JPH05125379A - Lubricant - Google Patents

Abstract

PURPOSE:To obtain a lubricant containing a specific amount of an intercalation compound consisting of a metal phosphorus chalcogenide and alkylamines, etc., reduced in cost because of simplified constitution and excellent in extreme- pressure property and resistance to burning action and abrasion resistance without requiring any thickener. CONSTITUTION:One or more kinds of intercalation compounds consisting of a metal phosphorus chalcogenide prepared by reacting a metal with phosphorus and a chalcogen element or a metal sulfide with phosphorus and the chalcogen element while heating and expressed by the formula MPX3 (M is Mg, Ca, V, Mn, Fe, Co, Ni, Pb, Zn, Cd, Hg, Sn or Nb; X is S, Se or Te) (e.g. ZnPS3) and alkylamine, aromatic amine, pyridine or alkylammonium chloride (e.g. octylamine) are blended with a petroleum based lubricating oil, etc., at an amount of >=0.1wt.% to provide the objective lubricant, excellent in extreme- pressure property, resistance to burning action and abrasion resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricant composition containing a metal phosphorus chalcogenide which is a crystal powder having a layered structure or an intercalation compound of the metal phosphorus chalcogenide, wherein the metal phosphorus chalcogenide is a host. The present invention relates to a solid lubricant having excellent extreme pressure properties, which comprises an intercalation compound in which a guest is an alkylamine, aromatic amine, pyridine or alkylammonium chloride, and extreme pressure lubrication in which the solid lubricant is dispersed. It relates to oil and extreme pressure grease.

[0002]

Lubricants are present between two solid surfaces that are in relative motion to reduce friction and wear on these solid surfaces, reduce power loss, and prevent seizure and fatigue damage. It is a generic term for substances having chemical properties, and is classified into liquid lubricants, semi-solid lubricants, and solid lubricants according to their forms. Liquid lubricants are petroleum-based lubricants (mineral oils), synthetic lubricants, etc., semi-solid lubricants are greases, compounds, etc., and solid lubricants are graphite, layered crystal powders such as molybdenum disulfide, etc. is there.

The functions of these lubricants are considered as follows. (1) Cooling action, (2) Sealing action, (3) Rust preventive action, (4)
Anti-seizure action, (5) Anti-friction action. Among these functions, (5) the anti-friction function is the most important purpose of the lubricant, and it possesses both liquid, semi-solid and solid lubricants.
However, liquid lubricants (1) have excellent cooling action, but (2) have poor sealing action, and (3) have rust prevention action.
(4) Although the seizure resistance is poor, these can be reinforced with additives. Semi-solid lubricants have excellent (1) cooling effect, but (2) sealing effect and (3) rust preventive effect. Also, (4) seizure resistance is poor, but additives can be added for reinforcement.

A solid lubricant is a liquid lubricant or a semi-solid lubricant because it is poor in (1) cooling action, (2) sealing action, (3) rust preventive action, and (4) seizure resistance action as a single powder. In addition, it is common to combine and add the advantages of these lubricants. In other words, it is the current situation that it is reinforced by the addition of extreme pressure additives.

On the other hand, it is preferable that the number of components of the lubricant composition is as small as possible in order to simplify the manufacturing process, material management, and cost reduction. The use of extreme pressure lubricating oils such as ester oils and extreme pressure thickeners such as chlorinated fatty acid metal soaps was also investigated, but the former has the property of swelling rubber materials such as packing, and rust preventive property due to the inclusion of water. The nature of
In addition, it has a drawback that it is expensive and the latter has a drawback that it has a poor ability to increase and has not been widely used.

[0006] Conventionally used solid lubricants are crystalline powders having a layered structure such as graphite and molybdenum disulfide, and the effect of slipping between the interlayer portions having a small shear strength for lubrication Is what is expected. Mica and bentonite also have the same layered structure. Further, intercalation compounds, which are reaction products of other molecules, atoms, ions, etc. (guests) entering these interlayer portions and reacting with the crystal layer (host layer), have been conventionally used as lubricants.

For example, fluorinated graphite, which is a product of fluorine invading and reacting between graphite layers, is used as a solid lubricant, and organized bentonite in which a quaternary ammonium salt or the like is reacted between bentonite layers is used as a thickener for grease. It is used.

However, all of these materials have an anti-friction effect due to slip between layers, and sulfur as is the case with sulfur-based extreme pressure additives and sulfur-phosphorus-based extreme pressure additives reacts with local friction. An iron sulfide film having a melting point of about 1000 ° C is formed to prevent metal contact, or to add a function to form a low melting point eutectic of iron phosphide and iron to smooth the friction surface. Such extreme pressure action is completely unexpected.

[0009]

The object of the present invention is to develop a solid lubricant having excellent extreme pressure properties, seizure resistance and wear resistance, thereby simplifying the structure of the lubricant composition and reducing the cost. Especially.

[0010]

[Means for Solving the Problems] A metal phosphorus chalcogenide has chalcogen elements such as sulfur (S), selenium (Se), and tellurium (Te) in its molecule, and also phosphorus (P). ,
It also contains metallic elements such as Pb. It was also found that this substance becomes a crystal having a layered structure, and that this substance is a solid lubricant excellent in extreme pressure properties and seizure resistance. Further, various guests can be inserted (intercalated) between layers in the metal phosphorus chalcogenide to form an intercalation compound. Although the experiment was repeated by using various guests focusing on this matter, the intercalation compound crystal powder itself was most likely to be used when the alkylamine, aromatic amine, pyridine or quaternary alkylammonium salt was used. Excellent extreme pressure resistance and seizure resistance were recognized, and it was found that the effect as a solid lubricant having excellent extreme pressure characteristics was remarkable.

Next, further research was conducted, and when the intercalation compound was dispersed in the lubricating oil, it was also found that it has an excellent thickening effect depending on the kind of the organic substance of the guest.

Here, a multipurpose substance which is a solid lubricant excellent in extreme pressure property and also serves as a thickener is obtained by the intercalation compound of the present invention, and the present invention is completed thereby.

Therefore, the metal phosphochalcogenide which is a layered crystal of the present invention or its intercalation compound can be used as a powder as a solid lubricant having an excellent extreme pressure property. For some intercalation compounds, it can be increased by dispersing it in a lubricating oil. An extreme pressure grease can be obtained by stirring, and it has excellent extreme pressure properties and can exhibit an anti-seizure action without adding an extreme pressure additive.

That is, in the present invention, 0.1 weight of one or more of the intercalation compounds in which the metal phosphorus chalcogenide or the host layer is the metal phosphorus chalcogenide and the guest is an alkylamine, aromatic amine, pyridine or alkylammonium chloride is used. % Of the lubricant composition. When the content of each of the metal phosphorus chalcogenide and the above-mentioned intercalation compound is less than 0.1% by weight, no remarkable effect of improving lubricity is exhibited, and the content of 100
There is no upper limit because weight%, that is, both the metal phosphorus chalcogenide and the intercalation compound can be used as a powdery solid lubricant even if they are simple substances.

The metal phosphorus chalcogenide used in the present invention is a compound represented by the molecular formula (1) and is prepared by heating and reacting metal and phosphorus with a chalcogen element, or a metal sulfide, phosphorus and a chalcogen element by a known method. It can be manufactured. MPX ₃ ----- (1) M in the molecular formula represents a metal element, Mg, Ca, V, Mn, Fe, C
O, Ni, Pb, Zn, Cd, Hg, Sn, Nb can be used, and X represents a chalcogen element, and S, Se, or Te can be used.

Therefore, specific examples of the metal phosphorus chalcogenide include ZnPS _3, ZnPSe ₃ , ZnPTe ₃ , NiPS _3, FePSe ₃ , MnPS ₃ ,
MgPS ₃ , MgPSe ₃ etc. can be mentioned. All of these have a layered crystal structure, and a guest penetrates between layers to form an intercalation compound.

The alkylamine used as a guest of the intercalation compound in the present invention is a compound represented by the molecular formula (2)

[Chemical 1] R ₁ , R ₂ and R ₃ represent a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms.

Specifically, n-butylamine, octylamine, 2-octylamine, dodecylamine, hexadecylamine, octadecylamine, oleylamine, N
-Methyloctadecylamine, N, N-dimethyldioctadecylamine and the like can be mentioned. Examples of aromatic amines include aniline, p-dodecylaniline, N-ethylene-toluidine and the like. In addition, pyridine, which is a nitrogen-containing heterocyclic compound, can be used.

The alkyl ammonium chloride used in the intercalation compound in the present invention is a compound represented by the molecular formula (3):

[Chemical 2] Two of R ₄ , R ₅ , R ₆ and R ₇ are methyl groups or have 4 carbon atoms
~ 24 straight or branched chain alkyl groups, the remaining two are methyl groups.

Specific examples include trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dioctadecyl ammonium chloride and the like.

The intercalation compound used in the present invention is (1) substance
It can be obtained by contacting and reacting (2) substance or (3) substance,
Although it is not necessary to specify the manufacturing method in particular, if one example is given, the substance (2) or substance (3) heated and vaporized under reduced pressure is used as (1).
Gas-phase reaction method in which substances are brought into contact with each other to react, mixing method in which both are directly mixed and stirred and heated if necessary, pressurization method in which both are mixed and pressurized and heated if necessary, (2) substance or (3)
There is a solvent method, etc. in which a substance is dissolved in water or an organic solvent and the solution is brought into contact with the substance to react (1) Insert a low molecular weight alkylamine, specifically n-butylamine, into the substance. In addition, an alkylamine, aromatic amine, pyridine, or ammonium chloride having a larger molecular weight is dissolved in a suitable solvent, and the n-butylamine intercalation compound prepared in advance is added to the solution to obtain a larger molecular weight. Alkyl amines, aromatic amines, pyridines, alkyl ammonium chlorides, etc. can be intercalated in the (1) substance.

Although any of these methods can be used, when a substance such as an amine or an ammonium compound which is easily deteriorated by heating and hardly vaporized is used as a guest to prevent the solvent from adsorbing and adversely affecting it, It is preferable to use a mixing method or a pressure method without heating. The reaction amount of (2) substance or (3) substance with respect to (1) substance is about 0.1 in molar ratio.
Is in the range of up to 5 mol.

[0023]

[Function] Both the metal phosphorus chalcogenide and the intercalation compound obtained therefrom are in the form of powder and are used as they are as a solid lubricant to be supplied to the lubrication surface as well as added to lubricating oils and greases. It is used as a pressure lubricating oil and extreme pressure grease and exhibits excellent effects.

The metal phosphorus chalcogenide and the intercalation compound of the present invention have a layered structure in which thin crystal layers are repeatedly piled up as described above. Particularly, in the intercalation compound, a long chain alkyl is formed between the host layers of (1). The guest substance (2), which has a group, an allyl group, an alkylallyl group, etc., and has a polar group and an ionic group and has excellent lubricity and reactivity, penetrates and reacts with the host layer to form a strong bond. , The interlayer distance is widened and the layers are extremely slippery.

Therefore, in particular, the intercalation compound is excellent in the lubrication action due to the slippage between the layers, and in addition, the metal phosphorus chalcogenide used as the host layer in the present invention is known to be effective as an extreme pressure agent. It contains a large amount of a combination of sulfur, selenium and tellurium. Zinc (Zn) and lead (P
b), tin (Sn) magnesium (Mg) is combined to form a metal phosphorus chalcogenide, so it has excellent extreme pressure properties.In addition, an intercalation compound obtained by reacting an amine having a long-chain alkyl group between layers is itself excellent. Extreme pressure lubricant. Therefore, the inter-layer compound lubricant of the present invention, which is such an extreme pressure lubricant and also has excellent sliding friction characteristics, can be said to be the most ideal lubricant. Further, according to the research conducted by the present inventors, it was found that the intercalation compound in this range is excellent in the effect of thickening the lubricating oil. Therefore, the grease using this intercalation compound as a thickener, unlike the ordinary extreme pressure grease, also acts as an extreme pressure additive, so it becomes an excellent extreme pressure grease without adding an extreme pressure additive. It is a thing.

When the intercalation compound of the present invention is used in combination with an oiliness improver such as acetylated fats and oils and fatty acid amides, the former extreme pressure lubricity, inter-layer sliding lubricity and the latter oiliness are combined to achieve wider lubrication conditions. You will be able to adapt. In this case, a soft acetylated oil and fat having a low melting point and a fatty acid amide having a higher melting point and a higher hardness than the former are suitable for lubrication under lighter conditions. Therefore, if both are used in combination with an intercalation compound, they can be adapted for the widest lubrication condition.

[0027]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.

1. Synthesis of Metal Phosphorus Chalcogenide The synthesis of the metal phosphorus chalcogenide having the composition of Examples 1a to 4b in Table 1 was performed as follows.

(1) Synthesis of ZnPS ₃ of Examples 1a and 1b Commercially available zinc sulfide, red phosphorus and powdered sulfur were mixed in a prescribed molar ratio and heated and synthesized in a sealed tube. That is, Were weighed and rubbed well in a mortar. After the mixture was put into a glass tube having one end sealed, the open portion of the glass tube was connected to a suction tube of a vacuum pump to evacuate the inside of the glass tube. The open part of the glass tube was then melted with a gas burner and sealed. This sealed glass tube was placed in a horizontal tubular furnace and gradually heated at 450 ° C ± 5 ° C for 1 week,
A pale tan product was obtained. This product was ground in a mortar and the crystal structure was examined by X-ray diffraction to obtain ZnPS ₃ having a layered crystal structure having a unique diffraction peak with an interlayer distance of 6.46Å.

(2) Synthesis of MgPS ₃ of Examples 2a and 2b Magnesium powder (reagent), red phosphorus, and powdered sulfur were mixed in the following ratio, and heat-synthesized in a sealed tube in the same manner as in (1). ..
However, the glass tube in item (1) is a quartz tube and the heating temperature is 800 ±
It was set to 5 ° C. Molar ratio Magnesium powder (reagent) 1.61 parts by weight --- 1 Red phosphorus 2.04 parts by weight --- 1 Powdered sulfur 6.35 parts by weight --- 3 From the X-ray diffraction diagram of the obtained product, the interlayer distance is 6.75Å MgPS ₃ with a unique diffraction peak was obtained.

(3) Synthesis of CaPS ₃ of Examples 3a and 3b Calcium sulfide (reagent), red phosphorus and powdered sulfur were mixed in the following ratios, and heat-synthesized in a sealed tube in the same manner as in (1). .. However, the glass tube in (1) is a quartz tube and the heating temperature is 750 ± 5.
℃ was made. Molar ratio Calcium sulfide (reagent) 4.31 parts by weight --- 1 Red phosphorus 1.85 parts by weight --- 1 Powdered sulfur 3.83 parts by weight --- 2 From the X-ray diffraction pattern of the obtained product, the peculiarity of the interlayer distance is 6.00Å CaPS ₃ with a diffraction peak of was obtained.

(4) Synthesis of Zn _0.7 Ca _0.3 PS ₃ of Examples 4a and 4b Zinc sulfide, calcium sulfide, red phosphorus and powdered sulfur were mixed in the following ratios, and sealed in a sealed tube by the same operation as (1). Was heated and synthesized.
However, the glass tube in (1) is a quartz tube and the heating temperature is 750 ±
It was set to 5 ° C. Molar ratio Commercially available zinc sulfide 3.68 parts by weight -0.7 Calcium sulfide (reagent) 1.17 parts by weight --- 0.3 Red phosphorus 1.61 parts by weight --- 1 Powdered sulfur 3.48 parts by weight --- 2 X-ray of the product obtained As for the diffraction pattern, Zn _0.7 Ca _0.3 PS ₃ with an interlayer distance of 6.46 Å was obtained with a diffraction peak similar to ZnPS ₃ .

2. Preparation of Intercalation Compound Intercalation compounds having the compositions of Examples 5 to 9 in Table 2 were prepared as follows. Example 5: ZnPS ₃ and n-butylamine were mixed at a molar ratio of 1: 2.5 and ground in a mortar to make a uniform sample. Example 6: ZnPS ₃ and octylamine were mixed at a molar ratio of 1: 1.5 and ground in a mortar to make a uniform sample. Example 7: a hardened beef tallow amine (main component octadecylamine) in ethyl alcohol, ZnPS _3: molar ratio of octadecyl amine 1 were dissolved in an amount corresponding to 0.3, prepared in Example 5 in the solution sample Was mixed, allowed to stand for a whole day and night, filtered, washed, dried, and then ground in a mortar to make a uniform sample. Example 8: N, N dimethyldioctadecyl ammonium chloride was dissolved in isopropyl alcohol in an amount corresponding to a molar ratio with ZnPS ₃ of 1: 0.2, and the sample prepared in Example 5 was mixed in this solution and left standing overnight. After that, it was filtered, washed, dried, and then ground in a mortar to give a sample. Example 9: An amount of p-dodecylaniline corresponding to ZnPS ₃ in a molar ratio of 1: 0.5 was dissolved in an ethyl alcohol solution, and the sample of Example 5 was mixed in this solution, and the mixture was allowed to stand overnight and filtered and washed. After drying, the sample was ground in a mortar and homogenized.

3. Extreme Pressure Test and Abrasion Resistance Test 3.1 Extreme Pressure Test Fale specified in ASTM D 2625 B method for each sample
The seizure load was measured by the x method and the effects were compared.

3.2 Abrasion Resistance Test For each sample, the effects were compared by using a SRV vibration wear tester (manufactured by Optimol, Germany) and measuring the coefficient of dynamic friction and the depth of the wear mark of the test piece. This testing machine
Combination of various metals or synthetic resins (metal / metal, metal / synthetic resin, synthetic resin / synthetic resin) and friction condition with or without lubricant can be reproduced by vibration sliding motion under high load. it can.

The device is shown in FIG. A fixed sample support 10 is connected to a test piece fixing holder 3 which is a movable compatible holder via upper and lower test pieces (5, 9).
These two are crimped by an electronically controlled loading device.
The vibration generated by the moving coil is transmitted to the test piece fixing holder 3. By selecting the test piece 9, it is possible to perform a friction test by various contacts such as a point contact test, a surface contact test, and a line contact test. Here, a point contact test was conducted. Evaluation can be performed by using a disk for the test piece holder 5 and a sphere for the test piece 9. Sample fixing support 10
Is a steel disk of 24 (diameter) x 7.85 mm as test piece 5,
As the test piece 9, a steel ball having a diameter of 10 mm was attached to the holder 3 for fixing the test piece.

The operating conditions of the tester were set as follows.
In FIG. 1, 1 is a fixing nut (screw is attached to the holder), 2 is a fixing screw, 4 is a vibrating stroke cylinder fixing chuck (female), 6 is a front holding of the test piece 5,
Reference numeral 7 indicates a (ball) holder of the test piece 9, and 8 indicates a chuck (male) with a fixing holder. Conditions Load 200 N Amplitude 1.0 mm Frequency 50 Hz Operating time 30 minutes Under these conditions, each sample shown in the examples and comparative examples was adhered between both test pieces, and the test was performed, and the dynamic friction coefficient during the test was measured by a recorder. Also, the depth of wear marks formed on the surface of the disc after the test was measured with a roughness meter, and the wear resistance of each sample was compared. The friction coefficient takes the average value during the test time, and the maximum peak value is shown in () when the fluctuation is particularly large.

4. Comparison of Effects 4.1 Examples of Table 1 (see Table 1) Examples 1a, 2a, 3a and 4a are the same as the petroleum-based lubricating oil of Comparative Example 1 (bright stock, ISO-VG 450 grade). 3% of chalcogen compound is mixed, and α-olefin.
Maleic acid copolymer was added 0.1% and then uniformly dispersed by a three-stage roll.Comparative Examples 3a to 4a are graphite and molybdenum disulfide, which are widely used as solid lubricants having a normal layered crystal structure. 3% for each of Examples 1a, 2a, 3
Add 0.1% of the dispersant used in a, 4a,
It is dispersed by the same operation as a and 4a.

In Examples 1b, 2b, 3b, and 4b, 5% of metal phosphorus chalcogenide was added to the lithium soap-based grease of Comparative Example 2 and uniformly dispersed by a three-stage roll. In Comparative Examples 3b and 4b, graphite and molybdenum disulfide were added to Comparative Example 2 at 5%.
It was added and uniformly dispersed by the same operation as in Examples 1b, 2b, 3b and 4b.

Compared to Comparative Example 1, Examples 1a, 2a, 3a and 4a have remarkably improved extreme pressure properties, and have a small coefficient of friction and a small wear scar depth in the SRV vibration friction test, resulting in wear resistance. However, it was demonstrated that the improvement was remarkable. Comparative Example 3a is extremely pressure resistant and higher than Examples 1a, 2a, 3a and 4a in abrasion resistance,
Further, in Comparative Example 4a, extreme pressure resistance and wear resistance were obtained in Examples 1a, 2a, 3a,
Inferior to 4a.

It was demonstrated that Examples 1b, 2b, 3b and 4b were significantly improved in both extreme pressure resistance and wear resistance as compared with Comparative Example 2. Also, as compared with Example 3b, the extreme pressure property is
b, 2b, 3b, 4b, but wear resistance of Examples 1b, 2
b, 3b, 4b were excellent, and in comparison with Comparative Example 4b, it was demonstrated that Examples 1b, 2b, 3b, 4b were superior in both extreme pressure properties and wear resistance.

When the powders of Examples 1a, 2a, 3a, 4a and Comparative Examples 3a, 4a were dispersed in a petroleum-based lubricating oil, the powders could be settled only by mechanical kneading such as a three-stage roll. However, adding a small amount of a dispersant such as methacrylate, diethyleraminoethylmethacrylate copolymer, α-olefin / maleic acid copolymer, etc. to this causes problems in practical use. Since it is possible to suppress the sedimentation of the powder to the extent that there is no such problem, it is possible to use the composition as in Examples 1a, 2a, 3a and 4a as a lubricant.

In Comparative Examples 3a to 4b, the appearance is black, and it is difficult to remove it once it adheres to clothes, skin, and the environment, and it takes a lot of effort to maintain a recent work environment in which amenity is strongly demanded. A white solid lubricant is desired. The solid lubricant according to the present invention properly meets the requirements of the industrial world, and opens new applications to precision parts robots, copying machines, etc. that are extremely resistant to dirt such as molybdenum disulfide and graphite.

4.2 Examples in Table 2 (see Table 2) In Examples 5 to 9, the petroleum-based lubricating oil of Comparative Example 5 (Brightstock ISO-VG 450 grade) was mixed with 3% of an intercalation compound and uniformly mixed by a three-stage roll. Comparative Examples 6 and 7 are obtained by mixing molybdenum disulfide and graphite in Comparative Example 5 and uniformly dispersing them with a three-stage roll. In Examples 5 to 9, the extreme pressure property was remarkably improved as compared with Comparative Example 5, and it was proved by the SRV vibration friction test that the friction coefficient and the wear scar depth were also small and the wear resistance was excellent. ..

In Comparative Examples 6 and 7, molybdenum disulfide and graphite, which are widely used as solid lubricants, were used in Examples 5 to 9.
Although it is dispersed in the same lubricating oil as the above, it easily separates from the powder, while the intercalation compound is well compatible with petroleum-based lubricating oil and can prevent the powder from settling in the lubricating oil. It can be said that it is one of the outstanding performances. Comparative Example 6 has a high extreme pressure property but is inferior to Example 5 in terms of abrasion resistance, and Comparative Example 7 is inferior to Example 5 in terms of extreme pressure property and abrasion resistance.

4.3 Examples in Table 3 (see Table 3) In Examples 10 to 14, 3% of an intercalation compound was added to a lithium soap-based grease and the mixture was uniformly dispersed by a three-stage roll. The effect was examined. Compared with the base grease of Comparative Example 8, the extreme pressure and wear resistance are remarkably improved. Comparative Examples 9 and 10 are examples in which molybdenum disulfide and graphite were added to the same soap-based grease as in the examples. In extreme pressure property, Comparative Example 9 shows a value equal to or higher than those of Examples 10 to 14, but there is a marked difference in wear resistance, and Comparative Example 10 is considerably inferior to Examples in both extreme pressure property and wear resistance. There is.

4.4 Examples of Table 4 (see Table 4) Examples 12a to 13d are the effects of addition of metal phosphorus chalcogenide and its intercalation compound to grease and lubricity, and SRV vibration friction test. The initial friction coefficient of the machine was added to the lithium soap base grease of Comparative Example 11 (corresponding to Comparative Example 2) 0.1 to 3.0% by weight of ZnPS ₃ (Example 1) and 0.1 to 3.0% by weight of the intercalation compound (Example 5). The results are compared. Compared to Comparative Example 11, the friction coefficient can be improved by adding a small amount of metal phosphorus chalcogenide or an intercalation compound. However, at 0.1% by weight, the difference from Comparative Example 11 was small, indicating that the addition amount was close to the limit.

4.5 Examples of Table 5 (see Table 5) Examples 14 to 18 are greases prepared by using 10% of an intercalation compound in a lubricating oil of the same type as Examples 5 to 9 and using acetone as a dispersant. This is the case. The thickening effect varies depending on the type of organic material intercalated between the layers. From a uniform compound-like viscous substance (separation of solid and liquid does not occur), No. 1 grade grease of consistency grade. Samples up to the shape are obtained. With respect to the thickening effect of the intercalation compound, if it is less than 1%, separation from powder occurs, and if it exceeds about 70%, it becomes brittle and it is difficult to obtain a uniform solid grease form. These compositions were compared with Comparative Examples 13 and 14
It is noteworthy that the example is superior in extreme pressure property and abrasion resistance to the commercially available grease of Example 1 and shows higher extreme pressure property than the commercial grease containing the extreme pressure additive. It was also found that depending on the selection of the guest, it shows a dropping point higher than that of lithium soap-based grease, and it can also be used as a heat resistant grease.

Comparative Example 12 is an example in which molybdenum disulfide is used as in the above, but molybdenum disulfide also has no thickening effect and powder separation occurs, which is not suitable for practical use. Further, although it is excellent in extreme pressure properties, it is significantly different from Examples 14 to 18 in wear resistance. As described above, it has been proved that the intercalation compound used in the present invention is a substance having three effects of a thickener for grease, an extreme pressure additive and a solid lubricant. Further, it was demonstrated that a grease having more heat resistance than a lithium soap-based grease which is widely available on the market can be obtained by selecting a guest.

4.6 Examples in Table 6 Examples 19 to 21 are examples in which an acetylated oil and fat and a fatty acid amide were used in combination with an intercalation compound, and compared with Comparative Example 15 (corresponding to Example 10), 16 and 17, and A low coefficient of friction can be obtained. Such a lubricant is applied to a lubricant that can meet special specifications such as a machine that requires smooth rotation or sliding under a relatively light lubrication condition and that suppresses noise generation. Further, a vibration friction test using a combination of plastic and steel showed a friction coefficient lower than that of the comparative example, and it was found that it can be used as a lubricant for plastics.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

As shown in Table 1, the lubricant of the present invention containing a metal phosphorus chalcogenide which is a crystal powder having a specific layered structure of the present invention is a solid lubricant excellent in extreme pressure property and wear resistance. And a lubricant containing an intercalation compound in which a metal phosphorus chalcogenide is used as a host layer and a guest is an alkylamine, aromatic amine, pyridine or alkylammonium chloride, as shown in Tables 2 and 3, extreme pressure resistance and As shown in Table 5, since the above-mentioned intercalation compound has excellent abrasion resistance and has an excellent thickening action,
It has been proved that an excellent extreme pressure grease can be obtained by using only the base oil and the intercalation compound without adding a thickener.

[Brief description of drawings]

FIG. 1 is a front view of an SRV vibration friction tester.

[Explanation of symbols]

 1 Fixing nut 2 Fixing screw 3 Specimen fixing holder 4 Vibrating stroke cylinder fixing chuck (female) 5 Specimen 6 Specimen front hold 7 Specimen (ball) holding 8 Fixing holder chuck (male) 9 test Piece (steel ball) 10 Fixed sample support

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[Procedure amendment]

[Submission date] August 30, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

As described above, the metal phosphorus chalcogenide and the intercalation compound of the present invention have a layered structure in which thin crystal layers are repeatedly piled up. Particularly, in the intercalation compound, a long chain alkyl is formed between the host layers of (1). The guest substance (2) having a group, an aryl group, an alkylaryl group, etc., and having a polar group and an ionic group and having excellent lubricity and reactivity penetrates and reacts with the host layer to form a strong bond. , The distance between layers is widened and the layers are extremely slippery.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

3.2 Abrasion resistance test For each sample, SRV vibration friction tester (German Optim
The effect was compared by measuring the coefficient of kinetic friction and the depth of the wear mark of the test piece using a product manufactured by ol Inc.). This tester is a combination of various metals or synthetic resins (metal / metal, metal / synthetic resin, synthetic resin / synthetic resin) and the frictional condition under the presence or absence of a lubricant. Can be reproduced by

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Examples 1b, 2b, 3b and 4b are comparative example 2
It was proved that both extreme pressure resistance and wear resistance were remarkably improved as compared with Further, compared with Comparative Example 3b, the extreme pressure property is equivalent to Examples 1b, 2b, 3b, 4b, but the wear resistance is excellent in Examples 1b, 2b, 3b, 4b, and Comparative Example 4b.
In comparison with Example 1, both extreme pressure resistance and abrasion resistance are shown in Example 1.
It was proved that b, 2b, 3b and 4b were superior.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

4.6 Examples in Table 6 Examples 19 to 21 are examples in which acetylated oils and fats and fatty acid amides were used in combination with an intercalation compound. Example 11 and Comparative Example 1
A lower coefficient of friction can be obtained as compared with Nos. 5 and 16. Such a lubricant has the following properties:
It is applied to lubricants that can meet special specifications such as machinery that requires smooth rotation or slippage and noise generation. Further, a vibration friction test using a combination of plastic and steel showed a friction coefficient lower than that of the comparative example, and it was found that it can be used as a lubricant for plastics.

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Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C10M 125: 24 133: 06 133: 12 133: 40) (C10M 123/02 113: 08 115: 08) C10N 10 : 04 10:08 10:10 10:14 10:16 20:06 Z 8217-4H 30:06 40:24 Z 8217-4H 50:10

Claims (6)

[Claims] 1. A lubricant comprising 0.1% by weight or more of one or more metal phosphorus chalcogenides. 2. A lubricant containing 0.1% by weight or more of one or more intercalation compounds consisting of a metal phosphorus chalcogenide and an alkylamine, an aromatic amine, pyridine or an alkylammonium chloride. 3. A grease, characterized in that 1 to 70% by weight of the intercalation compound according to claim 2 as a thickener is added to a base oil to thicken the base oil. 4. A lubricating oil agent for steel and plastics, characterized in that the intercalation compound according to claim 2 and an acetylated oil or fat are dissolved or dispersed in a lubricating oil. 5. A lubricating oil agent comprising the intercalation compound according to claim 2 and a fatty acid amide dissolved or dispersed in a lubricating oil. 6. A lubricating oil agent comprising the intercalation compound according to claim 2 and an acetylated oil / fat and / or a fatty acid amide dissolved or dispersed in a lubricating oil.