WO2010003918A1

WO2010003918A1 - Grease composition

Info

Publication number: WO2010003918A1
Application number: PCT/EP2009/058509
Authority: WO
Inventors: Keiji Tanaka; Takahiro Ozaki
Original assignee: Shell Internationale Research Maatschappij B.V.
Priority date: 2008-07-07
Filing date: 2009-07-06
Publication date: 2010-01-14
Also published as: BRPI0915731A2; WO2010003918A8; JP2010037529A; US20110160105A1; CN102124087A; EP2307534A1; KR20110033926A; JP5330773B2

Abstract

Grease composition for use in resin lubrication incorporating into a grease base material which includes a base oil and a thickener at least one saturated or unsaturated fatty acid having from 8 to 22 carbon atoms and/or fatty acid metal salt, being a metal salt of a linear saturated fatty acid having from 8 to 14 carbon atoms or a metal salt of an unsaturated fatty acid having from 16 to 22 carbon atoms and from 1 to 4 unsaturated groups, the metal having a valence of from 1 to 4, wherein the thickener excludes said fatty acid metal salts.

Description

GREASE COMPOSITION

Technical Field of the Invention

This invention relates to a grease composition for use in resin lubrication which is used at lubrication points where rolling or sliding occur when resin materials are employed.

Background of the Invention

In recent years, the use of resin materials for components in various industrial machines, not least in the automotive industry, has become prominent from many points of view, such as lighter weight, lower cost, lower friction, or recycling. But as the structural elements of the components have diversified, many new problems have emerged, and all sorts of technologies are being improved. For example, in the movable parts of electric door mirrors or the sliding parts of telescopic shafts in car steering, the various sliding parts of R&P steering rack guides, the power transmission gears of electric power steering devices, the internal sliding parts of various actuators and air cylinders, linear guides and ball screw retainers in machine tools, various bearing retainers, the sliding parts of crane booms, and also the resin gear parts in audio machines such as radio cassette players, videotape recorders and CD players, the resin gear parts in office automation equipment such as printers, photocopiers and faxes, and the sliding parts in various electrical switches, there are lubrication points where resin and resin or resin and a material other than resin such as a metal function by coming into a state of contact. Hitherto, in the field of lubrication almost all the structural elements of machines were of metallic materials, and so the history of research into friction and wear of metal against metal such as iron, aluminium, alloys thereof, brass and bronze is old and vast, and many techniques have been accumulated through this profound experience and knowledge.

For example, it is known that extreme pressure agents and anti-wear agents which contain elements such as phosphorus or sulphur are effective against the friction and wear of metal against metal, and that these additives form a film which proactively causes a chemical reaction with the metallic surface, thereby exhibiting the functions of reducing friction and wear and preventing machinery from seizing up. This technology is widely used in engine oils and gear oils and in high- performance industrial lubricating oils and greases.

However, despite the fact that the history of the technology of lubrication of resins against resins, or resins against different materials such as metals, is brief, as mentioned above their applications have broadened in recent years, but the present situation is that in the course of this diversification no technology has been presented that is able thoroughly to satisfy the various requirements imposed on lubricating greases. For example, in the case where technology using phosphorus or sulphur additives effective against friction or wear in the aforementioned metal-to-metal cases is applied to lubrication points of resins and metallic materials, virtually no friction reduction effect such as can be obtained for metal-to-metal is obtained. In fact there are by no means a few instances where the friction and anti-wear performance deteriorates and the life of the machine component is shortened.

This is thought to be because the chemical activity of the surfaces is much weaker in the case of resins than for metals, and there is virtually no reaction at the rubbing surfaces with organic additives such as those based on phosphorus or sulphur, and given that adsorption is also weak, the effect in regard to friction and wear is paltry, and accordingly the friction reducing effect is weak. Also, in cases where they are used at boundaries where temperature rises are deliberately effected, the active sulphur and phosphorus in these additives permeate into the resin components and cause cracks and brittleness. There are also cases where the contrary actions of friction and wear are promoted.

In order to improve the lubrication state of the aforementioned resins against resins or resins against different materials such as metals, a grease has been proposed (Japanese Laid-open Patent 2002-371290) for use in resin lubrication such that the static coefficient of friction of lubricated parts is reduced and the durability and life of lubricated parts are enhanced by incorporating montan wax in a grease composition which contains a base oil and a thickener. Also, a technology has been disclosed (Japanese Laid-open Patent 2003-

246996) in which oxidative stability of the grease and rust-preventing performance in respect of metal components are improved, with no detrimental effects such as stress cracks with regard to resinous lubrication point material or resinous casing material, by adding to a grease a phenolic rust preventative constituted by atoms of only three elements, carbon, oxygen and hydrogen. Further improvements are anticipated. This invention is an attempt to obtain a grease composition for use in resin lubrication wherein friction is attenuated and satisfactory lubrication performance is obtained at lubrication points where rolling and sliding and so on occur where at least one side of a paired structure, such as resin against resin or resin against a different material such as a metal, is comprised of a resinous material.

Having undertaken research and investigations on the basis of the theory of surface chemistry into the lubrication behaviour of resins in the past, the inventors have arrived at this invention by discovering that the extremely weak electrical charge that occurs at the surface of a resin and a paired material, such as resin against resin or resin against a different material such as a metal, interacts with certain saturated or unsaturated fatty acids and fatty acid metal salts which are added to greases, and further that these additives exhibit a binder function with the grease so that it is possible to form and maintain more reliably a lubrication film on the surface of the resin and resin or paired material, with the result that friction is reduced and satisfactory lubrication is obtained. Summary of the Invention This invention is for a grease composition for use in resin lubrication incorporating into a grease base material which includes a base oil and a thickener at least one saturated or unsaturated fatty acid having from 8 to 22 carbon atoms and/or fatty acid metal salt, being a metal salt of a linear saturated fatty acid having from 8 to 14 carbon atoms or a metal salt of an unsaturated fatty acid having from 16 to 22 carbon atoms and from 1 to 4 unsaturated groups, the metal having a valence of from 1 to 4, wherein the thickener excludes said fatty acid metal salts.

Preferably, the metals of the fatty acid metal salts include metals such as lithium, sodium, potassium, magnesium, calcium, zinc, aluminium and lead.

It is preferred that the total amount of saturated or unsaturated fatty acid and/or fatty acid metal salt used is in the order of from 0.1 to 10% by mass. It is possible to use as the grease thickener urea, bentonite, calcium phosphate or sodium terephthalamate and other thickeners, singly or in mixtures.

According to this invention friction is attenuated so that it is possible to obtain satisfactory lubrication performance at lubrication points such as rolling and sliding points between parts comprising resinous materials one against another, and it is possible to use it over a wide range as a grease composition for use in resin lubrication. Detailed Description of the Invention The base oil in this invention is one which may ordinarily be used as the base oil of a lubricating oil or as the base oil of a grease, and there are no special restrictions. As examples mention may be made of mineral oils, synthetic oils, animal and plant oils, and mixtures thereof.

In particular it is possible to use, singly or as mixtures, base oils which belong to Group I, Group II, Group III, Group IV and so on of the API (American Petroleum Institute) base oil categories. Group I base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as solvent refining, hydrorefining, and dewaxing in respect of lubricating oil ~~ G —

fractions obtained by atmospheric distillation of crude oil.

Group II base oils include, for example, paraffinic mineral oils obtained by a suitable combination of refining processes such as hydrorefining and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil. Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so are suitable for this invention.

Group III base oils and Group 11+ base oils include paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by the Isodewax process which dewaxes and substitutes the wax produced by the dewaxing process with isoparaffins, and base oils refined by the Mobil wax isomerisation process. These too are suitable for use in this invention.

Concrete examples of synthetic oils include polyolefins, polyoxyalkylene glycols such as polyethylene glycol or polypropylene glycol, esters such as di-2- ethylhexyl sebacate or di-2-ethylhexyl adipate, polyol esters such as trimethylolpropane esters or pentaerythritol esters, perfluoroalkyl ethers, silicone oils, polyphenyl ethers, and so on.

The aforementioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and α-olefins with five or more carbons. In the manufacture of polyolefins, one kind of the aforementioned olefins may be used singly or two or more kinds may be used in combination. Particularly suitable are the polyolefins called poly-α-olefins (PAO) . These are base oils of Group IV.

GTL (gas to liquid) base oils synthesised by the Fischer-Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.

As typical examples of animal and plant oils mention may be made of castor oil and rape-seed oil. The various aforementioned oils may be used singly or in mixtures for the base oil. The aforementioned examples are listed singly but the invention is not limited thereby.

For the thickener incorporated in the aforementioned base oil use is made singly or in mixtures of thickeners other than fatty acid metal salt thickeners, such as bentonite, clay, silica, tricalcium phosphate, calcium sulphonate complexes, ureas, sodium terephthalamate and other thickeners. The aforementioned fatty acid metal salts are those in which the fatty acid and metal are bonded, and they are normally called metallic soaps. As illustrative examples mention may be made of lithium soaps, sodium soaps, potassium soaps, magnesium soaps, calcium soaps, barium soaps, aluminium soaps, zinc soaps, lead soaps and complex soaps therefrom.

In specific cases it is also possible to use the aforementioned thickeners and fatty acid metal salts together as the thickener, but in such cases it is most often best to use a fatty acid metal salt that is different from the fatty acid metal salt used as the additive. The additive added to the grease base material which incorporates the aforementioned base oil and thickener is a saturated or unsaturated fatty acid having from 8 to 22 carbon atoms and/or a metal salt of a linear saturated fatty acid having from 8 to 14 carbon atoms or a metal salt of an unsaturated fatty acid having from 16 to 22 carbon atoms and from 1 to 4 unsaturated groups, and where the metal has a valence of from 1 to 4.

As examples of fatty acids forming the starting material of the aforementioned saturated or unsaturated fatty acids and fatty acid metal salts in this Invention, mention may be made of caprylic acid, pelargonic acid, capric acid, lauric acid, linderic acid, myristic acid, tsuzuic acid, physetoleic acid, myristoleic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, 12-hydroxystearic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, linolic acid, linolenic acid, elaeostearic acid, tuberculostearic acid, arachidic acid, eicosadienic acid, eicosatrienic acid, arachidonic acid, behenic acid, llgnoceric acid, nervonic acid, hexadocosanic acid, octadocosanic acid and erucic acid.

The saturated or unsaturated fatty acids in this invention as aforementioned are preferably those with from 8 to 22 carbon atoms, and in the case of fatty acid metal salts are preferably linear saturated fatty acid salts having from 8 to 14 carbon atoms or unsaturated fatty acid metal salts having from 16 to 22 carbon atoms. If the metals in the fatty acid metal salts of this invention are lithium, sodium, potassium, magnesium, calcium, zinc, aluminium, lead and so on, the effect of reducing the frictional force between materials at the lubrication points between the resin and material other than resin is large, and these metals and fatty acids can be reacted easily. The fatty acid salts are also stable chemically and are easy to maintain in the preferred lubrication state. As to the total amount of the aforementioned saturated or unsaturated fatty acids or the one or more aforementioned fatty acid metal salts, it is best to add these in an amount in the range of from 0.1 to 10% relative to the total amount of the grease composition, and preferably they should be used in the range of from

1 to 5% by mass. If they are present in an amount of less than 0.1% by mass, the electrochemical action on the surface is too small, and the effect of reducing the friction coefficient is too low. If the fatty acids or fatty acid metal salts are present in an amount of greater than 10% by mass, it becomes difficult to demonstrate the basic performance of the grease composition (for example, viscoelasticity, shear stability, heat resistance and so on} effectively, and it is likely that it will become difficult to maintain a stable state over the long term. Costs also rise.

Also, it is possible to add as appropriate to the grease composition of this invention anti-oxidants, rust preventatives, oiliness agents, extreme pressure additives, anti™wear agents, solid lubricants, metal deactivators, polymers and other additives.

The anti-oxidants include, for example, 2,6-di-t- butyl-4-methylphenol, 2, 6-di-t-butyl-paracresol, P, P'- _ i n _

dioctyldlphenylamine, N-phenyl-α-naphthylamine, phenothiazines and so on.

The rust preventatives include paraffin oxide, carboxylic acid metal salts, sulphonic acid metal salts, carboxylic acid esters, sulphonic acid esters, salicylic acid esters, succinic acid esters, sorbitan esters and various amine salts.

The oiliness agents, extreme pressure additives and anti-wear agents include, for example, sulphurised zinc dialkyl dithiophosphates, sulphurised zinc diaryl dithiophosphates, sulphurised zinc dialkyl dithiocarbamates, sulphurised zinc diaryl dithiocarbamates, sulphurised molybdenum dialkyl dithiophosphates, sulphurised molybdenum diaryl dithiophosphates, sulphurised molybdenum dialkyl dithiocarbamates, sulphurised molybdenum diaryl dithiocarbamates, organic molybdenum complexes, sulphurised olefins, triphenylphosphates, triphenylphosphorothionates, tricresylphosphates, other phosphate esters and sulphurised fats and oils. The solid lubricants include, for example, molybdenum disulphide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene) , tungsten disulphide, mica, graphite fluoride and so on. The metal deactivators include N,N' -disalicylidene-

1,2-diaminopropane, benzotriazole, benzoirnidazole, benzothiazole, thiadiazole and so on.

Since, in this invention, it is possible to reduce friction and obtain satisfactory performance at lubrication points where rolling and sliding are evident between materials where one of the pair of materials is constituted of resin, one of the paired materials must be a resin, but the part which pairs with this resin can be, in addition to a resin, not only various metallic materials such as iron, copper, aluminium or other metal, or alloys, thereof, but also rubber and glass, or non- polar materials such as ceramics, and so it can be widely used with no special restrictions.

Also, it is possible to any use ordinary plastic or engineering plastic for the aforementioned resin materials, and as examples mention may be made of polyamides, polyacetals, polycarbonates, polyethylene terephthalates, polybutylene terephthalates, polybutylene naphthalates, polyphenylene ethers, polyphenylene sulphide, fluorinated resins, polyacrylates, polyamidimides, polyether imides, polyether ether ketones, polysulphones, polyether sulphones, polyimides, polystyrenes, polyethylenes, polypropylenes, phenol resins, AS resins, ABS resins, AES resins, AAS resins, ACS resins, MBS resins, polyvinyl chloride resins, epoxy resins, diallyl phthalate resins, polyester resins, methacryl resins, and ABS/polycarbonate alloys, but they are not limited to these. Examples

The invention is further explained in detail below by means of examples and comparative examples, but the invention is in no way limited by these examples. The following materials were prepared for the examples and comparative examples.

1. Base oil A: a mineral oil with kinematic viscosity at 40⁰C of 101.1 mmVs.

2. Base oil B: a poly-α-olefin oil with kinematic viscosity at 40⁰C of 31.2 mrnVs.

3. Base oil C: a highly refined oil with kinematic viscosity at 40⁰C of 47.08 mmVs, viscosity index of 146, %CA of less than 1, %CN of 11.9, and %CP of not less than 85.

4. Thickener A: a diurea obtained by a synthesis reaction of 2 mol of octylamine and 1 mol of MDI (4,4'- diphenylmethanediisocyanate) in the base oil.

5. Thickener B: bentonite obtained by gelation after swelling bentonite with an organic solvent in a base oil.

6. Thickener C: obtained by gelation after swelling an hydroxyapatite/tricalcium phosphate composite as expressed by [Ca₃ (PO₄J₂] 3 * Ca(OH)₂ with an organic solvent.

7. Thickener D: sodium terephthalamate obtained by reaction of methyl N-octadecyl terephthalamate and sodium hydroxide in the base oil. The greases were prepared in a kettle using the base oils and thickeners in the proportions shown for Examples 1 to 24 in Tables 1 to 5, and the grease compositions were obtained by adding the various fatty acids and/or fatty acid metal salts. In specific detail, for the greases using thickener

A (a urea) in Examples 1, 3 to 9, 12 to 14, 20 and 23, the base oil, thickener A and the various^' fatty acids or fatty acid metal salts which are the additives were first weighed out in the proportions shown in Tables 1 to 5 so that the total amount of the grease composition would be 1000 g. Then, a portion of the base oil and the MDI (4, 4' -diphenylmethane diisocyanate) of thickener A were pasted into a kettle of capacity 3 kg specially used for preparation of greases. While heating and stirring to raise the temperature to 6O⁰C, a reaction was effected by pasting in the octylamine premixed and dissolved in the rest of the base oil. Once the temperature had further been raised to 180⁰C, cooling was effected at a fixed rate, The aforementioned fatty acids or fatty acid metal salts were pasted in and, after a homogeniser treatment, the grease compositions for use in resin lubrication for each of the examples were obtained. The fatty acid metals salts specified in Tables 3 to

5 were used as obtained by first reacting the fatty acids and metals in accordance with the molar ratios specified in Tables 3 to 5 (and similarly also in the descriptions below} . For the grease compositions using thickener B

(bentonite) in Examples 2, 10, 15 and 17, the base oil, thickener B and the various fatty acids or fatty acid metal salts which are the additives were first weighed out in the proportions shown in Tables 1 to 4 so that the total amount of the composition would be 1000 g. Then, the base oil and the bentonite, and an organic solvent to promote gelation, were pasted into a kettle of capacity 3 kg specially used for preparation of greases. While heating and stirring to raise the temperature gradually to 15O⁰C, and as the organic solvent became volatile it was allowed to diffuse homogeneously to effect swelling. Then cooling was effected at a fixed rate. The aforementioned fatty acids or fatty acid metal salts were pasted in and after homogeniser treatment, the grease compositions for use in resin lubrication for each of the examples were obtained.

For the grease composition using thickener C (tricalcium phosphate) in Example 19, the base oil, thickener C and the fatty acid metal salt which is the additive was first weighed out in the proportions shown in Table 4 so that the total amount of the composition would be 1000 g. Then, the base oil and the tricalcium phosphate, and an organic solvent to promote gelation, were pasted into a kettle of capacity 3 kg specially used for preparation of greases. While heating and stirring to raise the temperature gradually to 150⁰C, and as the organic solvent became volatile it was allowed to diffuse homogeneously to effect swelling. Then cooling was effected at a fixed rate. The aforementioned fatty acid metal salt was pasted in and, after homogeniser treatment, the grease composition for use in resin lubrication for the example was obtained. For the grease composition using thickener D {sodium terephthalamate) in Example 21, the base oil, thickener D and the fatty acid metal salt which is the additive was first weighed out in the proportions shown in Table 5 so that the total amount of the grease composition would be 1000 g. Then, the base oil and the methyl N- octadecylterephthalamate which was the raw material for thickener D were pasted into a kettle of capacity 3 kg specially used for preparation of greases. While heating and stirring, at a temperature of 9O⁰C a sodium hydroxide suspension which had previously been stirred and dispersed in water was folded into the kettle, and a reaction was effected while heating and stirring to raise the temperature gradually to 170⁰C. Then cooling was effected at a fixed rate. The aforementioned fatty acid metal salt was pasted in and, after homogeniser treatment, the grease composition for use in resin lubrication for Example 21 was obtained.

For the grease compositions using mixed thickeners in Examples 11, 16, 18, 22 and 24 greases prepared by the methods for the aforementioned thickeners were mixed at room temperature in the proportions shown in Tables 3 to 5 in a kettle specially used for preparation of greases. The fatty acids or fatty acid metal salts were pasted in and, after homogeniser treatment, the grease compositions for use in resin lubrication for each of the examples were obtained.

For Comparative Examples 1 to 10, the various raw materials were weighed out in accordance with the proportions shown in Tables 6 to 7, and grease compositions were prepared by following the method described for the aforementioned examples.

The following measurements and tests were carried out in order to compare the characteristics and performance of the examples and comparative examples.

1. Penetration: measured in accordance with JIS K2220-7,

2. Dropping point: measured in accordance with JIS K2220-8.

3. Kinematic viscosity of base oils: measured in accordance with JIS K2283.

4. Friction tests: Bowden type friction tests were carried out. In other words, the friction coefficient between a resin (test material Ib) and a paired material other than a resin (test material Ia) was measured under the following test conditions using a Bowden friction test rig.

(1) Test material Ia: Material - Copper alloy ALBC2 and steel S45C.

Dimensions - pin shape of outside diameter 5.0 mm and length 24 mm, the pin tip being a semi-spheroid of r = 2.5 mm, and the contact surface was machined to a flat area of approximately 1.0 mm diameter. (2) Test material Ib: Material - polyacetal resin

(Delrin 500P made by Dupont Ltd.) and polyamide resin (66 Nylon/Amilan made by Toray Ltd.) Dimensions - plate of length 200 mm, width 52 mm.

(3) Temperature: 25°C

(4) Sliding rate: 1.0 mm/s

(5) Load: 870 g (6) Surface pressure of contact surfaces: 10 MPa

A Bowden friction test was carried out on all the examples and on all the comparative examples for a polyamide resin and steel pairing, and tests were carried out selectively for a polyacetal resin and copper alloy pairing.

Test Results

These are as shown in Tables 1 to 7. Discussion

The grease compositions for resin lubrication of Examples 1 to 24 all displayed the grease characteristics of a semi-solid and the penetration displayed moderate hardness values in the range 266 to 297, while the dropping point was also of a satisfactory nature at not less than 260⁰C. Also, the friction coefficients between a polyamide resin and steel in the Bowden friction test were 0.059 to 0.067, and the friction coefficients between a polyacetal resin and copper alloy were uniformly low at 0.058 to 0.064, so that it was evident that a satisfactory lubrication performance was displayed between various resins and materials other than resins such as steel and alloys.

On the other hand, the grease compositions of Comparative Examples 1 to 10 all displayed the grease characteristics of a semi-solid, and the penetration displayed hardness values in the range 269 to 293, while the dropping point was also of a satisfactory nature at not less than 263°C, but the friction coefficients between a polyamide resin and steel in the Bowden friction test were 0.088 to 0.118, and the friction coefficients between a polyacetal resin and copper alloy were uniformly high at 0.096 to 0.121, so that it was evident that they were all inferior to the examples according to the present invention as regards the lubrication state between various resins and materials other than resins such as alloys or steel, and that no effect in improving lubrication performance was obtained. From these results it can be seen that the grease composition for resin lubrication of this invention exhibits satisfactory lubrication performance.

Table 1

Table 1 (continued)

Table 2

Table 2 (continued)

Table 3

Table 3 (continued)

Table 4

Table 4 (continued)

Table 5

Table 5 (continued)

Table 6

Table 6 (continued)

Table 7

Table 7 (continued)

Claims

C L A I M S

1. Grease composition for use in resin lubrication incorporating into a grease base material which includes a base oil and a thickener at least one saturated or unsaturated fatty acid having from 8 to 22 carbon atoms and/or fatty acid metal salt, being a metal salt of a linear saturated fatty acid having from 8 to 14 carbon atoms or a metal salt of an unsaturated fatty acid having from 16 to 22 carbon atoms and from 1 to 4 unsaturated groups, the metal having a valence of from 1 to 4, wherein the thickener excludes said fatty acid metal salts.

2. Grease composition for use in resin lubrication according to Claim 1 wherein the metal of the fatty acid metal salt is lithium, sodium, potassium, magnesium, calcium, zinc, aluminium or lead.

3. Grease composition for use in resin lubrication according to Claim 1 or 2 wherein the total content of the one or more saturated or unsaturated fatty acid and/or fatty acid metal salt is in the range of from 0.1 to 10% by mass relative to the total amount of the grease composition.

4. Grease composition for use in resin lubrication according to Claims 1 to 3 wherein at least one of a urea, bentonite, calcium phosphate or sodium terephthalamate is incorporated as the thickener.