CN110494538A

CN110494538A - The treatment fluid and wrist-watch of the lubricant compositions of wrist-watch, wrist-watch lubrication

Info

Publication number: CN110494538A
Application number: CN201880019811.2A
Authority: CN
Inventors: 赤尾祐司
Original assignee: Seikijo Toki Co Ltd
Current assignee: Seikijo Toki Co Ltd
Priority date: 2017-03-24
Filing date: 2018-02-14
Publication date: 2019-11-22
Anticipated expiration: 2038-02-14
Also published as: CH715086B1; WO2018173555A1; CN110494538B; JP7175262B2; JPWO2018173555A1

Abstract

The lubricant compositions of wrist-watch are characterized in that, it is the lubricant compositions of the wrist-watch comprising lubricant (A) and anti-wear agent (B), the lubricant (A) includes paraffin (A-1), or comprising at least one kind of in the sturated aliphatic hydrocarbon (A-2) that fusing point is 45 DEG C or more and carbon atom number is 23~38, the anti-wear agent (B) includes at least one kind of in neutral phosphate and neutral phosphite ester.

Description

The treatment fluid and wrist-watch of the lubricant compositions of wrist-watch, wrist-watch lubrication

Technical field

The present invention relates to the lubricant compositions of wrist-watch, the treatment fluid and wrist-watch of wrist-watch lubrication.

Background technique

Lubricant oil composite as wrist-watch, it is known to which a kind of lubricant oil composite contains comprising base oil (A1) Lubricant composition (A), the anti-wear agent comprising neutral phosphate (B-1) or neutral phosphite ester (B-2) with specific structure (B) and antioxidant (C), the total acid number of the composition are 0.8mgKOH/g or less (patent document 1).

Existing technical literature

Patent document

Patent document 1: International Publication No. 2014/115603

Summary of the invention

However, if the lubricant oil composite for the wrist-watch recorded in patent document 1 to be used for the sliding of mechanical type watch It is dynamic then to generate oil stream for portion.In addition, if the lubricant oil composite for the wrist-watch recorded in patent document 1 to be used for the table of wrist-watch It is dynamic then to generate oil stream for the watch buckle of band.

Therefore, the purpose of the present invention is to provide the watchbands of a kind of sliding part for being used in mechanical type watch or wrist-watch Watch buckle is also able to suppress the lubricant compositions of the dynamic wrist-watch of oil stream.

The lubricant compositions of wrist-watch of the invention are the lubrications of the wrist-watch comprising lubricant (A) and anti-wear agent (B) Agent composition, above-mentioned lubricant (A) include paraffin (A-1), or fusing point is 45 DEG C or more and carbon atom number is 23 comprising being selected from At least one kind of in~38 sturated aliphatic hydrocarbon (A-2), above-mentioned anti-wear agent (B) includes selected from neutral phosphate and neutral phosphorous It is at least one kind of in acid esters.

The lubricant compositions of wrist-watch of the invention are the watchband for being used in the sliding part or wrist-watch of mechanical type watch It is dynamic to be also able to suppress oil stream for watch buckle.

Detailed description of the invention

Fig. 1 is the figure for illustrating the wrist-watch of embodiment 1 (mechanical type watch).

Fig. 2 is the figure for illustrating the wrist-watch of embodiment 2.

Fig. 3 is the figure for illustrating the wrist-watch of embodiment 2.

Specific embodiment

Mode for carrying out the present invention (embodiment) is described in detail.The present invention is not by embodiment party below The content recorded in formula limits.In addition, can be readily apparent that in the constituent element recorded below comprising those skilled in the art Element, substantially the same element.In turn, the composition recorded below can be appropriately combined.Furthermore it is possible to not departing from the present invention Purport in the range of the various omissions, displacement or the change that are constituted.

The lubricant compositions of the wrist-watch of embodiment include lubricant (A) and anti-wear agent (B).

The lubricant compositions > of the wrist-watch of < embodiment 1

Firstly, being illustrated to the lubricant compositions of the wrist-watch of embodiment 1.In the present specification, will also implement The lubricant compositions of the wrist-watch of mode 1 are known as lubricant compositions (I).The lubricant combination of the wrist-watch of embodiment 1 Object includes lubricant (A) and anti-wear agent (B).In addition, from the viewpoint of making the film formed by lubricant compositions (I) be hardened, It is preferred that being free of aftermentioned mobility regulator (F).

(lubricant (A))

Lubricant (A) includes paraffin (A-1), or fusing point is 45 DEG C or more and carbon atom number is 23~38 comprising being selected from It is at least one kind of in sturated aliphatic hydrocarbon (A-2).Paraffin (A-1) and sturated aliphatic hydrocarbon (A-2) can use individually a kind, It can also be mixed with two or more.

The sliding part of escapement possessed by mechanical type watch bears very big pressure and vibration.Lubricating the sliding part When, if it is dynamic to generate oil stream sometimes using the lubricant oil composite of previous wrist-watch.Therefore, in order to inhibit oil stream dynamic, have When adhere to above-mentioned lubricant oil composite after carrying out refusing oil processing to above-mentioned sliding part.However, if carrying out refusing oil processing, compared with Adhere to the layer (lubricant layer) of above-mentioned lubricant oil composite thickly.There is resistance to sliding as a result, to become larger, the performance of mechanical type watch The case where reduction.In contrast, the lubricant compositions of the wrist-watch of embodiment 1 are due to comprising specific lubricant (A), because This, it is dynamic to be able to suppress oil stream.It does not need to carry out refusing oil processing in advance, the profit of the wrist-watch of embodiment 1 can be adhered to compared with unfertile land The layer (lubricant layer) of lubricant composition.Therefore, the increase of resistance to sliding is inhibited, and also can be improved the property of mechanical type watch Energy.In addition, due to not needing to refuse oil processing, it can easily lubricate the sliding part of escapement.In turn, embodiment 1 The lubricant compositions of wrist-watch be not easy to evaporate, therefore, above-mentioned sliding part can be lubricated for a long time.It should be noted that for machinery The escapement of formula wrist-watch, describes in detail below.

Paraffin (A-1) preferably fusing point is 45 DEG C~80 DEG C, more preferably 50 DEG C~75 DEG C.If fusing point is in the range, It then can suitably inhibit oil stream dynamic.As paraffin (A-1), such as it can enumerate and the vacuum distillation of petroleum is distillated by lost-wax process The unpurified paraffin (loose wax, acale wax etc.) that oil, vacuum distillation residue oil or heavy distillate oil etc. are isolated, by this Refined paraffin wax obtained by a little unpurified paraffin are decolourized, refined etc..

The fusing point of sturated aliphatic hydrocarbon (A-2) is 45 DEG C or more.Sturated aliphatic hydrocarbon (A-2) preferably fusing point be 80 DEG C with Under.In addition, the carbon atom number of sturated aliphatic hydrocarbon (A-2) is 23~38, the preferably sturated aliphatic hydrocarbon of straight chain, more preferably Tricosane, lignocerane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, melissane, 31 Alkane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane or three octadecanes.Such fat Race's saturated hydrocarbons (A-2) can suitably inhibit oil stream dynamic.

In order to be easily processed, more preferably paraffin (A-1) is used.

(anti-wear agent (B))

Anti-wear agent (B) includes at least one kind of in neutral phosphate and neutral phosphite ester.It is preferred that anti-wear agent (B) wraps Neutral phosphite ester (the B- indicated containing the neutral phosphate (B-1) and the following general formula (b-2) that are indicated selected from the following general formula (b-1) 2) at least one kind of in.Neutral phosphate (such as neutral phosphate (B-1)) and neutral phosphite ester (such as neutral phosphite ester (B-2)) a kind can be used individually, can also be mixed with two or more.It can also be by one kind or two or more neutral phosphor Acid esters (such as neutral phosphate (B-1)) and one kind or two or more neutral phosphite ester (such as neutral phosphite ester (B-2)) It is used in mixed way.

The sliding part of escapement possessed by mechanical type watch bears very big pressure and vibration.Lubricating the sliding part When, if using the lubricant oil composite of previous wrist-watch, generate sometimes abrasion powder, precipitate as rust and it is above-mentioned A part discoloration of sliding part is dark brown.It is thought that because previous lubricant oil composite is the quartz for cooperating compression resistance low Formula wrist-watch and manufacture.Additionally, it is believed that also in that the material of quartz type wrist-watch is phosphor bronze etc., in contrast, mechanical hand The material of table is ferrous material.In contrast, the lubricant compositions of the wrist-watch of embodiment 1 due to by lubricant (A) with And anti-wear agent (B) (especially neutral phosphate (B-1) or neutral phosphite ester (B-2)) combination, it therefore, being capable of improve wearability And extreme pressure property.The generation of precipitate as abrasion powder, rust is inhibited, and is also not susceptible to the discoloration of above-mentioned sliding part.Such as This, even if can also be fitted for a long time in the case where the escapement of the mechanical type watch for bearing very big pressure and vibration Locality lubrication.

In formula (b-1), R^b11~R^b14Each independently represent the aliphatic alkyl of carbon atom number 10~16.Carbon atom number 10 ~16 aliphatic alkyl can be straight chain, branch or cricoid aliphatic alkyl, or saturated or unsaturated fat Race's alkyl.As the aliphatic alkyl of carbon atom number 10~16, specifically, decyl, undecyl, 12 can be suitably used The alkyl of the straight-chains such as alkyl, tridecyl, myristyl, pentadecyl, cetyl (cetyl).

R^b15~R^b18Each independently represent the alkyl of the straight or branched of carbon atom number 1~6.As carbon atom number 1 The alkyl of~6 straight or branched can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, isopropyl, secondary Butyl, isobutyl group, tert-butyl, isopentyl, tertiary pentyl, neopentyl, isohesyl.

Neutral phosphate (B-1) is due in R^b15~R^b18With specific substituent group, therefore, even if bearing very big pressure It, also being capable of improve wearability and extreme pressure in the case where the lubricant compositions of power and the escapement of vibration using above-mentioned wrist-watch Property.It is thought that because if in R^b15~R^b18With specific substituent group, then the above-mentioned of the sliding part of escapement is attached to The film of the lubricant compositions of wrist-watch becomes secured.

In particular, if R^b15And R^b17For the alkyl of the straight-chain of carbon atom number 1~6, preferably 1~3, R^b16And R^b18For The alkyl of the branched of carbon atom number 3~6, preferably 3~4, then above-mentioned wearability and the improvement of extreme pressure property are further It improves.

R^b191And R^b192Each independently represent the alkyl of the straight or branched of hydrogen atom or carbon atom number 1~5.Make For the alkyl of the straight or branched of carbon atom number 1~5, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, isopropyl can be enumerated Base, sec-butyl, isobutyl group, tert-butyl, isopentyl, tertiary pentyl, neopentyl.

Wherein, R^b191And R^b192Carbon atom number add up to 1~5.Thus, for example in R^b191When for hydrogen atom, R^b192For The alkyl of the straight or branched of carbon atom number 1~5, in R^b191When for methyl, R^b192For the linear chain or branched chain of carbon atom number 1~4 The alkyl of shape, in R^b191When for ethyl, R^b192For the alkyl of the straight or branched of carbon atom number 2~3.Especially for above-mentioned The film of the lubricant compositions of wrist-watch becomes stronger, more preferable R^b191For hydrogen atom, R^b192For the straight chain of carbon atom number 1~5 Or the alkyl of branched.

In formula (b-2), R^b21~R^b24Each independently represent the aliphatic alkyl of carbon atom number 10~16.Carbon atom number 10 ~16 aliphatic alkyl can be straight chain, branched or cricoid aliphatic alkyl, or saturated or unsaturated Aliphatic alkyl.As the aliphatic alkyl of carbon atom number 10~16, specifically, can be suitably used decyl, undecyl, The alkyl of the straight-chains such as dodecyl, tridecyl, myristyl, pentadecyl, cetyl (cetyl).

R^b25~R^b28Each independently represent the alkyl of the straight or branched of carbon atom number 1~6.As carbon atom number 1 The alkyl of~6 straight or branched can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, isopropyl, secondary Butyl, isobutyl group, tert-butyl, isopentyl, tertiary pentyl, neopentyl, isohesyl.

Neutral phosphite ester (B-2) is due in R^b25~R^b28With specific substituent group, therefore, even if very big in receiving It, also being capable of improve wearability and pole in the case where the lubricant compositions of pressure and the escapement of vibration using above-mentioned wrist-watch Pressure property.It is thought that because if in R^b25~R^b28With specific substituent group, then the upper of the sliding part of escapement is attached to The film for stating the lubricant compositions of wrist-watch becomes secured.

Especially if R^b25And R^b27For the alkyl of the straight-chain of carbon atom number 1~6, preferably 1~3, R^b26And R^b28For The alkyl of the branched of carbon atom number 3~6, preferably 3~4, then above-mentioned wearability and the improvement of extreme pressure property are further It improves.

R^b291And R^b292Each independently represent the alkyl of the straight or branched of hydrogen atom or carbon atom number 1~5.Make For the alkyl of the straight or branched of carbon atom number 1~5, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, isopropyl can be enumerated Base, sec-butyl, isobutyl group, tert-butyl, isopentyl, tertiary pentyl, neopentyl.

Wherein, R^b291And R^b292Carbon atom number add up to 1~5.Thus, for example in R^b291When for hydrogen atom, R^b292For The alkyl of the straight or branched of carbon atom number 1~5, in R^b291When for methyl, R^b292For the linear chain or branched chain of carbon atom number 1~4 The alkyl of shape, in R^b291When for ethyl, R^b292For the alkyl of the straight or branched of carbon atom number 2~3.Especially for above-mentioned The film of the lubricant compositions of wrist-watch becomes stronger, more preferable R^b291For hydrogen atom, R^b292For the straight chain of carbon atom number 1~5 Or the alkyl of branched.

Due to thinking that structural stability is higher in the lubricant compositions for above-mentioned wrist-watch, it can be further Neutral phosphite ester (B-2) is suitably used.

As above-mentioned neutral phosphate, the neutral phosphate other than neutral phosphate (B-1) can be used, such as can make With tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, trioctyl phosphate, trimethylolpropane phosphate, triphenyl phosphate, phosphoric acid Three (nonyl phenyl) esters, triethyl phosphate, tricresyl phosphate (tridecyl) ester, tetraphenyl dipropylene glycol bisphosphate, tetraphenyl four (tridecyl) pentaerythrite tetraphosphate ester, four (tridecyl) -4,4 '-isopropylidene diphenyl phosphoesters, bis- (tridecanes Base) pentaerythritol diphosphate, bis- (nonyl phenyl) pentaerythritol diphosphates, tricresyl phosphate stearyl ester, distearyl Ji Wusi Alcohol bisphosphate, three (2,4- di-tert-butyl-phenyl) phosphates, hydrogenated bisphenol A-pentaerythritol phosphate polymer etc..

As above-mentioned neutral phosphite ester, the neutral phosphite ester other than neutral phosphite ester (B-2) can be used, such as Trioleyl phosphite, three monooctyl ester of phosphorous acid, trimethylolpropane phosphite ester, triphenyl, phosphorous can be used Sour three (nonyl phenyl) esters, triethyl phosphite, phosphorous acid three (tridecyl) ester, tetraphenyl dipropyleneglycol, Four phosphite ester of tetraphenyl four (tridecyl) pentaerythrite, four (tridecyl) -4,4 '-isopropylidene diphenyl phosphorous acid Ester, bis- (tridecyl) pentaerythritol diphosphites, bis- (nonyl phenyl) pentaerythritol diphosphites, phosphorous acid three are stearic Ester, distearyl pentaerythrityl diphosphite, three (2,4- di-tert-butyl-phenyl) phosphite esters, hydrogenated bisphenol A-pentaerythrite Polymeric phosphite etc..

Neutral phosphate (B-1) compared with the neutral phosphate other than it, can in the sliding part of mechanical type watch into One step inhibits oil stream dynamic.In addition, neutral phosphite ester (B-2) is compared with the neutral phosphite ester other than it, it can be mechanical It is dynamic that oil stream is further suppressed in the sliding part of wrist-watch.

(antioxidant (C))

The lubricant compositions of the wrist-watch of embodiment 1 can further include antioxidant (C).If embodiment The lubricant compositions of 1 wrist-watch include antioxidant (C), then can inhibit for a long time rotten.As antioxidant (C), can lift Phenolic antioxidant, amine antioxidant out.Antioxidant (C) can be used alone, and can also be mixed with two or more.

As phenolic antioxidant, 2,6-di-tert-butyl p-cresol, 2 can be enumerated, 4,6- tri-butyl-phenols, 4,4 '-is sub- Methyl bis(2,6-di-butyl phenol).

Diphenylamines can be suitably used in order to further suppress the rotten of lubricant compositions as amine antioxidant The hydrogen atom of the phenyl ring of derivative, i.e. diphenylamines is by the alkyl-substituted compound of the straight or branched of carbon atom number 1~10. As such compound, specifically, can the more appropriate diphenylamine derivatives (C-1) indicated using the following general formula (c-1).

In formula (c-1), R^c11And R^c12Each independently represent the alkyl of the straight or branched of carbon atom number 1~10.Make For the alkyl of the straight or branched of carbon atom number 1~10, can enumerate methyl, ethyl, n-propyl, normal-butyl, n-pentyl, just oneself Base, n-heptyl, n-octyl, n-nonyl, positive decyl, isopropyl, sec-butyl, isobutyl group, tert-butyl, isopentyl, tertiary pentyl, new penta Base, isohesyl, 2- ethylhexyl, 2,4,4- tri-methyl-amyl, 1,1,3,3- tetramethyl butyl etc..

P and q each independently represents 0~5 integer, preferably indicates 0~3 integer.Wherein, p and q do not indicate 0 simultaneously.

Diphenylamine derivatives (C-1) for example passes through diphenylamines and the straight or branched for importing carbon atom number 1~10 Alkyl as substituent group compound (ethylene, propylene, 1- butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene, 2- butylene, 2- metering system, 3-methyl-1-butene, 2-methyl-1-butene alkene, 4-methyl-1-pentene, 2- ethyl -1- Hexene, 2,4,4- trimethylpentene etc. have double bond compound) reaction and obtain.

It can also be suitably used following as amine antioxidant in order to further suppress the rotten of lubricant compositions The hindered amine compound (C-2) that general formula (c-2) indicates.

In formula (c-2), R^c21And R^c22Each independently represent the aliphatic alkyl of carbon atom number 1~10.Carbon atom number 1~ 10 aliphatic alkyl can be straight chain, branched or cricoid aliphatic alkyl, or saturated or unsaturated fat Race's alkyl.As the aliphatic alkyl of carbon atom number 1~10, specifically, methyl, ethyl, n-propyl, just can be suitably used Butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl, isopropyl, sec-butyl, isobutyl group, tert-butyl, isopentyl, uncle The alkyl of the straight or brancheds such as amyl, neopentyl, isohesyl, 2- ethylhexyl.Among these, from the viewpoint for improving durability It sets out, more preferably the alkyl of the straight or branched of carbon atom number 5~10.

R^c23Indicate the aliphatic alkyl of the divalent of carbon atom number 1~10.The aliphatic of divalent as carbon atom number 1~10 Alkyl, can be suitably used methylene, 1,2- ethylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene, 1,5- pentylidene, 1,6- it is sub- oneself Base, 1,7- heptamethylene, 1,8- octamethylene, 1,9- nonylene, 1,10- decylene, 3- methyl-1, the straight chain of the divalents such as 5- pentylidene Or the alkylidene of branched.Among these, from the viewpoint of improve durability, the more preferably divalent of carbon atom number 5~10 The alkylidene of straight or branched.

Especially from the viewpoint of improving the durability under high temperature, more preferably among the above R^c21、R^c22And R^c23Carbon it is former Subnumber and be 16~30.

As amine antioxidant, preferably by one kind or two or more diphenylamine derivatives (C-1) and one kind or two or more Hindered amine compound (C-2) be applied in combination.Even if as a result, in the sliding part for the escapement for bearing very big pressure and vibration In the case where lubricant compositions using the wrist-watch of embodiment 1, the generation of precipitate as abrasion powder, rust also into One step is inhibited, and is also further not susceptible to the discoloration of above-mentioned sliding part, can be improved durability.It is considered because if will Diphenylamine derivatives (C-1) and hindered amine compound (C-2) combination, even if then having in sliding because bearing very big pressure and vibration Dynamic and generation reactive species, also can be long-term innoxious.

(matal deactivator (D))

The lubricant compositions of the wrist-watch of embodiment 1 can also further include matal deactivator (D).If comprising Matal deactivator (D), then can further suppress corrosion of metal.As matal deactivator (D), from inhibition corrosion of metal Viewpoint is set out, preferably benzotriazole or derivatives thereof.Matal deactivator (D) can be used alone, and can also be used in mixed way Two or more.

As benzotriazole derivatives, specifically, 2- (2'- hydroxyl -5'- aminomethyl phenyl) benzotriazole, 2- can be enumerated [bis- (bis (alpha, alpha-dimethylbenzyl) base) phenyl of 2'- hydroxyl -3', 5'-]-benzotriazole, 2- (2'- hydroxyl -3', 5'- di-t-butyl-benzene Base)-benzotriazole, R, R', R " are the compound of the alkyl of carbon atom number 1~18 in structure shown in following formula, such as 1- (N, Bis- (2- ethylhexyl) amino methyls of N-) benzotriazole etc..

Inhibiting oil stream dynamic from the viewpoint of the sliding part in mechanical type watch, the lubrication of the wrist-watch of embodiment 1 Agent composition includes anti-wear agent (B) with 1 mass parts~200 mass parts amount preferably with respect to 100 mass parts of lubricant (A), more It is preferred that including anti-wear agent (B) with 1 mass parts~120 mass parts amount, further preferably with 1 mass parts~80 mass parts amount packet Containing anti-wear agent (B).If including with above-mentioned amount, can suitably lubricate for a long time.

In addition, antioxidant (C) is preferably with respect to total 100 mass parts of lubricant (A) and anti-wear agent (B) with 0.01 matter Measuring part~1.2 mass parts amount includes.If including with above-mentioned amount, durability can be further increased.Matal deactivator (D) preferably with respect to total 100 mass of lubricant (A) and anti-wear agent (B), with 0.01 mass parts~1.2 mass parts amount packet Contain.If including with above-mentioned amount, corrosion can be further suppressed.

The lubricant compositions of the wrist-watch of embodiment 1 are usually semi-solid at normal temperature.Room temperature refers to usual shape Ambient temperature under state, specifically 15 DEG C~30 DEG C, be 25 DEG C for typical.Semisolid refer to liquid and solid this The substance of the two attribute, and the substance under room temperature compared with liquid closer to solid.

The lubricant compositions of the wrist-watch of embodiment 1 are to be obtained by mixing mentioned component.Such as it can be on one side The fusing point of mentioned component or more is heated to be mixed on one side.Furthermore it is possible to which hydrocarbon solvent equal solvent is added in mentioned component and mixes After conjunction, evaporate above-mentioned solvent.In evaporation, warm wind can be blown.It as above-mentioned solvent, is not particularly limited, such as is using When paraffin (A-1), preferably hexane, nonane.In addition, when using sturated aliphatic hydrocarbon (A-2), can from hexane, toluene, It is suitably selected in THF, ether, chloroform, hexamethylene, heptane, hexahydrotoluene, ether and methanol.It so, it is possible preparation to implement The lubricant compositions of the wrist-watch of mode 1.

Wrist-watch (mechanical type watch) > of < embodiment 1

The wrist-watch (mechanical type watch) of embodiment 1 is attached with lubricant compositions (the lubricant group of above-mentioned wrist-watch It closes object (I)).Fig. 1 is the figure for illustrating the wrist-watch of embodiment 1 (mechanical type watch).As shown in Figure 1, mechanical type watch has There is escapement 1, escapement 1 is made of escape wheel 2 and escapement lever 3.Escape wheel 2 is that the power being unfolded by balance spring 4 is located at The gear of the wheel column of gear finally rotated.Escapement lever 3 and balance wheel 5 interlock, by based on the regular of reciprocating motion Vibration, makes the tooth of escape wheel 2 singly advance.At this point, the tooth of pawl 3a, 3b stop escape wheel 2 of escapement lever 3, Huo Zhecong The tooth of escape wheel 2 is detached from.Very big pressure and vibration are born in the sliding part of the tooth of pawl 3a, 3b and escape wheel 2 of the escapement lever 3 It is dynamic.In order to lubricate the sliding part, the lubricant compositions of above-mentioned wrist-watch can be suitably used.Specifically, making above-mentioned The lubricant compositions of wrist-watch are attached to the portion that above-mentioned sliding part is constituted in pawl 3a, 3b of escapement lever 3 and the tooth of escape wheel 2 Point.The lubricant compositions that above-mentioned wrist-watch is used due to can not occur oil stream it is dynamic in the case where it is attached compared with unfertile land as lubricant layer , therefore, the increase of resistance to sliding is inhibited, and also can be improved the performance of mechanical type watch.In addition, due to not needing to refuse oil Processing, therefore, can easily lubricate the sliding part of escapement.In turn, not due to the lubricant compositions of above-mentioned wrist-watch Easily evaporation, therefore, can lubricate above-mentioned sliding part for a long time.

The adherence method of lubricant compositions as above-mentioned wrist-watch can enumerate the lubricant combination to above-mentioned wrist-watch Object heat after making its softness, is coated on the part for constituting above-mentioned sliding part and makes the method for its attachment.Alternatively, can also To use the lubricant compositions of above-mentioned wrist-watch to prepare the treatment fluid of wrist-watch lubrication, it is coated on and constitutes above-mentioned sliding part Part and make its attachment.Here, the treatment fluid of wrist-watch lubrication is illustrated.

(treatment fluid of wrist-watch lubrication)

The treatment fluid of wrist-watch lubrication includes lubricant (A), anti-wear agent (B) and solvent (E).For lubricant (A) and Anti-wear agent (B), as above-mentioned wrist-watch lubricant compositions in explanation shown in.The treatment fluid of wrist-watch lubrication can be wrapped further Containing antioxidant (C), matal deactivator (D).For antioxidant (C) and matal deactivator (D), the profit of wrist-watch also described above In lubricant composition shown in explanation.These ingredients become the lubrication of above-mentioned wrist-watch preferably in the treatment fluid of wrist-watch lubrication The mode of the amount ratio illustrated in agent composition contains.

It as solvent (E), is not particularly limited, such as when using paraffin (A-1), preferably hexane, nonane.In addition, It, can be from hexane, toluene, THF, ether, chloroform, hexamethylene, heptane, methyl cyclohexane when using sturated aliphatic hydrocarbon (A-2) It is suitably selected in alkane, ether and methanol.Solvent (E) can be used alone, and can also be mixed with two or more.Solvent (E) it is preferably added in such a way that the concentration of lubricant (A) and anti-wear agent (B) is total as 0.1 mass of mass %~5 %.If It is used with above-mentioned amount, then the lubricant compositions of above-mentioned wrist-watch are suitably attached to above-mentioned sliding part.

Specifically, by the way that the lubricant compositions of above-mentioned wrist-watch are added in solvent (E) and are stirred, so as to Prepare the treatment fluid of wrist-watch lubrication.Then, the treatment fluid for the wrist-watch lubrication that Xiang Shangshu sliding part drippage obtains on a small quantity, makes molten Agent (E) evaporation.Adhere to the lubricant compositions of above-mentioned wrist-watch in above-mentioned sliding part as a result,.Include semi-solid that is, becoming The layer of the lubricant compositions of above-mentioned wrist-watch and adhere to.

It should be noted that in the lubricant compositions attachment of above-mentioned wrist-watch, as long as being attached to it constitutes above-mentioned sliding At least one party of the flank of the side pawl 3a, 3b and escape wheel 2 of escapement lever 3 in the part in portion.

As long as it should be noted that bear the sliding part of very big pressure and vibration in mechanical type watch, then above-mentioned implementation The lubricant compositions of the wrist-watch of mode 1 can be used for the sliding part other than the sliding part of above-mentioned escapement.At this point, Effect as described above can be played.As the sliding part for bearing very big pressure and vibration, specifically, gear can be enumerated The sliding part of wheel column, lever or the clockwork spring of moment amendment.

The lubricant compositions > of the wrist-watch of < embodiment 2

Next, being illustrated to the lubricant compositions of the wrist-watch of embodiment 2.It in the present specification, also will be real The lubricant compositions for applying the wrist-watch of mode 2 are known as lubricant compositions (II).The lubricant group of the wrist-watch of embodiment 2 Closing object includes lubricant (A) and anti-wear agent (B).In lubricant compositions (II), lubricant (A) and anti-wear agent (B) it is detailed Situation include preferred range inside with lubricant compositions (I) the case where it is same.If being in above-mentioned preferred range, The fastener of watch buckle can be lubricated for a long time.Lubricant compositions (II) further include mobility regulator (F).

Watch buckle possessed by the watchband of wrist-watch bears very big pressure when buckling or removing.If the watch buckle use with It is dynamic then to generate oil stream sometimes for the lubricant oil composite of past wrist-watch.In addition, can residual soil wiping.In contrast, The lubricant compositions of the wrist-watch of embodiment 2 due to comprising specific lubricant (A) and mobility regulator (F), It is dynamic to be able to suppress oil stream, and is capable of forming the film of the lubricant compositions (II) with preferred hardness.In addition, embodiment 2 Wrist-watch lubricant compositions due to being not easy to evaporate, the function for the watch buckle buckled or removed can be maintained for a long time.Into And therefore lubricant compositions (II) are not easy to be considered as dirt with the micro function of playing watch buckle.

As mobility regulator (F), known viscosity index improving agent can be used.Mobility regulator (F) It can be used alone, can also be mixed with two or more.As mobility regulator (F), such as polyacrylic acid can be enumerated Ester, polymethacrylates, polyisobutene, alkyl styrenes, polyester, alpha olefin copolymer, isobutene fumarate, benzene second Alkene maleate, vinyl acetate fumarate, Polybutadiene-styrene copolymer, polymethyl methacrylate-vinylpyridine Pyrrolidone copolymer, ethylene-acrylic acid alkyl ester copolymer.Among these, from the hardness of the film of lubricant compositions (II) Viewpoint is set out, and polyisobutene, alpha olefin copolymer can be suitably used, and can more suitably use polyisobutene.

As polyacrylate, specifically, the carbon atom number 1~10 of the polymer of acrylic acid, acrylic acid can be enumerated The polymer of Arrcostab.As polymethacrylates, the polymer of methacrylic acid, the carbon atom of methacrylic acid can be enumerated The polymer of the Arrcostab of number 1~10.Among these, preferably make polymethylacrylic acid made of methyl methacrylate polymerization Ester.

Polyisobutene is preferably homopolymer.In addition, polyisobutene preferred number average molecular weight (Mn) is 3000~80000, from From the perspective of lubricity, more preferably 3000~50000.Number-average molecular weight (Mn) is surveyed by gel permeation chromatography (GPC) Determine the value for the polystyrene conversion that method (standard substance: polystyrene) is found out.

As alkyl styrenes, poly alpha methylstyrene, poly- Beta-methyl styrene, poly- α-ethyl can be specifically enumerated Styrene, poly- β-ethyl styrene etc. have the polymer of the monoalkyl benzene ethylene of the substituent group of carbon atom number 1~18.

As polyester, can specifically enumerate by the carbon atom numbers such as ethylene glycol, propylene glycol, neopentyl glycol, dipentaerythritol 1 The polyacids such as~10 polyalcohol and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, phthalic acid obtain Polyester.

As alpha olefin copolymer, ethene-alpha-olefin copolymer can be specifically enumerated.Such as can enumerate ethylene (15~ 80 moles of %) copolymer with the alpha-olefin (20~85 moles of %) of carbon atom numbers 3~20 such as propylene, 1- butylene, 1- decene, it can Think no regulator, or block body.Alpha olefin copolymer preferable weight-average molecular weight (Mw) is 2000~9000, more preferably 3000~8000.Weight average molecular weight (Mw) is to be asked by gel permeation chromatography (GPC) measuring method (standard substance: polymerizing styrene) The value of polystyrene conversion out.

Lubricant compositions (II) can further include antioxidant (C) or matal deactivator (D).In lubricant combination In object (II), the details of antioxidant (C) and matal deactivator (D) include preferred range inside and lubricant combination The case where object (I), is same.If being in above-mentioned preferred range, the fastener of watch buckle can be lubricated for a long time.

For the lubricant compositions of the wrist-watch of embodiment 2, by lubricant (A), anti-wear agent (B) and stream It preferably include lubricant (A) with 10 mass parts~80 mass parts amount when dynamic property regulator (F) total is set as 100 mass parts It include anti-wear agent (B) with 20 mass parts~90 mass parts amount, more preferably with 25 mass with adding up to for mobility regulator (F) The amount of part~35 mass parts includes adding up to for lubricant (A) and mobility regulator (F), with 65 mass parts~75 mass parts amount Include anti-wear agent (B).If including to be able to suppress oil stream to move, and be capable of forming with preferred hardness with above-mentioned amount The film of lubricant compositions (II).Therefore, the fastener of watch buckle can be suitably lubricated for a long time.

For the lubricant compositions of the wrist-watch of embodiment 2, by lubricant (A) and mobility regulator It (F) preferably include lubricant (A) with 10 mass parts~90 mass parts amount, with 10 mass parts when total is set as 100 mass parts The amount of~90 mass parts includes mobility regulator (F).If with above-mentioned amount including that be able to suppress oil stream dynamic, and energy It is enough to form the film with the lubricant compositions (II) of preferred hardness.Therefore, the fastener of watch buckle can be suitably lubricated for a long time.

In addition, conjunction of the antioxidant (C) preferably with respect to lubricant (A), anti-wear agent (B) and mobility regulator (F) 100 mass parts, which are counted, with 0.01 mass parts~1.2 mass parts includes.If including with above-mentioned amount, can further increase resistance to Long property.Total 100 matter of the matal deactivator (D) preferably with respect to lubricant (A), anti-wear agent (B) and mobility regulator (F) Part, which is measured, with 0.01 mass parts~1.2 mass parts amount includes.If including with above-mentioned amount, corrosion can be further suppressed.

The lubricant compositions of the wrist-watch of embodiment 2 are usually paste at normal temperature.

The lubricant compositions of the wrist-watch of embodiment 2 are to be obtained by mixing above-mentioned ingredient.Such as it can be with one It is mixed on one side while being heated to above-mentioned ingredient.In the case where having heated, it is preferably returned to room temperature, further to mix The mode of refining mixed.It so, it is possible the lubricant compositions of the wrist-watch of preparation embodiment 2.

The wrist-watch > of < embodiment 2

The wrist-watch of embodiment 2 is attached with the lubricant compositions (lubricant compositions (II)) of above-mentioned wrist-watch.Example The fastener of watch buckle is attached with the lubricant compositions of above-mentioned wrist-watch such as in the watchband of wrist-watch.The fastener of watch buckle is being detained Very big pressure is born when above or removing.In order to lubricate above-mentioned fastener, the lubricant of above-mentioned wrist-watch can be suitably used Composition.Specifically, the lubricant compositions of above-mentioned wrist-watch is made to be attached to above-mentioned fastener.The lubricant of above-mentioned wrist-watch Composition can not occur oil stream it is dynamic in the case where as preferred hardness lubricant layer compared with unfertile land attachment.In addition, above-mentioned hand The lubricant compositions of table due to being not easy to evaporate, the function for the watch buckle buckled or removed can be maintained for a long time.In turn, Lubricant compositions (II) due to it is micro play watch buckle function, be not easy to be considered as dirt.

The wrist-watch of embodiment 2 preferably comprises the watchband of the wrist-watch of the fastener with the watch buckle for bearing especially big pressure. If the fastener for the watch buckle for bearing king-sized pressure, can more suitably play by lubricant compositions (II) band The effect come.The example of wrist-watch with such fastener is specifically described.

Fig. 2 and Fig. 3 is the figure for illustrating the wrist-watch of embodiment 2.As shown in Fig. 2, the watchband of wrist-watch has watch buckle knot Structure 10.Watch buckle structure 10 has watch buckle main body 24, can be sliding in the longitudinal direction of the watchband component 26 of a side with watch buckle main body 24 Dynamic mode installs the watchband component 26 of a side in the watch buckle main body 24.Watch buckle main body 24 has section substantially "U" word shape Slider box 28,32 structure of side wall that the both side edges of the width direction of the slider box 28 by bottom plate 30 and from the bottom plate 30 are uprightly arranged At.In addition, watch buckle main body 24 has pressing plate 34.The support projection 36 at the both ends of the width direction of the pressing plate 34 is formed in slightly Mode with clearance is entrenched in the long hole 38 for being formed in the side wall 32 of slider box 28.Support projection 36 is by long hole 38 as a result, Guidance, can movably install pressing plate 34 in above-below direction.The pressing plate 34 becomes with the upper surface of side's watchband component 26 gently The state of contact, slider box 28 becomes able to slide along the longitudinal direction of the watchband component 26 of a side as a result,.In addition, pressing plate Thus the watchband component 26 of one side is configured to be easy the bottom plate 30 of insertion slider box 28 by 34 front end slight curvature upwards Between pressing plate 34.On the other hand, have outside link plate 16, outside connection in the end of the watchband component 12 in another party Plate 16 is rotatably linked with pin 14.Other end of link plate 16 has inside link plate 20, inside connection on the outside of this Plate 20 is rotatably linked with pin 18 relative to outside link plate 16.In turn, the other end of inside link plate 20 is via pin 22 Link with watch buckle main body 24.In turn, the end of link plate 16 has locking plate 42 on the outside, and the locking plate 42 is opposite via pin 40 Rotatably link in outside link plate 16.The locking plate 42 is in the shape for folding outside link plate 16 and inside link plate 20 The engagement pawl 44 for being provided projectingly on locking plate 42 is engaged with pin 46 under state.Thereby, it is possible to reducing the diameter of the watchband of wrist-watch and Wrist-watch is worn in wrist.That is, inside link plate 20, outside link plate 16 and the composition of locking plate 42 are folded to watch buckle main body 24 Folding part.It should be noted that being equipped with locking frame 58 in pin 46.The locking frame 58 is made of a pair of side plates 60 and top plate 62, In These a pair of side plates 60 are formed with the locking protrusion portion 64 protruded inwardly.If making locking protrusion portion 64 and watch buckle main body 24 The locking of the side wall 32 of slider box 28 is engaged with hole 66, then is locked to the above-mentioned folding part of watch buckle main body 24 further reliably phase Watch buckle main body 24 is fixed.

Engagement pawl 44 and pin 46 bear king-sized pressure in locking or its releasing.If making lubricant compositions (II) It is attached to such fastener for bearing especially big pressure, then can more suitably be played by lubricant compositions (II) bring Effect.

In addition, as shown in figure 3, the watch buckle structure 10 of the watchband of wrist-watch is substantially same with watch buckle structure 10 shown in Fig. 2 The composition of sample.Identical reference number is marked in identical member of formation, omits detail explanation.The watch buckle structure 10 of Fig. 3 In, omit outside link plate 16, inside link plate 20 as folding part, the watchband component 12 of another party is configured to and The separation of the watchband component 26 of watch buckle main body 24 and a side.Moreover, having and can rotate in the end of the watchband component 12 of another party The locking plate portion 78 of ground connection, has been provided projectingly hook portion 80 at the back side in the locking plate portion 78.In addition, in the watchband structure of another party The end of part 12 has been provided projectingly hook portion 96.On the other hand, it is respectively arranged in the side wall 32 of the slider box 28 of watch buckle main body 24 The locking pin 100 that hook portion 80 was engaged locking pin 98, is used to engage hook portion 96.By such composition, by locking plate When portion 78 is engaged relative to watch buckle main body 24, firstly, the hook portion 96 of the end of the watchband component 12 of another party is locked to Engage pin 100.Then, the hook portion 80 at the back side in locking plate portion 78 is locked to locking pin 98.

Hook portion 80 and locking pin 98 bear king-sized pressure in locking or its releasing.If making lubricant compositions (II) it is attached to such fastener for bearing especially big pressure, then can more suitably be played by lubricant compositions (II) band The effect come.

The adherence method of lubricant compositions as above-mentioned wrist-watch can be enumerated above-mentioned hand using toilet's cotton swab The lubricant compositions of table are coated on above-mentioned fastener, wipe extra composition and make the method for its attachment.Become as a result, The layer of lubricant compositions comprising above-mentioned wrist-watch paste and adhere to.

It should be noted that the lubricant compositions of the wrist-watch of above-mentioned embodiment 2 can be used in mechanical type watch holding By the sliding part of very big pressure and vibration.Such as can enumerate the sliding part of above-mentioned escapement, gear wheel column, lever or when Carve the sliding part of the clockwork spring of amendment.At this point, can also play effect as described above.

In conclusion the present invention relates to the following contents.

(1) a kind of lubricant compositions of wrist-watch, which is characterized in that be the hand comprising lubricant (A) and anti-wear agent (B) The lubricant compositions of table,

Above-mentioned lubricant (A) includes selected from paraffin (A-1) and fusing point is 45 DEG C or more and carbon atom number is 23~38 At least one kind of in sturated aliphatic hydrocarbon (A-2), above-mentioned anti-wear agent (B) includes in neutral phosphate and neutral phosphite ester It is at least one kind of.

(2) lubricant compositions of the wrist-watch according to above-mentioned (1), which is characterized in that above-mentioned anti-wear agent (B) includes The neutral phosphite ester (B-2) indicated selected from the following general formula (b-1) neutral phosphate (B-1) indicated and the following general formula (b-2) In it is at least one kind of.

(in formula (b-1), R^b11~R^b14Each independently represent the aliphatic alkyl of carbon atom number 10~16, R^b15~R^b18 Each independently represent the alkyl of the straight or branched of carbon atom number 1~6, R^b191And R^b192Each independently represent hydrogen atom Or the alkyl of the straight or branched of carbon atom number 1~5, R^b191And R^b192Carbon atom number add up to 1~5)

(in formula (b-2), R^b21~R^b24Each independently represent the aliphatic alkyl of carbon atom number 10~16, R^b25~R^b28 Each independently represent the alkyl of the straight or branched of carbon atom number 1~6, R^b291And R^b292Each independently represent hydrogen atom Or the alkyl of the straight or branched of carbon atom number 1~5, R^b291And R^b292Carbon atom number add up to 1~5)

According to the lubricant compositions of above-mentioned wrist-watch, that is, it is used in the sliding part of mechanical type watch or the watchband of wrist-watch It is dynamic to be also able to suppress oil stream for watch buckle.

(3) lubricant compositions of the wrist-watch according to above-mentioned (1) or (2), which is characterized in that further include anti- Oxidant (C), above-mentioned antioxidant (C) include the diphenylamine derivatives (C-1) and following indicated selected from the following general formula (c-1) It is at least one kind of in the hindered amine compound (C-2) that general formula (c-2) indicates.

(in formula (c-1), R^c11And R^c12Each independently represent the alkyl of the straight or branched of carbon atom number 1~10, p 0~5 integer is each independently represented with q.Wherein, 0) p and q is not indicated simultaneously

(in formula (c-2), R^c11And R^c12Each independently represent the aliphatic alkyl of carbon atom number 1~10, R^c23Indicate carbon The aliphatic alkyl of the divalent of atomicity 1~10)

If can inhibit for a long time rotten comprising antioxidant as described above (C).

(4) lubricant compositions of the wrist-watch according to any one of above-mentioned (1)~(3), which is characterized in that into one Step includes matal deactivator (D).

If corrosion of metal can be further suppressed comprising above-mentioned matal deactivator (D).

(5) lubricant compositions of the wrist-watch according to any one of above-mentioned (1)~(4), which is characterized in that above-mentioned The fusing point of paraffin (A-1) is 45 DEG C~80 DEG C.

If it is dynamic that oil stream can be further suppressed comprising above-mentioned paraffin (A-1).

(6) lubricant compositions of the wrist-watch according to any one of above-mentioned (1)~(5), which is characterized in that above-mentioned Sturated aliphatic hydrocarbon (A-2) is tricosane, lignocerane, pentacosane, hexacosane, heptacosane, octacosane, 20 Nine alkane, melissane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane or Three octadecanes.

If it is dynamic that oil stream can be further suppressed comprising above-mentioned sturated aliphatic hydrocarbon (A-2).

(7) a kind for the treatment of fluid of wrist-watch lubrication, which is characterized in that be comprising lubricant (A), anti-wear agent (B) and molten The treatment fluid of the wrist-watch lubrication of agent (E), above-mentioned lubricant (A) include selected from paraffin (A-1) and fusing point be 45 DEG C or more and At least one kind of in the sturated aliphatic hydrocarbon (A-2) that carbon atom number is 23~38, above-mentioned anti-wear agent (B) includes selected from neutral phosphoric acid It is at least one kind of in ester and neutral phosphite ester.

(8) treatment fluid of the wrist-watch lubrication according to above-mentioned (7), which is characterized in that above-mentioned anti-wear agent (B) includes choosing From in the neutral phosphite ester (B-2) that the following general formula (b-1) neutral phosphate (B-1) indicated and the following general formula (b-2) indicate It is at least one kind of.

If, can be on the sliding part of mechanical type watch suitably adheres to using the treatment fluid of above-mentioned wrist-watch lubrication State the lubricant compositions of wrist-watch.

(9) a kind of wrist-watch, which is characterized in that be attached with the lubricant of wrist-watch described in any one of above-mentioned (1)~(6) Composition.

The performance of above-mentioned wrist-watch (such as mechanical type watch) also improves, and can suitably be lubricated for a long time.

(10) lubricant compositions of the wrist-watch according to any one of above-mentioned (1)~(6), which is characterized in that phase It include above-mentioned anti-wear agent (B) with 1 mass parts~200 mass parts amount for 100 mass parts of above-mentioned lubricant (A).

If including with above-mentioned amount, that is, it is used in the sliding that very big pressure and vibration are born in mechanical type watch Portion also can suitably lubricate for a long time.

(11) lubricant compositions of the wrist-watch according to any one of above-mentioned (1)~(6), which is characterized in that into One step includes mobility regulator (F), by above-mentioned lubricant (A), above-mentioned anti-wear agent (B) and above-mentioned mobility regulator It (F) include above-mentioned lubricant (A) and above-mentioned with 10 mass parts~80 mass parts total amount when total is set as 100 mass parts Mobility regulator (F) includes above-mentioned anti-wear agent (B) with 20 mass parts~90 mass parts amount.

If including with above-mentioned amount, the fastener of watch buckle can be suitably lubricated for a long time.

(12) lubricant compositions of the wrist-watch according to above-mentioned (11), which is characterized in that above-mentioned mobility adjustment Agent (F) is polyacrylate, polymethacrylates, polyisobutene, alkyl styrenes, polyester or alpha olefin copolymer.

If can suitably lubricate the fastener of watch buckle for a long time comprising mobility regulator (F) as described above.

[embodiment]

[embodiment 1-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as neutral phosphite ester (B-2) 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts are added in hexane and mix After conjunction, hexane is evaporated, obtains the lubricant compositions (lubricant compositions (I)) of wrist-watch.

Above-mentioned 0.9 mass parts of lubricant compositions are added in 99.1 mass parts of hexane as solvent (E) and are mixed, Obtain the treatment fluid of wrist-watch lubrication.

[embodiment 1-2]

It replaces making using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 5 mass parts With 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, in addition to this, with reality Apply the lubricant compositions (lubricant compositions (I)) that a 1-1 gets similarly wrist-watch.In addition, using above-mentioned wrist-watch Lubricant compositions get similarly the treatment fluid of wrist-watch lubrication with embodiment 1-1.

[embodiment 1-3]

It is replaced using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 120 mass parts Using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, in addition to this, with Embodiment 1-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, being used using above-mentioned wrist-watch Lubricant compositions, the treatment fluid of wrist-watch lubrication is got similarly with embodiment 1-1.

[embodiment 1-4]

It is replaced using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 200 mass parts Using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, in addition to this, with Embodiment 1-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, being used using above-mentioned wrist-watch Lubricant compositions, the treatment fluid of wrist-watch lubrication is got similarly with embodiment 1-1.

[embodiment 1-5]

It is replaced using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 40 mass parts Using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, in addition to this, with Embodiment 1-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, being used using above-mentioned wrist-watch Lubricant compositions, the treatment fluid of wrist-watch lubrication is got similarly with embodiment 1-1.

[embodiment 1-6]

By 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts, as 4,4 '-butylidenebis of neutral phosphite ester (B-2) (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, diphenylamine derivatives (trade name IRGANOX L 57, Ciba Specialty Chemicals Co. Ltd. systems) 0.9 mass parts, as the decanedioic acid of hindered amine compound (C-2) Bis- 0.9 mass parts of (2,2,6,6- tetramethyl -1- (octyloxy) piperidin-4-yl) ester are added in hexane and mix, and then, make oneself Alkane evaporation, obtains the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant of above-mentioned wrist-watch Composition gets similarly the treatment fluid of wrist-watch lubrication with embodiment 1-1.

[embodiment 1-7]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as neutral phosphite ester (B-2) 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts, as matal deactivator (D) 0.09 mass parts of benzotriazole are added in hexane and mix, and then, evaporate hexane, obtain the lubricant of wrist-watch Composition (lubricant compositions (I)).In addition, using the lubricant compositions of above-mentioned wrist-watch, in the same manner as embodiment 1-1 To the treatment fluid of wrist-watch lubrication.

[embodiment 1-8]

Instead of 130 °F of paraffin, using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, got similarly with embodiment 1-1 The lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant compositions of above-mentioned wrist-watch, with reality Apply the treatment fluid that a 1-1 gets similarly wrist-watch lubrication.

[embodiment 1-9]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 1-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 1-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 1-10]

Will as lignocerane (50~53 DEG C of fusing point) 100 mass parts of sturated aliphatic hydrocarbon (A-2), as neutral phosphorous 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts of acid esters (B-2) are added to It in toluene and mixes, then, evaporates toluene, obtain the lubricant compositions (lubricant compositions (I)) of wrist-watch.

Above-mentioned 0.9 mass parts of lubricant compositions are added in 99.1 mass parts of toluene as solvent (E) and are mixed, Obtain the treatment fluid of wrist-watch lubrication.

[embodiment 1-11]

Lignocerane is replaced using dotriacontane (69~72 DEG C of fusing point), in addition to this, in the same manner as embodiment 1-10 To the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant compositions of above-mentioned wrist-watch, with Embodiment 1-10 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 1-12]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as neutral phosphite ester (B-2) 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 80 mass parts mix while heating, Obtain the lubricant compositions (lubricant compositions (I)) of wrist-watch.

[embodiment 2-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as the 4 of neutral phosphate (B-1), 4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts are added in hexane and mix, so Afterwards, hexane is evaporated, obtains the lubricant compositions (lubricant compositions (I)) of wrist-watch.

[embodiment 2-2]

Using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 5 mass parts instead of using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts, in addition to this, with embodiment 2-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubrication of above-mentioned wrist-watch Agent composition gets similarly the treatment fluid of wrist-watch lubrication with embodiment 2-1.

[embodiment 2-3]

It replaces making using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 120 mass parts With 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts, in addition to this, with implementation Example 2-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the profit of above-mentioned wrist-watch Lubricant composition gets similarly the treatment fluid of wrist-watch lubrication with embodiment 2-1.

[embodiment 2-4]

It replaces making using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 200 mass parts With 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts, in addition to this, with implementation Example 2-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the profit of above-mentioned wrist-watch Lubricant composition gets similarly the treatment fluid of wrist-watch lubrication with embodiment 2-1.

[embodiment 2-5]

It replaces making using 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 40 mass parts With 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts, in addition to this, with implementation Example 2-1 gets similarly the lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the profit of above-mentioned wrist-watch Lubricant composition gets similarly the treatment fluid of wrist-watch lubrication with embodiment 2-1.

[embodiment 2-6]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 2-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 2-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 2-7]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 2-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 2-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 2-8]

Will as lignocerane (50~53 DEG C of fusing point) 100 mass parts of sturated aliphatic hydrocarbon (A-2), as neutral phosphoric acid 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 80 mass parts of ester (B-1) are added to toluene In and mix, then, evaporate toluene, obtain the lubricant compositions (lubricant compositions (I)) of wrist-watch.

[embodiment 2-9]

Lignocerane is replaced in addition to this to get similarly with embodiment 2-8 using dotriacontane (69~72 DEG C of fusing point) The lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant compositions of above-mentioned wrist-watch, with reality Apply the treatment fluid that a 2-8 gets similarly wrist-watch lubrication.

[embodiment 3-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as neutral phosphite ester (B-2) 80 mass parts of trioleyl phosphite are added in hexane and mix, and then, evaporate hexane, obtain the lubricant group of wrist-watch It closes object (lubricant compositions (I)).

[embodiment 3-2]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 3-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 3-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 3-3]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 3-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 3-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 3-4]

Will as lignocerane (50~53 DEG C of fusing point) 100 mass parts of sturated aliphatic hydrocarbon (A-2), as neutral phosphorous 80 mass parts of trioleyl phosphite of acid esters (B-2) are added in toluene and mix, and then, evaporate toluene, obtain wrist-watch Lubricant compositions (lubricant compositions (I)).

[embodiment 3-5]

Lignocerane is replaced in addition to this to get similarly with embodiment 3-4 using dotriacontane (69~72 DEG C of fusing point) The lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant compositions of above-mentioned wrist-watch, with reality Apply the treatment fluid that a 3-4 gets similarly wrist-watch lubrication.

[embodiment 4-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 100 mass parts of paraffin (A-1), as the phosphorus of neutral phosphate (B-1) Sour 80 mass parts of front three phenyl ester are added in hexane and mix, and then, evaporate hexane, obtain the lubricant compositions of wrist-watch (lubricant compositions (I)).

[embodiment 4-2]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 4-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 4-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 4-3]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly hand with embodiment 4-1 The lubricant compositions (lubricant compositions (I)) of table.In addition, using the lubricant compositions of above-mentioned wrist-watch, with implementation Example 4-1 gets similarly the treatment fluid of wrist-watch lubrication.

[embodiment 4-4]

Will as lignocerane (50~53 DEG C of fusing point) 100 mass parts of sturated aliphatic hydrocarbon (A-2), as neutral phosphoric acid The tricresyl phosphate of 80 mass parts of ester (B-1) is added in toluene and mixes, and then, evaporates toluene, obtains wrist-watch use Lubricant compositions (lubricant compositions (I)).

[embodiment 4-5]

Lignocerane is replaced in addition to this to get similarly with embodiment 4-4 using dotriacontane (69~72 DEG C of fusing point) The lubricant compositions (lubricant compositions (I)) of wrist-watch.In addition, using the lubricant compositions of above-mentioned wrist-watch, with reality Apply the treatment fluid that a 4-4 gets similarly wrist-watch lubrication.

[comparative example]

As comparative example, prepare the lubricant oil composite (trade name: 9415, MOEBIUS corporations) of wrist-watch.

[evaluation method and result]

In escapement 1 shown in Fig. 1, the profit of the wrist-watch obtained in pawl 3a, 3b coating Examples 1-1 of escapement lever 3 Sliding treatment fluid evaporates solvent (E).There is the mechanical type watch of escapement 1 using component production, make above-mentioned machinery Formula wrist-watch works 2 months and 3 months.For obtained in embodiment 1-2~1-11,2-1~2-9,3-1~3-5,4-1~4-5 The treatment fluid of wrist-watch lubrication similarly makes mechanical type watch work 2 months and 3 months.

In addition, in escapement 1 shown in Fig. 1, obtained in the coated embodiment 1-12 of pawl 3a, 3b of escapement lever 3 The lubricant compositions (lubricant compositions (I)) of wrist-watch.There is the mechanical hand of escapement 1 using component production Table makes above-mentioned mechanical type watch work 2 months and 3 months.

In addition, being carried out after refusing oil processing to pawl 3a, 3b of escapement lever 3, in escapement 1 shown in Fig. 1 in escapement lever The lubricant oil composite of the wrist-watch of 3 pawl 3a, 3b coating comparative example.There is the machinery of escapement 1 using component production Formula wrist-watch makes above-mentioned mechanical type watch work 2 months and 3 months.

For after mechanical type watch work 2 months and after work 3 months, whether investigation finds shifting to an earlier date and postponing for moment. Table 1~4 shows the evaluation result judged according to benchmark below.

A: it does not find in advance and postpones at the time of wrist-watch.

B: little delay is found at the time of wrist-watch.

C: found at the time of wrist-watch it is biggish in advance or biggish delay.

[table 1]

In the mechanical type watch of the lubricant compositions (lubricant compositions (I)) using wrist-watch obtained in embodiment In, after 2 months with 3 months after do not have to find the moment it is biggish in advance or biggish delay.Think if using embodiment Obtained in wrist-watch lubricant compositions (lubricant compositions (I)), then it is dynamic to be able to suppress oil stream, therefore, resistance to sliding Do not change, do not find the moment it is biggish in advance or biggish delay.

On the other hand, in the mechanical type watch of the lubricant oil composite of the wrist-watch using comparative example, after 2 months and After 3 months, the moment substantially shifts to an earlier date.Think the lubricant oil composite if the wrist-watch using comparative example, oil stream occurs and moves, because This, resistance to sliding is reduced, and is finding biggish shift to an earlier date constantly.

The treatment fluid of wrist-watch lubrication obtained in pawl 3a, 3b coating Examples 1-1 of escapement lever 3 shown in Fig. 1, makes Solvent (E) evaporation.In addition, making solvent after escape wheel 2 is dipped in the treatment fluid of wrist-watch lubrication obtained in embodiment 1-1 (E) it evaporates.There is the mechanical type watch of escapement 1 using the production of these components, make its work 2 months and 3 months.For this After mechanical type watch work 2 months and after work 3 months, whether investigation finds shifting to an earlier date and postponing for moment.With only in escapement lever 3 Pawl 3a, 3b coating wrist-watch lubrication treatment fluid the case where obtain identical evaluation result and (after 2 months and be after 3 months "A").For the treatment fluid of wrist-watch lubrication obtained in embodiment 1-2~1-11,2-1~2-9,3-1~3-5,4-1~4-5 Similarly.That is, with only identical comment is respectively obtained in the case where treatment fluid of pawl 3a, 3b coating wrist-watch lubrication of escapement lever 3 Valence result.

[embodiment 5-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts of paraffin (A-1), as the second of mobility regulator (F) Alkene-alpha olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight average molecular weight (Mw) 7000) 15 Mass parts, 4,4 '-butylidenebis (the 3- methyl-6-tert butyl phenyl double tridecyl phosphorous as neutral phosphite ester (B-2) Acid esters) 70 mass parts mix while heating.After mixture is returned to room temperature, further it is kneaded, obtains lubricant combination Object (II).

[embodiment 5-2]

Using 130 °F of 27 mass parts of paraffin and 3 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 5-1 Get similarly lubricant compositions (II).

[embodiment 5-3]

Using 130 °F of 21 mass parts of paraffin and 9 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 5-1 Get similarly lubricant compositions (II).

[embodiment 5-4]

Using 130 °F of 9 mass parts of paraffin and 21 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 5-1 Get similarly lubricant compositions (II).

[embodiment 5-5]

Using 130 °F of 3 mass parts of paraffin and 27 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 5-1 Get similarly lubricant compositions (II).

[embodiment 5-6]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 5-1 Lubricant composition (II).

[embodiment 5-7]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 5-1 Lubricant composition (II).

[embodiment 5-8]

130 °F of paraffin are replaced using lignocerane (50~53 DEG C of fusing point), in addition to this, in the same manner as embodiment 5-1 To lubricant compositions (II).

[embodiment 5-9]

Lignocerane is replaced in addition to this to get similarly with embodiment 5-1 using dotriacontane (69~72 DEG C of fusing point) Lubricant compositions (II).

[embodiment 5-10]

Use ethene-alpha-olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANTHC600, Weight-average molecular Measure (Mw) 4700) replacing ethene-alpha-olefin copolymer, (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight are equal Molecular weight (Mw) 7000), in addition to this, lubricant compositions (II) is got similarly with embodiment 5-1.

[embodiment 6-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts of paraffin (A-1), as the second of mobility regulator (F) Alkene-alpha olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight average molecular weight (Mw) 7000) 15 Mass parts, 4,4 '-butylidenebis (the 3- methyl-6-tert butyl phenyl double tridecyl phosphoric acid as neutral phosphate (B-1) Ester) 70 mass parts mix while heating.After mixture is returned to room temperature, further it is kneaded, obtains lubricant compositions (II)。

[embodiment 6-2]

Using 130 °F of 27 mass parts of paraffin and 3 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 6-1 Get similarly lubricant compositions (II).

[embodiment 6-3]

Using 130 °F of 21 mass parts of paraffin and 9 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 6-1 Get similarly lubricant compositions (II).

[embodiment 6-4]

Using 130 °F of 9 mass parts of paraffin and 21 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 6-1 Get similarly lubricant compositions (II).

[embodiment 6-5]

Using 130 °F of 3 mass parts of paraffin and 27 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 6-1 Get similarly lubricant compositions (II).

[embodiment 6-6]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 6-1 Lubricant composition (II).

[embodiment 6-7]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 6-1 Lubricant composition (II).

[embodiment 6-8]

130 °F of paraffin are replaced using lignocerane (50~53 DEG C of fusing point), in addition to this, in the same manner as embodiment 6-1 To lubricant compositions (II).

[embodiment 6-9]

Lignocerane is replaced in addition to this to get similarly with embodiment 6-1 using dotriacontane (69~72 DEG C of fusing point) Lubricant compositions (II).

[embodiment 6-10]

Use ethene-alpha-olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANTHC600, Weight-average molecular Measure (Mw) 4700) replacing ethene-alpha-olefin copolymer, (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight are equal Molecular weight (Mw) 7000), in addition to this, lubricant compositions (II) is got similarly with embodiment 6-1.

[embodiment 7-1]

It will 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts as paraffin (A-1), gathering as mobility regulator (F) Isobutene (JXTG Energy KK system, trade name: Tetrax Grade3T, number-average molecular weight (Mn) 49000) 15 mass parts, 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphite ester) 70 as neutral phosphite ester (B-2) Mass parts mix while heating.After mixture is returned to room temperature, further it is kneaded, obtains lubricant compositions (II).

[embodiment 7-2]

Using 130 °F of 27 mass parts of paraffin and 3 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 7-1 Get similarly lubricant compositions (II).

[embodiment 7-3]

Using 130 °F of 21 mass parts of paraffin and 9 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 7-1 Get similarly lubricant compositions (II).

[embodiment 7-4]

Using 130 °F of 9 mass parts of paraffin and 21 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 7-1 Get similarly lubricant compositions (II).

[embodiment 7-5]

Using 130 °F of 3 mass parts of paraffin and 27 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 7-1 Get similarly lubricant compositions (II).

[embodiment 7-6]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 7-1 Lubricant composition (II).

[embodiment 7-7]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 7-1 Lubricant composition (II).

[embodiment 7-8]

130 °F of paraffin are replaced using lignocerane (50~53 DEG C of fusing point), in addition to this, in the same manner as embodiment 7-1 To lubricant compositions (II).

[embodiment 7-9]

Lignocerane is replaced in addition to this to get similarly with embodiment 7-1 using dotriacontane (69~72 DEG C of fusing point) Lubricant compositions (II).

[embodiment 7-10]

Use polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 4T, number-average molecular weight (Mn) 59000) polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, number-average molecular weight (Mn) are replaced 49000) it, in addition to this, is got similarly with embodiment 7-1 lubricant compositions (II).

[embodiment 7-11]

Use polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 5T, number-average molecular weight (Mn) 69000) polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, number-average molecular weight (Mn) are replaced 49000) it, in addition to this, is got similarly with embodiment 7-1 lubricant compositions (II).

[embodiment 7-12]

Use polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 6T, number-average molecular weight (Mn) 80000) polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, number-average molecular weight (Mn) are replaced 49000) it, in addition to this, is got similarly with embodiment 7-1 lubricant compositions (II).

[embodiment 8-1]

It will 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts as paraffin (A-1), gathering as mobility regulator (F) Isobutene (JXTG Energy KK system, trade name: Tetrax Grade3T, number-average molecular weight (Mn) 49000) 15 mass parts, 4,4 '-butylidenebis (3- methyl-6-tert butyl phenyl double tridecyl phosphate) 70 mass as neutral phosphate (B-1) Part mixes while heating.After mixture is returned to room temperature, further it is kneaded, obtains lubricant compositions (II).

[embodiment 8-2]

Using 130 °F of 27 mass parts of paraffin and 3 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 8-1 Get similarly lubricant compositions (II).

[embodiment 8-3]

Using 130 °F of 21 mass parts of paraffin and 9 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 8-1 Get similarly lubricant compositions (II).

[embodiment 8-4]

Using 130 °F of 9 mass parts of paraffin and 21 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 8-1 Get similarly lubricant compositions (II).

[embodiment 8-5]

Using 130 °F of 3 mass parts of paraffin and 27 mass parts of ethene-alpha-olefin copolymer, in addition to this, with embodiment 8-1 Get similarly lubricant compositions (II).

[embodiment 8-6]

130 °F of paraffin are replaced using 120 °F of paraffin (50 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 8-1 Lubricant composition (II).

[embodiment 8-7]

130 °F of paraffin are replaced using 150 °F of paraffin (66 DEG C of fusing point), in addition to this, gets similarly profit with embodiment 8-1 Lubricant composition (II).

[embodiment 8-8]

130 °F of paraffin are replaced using lignocerane (50~53 DEG C of fusing point), in addition to this, in the same manner as embodiment 8-1 To lubricant compositions (II).

[embodiment 8-9]

Lignocerane is replaced in addition to this to get similarly with embodiment 8-1 using dotriacontane (69~72 DEG C of fusing point) Lubricant compositions (II).

[embodiment 8-10]

Using polyisobutene polyisobutene, (JXTG Energy KK system, trade name: Tetrax Grade4T, number are divided equally Son amount (Mn) 59000) replace polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, the equal molecule of number Measure (Mn) 49000), in addition to this, lubricant compositions (II) is got similarly with embodiment 8-1.

[embodiment 8-11]

Use polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 5T, number-average molecular weight (Mn) 69000) polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, number-average molecular weight (Mn) are replaced 49000) it, in addition to this, is got similarly with embodiment 8-1 lubricant compositions (II).

[embodiment 8-12]

Use polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 6T, number-average molecular weight (Mn) 80000) polyisobutene (JXTG Energy KK system, trade name: Tetrax Grade 3T, number-average molecular weight (Mn) are replaced 49000) it, in addition to this, is got similarly with embodiment 8-1 lubricant compositions (II).

[embodiment 9-1]

Will as 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts of paraffin (A-1), as the second of mobility regulator (F) Alkene-alpha olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight average molecular weight (Mw) 7000) 15 Mass parts mix while heating as 70 mass parts of trioleyl phosphite of neutral phosphite ester (B-2).By mixture Back to after room temperature, further it is kneaded, obtains lubricant compositions (II).

[embodiment 9-2]

Will as 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts of paraffin (A-1), as the second of mobility regulator (F) Alkene-alpha olefin copolymer (Mitsui Chemicals, Inc's system, trade name: LUCANT HC2000, weight average molecular weight (Mw) 7000) 15 Mass parts mix while heating as 70 mass parts of tricresyl phosphate of neutral phosphate (B-1).Mixture is returned To after room temperature, further it is kneaded, obtains lubricant compositions (II).

[embodiment 10-1]

It will 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts as paraffin (A-1), gathering as mobility regulator (F) Isobutene (JXTG Energy KK system, trade name: Tetrax Grade3T, number-average molecular weight (Mn) 49000) 15 mass parts, 70 mass parts of trioleyl phosphite as neutral phosphite ester (B-2) mix while heating.Mixture is returned to After room temperature, further it is kneaded, obtains lubricant compositions (II).

[embodiment 10-2]

It will 130 °F of paraffin (55 DEG C of fusing point) 15 mass parts as paraffin (A-1), gathering as mobility regulator (F) Isobutene (JXTG Energy KK system, trade name: Tetrax Grade3T, number-average molecular weight (Mn) 49000) 15 mass parts, 70 mass parts of tricresyl phosphate as neutral phosphate (B-1) mix while heating.Mixture is returned into room temperature Afterwards, it is further kneaded, obtains lubricant compositions (II).

[evaluation method and result]

The fastener of watch buckle shown in Fig. 2 is handled using the lubricant compositions (II) of preparation.It should be noted that place The fastener of watch buckle before reason is manufactured state, and fastener does not function.It is removed that is, can not buckle.Specifically, Utilize toilet's cotton swab lubricant compositions (II) obtained in the coated embodiment 5-1 of pin 46.Then, it is repeated a number of times The locking operation of fastener and its release operation apply pressure to pin 46, adhere to 46 surface of pin and engagement pawl 44 above-mentioned Composition.Then, the above-mentioned composition of extra attachment is wiped.In this way, being handled the surface of engagement pawl 44 and pin 46.It is logical The processing is crossed, fastener is functioned.For embodiment 5-2~5-10,6-1~6-10,7-1~7-12,8-1~8-12, Lubricant compositions obtained in 9-1~9-2 and 10-1~10-2 (II), the similarly surface to engagement pawl 44 and pin 46 It is handled.

Through this process, function fastener.It should be noted that after the treatment, not produced in fastener Raw dirt.

For being attached with the watch buckle of above-mentioned composition, the locking operation and its release operation of 1000 fasteners is repeated (locking/release operation repetition test).The lubricity of fastener after investigating locking/release operation repetition test, i.e. locking/solution Except can operation successfully carry out.In addition, whether investigation is in fastener generation dirt.It evaluates and ties according to evaluation criteria below Fruit.Show the results of the evaluation table 5~9.

Lubricity A: locking/release operation can be carried out successfully

B: locking/release operation slightly becomes tightly, carries out with can not be successfully

The generation A of dirt: dirt is not generated

B: dirt is generated

[table 2]

[table 3]

[table 9]

Symbol description

1 escapement

2 escape wheels

3 escapement levers

3a, 3b pawl

4 balance springs

5 balance wheels

10 watch buckle structures

The watchband component of 12 another party

24 watch buckle main bodys

The watchband component of 26 1 sides

44 engagement pawl

46 pins

80 hook portions

98 locking pins

Claims

1. a kind of lubricant compositions of wrist-watch, which is characterized in that be that the wrist-watch comprising lubricant (A) and anti-wear agent (B) is used Lubricant compositions,

The lubricant (A) includes paraffin (A-1), or fusing point is 45 DEG C or more and carbon atom number is 23~38 comprising being selected from It is at least one kind of in sturated aliphatic hydrocarbon (A-2),

The anti-wear agent (B) includes at least one kind of in neutral phosphate and neutral phosphite ester.

2. the lubricant compositions of wrist-watch according to claim 1, which is characterized in that the anti-wear agent (B) includes choosing From in the neutral phosphite ester (B-2) that the following general formula (b-1) neutral phosphate (B-1) indicated and the following general formula (b-2) indicate It is at least one kind of,

In formula (b-1), R^b11~R^b14Each independently represent the aliphatic alkyl of carbon atom number 10~16, R^b15~R^b18Respectively solely On the spot indicate the alkyl of the straight or branched of carbon atom number 1~6, R^b191And R^b192Each independently represent hydrogen atom or carbon The alkyl of the straight or branched of atomicity 1~5, R^b191And R^b192Carbon atom number add up to 1~5,

In formula (b-2), R^b21~R^b24Each independently represent the aliphatic alkyl of carbon atom number 10~16, R^b25~R^b28Respectively solely On the spot indicate the alkyl of the straight or branched of carbon atom number 1~6, R^b291And R^b292Each independently represent hydrogen atom or carbon The alkyl of the straight or branched of atomicity 1~5, R^b291And R^b292Carbon atom number add up to 1~5.

3. the lubricant compositions of wrist-watch according to claim 1 or 2, which is characterized in that further include anti-oxidant Agent (C),

The antioxidant (C) includes the diphenylamine derivatives (C-1) and the following general formula (c- indicated selected from the following general formula (c-1) It is 2) at least one kind of in the hindered amine compound (C-2) indicated,

In formula (c-1), R^c11And R^c12The alkyl of the straight or branched of carbon atom number 1~10 is each independently represented, p and q are each From the integer for independently indicating 0~5, wherein p and q do not indicate 0 simultaneously,

In formula (c-2), R^c11And R^c12Each independently represent the aliphatic alkyl of carbon atom number 1~10, R^c23Indicate carbon atom number The aliphatic alkyl of 1~10 divalent.

4. the lubricant compositions of wrist-watch described in any one of claim 1 to 3, which is characterized in that further packet Containing matal deactivator (D).

5. the lubricant compositions of wrist-watch according to any one of claims 1 to 4, which is characterized in that the paraffin (A-1) fusing point is 45 DEG C~80 DEG C.

6. the lubricant compositions of wrist-watch according to any one of claims 1 to 5, which is characterized in that the fat Race's saturated hydrocarbons (A-2) is tricosane, lignocerane, pentacosane, hexacosane, heptacosane, octacosane, 29 Alkane, melissane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane or three Octadecane.

7. a kind for the treatment of fluid of wrist-watch lubrication, which is characterized in that be comprising lubricant (A), anti-wear agent (B) and solvent (E) Wrist-watch lubrication treatment fluid,

8. the treatment fluid of wrist-watch lubrication according to claim 7, which is characterized in that the anti-wear agent (B) includes to be selected from In the neutral phosphite ester (B-2) that the neutral phosphate (B-1) and the following general formula (b-2) that the following general formula (b-1) indicates indicate It is at least one kind of,

9. a kind of wrist-watch, which is characterized in that be attached with the lubricant combination of wrist-watch according to any one of claims 1 to 6 Object.

10. the lubricant compositions of wrist-watch described according to claim 1~any one of 6, which is characterized in that relative to institute 100 mass parts of lubricant (A) are stated, include the anti-wear agent (B) with 1 mass parts~200 mass parts amount.

11. the lubricant compositions of wrist-watch described according to claim 1~any one of 6, which is characterized in that further packet Regulator containing mobility (F),

The lubricant (A), the anti-wear agent (B) and the total of the mobility regulator (F) are being set as 100 mass parts When, it include the lubricant (A) and the mobility regulator (F) with 10 mass parts~80 mass parts total amount, with 20 matter Measuring part~90 mass parts amount includes the anti-wear agent (B).

12. the lubricant compositions of wrist-watch according to claim 11, which is characterized in that the mobility regulator It (F) is polyacrylate, polymethacrylates, polyisobutene, alkyl styrenes, polyester or alpha olefin copolymer.