CN108239569A - Ornament lubricated agent, the manufacturing method and clock and watch of clock and watch - Google Patents

Ornament lubricated agent, the manufacturing method and clock and watch of clock and watch Download PDF

Info

Publication number
CN108239569A
CN108239569A CN201711431220.XA CN201711431220A CN108239569A CN 108239569 A CN108239569 A CN 108239569A CN 201711431220 A CN201711431220 A CN 201711431220A CN 108239569 A CN108239569 A CN 108239569A
Authority
CN
China
Prior art keywords
compound
formula
carbon atom
atom number
watch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711431220.XA
Other languages
Chinese (zh)
Other versions
CN108239569B (en
Inventor
赤尾祐司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Citizen Holdings Co Ltd
Citizen Watch Co Ltd
Original Assignee
Citizen Watch Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017225101A external-priority patent/JP6814721B2/en
Application filed by Citizen Watch Co Ltd filed Critical Citizen Watch Co Ltd
Publication of CN108239569A publication Critical patent/CN108239569A/en
Application granted granted Critical
Publication of CN108239569B publication Critical patent/CN108239569B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 present invention relates to ornament lubricated agent, the manufacturing methods and clock and watch of clock and watch.The present invention provides a kind of ornament for not generating stain lubricated agent.Ornament includes the compound (A) represented by formula (A) and the compound (B) represented by formula (B) with lubricated agent, the amount of more than 1 mass % to be added up to include compound (A) and compound (B).(in formula (A), RA1、RA2And RA3In at least one be the group represented by formula (a), remaining be OH bases.In formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.In formula (B), RB1、RB2And RB3In 2 for OH bases, remaining is the group represented by formula (b).In formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.)

Description

Ornament lubricated agent, the manufacturing method and clock and watch of clock and watch
Technical field
The present invention relates to a kind of lubricated agent of ornament, the manufacturing methods and clock and watch of clock and watch.
Background technology
Metal watch buckle (in stay) in the watchband of wrist-watch used as 6 side bands of connection and the component of 12 side bands. The watch buckle has fastener in order to which wrist-watch is worn in wrist.And then in order to make it have the function of adjusting watchband length, Sometimes there is sliding part.
In addition, the processing of the watch buckle of manufacture is attached into enforcement lubricating composition.It, can be with use example as lubricating composition Such as comprising hydrocarbon and/or ether, neutral phosphate and/or neutral phosphite ester, the lubricating composition (patent document 1) of paraffin.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-1333 bulletins
Invention content
However, when making the above-mentioned lubricating composition be attached to the watch buckle of manufacture, stain occurs over time sometimes. In addition, make the situation of component that above-mentioned lubricating composition is attached to other than watch buckle (specifically, adhering to above-mentioned lubricating composition The situation on slipping part included in ornaments such as clock and watch, bracelets) under, stain can also occur over time sometimes. As above-mentioned slipping part, gear, bearing, the connecting pin of belt segment (バ ン ド Horse) and connecting hole etc. can be enumerated.
Therefore, it (other than the watch buckle of watchband, is further included for ornament the object of the present invention is to provide one kind Clock and watch, bracelet are when the slipping part that ornaments are included) when can inhibit stain generation ornament lubricated agent.
The ornament of the present invention with lubricator includes the compound (A) represented by following formula (A) and is represented by following formula (B) Compound (B), with add up to more than 1 mass % amount include above compound (A) and above compound (B).
(in formula (A), RA1、RA2And RA3In at least one be each independently the group that is represented by following formula (a), RA1、 RA2And RA3In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2 ~4 alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 Integer.)
(in formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.)
(in formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) group represented, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is respectively independent Ground is more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.)
(in formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.)
The present invention the agent of ornament lubricated use ornament (other than the watch buckle of watchband, clock and watch, bracelet etc. The slipping part that is included of ornament) when, the generation of stain can be inhibited.
Description of the drawings
Fig. 1 is the stereogram of watch buckle.
Fig. 2 is the stereogram of the decomposing state of watch buckle.
Symbol description
16 side bands
2 12 side bands
Plate in 3
4 outside plates
5 central folding means
6 watch buckles
6a watch buckle main bodys
9 engagement pawls
9a axle portions
9b umbrellas portion
16 watch buckle frames
17 push button holding members
18 sliding panels
19th, 20 push button
35 plate bodies
36 opening portions
37 ratchets
37a engages side
38 button bodies
39 notch sections
40 holding sections
41 snap fit tabs
Specific embodiment
For being used to implement the mode (embodiment) of the present invention, it is described in detail with reference to attached drawing.The present invention is not It is defined in the content described in following embodiment.In addition, those skilled in the art are included in the inscape recorded below Inscape, the practically identical inscape being readily apparent that.In addition, the composition recorded below can be appropriately combined.This Outside, various omissions, displacement or the change that can be formed without departing from the spirit and scope of the invention.
<Watchband lubricated agent>
The watchband of embodiment includes compound (A) and compound (B) with lubricated agent.
Compound (A) is represented by following formula (A).Compound (A) can use individually one kind, can also mix two or more It uses.The lubricity of compound (A) is excellent.
In formula (A), RA1、RA2And RA3At least one of be each independently the group that is represented by following formula (a).RA1、 RA2And RA3In other than the group represented by following formula (a) be OH bases (hydroxyl).In other words, for compound (A), such as Aftermentioned compound (a1) can be R like thatA1、RA2And RA3It is all the group represented by following formula (a) each independently.This Outside, it can also be RA1、RA2And RA3In 2 be each independently the group that is represented by following formula (a), in addition to by following formula (a) Group other than the group of expression is OH bases.Specifically, R can be enumeratedA1And RA2=group, the R represented by following formula (a)A3 The situation of=OH bases；RA1And RA3=group, the R represented by following formula (a)A2The situation of=OH bases；RA2And RA3=by following formula (a) group, the R representedA1The situation of=OH bases.In addition, compound (a2) as be described hereinafter is like that or RA1、RA2And RA3In 2 for OH bases, the group other than OH bases is the group represented by following formula (a).Specifically, R can be enumeratedA1With RA2=OH bases, RA3The situation of=the group represented by following formula (a)；RA1And RA3=OH bases, RA2=represented by following formula (a) The situation of group；RA2And RA3=OH bases, RA1The situation of=the group represented by following formula (a).Wherein, RA1、RA2And RA3All In the case of being each independently the group represented by following formula (a), the lubricity of watchband with lubricator can be more improved.
In formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.RaFor During unsaturated alkyl, due to unsaturated alkyl and metal interaction, lubricity can be more improved.RaPreferably carbon is former The saturation of the saturated hydrocarbyl of subnumber 13~19 or the unsaturated alkyl, more preferably carbon atom number 13~17 of carbon atom number 13~19 The sturated aliphatic hydrocarbon base of the unsaturated alkyl of alkyl or carbon atom number 13~17, further preferably carbon atom number 13~17 or The unsaturated aliphatic hydrocarbon base of carbon atom number 13~17.When carbon atom number is in above range, lubricity can be more improved.
Specifically, as Ra- (CH can be enumerated2)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)7CH3, particularly preferred use-(CH2)16CH3、-(CH2)7CH=CH (CH2)7CH3。
In formula (A), R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4.It, can as above-mentioned alkylidene Enumerate ethylidene, n-propylene, positive butylidene.R1、R2、R3And R4Preferably ethylidene.When using ethylidene, Neng Gouti The dissolubility of high compound (A) in water, and the adsorption capacity to metal surface can be improved.
In formula (A), n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~ 20 integer.Work as n1、n2、n3And n4In above range, the dissolubility of compound (A) in water can be improved, additionally is able to carry Height is to the adsorption capacity of metal surface.
As compound (A), compound (a1) and compound (a2) are preferably comprised.Combination of compounds (a1) and compound (a2) watchband is more excellent with the lubricity of lubricated agent.
Compound (a1) is represented by following formula (a1).
In formula (a1), Ra11、Ra12And Ra13Group to be represented by following formula (aa1) each independently.As described above, In this case, it can more improve the lubricity of watchband lubricated agent.
In formula (aa1), Raa1For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number. For Raa1, in formula (A) to RaExplanation it is identical.
In formula (a1), R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Respectively solely It is on the spot more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.For R1、R2、R3And R4And n1、n2、 n3And n4, in formula (A) to R1、R2、R3And R4And n1、n2、n3And n4Explanation it is identical.
Compound (a2) is represented by following formula (a2).
In formula (a2), Ra21、Ra22And Ra23In 2 for OH bases, Ra21、Ra22And Ra23In other than OH bases be by following The group that formula (aa2) represents.As described above, specifically, R can be enumerateda21And Ra22=OH bases, Ra23=by following formula (aa2) The situation of the group of expression；Ra21And Ra23=OH bases, Ra22The situation of=the group represented by following formula (aa2)；Ra22And Ra23= OH bases, Ra21The situation of=the group represented by following formula (aa2).Wherein, Ra21And Ra22=OH bases, Ra23=by following formula (aa2) in the case of the group represented, when being combined with compound (a1), the lubrication of watchband lubricated agent can more be improved Property.
In formula (aa2), Raa2For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number. For Raa2, in formula (A) to RaExplanation it is identical.
In formula (a2), R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Respectively solely It is on the spot more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.For R1、R2、R3And R4And n1、n2、 n3And n4, in formula (A) to R1、R2、R3And R4And n1、n2、n3And n4Explanation it is identical.
Compound (B) is represented by following formula (B).Compound (B) can be used alone, and can also mix two or more It uses.The lubricity of compound (B) and dissolubility in water are excellent.
In formula (B), RB1、RB2And RB3In 2 be OH bases, RB1、RB2And RB3In other than OH be by following formula (b) table The group shown.Specifically, R can be enumeratedB1And RB2=OH bases, RB3The situation of=the group represented by following formula (b)；RB1With RB3=OH bases, RB2The situation of=the group represented by following formula (b)；RB2And RB3=OH bases, RB1=represented by following formula (b) The situation of group.Wherein, RB1And RB2=OH bases, RB3In the case of=the group by following formula (b) expression, dissolving in water Property is more excellent.
In formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.RbFor During unsaturated alkyl, unsaturated alkyl and metal interaction, therefore can more improve lubricity.RbPreferably carbon atom number The aliphatic saturation of 3~11 saturated hydrocarbyl or the unsaturated alkyl of carbon atom number 3~11, more preferably carbon atom number 3~11 The unsaturated aliphatic hydrocarbon base of alkyl or carbon atom number 3~11.When carbon atom number is in above range, can more improve in water In dissolubility.
Specifically, as Rb,-(CH can be enumerated2)10CH3、-(CH2)8CH3、-(CH2)6CH3、-(CH2)2CH3。
In formula (B), R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Respectively solely It is on the spot more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.For R1、R2、R3And R4And n1、n2、 n3And n4, in formula (A) to R1、R2、R3And R4And n1、n2、n3And n4Explanation it is identical.
In addition, the watchband of embodiment be preferably only made of with lubricated agent mentioned component or in addition to mentioned component and Other ingredients are not included other than water.In such a case it is possible to think the generation of more inhibition stain.Further, it is also possible to not hindering Hinder in the range of the effect of the watchband lubricated agent of embodiment comprising other ingredients.In addition, including other ingredients In the case of, such as relative to total 100 mass parts of compound (A) and compound (B) include 3 amounts below mass part.
For wrist-watch watchband watch buckle usually by manufactures such as ion plating method, sputtering methods, therefore the table of the watch buckle manufactured Face is very clean.Therefore, it some times happens that frictional force is excessive and can not realize the locking of fastener and its releasing or sliding part Skid-resistant situation.In this case, it can not realize the wearing of wrist-watch and remove or can not adjust the length of watchband.
Therefore, the processing of the watch buckle of manufacture is attached into enforcement lubricating composition.As lubricant oil composite, such as can be with Using including hydrocarbon and/or ester, neutral phosphate and/or neutral phosphite ester, the lubricating composition of paraffin.Pass through the processing, card Stop and sliding part can play a role.
However, the lubricating composition in order to the sliding part to watch buckle body interior be lubricated processing and to be injected into watch buckle The mode of body interior is adhered to.At this moment, since the extra lubricating composition of injection can not be wiped, watch buckle main body is remained in It is internal.The extra remaining lubricating composition is difficult to fully dry and easily flows out.In addition, sometimes neutral phosphate and/or Neutral phosphite ester is detached and is flowed out.Therefore, since injection as time goes by, above-mentioned composition is gradually from watch buckle master Internal portion's exudation, and the part for expanding to the surface for being exposed to watch buckle (also has when being not only to wear wrist-watch and also can when removing wrist-watch The part seen).In addition, the above-mentioned lubricating composition for being attached to metal surface is easily shown as stain as time goes by Shape.Therefore, stain is generated in the part on the surface for being exposed to watch buckle sometimes.It is also to generate dirt in the manufacturing process of clock and watch Wiping operation is carried out during point.
In addition, fastener is the part for being exposed to watch buckle surface, removes part visual during clock and watch.In order to fastener Processing is lubricated, above-mentioned lubricating composition is made to be attached at this, and wipes extra lubricating composition and prevents stain It generates.But look like stain shape sometimes as time goes by.
In contrast, the watchband of embodiment lubricated agent includes compound (A) and compound (B), therefore use During watchband lubricated agent, fastener and sliding part can play a role.In addition, the watchband by embodiment lubricates The processing of inorganic agent, the compound (A) and compound (B) for being attached to watch buckle body interior are stayed in the position, it is not easy to be oozed out.Cause This, can inhibit the part for being exposed to the surface of watch buckle to generate stain.After all, it is attached to the change on metal watch buckle surface It closes object (A) and compound (B) is also not easy to look like stain shape as time goes by.Therefore, even if in dew such as fasteners For the part attachment compound (A) and compound (B) on watch buckle surface, it can also inhibit the generation of stain.
In addition, since the compound (A) and compound (B) that are attached to watch buckle body interior stop in the position, lead to The watchband lubricated agent of embodiment is crossed, fastener and sliding part long-term role can be made.
Accordingly, it may be concluded that in the structure of compound (A) and compound (B), since the part of alkyl has lubrication Property, therefore during the watchband lubricated agent of use embodiment, fastener and sliding part function.On the other hand, it is dehydrated D-sorbite skeleton, polyoxyethylene moities and ester bond part (the in other words part other than alkyl), especially ester bond part have parent It is aqueous, metal surface is adsorbed in, therefore compound (A) and compound (B) are readily retained in specific position.
The watchband of embodiment with lubricated agent in the inorganic agent (100 mass %), with add up to more than 1 mass % Amount includes compound (A) and compound (B).The watchband lubricated agent of embodiment can only comprising compound (A) and Compound (B).In addition, the watchband of embodiment is preferably aqueous solution with lubricated agent, more preferably in aqueous solution (100 matter Measure %) in, the amount of the mass % of 3 mass %~30 to be added up to include compound (A) and compound (B).
The situation of heating or in the case of applying ultrasonic wave when carrying out the processing using watchband lubricated agent, greatly Amount can also be used well comprising compound (A) and compound (B) and the higher watchband of viscosity with lubricated agent.In addition, When carrying out the processing using watchband lubricated agent in the case where not heating, not applying ultrasonic wave, not comprising too many Compound (A) and compound (B) and the relatively low watchband of ratio of viscosities can be used preferably with lubricated agent.
Embodiment watchband in lubricated agent, 100 mass parts are added up to compound (A) and compound (B) When, preferably comprise the compound of the amount of the mass parts of the compound (A) of the amount of the mass parts of 3 mass parts~60,40 mass parts~97 (B).When including compound (A) and compound (B) with above-mentioned amount, lubricity can be improved.In addition, using compound (a1) and When compound (a2) is as compound (A), when adding up to 100 mass parts with compound (a1) and compound (a2), preferably comprise The compound (a2) of the amount of the mass parts of the compound (a1) of the amount of the mass parts of 40 mass parts~60,60 mass parts~40.More than When the amount stated includes compound (a1) and compound (a2), lubricity can be more improved.
The preparation method of watchband lubricated agent as embodiment, if can obtain comprising compound (A) and The aqueous solution of compound (B), is not particularly limited.However, it is possible to prepare watchband lubricated for example, by following methods Agent.
First, compound (A) is added in compound (B) and is mixed makes it uniformly.Then, obtained mixture is dissolved Into water, so as to obtain aqueous solution.By this method, the watchband lubricated agent as aqueous solution is prepared.In addition, as chemical combination Object (A), during using compound (a1) and compound (a2), compound (a1) is added in a part of compound (B) and is mixed makes It is uniformly.Next, obtained mixture is dissolved into water, so as to obtain aqueous solution (1).In addition, in remaining compound (B) compound (a2) is added in and is mixed makes it uniformly.Next, obtained mixture is dissolved into water, so as to obtain water Solution (2).Obtained aqueous solution (1) and aqueous solution (2) are mixed, so as to prepare at the watchband lubrication as aqueous solution Manage agent.In addition, in the case where the watchband for only including compound (A) and compound (B) is with lubricated agent, at compound (B) Middle addition compound (A) and mixing make it uniformly, so as to prepare watchband lubricated agent.It should be explained that it is used in watchband In the preparation of lubricated agent, it is desirable to in aqueous solution compound (A) and the concentration of compound (B), compound (A) and chemical combination The amount ratio or the amount of compound (a1) and compound (a2) of object (B) are than the preferred scope for above-mentioned watchband lubricated agent Mode prepared.
<The manufacturing method of clock and watch>
The manufacturing method of the clock and watch of embodiment including the use of watchband with lubricated agent to metal watch buckle at The treatment process of reason uses the assembling procedure of above-mentioned watch buckle assembling clock and watch handled in above-mentioned treatment process.It obtains as a result, Adhere to the clock and watch of compound (A) and compound (B) in watch buckle.The lubricity of the watch buckle of this clock and watch is excellent, and can inhibit The generation of stain in watch buckle.
First, it is more specific come the structure of watch buckle used in the manufacturing method of the clock and watch (wrist-watch) to embodiment with attached drawing Ground illustrates.Fig. 1 is the stereogram of watch buckle.Fig. 2 is the stereogram of the decomposing state of watch buckle.
As shown in Figure 1, watch buckle 6 is made of metal, and link with 6 side bands 1 and 12 side bands 2.In addition, 61 Hes of side band Finally link clock and watch main body on 12 side bands 2 and become wrist-watch.Watch buckle 6 is made of central folding means 5 and watch buckle main body 6a.In Centre folding means 5 are made of the outside plate 4 of middle plate 3 and the frame-shaped for the end for being pivotally attached at middle plate 3.Middle plate 3 Surface side is implanted with engagement pawl 9.The engagement pawl 9 is formed with umbrella portion 9b in the end of axle portion 9a.
As shown in Figure 1 and Figure 2, watch buckle main body 6a by watch buckle frame 16, push button holding member 17, sliding panel 18, from Dynamic reset button 19,20 is formed.
In addition, sliding panel 18 has plate body 35, opening portion 36 is formed in the plate body 35.The both sides of the opening portion 36 Edge is formed with the multiple ratchets 37 for forming engaging teeth portion to watchband length direction.In this case, ratchet 37 is this to be engaged The mode of side 37a towards 12 2 sides of side band is formed.Push button 19,20 has button body 38, the button body 38 The side of front end form jagged 39.The front end side of the notch 39 is formed with the holding section 40 of circular shape, notch 39 Main body side is formed with snap fit tabs 41.
Push button 19,20 is automatically reset button holding member 17 and engages, and sliding panel 18 is limited to watch buckle frame Between 16 and push button holding member 17.
Fastener is made of engagement pawl 9 and holding section 40, above-mentioned engagement pawl 9 have axle portion 9a and umbrella portion 9b, sliding part by Snap fit tabs 41 and the ratchet 37 with locking side 37a are formed.
Then, the wearing operation and removal operation that the clock and watch of the watch buckle 6 for the treatment of process are have passed through to having (in other words engage The locking operation in portion and its release operation) it illustrates.In wearing and operating, after wrist is passed through wrist-watch, by middle plate 3 to outside plate 4 sides fold, and the engagement pawl 9 being arranged on middle plate 3 is sticked in holding section 40.Specifically, axle portion 9a is sticked in engaging Portion 40.By this method, watchband is worn in wrist.On the other hand, in removal operation, by pressing for push button 19,20 Button main body 38 is pressed from both sides, is pushed holding section 40 and is released the engaging of engagement pawl 9, by middle plate 3 to external opening, extracts hand Wrist.
In addition, it have passed through length adjustment operation (the in other words cunning of sliding part of the clock and watch of the watch buckle 6 for the treatment of process to having Dynamic operation) it illustrates.When towards the direction for shortening watchband, i.e., when moving outside plate 4 towards 61 sides of side band, sliding panel 18 moves And ratchet 37 slides in the snap fit tabs 41 of push button 19,20, when stop sliding panel 18 it is mobile when snap fit tabs 41 are sticked in ratchet 37.This by sliding panel 18 ratchet 37 make its engage side 37a towards 12 2 sides of side band and formed come It realizes.By this method, length adjustment operation is carried out towards the direction for shortening watchband.
On the other hand, in the case where carrying out length adjustment operation towards the direction for extending watchband, it is necessary to will automatically reset Button 19,20 presses inwardly.This forms to realize by the locking side 37a of ratchet 37 towards 12 2 sides of side band.That is, Even if drawing 12 side bands 2 towards from the direction that 6 side bands 1 detach, locking side 37a engagings with snap fit tabs 41 are also tieed up It holds, sliding panel 18 does not move.When pressing push button 19,20, snap fit tabs 41 are detached from the ratchet 37 of sliding panel 18. In the case where keeping the state, 12 side bands 2 are drawn towards from the direction that 6 side bands 1 detach, so as to move sliding panel 18.It is advising The pressing of push button 19,20 is released after fixed micro-adjustment and is moved outward, so as to which snap fit tabs 41 are sticked in cunning On the ratchet 37 of movable plate 18.By this method, length adjustment operation is carried out towards the direction for stretching watchband.
(treatment process)
In treatment process, using usually by the watch buckle 6 of the manufactures such as ion plating method, sputtering method, the surface of the watch buckle 6 is non- It is often clean and with above structure.The watch buckle 6 is in that frictional force is excessive and state that fastener and sliding part cannot play a role.
In treatment process, above-mentioned watch buckle 6 is impregnated in aqueous solution of the above-mentioned watchband with lubricated agent.To water-soluble The dipping of liquid can carry out at normal temperatures.Alternatively, it is for example carried out while 30~60 temperature is heated up to.Further, it is also possible to It is carried out while ultrasonic wave is applied.Next, washing with water watch buckle 6, and it is dried.By the treatment process, in table Attachment compound (A) and compound (B) on the surface of mouth 6.Watchband is aqueous solution with lubricated agent, and watch buckle 6 is impregnated in this In aqueous solution, therefore the inside of watch buckle main body 6a can also adhere to compound (A) and compound (B).
By the treatment process, wearing operation, removal operation and the length adjustment operation of above-mentioned clock and watch can be realized (in other words the locking operation of fastener and the slide of its release operation and sliding part).That is, fastener and sliding part can To function.In addition, by the treatment process, the generation of stain can be inhibited.As described above, even if compound (A) and change It closes object (B) and is attached to the surface for being exposed to watch buckle, it appears that also be difficult to become stain shape.It is therefore possible to use locking will be included 6 mass-impregnation of watch buckle of portion and sliding part in aqueous solution, make compound (A) and compound (B) be attached to watch buckle 6 surface it is whole The easy processing sequence of body.
(assembling procedure)
In assembling procedure, clock and watch are assembled with the above-mentioned watch buckle 6 handled in above-mentioned treatment process.Specifically, it can use Well known component is simultaneously carried out with well known method.
As long as the watch buckle using the manufacturing method of the clock and watch of embodiment has fastener or sliding part, it is not limited to Watch buckle 6 with above structure.In addition, as long as wrist-watch can be worn in wrist by fastener, it is not limited to above-mentioned The fastener of structure.As long as length regulation function of the sliding part with watchband is not limited to the sliding part of above structure. Further, it is also possible to after treatment process, in assembling procedure, 6 side bands, 1,12 side band 2 and watch buckle 6 are assembled.
<Clock and watch>
The clock and watch of embodiment have metal watch buckle.For the structure of watch buckle, specifically, such as the system in clock and watch Make the explanation in method.Above-mentioned watch buckle (being specially the surface of watch buckle) be attached with the compound (A) that is represented by above-mentioned formula (A) and by The compound (B) that above formula (B) represents.For compound (A) and compound (B), as at the watchband lubrication of embodiment Manage the explanation in agent.In the clock and watch of embodiment, the lubricity of watch buckle is excellent, can inhibit to generate stain in watch buckle.
Herein, the attachment of compound (A) and compound (B) can be true by liquid chromatograph mass spectrography (LC-MS) etc. Recognize.As long as in addition, the clock and watch of embodiment with watch buckle with fastener or sliding part, be not limited to have above-mentioned The watch buckle 6 of structure.In addition, as long as wrist-watch can be worn in wrist by fastener, it is not limited to the card of above structure Stop.As long as length regulation function of the sliding part with watchband is not limited to the sliding part of above structure.
In addition, the processing work that the clock and watch of embodiment can illustrate in the manufacturing method for example, by the clock and watch of embodiment Sequence and assembling procedure obtain.
<Other embodiment>
In the above-described embodiment, watchband is illustrated with lubricated agent in lubricated agent in ornament. As other embodiment (the lubricated agent of other ornaments), such as the ornaments such as clock and watch, bracelet can be enumerated and included Slipping part lubricated agent.In other embodiments, as slipping part, the connection of gear, bearing, belt segment can be enumerated Pin and connecting hole etc. slide component.For other embodiment, the detailed contents such as ingredient and its ratio, preparation method and above-mentioned table Band is identical with lubricated agent.In addition, the slipping part lubricated agent can be applied to suitably according to above-mentioned treatment process Slipping part.For other embodiment, the effect of performance is also identical with lubricated agent with above-mentioned watchband.That is, it can inhibit dirty The generation of point, and excellent lubricity can be maintained in a long time.
Therefore, the present invention relates to the following contents.
[1] a kind of ornament lubricated agent, which is characterized in that comprising the compound (A) represented by following formula (A) and The compound (B) represented by following formula (B), the amount of more than 1 mass % to be added up to include above compound (A) and above compound (B)。
(in formula (A), RA1、RA2And RA3In at least one be each independently the group that is represented by following formula (a), RA1、 RA2And RA3In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2 ~4 alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 Integer.)
(in formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.)
(in formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) group represented, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is respectively independent Ground is more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.)
(in formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.)
[2] the ornament lubricated agent according to [1], which is characterized in that above-mentioned ornament lubricated agent For the amount of the mass % of 3 mass %~30 to be added up to include the aqueous solution of above compound (A) and above compound (B).
Above-mentioned ornament lubricated agent is for example for can inhibit the generation of stain during the watch buckle of watchband.
[3] the ornament lubricated agent according to [1] or [2], which is characterized in that comprising by following formula (a1) table The compound (a1) shown and the compound (a2) represented by following formula (a2) are as above compound (A).
(in formula (a1), Ra11、Ra12And Ra13It is each independently the group represented by following formula (aa1), R1、R2、R3And R4 It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、 n3And n4The integer for adding up to 6~20.)
(in formula (aa1), Raa1For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated hydrocarbons of more than 12 carbon atom number Base.)
(in formula (a2), Ra21、Ra22And Ra23In 2 for OH bases, Ra21、Ra22And Ra23In other than OH bases be under State the group of formula (aa2) expression, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Respectively From the integer for independently being more than 1, and n1、n2、n3And n4The integer for adding up to 6~20.)
(in formula (aa2), Raa2For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated hydrocarbons of more than 12 carbon atom number Base.)
Above-mentioned ornament lubricated agent is for example for can inhibit the generation of stain during the watch buckle of watchband.
[4] a kind of manufacturing method of clock and watch, which is characterized in that including：
The treatment process handled using watchband with lubricated agent metal watch buckle,
Utilize the assembling procedure of above-mentioned watch buckle assembling clock and watch handled in above-mentioned treatment process；
Above-mentioned watchband is represented with lubricated agent comprising the compound (A) represented by following formula (A) and by following formula (B) Compound (B), the amount of more than 1 mass % to be added up to include above compound (A) and above compound (B).
(in formula (A), RA1、RA2And RA3At least one of be each independently the group that is represented by following formula (a), RA1、 RA2And RA3In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2 ~4 alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 Integer.)
(in formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.)
(in formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) group represented, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is respectively independent Ground is more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.)
(in formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.)
[5] manufacturing method of the clock and watch according to [4], which is characterized in that above-mentioned watchband lubricated agent is to close The amount for counting the mass % of 3 mass %~30 includes the aqueous solution of above compound (A) and above compound (B).
According to the manufacturing method of above-mentioned clock and watch, it can obtain inhibiting in the watch buckle of watchband the clock of the generation of stain Table.
[6] a kind of clock and watch are the clock and watch with metal watch buckle, which is characterized in that above-mentioned watch buckle is attached with by following The compound (A) that formula (A) represents and the compound (B) represented by following formula (B).
(in formula (A), RA1、RA2And RA3At least one of be each independently the group that is represented by following formula (a), RA1、 RA2And RA3In other than the base represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2~4 Alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 it is whole Number.)
(in formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.)
(in formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) group represented, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is respectively independent Ground is more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20.)
(in formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.)
Above-mentioned clock and watch can inhibit the generation of stain in the watch buckle of watchband.
[7] the ornament lubricated agent according to any one of [1]~[3], which is characterized in that for watchband.
Above-mentioned ornament when for the watch buckle of watchband, can inhibit the generation of stain with lubricated agent.
[embodiment]
[embodiment 1-1]
As compound (A), the polyoxyethylene sorbitan trioleate (compound (a1) of 20 mass parts is used； In above-mentioned formula (a1), Ra11、Ra12And Ra13For the group represented by above-mentioned formula (aa1), R1、R2、R3And R4For ethylidene, n1、n2、 n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20, above-mentioned formula (aa1) In, Raa1For-(CH2)7CH=CH (CH2)7CH3Situation) and 25 mass parts polyoxyethylene sorbitan monostearate Ester (compound (a2)；In above-mentioned formula (a2), Ra21And Ra22For OH bases, Ra23For the group represented by above-mentioned formula (aa2), R1、R2、 R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 Integer, in above-mentioned formula (aa2), Raa2For-(CH2)16CH3Situation), as compound (B), used the poly- of 55 mass parts Ethylene oxide sorbitan monolaurate (in above-mentioned formula (B), RB1And RB2For OH bases, RB3For what is represented by above-mentioned formula (b) Group, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4's Add up to 6~20 integer, in above-mentioned formula (b), RbFor-(CH2)10CH3Situation).
First, compound (a1) is added in a part of compound (B) (30 mass parts) and is mixed makes it uniformly.It connects down Come, obtained mixture is dissolved in the water, so as to obtain aqueous solution (1).In addition, in remaining compound (B) (25 mass Part) in add in compound (a2) and mix make its uniformly.Next, obtained mixture is dissolved in the water, so as to obtain Aqueous solution (2).Obtained aqueous solution (1) and aqueous solution (2) are mixed, so as to be prepared at the watchband lubrication as aqueous solution Manage agent.Herein, become that the amount of 15 mass % is added up to include compound (A) and compound (B) with watchband lubricated agent It is prepared by the mode of aqueous solution.
[embodiment 1-2]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-1.
[embodiment 1-3]
Become that the amount of 10 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-1.
[embodiment 1-4]
Become that the amount of 20 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-1.
[embodiment 1-5]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-1.
[embodiment 1-6]
Compound (a1) has been used with the amount of 5 mass parts, compound (a2) has been used, and with 90 matter with the amount of 5 mass parts The amount of amount part has used compound (B) and the compound (B) of 45 mass parts has been used in the preparation of aqueous solution (1), in water The compound (B) of 45 mass parts has been used in the preparation of solution (2), in addition to this, has been obtained by the mode identical with embodiment 1-1 Watchband lubricated agent is arrived.
[embodiment 1-7]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-6.
[embodiment 1-8]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-6.
[embodiment 1-9]
Compound (a1) has been used with the amount of 25 mass parts, compound (a2) has been used, and with 55 with the amount of 20 mass parts The amount of mass parts has used compound (B) and the compound (B) of 35 mass parts has been used in the preparation of aqueous solution (1), The compound (B) of 20 mass parts has been used in the preparation of aqueous solution (2), in addition to this, has passed through the mode identical with embodiment 1-1 Watchband lubricated agent is obtained.
[embodiment 1-10]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-9.
[embodiment 1-11]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 1-9.
[embodiment 1-12]
As compound (a1), following compound has been used：In above-mentioned formula (a1), Ra11、Ra12And Ra13For by above-mentioned formula (aa1) group represented, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、 n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (aa1), Raa1For-(CH2)12CH3Compound, in addition to this, lead to It crosses the mode identical with embodiment 1-1 and has obtained watchband lubricated agent.
[embodiment 1-13]
As compound (a2), following compound has been used：In above-mentioned formula (a2), Ra21And Ra22For OH bases, Ra23For by upper State the group of formula (aa2) expression, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4More than 1 integer is each independently, and And n1、n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (aa2), Raa2For-(CH2)12CH3Compound, except this with Outside, watchband lubricated agent has been obtained by the mode identical with embodiment 1-1.
[embodiment 1-14]
As compound (B), following compound has been used：In above-mentioned formula (B), RB1And RB2For OH bases, RB3For by above-mentioned formula (b) group represented, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、 n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (b), RbFor-(CH2)2CH3Compound, in addition to this, with implementation Mode identical example 1-1 has obtained watchband lubricated agent.
[embodiment 2-1]
As compound (A), the polyoxyethylene sorbitan trioleate (compound of 40 mass parts has been used (a1)；In above-mentioned formula (a1), Ra11、Ra12And Ra13For the group represented by above-mentioned formula (aa1), R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20, above-mentioned formula (aa1) in, Raa1For-(CH2)7CH=CH (CH2)7CH3Situation), as compound (B), used the polyoxy second of 60 mass parts Alkene sorbitan monolaurate (in above-mentioned formula (B), RB1And RB2For OH bases, RB3For the group represented by above-mentioned formula (b), R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 integer, in above-mentioned formula (b), RbFor-(CH2)10CH3Situation).
First, compound (A) is added in compound (B) and is mixed makes it uniformly.It is next, obtained mixture is molten In solution to water, and it is prepared for the watchband lubricated agent as aqueous solution.Herein, become to close with watchband lubricated agent It is prepared by the mode of aqueous solution that the amount for counting 15 mass % includes compound (A) and compound (B).
[embodiment 2-2]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 2-1.
[embodiment 2-3]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 2-1.
[embodiment 2-4]
With the amount of 20 mass parts using compound (A), and in addition to this, led to using compound (B) with the amount of 80 mass parts It crosses the mode identical with embodiment 2-1 and has obtained watchband lubricated agent.
[embodiment 2-5]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 2-4.
[embodiment 2-6]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 2-4.
[embodiment 2-7]
As compound (A) (compound (a1)), following compound has been used：In above-mentioned formula (a1), Ra11、Ra12And Ra13 For the group represented by above-mentioned formula (aa1), R1、R2、R3And R4For ethylidene, n1、n2、n3And n4Be each independently more than 1 it is whole Number, and n1、n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (aa1), Raa1For-(CH2)12CH3Compound, remove Other than this, watchband lubricated agent has been obtained by the mode identical with embodiment 2-1.
[embodiment 2-8]
As compound (B), following compound has been used：In above-mentioned formula (B), RB1And RB2For OH bases, RB3For by above-mentioned formula (b) group represented, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、 n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (b), RbFor-(CH2)2CH3Compound, in addition to this, by with Mode identical embodiment 2-1 has obtained watchband lubricated agent.
[embodiment 3-1]
As compound (A), the polyoxyethylene sorbitan monostearate (compound of 60 mass parts has been used (a2)；In above-mentioned formula (a2), Ra21And Ra22For OH bases, Ra23For the group represented by above-mentioned formula (aa2), R1、R2、R3And R4For Asia Ethyl, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20, on It states in formula (aa2), Raa2For-(CH2)16CH3Situation), as compound (B), used the polyoxyethylene of 40 mass parts D-sorbite monolaurate (in above-mentioned formula (B), RB1And RB2For OH bases, RB3For the group represented by above-mentioned formula (b), R1、R2、 R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4Add up to 6~20 Integer, in above-mentioned formula (b), RbFor-(CH2)10CH3Situation).
First, compound (A) is added in compound (B) and carries out mixing makes it uniformly.Then, the mixture that will be obtained It is dissolved into water, so as to be prepared for the watchband lubricated agent as aqueous solution.Herein, become with watchband lubricated agent It is prepared in a manner of the aqueous solution that the amount for adding up to 15 mass % includes compound (A) and compound (B).
[embodiment 3-2]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-1.
[embodiment 3-3]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-1.
[embodiment 3-4]
With the amount of 40 mass parts using compound (A), and in addition to this, led to using compound (B) with the amount of 60 mass parts It crosses the mode identical with embodiment 3-1 and has obtained watchband lubricated agent.
[embodiment 3-5]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-4.
[embodiment 3-6]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-4.
[embodiment 3-7]
Compound (A) has been used, and used compound (B) with the amount of 80 mass parts with the amount of 20 mass parts, except this with Outside, watchband lubricated agent has been obtained by the mode identical with embodiment 3-1.
[embodiment 3-8]
Become that the amount of 3 mass % is added up to include the water-soluble of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of liquid, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-7.
[embodiment 3-9]
Become that the amount of 30 mass % is added up to include the water of compound (A) and compound (B) with watchband lubricated agent Prepared by the mode of solution, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-7.
[embodiment 3-10]
As compound (A) (compound (a2)), following compound has been used：In above-mentioned formula (a2), Ra21And Ra22For OH Base, Ra23For the group represented by above-mentioned formula (aa2), R1、R2、R3And R4For ethylidene, n1、n2、n3And n4Be each independently 1 with On integer, and n1、n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (aa2), Raa2For-(CH2)12CH3Change Object is closed, in addition to this, watchband lubricated agent has been obtained by the mode identical with embodiment 3-1.
[embodiment 3-11]
As compound (B), following compound has been used：In above-mentioned formula (B), RB1And RB2For OH bases, RB3For by above-mentioned formula (b) group represented, R1、R2、R3And R4For ethylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、 n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (b), RbFor-(CH2)2CH3Compound, in addition to this, by with Mode identical embodiment 3-1 has obtained watchband lubricated agent.
[comparative example 1]
As compound (B), used Tween 20 (in above-mentioned formula (B), RB1With RB2For OH bases, RB3For the group represented by above-mentioned formula (b), R1、R2、R3And R4For ethylidene, n1、n2、n3And n4Each independently For more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20, in above-mentioned formula (b), RbFor-(CH2)10CH3's Situation).Compound (B) is dissolved into water, is prepared for the aqueous solution that compound (B) is included with the amount of 15 mass %.
<Evaluation method and evaluation result>
Using the watchband lubricated agent of preparation, Fig. 1 and watch buckle shown in Fig. 26 are handled.It specifically, will Watch buckle 6 is impregnated into the aqueous solution of watchband lubricated agent.It is carried out at normal temperatures to the dipping of aqueous solution.Then, it is washed with water It washs watch buckle 6 and is dried.By the processing, compound (A) and compound (B) is made to be attached to surface (the watch buckle main body of watch buckle 6 The interior surface of 6a).
It for watch buckle 6 just after treatment, has checked whether sliding part can lubricate, i.e., whether can carry out towards shortening table The slide in the direction of band.Then, for treated watch buckle 6, the direction carried out continuous 10 minutes shortens the direction of watchband Slide and towards extend watchband direction slide.For the watch buckle 6 after continuously slipping operation, slip is had checked Whether portion can lubricate, i.e., whether can carry out the slide towards the direction for shortening watchband.In addition, for treated table Button 6, in 95 DEG C of humidity 80%RH, temperature etching tests for having carried out 150 hours.For the watch buckle 6 after etching test, have checked Whether sliding part can lubricate, i.e., whether can carry out slide towards the direction for shortening watchband.Herein, it is for sliding part It is no to lubricate, in (20 DEG C) progress of room temperature.Result is evaluated by following evaluation criteria.Will evaluation result is shown in table 1~table 3.It should be explained that in table 1, as comparative example 2, further it is shown that for not carrying out utilizing watchband lubricated agent Processing watch buckle 6 evaluation result.
AA：The slide towards the direction for shortening watchband can be carried out with smaller pushing force.
A：The slide towards the direction for shortening watchband can be carried out with larger pushing force compared with AA.
B：The slide towards the direction for shortening watchband can be carried out with pushing force sizable compared with AA.
C：The slide towards the direction for shortening watchband can not be carried out even if apply pushing force.
In addition, for watch buckle 6 just after treatment, have checked and whether generate stain.The table prepared in embodiment has been used In the case of any one in band lubricated agent, all without generating stain.In addition, for the watch buckle after continuously slipping operation 6 and etching test after watch buckle 6, check whether and produce stain.The watchband lubricated prepared in embodiment is used In the case of any one in agent, all without generating stain.Like this, the watchband lubricated agent of present embodiment can press down The generation of stain processed, and can also improve lubricity.
【Table 1】
(table 1)
Just after treatment After continuously slipping operation After etching test
Embodiment 1-1 AA AA AA
Embodiment 1-2 AA AA AA
Embodiment 1-3 AA AA AA
Embodiment 1-4 AA AA AA
Embodiment 1-5 AA AA AA
Embodiment 1-6 AA AA AA
Embodiment 1-7 AA AA AA
Embodiment 1-8 AA AA AA
Embodiment 1-9 AA AA AA
Embodiment 1-10 AA AA AA
Embodiment 1-11 AA AA AA
Embodiment 1-12 AA AA AA
Embodiment 1-13 AA AA AA
Embodiment 1-14 AA AA AA
Comparative example 1 B C C
Comparative example 2 C - -
【Table 2】
(table 2)
Just after treatment After continuously slipping operation After etching test
Embodiment 2-1 AA AA AA
Embodiment 2-2 AA AA AA
Embodiment 2-3 AA AA AA
Embodiment 2-4 AA AA AA
Embodiment 2-5 AA AA AA
Embodiment 2-6 AA AA AA
Embodiment 2-7 AA AA AA
Embodiment 2-8 AA AA AA
【Table 3】
(table 3)
Just after treatment After continuously slipping operation After etching test
Embodiment 3-1 AA AA A
Embodiment 3-2 AA AA A
Embodiment 3-3 AA AA A
Embodiment 3-4 AA AA A
Embodiment 3-5 AA AA A
Embodiment 3-6 AA AA A
Embodiment 3-7 AA AA A
Embodiment 3-8 AA AA A
Embodiment 3-9 AA AA A
Embodiment 3-10 AA AA A
Embodiment 3-11 AA AA A
Above-described embodiment is the embodiment for watchband lubricated agent.Other ornaments are can consider by these results It can also be played and above-mentioned table with lubricated agent (such as the ornaments such as clock and watch, bracelet included the agent of sliding lubricated) The band identical effect of lubricated agent.That is, the generation of stain can be inhibited, and excellent lubricity can be maintained for a long time.

Claims (7)

1. a kind of ornament lubricated agent, which is characterized in that comprising the compound (A) represented by following formula (A) and under The compound (B) of formula (B) expression is stated, the amount of more than 1 mass % to be added up to include the compound (A) and the compound (B),
In formula (A), RA1、RA2And RA3In at least one be each independently the group that is represented by following formula (a), RA1、RA2And RA3 In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently the Asia of carbon atom number 2~4 Alkyl, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number,
In formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) represent Group, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Be each independently 1 with On integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.
2. ornament according to claim 1 lubricated agent, which is characterized in that ornament lubricated agent For the amount of the mass % of 3 mass %~30 to be added up to include the aqueous solution of the compound (A) and the compound (B).
3. ornament according to claim 1 or 2 lubricated agent, which is characterized in that comprising by following formula (a1) table The compound (a1) shown and compound (a2) the conduct compound (A) represented by following formula (a2),
In formula (a1), Ra11、Ra12And Ra13It is each independently the group represented by following formula (aa1), R1、R2、R3And R4Respectively solely It is on the spot the alkylidene of carbon atom number 2~4, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4 The integer for adding up to 6~20,
In formula (aa1), Raa1For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number,
In formula (a2), Ra21、Ra22And Ra23In 2 for OH bases, Ra21、Ra22And Ra23In other than OH bases be by following formula (aa2) group represented, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Respectively solely It is on the spot more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (aa2), Raa2For the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number.
4. a kind of manufacturing method of clock and watch, which is characterized in that including：
The treatment process handled using watchband with lubricated agent metal watch buckle,
Utilize the assembling procedure of watch buckle assembling clock and watch handled in the treatment process；
The watchband includes the compound (A) represented by following formula (A) and the chemical combination represented by following formula (B) with lubricated agent Object (B), the amount of more than 1 mass % to be added up to include the compound (A) and the compound (B),
In formula (A), RA1、RA2And RA3At least one of be each independently the group that is represented by following formula (a), RA1、RA2With RA3In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2~4 Alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number,
In formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) represent Group, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Be each independently 1 with On integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.
5. the manufacturing method of clock and watch according to claim 4, which is characterized in that the watchband lubricated agent is to close The amount for counting the mass % of 3 mass %~30 includes the aqueous solution of the compound (A) and the compound (B).
6. a kind of clock and watch are the clock and watch with metal watch buckle, which is characterized in that the watch buckle is attached with by following formula (A) The compound (A) of expression and the compound (B) represented by following formula (B),
In formula (A), RA1、RA2And RA3At least one of be each independently the group that is represented by following formula (a), RA1、RA2With RA3In other than the group represented by following formula (a) for OH bases, R1、R2、R3And R4It is each independently carbon atom number 2~4 Alkylidene, n1、n2、n3And n4It is each independently more than 1 integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (a), RaFor the saturated hydrocarbyl of more than 12 carbon atom number or the unsaturated alkyl of more than 12 carbon atom number,
In formula (B), RB1、RB2And RB3In 2 for OH bases, RB1、RB2And RB3In other than OH bases be by following formula (b) represent Group, R1、R2、R3And R4It is each independently the alkylidene of carbon atom number 2~4, n1、n2、n3And n4Be each independently 1 with On integer, and n1、n2、n3And n4The integer for adding up to 6~20,
In formula (b), RbThe unsaturated alkyl of saturated hydrocarbyl or carbon atom number below 11 for being carbon atom number below 11.
7. ornament described in any one of claim 1 to 3 lubricated agent, which is characterized in that for watchband.
CN201711431220.XA 2016-12-27 2017-12-26 Lubricating agent for decorative article, method for manufacturing timepiece, and timepiece Active CN108239569B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-254063 2016-12-27
JP2016254063 2016-12-27
JP2017-225101 2017-11-22
JP2017225101A JP6814721B2 (en) 2016-12-27 2017-11-22 Lubricants for ornaments, how to make watches and watches

Publications (2)

Publication Number Publication Date
CN108239569A true CN108239569A (en) 2018-07-03
CN108239569B CN108239569B (en) 2021-12-28

Family

ID=62700547

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711431220.XA Active CN108239569B (en) 2016-12-27 2017-12-26 Lubricating agent for decorative article, method for manufacturing timepiece, and timepiece

Country Status (1)

Country Link
CN (1) CN108239569B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109188887A (en) * 2018-10-09 2019-01-11 邱晖 A kind of multi-function watch with global positioning function and automatic time service based on Beidou Navigation System
CN112996891A (en) * 2018-11-16 2021-06-18 西铁城时计株式会社 Lubricating composition for watch band, method for producing watch band, and watch band

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1126745A (en) * 1994-11-22 1996-07-17 法国石油研究所 Lubricating composition including an esteruse of the composition and well fluid including the composition
WO2002090618A1 (en) * 2001-05-09 2002-11-14 Citizen Watch Co., Ltd. Peak torque lowering composition, part with sliding part using the composition, and press-fitting method using the composition
JP2004107768A (en) * 2002-09-20 2004-04-08 Citizen Watch Co Ltd Surface treatment composition for self-tapping, part surface-treated therewith, precision instrument using the part and joining method for the precision instrument
EP1640031A2 (en) * 2004-09-28 2006-03-29 Nipro Corporation Syringe coated with lubricant containing silicone oil and silica powder
CN102102312A (en) * 2010-11-13 2011-06-22 东莞市汉维新材料科技有限公司 Water-based zinc stearate dispersion liquid and preparation method thereof
US20120220508A1 (en) * 2009-09-23 2012-08-30 Cognis Ip Management Gmbh Lubricant Compositions
CN103789073A (en) * 2012-10-26 2014-05-14 北京白象新技术有限公司 Medical apparatus fast-drying oil agent for bacteriostasis, lubrication and rust prevention
CN104403772A (en) * 2014-10-13 2015-03-11 巢湖广丰金属制品有限公司 High-performance metal cutting fluid
EP2949734A1 (en) * 2013-01-22 2015-12-02 Citizen Holdings Co., Ltd. Clock lubricating-oil composition and clock
CN107338085A (en) * 2017-06-09 2017-11-10 中国石油化工股份有限公司 Stern tube shaft emulsifier composition and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1126745A (en) * 1994-11-22 1996-07-17 法国石油研究所 Lubricating composition including an esteruse of the composition and well fluid including the composition
WO2002090618A1 (en) * 2001-05-09 2002-11-14 Citizen Watch Co., Ltd. Peak torque lowering composition, part with sliding part using the composition, and press-fitting method using the composition
CN1462320A (en) * 2001-05-09 2003-12-17 西铁城钟表株式会社 Peak torque lowering compostion, part with sliding part using the composition and press-fitting method using the composition
JP2004107768A (en) * 2002-09-20 2004-04-08 Citizen Watch Co Ltd Surface treatment composition for self-tapping, part surface-treated therewith, precision instrument using the part and joining method for the precision instrument
EP1640031A2 (en) * 2004-09-28 2006-03-29 Nipro Corporation Syringe coated with lubricant containing silicone oil and silica powder
US20120220508A1 (en) * 2009-09-23 2012-08-30 Cognis Ip Management Gmbh Lubricant Compositions
CN102102312A (en) * 2010-11-13 2011-06-22 东莞市汉维新材料科技有限公司 Water-based zinc stearate dispersion liquid and preparation method thereof
CN103789073A (en) * 2012-10-26 2014-05-14 北京白象新技术有限公司 Medical apparatus fast-drying oil agent for bacteriostasis, lubrication and rust prevention
EP2949734A1 (en) * 2013-01-22 2015-12-02 Citizen Holdings Co., Ltd. Clock lubricating-oil composition and clock
CN104403772A (en) * 2014-10-13 2015-03-11 巢湖广丰金属制品有限公司 High-performance metal cutting fluid
CN107338085A (en) * 2017-06-09 2017-11-10 中国石油化工股份有限公司 Stern tube shaft emulsifier composition and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MUSTAFA AKKAYA: "The effect of Triton X-100 and Tween 80 Surfactants on the Thermal Performance of a Nano-Lubricant:An Experimental Study", 《INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING-GREEN TECHNOLOGY》 *
王伟旭: "绿色水溶性添加剂的摩擦学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109188887A (en) * 2018-10-09 2019-01-11 邱晖 A kind of multi-function watch with global positioning function and automatic time service based on Beidou Navigation System
CN112996891A (en) * 2018-11-16 2021-06-18 西铁城时计株式会社 Lubricating composition for watch band, method for producing watch band, and watch band
CN112996891B (en) * 2018-11-16 2023-03-10 西铁城时计株式会社 Lubricating composition for watch band, method for producing watch band, and watch band

Also Published As

Publication number Publication date
CN108239569B (en) 2021-12-28

Similar Documents

Publication Publication Date Title
CN108239569A (en) Ornament lubricated agent, the manufacturing method and clock and watch of clock and watch
WO2010046456A1 (en) Fitting for household appliances and lubricant
EP1674556A3 (en) An anti-wear additive composition and lubricating oil composition comprising the same
EP0972821A3 (en) Grease composition suitable for a constant velocity joint
CN103509057B (en) Preparation method of oil-soluble molybdenum dialkyl dithiocarbamate additive
WO2009120751A3 (en) A method of lubricating a conveyor belt
WO2008133194A1 (en) Rolling bearing
CN107674736A (en) A kind of lubricant composition and preparation method thereof
EP0902828A1 (en) Lubricating grease compositions
WO2008114190A3 (en) Deodorant compositions and methods for making same
WO2004026811A3 (en) Succinic acid semi-amides as anti-corrosives agents
JP6814721B2 (en) Lubricants for ornaments, how to make watches and watches
JP5215747B2 (en) Lubricating composition for watch band and watch band using the same
EP1672050A4 (en) Lube base oil and lubricating oil composition
CN102433209A (en) High-toughness anti-extreme pressure lubricating grease
DE102005054372A1 (en) Switchable plunger of a valve train of an internal combustion engine
BRPI0704195A (en) A method of manufacturing a friction pad comprising a friction face and a bearing face, in particular for clutches or brakes
CN103695100B (en) A kind of preparation method of degradable engine oil
CN102337427A (en) Nickel-based wide temperature-range high-temperature self-lubricating material and preparation method thereof
DE4217566C2 (en) Bearing arrangement
DE3341147A1 (en) FRICTION PAIRING FOR SYNCHRONIZING DEVICES IN GEAR GEARS
EP1386982B1 (en) Peak torque lowering composition, part with sliding part using the composition
CA2106036A1 (en) Carrier-free metalworking lubricant and method of making and using same
WO2008123226A1 (en) Lubricating oil composition intended to be contacted with silver-containing material
DE536080C (en) Process for making antiseptic agents

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant