and a solvent,
   The lubricant (A) contains at least paraffin wax (A-1) or has a melting point of 45 ° C. or higher and is selected from at least aliphatic saturated hydrocarbons (A-2) having 23 to 38 carbon atoms. Including one
   The antiwear agent (B) includes a neutral phosphoric acid ester (B-1) represented by the following general formula (b-1) and a neutral phosphorous acid ester (B) represented by the following general formula (b-2). -2) containing at least one selected from
   The fluorescent agent (D) contains at least one selected from coumarin and coumarin derivatives,
   In the lubricating composition for a watch band, the concentrations of the lubricant (A), the fluorescent agent (D) and the antiwear agent (B) are 0.0025 mass% or more and less than 0.1 mass% in total. ,
   The lubricant (A) and the fluorescent agent (D) are contained in total in an amount (parts by mass) equal to or more than the amount of the antiwear agent (B).
   Lubricating composition for watch band.
   

   

   (In the formula ^{(b-1), R b11} ~ R b14 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b15 ~ R} b18 each independently represent a carbon atom 1 R ^b191 and R ^b192 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b191 And} the total number of carbon atoms of R ^b192 is 1 to 5.)
   

   

   (In the formula ^{(b-2), R b21} ~ R b24 each independently represent an aliphatic hydrocarbon group having a carbon number of ^{10 ~ 16, R b25 ~ R} b28 each independently represent a carbon atom 1 R ^b291 and R ^b292 each independently represent a hydrogen atom or a straight chain or branched alkyl group having 1 to 5 carbon atoms, and R ^{b291 And} the total number of carbon atoms of R ^b292 is 1 to 5.)