KR20110031482A - Grease composition - Google Patents

Abstract

The present invention relates to a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and / or a straight chain saturated fatty acid metal salt having 8 to 14 carbon atoms or 16 to 22 carbon atoms having 1 to 4 unsaturated groups on a grease base including a base oil and a fatty acid metal salt thickener. A grease composition for use in lubricating resins, which comprises at least one fatty acid metal salt and at least one fatty acid metal salt having a metal valence of 1 to 4 (excluding fatty acid metal salts used in thickeners). The grease composition of the present invention provides satisfactory lubricity between resin and resin or between other materials such as resin and metal.

Description

Grease Composition {GREASE COMPOSITION}

The present invention relates to a grease composition for use in lubricating a resin, which is used at a lubrication point where rolling or sliding occurs when a resin material is used.

In recent years, the use of resin materials for parts in various industrial machines, especially in the automotive industry, has become prominent in many respects, such as light weight, low cost, low friction, or recycling. However, as components of components diversify, many new problems emerge and all kinds of technologies are improving.

For example, sliding parts of telescopic shafts or movable parts of electric door mirrors in car steering, various sliding parts of R & P steering rack guides, electric Power transmission gears of power steering devices, various actuators and internal sliding parts of air cylinders, linear guides and ball screw retainers of machine tools, various bearing retainers, cranes Sliding parts of crane booms, and also resin gear parts of audio equipment such as radio cassette players, videotape recorders and CD players, resin gear parts of office automation equipment such as printers, photocopiers and fax machines, and various electrical switches. There is a lubrication point in the sliding part of which the resin and the resin, or a material other than the resin such as the resin and the metal function in a contact state.

Up to now, almost all components of the machine in the field of lubrication are metallic materials, so the history of research on friction and wear between metals such as iron, aluminum, their alloys, brass and bronze is long and huge, and many technologies Accumulated through this deep experience and knowledge.

For example, extreme pressure agents and antiwear agents containing elements such as phosphorus or sulfur are effective in preventing friction and abrasion between metals, and these additives actively chemically react with metallic surfaces. It is known to form a coating, thus exhibiting functions of reducing friction and wear and preventing failure of the machine. The technique is widely used in engine oils and gear oils and high performance industrial lubricants and greases.

However, despite the fact that the history of lubrication techniques between resins and resins, or between different materials such as resins and metals, is short, their application has expanded in recent years as mentioned above, but in the process of diversification grease At present, there is no technology that can fully satisfy the various demands placed on lubrication.

For example, if a technique using phosphorus or sulfur additives effective in the friction or wear protection in the case between the metal and the metal is applied at the lubrication point of the resin and the metallic material, such friction that can be obtained in fact between the metal and the metal The reduction effect is not obtained. In fact, friction and abrasion resistance are poor and the life of mechanical parts is short.

Considering that the chemical activity of the surface is weaker in the case of resin than the metal, organic additives such as phosphorus or sulfur based additives, the reaction on the rubbing surface is virtually not carried out, and the adsorption is also weak, Since the effect on wear is very small, the friction reducing effect is considered to be weak accordingly. In addition, when they are used at the boundary at which the temperature rise is intentionally carried out, active sulfur and phosphorus in the additive penetrate the resin parts, making cracks or fragile. In addition, reaction friction and wear are sometimes promoted.

In order to improve the lubrication state between the resin and the resin or between different materials such as resins and metals, a mixture of alkylene oxide-polyalcohol-added polymerization oligomers and chained hydrocarbon oligomers in lithium grease is used as the dispersant and the quaternary. Greases for use in lubricating plastics, contained with ammonium salt-containing clay minerals, have been proposed (Japanese Patent H6-43594 (1994)). Also for base oils such as poly-α-olefin oils, mineral oils or highly refined mineral oils and grease compositions for use in lubricating resins containing non-polar or polar waxes with metallic soaps or metallic complex soap thickeners. A technique is disclosed (Japanese Patent Laid-Open No. 2005-54024). Further improvement is expected.

In the present invention, the friction is weakened and satisfactory lubrication performance is achieved by lubricating points (where rolling and sliding, etc. occur, and at least one of the paired structures such as between resin and resin or between different materials such as resin and metal is resinous). Obtained from a material), to obtain a grease composition for use in lubricating the resin.

Inventors who have conducted research and investigations based on surface chemistry theory of the lubrication behavior of resins in the past have developed extremely weak charges at the surface between materials paired with resins, such as between resins and resins or between different materials such as resins and metals. Interacting with certain saturated or unsaturated fatty acids and fatty acid metal salts added to the grease, and in addition these additives act as a binder with the grease to more reliably form a lubricating film on the surface of the resin or resin or paired material. The present invention has been reached by discovering that friction can be reduced and consequently reduced friction and satisfactory lubrication can be obtained.

Summary of the Invention

The present invention relates to a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and / or a straight chain saturated fatty acid metal salt having 8 to 14 carbon atoms or 16 to 22 carbon atoms having 1 to 4 unsaturated groups on a grease base including a base oil and a fatty acid metal salt thickener. A grease composition for use in lubricating resins, which comprises at least one fatty acid metal salt and at least one fatty acid metal salt having a metal valence of 1 to 4 (excluding fatty acid metal salts used in thickeners).

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

The total amount of saturated or unsaturated fatty acids and / or fatty acid metal salts used is preferably on the order of 0.1 to 10% by mass. In addition, it is possible to use other types of thickeners, such as urea, bentonite, calcium phosphate or sodium terephthalamate, alone or in combination with fatty acid metal salt thickeners.

Friction is reduced according to the invention, which makes it possible to obtain satisfactory lubrication performance at lubrication points, such as rolling and sliding points between parts made of one resinous material and the other, and are widely used as grease compositions for use in lubricating resins. It is possible to use it.

Detailed description of the invention

The base oil of this invention can be used normally as a base oil of lubricating oil, or base oil of grease, and there is no special limitation. Examples include mineral oils, synthetic oils, animal oils and vegetable oils, and mixtures thereof.

In particular, it is possible to use base oils belonging to the Group (I), Group II, Group III, Group IV, etc. of the API (American Petroleum Institute) base oil category alone or in mixture.

Group I base oils include, for example, paraffin mineral oils obtained by appropriate combinations of purification processes such as solvent purification, hydrorefining, and dewaxing on lubricating oil fractions obtained by atmospheric distillation of crude oil. .

Group II base oils include, for example, paraffin mineral oils obtained by appropriate combinations of purification processes such as hydrorefining and dewaxing for lubricating oil fractions obtained by atmospheric distillation of crude oil. Group II base oils purified by a hydrorefining method such as the Gulf method have a total sulfur content of less than 10 ppm and an aromatic content of 5% or less and are suitable for the present invention.

Group III base oils and Group II + base oils are used in the Isodewax process, which dewaxes and substitutes waxes produced by the waxing process of paraffin mineral oil, isoparaffin, prepared by highly hydrorefining of lubricating oil fractions obtained by atmospheric distillation of crude oil. Base oils purified by, and base oils purified by the Mobil wax isomerisation process. These are also suitable for use in the present invention.

Specific 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 ester Or pentaerythritol esters, perfluoroalkyl ethers, silicone oils, polyphenyl ethers, and the like.

The polyolefin includes polymers of various olefins or hydrides thereof. Any olefin can be used, and examples include ethylene, propylene, butene and α-olefins having 5 or more carbon atoms. In preparing the polyolefin, one of the above olefins may be used alone, or two or more thereof may be used in combination. Particularly suitable are polyolefins called poly-α-olefins (PAO). This is the base oil of group IV.

GTL (gas to liquid) base oil synthesized by Fischer-Tropsch method of converting natural gas into liquid fuel has very low sulfur and aromatic content and very high paraffin content compared to mineral oil refined from crude oil, resulting in excellent oxidation stability. They are also suitable as base oils in the present invention because they have extremely low evaporation losses.

Typical examples of animal oils and vegetable oils include castor oil and rapeseed oil.

Various such oils may be used alone or in mixtures for base oils. The above examples are presented alone, but the present invention is not limited thereto.

Thickeners of the present invention use fatty acid metal salts. The fatty acid metal salt is a combination of fatty acid and metal, which is usually called metallic soap. Illustrative examples of the description include lithium soap, sodium soap, potassium soap, magnesium soap, calcium soap, barium soap, aluminum soap, zinc soap, lead soap, and complex soaps therefrom. These may be used alone or in mixtures thereof.

In particular, in addition to fatty acid metal salt thickeners, it is also possible to suitably use other thickeners such as bentonite, clay, silica, tricalcium phosphate, calcium sulfonate complexes, urea and sodium terephthalamate in combination.

The additives added to the grease base including the base oil and the thickener include saturated or unsaturated fatty acids having 8 to 22 carbon atoms and / or straight chain saturated fatty acid metal salts having 8 to 14 carbon atoms or unsaturated fatty acids having 16 to 22 carbon atoms having 1 to 4 unsaturated groups. Fatty acid metal salts with the metal valence of 1 to 4, excluding fatty acid metal salts used in thickeners.

As examples of fatty acids which form starting materials of the saturated or unsaturated fatty acids and fatty acid metal salts in the present invention, caprylic acid, perargonic acid, capric acid, lauric acid, linderic acid, myristic acid, tzuzuic acid, and pisetol Leic acid, myristoleic acid, pentadecyl acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, 12-hydroxystearic acid, petroleic acid, oleic acid, elideic acid, bacenic acid, linoleic acid, linolenic acid, ellanic acid Eostearic acid, tuberculostearic acid, arachidic acid, eicosadienoic acid, eicosatieric acid, arachidonic acid, behenic acid, lignoseric acid, nerbonic acid, hexadocoic acid, octadocoic acid and e Luc acid is mentioned.

The saturated or unsaturated fatty acids of the present invention are preferably fatty acids having 8 to 22 carbon atoms, and in the case of fatty acid metal salts, preferably linear saturated fatty acid salts having 8 to 14 carbon atoms or unsaturated fatty acid metal salts having 16 to 22 carbon atoms.

When the metal in the fatty acid metal salt of the present invention is lithium, sodium, potassium, magnesium, calcium, zinc, aluminum, lead or the like, the effect of reducing friction between materials at the lubrication point between the resin and the non-resin material is large, and these metals and Fatty acids can react easily. Fatty acid salts are also chemically stable and easy to maintain in the desired lubrication state.

With respect to the total amount of saturated or unsaturated fatty acids or at least one fatty acid metal salt, it is best to add them in an amount in the range of 0.1 to 10% relative to the total amount of the grease composition, preferably they should be used in the range of 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 small. When they are present in an amount of more than 10% by mass, it becomes difficult to effectively exhibit the basic performance (eg, viscoelasticity, shear stability, heat resistance, etc.) of the grease composition, and it is likely to be difficult to maintain a stable state in the long term. The cost also goes up.

It is also possible to appropriately add antioxidants, rust inhibitors, oiliness agents, extreme pressure additives, antiwear agents, solid lubricants, metal deactivators, polymers and other additives to the grease composition of the present invention.

Antioxidants are for example 2,6-di-t-butyl-4-methylphenol, 2, 6-di-t-butyl-paracresol, P, P'-dioctyldiphenylamine, N-phenyl-α Naphthylamine, phenothiazine, and the like.

Rust inhibitors include paraffin oxides, carboxylic acid metal salts, sulfonic acid metal salts, carboxylic acid esters, sulfonic acid esters, salicylic acid esters, succinic acid esters, sorbitan esters and various amine salts.

Oily agents, extreme pressure additives and antiwear agents are, for example, zinc sulfide dialkyl dithiophosphates, zinc sulfide diaryl dithiophosphates, zinc sulfide dialkyl dithiocarbamates, zinc sulfide diaryl dithiocarbamates, sulfides Molybdenum dialkyl dithiophosphate, molybdenum sulfide diaryl dithiophosphate, molybdenum sulfide dialkyl dithiocarbamate, molybdenum sulfide diaryl dithiocarbamate, organic molybdenum complex, sulfide olefin, triphenylphosphate, triphenylphosphoro Thionate, tricresylphosphate, other phosphate esters and sulfided fats and oils.

Solid lubricants include, for example, molybdenum disulfide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene), tungsten disulfide, mica, graphite fluoride and the like.

Metal deactivators include N, N'-disalicylidene-1, 2-diaminopropane, benzotriazole, benzoimidazole, benzothiazole, thiadiazole and the like.

In the present invention, one of the paired materials must be a resin, because it is possible to reduce the friction so that one of the pair of materials can achieve satisfactory performance at the point of lubrication where rolling and sliding between the materials made of the resin are obvious. The portion to be paired with the resin may be rubber and glass, or nonpolar materials such as ceramics, etc. as well as various metallic materials such as iron, copper, aluminum or other metals or alloys thereof in addition to the resin, which may be widely used without particular limitation. Can be.

It is also possible to arbitrarily use ordinary plastics or engineering plastics for the above resin materials, and for example, polyamide, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polybutylene naphthalate, poly Phenylene ether, polyphenylene sulfide, fluorinated resin, polyacrylate, polyamideimide, polyether imide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polystyrene, polyethylene, polypropylene, phenolic resin , AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, polyvinyl chloride resin, epoxy resin, diallyl phthalate resin, polyester resin, methacryl resin, and ABS / polycarbonate alloy Although it can do it, it is not limited to this.

Example

Although the present invention is described in detail below by way of examples and comparative examples, the present invention is not limited by the above examples.

The following materials were prepared for the examples and comparative examples.

1. Base oil A: Mineral oil having a dynamic viscosity of 101.1 mm ² / s at 40 ° C.

2. Base oil B: Poly-α-olefin oil having a dynamic viscosity of 31.2 mm ² / s at 40 ° C.

3. Base oil C: Highly refined oil having a kinematic viscosity of 47.08 mm ² / s at 40 ° C., a viscosity index of 146,% CA of less than 1,% CN of 11.9, and% CP of 85 or more.

4. Thickener A: Lithium 12-hydroxystearate soap obtained by reaction of 12-hydroxystearic acid with lithium hydroxide in base oil.

5. Thickener B: Diurea obtained by the synthesis reaction of 2 mol octylamine in base oil and 1 mol of MDI (4,4'-diphenylmethane diisocyanate).

6. Thickener C: Bentonite obtained by gelation after expansion of bentonite with an organic solvent in base oil.

7. Thickener D: Sodium terephthalamate obtained by reaction of methyl N-octadecyl terephthalamate with sodium hydroxide in base oil.

8. Thickener E: Obtained by gelation of a hydroxyapatite / tricalcium phosphate composite represented by [Ca ₃ (PO ₄ ) ₂ ] ₃ Ca (OH) ₂ with an organic solvent.

Grease was prepared in a kettle using the base oils and thickeners in the proportions shown in Examples 1-13 of Tables 1-3, and the grease composition was obtained by adding various fatty acids and / or fatty acid metal salts.

Specifically, in the case of the grease using the thickener A (lithium soap) of Examples 1 to 8, various fatty acids or fatty acid metal salts as base oils, thickeners and additives are shown in Tables 1 to 2 so that the total amount of the grease composition is 1000 g. It was first weighed in proportion. Subsequently, base oil and 12-hydroxystearic acid and lithium hydroxide were attached together with a small amount of water to a kettle of a capacity of 3 kg dedicated to grease production. After sealing, the saponification reaction was carried out with heating and stirring and the pressure was raised to approximately 0.35 MPa at approximately 150 ° C. Thereafter, water was gradually removed and the contents were dissolved by further heating to 215 ° C. Thereafter, cooling is carried out at a constant rate, the soap fibers are grown, and then the additives, fatty acids or fatty acid metal salts are added and homogenizers are used, followed by lubrication of the resin in each of Examples 1 to 8. A grease composition was obtained.

The fatty acid metal salts shown in Tables 1 to 3 were used as obtained by first reacting the fatty acids with the metals according to the molar ratios shown in Tables 1 to 3 (similar also in the comparative examples of Table 4 below).

For greases using thickeners A (lithium soap) with other thickeners B-E in Examples 9-13 of Tables 2 and 3, greases prepared as described below using thickeners B-E were specially prepared, and Table 2 And in a kettle dedicated to grease preparation at room temperature in the proportions indicated for thickeners in 3 and 3. After attaching various fatty acids and fatty acid metal salts, and after homogenizing treatment, in each of Examples 9-13, a grease composition for use in lubricating the resin was obtained.

In the case of grease using thickener B (urea), the base oil, the thickener B and the various fatty acids or fatty acid metal salts, which were base oils, thickeners B and additives, were first weighed in the proportions shown in Tables 2 and 3 so that the total amount of the grease composition was 1000 g. Then, MDI (4,4'- diphenylmethane diisocyanate) which is a part of base oil and the raw material of thickener B was stuck to the kettle of 3 kg of volumes exclusively for grease manufacture. With heating and stirring, the temperature was raised to 60 ° C. and reacted by adding octylamine already dissolved and mixed to the remainder of the base oil. The temperature was further raised to 180 ° C., then cooled at a constant rate, the various fatty acids or fatty acid metal salts were added and the grease composition was obtained after homogenizing treatment.

In the case of grease using thickener C (bentonite), the base oil, the thickener C and the various fatty acids or fatty acid metal salts as base oils were first weighed in the proportions shown in Table 3 so that the total amount of the grease composition was 1000 g. Thereafter, base oil, thickener C which is bentonite, and an organic solvent for promoting gelation were attached to a kettle having a capacity of 3 kg dedicated to grease production. While heating and stirring, the temperature was gradually raised to 150 ° C. to facilitate evaporation of the organic solvent sufficiently, resulting in homogeneous diffusion and expansion. Thereafter, the mixture was cooled at a constant rate, the various fatty acids or fatty acid metal salts were added thereto, and a grease composition was obtained after homogenizing treatment.

In the case of grease using thickener D (sodium terephthalamate), the base oil, the thickener D and the various fatty acids or fatty acid metal salts as base oils were first weighed in the proportions given in Table 3 so that the total amount of the grease composition was 1000 g. Thereafter, methyl N-octadecyl terephthalate, which is a raw material of the base oil and the thickener D, was attached to a kettle having a capacity of 3 kg exclusively for grease production. Under heating and stirring, a suspension of sodium hydroxide already stirred and dispersed in water was added to the kettle at a temperature of 90 ° C. and reacted with heating and stirring slowly until the temperature reached 170 ° C. Thereafter, the mixture was cooled at a constant rate, the fatty acid metal salt was added thereto, and a grease composition was obtained after the homogenizing treatment.

In the case of grease using thickener E (tricalcium phosphate), the base oil, the thickener E and various fatty acids or fatty acid metal salts, which are base oils, thickener E and additives, were first weighed in the proportions shown in Table 3 so that the total amount of the grease composition was 1000 g. Thereafter, base oil, tricalcium phosphate, and an organic solvent for promoting gelation were attached to a kettle of a capacity of 3 kg dedicated to grease production. While heating and stirring, the temperature was gradually raised to 150 ° C. to facilitate evaporation of the organic solvent sufficiently to allow for homogeneous diffusion and expansion. Thereafter, the mixture was cooled to a constant temperature, the fatty acid metal salt was added thereto, and a grease composition was obtained after the homogenizing agent treatment.

In Comparative Examples 1-6, various raw materials were weighed according to the ratios shown in Table 4, and the grease composition was prepared following the method described in the above examples.

The following measurements and tests were conducted to compare the features and performance of the Examples with Comparative Examples.

1.Penetration: measured according to JIS K2220-7,

2. Dropping point: measured according to JIS K2220-8.

3. Dynamic viscosity of base oil: measured according to JIS K2283.

4. Friction test: Bowden type friction test was performed. In other words, the coefficient of friction between the resin (test material 1b) and the paired material (test material 1a) other than the resin was measured using a Bowden friction test apparatus under the following test conditions.

(1) test material 1a:

Material-Copper Alloy

ALBC2 and steel S45C.

Size-Fin shape with outer diameter 5.0 mm and length 24 mm, pin tip is semi-spheroid with r = 2.5 mm, and contact surface was machined into planar area approximately 1.0 mm diameter.

(2) test material 1b:

Material-Polyacetal Resin

(Dupont Ltd.Delrin 500P)

And polyamide resins (Toray Ltd. 66 Nylon / Amilan)

Size-plate 200 mm long and 52 mm wide.

(3) temperature: 25 ℃

(4) sliding speed: 1.0 mm / s

(5) Load: 870 g

(6) Surface pressure of contact surface: 10 MPa

Bowden friction tests on polyamide resin and steel pairs were performed in all examples and all comparative examples, and tests on polyacetal resin and copper alloy pairs were optionally performed.

Test results

This is shown in Tables 1-4.

debate

The grease compositions for lubricating the resins of Examples 1 to 13 all exhibited semisolid grease characteristics, while the lead exhibited moderate hardness values ranging from 267 to 290, while the dropping point also exhibited satisfactory properties above 177 to 210 ° C. Had Also, in the Bowden friction test, the coefficient of friction between polyamide resin and steel was 0.060 to 0.069, and the coefficient of friction between polyacetal resin and copper alloy was uniformly low, ranging from 0.062 to 0.066, resulting in various resins and materials other than resins such as steel and alloys. It was clear that satisfactory lubrication performance was shown.

On the other hand, the grease compositions of Comparative Examples 1 to 6 all exhibited semi-solid grease characteristics, while the lead showed hardness values in the range of 265 to 281, while the dropping point also had satisfactory properties of 180 to 207 ° C., but Bowden friction In the test, the coefficients of friction between the polyamide resin and the steel were 0.082 to 0.099, and the coefficients of friction between the polyacetal resin and the copper alloy were both 0.099 or 0.101, so that the lubrication state between various resins and materials other than resins such as alloys or steels was high. It was clear that all were inferior to the embodiments of the present invention and had no effect in improving the lubrication performance.

From the above results, it can be seen that the grease composition for resin lubrication of the present invention exhibits satisfactory lubrication performance.

Claims (4)

A grease base comprising a base oil and a fatty acid metal salt thickener, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and / or a straight saturated fatty acid metal salt having 8 to 14 carbon atoms or 16 to 22 carbon atoms having 1 to 4 unsaturated groups. A grease composition for use in lubricating a resin, comprising at least one fatty acid metal salt of an unsaturated fatty acid metal salt having a valence of 1 to 4 (excluding fatty acid metal salts used in thickeners). The grease composition according to claim 1, wherein the metal of the fatty acid metal salt is lithium, sodium, potassium, magnesium, calcium, zinc, aluminum or lead. The grease composition according to claim 1 or 2, wherein the total content of at least one saturated or unsaturated fatty acid and / or fatty acid metal salt is in the range of 0.1 to 10% by mass relative to the total amount of the grease composition. The grease composition according to any one of claims 1 to 3, wherein at least one of urea, bentonite, calcium phosphate or sodium terephthalamate is included as a thickener with the fatty acid metal salt thickener.