CN1280381C - Oil-keeping treating agent, oil-keeping treating method and treated colck and watch by the same method - Google Patents
Oil-keeping treating agent, oil-keeping treating method and treated colck and watch by the same method Download PDFInfo
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- CN1280381C CN1280381C CN 03154094 CN03154094A CN1280381C CN 1280381 C CN1280381 C CN 1280381C CN 03154094 CN03154094 CN 03154094 CN 03154094 A CN03154094 A CN 03154094A CN 1280381 C CN1280381 C CN 1280381C
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Abstract
To provide an oil retaining agent excellent in oil retaining performance in precision apparatus such as a watch, used in both metal parts and plastic parts, and to provide a watch using the same. The oil retaining agent comprises at least a kind of organic fluoro compound ''a'' selected from fluoro compounds containing at least an atom selected from phosphorus, nitrogen and sulfur and a hydrocarbon group having a part or whole of the hydrogen are substituted with F in the molecule, in a solvent.
Description
Technical field
The present invention relates to be used for guarantor's oil-treatment agent of precision meter such as clock and watch, that is, prevent the treatment agent of watch oil diffusion and use the clock and watch of this guarantor's oil-treatment agent.The base plate, wheel sheet and the gear that more specifically relate to clock and watch are protected guarantor's oil-treatment agent that oil treatment is used.
Technical background
Clock and watch include clockwork driven mechanical clock and the power-actuated electronic watch of battery are housed.No matter be mechanical clock or electronic watch, all have from the drive disk assembly of drive source transfer function power.Drive disk assembly is made of gear and wheel sheet etc.
In mechanical clock, since the bigger motivating force that part is continued, the metal part of therefore main use.And in electronic watch,,, bring into use plastics (engineering plastics etc.) part because of the bigger motivating force that part is not continued though also be to use metal part at present.
Usually, from using on the character, wish all that generally clock and watch can long term operation.For this reason, add clock and watch lubricating oil at rotatable parts, prevent the deterioration that frictional wear causes, the inhibition rotatable parts are deterioration with the increase of duration of service.
But, even add clock and watch lubricating oil, but, constantly vibrated because wrist-watch is worn on the wrist at rotatable parts, therefore exist clock and watch with lubricating oil easily from the effusive problem of rotatable parts.If lubricating oil flows out problem will take place, promptly can not prevent frictional wear, along with the increase of duration of service, the phenomenon that clock and watch stop walking finally takes place in the rotatable parts deterioration like this.
Therefore, with the increase deterioration of duration of service, must protect oil treatment, diffuse out from rotatable parts with lubricating oil to prevent clock and watch to the position of apply oil for preventing rotatable parts.
Usually, as preventing the method for lubricating oil from the position diffusion of apply oil, the known grease proofing treatment process that the use oil-proofing agent is arranged.Processing such as the useful fluorine based compound of this grease proofing treatment process have added the surface in addition, position (position that will keep lubricating oil) of lubricating oil, make this surface have grease proofness, thereby prevent the method (the Japanese Patent spy opens the 2001-288452 communique) of the diffusion (outflow) of lubricating oil.
But in this class precision meter of clock and watch, because each part is little, above-mentioned anti-oil treatment is difficult to carry out.Therefore, existing clock and watch with protect the oil treatment method be fluorine with high density be tensio-active agent (for example, 3M corporate system Off ロ ラ-De 722) is dissolved in a large amount of lower boiling fluorine series solvents, guarantor's oil-treatment agent of modulation lower concentration, the part that will have metal system or plastic rotatable parts again is immersed in this solution, and to make fluorine be tensio-active agent attached to the surface of part to keep lubricating oil.
But, this method is that utilization is that surface and the lubricated oil surface tension that tensio-active agent is handled keeps lubricating oil through fluorine, when not considering to rotate basically the rub resistance abradability of (lubricating oil is done the time spent) and and the interaction of lubricating oil, can not obtain to protect fully the oiliness energy.Also have, existing fluorine is a tensio-active agent owing to be to use fluorine series solvent as thinner modulation treatment liquid, therefore can not be with same solution-treated plastic material and metallic substance, and must modulation treatment solution suitable, correspondence.Also have, using this fluorine is tensio-active agent when carrying out surface treatment, exists the surface can the residual problem that spot shape vestige is arranged.
And fluorine series solvent unit price height and usage quantity are big, and like this with regard to problems economically such as the price that has treatment solution increase, and the heating that removes when desolvating can produce obnoxious flavour, and fluorine is that tensio-active agent such as is difficult to decompose at the problem on the environment.
As the method for this class problem of solution, the nickel composite deposite that utilizes that has proposed not need to prevent the oil diffusion carries out the scheme of solid lubrication (No. the 3269090th, Japanese Patent).But adopt this method to have the color blackening and the loaded down with trivial details problem of treatment process of part.
The purpose of this invention is to provide a kind of guarantor's oil-treatment agent, it has good guarantor's oiliness energy to precision meters such as clock and watch.Another purpose provides does not use guarantor's oil-treatment agent that can both use at metal workpieces and plastics workpieces of fluorine series solvent and the clock and watch that use this guarantor's oil-treatment agent.
Summary of the invention
In order to address the above problem, the present inventor has carried out deep research, found that with comprising and have the guarantor's oil-treatment agent of fluorine based compound that shows the phosphorus atom etc. of very strong affinity with metal and plastics etc. the part of precision meters such as clock and watch is carried out surface treatment, maintenance lubricating grease that can be more stable and lubricated wet goods lubricant, thus the present invention finished.
Promptly, the feature of guarantor's oil-treatment agent of the present invention is, contain at least a kind of organofluorine compound a that is selected from the fluorine cpd class in the solvent, part or all that contains a kind of atom being selected from phosphorus, nitrogen and sulphur and the hydrogen in the alkyl in the molecule of above-mentioned fluorine cpd class replaced by fluorine and the group that forms.
Above-mentioned alkyl is that carbonatoms is 1～20 alkyl, is preferably to comprise straight chain shape or catenate aliphatic alkyl and/or aromatic ring.
Above-mentioned organofluorine compound a is preferably at least a kind of organofluorine compound of the phosphorated fluorine cpd class that arbitrary formula of being selected from following formula (1)～(3) represents,
In the formula (1), R
1, R
2And R
3Respectively independently expression contain hydrogen in the alkyl that carbonatoms is 1～12 straight chain shape or a catenate aliphatic alkyl and/or aromatic ring part or all replaced the group that forms by fluorine;
In the formula (2), R
4, R
5And R
6Respectively independently expression contain hydrogen in the alkyl that carbonatoms is 1～12 straight chain shape or a catenate aliphatic alkyl and/or aromatic ring part or all replaced the group that forms by fluorine;
In the formula (3), R
7And R
8Respectively independently expression contain hydrogen in the alkyl that carbonatoms is 1～12 straight chain shape or a catenate aliphatic alkyl and/or aromatic ring part or all replaced the group that forms, R by fluorine
9Expression ethanoyl or methoxycarbonyl methyl.
Be preferably also to comprise in guarantor's oil-treatment agent of the present invention and be selected from that part or all that contain the functional group that is selected from carbonyl, hydroxyl, ester group and ether and the hydrogen in the alkyl in the molecule replaced by fluorine and at least a kind of organofluorine compound b of the fluorine cpd class of the group that forms.
Alkyl among the above-mentioned organofluorine compound b is that carbonatoms is 1～20 alkyl, is preferably to comprise straight chain shape or catenate aliphatic alkyl and/or aromatic ring.
Above-mentioned organofluorine compound b is preferably at least a kind of organofluorine compound of the ether compound class that is selected from following formula (4) or (5) expression,
In the formula (4), R
10Expression contain hydrogen in the alkyl that carbonatoms is 3～12 straight chain shape or a catenate aliphatic alkyl and/or aromatic ring part or all replaced the group that forms, R by fluorine
11The expression carbonatoms is 1～3 alkylidene group, and n is 1～5;
In the formula (5), R
12And R
13Respectively independently expression contain hydrogen in the alkyl that carbonatoms is 3～12 straight chain shape or a catenate aliphatic alkyl and/or aromatic ring part or all replaced the group that forms, R by fluorine
14The expression carbonatoms is 1～3 alkylidene group, and n is 1～5.
The feature of clock and watch of the present invention is to use above-mentioned arbitrary guarantor's oil-treatment agent that at least 1 clock and watch part has been carried out guarantor's oil treatment.
Clock and watch best combination of the present invention is used the guarantor's oil-treatment agent through containing sulfur-bearing organofluorine compound a to carry out protecting the clock and watch part of oil treatment and contained sulphur is wear-resistant dose lubricating oil and making, and being used in combination perhaps that guarantor's oil-treatment agent through containing phosphorous organofluorine compound a carried out protecting the clock and watch part of oil treatment and contained phosphorus is wear-resistant dose lubricating oil and making.
The feature of guarantor's oil treatment method of the present invention is to keep the position of lubricating oil to implement with above-mentioned any guarantor's oil-treatment agent to need and protect oil treatment, make the surface of above-mentioned organic fluoride a attached to this position at least.
Be preferably guarantor's oil treatment method of the present invention and comprise that (I) immerses precision meter in above-mentioned guarantor's oil-treatment agent with part, make the step of this guarantor's oil-treatment agent attached to piece surface; (II) precision meter that obtains after the above-mentioned impregnation steps is carried out warm air drying to remove the step of desolvating with part.Be more preferably in the above-mentioned steps (I) dipping precision meter part when carrying out ultrasonication.
Be more preferably guarantor's oil treatment method of the present invention and after above-mentioned steps (I), carry out (III) precision meter is immersed in the solvent removing the step attached to unnecessary guarantor's oil-treatment agent of piece surface with part, and then carry out above-mentioned steps (II).Be more preferably in the above-mentioned steps (III), in above-mentioned solvent, shake the precision meter part that immerses this solvent.
Description of drawings
Fig. 1 represents the time dependent situation of contact angle.
Embodiment
＜guarantor oil-treatment agent 〉
Contain at least a kind of organofluorine compound a that is selected from the fluorine cpd class in the solvent of guarantor's oil-treatment agent of the present invention, part or all that contains the atom that is selected from phosphorus, nitrogen and sulphur and the hydrogen in the alkyl in the molecule of above-mentioned fluorine cpd class replaced by fluorine and the group that forms.
＜organofluorine compound a 〉
Organofluorine compound a used in the present invention is adsorbed on the surface of metal parts and plastic paste owing to its polar effect.Particularly the interaction of phosphorus atom, nitrogen-atoms and sulphur atom and metal is strong, optionally is adsorbed on the metallic surface.
In the above-mentioned organofluorine compound class, contain the organofluorine compound better effects if of phosphorus atom or nitrogen-atoms in the molecule, the organofluorine compound effect that contains phosphorus atom in the molecule is good especially.The organofluorine compound that contains phosphorus atom or nitrogen-atoms in the molecule can not cause the corrosion of part can keep lubricating oil more chronically.And the affinity that contains the organofluorine compound of phosphorus atom and metal in the molecule is good especially, can not only significantly improve to protect the oiliness energy, and lubricating oil is not perishable, can further strengthen the rub resistance abradability.
Also have, the alkyl among the above-mentioned organofluorine compound a is that carbonatoms is 1～20 alkyl, is preferably to comprise straight chain shape or catenate aliphatic alkyl and/or aromatic ring.In this alkyl, a straight chain shape or a catenate alkyl are desirable especially.The organofluorine compound that contains the group that derives from a straight chain shape or a catenate alkyl is easy to be dissolved in the solvent described later, and demonstrates good guarantor's oiliness energy.
The part of the hydrogen in the alkyl replaced by fluorine and in the group that forms the mol ratio (F/H) of contained fluorine and hydrogen as long as can make the guarantor's oil-treatment agent that obtains have the oiliness of guarantor can, there is no particular limitation, is preferably more than 1.If F/H obviously reduces, then lubricating oil flows out easily, protects oiliness and can reduce.
Below, specifically introduce organofluorine compound a used in the present invention.
(organofluorine compound that contains sulphur atom in the molecule)
The organofluorine compound that contains sulphur atom in the molecule used in the present invention comprise hydrogen in the alkyl of sulphones part or all replaced by fluorine and the compound that forms.
Above-mentioned sulphones for example has the sulfone class of following formula (6) expression,
R
21-SO
2-R
22(6) in the formula (6), R
21And R
22Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (6)
21And R
22The sulphones of representing amyl group or octyl group respectively individually.
Part or all of hydrogen replaced by fluorine and the compound that forms in the alkyl that organofluorine compound a used in the present invention better is above-mentioned sulphones.
Be preferably (CF specifically
2H (CFH)
3CF
2)
2SO
2, (CF
3(CF
2)
6CH
2)
2SO
2
(organofluorine compound that contains nitrogen-atoms in the molecule)
The organofluorine compound that contains nitrogen-atoms in the molecule used in the present invention comprise hydrogen in the alkyl of amine compound part or all replaced by fluorine and the compound that forms.
Above-mentioned amine compound for example has the amine of following formula (7) expression,
In the formula (7), R
23, R
24And R
25Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (7)
23, R
24And R
25The amine compound of representing ethyl, butyl, isobutyl-, hexyl, different heptyl, octyl group, tridecyl, phenyl, tolyl, 3,5-dimethylphenyl or nonyl phenyl respectively individually.
Comprise aniline, Diethyl Aniline, two (diethyl phenyl) amine, four (tridecyl)-4,4 '-isopropylidene diphenyl diamine by the amine compound beyond the amine compound of following formula (7) expression.
Part or all of hydrogen in the alkyl that organofluorine compound a used in the present invention better is above-mentioned amine compound replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
{(CF
3)
3C}
3N、
(CHF
2CF
2CHFCF
2)
3N、
(C
6F
13)
3N、
{CH
3CH
2(CF
2)
4}
3N
{(CF
3)
3C(CF
2)
2CH}
3N、
(C
6F
5)
3N、
In addition, contain the organofluorine compound of nitrogen-atoms and to have lubricating oil or wear-resistant dose of combined effect of sufficient rub resistance abradability also fine in the molecule.
(organofluorine compound that contains phosphorus atom in the molecule)
The organofluorine compound that contains phosphorus atom in the molecule used in the present invention comprise hydrogen in the alkyl of phosphoric acid ester such as acid phosphoric acid ester, acid phosphorous acid ester, neutral phosphate, neutral phosphorous acid ester or phosphonic acid ester part or all replaced by fluorine and the compound that forms.
Wherein good especially is the phosphorous organofluorine compound that is obtained by neutral phosphate, neutral phosphorous acid ester or phosphonic acid ester.The guarantor's oil-treatment agent that contains this phosphorous organofluorine compound has more secular good guarantor's oiliness energy.
Above-mentioned neutral phosphate for example has the phosphoric acid ester of following formula (8) expression,
In the formula (8), R
26, R
27And R
28Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (8)
26, R
27And R
28The neutral phosphate of representing ethyl, amyl group, octyl group, decyl, tridecyl, stearyl, phenyl, tolyl, di-tert-butyl-phenyl or nonyl phenyl respectively individually.
Comprise trishydroxymethyl phosphoric acid ester, tetraphenyl dipropylene glycol bisphosphate, tetraphenyl four (tridecyl) tetramethylolmethane four phosphoric acid ester, four (tridecyl)-4 by the neutral phosphate beyond the neutral phosphate of following formula (8) expression, 4 '-isopropylidene phenylbenzene bisphosphate, two (tridecyl) pentaerythritol diphosphate, two (nonyl phenyl) pentaerythritol diphosphate, distearyl pentaerythritol diphosphate, three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester.
Part or all of hydrogen in the alkyl that organofluorine compound a used in the present invention better is above-mentioned neutral phosphate replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
(CF
3CH
2O)
3P＝O、
{CHF
2(CF
2)
3CH
2O}
3P＝O、
(CHF
2CF
2CH
2CF
2CH
2O)
3P＝O、
{CF
3(CF
2)
2CHF(CF
2)
3CH
2O}
3P＝O、
(C
8F
17O)
3P＝O、
{CF
3(CF
2)
6CH
2CF
2CHFO}
3P＝O、
(C
18F
37O)
3P＝O、
Above-mentioned neutral phosphorous acid ester for example has the phosphoric acid ester of following formula (9) expression,
In the formula (9), R
29, R
30And R
31Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (9)
29, R
30And R
31The neutral phosphorous acid ester of representing ethyl, decyl, octyl group, tridecyl, oil base, stearyl, phenyl, tolyl, 3,5-dimethylphenyl, di-tert-butyl-phenyl or nonyl phenyl respectively individually.
Comprise trishydroxymethyl phosphorous acid ester, tetraphenyl dipropylene glycol diphosphites, tetraphenyl four (tridecyl) tetramethylolmethane four phosphorous acid esters, four (tridecyl)-4 by the neutral phosphorous acid ester beyond the neutral phosphorous acid ester of following formula (9) expression, 4 '-isopropylidene phenylbenzene diphosphites, two (tridecyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Part or all of hydrogen in the alkyl that organofluorine compound a used in the present invention better is above-mentioned neutral phosphorous acid ester replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
(CF
3CH
2O)
3P、
(C
8F
17O)
3P、
{CF
3(CF
2)
6CH
2CF
2CHFO}
3P、
(C
18F
37O)
3P、
Above-mentioned phosphonic acid ester for example has the phosphoric acid ester of following formula (10) expression,
In the formula (10), R
32And R
33Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring, R
34Expression ethanoyl or methoxycarbonyl methyl.
Wherein be preferably the R in the formula (10)
32And R
33The phosphonic acid ester of representing ethyl or phenyl respectively individually.
Part or all of hydrogen in the alkyl that organofluorine compound a used in the present invention better is above-mentioned phosphonic acid ester replaced by fluorine and the compound that forms.
Be preferably (CH specifically
3COOCH
2) P (O) (OCH
2CF
3)
2And (CH
3CO) P (O) { OCH
2CHF (CF
2)
2CF
3}
2
＜organofluorine compound b 〉
Guarantor's oil-treatment agent of the present invention preferably contains the organofluorine compound class organofluorine compound in addition of above-mentioned organofluorine compound a and above-mentioned sulfur atom-containing, nitrogen-atoms or phosphorus atom.
This organofluorine compound preferably contain the functional group that is selected from carbonyl, hydroxyl, ester group and ether and the hydrogen in the alkyl in the molecule part or all replaced by fluorine and at least a kind of organofluorine compound b in the fluorine cpd class of the group that forms.
This organofluorine compound also is the surface that is adsorbed on metal parts and plastic paste owing to its polar effect.Particularly plastic paste has functional groups such as ehter bond and ester bond mostly, and the functional group in functional group such as the ester group of above-mentioned organofluorine compound b, ether and the plastic paste interacts, and makes to protect oil-treatment agent and more stably be adsorbed on the plastic paste surface.And, contain the compound that demonstrates biological degradability in the organofluorine compound class of ester group or ether in addition in the molecule.
Alkyl among the above-mentioned organofluorine compound b is that carbonatoms is 1～20 alkyl, is preferably to comprise straight chain shape or catenate aliphatic alkyl and/or aromatic ring.In this alkyl, a straight chain shape or a catenate alkyl are desirable especially.The organofluorine compound that contains the group that derives from a straight chain shape or a catenate alkyl is easy to be dissolved in the solvent described later, and demonstrates good guarantor's oiliness energy.
The part of the hydrogen in the alkyl replaced by fluorine and in the group that forms the mol ratio (F/H) of contained fluorine and hydrogen as long as can make the guarantor's oil-treatment agent that obtains have the oiliness of guarantor can, there is no particular limitation, is preferably more than 1.If F/H obviously reduces, then lubricating oil flows out easily, protects oiliness and can reduce.
Below, specifically introduce organofluorine compound b used in the present invention.
(organofluorine compound that contains carbonyl in the molecule)
The organofluorine compound that contains carbonyl in the molecule used in the present invention comprise hydrogen in the alkyl of the hydrocarbon polymer that contains carbonyl part or all replaced by fluorine and the compound that forms.
The above-mentioned hydrocarbon polymer that contains carbonyl for example has the carbonyl compound of following formula (11) expression,
In the formula (11), R
35And R
36Representing to contain carbonatoms respectively independently is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (11)
35And R
36The carbonyl compound of representing octyl group or phenyl respectively individually.
The organofluorine compound that contains carbonyl in the molecule used in the present invention better is that part or all of hydrogen in the alkyl of above-mentioned carbonyl compound replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
(n-C
8F
17)
2C=O, and
(organofluorine compound that contains hydroxyl in the molecule)
The organofluorine compound that contains hydroxyl in the molecule used in the present invention comprise hydrogen in the alkyl of the hydrocarbon polymer that contains hydroxyl part or all replaced by fluorine and the compound that forms.
The above-mentioned hydrocarbon polymer that contains hydroxyl for example has the hydrocarbon polymer of the hydroxyl of following formula (12) expression,
R
37-(R
38)
kIn-OH (12) formula (12), R
37It is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring that expression contains carbonatoms, R
38The expression carbonatoms is 1～5 alkylidene group, and k is 1～5.
Wherein be preferably the R in the formula (12)
37Be octyl group or nonyl, R
38Hydrocarbon polymer for ethylidene or butylidene.
The organofluorine compound that contains hydroxyl in the molecule used in the present invention better is that part or all of hydrogen in the alkyl of hydrocarbon polymer of above-mentioned hydroxyl replaced by fluorine and the compound that forms.
Be preferably n-C specifically
9F
19-(CH
2)
4-OH and n-C
8F
17-(CH
2)
2-OH.
(organofluorine compound that contains ester group in the molecule)
The organofluorine compound that contains ester group in the molecule used in the present invention comprise hydrogen in the alkyl of the hydrocarbon polymer that contains ester bond part or all replaced by fluorine and the compound that forms.The above-mentioned hydrocarbon polymer that contains ester group preferably has ehter bond.This hydrocarbon polymer with ehter bond is adsorbed on metallic surface and frosting, and its degree of absorption can pass through ehter bond, the number of repeat unit of oxirane is changed control.
The above-mentioned hydrocarbon polymer that contains ester group for example has the ester cpds of following formula (13) expression,
In the formula (13), R
39It is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring that expression contains carbonatoms, R
40The expression carbonatoms is that 1～5 alkylidene group or carbonatoms are 1～5 epoxy alkyl, R
41The expression carbonatoms is 1～5 alkyl, and m is 1～5.
Wherein be preferably the R in the formula (13)
39Be octyl group or nonyl, R
40Be methylene radical, ethylidene, propylidene or butylidene, R
41Hydrocarbon polymer for methyl.
The ionic compound that contains ester group that the ester cpds hydrocarbon polymer of being represented by following formula (13) that contains ester group in addition for example has following formula (14) to represent,
In the formula (14), R
42, R
43And R
44Representing to contain carbonatoms respectively independently is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring.
Wherein be preferably the R in the formula (14)
42Be octyl group or nonyl, R
43And R
44Ionic compound for butyl.
The organofluorine compound that contains ester group in the molecule used in the present invention better is that part or all of hydrogen in the alkyl of the above-mentioned hydrocarbon polymer that contains ester group replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
n-C
9F
19-O-(CH
2)
m-OCOCH
3(m＝1～4)、
N-C
8F
17-O-(CH
2)
2-OCOCH
3, and
n-C
8F
17-COO
-+NH
2{(CH
2)
3CH
3}
2。
(organofluorine compound that contains ether in the molecule)
The organofluorine compound that contains ether in the molecule used in the present invention comprise hydrogen in the alkyl of the hydrocarbon polymer that contains ehter bond part or all replaced by fluorine and the compound that forms.Contain in this molecule in the organofluorine compound of ether and can contain hydroxyl.
This hydrocarbon polymer with ehter bond is adsorbed on metallic surface and frosting, and the degree of its absorption can be passed through ehter bond, the number of repeat unit of oxirane is changed control.
The above-mentioned hydrocarbon polymer that contains ehter bond for example has the ether compound of following formula (15) expression,
In the formula (15), R
45It is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring that expression contains carbonatoms, R
46The expression carbonatoms is 1～3 alkylidene group, and n is 1～5.
Wherein be preferably the R in the formula (15)
45Be octyl group or nonyl, R
46Ether compound for ethylidene or butylidene.
The organofluorine compound that contains ether in the molecule used in the present invention better is that part or all of hydrogen in the alkyl of the above-mentioned hydrocarbon polymer that contains ether replaced by fluorine and the compound that forms.
Be preferably n-C specifically
9F
19-O-(CH
2)
4-OH and n-C
8F
17-O-(CH
2)
2-OH.
In addition, the above-mentioned hydrocarbon polymer that contains ehter bond for example has the ether compound of following formula (16) expression,
In the formula (16), R
47And R
48Representing to contain carbonatoms respectively independently is 3～12 straight chain shape or the alkyl that props up catenate aliphatic alkyl and/or aromatic ring, R
49The expression carbonatoms is 1～3 alkylidene group, and n is 1～5.
Wherein be preferably the R in the formula (16)
47And R
48Represent octyl group or nonyl respectively individually, and R
49Ether compound for ethyl.
The organofluorine compound that contains ether in the molecule used in the present invention better is that part or all of hydrogen in the alkyl of the above-mentioned hydrocarbon polymer that contains ether replaced by fluorine and the compound that forms.
Be preferably following compound specifically:
＜solvent 〉
Among the present invention, solvent also can use the solvent of fluorine system, owing to can produce toxic gas after the fluorine series solvent heating, therefore preferably uses non-fluorine series solvent.Also have, protect the also corresponding increase of oil treatment expense, therefore preferably use more cheap non-fluorine series solvent because fluorine series solvent price height makes.
As the non-preferably fluorine series solvent of effect that uses in the present invention, preferably in molecule, contain the non-fluorine series solvent at the position that can form polar group or hydrogen bond, for example, ketone, alcohol, ester.
There is no particular limitation to the boiling point of this solvent, better is below 200 ℃.If use boiling point, then after protecting oil treatment, must not clean the assembling that just can be used for precision meters such as clock and watch behind the convection drying at the solvent below 200 ℃.In addition, owing to be at low temperatures and the short period of time drying, so preferably use low-boiling solvent.
Can be used as above-mentioned non-fluorine series solvent and comprise ketone series solvents such as acetone, butanone, hexone; Alcohol such as methyl alcohol, ethanol, IPA; Ester such as ethyl acetate, butylacetate series solvent.
Water-soluble solvent in this solvent can mix use with water.So just can protect oil treatment with lower cost.
Above-mentioned non-fluorine series solvent can use any solvent under the situation that the part of precision meters such as clock and watch is made by Derlin (POM).But, under the part situation that so low resin of solvent resistance is made by polycarbonate (PC), should use alcohol.On the other hand, the part of precision meters such as clock and watch is under the metal situation, also can use any solvent.
Therefore, guarantor's oil-treatment agent of the present invention can be used in metal system and plastic any precision instrument part.
＜guarantor oil treatment composition 〉
At least contain above-mentioned organofluorine compound a in the solvent of guarantor's oil treatment composition of the present invention.This organofluorine compound a may be used singly or in combination of two or more.The concentration of organofluorine compound a is generally 0.1～10.0 weight %, is preferably 0.1～5.0 weight %, more preferably 0.5～3.0 weight %.Mix under the situation about using at organofluorine compound a more than 2 kinds, the concentration of each organofluorine compound is preferably in the above-mentioned scope.
In addition, preferably also contain above-mentioned organofluorine compound b in guarantor's oil treatment composition of the present invention.This organofluorine compound b may be used singly or in combination of two or more.The concentration of organofluorine compound b is generally 0.1～10.0 weight %, is preferably 0.1～5.0 weight %, more preferably 0.5～3.0 weight %.Mix under the situation about using at organofluorine compound b more than 2 kinds, the concentration of each organofluorine compound is preferably in the above-mentioned scope.
＜guarantor oil treatment method 〉
Guarantor's oil treatment method of the present invention be to must keep in the surface of the part of precision meters such as clock and watch lubricating oil the position implement guarantor's oil treatment with above-mentioned guarantor's oil-treatment agent, the method that makes the surface at this position adhere to organofluorine compound a at least.
At first, precision meter part and lubricating oil are described.
＜precision meter part 〉
The part of precision meters such as clock and watch used in the present invention is metal systems or plastic.Metal system precision meter comprises the various alloys of copper system and the various alloys of iron system with the material of part, and has carried out the material that obtains after coating such as nickel, gold, rhodium are handled on the surface of above-mentioned metallic substance.
Plastics system precision meter comprises the molding that is obtained by the synthetic resins (PC/PBT) of Derlin (POM), polycarbonate (PC), polycarbonate and polybutylene terephthalate etc. and mineral filler with part.
＜lubricating oil 〉
Lubricating oil used in the present invention comprises polyalkylene glycol oil, ester oil, hydrocarbon ils (poly-a-olefin oil) etc.When precision meter is mechanical clock and the electronic watch with metal system base plate (metal quartz clock),, therefore also can use above-mentioned any lubricating oil because rotatable parts mainly are metal.
On the other hand, when precision meter is the electronic watch (plastics system quartz clock) with plastics system base plate, because rotatable parts are mainly plastic, therefore should use the lubricating oil that when being used for plastic or other material, does not have intermiscibility with it, use hydrocarbon ils (for example, the hydro carbons lubricating oil of being put down in writing among the international open WO 01/59043) effect better.
The lubricating oil that the present invention uses mixes result of use with rub resistance wearing and tearing agent, oxidation inhibitor and metal passivator etc. better.Above-mentioned rub resistance wearing and tearing agent comprises that phosphorus such as neutral phosphorous acid ester, neutral phosphate are that sulphur such as rub resistance wearing and tearing agent, zinc dithiophosphate are rub resistance wearing and tearing agent.
＜guarantor oil treatment 〉
Specifically can protect oil treatment by the following method.
At first, precision meter is immersed in guarantor's oil-treatment agent with part.At this moment, in order to implement guarantor's oil treatment equably at piece surface, preferably ultrasonication limit dipping is carried out on the limit.Can take to shake the method for part in addition.Under the complex-shaped situation of and part little, preferably carry out ultrasonication at accessory size.By ultrasonication, can make and protect each corner that oil-treatment agent is attached to part.There is no particular limitation to dipping time, was advisable with 30 seconds～5 minutes.
Take out part then, remove by warm air drying and desolvate, the warm air drying temperature can suitably be set according to the boiling point of solvent.In addition, time of drying can be regulated.
In guarantor's oil treatment method of the present invention, when containing sulphur and be the lubricating oil assembling precision meter of rub resistance wearing and tearing agent, preferably adopt the guarantor's oil-treatment agent that contains sulfur-bearing organofluorine compound a.When containing phosphorus and be the lubricating oil assembling precision meter of rub resistance wearing and tearing agent, preferably adopt the guarantor's oil-treatment agent that contains phosphorous organofluorine compound a.
The part that has carried out guarantor's oil treatment by aforesaid method can show guarantor's oiliness energy by following mechanism.
Guarantor's oil-treatment agent of the present invention comprises and has the compound that shows higher interactional atom with metal, for example phosphorous organofluorine compound.Therefore, if metal parts is protected oil treatment with guarantor's oil-treatment agent of the present invention, then to the strong phosphorous organofluorine compound of the adsorptive power of metal just optionally attached to the metallic surface.Other organofluorine compound be adsorbed on this phosphorous organofluorine compound around.Particularly protect and comprise the organofluorine compound that has polar functional group in the molecular structure in the oil-treatment agent, the organofluorine compound that for example has ehter bond, can carry out more powerful absorption, just formed the organofluorine compound film like this in the metallic surface, have lipophilicity because organofluorine compound is fluoridized the alkyl of back formation, show thus and protect the oiliness energy.
On the other hand, under the situation for plastic paste, mainly be to rely on the polarity effect of polarity that plastics have and organofluorine compound and be adsorbed in plastic paste, form the organofluorine compound film on the surface, can show equally and protect the oiliness energy.
＜antifouling processing 〉
Among the present invention, before the warm air drying in above-mentioned guarantor's oil treatment method (remove and the desolvate) operation, preferably carry out antifouling processing.Owing in having used guarantor's oil treatment process of liquid, be easy to generate stain and variable color, therefore the part of precision meters such as clock and watch etc. is paid attention to the part of visual appearance, be even more important.
Antifouling processing is to utilize solvent, preferably utilizes varsol to remove unnecessary guarantor's oil-treatment agent attached to piece surface.Because varsol is non-polar, thus can remove unnecessary guarantor's oil-treatment agent at an easy rate, but can not remove through protecting oil treatment attached to guarantor's oil-treatment agent of piece surface.
Above-mentioned hydrocarbon-based solvent be boiling point at the hydro carbons below 180 ℃, for example, effects such as n-decane, hexane, octane, nonane are better.
Concrete anti-fouling method is that the part that will obtain after protecting the oil-treatment agent dipping before solvent evaporation is immersed in the varsol, and shakes for several times.In this state, can remove attached to the unwanted molecule beyond the molecule of piece surface.Then, take out part from varsol, warm air drying is also removed with suction strainer drying and centrifuge separator in case of necessity and is desolvated dry part.
Above-mentioned warm air drying is preferably in 120～150 ℃ the hot blast carries out.Adopt the said temperature scope hot blast can 30 minutes with the interior boiling point of removing at the hydro carbons below 180 ℃.
＜clock and watch 〉
After as stated above at least 1 clock and watch part being implemented guarantor's oil treatment, obtain clock and watch of the present invention with this clock and watch part and the assembling of above-mentioned lubricating oil.Lubricating oil in these clock and watch can not flow out, and is retained in rotatable parts, shows stable serviceability.Particularly carried out protecting the clock and watch of oil treatment, and can keep the oiliness energy for a long time, showed stable serviceability with the guarantor's oil-treatment agent that contains phosphorous organofluorine compound.
Below, by embodiment the present invention is described, but the present invention is not limited to embodiment.
(raw material)
Fluorinated alkyl compound a-1:
Three (1H, 1H, the 5H-ten tetrafluoro octyl groups) phosphoric acid ester that is expressed from the next,
Fluorinated alkyl compound a-2:
Two (1H, 1H, 2H-octafluoro amyl group) the acetyl phosphonic acid ester that is expressed from the next,
Fluorinated alkyl compound a-3:
Three (1H, 1H, the 5H-octafluoro amyl group) phosphoric acid ester that is expressed from the next,
Fluorinated alkyl compound a-4:
Two (2,2, the 2-trifluoroethyl) the methoxycarbonyl methylphosphonate that is expressed from the next,
Fluorinated alkyl compound a-5:
Three (1H, 1H, 3H, 3H, the 5H-hexafluoro amyl group) phosphoric acid ester that is expressed from the next,
Fluorinated alkyl compound a-6:
Three (5H, 5H, 6H, 6H, the 6H-octafluoro hexyl) amine that is expressed from the next,
Fluorinated alkyl compound a-7:
Three (1H, the 1H-15 fluorine octyl groups) sulfone that is expressed from the next,
Fluorinated alkyl compound b-1:
The 19 fluorine nonyl-oxo-ethanol that are expressed from the next,
n-C
9F
19-O-C
2H
4-OH
Fluorinated alkyl compound b-2:
Two (the 17 fluorine octyl group-oxygen ethyl) ethers that are expressed from the next,
Fluorinated alkyl compound b-3:
The mixture of the fluorinated alkyl compound of the n=1 that is expressed from the next～3,
Fluorinated alkyl compound b-4:
The mixture of n=1 that is expressed from the next and 2 fluorinated alkyl compound.
＜embodiment 1 〉
Fluorinated alkyl compound a-1, a-2, b-1 and b-2 are blended in the Virahol with the concentration of 0.5 weight % respectively, modulate guarantor's oil-treatment agent.
To copper alloy substrate, copper alloy nickel plating substrate or plastic base (POM system) while carrying out after ultrasonication is immersed in guarantor's oil-treatment agent of gained, from protect oil-treatment agent, take out copper alloy substrate, copper alloy nickel plating substrate or plastic base, warm air drying is removed and is desolvated, and has implemented guarantor's oil treatment on the surface of copper alloy substrate, copper alloy nickel plating substrate or plastic base (POM system).
The lubricating oil (Citizen Watch Co., Ltd system AO-3) that drips on the surface of each substrate is measured and had been carried out protecting the substrate surface of oil treatment and the contact angle of lubricating oil.Then, these substrates are kept under 80 ℃ the temperature, measure contact angle over time.Copper alloy nickel plating substrate the results are shown in Figure 1.Other substrate also shows the feature identical with Fig. 1.
Guarantor's oil-treatment agent with gained is protected oil treatment to the part with rotatable parts of the system system-Block メ Application ト #20 of Citizen Watch Co., Ltd (the mainly quartz clock of being assembled by metal workpieces), #82 (mechanical clock) and #10 (the mainly quartz clock of being assembled by the plastics workpieces) respectively, and (the system AO-2 of Citizen Watch Co., Ltd) assembles clock and watch with hydro carbons lubricating oil.
After these clock and watch have been confirmed that lubricating oil has the rotatable parts of having no way of to flow out (protecting the oiliness energy), carry out its work (rotations) affirmation, the results are shown in Table 1 in order to method down.
Protect the metewand of oiliness energy:
A: unlubricated oil flows out from rotatable parts under common carrying caused by operations vibration.
B: under common carrying caused by operations vibration, have lubricating oil to flow out from rotatable parts.
(work confirmation method (accelerated test))
The clock and watch that assembled are put into 60 ℃ thermostatic bath, make the rotatable parts work of clock and watch, under the situation for mechanical clock, 8 times (walking speed of 1 second interior clock and watch of kind is 8 seconds under common speed) with common speed, under the situation for quartz clock, with 32 times of common speed (walking speed of clock and watch is 32 seconds under speed usually in 1 second kind), by the time chien shih watchmaking of setting.
Then, take out clock and watch, confirm the variable color and the wear pattern of the part of the operating accuracy of these clock and watch and rotatable parts at normal temperatures from thermostatic bath.
The metewand of serviceability:
AA: even implement the accelerated test in 10 years, operating accuracy is no change also, rotatable parts nondiscoloration and not wearing and tearing.
A: after implementing the accelerated test in 3 years, the operating accuracy no change, rotatable parts nondiscoloration and not wearing and tearing, but after carrying out the accelerated test in 5 years, wearing and tearing appear in rotatable parts.
B: after implementing the accelerated test in 3 years, the operating accuracy no change, rotatable parts nondiscoloration and not wearing and tearing, but after carrying out the accelerated test in 5 years, the rotatable parts variable color.
C: operating accuracy no change before the accelerated test, rotatable parts nondiscoloration and not wearing and tearing, but after carrying out the accelerated test in 3 years, wearing and tearing appear in rotatable parts.
＜embodiment 2 〉
Except that replace fluorinated alkyl compound a-1, a-2, b-1 and b-2 with fluorinated alkyl compound a-3, a-4, b-3 and b-4, other operation is identical with embodiment 1, and oil-treatment agent is protected in modulation, and has carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜embodiment 3 〉
Except that replace fluorinated alkyl compound a-3 with fluorinated alkyl compound a-5, other operation is identical with embodiment 2, and oil-treatment agent is protected in modulation, and has carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜embodiment 4 〉
Except that replace fluorinated alkyl compound a-3 with fluorinated alkyl compound a-6, other operation is identical with embodiment 2, and oil-treatment agent is protected in modulation, and has carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜embodiment 5 〉
Except that the mixed solvent with Virahol 75% and water 25% replaced Virahol, other operation was identical with embodiment 2, and oil-treatment agent is protected in modulation, and had carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜embodiment 6 〉
Except that the mixed solvent with ethanol 75% and water 25% replaced Virahol, other operation was identical with embodiment 2, and oil-treatment agent is protected in modulation, and had carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜embodiment 7 〉
Except that replace fluorinated alkyl compound a-3 with fluorinated alkyl compound a-7, other operation is identical with embodiment 2, and oil-treatment agent is protected in modulation, and has carried out the work affirmation of measurement of contact angle and clock and watch.The results are shown in Figure 1 and table 1.
＜comparative example 1 〉
Fluorinated alkyl compound b-1 and b-2 are dissolved in the Virahol with the concentration of 0.5 weight % respectively, and oil-treatment agent is protected in modulation.
Identical with embodiment 1, this is protected oil-treatment agent carried out measurement of contact angle, the results are shown in Figure 1.
In addition, identical with embodiment 1, assemble 3 kinds of clock and watch, and carry out the work affirmation of clock and watch.The results are shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | |
| Fluorinated alkyl compound a | a-1/a-2 | a-3/a-4 | a-5/a-4 | a-6/a-4 | a-3/a-4 | a-3/a-4 | a-7/a-4 | a-1/a-2 |
| Fluorinated alkyl compound b | b-1/b-2 | b-3/b-4 | b-3/b-4 | b-3/b-4 | b-3/b-4 | b-3/b-4 | b-3/b-4 | b-1/b-2 |
| Solvent | IPA | IPA | IPA | IPA | IPA:75% water: 25% | EtOH:75% water: 25% | IPA | IPA |
| Metal system quartz clock is protected oiliness can serviceability | A AA | A AA | A AA | A A | A AA | A AA | A B | B C |
| Mechanical clock is protected oiliness can serviceability | A AA | A AA | A AA | A A | A AA | A AA | A B | B C |
| Plastics system quartz clock is protected oiliness can serviceability | A AA | A AA | A AA | A A | A AA | A AA | A B | B C |
IPA: Virahol, EtOH: ethanol
As shown in Figure 1, existing guarantor's oil-treatment agent is along with the increase of duration of service, and contact angle reduces, and lubricating oil flows out, but the contact angle of guarantor's oil-treatment agent of the present invention do not change with the increase of duration of service, does not find lubricated oil-out.
As shown in table 1, contain guarantor's oil-treatment agent of fluorinated alkyl compound, shown good guarantor's oiliness energy, with organic solvents such as alcohol the time, also can implement to protect oil treatment.And, adopted the clock and watch of guarantor's oil-treatment agent of the present invention, compare with the clock and watch that adopt existing guarantor's oil-treatment agent, show good serviceability, wherein, adopted the clock and watch of phosphorous guarantor's oil-treatment agent to show good especially serviceability.
Guarantor's oil-treatment agent of the present invention can improve guarantor's oiliness energy of precision meters such as clock and watch.And guarantor's oil-treatment agent of the present invention can both use in plastics workpieces and metal workpieces.
After guarantor's oil-treatment agent enforcement guarantor of the present invention oil treatment, the lubricating oil of precision meter inside such as clock and watch can not flow out, and can provide to have the good guarantor's oiliness energy and the precision meters such as clock and watch of serviceability.
Have above-mentioned good guarantor's oiliness can precision meters such as clock and watch can reduce the wearing and tearing of its drive part (rotatable parts), weather resistance significantly improves.Like this, this precision meter is not maintained and can work steadily in the long term.In addition, obviously improve the work-ing life of this precision meter compared with the existing, by implementing guarantor's oil treatment of the present invention, can suppress the discharge of new waste.
Claims (8)
1, protect oil-treatment agent, it is characterized in that, contain organofluorine compound a in the non-fluorine series solvent,
Have the position that can form polar group or hydrogen bond in the molecule of described non-fluorine series solvent,
Described organofluorine compound a is that part or all of hydrogen of alkyl that be selected from the sulphones of phosphorated fluorine cpd class that arbitrary formula of following formula (1)～(3) represents, following formula (6) expression replaced by fluorine and part or all of the hydrogen of the alkyl of the amine compound of the compound that forms and following formula (7) expression replaced by fluorine and a kind of organofluorine compound in the compound that forms at least
In the formula (1), R
1, R
2And R
3Respectively independently expression contain hydrogen in the alkyl that carbonatoms is a straight chain shape of 1～12 or a catenate aliphatic alkyl part or all replaced the group that forms by fluorine;
In the formula (2), R
4, R
5And R
6Respectively independently expression contain hydrogen in the alkyl that carbonatoms is a straight chain shape of 1～12 or a catenate aliphatic alkyl part or all replaced the group that forms by fluorine;
In the formula (3), R
7And R
8Respectively independently expression contain hydrogen in the alkyl that carbonatoms is a straight chain shape of 1～12 or a catenate aliphatic alkyl part or all replaced the group that forms, R by fluorine
9Expression ethanoyl or methoxycarbonyl methyl;
R
21-SO
2-R
22 (6)
In the formula (6), R
21And R
22Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up the catenate aliphatic alkyl;
In the formula (7), R
23, R
24And R
25Representing to contain carbonatoms respectively independently is 1～12 straight chain shape or the alkyl that props up the catenate aliphatic alkyl.
2, guarantor's oil-treatment agent as claimed in claim 1, its feature also are, also comprise at least a kind of organofluorine compound b of the ether compound class that is selected from following formula (4) or (5) expression,
In the formula (4), R
10Expression contain hydrogen in the alkyl that carbonatoms is a straight chain shape of 3～12 or a catenate aliphatic alkyl part or all replaced the group that forms, R by fluorine
11The expression carbonatoms is 1～3 alkylidene group, and n is 1～5;
In the formula (5), R
12And R
13Respectively independently expression contain hydrogen in the alkyl that carbonatoms is a straight chain shape of 3～12 or a catenate aliphatic alkyl part or all replaced the group that forms, R by fluorine
14The expression atomicity is 1～3 alkylidene group, and n is 1～5.
3. guarantor's oil-treatment agent as claimed in claim 2 is characterized in that, described non-fluorine series solvent is selected from ketone, alcohol, ester.
4, protect the oil treatment method, it is characterized in that, keep the position of lubricating oil to implement with each described guarantor's oil-treatment agent in the claim 1～3 to need and protect oil treatment, make the surface of above-mentioned organic fluoride a attached to this position.
5, guarantor's oil treatment method as claimed in claim 4, its feature also are, comprise that (I) immerses precision meter in above-mentioned guarantor's oil-treatment agent with part, make the step of this guarantor's oil-treatment agent attached to piece surface; (II) precision meter that obtains after the above-mentioned impregnation steps is carried out warm air drying to remove the step of desolvating with part.
6, guarantor's oil treatment method as claimed in claim 5, its feature also are, in the above-mentioned steps (I), flood the precision meter part when carrying out ultrasonication.
7, as claim 5 or 6 described guarantor's oil treatment methods, its feature also is, after above-mentioned steps (I), carry out (III) precision meter is immersed in the solvent removing the step attached to unnecessary guarantor's oil-treatment agent of piece surface with part, and then carry out above-mentioned steps (II).
8, guarantor's oil treatment method as claimed in claim 7, its feature also are, in the above-mentioned steps (III), shake the precision meter part that immerses in the above-mentioned solvent in above-mentioned solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002237402 | 2002-08-16 | ||
| JP2002237402 | 2002-08-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1487051A CN1487051A (en) | 2004-04-07 |
| CN1280381C true CN1280381C (en) | 2006-10-18 |
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ID=34179471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03154094 Expired - Fee Related CN1280381C (en) | 2002-08-16 | 2003-08-15 | Oil-keeping treating agent, oil-keeping treating method and treated colck and watch by the same method |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1280381C (en) |
| HK (1) | HK1063480A1 (en) |
| MY (1) | MY135885A (en) |
| SG (1) | SG121787A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264881B (en) * | 2008-12-26 | 2014-05-21 | 西铁城电子株式会社 | Lubrication kit and small electronic device utilizing the lubrication kit |
| JP7026538B2 (en) * | 2018-03-09 | 2022-02-28 | セイコーインスツル株式会社 | Watch parts, movements and watches |
-
2003
- 2003-08-14 SG SG200304576A patent/SG121787A1/en unknown
- 2003-08-15 CN CN 03154094 patent/CN1280381C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1487051A (en) | 2004-04-07 |
| SG121787A1 (en) | 2006-05-26 |
| MY135885A (en) | 2008-07-31 |
| HK1063480A1 (en) | 2004-12-31 |
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