CN101273117A - Waterproof grease and hermetically filled with the grease, rolling bearing and hub bearing - Google Patents
Waterproof grease and hermetically filled with the grease, rolling bearing and hub bearing Download PDFInfo
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- CN101273117A CN101273117A CNA2006800358354A CN200680035835A CN101273117A CN 101273117 A CN101273117 A CN 101273117A CN A2006800358354 A CNA2006800358354 A CN A2006800358354A CN 200680035835 A CN200680035835 A CN 200680035835A CN 101273117 A CN101273117 A CN 101273117A
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Abstract
A waterproof grease that even under harsh lubrication conditions such as those causing water mixing in grease at the time of bearing operation, improves the resistance to surface starting peeling of bearing of, for example, carbon steel for mechanical structure; and making use of the grease and exhibiting prolonged life, a rolling bearing and hub bearing. There is provided a waterproof grease comprising a nonaqueous base oil, a thickening agent and, as an additive, a water dispersant, wherein the saturated water content dispersible in the waterproof grease is in the range of 30 to 60 wt.%, and wherein the water dispersant capable of dispersing water in the waterproof grease is a surfactant, and wherein the nonaqueous base oil is a mineral oil and the thickening agent is a urea compound. Further, there are provided, hermetically filled with the grease, a rolling bearing and hub bearing.
Description
Technical field
The present invention relates to sneak into the hydraulic grease of enclosing in the bearing that uses under the dangerous environment, the rolling bearing of having enclosed this lubricating grease and hub bearing (hub bearing) having water.
Background technology
Can be as the typical example of the bearing that under water submerged environment, uses and the wheel bearing (hub bearing) of the automobile of enumerating, to the eighties in 20th century, in order to improve assembleability, the automaker begins to adopt integrated double-row angular contact bal bearing that forms of the foreign steamer that makes back side split bearing or double-row conical bearing.It is known as first-generation hub bearing.By foreign steamer is integrated, set initial stage end play for appropriate value during the bearing assembling, do not need the precompressed adjustment when therefore on automobile, assembling.In addition, the foreign steamer of also having developed the first-generation is provided with the double-row bearing that is called s-generation hub bearing of flange portion.This is only to adopt standard rolling bearing having the limit aspect lightweight and the size reduction, by carrying out blocking and realized minimizing components number and light-weighted result with axle (wheel hub wheel), coupling band (steering knuckle) as the circumferential component of bearing.By will becoming bolted by being pressed into, assemble on the car body and also become easy to the fixing of steering knuckle.In addition, third generation hub bearing is integrated with the interior wheel of axle (wheel hub wheel) and bearing, further improves the assembling of production line when reducing burr.Also developed recently with hub bearing and constant speed ratio coupling incorporate the 4th generation the wheel hub shaft coupling.
In recent years automobile hub bearing is considered assembly operation, lightweight, miniaturization to car body, and the employing of the hub bearing of the s-generation and the third generation is recently increasing.
If be conceived to the bearing material, when the first-generation in foreign steamer all adopt bearing steel (for example SUJ2), and be provided with the s-generation of flange, the hub bearing of the third generation for foreign steamer, use and forge the good and inexpensive physical construction carbon steels such as S53C of property.Physical construction is handled by orbit portion is implemented high frequency heat with carbon steel, has guaranteed the rolling contact fatigue intensity of bearing portion.But because alloying constituent is few, so a little less than the surface strength, the patience that surperficial starting point is peeled off is than bearing steel difference.Therefore, under the lubricating system identical with the first-generation, the occasion abominable in working conditions had poor durability.
From its purposes, hub bearing is not only in the travelling of fine day, and also uses under the condition of the non-constants of environment for use such as travelling of rainy day, difference road, seashore.Suppress also not thorough in water and the foreign matter intrusion bearing by sealing.Therefore, water and foreign matter are invaded in the bearing just inevitable.In addition, from energy-conservation viewpoint, also require the low moment of torsionization of hub bearing.As one of its method, consider the light contactization of sealing.Therefore, the possibility of water intrusion further improves, the lubricating status variation in the bearing.This problem is common in each generation, and for the s-generation, the third generation and the hub bearing in four generation of bearing materials utilization structure with steel, the danger that the then surperficial starting point type of lubricating status difference is peeled off generation is bigger.
Improvement for hydraulic grease, known to adopting the low viscosity base oil to reduce torque (with reference to patent documentation 1), give electroconductibility removing static (with reference to patent documentation 2), but the research that is used for keeping bearing property when water is blended into lubricating grease is not carried out as yet.
If sneaking in the bearing, water produces following problem.When water droplet immersed load area, oil film disconnects midway, and was unfavorable aspect oilness; Produce metallic contact owing to oil film disconnects midway, exist to produce the danger that abrasion, surperficial starting point type are peeled off (peel off, set-off etc.), peeled off in early days.What is called is peeled off in early days, be meant peeling off of changing with the white tissue of near surface, on the rotating direction of rolling body and the direction opposite with it peeling off near surface be full of cracks development.In addition, because the existence of the water in the bearing, at the inner rust that produces of bearing.
Patent documentation 1: the spy opens the 2003-239999 communique
Patent documentation 2: the spy opens the 2004-169862 communique
Summary of the invention
The problem that invention will solve
The present invention is the research of finishing in order to address the above problem, even its purpose is to provide when bearing operation water to sneak in the lubricating grease like this under the bad lubricating conditions, improve used physical construction with the hydraulic grease of the anti-surperficial starting point type separability of the bearing of carbon steel with used long-life rolling bearing of demonstrating of this lubricating grease and hub bearing.
Be used to solve the method for problem
Hydraulic grease of the present invention is that the basic lubricating grease that will contain non-water system base oil and thickening material cooperates the hydraulic grease that forms with additive, it is characterized in that: above-mentioned additive contains at least can make water be evenly dispersed in water dispersant in this hydraulic grease, and the use level of this water dispersant is that the saturation water component that can enable to be dispersed in this hydraulic grease is the amount of 30～60 weight %.
Among the present invention, so-called saturation water component is meant the amount of moisture that can make as the maximum of water-dispersion in lubricating grease of fine particle.
It is characterized in that: can make the water dispersant of water-dispersion in hydraulic grease is tensio-active agent.
It is characterized in that: above-mentioned tensio-active agent is at least a kind that is selected from calcium sulphonate and the dehydrating sorbitol monooleate.
It is characterized in that:, cooperate the above-mentioned calcium sulphonate of 0.5～2 weight part, the dehydrating sorbitol monooleate of 0.2～1 weight part respectively with respect to above-mentioned basic lubricating grease 100 weight parts.It is characterized in that: when using separately, cooperate the calcium sulphonate of 1.5～4 weight parts, the dehydrating sorbitol monooleate of 0.4～2 weight part.
It is characterized in that: above-mentioned additive contains zinc dithiophosphate and amine is antioxidant.
It is characterized in that: with respect to above-mentioned basic lubricating grease 100 weight parts, be combined with the above-mentioned zinc dithiophosphate of 2 weight parts respectively, the above-mentioned amine of 1 weight part is antioxidant.
It is characterized in that: the base number of above-mentioned calcium sulphonate is 50～500.Among the present invention, so-called base number is represented the amount of the alkaline matter that contains in 1 molecule, is the numerical value of measuring according to the method for regulation among the JIS K 2501.
It is characterized in that: the non-water system base oil that constitutes hydraulic grease of the present invention is a mineral oil, and thickening material is the urea based compound of following formula (1) expression, and with respect to above-mentioned basic lubricating grease 100 weight parts, cooperates 1～40 weight part.
[changing 2]
(in the formula, R
2Expression C
6-15Aromatic hydrocarbyl, R
1With R
3Expression is selected from least a alkyl in alicyclic alkyl and the aromatic hydrocarbyl respectively).
Above-mentioned water dispersant is characterized in that: in the total amount with respect to above-mentioned basic lubricating grease, water dispersant and water, the particle diameter of measuring when water ratio is 20 weight % by above-mentioned water dispersant dispersive water is below the 50 μ m.
Among the present invention, the particle diameter of water is the numerical value that the diameter to dispersive water droplet in the basic lubricating grease of the water ratio 20 weight %s of press-stretched on sheet glass under the load 600N obtains with measurement microscope.
Rolling bearing of the present invention is characterized in that: have interior wheel and foreign steamer and be present in the rolling body between wheel and foreign steamer in this, enclosed above-mentioned hydraulic grease around this rolling body.
Hub bearing of the present invention is characterized in that: be to enclose above-mentioned hydraulic grease, have the hub bearing of being made with carbon steel by physical construction that the automobile that slips the position is used or rail truck is used.Wherein, what is called is slipped the position, for example be meant in hub bearing shown in Figure 2 as described later to have interior side's member 25 of wheel hub wheel 21 and interior wheel 22, as foreign side's member 23 of foreign steamer be present in the rolling contact section of the rolling body 24,24 of the biserial between two members.In addition, in hub bearing 26, hydraulic grease of the present invention is sealing into by interior side's member 25, foreign side's member 23 and with seal between two members and 2 containment members, 27,28 annuluses that surrounded that the form of the rolling body of clamping biserial vertically 24 is installed in.
The invention effect
Hydraulic grease of the present invention, it is the hydraulic grease that is sealing in the bearing, this lubricating grease cooperates the dispersion agent of water-dispersion in lubricating grease that can make as fine particle in the basic lubricating grease that contains non-water system base oil and thickening material, the saturation water component that can be dispersed in the hydraulic grease is controlled at 30～60 weight %, and therefore can make the water-dispersion of immersing in the bearing is particulate.Therefore, even water is blended in the lubricating grease, also can suppress to hinder the effect of the moisture that oil film forms.
For rust inhibition, constitute the steel of bearing and contacting of blocky water constituent owing to can reduce, therefore the generation that can suppress to become rusty.
In addition, hydraulic grease of the present invention, by cooperating dispersion agent, can make the water-dispersion of immersing in the bearing become particle diameter is the following particulate of certain value.Therefore, even water is blended in the lubricating grease, also can suppress to hinder the effect of the moisture that oil film forms.
Therefore, can suppress surperficial starting point type and peel off, badly also can make the bearing of having enclosed lubricating grease obtain the long lifetime even lubricating condition becomes.
Hub bearing of the present invention, be to have the hub bearing made from carbon steel by physical construction that slips the position, therefore in this hub bearing, enclosed above-mentioned hydraulic grease,, also can suppress to hinder the effect of the moisture that oil film forms even water is blended in the hub bearing.Therefore, can suppress surperficial starting point type and peel off, badly also can obtain the long lifetime even lubricating condition becomes.
Description of drawings
Fig. 1 is the sectional view of rolling bearing.
Fig. 2 is the sectional view of hub bearing.
Nomenclature
1 rolling bearing
Wheel in 2
3 foreign steamers
4 rolling bodys
5 retainers
6 containment members
7 lubricating grease
21 take turns hub wheel
The inboard rolling face of 21a
21b path end difference
21c banding portion
21d wheel mounting flange
Wheel in 22
The inboard rolling face of 22a
23 foreign side's members
23a outside rolling face
23b car body mounting flange
24 rolling bodys
Square member in 25
26 hub bearings
27 containment members
28 containment members
Embodiment
For use its as physical construction with carbon steel and implemented the heat treated material of high frequency and constitute a part, have this material at the position of slipping with rolling body, study having the weather resistance that water immerses the bearing that uses dangerous position.It found that, utilizes additive sight-feed lubricator fat to the affinity of water and optimized bearing, also can not reduce and reaches the long lifetime even water immerses the lubricity of bearing neck bearing slipping plane.Discovery is separated into small water droplet by making the water that immerses in the bearing in lubricating grease, it can be absorbed.
Enclosed the bearing of lubricating grease, thereby this lubricating grease makes the saturation water component controlled by cooperating the dispersion agent that can make water be separated into particulate in lubricating grease, immerses even find water, the lubricity of rolling contact section can not reduce yet and continue.This is considered to: the lubricating grease that the saturation water component is controlled, and owing to becoming small water particle, submerged water is dispersed in the lubricating grease, be sealed in the lubricating grease as external phase, therefore can not hinder lubricating grease and form oil film, the weather resistance of bearing improves thus.The present invention is based on this experience and finishes.
Hydraulic grease of the present invention is by the hydraulic grease that cooperates the additive contain dispersion agent that can disperse water to obtain in the basic lubricating grease that contains non-water system base oil and thickening material, to immersing glassware for drinking water in the bearing affinity of setting is arranged.With the expression this affinity numerical value be called " saturation water component ", as shown in the formula define.
Saturation water component (weight %)=can be dispersed in maximum amount of moisture * 100/ (lubricating grease weight+can be dispersed in the maximum amount of moisture in the lubricating grease) in the lubricating grease
In hydraulic grease of the present invention, the use level of water dispersant is that can to make the saturation water component of this lubricating grease shown in the above-mentioned formula be the amount of 30～60 weight %, is preferably the scope of 40～50 weight %.If be this scope, can suppress moisture and hinder oil film formation.
If make the use level of saturation water component less than the water dispersant of 30 weight %, be difficult to absorb moisture, submerged water exists as big water droplet in bearing inside, hinders oil film and forms.In addition, if than the big use level of 60 weight %, at inner a large amount of moisture, the generation rust of excessively keeping of bearing.
In addition, water dispersant, in the total amount with respect to above-mentioned basic lubricating grease, water dispersant and water, the particle diameter of measuring when water ratio is 20 weight % by water dispersant dispersive water is below the 50 μ m.If the following water droplet of 50 μ m, moisture can not hinder hydraulic grease and form oil film.Be preferably below the 30 μ m, more preferably the scope of 5～25 μ m.If be more than the 50 μ m, hinder oil film and form, bearing life is extremely shortened.
As making water be evenly dispersed in the lubricating grease among the present invention and can controlling the dispersion agent of saturation water component, can use tensio-active agent.Be used for making water-dispersion to eliminate the harm of moisture at lubricating grease in tensio-active agent, thereby even water immerses and also can not produce oil film in the hub bearing and interrupt and get rusty.The water particle that water in the dip lubrication fat is small because of tensio-active agent becomes is dispersed in the lubricating grease.Lubricating grease exists as external phase, thinks that therefore not producing oil film interrupts.
In addition, similarly as also extremely low with the probability that the structure iron that constitutes the hub bearing main body contacts by the water particle of the discontinuous phase of the sealed in grease of external phase, think with low probability attached to the water particle on the structure iron also because of the rotation with the rolling body of the rotation campaign of hub bearing main body is used as the lubricating grease displacement of external phase at once, so structure iron is got rusty.
Can be used in tensio-active agent of the present invention, be W/O (water is dispersed in the state in the oil phase (lubricating grease)) the type tensio-active agent of catching easily in as the lubricating grease of external phase as the water particle of discontinuous phase, HLB (hydrophilic-lipophilic balance) value of the degree of the affinity of presentation surface promoting agent and water and oil is preferably 5～18 scope.
As the tensio-active agent that uses among the present invention, specifically, can enumerate polyalkylene glycol system, carboxylic acid alkylidene diol ester system, glycol such as carboxylic acid polyalkylene glycol ester system are tensio-active agent, short and long-chain acyl triglyceride molecules system, carboxylic acid polyoxyalkylene glyceryl ester system, glycerine such as short and long-chain acyl triglyceride molecules system are tensio-active agent, Polyglycerine carboxylicesters system, glycerine base system tensio-active agents such as polyoxyalkylene glycerine carboxylicesters system, polyoxyalkylene alkyl system, ethers such as carboxylic acid polyoxyalkylene alkyl system are tensio-active agent, carboxylic acid polyoxyalkylene alkyl diester-based, esters such as sorbitan esters system are tensio-active agent, polyoxyalkylene hardened castor oil system, Viscotrol C such as carboxylic acid polyoxyalkylene hardened castor oil system are tensio-active agent, carboxylic acid polyoxyalkylene TriMethylolPropane(TMP) is a tensio-active agent, metal sulfonate is a tensio-active agent, and sorbitan esters is a tensio-active agent etc.
In these, preferable alloy sulfonate is that tensio-active agent, carboxylic acid polyalkylene glycol ester are that tensio-active agent or sorbitan esters are tensio-active agent.Preferred especially calcium sulphonate and dehydrating sorbitol monooleate.
Metal sulfonate is that tensio-active agent, carboxylic acid polyalkylene glycol ester are that tensio-active agent or sorbitan esters are that tensio-active agent can make the saturation water component reach in the scope of 30～60 weight % in the scope of following cooperation ratio.
Can be used in the cooperation ratio of tensio-active agent of the present invention, basic lubricating grease 100 weight parts with respect to containing non-water system base oil and thickening material are preferably 0.4～4 weight part.When being less than 0.4 weight part, because can not make the saturation water component is more than the 30 weight %, therefore be difficult to fully obtain desired effect, in addition, because tensio-active agent deficiency, the particle diameter of water surpasses 50 μ m, and the formation of the oil-bound film of lubricating grease becomes insufficient, therefore is difficult to obtain fully desired effect.On the other hand, when surpassing 4 weight parts, produce the situation that the saturation water component surpasses 60 weight %, desired effects such as oil film rate of formation reach capacity, in addition, and for the particle diameter ratio 50 μ m of the water effect of the water-dispersion of microminiaturization more, also reach capacity, make lubricating grease characteristic reductions such as bearing life.
Adding among the present invention in the additive in the basic lubricating grease, is tensio-active agent as the water dispersant that can make water-dispersion in lubricating grease, preferably uses calcium sulphonate and dehydrating sorbitol monooleate.
Can be used in the calcium sulphonate among the present invention, preferably its base number is 50～500 scope.Base number is represented the amount of the alkaline matter that contains in 1 molecule, and it is high numerical value to the amount of the Ca that additive contains for a long time.The calcium sulphonate of alkalescence is not only given rustless property, and can give extreme pressure property.
That is, with respect to basic lubricating grease 100 weight parts, when cooperating 0.5～2 weight part calcium sulphonate, base number becomes insufficient less than 50 o'clock extreme pressure properties among the present invention, even base number surpasses 500, also can not get this above effect.
Can be used in dehydrating sorbitol monooleate of the present invention is non-ionic tenside, the presentation surface promoting agent has about 9 the HLB value of the degree of the affinity of water and oil, have oil loving character, be used from the dispersiveness of guaranteeing the base oil in the hydraulic grease with above-mentioned calcium sulphonate one.
As the calcium sulphonate of tensio-active agent and the use level of dehydrating sorbitol monooleate, with respect to basic lubricating grease 100 weight parts, preferably making calcium sulphonate is 0.5～2 weight part among the present invention, and making dehydrating sorbitol monooleate is 0.2～1 weight part.
In addition, when using separately, preferably cooperate the calcium sulphonate of 1.5～4 weight parts, the dehydrating sorbitol monooleate of 0.4～2 weight part.
By in above-mentioned scope with both and usefulness, the saturation water component of hydraulic grease can be controlled at 30～60 weight %.In addition, needn't worry that desired effects such as oil film rate of formation reach capacity, and make lubricating grease characteristic reductions such as bearing life etc.
In hydraulic grease of the present invention, can cooperate other additives.Especially preferably cooperate extreme pressure agent and antioxidant, preferably use zinc dithiophosphate as the extreme pressure agent of giving extreme pressure property, using amine is that antioxidant is as antioxidant.
As can be used in zinc dithiophosphate of the present invention, can enumerate the dialkyl dithiophosphate zinc shown in for example following formula (1), be used to give the extreme pressure property of lubricating grease and cooperate.
[changing 3]
(in the formula, R represents alkyl).
As alkyl, can enumerate primary alkyl, secondary alkyl and aryl, the preferred good secondary alkyl of balance that uses stability for water, attrition resistance etc.
The use level of zinc dithiophosphate with respect to basic lubricating grease 100 weight parts, preferably cooperates 0.5～2.0 weight part.Most preferably, be 2.0 weight parts with respect to basic lubricating grease 100 weight parts.
During less than 0.5 weight part, it is insufficient that extreme pressure property becomes, and is difficult to obtain fully the effect of institute's phase, in addition, surpasses 2.0 weight parts even add, and can not obtain this above effect.
The amine that uses among the present invention is antioxidant, cooperates for the oxidative degradation that suppresses lubricating grease.As amine is antioxidant, can enumerate for example phenyl-1-naphthylamine, phenyl-2-naphthylamines, phenylbenzene-Ursol D, bipyridyl amine, thiodiphenylamine, N-methyl thiodiphenylamine, N-ethyl thiodiphenylamine, 3,7-dioctyl thiodiphenylamine, right, right '-dioctyl diphenylamine, N, N '-di-isopropyl-Ursol D etc.
Amine is the use level of antioxidant, with respect to basic lubricating grease 100 weight parts, preferably cooperates 0.5～2.0 weight part.During less than 0.5 weight part, it is insufficient that antioxidant property becomes, and is difficult to obtain fully desired effect, in addition, surpasses 2.0 weight parts even add, and also can't wish the effect that it is above.Most preferably, be 1 weight part with respect to basic lubricating grease 100 weight parts.
As the non-water system base oil that can be used in the hydraulic grease of the present invention, for example can enumerate mineral oil, poly-alpha-olefin (hereinafter referred to as PAO) oil, ester oil, phenyl ether oil, fluorocarbon oil and by Fischer-Tropsch reaction synthetic synthetic hydrocarbon oil (GTL base oil) etc.Can also use these oily mixtures.
As mineral oil, any mineral oil that can use for example naphthene series mineral oil, paraffin series mineral oil, whiteruss, Hydrodewaxing wet goods in lubricating oil or lubricating grease field, to use usually.
As PAO oil, can enumerate the multipolymer of polymkeric substance, alpha-olefin and alkene of alpha-olefin or polybutene etc.These are the oligomers that are made as the oligopolymer of alpha-olefin, the structure that the terminal double link hydrogenation of oligomer is formed.In addition, also can use a kind of polybutene as alpha-olefin, polybutene can carry out polymerization by the catalyzer such as starting raw material use aluminum chloride based on iso-butylene and make.Polybutene can directly use, and also can use by hydrogenation.
Other concrete example as alpha-olefin, can enumerate 1-octene, 1-nonene, 1-decene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene, 1-two dodecylenes, 1-tetracosene etc., use the mixture of these alpha-olefins usually.
In addition, consider lubricity and price, the preferred mineral oil that uses in these non-water system base oils.
Can be used in non-water system base oil of the present invention, at room temperature is liquid, and the kinematic viscosity under 40 ℃ is 30～200mm
2/ second.Be preferably 40～120mm
2/ second.Be lower than 30mm
2The occasion of/second, non-water system base oil deterioration in the short period of time because the deterioration thing that generates promotes the overall deterioration of non-water system base oil, becomes short life so the weather resistance of bearing is reduced.And above 200mm
2During/second, not preferred because the rising of the temperature of the bearing that the increase of rotary torque causes increases.
Non-water system base oil shared cooperation ratio in basic lubricating grease 100 weight parts is preferably 60～99 weight parts among the present invention, is more preferably 70～95 weight parts.
When the cooperation ratio of non-water system base oil was lower than 60 weight parts, lubricating grease was hard, the poor lubricity during low temperature.And the soft and easy leakage of matter when surpassing 99 weight parts.
As spendable thickening material in the hydraulic grease of the present invention, can enumerate soap classes such as bentonite, silica gel, fluorine cpd, lithium soap, lithium compound soap, calcium soap, calcium compound soap, aluminium soap, aluminium compound soap, urea based compounds such as two carbamide compounds, polyurea compound.If consider then preferred urea based compound such as thermotolerance, cost.
The urea based compound is for example used following formula (1) expression.
[changing 4]
(R
2Expression C
6-15Aromatic hydrocarbyl, R
1With R
3Can be same to each other or different to each other, expression is selected from C respectively
6-12Aromatic group, alicyclic group and aliphatic group at least a group).
The urea based compound makes by making the reaction of isocyanate compound and amine compound.Do not have reactive radical for residual, equivalent ground cooperates preferably to make the isocyanate group of isocyanate compound become roughly with the amino of amine compound.
Two carbamide compounds of formula (1) expression for example, can obtain by the reaction of vulcabond and monoamine.As vulcabond, can enumerate phenylene diisocyanate, biphenyl diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate, 3,3-dimethyl-4,4-biphenyl diisocyanate, octadecane vulcabond, decane vulcabond, hexane diisocyanate etc. as monoamine, can be enumerated octylame, amino dodecane, cetylamine, stearylamine, oleyl amine, aniline, para-totuidine, hexahydroaniline etc.
Among the present invention, preferred alicyclic-aromatic series urea based compound or the aromatic series urea based compound that obtains by aromatic diisocyanate and alicyclic monoamine and aromatic series monoamine or the monomeric reaction of aromatic series monoamine.Especially preferably will also use as the hexahydroaniline of alicyclic monoamine with as the aniline of aromatic series monoamine.
Reaction, after for example making in monobasic amino acid and the diisocyanates non-water system base oil about 70～120 ℃ reaction fully, temperature is risen, kept about 1～2 hour down at 120～180 ℃, cooling then, finish by using homogenizing such as homogenizer, three roller mixing rolls to handle, obtain being used to cooperate the basic lubricating grease of each additive.
Thickening material shared cooperation ratio in basic lubricating grease 100 weight parts among the present invention, preferably 1～40 weight part is more preferably 3～25 weight parts.When the cooperation ratio of thickening material was lower than 1 weight part, thickening effectiveness reduced, and it is difficult that lubricating greaseization becomes, and lubricating grease becomes really up to the mark when surpassing 40 weight parts, seldom arrives desired effect.
In the hydraulic grease of the present invention, in the scope of not destroying function, can add above-mentioned known additive in addition as required.As additive, for example can enumerate antioxidants such as phenol system, chalcogenide compound, abrasion such as sulphur system, phosphorus series compound inhibitor, rust-preventive agent such as metal sulfonate, polyol ester, detergent dispersants such as metal sulfonate, metal phosphate etc.These additives can add separately or combination interpolation more than 2 kinds.
One of rolling bearing of the present invention is illustrated in Fig. 1.Fig. 1 is a sectional view of having enclosed the rolling bearing of lubricating grease.
Rolling bearing 1 disposes periphery with one heart and has the interior wheel 2 of interior wheel rolling face 2a and the foreign steamer 3 that inner peripheral surface has foreign steamer rolling face 3a, a plurality of rolling bodys 4 of configuration between interior wheel rolling face 2a and foreign steamer rolling face 3a.Constitute by retainer 5 that keeps these a plurality of rolling bodys 4 and the containment member 6 that is fixed on foreign steamer 3 grades.At least around rolling body 4, enclose above-mentioned hydraulic grease.
One example of hub bearing of the present invention (follow-up pulley third generation hub bearing) is shown in Fig. 2.Fig. 2 is the sectional view of hub bearing.Hub bearing 26 possesses and has wheel hub wheel 21 with interior side's member 5 of interior wheel 22, as the foreign side's member 23 of foreign steamer and the rolling body 24,24 of biserial.Wheel hub wheel 21 has installation wheel (not have illustrate) usefulness integratedly in the one end wheel mounting flange 21d, the path end difference 1b that forms inboard rolling face 21a and extend vertically in periphery from this inboard rolling face 21a.
In this specification sheets, be meant on the vehicle under the installment state outside the width of cloth direction what is called " interior " fingerbreadth direction center side with regard to axial speech so-called " outward ".
In the path end difference 21b of wheel hub wheel 21, be pressed into the interior wheel 22 that periphery has formed inboard rolling face 22a.And viscous deformation takes place and the 21c of banding portion that forms in foreign side radially in the end that utilizes the path end difference 21b make wheel hub wheel 21, in preventing wheel 22 with respect to wheel hub wheel 21 towards axial disengaging.
Foreign side's member 23, has car body mounting flange 23b outside week integratedly, at the outside in interior week rolling face 23a, 23a, and roll between the outside rolling face 23a of these biserials, 23a opposed inside rolling face 21a, 22a and contain the rolling body 24,24 of biserial freely.
Hydraulic grease of the present invention is sealing in the space that is surrounded by containment member 27, foreign side's member 23, containment member 28, interior side's member 25 and wheel hub wheel 21, around the rolling body 24,24 of the biserial of cover foreign side member 23 and 25 clampings of Nei Fang member, be used for rolling contact section lubricated of rolling surface, inboard rolling face 21a, 22a and outside rolling face 23a, the 23a of rolling body 24,24.
Hydraulic grease of the present invention also can be used in the bearing that applies high loading beyond the hub bearing.
Spendable material in the hub bearing of the present invention can be enumerated bearing steel, converted steel or physical construction carbon steel.The wherein preferred good and inexpensive physical construction carbon steels such as S53C of forging property that use.This carbon steel is generally handled by implementing high frequency heat, uses after guaranteeing the rolling contact fatigue intensity of bearing portion.Yet, handle even physical construction is implemented high frequency heat with carbon steel because so alloying constituent is less a little less than the surface strength, to the patience peeled off in the surperficial starting point type that slips the position than bearing steel difference.To the problem that this surperficial starting point type is peeled off, hydraulic grease of the present invention improves by making the lubricity of slipping the position, can prevent that the physical construction of using in the hub bearing from peeling off with the surperficial starting point type of carbon steel.
Embodiment
By embodiment and comparative example the present invention is described particularly, but be not subjected to any restriction of these examples.
Preparation is dispersed in as in the mineral oil of non-water system base oil and the mineral oil/urea that obtains is basic lubricating grease (JIS denseness No.2 level, a denseness: 265～295) carbamide compound as thickening material.
In the 2000g mineral oil (kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second) in, making ditan-4,4 '-vulcabond 231.7g, aniline 86.2g and hexahydroaniline 91.7g reaction makes the carbamide compound homodisperse of generation and obtains basic lubricating grease.In this basic lubricating grease, cooperate additive and obtain test lubricating grease with the cooperation shown in the table 1.
For the test lubricating grease that obtains, supply to oil film rate of formation shown below test 1 and water-dispersion validation test, measure the oil film rate of formation, with the hybrid mode and the water particle footpath of water.The result gathered be shown in table 1.
＜oil film rate of formation test 1 〉
Use bearing: angular contact ball bearing 7006ADLLB is modeled to hub bearing and uses.
Test conditions: the grease for hub bearing that 1.0g obtains is enclosed among the angular contact ball bearing 7006ADLLB, under radial load 650N, axial load 200N, bearing revolution 1000rpm, make under the state of its rotation, measure oil film rate of formation with the lubricating grease of water injection rate 0.35ml/ hour water filling in the time of 10 hours.The oil film rate of formation is measured with electrical resistance method.
＜water-dispersion validation test 〉
In order to confirm water dispersive degree in lubricating grease, following enforcement.
Water and lubricating grease are mixed so that measure 100 weight parts with respect to the total of water and lubricating grease, water content is 20 weight parts, stir, the mixture that obtains is taked on the sheet glass, the spacing washer of thick 0.025mm is placed on the two ends of sheet glass, from the top with another sheet glass clamping, to sheet glass integral body applying load equably, lubricating grease is launched, with the particle diameter of the water droplet that exists in the measurement microscope lubricating grease.
Preparation is dispersed in as in the mineral oil of base oil and the mineral oil/urea that obtains is basic lubricating grease (JIS denseness No.2 level, a denseness: 265～295) carbamide compound as thickening material.
In 2000g mineral oil (Nippon Oil(Nippon Mitsubishi Oil) society system ス one パ one ォ ィ Le C, the kinematic viscosity under 40 ℃: 100mm
2/ second) in, making ditan-4,4 '-vulcabond 234.8g and aniline 174.8g reaction makes the carbamide compound homodisperse of generation and obtains basic lubricating grease.In this basic lubricating grease, cooperate additive and obtain grease for hub bearing with the cooperation shown in the table 1.
For the grease for hub bearing that obtains, estimate similarly to Example 1.The result gathered be shown in table 1.
[table 1]
1) kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second
2) aniline
3) hexahydroaniline
4) loose village oil society system ス Le ホ one Le CA-45
5) and the pure pharmaceutical worker of light industry society system reagent
6) バ Application ダ one PVC Le ト society system バ Application Le-Block SL
7) Le Block リ ゾ one Le society system Le Block リ ゾ one Le 1395
The water particle footpath that water is evenly dispersed in the lubricating grease in the lubricating grease is small.In addition,, in the dispersion of water becomes uniform lubricating grease, kept the formation of oil film, but in the dispersion of water becomes uneven lubricating grease, do not formed oil film for the oil film rate of formation.
As known from the above, water is blended under the situation in the lubricating grease, can not make the homodisperse lubricating grease of water can not form oil film, might cause that surperficial starting point type peels off, but can make the homodisperse lubricating grease of water owing to can form oil film, therefore can prevent the generation of surface damage.
Preparation is dispersed in as in the mineral oil of non-water system base oil and the mineral oil/urea that obtains is basic lubricating grease (JIS denseness No.2 level, a denseness: 265～295) carbamide compound as thickening material.
In the 2000g mineral oil (kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second) in, making ditan-4,4 '-vulcabond 231.7g, aniline 86.2g and hexahydroaniline 91.7g reaction makes the carbamide compound homodisperse of generation and obtains basic lubricating grease.In this basic lubricating grease, cooperate additive and obtain test lubricating grease with the cooperation shown in table 2 and the table 3.
For the test lubricating grease that obtains, supply to oil film rate of formation test 2 shown below, bearing life test and saturation moisture flow measurement, measure oil film rate of formation, bearing life time, saturation water component and have or not to produce and become rusty.The result gathered be shown in table 2 and table 3.
＜oil film rate of formation test 2 〉
Use bearing: angular contact ball bearing 7006ADLLB is modeled to hub bearing and uses.
Test conditions: the test that 1.0g is obtained is with among the grease-enclosed angular contact ball bearing 7006ADLLB, under radial load 8000N, axial load 3000N, bearing revolution 1000rpm, make under the state of its rotation, measure with the oil film rate of formation of the test of water injection rate 1.0ml/ hour water filling in the time of 10 hours with lubricating grease.The oil film rate of formation is measured with electrical resistance method.
＜bearing life test 〉
Use bearing: angular contact ball bearing 7006ADLLB is modeled to hub bearing and uses.
Test conditions: the test that 1.0g is obtained is with among the grease-enclosed angular contact ball bearing 7006ADLLB, under radial load 8000N, axial load 3000N, bearing revolution 1000rpm, make under the state of its rotation the bearing life when measuring with water filling in water injection rate 1.0ml/ hour.Bearing life is to make the time of vibration increase as bearing life with any damage in foreign steamer rolling surface, interior wheel rolling surface, steel ball.
＜saturation moisture flow measurement 〉
Take a certain amount of test with in the lubricating grease in weighing, the ratio of sneaking into of water is changed with each 5 weight % and add, use miniature spatula with manually stirring, obtain the amount of moisture of the maximum of the water-dispersion that can make adding, use and calculate the saturation water component with following formula.Can disperse following definite: will test with lubricating grease and take on the sheet glass, the spacing washer of thick 0.025mm is placed on the two ends of sheet glass, square from it with another sheet glass clamping, apply the load of 600N equably to sheet glass integral body, test is launched with lubricating grease, when using microscopic examination, the particle diameter of the maximum water droplet that exists in the lubricating grease is that 50 μ m are defined as and can disperse when following.
Maximum amount of moisture * 100/ in the lubricating grease of saturation water component (weight %)=can be dispersed in (test with lubricating grease weight+can be dispersed in the maximum amount of moisture in the lubricating grease)
[table 2]
1) kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second
2) aniline
3) hexahydroaniline
4) キ Application グ society system, NA-SUL CA50
5) Japanese ェ マ Le ジ ョ Application society system
6) Japanese ェ マ Le ジ ョ Application society system
7) reagent
8) zero: do not take place, *: take place
[table 3]
1) kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second
2) aniline
3) hexahydroaniline
4) the emerging chemical society of imperial palace system, ノ Network ラ ッ Network AD-F
5) キ Application グ society system, NA-SUL CA50
6) WITCO society system, Bryton C500
7) reagent
8) Lubrizol society system, Lubrizol 677A
Shown in table 2 and table 3, the saturation water component is the scope (particularly 40～50 weight %) of 30～60 weight %, becomes high oil film rate of formation.
Sneaked under the situation of water, less than the lubricating grease of 30 weight % with surpass the lubricating grease of 60 weight %,, therefore produced metallic contact and get rusty because the formation of oil film suffers damage for the saturation water component.If be 30～60 weight %, owing to can form oil film, cause the dangerous little of metallic contact, so bearing life is also long, and then the generation that can suppress to become rusty.
In addition, as shown in table 3, the fashionable bearing life of water logging is the long lifetime under the additive of embodiment 9 is formed.Therefore, produce effect in the purposes such as the bearing that under the easy submerged environment of the water capacity, uses, automobile traveling part, rail truck, iron and steel roller mill.
Embodiment 15～embodiment 18 and comparative example 9～comparative example 10
Preparation is dispersed in as in the mineral oil of non-water system base oil and the mineral oil/urea that obtains is basic lubricating grease (JIS denseness No.2 level, a denseness: 265～295) carbamide compound as thickening material.
In the 2000g mineral oil (kinematic viscosity under 100,40 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second) in, making ditan-4,4 '-vulcabond 231.7g, aniline 86.2g and hexahydroaniline 91.7g reaction makes the carbamide compound homodisperse of generation and obtains basic lubricating grease.In this basic lubricating grease, cooperate additive and obtain test lubricating grease with the cooperation shown in the table 4.
For the test lubricating grease that obtains, supply to that water particle shown below is directly measured, the test 2 of above-mentioned oil film rate of formation and bearing life experiment, measure water particle footpath, oil film rate of formation and bearing life time.The result gathered be shown in table 4.
[table 4]
1) kinematic viscosity under 100,4 ℃ of the Nippon Oil(Nippon Mitsubishi Oil) society system one PVC Application: 100mm
2/ second
2) aniline
3) hexahydroaniline
4) キ Application グ society system, NA-SUL CA50
5) Japanese ェ マ Le ジ ョ Application society system
6) Japanese ェ マ Le ジ ョ Application society system
7) reagent
8) owing to fine dispersion, so particle diameter can not be measured
As shown in table 4, water particle footpath D (20) is the following scopes (particularly 15～25 μ m) of 50 μ m, becomes high oil film rate of formation.
Under the situation that water is sneaked into, for the big lubricating grease of D (20) ratio 50 μ m, because the formation of oil film is impaired, therefore might cause metallic contact, but for D (20) is the following lubricating grease of 50 μ m, owing to can form oil film, therefore causes that the danger of metallic contact reduces, bearing life is long, and then the generation that also can suppress to become rusty.
The possibility of utilizing on the industry
Hydraulic grease of the present invention is owing to containing the basis profit of non-water system base oil and thickener Cooperate in the consistent lubricant to make water be evenly dispersed in dispersant in the lubricating grease as additive, because of Even this water when having enclosed the bearing operation of this lubricating grease has been sneaked in the lubricating grease, also can press down System forms the effect that produces the moisture that hinders to the oil film of lubricating grease, therefore can suppress bearing Surface starting point type is peeled off, and is even used structure with in the bearing of carbon steel in rail wheel, lubricated Condition becomes badly, also can obtain the long-life. Therefore, immerse at possible long-time water Under the environment, can be suitable as the rail truck that requires abrasion performance and long-time durability, build If the hydraulic grease of the bearing that uses in machinery, the automobile electric slave etc.
Claims (12)
1. hydraulic grease is that the basic lubricating grease that will contain non-water system base oil and thickening material cooperates the hydraulic grease that forms with additive, it is characterized in that:
Above-mentioned additive contains at least can make water be evenly dispersed in water dispersant in this hydraulic grease,
The use level of this water dispersant is that the saturation water component that can enable to be dispersed in the above-mentioned hydraulic grease is the amount of 30～60 weight %.
2. the described hydraulic grease of claim 1, it is characterized in that: above-mentioned water dispersant is a tensio-active agent.
3. the described hydraulic grease of claim 2, it is characterized in that: above-mentioned tensio-active agent is at least a kind that is selected from calcium sulphonate and the dehydrating sorbitol monooleate.
4. the described hydraulic grease of claim 3 is characterized in that: with respect to above-mentioned basic lubricating grease 100 weight parts, cooperate the above-mentioned calcium sulphonate of 0.5～2 weight part, the dehydrating sorbitol monooleate of 0.2～1 weight part respectively.
5. the described hydraulic grease of claim 1 is characterized in that: above-mentioned additive contains that to be selected from zinc dithiophosphate and amine be in the antioxidant at least a kind.
6. the described hydraulic grease of claim 5 is characterized in that: with respect to above-mentioned basic lubricating grease 100 weight parts, be combined with the above-mentioned zinc dithiophosphate of 2 weight parts respectively, the above-mentioned amine of 1 weight part is antioxidant.
7. the described hydraulic grease of claim 3, it is characterized in that: the base number of above-mentioned calcium sulphonate is 50～500.
8. the described hydraulic grease of claim 1, it is characterized in that: above-mentioned non-water system base oil is a mineral oil.
9. the described hydraulic grease of claim 1 is characterized in that: above-mentioned thickening material is the urea based compound of following formula (1) expression, and with respect to above-mentioned basic lubricating grease 100 weight parts, cooperates 1～40 weight part,
[changing 1]
In the formula, R
2Expression C
6-15Aromatic hydrocarbyl, R
1With R
3Expression is selected from least a alkyl in alicyclic alkyl and the aromatic hydrocarbyl respectively.
10. the described hydraulic grease of claim 1, it is characterized in that: above-mentioned water dispersant, in the total amount with respect to above-mentioned basic lubricating grease, water dispersant and water, the particle diameter of measuring when water ratio is 20 weight % by above-mentioned water dispersant dispersive water is below the 50 μ m.
11. rolling bearing, be to have interior wheel and foreign steamer and be present in the rolling body between wheel and foreign steamer in this, enclosed the rolling bearing that hydraulic grease forms around this rolling body, it is characterized in that: above-mentioned hydraulic grease is the described hydraulic grease of claim 1.
12. hub bearing is to have enclosed the hub bearing that hydraulic grease forms at the position of slipping of being made with carbon steel by physical construction, it is characterized in that: this hydraulic grease is the described hydraulic grease of claim 1.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP282315/2005 | 2005-09-28 | ||
| JP2005282315A JP4942321B2 (en) | 2005-09-28 | 2005-09-28 | Hub bearing |
| JP075470/2006 | 2006-03-17 | ||
| JP075471/2006 | 2006-03-17 | ||
| JP175284/2006 | 2006-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101273117A true CN101273117A (en) | 2008-09-24 |
Family
ID=37977941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800358354A Pending CN101273117A (en) | 2005-09-28 | 2006-09-28 | Waterproof grease and hermetically filled with the grease, rolling bearing and hub bearing |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4942321B2 (en) |
| CN (1) | CN101273117A (en) |
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| CN102165052A (en) * | 2008-09-26 | 2011-08-24 | 协同油脂株式会社 | Grease composition and bearing |
| CN103403137A (en) * | 2011-03-04 | 2013-11-20 | 协同油脂株式会社 | Grease composition and grease-packed rolling bearing |
| CN104160167A (en) * | 2012-02-07 | 2014-11-19 | Ntn株式会社 | Wheel bearing device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0331394A (en) * | 1989-06-27 | 1991-02-12 | Nippon Sekiyu Kako Kk | Grease composition |
| JP3280548B2 (en) * | 1995-09-21 | 2002-05-13 | 協同油脂株式会社 | Water resistant grease composition |
| JP2004018725A (en) * | 2002-06-18 | 2004-01-22 | Nsk Ltd | Biodegradable grease composition and rolling bearing |
| JP4118624B2 (en) * | 2002-07-24 | 2008-07-16 | Ｎｔｎ株式会社 | Anti-rust grease and bearing with grease |
| JP2004346120A (en) * | 2003-05-20 | 2004-12-09 | Nsk Ltd | Grease composition and rolling bearing using the same |
| JP2006016441A (en) * | 2004-06-30 | 2006-01-19 | Nsk Ltd | Grease composition and rolling bearing |
| EP1806391A1 (en) * | 2004-10-18 | 2007-07-11 | NSK Ltd. | Waterproof grease composition and roller bearing for wheel support |
-
2005
- 2005-09-28 JP JP2005282315A patent/JP4942321B2/en not_active Expired - Fee Related
-
2006
- 2006-09-28 CN CNA2006800358354A patent/CN101273117A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4942321B2 (en) | 2012-05-30 |
| JP2007091860A (en) | 2007-04-12 |
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Application publication date: 20080924 |