CN108239569B - Lubricating agent for decorative article, method for manufacturing timepiece, and timepiece - Google Patents

Lubricating agent for decorative article, method for manufacturing timepiece, and timepiece Download PDF

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CN108239569B
CN108239569B CN201711431220.XA CN201711431220A CN108239569B CN 108239569 B CN108239569 B CN 108239569B CN 201711431220 A CN201711431220 A CN 201711431220A CN 108239569 B CN108239569 B CN 108239569B
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compound
formula
carbon atoms
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CN108239569A (en
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赤尾祐司
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Citizen Watch Co Ltd
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Citizen Watch Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention relates to a lubricant for decorative articles, a method for manufacturing timepieces, and a timepiece. The invention provides a lubricating agent for ornaments which does not cause stains. A lubricant treatment agent for ornaments contains a compound (A) represented by the formula (A) and a compound (B) represented by the formula (B), and the compound (A) and the compound (B) are contained in an amount of 1 mass% or more in total. (in the formula (A), RA1、RA2And RA3At least 1 of them is a group represented by the formula (a), and the others are OH groups. In the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. In the formula (B), RB1、RB2And RB32 of them are OH groups, and the remainder are groups represented by the formula (b). In the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. )
Figure DDA0001524934940000011
Figure DDA0001524934940000012

Description

Lubricating agent for decorative article, method for manufacturing timepiece, and timepiece
Technical Field
The invention relates to a lubricating agent for a decorative article, a method for manufacturing a timepiece, and a timepiece.
Background
A metal clasp (left) as a member for connecting the 6-point side band and the 12-point side band was used as a band of a wristwatch. The clasp has a locking part for wearing the watch on the wrist. Further, a slide portion may be provided to adjust the length of the band.
Further, a treatment for adhering the lubricating composition to the manufactured watch buckle was performed. As the lubricating composition, for example, a lubricating composition containing a hydrocarbon and/or an ether, a neutral phosphate and/or a neutral phosphite, paraffin wax can be used (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2010-1333
Disclosure of Invention
However, when the lubricating composition is attached to a manufactured buckle, stains may occur over time. In addition, when the lubricating composition is attached to a component other than a buckle (specifically, when the lubricating composition is attached to a sliding portion included in an accessory such as a timepiece or a bracelet), stains may occur with time. Examples of the sliding portion include gears, bearings, coupling pins and coupling holes of the belt segment (バンド ).
Therefore, an object of the present invention is to provide a lubricating agent for ornaments which can suppress the occurrence of stains when used for ornaments (including, in addition to a clasp of a watch band, a sliding portion included in ornaments such as a timepiece and a bracelet).
The lubricant for ornaments of the present invention comprises a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B), and the compound (A) and the compound (B) are contained in an amount of 1% by mass or more in total.
Figure BDA0001524934920000021
(in the formula (A), RA1、RA2And RA3At least 1 of eachIndependently a group represented by the following formula (a), RA1、RA2And RA3Wherein other than the group represented by the following formula (a) is an OH group, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000022
(in the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
Figure BDA0001524934920000023
(in the formula (B), RB1、RB2And R B32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000024
(in the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. )
The lubricating treatment agent for accessories of the present invention can suppress the occurrence of stains when accessories (sliding parts included in accessories such as timepieces and bracelets, in addition to a clasp of a watch band) are used.
Drawings
Fig. 1 is a perspective view of a clasp.
Fig. 2 is a perspective view of the clasp in an exploded state.
Description of the symbols
16-point side belt
212 point side belt
3 middle plate
4 outer plate
5 center folding part
6 watch buckle
6a watch buckle main body
9 clamping claw
9a shaft part
9b umbrella part
16 watch buckle frame
17 automatic reset button holding part
18 sliding plate
19. 20 automatic reset button
35 plate body
36 opening part
37 ratchet tooth
37a locking side part
38 button body
39 notch part
40 engaging part
41 engaging projection
Detailed Description
Embodiments (embodiments) 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. The components described below include components that can be easily conceived by those skilled in the art, and substantially the same components. The following configurations may be combined as appropriate. Various omissions, substitutions, and changes in the configuration may be made without departing from the spirit of the invention.
< lubricating agent for watch band >
The lubricating treatment agent for a wristband according to an embodiment includes a compound (a) and a compound (B).
The compound (A) is represented by the following formula (A). The compound (a) may be used alone or in combination of two or more. The compound (a) is excellent in lubricity.
Figure BDA0001524934920000041
In the formula (A), RA1、RA2And RA3At least one of (a) is each independently a group represented by the following formula (a). RA1、RA2And RA3Wherein the group other than the group represented by the following formula (a) is an OH group (hydroxyl group). In other words, the compound (A) may be R as in the compound (a1) described laterA1、RA2And RA3Each independently represents a group represented by the following formula (a). In addition, R may beA1、RA2And RA3Each of 2 of (a) is independently a group represented by the following formula (a), and the groups other than the group represented by the following formula (a) are OH groups. Specifically, R may be mentionedA1And RA2A group represented by the following formula (a), RA3In the case of an OH group; rA1And RA3A group represented by the following formula (a), RA2In the case of an OH group; rA2And RA3A group represented by the following formula (a), RA1In the case of OH groups. Further, R may be R as in the compound (a2) described laterA1、RA2And R A32 of them are OH groups, and the groups other than the OH groups are groups represented by the following formula (a). Specifically, R may be mentionedA1And RA2OH group, RA3A group represented by the following formula (a); rA1And RA3OH group, RA2A group represented by the following formula (a); rA2And RA3OH group, RA1The group represented by the following formula (a). Wherein R isA1、RA2And RA3When all of them are independently a group represented by the following formula (a), the lubricating property of the lubricating agent for a band can be further improved.
Figure BDA0001524934920000051
In the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. RaIn the case of the unsaturated hydrocarbon group, the unsaturated hydrocarbon group interacts with the metal, so that the lubricity can be further improved. RaPreferably a saturated hydrocarbon group having 13 to 19 carbon atoms or an unsaturated hydrocarbon group having 13 to 19 carbon atoms, more preferably a saturated hydrocarbon group having 13 to 17 carbon atoms or an unsaturated hydrocarbon group having 13 to 17 carbon atoms, and still more preferably an aliphatic saturated hydrocarbon group having 13 to 17 carbon atoms or an aliphatic unsaturated hydrocarbon group having 13 to 17 carbon atoms. When the number of carbon atoms is within the above range, lubricity can be further improved.
Specifically, as RaMay be mentioned- (CH)2)12CH3、-(CH2)14CH3、-(CH2)16CH3、-(CH2)14-CH(CH3)2、-(CH2)7CH＝CH(CH2)5CH3、-(CH2)7CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CH(CH2)7CH3Particular preference is given to using- (CH)2)16CH3、-(CH2)7CH＝CH(CH2)7CH3。
In the formula (A), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group include an ethylene group, an n-propylene group, and an n-butylene group. R1、R2、R3And R4Ethylene is preferred. When ethylene is used, the solubility of the compound (a) in water can be improved, and the adsorption force to the metal surface can be improved.
In the formula (A), n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. When n is1、n2、n3And n4When the amount is within the above range, the solubility of the compound (a) in water can be improved, and the adsorption force to the metal surface can be improved.
The compound (a) preferably includes the compound (a1) and the compound (a 2). The lubricating treatment agent for a watch band, which combines compound (a1) and compound (a2), is more excellent in lubricity.
Compound (a1) is represented by formula (a 1).
Figure BDA0001524934920000061
In the formula (a1), Ra11、Ra12And Ra13Each independently is a group represented by the following formula (aa 1). As described above, in this case, the lubricity of the lubricating treatment agent for a band can be further improved.
Figure BDA0001524934920000062
In the formula (aa1), Raa1Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. For Raa1And pair R in formula (A)aThe same description applies.
In the formula (a1), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. For R1、R2、R3And R4And n1、n2、n3And n4And pair R in formula (A)1、R2、R3And R4And n1、n2、n3And n4The same description applies.
Compound (a2) is represented by formula (a 2).
Figure BDA0001524934920000063
In the formula (a2), Ra21、Ra22And R a232 in (a) are OH groups, Ra21、Ra22And Ra23Except for the OH group, is a group represented by the following formula (aa 2). As mentioned above, specifically, R is exemplifieda21And Ra22OH group, Ra23A group represented by the following formula (aa 2); ra21And Ra23OH group, Ra22A group represented by the following formula (aa 2); ra22And Ra23OH group, Ra21In the case of a group represented by the following formula (aa 2). Wherein R isa21And Ra22OH group, Ra23When the compound (a1) is combined with a group represented by the following formula (aa2), the lubricity of the lubricating treatment agent for a band can be further improved.
Figure BDA0001524934920000071
In the formula (aa2), Raa2Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. For Raa2And pair R in formula (A)aThe same description applies.
In the formula (a2), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. For R1、R2、R3And R4And n1、n2、n3And n4And pair R in formula (A)1、R2、R3And R4And n1、n2、n3And n4The same description applies.
The compound (B) is represented by the following formula (B). The compound (B) may be used alone or in combination of two or more. The compound (B) is excellent in lubricity and solubility in water.
Figure BDA0001524934920000072
In the formula (B), RB1、RB2And R B32 in (a) are OH groups, RB1、RB2And RB3Wherein the group is represented by the following formula (b) except OH. Specifically, R may be mentionedB1And RB2OH group, RB3A group represented by the following formula (b); rB1And RB3OH group, RB2A group represented by the following formula (b); rB2And RB3OH group, RB1The group represented by the following formula (b). Wherein R isB1And RB2OH group, RB3In the case of a group represented by the following formula (b), the solubility in water is further excellent.
Figure BDA0001524934920000081
In the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. RbIn the case of the unsaturated hydrocarbon group, the unsaturated hydrocarbon group interacts with the metal, and thus the lubricity can be further improved. RbPreferably a saturated hydrocarbon group having 3 to 11 carbon atoms or an unsaturated hydrocarbon group having 3 to 11 carbon atoms, and more preferably an aliphatic saturated hydrocarbon group having 3 to 11 carbon atoms or an aliphatic unsaturated hydrocarbon group having 3 to 11 carbon atoms. When the number of carbon atoms is within the above range, the solubility in water can be further improved.
Specifically, as RbExamples thereof include- (CH)2)10CH3、-(CH2)8CH3、-(CH2)6CH3、-(CH2)2CH3。
In the formula (B), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. For R1、R2、R3And R4And n1、n2、n3And n4And pair R in formula (A)1、R2、R3And R4And n1、n2、n3And n4The same description applies.
The lubricating treatment agent for a band of the embodiment is preferably composed of the above-mentioned components alone or contains no other components except for the above-mentioned components and water. In this case, it is considered that the generation of stain is more suppressed. In addition, other components may be contained within a range that does not inhibit the effects of the lubricating treatment agent for a band of the embodiment. When other components are contained, the amount is, for example, 3 parts by mass or less based on 100 parts by mass of the total of the compound (a) and the compound (B).
A watch case used for a band of a wristwatch is generally manufactured by an ion plating method, a sputtering method, or the like, and thus the surface of the manufactured watch case is very clean. Therefore, the frictional force may be too large to lock and unlock the locking portion, or the sliding portion may not slide. In this case, the watch cannot be worn or removed, or the length of the band cannot be adjusted.
Therefore, a treatment for adhering the lubricating composition to the manufactured surface fastener was performed. As the lubricating oil composition, for example, a lubricating composition containing a hydrocarbon and/or an ester, a neutral phosphate and/or a neutral phosphite, and paraffin may be used. By this process, the locking portion and the sliding portion can function.
However, the lubricating composition adheres to the sliding portion inside the buckle main body by being poured into the buckle main body for the purpose of lubricating the sliding portion inside the buckle main body. In this case, the excess lubricating composition injected cannot be wiped off, and therefore remains inside the buckle body. The excess residual lubricating composition is difficult to dry sufficiently and is liable to flow out. In addition, sometimes the neutral phosphate ester and/or the neutral phosphite ester are separated and flow out. Therefore, the composition gradually oozes out from the interior of the clasp body over time from the start of injection, and spreads to a portion exposed to the surface of the clasp (not only a portion visible when wearing the watch but also when removing the watch). Further, the above lubricating composition adhering to the metal surface is liable to show a smear-like state with the lapse of time. Therefore, stains may be generated in the portion exposed on the surface of the buckle. In the manufacturing process of the timepiece, a wiping operation is performed when a stain is generated.
The locking portion is a portion exposed on the surface of the clasp, i.e., a portion visible when the timepiece is removed. In order to lubricate the locked portion, the lubricating composition is adhered to the locked portion, and the excess lubricating composition is wiped off to prevent the occurrence of stain. However, it sometimes looks like a stain over time.
In contrast, since the lubricating treatment agent for a band of the embodiment includes the compound (a) and the compound (B), the locking portion and the sliding portion can function when the lubricating treatment agent for a band is used. In addition, by the treatment with the lubricating treatment agent for a band of the embodiment, the compound (a) and the compound (B) attached to the inside of the watch buckle body remain at the positions, and are less likely to bleed out. Therefore, the stain can be prevented from being generated on the portion exposed on the surface of the buckle. As a result, the compounds (a) and (B) adhering to the surface of the metal clasp do not easily look like stains with time. Therefore, even if the compound (a) and the compound (B) adhere to the portion exposed to the surface of the clasp such as the locking portion, the occurrence of stain can be suppressed.
Further, since the compound (a) and the compound (B) attached to the interior of the clasp body stay at these positions, the locking part and the sliding part can be made to function for a long period of time by the lubricating treatment agent for a band of the embodiment.
Further, in the structures of the compound (a) and the compound (B), since the hydrocarbon group portion has lubricity, it is considered that the locking portion and the sliding portion function when the lubricating treatment agent for a band of the embodiment is used. On the other hand, the sorbitan skeleton, the polyoxyethylene moiety, and the ester bond moiety (in other words, the moiety other than the hydrocarbon group), particularly the ester bond moiety, have hydrophilicity and are adsorbed on the metal surface, so that the compound (a) and the compound (B) are likely to remain at specific positions.
The lubricating treatment agent for a band of the embodiment contains the compound (a) and the compound (B) in an amount of 1 mass% or more in total in the treatment agent (100 mass%). The lubricating treatment agent for a wristwatch band of an embodiment may contain only the compound (a) and the compound (B). The lubricating treatment agent for a band of the embodiment is preferably an aqueous solution, and more preferably contains the compound (a) and the compound (B) in an amount of 3 to 30% by mass in total in the aqueous solution (100% by mass).
When the treatment with the lubricating treatment agent for a band is performed, the lubricating treatment agent for a band containing a large amount of the compound (a) and the compound (B) and having a high viscosity can be suitably used even in the case of heating or in the case of applying ultrasonic waves. Further, when the treatment with the lubricating treatment agent for a band is performed, the lubricating treatment agent for a band, which does not contain too much of the compound (a) and the compound (B) and has a relatively low viscosity, can be preferably used without heating or applying ultrasonic waves.
In the lubricating treatment agent for a band of the embodiment, it is preferable that the compound (a) is contained in an amount of 3 to 60 parts by mass and the compound (B) is contained in an amount of 40 to 97 parts by mass, based on 100 parts by mass of the total of the compound (a) and the compound (B). When the compound (a) and the compound (B) are contained in the above amounts, lubricity can be improved. When compound (a1) and compound (a2) are used as compound (a), compound (a1) is preferably contained in an amount of 40 to 60 parts by mass and compound (a2) is preferably contained in an amount of 60 to 40 parts by mass, based on 100 parts by mass of the total of compound (a1) and compound (a 2). When compound (a1) and compound (a2) are contained in the above amounts, lubricity can be more improved.
The method for producing the lubricating treatment agent for a wristwatch band of the embodiment is not particularly limited as long as an aqueous solution containing the compound (a) and the compound (B) can be obtained. However, the lubricating treatment agent for watch bands can be prepared by, for example, the following method.
First, the compound (a) is added to the compound (B) and mixed to be uniform. Next, the obtained mixture was dissolved in water to obtain an aqueous solution. In this way, the lubricating treatment agent for a watch band was prepared as an aqueous solution. Further, when the compound (a1) and the compound (a2) are used as the compound (a), the compound (a1) is added to a part of the compound (B) and mixed to be uniform. Next, the resulting mixture was dissolved in water, thereby obtaining an aqueous solution (1). Further, compound (a2) was added to the remaining compound (B) and mixed to make uniform. Next, the resulting mixture was dissolved in water, thereby obtaining an aqueous solution (2). The obtained aqueous solution (1) and the aqueous solution (2) were mixed to prepare a lubricating treatment agent for a watch band as an aqueous solution. In addition, in the case of a lubricating treatment agent for a watch band comprising only the compound (a) and the compound (B), the compound (a) is added to the compound (B) and mixed to be uniform, whereby the lubricating treatment agent for a watch band can be prepared. In the preparation of the lubricating treatment agent for a watch band, it is preferable to prepare the lubricating treatment agent for a watch band so that the concentration of the compound (a) and the compound (B), the amount ratio of the compound (a) and the compound (B), or the amount ratio of the compound (a1) and the compound (a2) in the aqueous solution fall within the preferable range of the lubricating treatment agent for a watch band.
< method for manufacturing timepiece >
The method of manufacturing a timepiece of an embodiment includes a processing step of processing a metal clasp with a band lubricating agent, and an assembling step of assembling a timepiece using the clasp processed in the processing step. Thus, a watch with the compound (a) and the compound (B) attached to the watch button was obtained. The watch clasp of this watch is excellent in lubricity and can suppress the occurrence of stain in the clasp.
First, the structure of a clasp used in the method of manufacturing a timepiece (wristwatch) according to the embodiment will be described in more detail with reference to the drawings. Fig. 1 is a perspective view of a clasp. Fig. 2 is a perspective view of the clasp in an exploded state.
As shown in fig. 1, the clasp 6 is made of metal and is connected to the 6-point side band 1 and the 12-point side band 2. The watch body is finally connected to the 6 o 'clock band 1 and the 12 o' clock band 2 to form a wristwatch. The clasp 6 is composed of a central folding member 5 and a clasp main body 6 a. The center folding member 5 is composed of a middle plate 3 and a frame-shaped outer plate 4 rotatably connected to an end of the middle plate 3. An engaging claw 9 is implanted on the front surface side of the middle plate 3. The engaging claw 9 has an umbrella portion 9b formed at an end of the shaft portion 9 a.
As shown in fig. 1 and 2, the clasp main body 6a includes a clasp frame 16, an automatic-return-button holding member 17, a slide plate 18, and automatic-return buttons 19 and 20.
The slide plate 18 includes a plate body 35, and the plate body 35 has an opening 36 formed therein. A plurality of ratchet teeth 37 constituting an engaging tooth portion are formed in both side edge portions of the opening portion 36 in the band longitudinal direction. In this case, the ratchet 37 is formed so as to direct the locking side portion 37a toward the 12-point side belt 2 side. The automatic reset buttons 19 and 20 have a button body 38, and a notch 39 is formed on one side of the front end of the button body 38. An arc-shaped engaging portion 40 is formed on the tip end side of the notch 39, and an engaging projection 41 is formed on the main body side of the notch 39.
The automatic reset buttons 19 and 20 are locked by the automatic reset button holding member 17, and the slide plate 18 is locked between the watch case 16 and the automatic reset button holding member 17.
The locking part is composed of an engaging claw 9 and an engaging part 40, the engaging claw 9 has a shaft part 9a and an umbrella part 9b, and the sliding part is composed of an engaging protrusion 41 and a ratchet 37 having a locking side part 37 a.
Next, the operation of putting on and taking off the timepiece having the timepiece 6 having the timepiece after the processing step (in other words, the operation of locking the locking portion and the operation of releasing the locking portion) will be described. In the wearing operation, after the wrist is put through the wristwatch, 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 engages with the engaging portion 40. In this way, the wristband is worn on the wrist. On the other hand, in the removal operation, the button main bodies 38 of the automatic reset buttons 19 and 20 are pushed from both sides, the engagement portions 40 are pushed, the engagement of the engagement claws 9 is released, the middle plate 3 is opened to the outside, and the wrist is pulled out.
The length adjustment operation (in other words, the sliding operation of the sliding portion) of the timepiece having the watch bezel 6 having undergone the processing step will be described. When the outer plate 4 is moved in the direction of shortening the band, i.e., toward the 6-point side band 1 side, the slide plate 18 is moved and the ratchet teeth 37 are slid on the engaging projections 41 of the automatic return buttons 19, 20, and when the movement of the slide plate 18 is stopped, the engaging projections 41 are engaged with the ratchet teeth 37. This is achieved by the ratchet teeth 37 being formed on the slide plate 18 such that the engaging side portions 37a thereof face the 12-point side belt 2 side. In this way, the length adjustment operation is performed toward the direction of shortening the band.
On the other hand, when the length adjustment operation is performed in a direction to extend the band, the automatic reset buttons 19 and 20 must be pushed inward. This is achieved by the locking side portion 37a of the ratchet 37 being formed toward the 12-point side belt 2 side. That is, even if the 12-point side belt 2 is pulled in the direction of separating from the 6-point side belt 1, the engagement between the locking side portion 37a and the engaging projection 41 is maintained, and the slide plate 18 does not move. When the automatic reset buttons 19, 20 are pressed, the catching projections 41 are separated from the ratchet teeth 37 of the slide plate 18. In this state, the 12-point side belt 2 is pulled in a direction separating from the 6-point side belt 1, and the slide plate 18 is moved. After a predetermined fine adjustment, the pressing of the automatic reset buttons 19 and 20 is released and the automatic reset buttons are moved outward, so that the engaging protrusion 41 is engaged with the ratchet 37 of the slide plate 18. In this way, the length adjustment operation is performed toward the direction in which the band is stretched.
(treatment Process)
In the treatment process, the surface of the surface fastener 6 is very clean and has the above-described structure, and the surface fastener 6 is usually manufactured by an ion plating method, a sputtering method, or the like. The clasp 6 is in a state where the frictional force is too large and the engaging portion and the sliding portion are not able to function.
In the treatment step, the watch buckle 6 is immersed in the aqueous solution of the lubricating treatment agent for a watch band. The impregnation into the aqueous solution may be carried out at ordinary temperature. Alternatively, the heating is performed, for example, while heating to a temperature of 30 to 60 ℃. Alternatively, the ultrasonic wave may be applied. Next, the watch buckle 6 is washed with water and dried. In this treatment step, the compound (a) and the compound (B) are adhered to the surface of the front opening 6. Since the lubricating agent for a band is an aqueous solution and the watch buckle 6 is immersed in the aqueous solution, the compound (a) and the compound (B) can be adhered to the inside of the watch buckle body 6 a.
By this processing step, the above-described attaching operation, detaching operation, and length adjusting operation (in other words, the locking operation and releasing operation of the locking portion, and the sliding operation of the sliding portion) of the timepiece can be realized. That is, the locking portion and the sliding portion can function. In addition, the occurrence of stain can be suppressed by this treatment step. As described above, even if the compound (a) and the compound (B) adhere to the surface exposed to the surface of the buckle, it seems that the compound (a) and the compound (B) hardly form spots. Therefore, a simple treatment procedure can be adopted in which the whole of the surface of the clasp 6 including the locking part and the sliding part is immersed in an aqueous solution to adhere the compound (a) and the compound (B) to the whole surface of the clasp 6.
(Assembly Process)
In the assembling step, the timepiece is assembled by using the clasp 6 processed in the processing step. Specifically, the reaction can be carried out by a known method using a known member.
The clasp used in the method of manufacturing a timepiece of the embodiment is not limited to the clasp 6 having the above-described structure, as long as it has a locking portion or a sliding portion. The locking portion is not limited to the locking portion having the above-described configuration, as long as the wristwatch can be worn on the wrist. The slide portion is not limited to the slide portion having the above-described structure as long as it has a function of adjusting the length of the band. Further, after the treatment step, in the assembling step, the 6-point side band 1, the 12-point side band 2, and the buckle 6 may be assembled.
< timepiece >
The timepiece of the embodiment has a metal clasp. The structure of the watch clasp is as described in the manufacturing method of the timepiece, specifically. The compound (a) represented by the formula (a) and the compound (B) represented by the formula (B) are attached to the clasp (specifically, the surface of the clasp). The compound (a) and the compound (B) are as described in the lubricating treatment agent for a band of the embodiment. In the timepiece of the embodiment, the lubricity of the clasp is excellent, and the occurrence of stain in the clasp can be suppressed.
Here, the attachment of the compound (a) and the compound (B) can be confirmed by liquid chromatography-mass spectrometry (LC-MS) or the like. The timepiece of the embodiment is not limited to the timepiece 6 having the above-described structure, as long as the timepiece has a locking portion or a sliding portion. The locking portion is not limited to the locking portion having the above-described configuration, as long as the wristwatch can be worn on the wrist. The slide portion is not limited to the slide portion having the above-described structure as long as it has a function of adjusting the length of the band.
The timepiece of the embodiment can be obtained, for example, by the processing step and the assembling step described in the manufacturing method of the timepiece of the embodiment.
< other embodiment >
In the above embodiments, the lubricating treatment agent for a watchband is described as the lubricating treatment agent for a decorative article. In another embodiment (lubricant for other accessories), for example, a lubricant for a sliding portion included in accessories such as watches and bracelets is mentioned. In another embodiment, the sliding portion may be a sliding member such as a gear, a bearing, a joint pin, a joint hole, or the like. In other embodiments, the details of the components, their proportions, the production method, and the like are the same as those of the above-described lubricating treatment agent for a watch band. The lubricant treatment agent for a sliding portion can be applied to an appropriate sliding portion according to the above-described treatment process. The other embodiments also exhibit the same effects as those of the above-described lubricating agent for a band. That is, the generation of stain can be suppressed, and excellent lubricity can be maintained for a long time.
Accordingly, the present invention relates to the following.
[1] A lubricating agent for a decorative article, characterized by comprising a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B), wherein the compound (A) and the compound (B) are contained in an amount of 1% by mass or more in total.
Figure BDA0001524934920000141
(in the formula (A), RA1、RA2And RA3At least 1 of which are each independently a group represented by the following formula (a), RA1、RA2And RA3Wherein other than the group represented by the following formula (a) is an OH group, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000142
(in the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
Figure BDA0001524934920000151
(in the formula (B), RB1、RB2And R B32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000152
(in the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. )
[2] The lubricant for ornaments according to [1], which is an aqueous solution containing the compound (A) and the compound (B) in an amount of 3 to 30% by mass in total.
The lubricating agent for decorative articles can suppress the occurrence of stains when used for a watch buckle of a watch band, for example.
[3] The lubricant treatment agent for ornaments according to [1] or [2], which comprises a compound (a1) represented by the following formula (a1) and a compound (a2) represented by the following formula (a2) as the compound (A).
Figure BDA0001524934920000153
(in the formula (a1), Ra11、Ra12And Ra13Each independently is a group represented by the following formula (aa1)1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000161
(in the formula (aa1), Raa1Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
Figure BDA0001524934920000162
(in the formula (a2), Ra21、Ra22And Ra23In (1)2 is OH, Ra21、Ra22And Ra23Wherein other than the OH group, is a group represented by the following formula (aa2), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000163
(in the formula (aa2), Raa2Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
The lubricating agent for decorative articles can suppress the occurrence of stains when used for a watch buckle of a watch band, for example.
[4] A method of manufacturing a timepiece, comprising:
a treatment step of treating the metal watch clasp with a lubricating treatment agent for a watch band,
an assembling step of assembling a timepiece by using the watch buckle processed in the processing step;
the lubricating treatment agent for a watch band contains a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B), and the compound (A) and the compound (B) are contained in an amount of 1 mass% or more in total.
Figure BDA0001524934920000171
(in the formula (A), RA1、RA2And RA3At least one of (a) and (b) is each independently a group represented by the following formula (a), RA1、RA2And RA3Wherein other than the group represented by the following formula (a) is an OH group, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000172
(in the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
Figure BDA0001524934920000173
(in the formula (B), RB1、RB2And R B32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000174
(in the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. )
[5] The method of manufacturing a timepiece according to [4], wherein the lubricating treatment agent for a band is an aqueous solution containing the compound (A) and the compound (B) in an amount of 3% by mass to 30% by mass in total.
According to the method for manufacturing a timepiece described above, a timepiece in which the occurrence of a stain can be suppressed in a clasp of a band can be obtained.
[6] A timepiece having a metal clasp, characterized in that a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B) are attached to the clasp.
Figure BDA0001524934920000181
(in the formula (A), RA1、RA2And RA3At least one of (a) and (b) is each independently a group represented by the following formula (a), RA1、RA2And RA3Wherein is an OH group, R is other than the group represented by the following formula (a)1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000182
(in the formula (a), RaIs a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms. )
Figure BDA0001524934920000183
(in the formula (B), RB1、RB2And R B32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20. )
Figure BDA0001524934920000191
(in the formula (b), RbIs a saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms. )
The timepiece can suppress the generation of a stain in a clasp of a band.
[7] The lubricating treatment agent for a decorative article according to any one of [1] to [3], which is used for a watch band.
The lubricating agent for ornaments can inhibit the generation of stains when used for watchbands.
[ examples ]
[ example 1-1]
As the compound (A), 20 parts by mass of polyoxyethylene sorbitan trioleate (compound (a 1); in the formula (a1), Ra11、Ra12And Ra13Is a group represented by the above-mentioned formula (aa1), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa1), R is an integer of 6 to 20 in totalaa1Is- (CH)2)7CH＝CH(CH2)7CH3The case of (a) and 25 parts by mass of polyoxyethylene sorbitan monostearate (compound (a 2); in the above formula (a2), Ra21And Ra22Is OH group, Ra23Is a group represented by the above-mentioned formula (aa2), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa2), R is an integer of 6 to 20 in totalaa2Is- (CH)2)16CH3In the case of (1)), 55 parts by mass of polyoxyethylene sorbitan monolaurate (in the formula (B), R is used as the compound (B)B1And RB2Is an OH group，RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)10CH3The case(s).
First, compound (a1) was added to a part of compound (B) (30 parts by mass) and mixed to be uniform. Next, the obtained mixture was dissolved in water, thereby obtaining an aqueous solution (1). Further, compound (a2) was added to the remaining compound (B) (25 parts by mass) and mixed to be uniform. Next, the obtained mixture was dissolved in water, thereby obtaining an aqueous solution (2). The obtained aqueous solution (1) and the aqueous solution (2) were mixed to prepare a lubricating treatment agent for a watch band as an aqueous solution. Here, the lubricating treatment agent for a wristwatch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 15 mass% in total.
[ examples 1-2]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1, except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 1 to 3]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 10 mass% in total.
[ examples 1 to 4]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 20 mass% in total.
[ examples 1 to 5]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1, except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 1 to 6]
A lubricating treatment agent for watch bands was obtained in the same manner as in example 1-1, except that compound (a1) was used in an amount of 5 parts by mass, compound (a2) was used in an amount of 5 parts by mass, and compound (B) was used in an amount of 90 parts by mass, and compound (B) was used in the preparation of aqueous solution (1) and 45 parts by mass in the preparation of aqueous solution (2).
[ examples 1 to 7]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 1 to 6, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 1 to 8]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 1 to 6, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 1 to 9]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1, except that the compound (a1) was used in an amount of 25 parts by mass, the compound (a2) was used in an amount of 20 parts by mass, and the compound (B) was used in an amount of 55 parts by mass, and the compound (B) was used in the preparation of the aqueous solution (1) and 35 parts by mass and the compound (B) was used in the preparation of the aqueous solution (2).
[ examples 1 to 10]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 1 to 9 except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 1 to 11]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 1 to 9, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 1 to 12]
As compound (a1), the following compounds were used: in the above formula (a1), Ra11、Ra12And Ra13Is a group represented by the above-mentioned formula (aa1), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa1), R is an integer of 6 to 20 in totalaa1Is- (CH)2)12CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1.
[ examples 1 to 13]
As compound (a2), the following compounds were used: in the above formula (a2), Ra21And Ra22Is OH group, Ra23Is a group represented by the above-mentioned formula (aa2), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa2), R is an integer of 6 to 20 in totalaa2Is- (CH)2)12CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1.
[ examples 1 to 14]
As compound (B), the following compounds were used: in the above formula (B), RB1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently isAn integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)2CH3A lubricating treatment agent for a watch band was obtained in the same manner as in example 1-1 except for the above-mentioned exceptions.
[ example 2-1]
As the compound (A), 40 parts by mass of polyoxyethylene sorbitan trioleate (compound (a 1); in the formula (a1), Ra11、Ra12And Ra13Is a group represented by the above-mentioned formula (aa1), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa1), R is an integer of 6 to 20 in totalaa1Is- (CH)2)7CH＝CH(CH2)7CH3In the case of (1)), 60 parts by mass of polyoxyethylene sorbitan monolaurate (in the formula (B), R is used as the compound (B)B1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)10CH3The case(s).
First, the compound (a) is added to the compound (B) and mixed to be uniform. Next, the resulting mixture was dissolved in water, and a lubricating treatment agent for a watch band was prepared as an aqueous solution. Here, the lubricating treatment agent for a wristwatch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 15 mass% in total.
[ examples 2-2]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 2-1, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 2 to 3]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 2-1, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 2 to 4]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 2-1, except that the compound (A) was used in an amount of 20 parts by mass and the compound (B) was used in an amount of 80 parts by mass.
[ examples 2 to 5]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 2 to 4 except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 2 to 6]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 2 to 4, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 2 to 7]
As the compound (a) (compound (a1)), the following compounds were used: in the above formula (a1), Ra11、Ra12And Ra13Is a group represented by the above-mentioned formula (aa1), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa1), R is an integer of 6 to 20 in totalaa1Is- (CH)2)12CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 2-1.
[ examples 2 to 8]
As compound (B), the following compounds were used: in the above formula (B), RB1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)2CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 2-1.
[ example 3-1]
As the compound (A), 60 parts by mass of polyoxyethylene sorbitan monostearate (compound (a 2); R in the formula (a2)a21And Ra22Is OH group, Ra23Is a group represented by the above-mentioned formula (aa2), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa2), R is an integer of 6 to 20 in totalaa2Is- (CH)2)16CH3In the case of (1)), 40 parts by mass of polyoxyethylene sorbitan monolaurate (in the formula (B), R is used as the compound (B)B1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)10CH3The case(s).
First, the compound (a) is added to the compound (B) and mixed to be uniform. Next, the obtained mixture was dissolved in water to prepare a lubricating treatment agent for a watch band as an aqueous solution. Here, the lubricating treatment agent for a wristwatch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 15 mass% in total.
[ examples 3-2]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 3 to 3]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1, except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 3 to 4]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1, except that the compound (A) was used in an amount of 40 parts by mass and the compound (B) was used in an amount of 60 parts by mass.
[ examples 3 to 5]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 3 to 4, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 3 to 6]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 3 to 4, except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 3 to 7]
A lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1, except that the compound (A) was used in an amount of 20 parts by mass and the compound (B) was used in an amount of 80 parts by mass.
[ examples 3 to 8]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 3 to 7, except that the lubricating treatment agent for a watch band was prepared in the form of an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 mass% in total.
[ examples 3 to 9]
A lubricating treatment agent for a watch band was obtained in the same manner as in examples 3 to 7, except that the lubricating treatment agent for a watch band was prepared so as to be an aqueous solution containing the compound (a) and the compound (B) in an amount of 30 mass% in total.
[ examples 3 to 10]
As the compound (a) (compound (a2)), the following compounds were used: in the above formula (a2), Ra21And Ra22Is OH group, Ra23Is a group represented by the above-mentioned formula (aa2), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (aa2), R is an integer of 6 to 20 in totalaa2Is- (CH)2)12CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1.
[ examples 3 to 11]
As compound (B), the following compounds were used: in the above formula (B), RB1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)2CH3Except for the above, a lubricating treatment agent for a watch band was obtained in the same manner as in example 3-1.
Comparative example 1
As the compound (B), polyoxyethylene sorbitan is usedMonolaurate (in the above formula (B), RB1And RB2Is OH group, RB3Is a group represented by the above formula (b), R1、R2、R3And R4Is ethylene, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4In the formula (b), R is an integer of 6 to 20 in totalbIs- (CH)2)10CH3The case(s). Compound (B) was dissolved in water to prepare an aqueous solution containing compound (B) in an amount of 15 mass%.
< evaluation method and evaluation result >
The watch buckle 6 shown in fig. 1 and 2 was treated with the prepared lubricating treatment agent for a watch band. Specifically, the watch buckle 6 is immersed in an aqueous solution of the lubricating treatment agent for a watch band. The impregnation into the aqueous solution is carried out at normal temperature. Subsequently, the watch bezel 6 was washed with water and dried. By this treatment, the compound (a) and the compound (B) are attached to the surface of the buckle 6 (the inner surface of the buckle body 6 a).
With regard to the watch buckle 6 immediately after the treatment, it was checked whether the sliding portion was able to be lubricated, that is, whether the sliding operation in the direction of shortening the band was possible. Next, the treated clasp 6 was subjected to a sliding operation in a direction to shorten the band and a sliding operation in a direction to lengthen the band for 10 minutes in succession. With respect to the clasp 6 after the continuous sliding operation, it was checked whether the sliding portion can be lubricated, that is, whether the sliding operation toward the direction of shortening the band can be performed. Further, the etching test was performed on the treated watch button 6 at a humidity of 80% RH and a temperature of 95 ℃ for 150 hours. With respect to the watch buckle 6 after the etching test, it was checked whether the sliding portion was able to be lubricated, that is, whether the sliding operation was able to be performed in the direction of shortening the band. Here, whether or not the sliding portion can be lubricated is performed at room temperature (20 ℃ C.). The results were evaluated according to the following evaluation criteria. The evaluation results are shown in tables 1 to 3. Table 1 also shows the evaluation results of the watchband 6 that was not treated with the lubricating treatment agent for watchbands as comparative example 2.
AA: the slide operation in the direction of shortening the band can be performed with a small pressing force.
A: the slide operation in the direction of shortening the band can be performed with a pressing force larger than AA.
B: the slide operation in the direction of shortening the band can be performed with a pressing force considerably larger than AA.
C: even if a pressing force is applied, the slide operation in the direction of shortening the band cannot be performed.
Further, with respect to the buckle 6 immediately after the treatment, whether or not a stain was generated was checked. In the case where any of the lubricating treatment agents for a watch band prepared in examples was used, no stain was generated. In addition, it was checked whether or not stains were generated in the surface fastener 6 after the continuous sliding operation and the surface fastener 6 after the etching test. In the case of using any of the lubricating treatment agents for watch bands prepared in examples, no stain was generated. As described above, the lubricating treatment agent for a band of the present embodiment can suppress the occurrence of stain and can also improve the lubricity.
[ TABLE 1]
(Table 1)
Immediately after treatment After continuous sliding operation After etching test
Examples 1 to 1 AA AA AA
Examples 1 to 2 AA AA AA
Examples 1 to 3 AA AA AA
Examples 1 to 4 AA AA AA
Examples 1 to 5 AA AA AA
Examples 1 to 6 AA AA AA
Examples 1 to 7 AA AA AA
Examples 1 to 8 AA AA AA
Examples 1 to 9 AA AA AA
Examples 1 to 10 AA AA AA
Examples 1 to 11 AA AA AA
Examples 1 to 12 AA AA AA
Examples 1 to 13 AA AA AA
Examples 1 to 14 AA AA AA
Comparative example 1 B C C
Comparative example 2 C - -
[ TABLE 2]
(Table 2)
Immediately after treatment After continuous sliding operation After etching test
Example 2-1 AA AA AA
Examples 2 to 2 AA AA AA
Examples 2 to 3 AA AA AA
Examples 2 to 4 AA AA AA
Examples 2 to 5 AA AA AA
Examples 2 to 6 AA AA AA
Examples 2 to 7 AA AA AA
Examples 2 to 8 AA AA AA
[ TABLE 3]
(Table 3)
Immediately after treatment After continuous sliding operation After etching test
Example 3-1 AA AA A
Examples 3 to 2 AA AA A
Examples 3 to 3 AA AA A
Examples 3 to 4 AA AA A
Examples 3 to 5 AA AA A
Examples 3 to 6 AA AA A
Examples 3 to 7 AA AA A
Examples 3 to 8 AA AA A
Examples3-9 AA AA A
Examples 3 to 10 AA AA A
Examples 3 to 11 AA AA A
The above examples are examples of the lubricating treatment agent for a watch band. From these results, it is considered that other lubricating treatment agents for accessories (for example, lubricating treatment agents for sliding contained in accessories such as watches and bracelets) can also exhibit the same effects as those of the lubricating treatment agents for watchbands. That is, the generation of smear can be suppressed, and excellent lubricity can be maintained for a long period of time.

Claims (7)

1. A lubricating treatment agent for a decorative article, characterized by comprising a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B), the compound (A) and the compound (B) being contained in an amount of 1% by mass or more in total, and a compound (a1) represented by the following formula (a1) being contained as the compound (A),
Figure FDA0003267912560000011
in the formula (A), RA1、RA2And RA3At least 1 of which are each independently a group represented by the following formula (a), RA1、RA2And RA3Except that represented by the following formula (a)The radicals other than OH, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000012
in the formula (a), RaA saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms,
Figure FDA0003267912560000013
in the formula (B), RB1、RB2And RB32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000021
in the formula (b), RbA saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms,
Figure FDA0003267912560000022
in the formula (a1), Ra11、Ra12And Ra13Each independently is a group represented by the following formula (aa1)1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000023
in the formula (aa1), Raa1Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms.
2. The lubricant treatment agent for ornaments according to claim 1, wherein the lubricant treatment agent for ornaments is an aqueous solution containing the compound (a) and the compound (B) in an amount of 3 to 30% by mass in total.
3. The lubricant treatment agent for ornaments according to claim 1 or 2, further comprising a compound (a2) represented by the following formula (a2) as the compound (A),
Figure FDA0003267912560000024
in the formula (a2), Ra21、Ra22And Ra232 in (a) are OH groups, Ra21、Ra22And Ra23Wherein other than the OH group, is a group represented by the following formula (aa2), R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000031
in the formula (aa2), Raa2Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms.
4. A method of manufacturing a timepiece, comprising:
a treatment step of treating the metal watch clasp with a lubricating treatment agent for a watch band,
an assembling step of assembling a timepiece using the bezel processed in the processing step;
the lubricating treatment agent for a watchband comprises a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B), comprises the compound (A) and the compound (B) in an amount of 1 mass% or more in total, and comprises a compound (a1) represented by the following formula (a1) as the compound (A),
Figure FDA0003267912560000032
in the formula (A), RA1、RA2And RA3At least one of (a) and (b) is each independently a group represented by the following formula (a), RA1、RA2And RA3Wherein other than the group represented by the following formula (a) is an OH group, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000041
in the formula (a), the reaction mixture is,Raa saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms,
Figure FDA0003267912560000042
in the formula (B), RB1、RB2And RB32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000043
in the formula (b), RbA saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms,
Figure FDA0003267912560000044
in the formula (a1), Ra11、Ra12And Ra13Each independently is a group represented by the following formula (aa1)1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000051
in the formula (aa1), Raa1Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms.
5. The method for manufacturing a timepiece according to claim 4, wherein the lubricating treatment agent for a band is an aqueous solution containing the compound (A) and the compound (B) in an amount of 3% by mass to 30% by mass in total.
6. A timepiece having a metal clasp, characterized in that a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B) are attached to the clasp, and a compound (a1) represented by the following formula (a1) is contained as the compound (A),
Figure FDA0003267912560000052
in the formula (A), RA1、RA2And RA3At least one of (a) and (b) is each independently a group represented by the following formula (a), RA1、RA2And RA3Wherein other than the group represented by the following formula (a) is an OH group, R1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000053
in the formula (a), RaA saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms,
Figure FDA0003267912560000061
in the formula (B), RB1、RB2And RB32 in (a) are OH groups, RB1、RB2And RB3Wherein R is a group represented by the following formula (b) except OH group1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000062
in the formula (b), RbA saturated hydrocarbon group having 11 or less carbon atoms or an unsaturated hydrocarbon group having 11 or less carbon atoms,
Figure FDA0003267912560000063
in the formula (a1), Ra11、Ra12And Ra13Each independently is a group represented by the following formula (aa1)1、R2、R3And R4Each independently an alkylene group having 2 to 4 carbon atoms, n1、n2、n3And n4Each independently is an integer of 1 or more, and n1、n2、n3And n4The total of (a) and (b) is an integer of 6 to 20,
Figure FDA0003267912560000064
in the formula (aa1), Raa1Is a saturated hydrocarbon group having 12 or more carbon atoms or an unsaturated hydrocarbon group having 12 or more carbon atoms.
7. The lubricating treatment agent for ornaments according to claim 1 or 2, which is used for a watch band.
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