JP2005098495A - Low friction sliding mechanism, low friction agent composition, and friction reducing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low friction sliding mechanism with a sliding face existing under various kinds of applications and having extremely superior low friction property, particularly, further improved low friction property by combining a conventional steel material with an organic Mo compound, and to provide a low friction agent composition, a friction reducing method, a manual transmission, and a final reducer. <P>SOLUTION: The low friction sliding mechanism has a sliding face formed by a DLC coating sliding member and a sliding member where an oxygen containing organic compound and a fatty amine compound exist. The low friction agent composition contains an oxygen containing organic compound and a fatty amine compound. In the friction reducing method, the sliding face formed by the DLC coating sliding member and the sliding member is lubricated by supplying the low friction agent composition thereto. The manual transmission has a DLC coated sliding portion on at least one sliding member. The final reducer has a DLC coated sliding portion on at least one sliding member. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a low friction sliding mechanism, a low friction agent composition, a friction reducing method, a manual transmission, and a final reduction gear, and more specifically, various sliding in an internal combustion engine, a drive train transmission engine, and the like. Low friction sliding mechanism that can improve the frictional characteristics of the surface, low friction agent composition and friction reducing method, low friction coefficient, sliding part with excellent seizure resistance and wear resistance, excellent for a long time The manual transmission that can achieve high fuel efficiency, and the friction coefficient at the sliding part can be reduced to improve the seizure resistance and wear resistance. The present invention relates to a final reduction gear that can be improved.

Warming global environmental problems on a global scale, such as destruction of the ozone layer are largely closeup, especially in the regulation value in each country for the CO ₂ reduction that is said to have great influence on the global warming of the whole earth It has attracted a great deal of interest over how to decide.
Regarding CO ₂ reduction, reduction of energy loss due to friction loss of machines and devices, particularly reduction of fuel consumption of automobiles is one of the major issues, and the role played by the sliding material and the lubricant is large.
The role of the sliding material is to exhibit excellent wear resistance and a low coefficient of friction for parts where the frictional wear environment is severe among the sliding parts of the engine. Application is progressing. A general DLC material is expected as a low-friction sliding material because its friction coefficient in air and in the absence of lubricating oil is lower than that of a hard-wearing material such as TiN or CrN.

  In addition, energy-saving measures in lubricating oil, such as engine fuel efficiency measures, are as follows: 1) Reduction of viscosity resistance in the fluid lubrication region and agitation resistance in the engine by lowering viscosity; 2) Optimal friction modifier and various additives Mixing by blending and reduction of friction loss under boundary lubrication are suggested. For example, many studies have been made with a focus on organic Mo compounds such as MoDTC and MoDTP as friction modifiers, and organic Mo that exhibits an excellent low friction coefficient at the beginning of use on a sliding surface made of a conventional steel material. A lubricating oil composition containing the compound has been applied and has been effective.

On the other hand, it has been reported that a general DLC material excellent in low friction characteristics in air has a small friction reducing effect in the presence of lubricating oil (for example, Non-Patent Document 1). It has been found that even if a lubricating oil composition containing an organomolybdenum compound is applied, the friction reducing effect is not sufficiently exhibited (for example, Non-Patent Document 2).
Proceedings of Japan Society of Tribology, Tokyo 1999.5, p11-12, Kano et al. World Tribology Congress 2001.9, Vienna, Proceeding p342, Kano et. al.

Further, with regard to the fuel-saving technology of a manual transmission for automobiles, it has been proposed to prevent the reduction of power transmission efficiency due to agitation resistance by avoiding or extremely small agitation of lubricating oil by a power distribution device (for example, Patent Document 1).
JP-A-10-166877

On the other hand, with regard to the lubricating oil used in such transmissions, a lubricating oil composition in which a boron-containing ashless dispersant, an alkaline earth metal detergent and a sulfur-based additive are blended with a lubricating base oil has been proposed. (See Patent Document 2), and further, a base oil having a low sulfur content and a predetermined viscosity, a primary dithiophosphate zinc, an alkaline earth metal detergent, a alkenyl succinimide having a polybutenyl group having a predetermined molecular weight, and derivatives thereof A gear oil containing an amine salt of a phosphate ester and a sulfur compound has been proposed (see Patent Document 3).
Japanese Patent Laid-Open No. 2003-82377 Japanese Patent Laid-Open No. 11-181463

Furthermore, with regard to fuel efficiency technology for automobile final reduction gears, for the purpose of improving transmission efficiency in differential gears, phosphorus-based extreme pressure agents selected from a specific range, organic acids of a specific structure, and from a specific range There has been proposed a lubricating oil composition for a final reduction gear that contains a selected sulfur-based extreme pressure agent in a lubricating base oil (see Patent Document 4).
Japanese Patent Laid-Open No. 6-200274

  In addition, for the purpose of reducing sliding friction loss between the roller end face and the inner ring large collar, a tapered roller bearing in which the cone center of the outer diameter surface of the tapered roller is shifted from the central axis of the inner ring, and such a tapered roller bearing is used for automobiles. It has been proposed to be used for a differential (see Patent Document 5).

JP 2000-192951 A

In the manual transmission described in Patent Document 1 described above, the reduction of the agitation resistance of the lubricating oil has been studied as described above. The compatibility between the member and lubricating oil has not been studied.
In addition, the lubricant alone is configured as shown in the examples of Patent Documents 2 and 3 described above, so as to prevent wear, improve the fatigue life, and improve the friction characteristics between the synchronizer ring and the gear cone. However, the reduction of the coefficient of friction in consideration of the characteristics of the sliding member has not been particularly studied.

  Further, in the lubricating oil composition for a final reduction gear described in Patent Document 4 above, improvement in transmission efficiency of the gear part by improving the formulation has been studied. In Patent Document 5, friction by improving the structure of the tapered roller bearing is studied. Although the reduction of loss has been studied, the reduction of the friction of the sliding surface itself and the compatibility between the sliding member and the lubricating oil have not been studied.

The present invention has been made in view of such problems of the prior art, and the object of the present invention is to exhibit extremely excellent low friction characteristics on a sliding surface existing under various uses. Another object of the present invention is to provide a low-friction sliding mechanism, a low-friction agent composition, and a friction-reducing method that have a low-friction characteristic even better than a combination of a conventional steel material and an organic Mo compound.
Further, the object of the present invention is to reduce the coefficient of friction at various sliding parts in a manual transmission, such as a bearing part, to improve seizure resistance and wear resistance, and to slide each part. An object of the present invention is to provide a manual transmission that can reduce resistance and contribute to an improvement in fuel consumption of an automobile.
Furthermore, the object of the present invention is to reduce the coefficient of friction between various sliding parts in the final reduction gear, for example, between the back side of the side gear that is in sliding contact with the washer and the inner surface of the differential case, and to improve seizure resistance and wear resistance. An object of the present invention is to provide a final reduction gear that can improve the fuel consumption of an automobile by improving the sliding resistance of each part.

As a result of intensive studies to solve the above problems, the present inventors have found that a combination of a sliding member and at least one of which is a DLC material and a specific compound cannot be realized from conventional lubrication theory. The inventors have found that the present invention exhibits extremely excellent low friction characteristics, and have completed the present invention.
In addition, the present inventors can significantly reduce the friction coefficient under the intervention of the low friction agent composition by forming a hard carbon thin film having a low hydrogen content on one or both of the sliding surfaces that are in sliding contact with each other. In order to achieve a low friction coefficient and improve seizure resistance and wear resistance in a sliding member coated with such a hard carbon thin film, an additive in the low friction agent composition used is used. The inventors have found that the influence is not small, and have completed the present invention.

The low friction sliding mechanism of the present invention has a conventional sliding member and a low friction agent composition by interposing an oxygen-containing organic compound or an aliphatic amine compound on the sliding surface formed by the DLC coating sliding member. It has low friction characteristics superior to the combination of
In addition, the manual transmission of the present invention reduces the friction coefficient at various sliding parts such as the bearing part, improves seizure resistance and wear resistance, and reduces the sliding resistance at each part. Contributes to improved fuel efficiency of automobiles.
Further, the final reduction gear of the present invention reduces the friction coefficient between the back side of the side gear and the inner surface of the differential case, improves seizure resistance and wear resistance, reduces sliding resistance at each part, and reduces the fuel consumption of the automobile. Contributes to improvement.

  Hereinafter, the low friction sliding mechanism and the low friction agent composition of the present invention will be described in more detail. In the present specification, “%” indicates a mass percentage unless otherwise specified.

  Such a low friction sliding mechanism has a low friction agent composition interposed on the sliding surface formed by the sliding members when the DLC coating sliding member (A) and the sliding member (B) are slid. Become. In addition, as the low friction agent composition, one containing at least one selected from the group consisting of an oxygen-containing organic compound (C) and an aliphatic amine compound (D) is used. As a result, the DLC-coated sliding member and the sliding member slide with extremely lower friction than in the past.

Here, the DLC (diamond-like carbon) material used for the DLC coating sliding member (A) is amorphous mainly composed of carbon elements, and the bonding form between carbons is a diamond structure (SP ³ bond). And graphite bonds (SP ² bonds). Specifically, aC (amorphous carbon) consisting only of carbon elements, aC: H (hydrogen amorphous carbon) containing hydrogen, and some metal elements such as titanium (Ti) and molybdenum (Mo). MeC included in In the low-friction sliding mechanism of the present invention, the DLC material is preferably made of an aC-based material that does not contain hydrogen from the viewpoint of exhibiting a significant friction reducing effect. The DLC material preferably has a hydrogen content of 20 atomic% or less because the coefficient of friction increases as the hydrogen content increases. Furthermore, in order to sufficiently reduce the friction coefficient at the time of sliding in the low friction agent composition and to secure more stable sliding characteristics, it is desirably 10 atomic% or less, more desirably 5 atomic% or less. More desirably, it is 0.5 atomic% or less. Such a DLC material having a low hydrogen content can be obtained by forming a film by a PVD method that substantially does not use hydrogen or a hydrogen-containing compound, such as a sputtering method or an ion plating method.
In this case, in addition to using a gas not containing hydrogen at the time of film formation, in some cases, the film may be formed after sufficiently baking the reaction vessel or the base material holder or cleaning the surface of the base material. It is desirable to reduce the amount of hydrogen.

Moreover, as a base material used for the said DLC coating sliding member (A), nonferrous metals, such as carburized steel, hardened steel, aluminum, etc. can be used, for example.
Regarding the surface roughness of the substrate before DLC coating, since the film thickness of the hard carbon thin film is considerably thin, the surface roughness Ra (centerline average) is greatly affected by the film surface roughness after film formation. The roughness is desirably 0.1 μm or less. That is, when the surface roughness Ra of the substrate is more than 0.1 μm, the protrusion due to the roughness of the film surface increases the local contact surface pressure with the counterpart material and induces cracking of the film. This is because the possibility increases.

The constituent material of the sliding member (B) is not particularly limited, and specific examples include metal materials such as iron-based materials, aluminum-based materials, magnesium-based materials, and titanium-based materials. In particular, iron-based materials, aluminum-based materials, and magnesium-based materials are preferable because they can be easily applied to sliding parts of existing machines and devices and can contribute to energy saving measures widely in various fields.
Furthermore, as the constituent material of the sliding member (B), non-metallic materials such as resin, plastic, and carbon can be used.
Furthermore, materials obtained by applying various thin film coatings to these metal materials and non-metal materials are also useful.

There is no restriction | limiting in particular as said iron-type material, Not only high purity iron but various iron-type alloys (Nickel, copper, zinc, chromium, cobalt, molybdenum, lead, silicon, or titanium, and these are arbitrarily combined) Etc.) can be used. Specific examples include carburized steel SCM420 and SCr420 (JIS).
Moreover, there is no restriction | limiting in particular as said aluminum type material, Not only high purity aluminum but various aluminum type alloys can be used. Specifically, for example, it is desirable to use a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing 4 to 20% of silicon (Si) and 1.0 to 5.0% of copper (Cu). Preferable examples of the aluminum alloy include AC2A, AC8A, ADC12 and ADC14 (JIS).

  Moreover, there is no restriction | limiting in particular as a metal material which gave various coatings among the said sliding members (B), Specifically, various metal type materials, for example, the said iron-type material, aluminum-type material, magnesium, are mentioned. Examples of the metal-based material or titanium-based material include TiN, CrN, or the like, or a metal-based material having the above-mentioned DLC material or the like coated with a thin film on the surface. . Further, the DLC material is more preferably aC-based diamond-like carbon containing no hydrogen.

  The surface roughness Ra of each of the DLC coating sliding member (A) and the sliding member (B) (for example, a metallic material or the metallic material subjected to various thin film coatings) is 0.1 μm or less, preferably The thickness is preferably 0.08 μm or less from the viewpoint of sliding stability. When it exceeds 0.1 μm, scuffing is locally formed, and the friction coefficient may be greatly improved.

Furthermore, the DLC coating sliding member (A) preferably has a surface hardness of Hv 1000 to 3500 in terms of micro Vickers hardness (10 g load) and a DLC film thickness of 0.3 to 2.0 μm. In addition, when the surface hardness and thickness of the DLC coating sliding member (A) are out of the above ranges, the DLC coating sliding member (A) is easily worn out when the thickness is less than Hv1000 and the thickness is less than 0.3 μm. If the surface hardness of the iron base member deviates from the above, the iron base member may be buckled under high surface pressure and easily peeled off if it is less than HRC45.
Moreover, when using an iron-type material for the said sliding member (B), it is preferable that the surface hardness is Rockwell hardness and is HRC45-60 in C scale. This case is effective because the durability of the film can be maintained even under sliding conditions under a high surface pressure of about 700 MPa as in a cam follower member.
Further, when the sliding member (B) is an aluminum-based material, its surface hardness is preferably a Brinell hardness _H B 80 to 130. If the surface hardness of the aluminum-based material deviates from the above, if it is less than H _B 80, the aluminum-based material may be easily worn.
Furthermore, when the sliding member (B) is made of a metal material coated with a thin film, particularly when the sliding member (B) is made of a metal material coated with a DLC material, the surface hardness is Hv1000 in terms of micro Vickers hardness (10 g load). It is preferable that the DLC film thickness is 0.3 to 2.0 μm. If the surface hardness and thickness are out of the above ranges, they are likely to be worn when the Hv is less than 1000 and the thickness is less than 0.3 μm.

The sliding surface composed of the DLC-coated sliding member (A) and the sliding member (B) is not limited as long as it is a sliding surface that comes into contact with two sliding surfaces with a low friction agent composition interposed therebetween. Can be used. For example, sliding parts of internal combustion engines such as 4-cycle and 2-cycle engines (for example, valve trains, pistons, piston rings, piston skirts, cylinder liners, connecting rods, crankshafts, bearings, bearings, metals, gears, chains, belts, Oil pumps), drive system transmission mechanisms (for example, gears), hard disk drive sliding parts, and other various sliding surfaces that require severe frictional conditions and low friction. In these sliding surfaces, at least one sliding member is subjected to DLC coating, and only at least one selected from an oxygen-containing organic compound and an aliphatic amine-based compound is supplied. It is effective because it has excellent low friction characteristics.
For example, preferred embodiments in the valve train of an internal combustion engine include a disk-shaped shim or lifter crown coated with DLC on a steel material base, low alloy chilled cast iron, carburized steel or tempered carbon steel, and these The sliding surface which consists of a cam lobe using the material which concerns on arbitrary combinations of these etc. is mentioned.

On the other hand, the oxygen-containing organic compound (C) in the low friction sliding mechanism of the present invention is not particularly limited as long as it is an organic compound containing oxygen in the molecule. For example, it may be an oxygen-containing organic compound composed of carbon, hydrogen and oxygen, and contains other elements such as nitrogen, sulfur, halogen (fluorine, chlorine, etc.), phosphorus, boron, metal, etc. in the molecule. An oxygen-containing organic compound may be used. In particular, from the point that the friction between the sliding surfaces formed by the DLC-coated sliding member (A) and the sliding member (B) can be further reduced, an oxygen-containing organic compound having a hydroxyl group and comprising carbon, hydrogen and oxygen, and Its derivatives are preferred. Moreover, it is more preferable to have two or more hydroxyl groups. For the same reason as described above, an oxygen-containing organic compound having a low sulfur content or no sulfur is more preferable.
The “derivative” here is typically an oxygen-containing organic compound composed of carbon, hydrogen and oxygen, such as a nitrogen-containing compound, a phosphorus-containing compound, sulfur or a sulfur-containing compound, a boron-containing compound, a halogen Examples include elements and halogen element-containing compounds, metal elements and metal-containing compounds (regardless of organic or inorganic), compounds obtained by reacting alkylene oxide, and the like.

  Specific examples of the oxygen-containing organic compound (C) include a compound having a hydroxyl group, a carboxyl group, a carbonyl group, a compound having an ester bond, an ether bond, etc. (these are two or more groups). Or may have a bond), and preferably has one or two or more groups selected from a hydroxyl group, a carboxyl group, a carbonyl group, and an ester bond, and a hydroxyl group, a carboxyl group, and an ester. More preferably, it is a group selected from a bond or an oxygen-containing organic compound having one or more bonds, and is an oxygen-containing organic compound having one or more groups selected from a hydroxyl group or a carboxyl group Is more preferable, and an oxygen-containing organic compound having one or more hydroxyl groups is particularly preferable. There.

  More specifically, I) alcohols, II) carboxylic acids, III) esters, IV) ethers, V) ketones, VI) aldehydes, VII) carbonates (these are hydroxyl groups, carboxyl groups, A carbonyl group, an ester bond, or an ether bond, which may further have one or two or more groups or bonds), derivatives thereof, and any mixtures thereof.

  Here, I) alcohols are represented by the following general formula (1)

      R- (OH) n (1)

And a compound having one or more hydroxyl groups.

Specific examples of the alcohols (I) include the following.
・ Monohydric alcohols (I-1)
・ Divalent alcohols (I-2)
・ Trivalent or higher alcohols (I-3)
-1 type, or 2 or more types of mixtures chosen from said 3 types of alcohol (I-4)

  The monohydric alcohol (I-1) has one hydroxyl group in the molecule. For example, methanol, ethanol, propanol (1-propanol, 2-propanol), butanol (1-butanol, 2- Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol), pentanol (1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1 -Butanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 2,2-dimethyl-1-propanol), hexanol (1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1- Pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pen , 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 2,3-dimethyl-1-butanol, 2, 3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2,2-dimethylbutanol), heptanol (1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-1-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl-2-hexanol, 3-ethyl-3-pentanol, 2 , 2-dimethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 4,4-dimethyl 2-pentanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-ethylpentanol), octanol (1-octanol, 2-octanol, 3-octanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2-ethyl-1-hexanol, 2-propyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 3,5- Dimethyl-1-hexanol, 2-methyl-1-heptanol, 2,2-dimethyl-1-hexanol), nonanol (1-nonanol, 2-nonanol, 3,5,5-trimethyl-1-hexanol, 2,6 -Dimethyl-4-heptanol, 3-ethyl-2,2-dimethyl-3-pentanol, 5-methyloctanol, etc.) , Decanol (1-decanol, 2-decanol, 4-decanol, 3,7-dimethyl-1-octanol, 2,4,6-trimethylheptanol, etc.), undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol , Hexadecanol, heptadecanol, octadecanol (stearyl alcohol, etc.), nonadecanol, eicosanol, heneicosanol, tricosanol, tetracosanol, etc., monovalent alkyl alcohols having 1 to 40 carbon atoms (these alkyl groups are Straight chain or branched); monovalent alkenyl alcohols having 2 to 40 carbon atoms such as ethenol, propenol, butenol, hexenol, octenol, decenol, dodecenol, octadecenol (oleyl alcohol, etc.) ( These alkenyl groups may be linear or branched, and the position of the double bond is arbitrary); cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclo Pentanol, methylcyclohexanol, dimethylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, dimethylcyclohexanol, cyclopentylmethanol, cyclohexylmethanol (1-cyclohexylethanol, 2-cyclohexylethanol, etc.), cyclohexylethanol, cyclohexylpropanol (Such as 3-cyclohexylpropanol), cyclohexylbutanol (such as 4-cyclohexylbutanol), butylcyclohexanol, 3, 3, 5, -Monovalent (alkyl) cycloalkyl alcohols having 3 to 40 carbon atoms such as tetramethylcyclohexanol (these alkyl groups may be linear or branched, and alkyl groups, hydroxyl groups Is also optional); phenyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creole, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butylmethylphenyl alcohol (3 -Methyl-6-tert-butylphenyl alcohol), dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol (2,6-di-tert-butylphenyl alcohol, 2,4-di-tert-butylphenyl alcohol) Etc.), dibutylmethylphenyl alcohol (2,6-di-tert-butyl-4methylphenyl alcohol etc.), dibutylethylphenyl alcohol (2,6-di-tert-butyl-4ethylphenyl alcohol etc.), tributylphenyl alcohol (2,4,6-tri-tert-butylphenyl alcohol, etc.), naphthol (α-naphthol, β-naphthol, etc.), dibutylnaphthol (2,4-di-tert-butyl-α-naphthol, etc.) Alkyl) aryl alcohols (these alkyl groups may be linear or branched, and the substitution position of the alkyl group or hydroxyl group is also arbitrary); 6- (4-oxy- 3,5-di-tert-butyl-anilino) -2,4-bis- (n-octyl-thio) -1,3,5-to Azine and mixtures thereof.

  In these monohydric alcohols, the friction of the sliding surface composed of the DLC-coated sliding member (A) and the sliding member (B) can be further reduced, and the volatility is low and high temperature conditions (for example, sliding of internal combustion engine etc. It is more preferable to use linear or branched alkyl alcohols or alkenyl alcohols having 12 to 18 carbon atoms, such as oleyl alcohol and stearyl alcohol, from the viewpoint that a friction reducing effect can be exhibited even under dynamic conditions.

  Moreover, as said dihydric alcohol (I-2), specifically, it has two hydroxyl groups in a molecule | numerator, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene Glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexane Diol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanedio 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecane Candiol, 1,14-tetradecanediol, 1,15-heptadecanediol, 1.16-hexadecanediol, 1,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1, C2-C40 alkyl or alkenyl diols such as 20-icosadecanediol (the alkyl group or alkenyl group may be linear or branched, and the position of the double bond of the alkenyl group is arbitrary, The substitution position of the hydroxyl group is also arbitrary); cyclohexanediol, methylcyclohexanediol, etc. Alkyl) cycloalkanediols (the alkyl group may be linear or branched, and the substitution position of the alkyl group and hydroxyl group is arbitrary), benzenediol (catechol, etc.), methylbenzenediol, ethylbenzenediol, butylbenzene Diols (such as p-tert-butylcatechol), dibutylbenzenediol (such as 4,6-di-tert-butyl-resorcin), 4,4′-thiobis- (3-methyl-6-tert-butyl-phenol), 4,4′-butylidenebis- (3-methyl-6-tert-butyl-phenol), 2,2′-methylenebis- (4-methyl-6-tert-butyl-phenol), 2,2′-thiobis- ( 4,6-di-tert-butyl-resorcin), 2,2′-methylenebis (4-ethyl-6- tert-butyl-phenol), 4,4′-methylenebis- (2,6-di-tert-butyl-phenol), 2,2 ′-(3,5-di-tert-butyl-4-bidoxy) propane, Divalent (alkyl) aryl alcohols having 2 to 40 carbon atoms such as 4,4′-cyclohexylidenebis- (2,6-di-tert-butyl-phenol) (the alkyl group is linear or branched) The substitution position of the alkyl group and the hydroxyl group is arbitrary), etc .; condensates of p-tert-butylphenol and formaldehyde, condensates of p-tert-butylphenol and acetaldehyde, etc .; and mixtures thereof Can be mentioned.

  In these dihydric alcohols, ethylene glycol, propylene glycol, neopentyl glycol, 1, 4 are used because the friction of the sliding surface composed of the DLC coating sliding member (A) and the sliding member (B) can be further reduced. -Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 1, It is preferable to use 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like. Further, hindered alcohols having a molecular weight of 300 or more, preferably 400, such as 2,6-di-tert-butyl-4- (3,5-di-tert-butyl-4-hydroxy-benzyl) phenyl alcohol. Is preferable in that it does not volatilize even under high temperature conditions (for example, sliding conditions for internal combustion engines, etc.), is excellent in heat resistance, exhibits a friction reducing effect, and can impart excellent oxidation stability.

  Furthermore, as trihydric or higher alcohols (I-3), specifically, those having three or more hydroxyl groups, usually 3 to 10 valents, preferably 3 to 6 valent polyhydric alcohols are used. It is done. Specific examples include trimethylol alkanes such as glycerin, trimethylolethane, trimethylolpropane and trimethylolbutane, erythritol, pentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2 , 6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, adonitol, arabitol, xylitol, mannitol, etc., and polymers or condensates thereof (for example, diglycerin, triglycerin, tetraglycerin, etc. Condensation compounds such as glycerin 2- to 8-mer, di-methylol propane 2-to 8-mer, dipentaerythritol 2-tetramer, etc., sorbitan, sorbitol glycerin condensate, etc. (Intramolecular contraction Compound, the intermolecular condensation compounds or self-condensation compound), and the like.

  In addition, saccharides such as xylose, arabitol, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, mannose, isomaltose, trehalose, sucrose can be used.

  Among these trihydric or higher alcohols, glycerin, trimethylolalkane (eg, trimethylolethane, trimethylolpropane, trimethylolbutane), pentaerythritol, 1,2,4-butanetriol, 1,3,5-pentane Triol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, 3-6-valent polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, and the like These mixtures are more preferred, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan and mixtures thereof are more preferred, and the oxygen content is 20% or more, preferably 30% or more, particularly preferably 40. It is especially preferred polyhydric alcohols are. In addition, in the case of polyhydric alcohol exceeding 6 values, the viscosity becomes too high.

  Carboxylic acids (II) are represented by the following general formula (2)

      R- (COOH) n (2)

And a compound having one or two or more carboxyl groups.

Specific examples of the carboxylic acids (II) include the following.
Aliphatic monocarboxylic acids (fatty acids) (II-1)
-Aliphatic polycarboxylic acids (II-2)
・ Carbocyclic carboxylic acids (II-3)
・ Heterocyclic carboxylic acids (II-4)
-A mixture of two or more selected from the above four carboxylic acids (II-5)

  The aliphatic monocarboxylic acids (fatty acids) (II-1) are specifically aliphatic monocarboxylic acids having one carboxyl group in the molecule, such as methanoic acid, ethanoic acid (acetic acid), propane. Acids (propionic acid), butanoic acid (butyric acid, isobutyric acid, etc.), pentanoic acid (valeric acid, isovaleric acid, pivalic acid, etc.), hexanoic acid (caproic acid, etc.), heptanoic acid, octanoic acid (caprylic acid, etc.), Nonanoic acid (such as pelargonic acid), decanoic acid, undecanoic acid, dodecanoic acid (such as lauric acid), tridecanoic acid, tetradecanoic acid (such as myristic acid), pentadecanoic acid, hexadecanoic acid (such as palmitic acid), heptadecanoic acid, octadecanoic acid (such as Stearic acid, etc.), nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, C1-C40 saturated aliphatic monocarboxylic acids such as sacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid and triacontanoic acid (these saturated aliphatics may be linear or branched); propenoic acid ( Acrylic acid, etc.), propionic acid (propiolic acid, etc.), butenoic acid (methacrylic acid, crotonic acid, isocrotonic acid, etc.), pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid , Tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid (oleic acid, etc.), nonadecenoic acid, icosenic acid, henicosenic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacenoic acid , Octacosenoic acid, nonacosenic acid, triacontene Unsaturated aliphatic monocarboxylic acids having 1 to 40 carbon atoms and the like (the unsaturated aliphatic may be and straight-chain or branched, and the position of the unsaturated bond is also arbitrary), and the like.

  The aliphatic polycarboxylic acids (II-2) include ethanedioic acid (oxalic acid), propanedioic acid (malonic acid etc.), butanedioic acid (succinic acid, methylmalonic acid etc.), pentanedioic acid. (Glutaric acid, Ethylmalonic acid, etc.), Hexanedioic acid (Adipic acid, etc.), Heptanedioic acid (Pimelic acid, etc.), Octanedioic acid (Suberic acid, etc.), Nonanedioic acid (Azelaic acid, etc.), Decanedioic acid ( Sebacic acid, etc.), propene diacid, butenedioic acid (maleic acid, fumaric acid, etc.), pentene diacid (citraconic acid, mesaconic acid, etc.), hexene diacid, heptene diacid, octenedioic acid, nonene diacid, decene C2-C40 saturated or unsaturated aliphatic dicarboxylic acid such as diacid (These saturated aliphatic or unsaturated aliphatic may be linear or branched, and the position of the unsaturated bond is arbitrary) Propanetrica Saturated or unsaturated aliphatic tricarboxylic acids such as bonic acid, butanetricarboxylic acid, pentanetricarboxylic acid, hexanetricarboxylic acid, heptanetricarboxylic acid, octanetricarboxylic acid, nonanetricarboxylic acid, decanetricarboxylic acid (these saturated aliphatic or unsaturated aliphatic May be linear or branched, and the position of the unsaturated bond is arbitrary); saturated or unsaturated aliphatic tetracarboxylic acid (these saturated aliphatic or unsaturated aliphatic are linear or branched) And the position of the unsaturated bond is also arbitrary).

  Furthermore, the carbocyclic carboxylic acids (II-3) are specifically carboxylic acids having one or more carboxyl groups in the molecule in the carbocycle, such as cyclohexane monocarboxylic acid and methylcyclohexane. Monocarboxylic acid, ethylcyclohexane monocarboxylic acid, propylcyclohexane monocarboxylic acid, butylcyclohexane monocarboxylic acid, pentylcyclohexane monocarboxylic acid, hexylcyclohexane monocarboxylic acid, heptylcyclohexane monocarboxylic acid, octyl Mono-, di-, tri-, or tetra-carboxylic acids having 3 to 40 carbon atoms, such as cyclohexane monocarboxylic acid, cycloheptane monocarboxylic acid, cyclooctane monocarboxylic acid, trimethylcyclopentane dicarboxylic acid (such as camphoric acid) and the like, and having a naphthene ring Acid (alkyl group When having an alkenyl group as a substituent, they may be linear or branched, the position of the double bond is arbitrary, the number of substitutions and the position of substitution are also arbitrary, and benzenecarboxylic acid (benzoic acid) Acid), methylbenzenecarboxylic acid (toluic acid, etc.), ethylbenzenecarboxylic acid, propylbenzenecarboxylic acid, benzenedicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, etc.), benzenetricarboxylic acid (trimellitic acid, etc.), benzenetetracarboxylic acid Acids (such as pyromellitic acid) naphthalenecarboxylic acid (such as naphthoic acid), aromatic monocarboxylic acids having 7 to 40 carbon atoms, phenylpropanoic acid (hydroatropic acid), phenylpropenoic acid (such as atropic acid, cinnamic acid), Salicylic acid, alkyl salicy having one or more alkyl groups having 1 to 30 carbon atoms Mono-, di-, tri-, or tetracarboxylic acids having an aryl group of 7 to 40 carbon atoms such as acids (in the case of having an alkyl group or an alkenyl group as a substituent, they may be linear or branched, and have a double bond And the number of substitutions and substitution positions are also arbitrary.

  Furthermore, the heterocyclic carboxylic acids (II-4) are specifically heterocyclic carboxylic acids having one or more carboxyl groups in the molecule, such as furan carboxylic acid and thiophene. Examples thereof include heterocyclic carboxylic acids having 5 to 40 carbon atoms such as carboxylic acid and pyridinecarboxylic acid (nicotinic acid, isonicotinic acid and the like).

  Esters (III) are represented by the following general formula (3)

      R- (COO-R ') n (3)

And a compound having one or two or more ester bonds.

Specific examples of the esters (III) include the following.
-Esters of fatty acid monocarboxylic acids (fatty acids) (III-1)
· Esters of aliphatic polycarboxylic acids (III-2)
-Esters of carbocyclic carboxylic acids (III-3)
.Esters of heterocyclic carboxylic acids (III-4)
-Arbitrary mixture (III-5) selected from the above five types of esters
The esters listed in III-1 to III-5 may be complete esters in which all hydroxyl groups or carboxyl groups are esterified, or may be partial esters in which some hydroxyl groups or carboxyl groups remain.

  The fatty acid monocarboxylic acid (fatty acid) ester (III-1) is one or more selected from the above-mentioned fatty acid monocarboxylic acids (II-1) and the above-mentioned monovalent, divalent, or trivalent. One or two or more esters selected from the above alcohols (I-1 to 3). Examples of such esters include aliphatic monocarboxylic acids such as glycerol monooleate, glycerol diolate, sorbitan monooleate, and sorbitan diolate.

  Further, the ester (III-2) of the aliphatic polyvalent carboxylic acid is one or more selected from the above-mentioned aliphatic polyvalent carboxylic acids (II-2) and the above-mentioned monovalent, divalent, or 3 One or two or more esters selected from alcohols (I-1 to 3) having higher valences. Specifically, for example, dibutyl maleate, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate and the like, preferably 4 to 4 carbon atoms. 1 to 2, particularly preferably 6 to 12 dicarboxylic acids or two or more polyvalent carboxylic acids, 4 to 40 carbon atoms, preferably 4 to 18 carbon atoms, particularly preferably 1 to 6 to 14 carbon atoms. Diesters with one or more selected from monohydric alcohols, copolymers of these diesters (such as dibutyl maleate) with polyalphaolefins having 4 to 16 carbon atoms, alpha olefins with acetic anhydride, etc. And an ester of a compound to which an alcohol is added and an alcohol having 1 to 40 carbon atoms.

  Furthermore, as ester (III-3) of carbocyclic carboxylic acid, 1 type, 2 or more types chosen from the above-mentioned carbocyclic carboxylic acid (II-3), and the above-mentioned monovalent, bivalent, or trivalent or more are used. Examples thereof include esters with one or more selected from alcohols (I-1 to 3). Specific examples include aromatic carboxylic acid esters such as phthalic acid esters, trimellitic acid esters, pyromellitic acid esters, and salicylic acid esters.

  Furthermore, as the ester (III-4) of the heterocyclic carboxylic acid, one or more selected from the above-mentioned heterocyclic carboxylic acids (II-4) and the above-mentioned monovalent, divalent, or 3 Examples thereof include esters with one or more alcohols selected from monovalent or higher alcohols (I-1 to 3).

  Ethers (IV) are represented by the following general formula (4)

      R- (O-R ') n (4)

And a compound having one or more ether bonds.

Specific examples of the ethers (IV) include the following.
・ Saturated or unsaturated aliphatic ethers (IV-1)
・ Aromatic ethers (IV-2)
・ Cyclic ethers (IV-3)
・ Polyhydric alcohol ethers (IV-4)
・ A mixture of two or more selected from the above three ethers (IV-5)

  Specific examples of saturated or unsaturated aliphatic ethers (aliphatic single ethers) (IV-1) include dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, and diisobutyl. Ether, di-n-amyl ether, diisoamyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditridecyl ether, ditetradecyl ether, dipenta Decyl ether, dihexadecyl ether, diheptadecyl ether, dioctadecyl ether, dinonadecyl ether, diicosyl ether, methyl ethyl ether, methyl-n-propyl ether, methyl isopropyl ether Methyl isobutyl ether, methyl tert-butyl ether, methyl n-amyl ether, methyl isoamyl ether, ethyl n-propyl ether, ethyl isopropyl ether, ethyl isobutyl ether, ethyl tert-butyl ether, ethyl n-amyl ether, C1-C40 saturated or unsaturated aliphatic ethers such as ethyl isoamyl ether, divinyl ether, diallyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether, etc. (These saturated or unsaturated aliphatics are linear And the position of the unsaturated bond is arbitrary).

  Specific examples of the aromatic ethers (IV-2) include anisole, phenetole, phenyl ether, benzyl ether, phenylbenzyl ether, α-naphthyl ether, β-naphthyl ether, polyphenyl ether, and perphenyl ether. Fluoro ethers and the like, which may have a saturated or unsaturated aliphatic group (the saturated or unsaturated aliphatic group may be linear or branched, and the position of the unsaturated bond is arbitrary). And the substitution position and number are arbitrary). These are preferably in a liquid state under the use conditions, particularly at room temperature.

  Further, as the cyclic ethers (IV-3), specifically, for example, cyclic groups having 2 to 40 carbon atoms such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane, glycidyl ethers and the like. Ethers, which may have saturated or unsaturated aliphatic groups, carbocycles, carbocycles having saturated or unsaturated aliphatic groups (these saturated or unsaturated aliphatics may be linear It may be branched, the position of the unsaturated bond is arbitrary, and the substitution position and number are also arbitrary).

  The polyhydric alcohol ethers (IV-4) are one or two or more polyhydric alcohols selected from the above-mentioned dihydric or trihydric or higher alcohols (I-2 to 3) and monohydric alcohols (I -1) is one type or two or more types of ether selected from. The ether referred to here may be a complete ether in which all the hydroxyl groups of the polyhydric alcohol are etherified, or a partial ether in which some hydroxyl groups remain, but it is a partial ether because of its lower friction characteristics. Preferably there is.

  Ketones (V) are represented by the following general formula (5)

      R- (CO-R ') n (5)

And a compound having one or two or more carbonyl bonds.

Specific examples of the ketones (V) include the following.
・ Saturated or unsaturated aliphatic ketones (V-1)
・ Carbocyclic ketones (V-2)
・ Heterocyclic ketones (V-3)
・ Ketone alcohols (V-4)
Ketone acids (V-5)
-A mixture of two or more selected from the above five ketones (V-6)

  Specific examples of the saturated or unsaturated aliphatic ketones (V-1) include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, pinacolone, diethyl ketone, butyrone, and diisopropyl. C1-C40 saturated or unsaturated aliphatic ketones such as ketone, methyl vinyl ketone, mesityl oxide, and methylfeptenone (these saturated or unsaturated aliphatics may be linear or branched, The position of the saturated bond is arbitrary).

  Specific examples of the carbocyclic ketones (V-2) include cyclobutanone, cyclopentanone, cyclohexanone, acetophenone, propiophenone, butyrophenone, valerophenone, benzophenone, dibenzyl ketone, and 2-acetonaphthone. Examples thereof include carbocyclic ketones having 1 to 40 carbon atoms, which may have a saturated or unsaturated aliphatic group (the saturated or unsaturated aliphatic group may be linear or branched, unsaturated The position of the saturated bond is arbitrary, and the substitution position and number are also arbitrary.)

  Furthermore, specific examples of the heterocyclic ketones (V-3) include C1-C40 carbocyclic ketones such as acethienone and 2-acetofurone, which are saturated or unsaturated aliphatic. It may have a group (the saturated or unsaturated aliphatic group may be linear or branched, the position of the unsaturated bond is arbitrary, and the substitution position and number are also arbitrary).

  Furthermore, as the ketone alcohol (ketol) (V-4), specifically, for example, a ketone having 1 to 40 carbon atoms such as acetol, acetoin, acetoethyl alcohol, diacetone alcohol, phenacyl alcohol, benzoin and the like. Examples thereof include alcohols, which may have a carbocyclic or heterocyclic ring, and may have a carbocyclic or heterocyclic ring having a saturated or unsaturated aliphatic group (these saturated or unsaturated). The aliphatic group may be linear or branched, the position of the unsaturated bond is arbitrary, and the substitution position and number are also arbitrary).

  Specific examples of the ketone acids (V-5) include α-ketone acids such as pyruvic acid, benzoylformic acid, and phenylpyruvic acid, β-ketone acids such as acetoacetic acid, propionylacetic acid, and benzoylacetic acid, Examples thereof include ketone acids having 1 to 40 carbon atoms such as levulinic acid and γ-ketonic acids such as β-benzoylpropionic acid.

  Aldehydes (VI) are represented by the following general formula (6)

      R- (CHO) n (6)

And a compound having one or two or more aldehyde groups.

Specific examples of the aldehydes (VI) include the following.
・ Saturated or unsaturated aliphatic aldehydes (VI-1)
・ Carbocyclic aldehydes (VI-2)
・ Heterocyclic aldehydes (VI-3)
-A mixture of two or more selected from the above three aldehydes (VI-4)

  Specific examples of the saturated or unsaturated aliphatic aldehydes (VI-1) include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, pivalin aldehyde, capronaldehyde, Ptoaldehyde, caprylaldehyde, pelargonaldehyde, chemical purine aldehyde, undecyl aldehyde, laurin aldehyde, tridecyl aldehyde, myristic aldehyde, pentadecyl aldehyde, palmitic aldehyde, margarine aldehyde, stearaldehyde, acrolein, croton aldehyde, propiol aldehyde, C1-C40 saturated or unsaturated aliphatic aldehydes such as glyoxal and succindialdehyde (these saturated Unsaturated aliphatic may be a branched be linear, the position of the unsaturated bond include any a of) the like.

  Specific examples of the carbocyclic aldehydes (VI-2) include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, salicylaldehyde, cinnamaldehyde, α-naphthaldehyde, β -C1-C40 carbocyclic aldehydes, such as naphthaldehyde, etc. are mentioned, These may have a saturated or unsaturated aliphatic group (These are saturated or unsaturated aliphatic even if it is linear. It may be branched, the position of the unsaturated bond is arbitrary, and the position and number of substitution are arbitrary).

  Furthermore, specific examples of the heterocyclic aldehyde (VI-3) include, for example, heterocyclic aldehydes having 1 to 40 carbon atoms such as furfural, which have a saturated or unsaturated aliphatic group. (In these, saturated or unsaturated aliphatic groups may be linear or branched, the position of the unsaturated bond is arbitrary, and the position and number of substitution are also arbitrary).

  Carbonates (VII) are represented by the following general formula (7)

      R- (O-COO-R ') n (7)

And a compound having one or two or more carbonate bonds.

  Specific examples of the carbonates (VII) include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ditertbutyl carbonate, dipentyl carbonate, and dihexyl carbonate. , Diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, diundecyl carbonate, didodecyl carbonate, ditridecyl carbonate, ditetradecyl carbonate, dipentadecyl carbonate, dihexadecyl carbonate, diheptadecyl carbonate, dioctadecyl C1-C40 saturated or unsaturated aliphatic, carbocyclic, such as carbonate and diphenyl carbonate Carbon rings having a saturated or unsaturated aliphatic group, carbonates having a saturated or unsaturated aliphatic group having a carbocyclic ring (the saturated or unsaturated aliphatic group may be linear or branched, and the position of the unsaturated bond) Are arbitrary, the number of substitution positions and the number is also arbitrary, and the like, or hydroxy (poly) oxyalkylene carbonates obtained by adding alkylene oxide to these carbonates.

On the other hand, R and R ′ in the general formulas (1) to (7) are each independently an alkyl group, alkenyl group, alkylene group, cycloalkyl group, alkylcycloalkyl group, aryl group, alkylaryl group, arylalkyl group. Or hydrocarbon groups obtained by removing one or more hydrogen atoms from these hydrocarbon groups (the hydrocarbon groups are selected from hydroxyl groups, carboxyl groups, carbonyl groups, ester bonds, ether bonds) One or more groups or bonds may further be included, and elements other than carbon, hydrogen and oxygen, such as nitrogen and sulfur (for example, heterocyclic compounds), halogen (fluorine, chlorine, etc.), phosphorus, It may contain boron, metal, etc.).
In addition, although the said hydrocarbon group does not have a restriction | limiting in carbon number at all, Preferably it is C1-C40, More preferably, it is C2-C30, Most preferably, it is C3-C20.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or branched pentyl group, straight chain or Branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group , Linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched A branched heptadecyl group, a linear or branched octadecyl group, a linear or branched nonadecyl group, a linear or branched icosyl group, a linear or branched heicosyl group, a linear or branched docosyl group, Linear or branched tricosyl group, straight Or an alkyl group having 1 to 40 carbon atoms such as branched tetracosyl group, and preferably an alkyl group having 2 to 30 carbon atoms, particularly preferably an alkyl group having 3 to 20 carbon atoms.

  Examples of the alkenyl group include a vinyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, a linear or branched hexenyl group, and a linear chain. Or a branched heptenyl group, a linear or branched octenyl group, a linear or branched nonenyl group, a linear or branched decenyl group, a linear or branched undecenyl group, a linear or branched dodecenyl group Group, linear or branched tridecenyl group, linear or branched tetradecenyl group, linear or branched pentadecenyl group, linear or branched hexadecenyl group, linear or branched heptadecenyl group, linear or Branched octadecenyl group, linear or branched nonadecenyl group, linear or branched icocenyl group, linear or branched henicosenyl group, linear or branched dococenyl group, linear or branched tricosenyl group , Linear or minute Such alkenyl group having 2 to 40 carbon atoms can be mentioned such as a tetracosenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, particularly preferably alkenyl groups having 3 to 20 carbon atoms.

Furthermore, examples of the cycloalkyl group include cycloalkyl groups having 3 to 40 carbon atoms such as cyclopentyl group, cyclohexyl group, and cycloheptyl group cyclooctyl group, preferably cycloalkyl groups having 3 to 20 carbon atoms, particularly Preferably it is a C5-C8 cycloalkyl group.
Furthermore, examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group (including all structural isomers), a methylethylcyclopentyl group (including all structural isomers), a diethylcyclopentyl group (all Including structural isomers), methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (all structural isomers) ), Methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (including all structural isomers), diethylcycloheptyl group (all structural isomers) And alkyl cycloalkyl groups having 4 to 40 carbon atoms such as Is preferably an alkyl cycloalkyl group having 5 to 20 carbon atoms, particularly preferably an alkylcycloalkyl group having 6 to 12 carbon atoms.

Moreover, as said aryl group, they are C6-C20 aryl groups, such as a phenyl group and a naphthyl group, Preferably it is a C6-C10 aryl group.
Further, the alkylaryl group includes a tolyl group (including all structural isomers), an ethylphenyl group (including all structural isomers), a linear or branched propylphenyl group (all structural isomers). ), Linear or branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl group (including all structural isomers), linear or branched Branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (including all structural isomers), straight chain or branched octylphenyl group (all structural isomers) ), Linear or branched nonylphenyl group (including all structural isomers), linear or branched decylphenyl group (including all structural isomers), linear or branched Branched undecylphenyl group (all structural isomers Mono-substituted phenyl groups such as linear or branched dodecylphenyl groups (including all structural isomers); xylyl groups (including all structural isomers), diethylphenyl groups, dipropyl Phenyl group, 2-methyl-6-tert-butylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group, 2,6-di-tert-butyl-4- (3,5-di-) aryl groups having two or more same or different linear or branched alkyl groups such as tert-butyl-4-benzyl) phenyl group (an alkyl group further includes an aryl group, an alkylaryl group, and an arylalkyl group). An alkylaryl group having 7 to 40 carbon atoms, preferably an alkylaryl having 7 to 20 carbon atoms, and the like. , Particularly preferably an alkyl aryl group having 7 to 12 carbon atoms.

  Further, arylalkyl groups include benzyl, phenylethyl, phenylpropyl (including propyl isomers), phenylbutyl (including butyl isomers), and phenylpentyl (pentyl isomers). And arylalkyl groups having 7 to 40 carbon atoms such as phenylhexyl groups (including isomers of hexyl groups), preferably arylalkyl groups having 7 to 20 carbon atoms, particularly preferably 7 to 7 carbon atoms. 12 arylalkyl groups.

The oxygen-containing organic compound (C) can be similarly used even if it is a derivative of each compound described above. Derivatives include nitrogen-containing compounds, sulfur and sulfur-containing compounds, boron-containing compounds, halogen elements and halogen element compounds, metal elements and metal-containing compounds (regardless of organic and inorganic), compounds obtained by reacting alkylene oxides, etc. However, it is not limited to these. Specifically, for example, a compound obtained by sulfurizing one kind selected from the above alcohols, carboxylic acids, esters, ethers, ketones, aldehydes, and carbonates, and a halogenated (fluorinated, chlorinated, etc.) compound. Reaction with sulfuric acid, nitric acid, boric acid, phosphoric acid and esters or metal salts of these acids, and reaction with metals, metal-containing compounds, or alkylene oxide adducts or amine compounds reacted with alkylene oxides Products, etc.
Among these, reaction products (for example, Mannich reaction products, acylation reaction products, amides, etc.) of one or more selected from alcohols, carboxylic acids and aldehydes and derivatives thereof with amine compounds ) Is a preferred example.

Examples of the amine compound include ammonia, monoamine, diamine, and polyamine. More specifically, ammonia; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, penta Decylamine, hexadecylamine, heptadecylamine, octadecylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, Didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, di It has an alkyl group having 1 to 30 carbon atoms, such as tadecylamine, methylethylamine, methylpropylamine, methylbutylamine, ethylpropylamine, ethylbutylamine, and propylbutylamine (these alkyl groups may be linear or branched) Alkylamines;
Alkenyl amines having 2 to 30 carbon atoms such as ethenylamine, propenylamine, butenylamine, octenylamine, and oleylamine (these alkenyl groups may be linear or branched); methanolamine, ethanolamine, propanolamine , Butanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonanolamine, methanol ethanolamine, methanolpropanolamine, methanolbutanolamine, ethanolpropanolamine, ethanolbutanolamine, propanolbutanolamine, etc. Alkanolamines having 1 to 30 alkanol groups (these alkanol groups may be linear or branched);
Alkylene diamines having 1-30 carbon atoms such as methylene diamine, ethylene diamine, propylene diamine, and butylene diamine; polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine; undecyl diethylamine, undecyl Diethanolamine, dodecyldipropanolamine, oleyldiethanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and other monoamines, diamines, polyamines having an alkyl group or alkenyl group having 8 to 20 carbon atoms, N-hydroxyethyloleylimidazoline, etc. And heterocyclic compounds of these compounds; alkylene oxide adducts of these compounds; and mixtures thereof.
Among these nitrogen compounds, alkylamines or alkenylamines having a C10-20 alkyl group or alkenyl group such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine (these are linear And may be branched or branched).
Among these derivatives of oxygen-containing organic compounds, among the above-mentioned fatty acid monocarboxylic acids (fatty acids) (II-1) such as oleic acid amide, an amide of a carboxylic acid having 8 to 20 carbon atoms and the above-described amine compound Is a preferred example.

  As described above, the oxygen-containing organic compound has been described. Among these, those having a hydroxyl group are preferable because they are more excellent in friction reduction effect. Of the hydroxyl groups, an alcoholic hydroxyl group is more preferable than a hydroxyl group directly bonded to a carbonyl group such as a carboxyl group because the friction reducing effect is more excellent. Further, the number of such hydroxyl groups in the compound is not particularly limited, but it is preferable to have more hydroxyl groups because of more excellent friction reduction effect. However, when used together with a medium such as a lubricating base oil to be described later, the number of hydroxyl groups may be limited from the viewpoint of solubility.

  On the other hand, the aliphatic amine compound (D) in the low friction agent composition of the present invention is a straight chain having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, particularly preferably 10 to 20 carbon atoms. The thing which has an aliphatic hydrocarbon group can be mentioned. When the carbon number is outside the range of 6 to 30, there is a possibility that the friction reducing effect cannot be obtained sufficiently. In addition, as long as it has the linear or branched aliphatic hydrocarbon group of the said range, it is natural that you may have another hydrocarbon group.

Specific examples of the linear or branched aliphatic hydrocarbon group having 6 to 30 carbon atoms include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triaconyl Group such as alkyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonacenyl group, icosenyl group Group, can be exemplified henicosenyl group, docosenyl, tricosenyl group, tetracosenyl group, Pentakoseniru group, Hekisakoseniru group, Heputakoseniru group, Okutakoseniru group, Nonakoseniru group, an alkenyl group such as tri container group.
The alkyl group and alkenyl group include all possible linear structures and branched structures, and the position of the double bond in the alkenyl group is arbitrary.

Examples of the aliphatic amine compound (D) include nitrogen-containing heterocyclic compounds such as monoamines, polyamines, alkanolamines, and imidazoline compounds having the above-described linear or branched aliphatic hydrocarbon group having 6 to 30 carbon atoms. Examples of these various amine compounds and derivatives thereof.
Specific examples of the monoamine include laurylamine, lauryldiethylamine, palmitylamine, stearylamine, oleylamine and the like.
Specific examples of the polyamine include stearyltetraethylenepentamine and oleylpropylenediamine.
Specific examples of the alkanolamine include lauryl diethanolamine, dodecyl dipropanolamine, and oleyl diethanolamine.
Specific examples of the nitrogen-containing heterocyclic compound include N-hydroxyethyl oleylimidazoline and the like.
Examples of the derivatives include alkylene oxide adducts and acid-modified compounds.
Examples of the alkylene oxide adduct include those obtained by adding alkylene oxide to nitrogen atoms in the various amine compounds described above. Specifically, an N, N-dipolyoxyalkylene-N-alkyl (alkenyl) amine obtained by adding an alkylene oxide to a primary monoamine having an alkylene group or alkenyl group having 6 to 28 carbon atoms, More specifically, N, N-dipolyoxyethylene-N-oleylamine and the like can be mentioned.
Examples of the acid-modifying compound include the above-mentioned various amine compounds, the above-mentioned carboxylic acids (II), preferably the above-mentioned aliphatic monocarboxylic acids (II-1) (more preferably having 2 to 30 carbon atoms), and the above-mentioned aliphatic polyvalent compounds. Carboxylic acids (II-2) (more preferably having 2 to 30 carbon atoms; including oxalic acid, etc.), the above-mentioned carbocyclic carboxylic acids (II-3) (more preferably having 6 to 30 carbon atoms; phthalic acid, tri And those obtained by neutralizing or amidating part or all of the amino group and / or imino group by the action of merit acid, pyromellitic acid, etc.).

The oxygen-containing organic compound (C) and the aliphatic amine compound (D) are applied to the sliding surface composed of the DLC-coated sliding member (A) and the sliding member (B) as a low friction agent composition in the present invention. When used alone (ie, 100%), it exhibits extremely low friction characteristics. However, as the low friction agent composition in the present invention, an oxygen-containing organic compound (C) and / or an aliphatic amine compound (D) blended with other components is used on the sliding surface. It may be supplied and lubricated. Examples of other components include a medium such as a lubricating base oil, and various additives.
The content of the oxygen-containing organic compound (C) and the aliphatic amine compound (D) is not particularly limited, but the lower limit is usually 0 on the basis of the total amount of the low friction agent composition from the viewpoint of the friction reducing effect. 0.001%, preferably 0.05%, more preferably 0.1%, particularly preferably 0.5%. On the other hand, the upper limit is 100% as described above. However, when other components, particularly a medium, are blended, from the viewpoint of solubility in the medium and storage stability, it is usually based on the total amount of the low friction agent composition. 50%, preferably 20%, more preferably 10%, particularly preferably 5%. In the present invention, the oxygen-containing organic compound (C) and the aliphatic amine compound (D) can exhibit excellent low friction characteristics even when added in a small amount of about 0.1 to 2%. Moreover, you may make it contain exceeding 3.0%. In addition, when importance is attached to the solubility of the aliphatic amine compound (D) in the medium and the storage stability, the upper limit is preferably 3.0%, and more preferably 2.0%. More preferably, it is 1.4%.

  Specifically, as the above-mentioned medium, for example, mineral oil, synthetic oil, natural fats and oils, diluent oil, grease, wax, hydrocarbons having 3 to 40 carbon atoms, hydrocarbon solvents, organic solvents other than hydrocarbons, Water, etc., and mixtures thereof, particularly those which are liquid, grease-like or wax-like at the sliding conditions and at normal temperature.

  Further, as the medium, it is particularly preferable to use a lubricating base oil. Further, such a lubricating base oil is not particularly limited, and can be used regardless of whether it is a mineral base oil or a synthetic base oil, as long as it is normally used as a base oil of a lubricating oil composition. it can.

  As mineral oil base oils, specifically, lubricating oil fractions obtained by subjecting crude oil to atmospheric distillation and vacuum distillation can be desolvated, solvent extraction, hydrocracking, solvent dewaxing, hydrorefining In addition, those obtained by refining by one or more treatments such as wax isomerization are used, and in particular, various base oils such as those subjected to hydrocracking treatment, hydrorefining treatment or wax isomerization treatment are used. Can do. Among these, isoparaffinic compounds obtained by isomerizing GTL (Gas Liquid Liquid) wax by hydrorefining or hydrocracking mineral oil, Fischer-Tropsch process, and waxes containing a large amount of normal paraffin obtained in the dewaxing process of lubricating oil Mineral oil is preferred.

  Specific examples of synthetic lubricating base oils include alkylnaphthalene, alkylbenzene, polybutene or hydrides thereof; poly-α-olefins such as 1-octene oligomers, 1-decene oligomers, ethylene-propylene oligomers, or hydrides thereof. Isobutene oligomer, hydride of isobutene oligomer; isoparaffin, alkylbenzene, alkylnaphthalene, diester (for example, ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, dioctyl sebacate, etc.), polyol ester (for example, trimethylolpropane) Trimethylolpropane esters such as caprylate, trimethylolpropane pelargonate, trimethylolpropane isostearinate; pentaerythritol Le 2-ethylhexanoate, pentaerythritol ester such as pentaerythritol pelargonate), polyoxyalkylene glycols, dialkyl ethers, polyphenyl ethers and the like; and mixtures thereof and the like. Preferred examples of the synthetic lubricating base oil include poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof.

  In addition to using mineral oil base oil or synthetic base oil alone or in combination, it may be a mixture of two or more mineral base oils or two or more synthetic base oils. . Further, the mixing ratio of two or more kinds of base oils in the above mixture is not particularly limited and can be arbitrarily selected.

  Further, the total aromatic content of the lubricating base oil is not particularly limited, but is preferably 15% or less, more preferably 10% or less, and still more preferably 8%. When the total aromatic content of the lubricating base oil exceeds 15%, oxidation stability is inferior, which is not preferable. In addition, high hydrocracked mineral oil or wax isomerized mineral oil, poly-α-olefin or its hydride 1-decene oligomer hydride, polyol ester and other ester-based lubricant base oils, and mixtures thereof, etc. Even if the total aromatic content of the oil is 2% or less, or 0%, a composition having a high friction reducing effect can be obtained. In addition, when the content of the oxygen-containing organic compound (C) (excluding esters as a lubricating base oil) is large, for example, when it exceeds 2%, storage stability may be inferior. If necessary, adjust the total aromatic content of the lubricating base oil by blending solvent refined mineral oil or alkylbenzene as necessary (for example, 2% or more), or use esters as the lubricating base oil. By doing so, it is preferable to enhance the solubility of the oxygen-containing compound (C). Here, the “total aromatic content” means an aromatic fraction content measured in accordance with ASTM D2549. Usually, this aromatic fraction includes alkylbenzene, alkylnaphthalene, anthracene. Phenanthrene, and alkylated products thereof, compounds in which four or more benzene rings are condensed, or compounds having heteroaromatics such as pyridines, quinolines, phenols, naphthols, and the like.

  Further, the sulfur content in the lubricating base oil is not particularly limited, but is preferably 0.2% or less, more preferably 0.1% or less, and even 0.05% based on the total amount of the base oil. The following is preferable. In particular, since the sulfur content of hydrorefined mineral oil or synthetic base oil is 0.005% or less, or contains substantially no sulfur content (5 ppm or less), these are preferably used as the base oil.

Furthermore, the kinematic viscosity of the lubricating base oil is not particularly limited, but when used as a lubricating oil composition for an internal combustion engine, the kinematic viscosity at 100 ° C. is preferably 2 mm ² / s or more, More preferably, it is 3 mm ² / s or more. On the other hand, the upper limit is preferably 20 mm ² / s or less, preferably 10 mm ² / s or less, and particularly preferably 8 mm ² / s or less. A composition in which the kinematic viscosity at 100 ° C. of the lubricating base oil is 2 mm ² / s or more is sufficient to form an oil film, has excellent lubricity, and has a smaller base oil evaporation loss under high conditions. Can be obtained. On the other hand, by setting the kinematic viscosity at 100 ° C. to 20 mm ² / s or less, the fluid resistance becomes small, so that a composition having a smaller frictional resistance at the lubrication point can be obtained. In addition, when kinematic viscosity is less than 2 mm < ² > / s, since sufficient abrasion resistance is not acquired and an evaporation characteristic may be inferior, it is unpreferable. On the other hand, when the kinematic viscosity exceeds 20 mm ² / s, it is difficult to exhibit low friction performance, and low temperature performance may be deteriorated. In the present invention, a mixture of any two or more base oils selected from the above base oils can be used, and the base oil alone is used as long as the kinematic viscosity at 100 ° C. falls within the above preferred range. Even if the kinematic viscosity is other than the above, it can be used.

  The viscosity index of the lubricating base oil is not particularly limited, but is preferably 80 or more. When used as a lubricating oil composition for an internal combustion engine, it is preferably 100 or more, and 120 or more. More preferably, it may be 140 or more and 250 or less. By selecting a lubricant base oil having a high viscosity index, it is possible to obtain a composition that not only has excellent low-temperature viscosity characteristics, but also has low oil consumption, excellent low-temperature viscosity characteristics, fuel-saving performance, and friction reduction effect. .

  The low friction agent composition further includes an ashless dispersant, an antiwear or extreme pressure agent, a metallic detergent, an antioxidant, a viscosity index improver, a friction modifier other than (C) and (D), Various additives such as a rusting agent, a nonionic surfactant, a demulsifier, a metal deactivator, and an antifoaming agent can be blended singly or in combination of a plurality of types to enhance the required performance.

Various known ashless dispersants can be used as the ashless dispersant, and it is preferable to contain, for example, polybutenyl succinimide and derivatives thereof.
Examples of the polybutenyl succinimide include the following chemical formulas (1) and (2)

The compound represented by these is mentioned. PIB in these chemical formulas represents a polybutenyl group, and the number average molecular weight obtained by polymerizing a high purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst is 900 to 3500, preferably 1000. Obtained from ˜2000 polybutenes. When the average molecular weight is less than 900, the cleanability effect tends to be poor, and when it exceeds 3500, the low temperature fluidity tends to be poor.
Further, n in the chemical formula is preferably an integer of 1 to 5, more preferably an integer of 2 to 4, from the viewpoint of excellent cleanliness. Further, the polybutene is used to remove a trace amount of fluorine and chlorine remaining due to the catalyst in the production process by an appropriate method such as an adsorption method or sufficient water washing, and is preferably 50 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm. It is also possible to use after removing to the following.

  Furthermore, the method for producing the polybutenyl succinimide is not particularly limited. For example, the polybutene chlorinated product or polybutene from which chlorine or fluorine is sufficiently removed and maleic anhydride are reacted at 100 to 200 ° C. The butenyl succinic acid obtained by reacting with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine can be obtained.

  On the other hand, as a derivative of the polybutenyl succinimide, a boron compound or an oxygen-containing organic compound is allowed to act on the compounds represented by the chemical formulas (1) and (2) to form a remaining amino group and / or imino group. Examples thereof include so-called boron-modified compounds or acid-modified compounds that are partially or completely neutralized or amidated. Typically, it is more desirable to use boron-containing polybutenyl succinimide, particularly boron-containing bispolybutenyl succinimide.

Examples of the boron compound include boric acid, borates, and borate esters. Specifically, examples of the boric acid include orthoboric acid, metaboric acid, and paraboric acid. Examples of the borate include ammonium salts such as ammonium borate such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate. Further, as boric acid ester, ester of boric acid and alkyl alcohol (preferably having 1 to 6 carbon atoms), for example, monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate Preferred examples include monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate and tributyl borate. In addition, the mass ratio “B / N” of the boron content B and the nitrogen content N in the boron-containing polybutenyl succinimide is usually 0.1 to 3, and preferably 0.2 to 1.
Specific examples of the oxygen-containing organic compound include formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, and undecyl acid. , Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid and eicosanoic acid, etc., monocarboxylic acid having 1 to 30 carbon atoms, oxalic acid, phthalic acid, trimellit Examples thereof include polycarboxylic acids having 2 to 30 carbon atoms such as acid and pyromellitic acid and anhydrides or ester compounds thereof, alkylene oxides having 2 to 6 carbon atoms, and hydroxy (poly) oxyalkylene carbonate.

In the low friction agent composition used in the present invention, the content of polybutenyl succinimide and / or its derivative is not particularly limited, but is preferably 0.1 to 15%, and more preferably 1.0 to 12. %. If it is less than 0.1%, the cleaning effect may be poor, and if it exceeds 15%, it is difficult to obtain a cleaning effect corresponding to the content, and the demulsibility tends to deteriorate.
Other ashless dispersants include polybutenylbenzylamine and polybutenylamine having a polybutenyl group having a number average molecular weight of 900 to 3500, and polybutenyl succinimide having a polybutenyl group having a number average molecular weight of less than 900. And derivatives thereof.

  As the antiwear agent or extreme pressure agent, various known materials can be blended. For example, the following chemical formula (3)

It is preferable to contain the zinc dithiophosphate represented by these.
R ⁴ , R ⁵ , R ⁶ and R ⁷ in the chemical formula (3) each independently represent a hydrocarbon group having 1 to 24 carbon atoms. Examples of these hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, linear or branched alkenyl groups having 3 to 24 carbon atoms, and cycloalkyl groups having 5 to 13 carbon atoms. Or a linear or branched alkylcycloalkyl group, an aryl group having 6 to 18 carbon atoms, or a linear or branched alkylaryl group, an arylalkyl group having 7 to 19 carbon atoms, or the like. It is desirable to be. The alkyl group or alkenyl group may be any of primary, secondary, and tertiary.

Specific examples of R ⁴ , R ⁵ , R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Alkyl groups such as undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group and tetracosyl group, propenyl group, Isopropenyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and oleyl Octade Nyl group, nonadecenyl group, icocenyl group, hencocenyl group, dococenyl group, alkenyl group such as tricocenyl group and tetracocenyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group, methylcyclopentyl group, dimethylcyclopentyl group, Ethylcyclopentyl group, propylcyclopentyl group, ethylmethylcyclopentyl group, trimethylcyclopentyl group, diethylcyclopentyl group, ethyldimethylcyclopentyl group, propylmethylcyclopentyl group, propylethylcyclopentyl group, di-propylcyclopentyl group, propylethylmethylcyclopentyl group, methylcyclohexyl Xyl group, dimethylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, ethylmethylcyclohexane Xyl group, trimethylcyclohexyl group, diethylcyclohexyl group, ethyldimethylcyclohexyl group, propylmethylcyclohexyl group, propylethylcyclohexyl group, di-propylcyclohexyl group, propylethylmethylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group Group, ethylcycloheptyl group, propylcycloheptyl group, ethylmethylcycloheptyl group, trimethylcycloheptyl group, diethylcycloheptyl group, ethyldimethylcycloheptyl group, propylmethylcycloheptyl group, propylethylcycloheptyl group, di-propylcyclo Alkyl cycloalkyl groups such as heptyl and propylethylmethylcycloheptyl, aryl groups such as phenyl and naphthyl, tolyl, xylyl , Ethylphenyl group, propylphenyl group, ethylmethylphenyl group, trimethylphenyl group, butylphenyl group, propylmethylphenyl group, diethylphenyl group, ethyldimethylphenyl group, tetramethylphenyl group, pentylphenyl group, hexylphenyl group, heptyl Alkyl groups such as phenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl, benzyl, methylbenzyl, dimethylbenzyl, phenethyl, methylphenethyl and dimethylphenethyl An arylalkyl group such as
The hydrocarbon group includes all possible straight chain structures and branched structures, and also includes the position of the double bond of the alkenyl group, the position of bond of the alkyl group to the cycloalkyl group, and the alkyl group. The position of bonding of the aryl group to the aryl group and the position of bonding of the aryl group to the alkyl group are arbitrary.

  Preferred examples of the zinc dithiophosphate include, for example, zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-sec-pentyldithiophosphate, zinc di-n-hexyldithiophosphate. , Zinc di-sec-hexyldithiophosphate, zinc di-octyldithiophosphate, zinc di-2-ethylhexyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, zinc diisotridecyldithiophosphate , And mixtures of these arbitrary combinations.

  The content of the zinc dithiophosphate is not particularly limited, but is preferably 0.1% or less in terms of the total amount of the composition and in terms of phosphorus element, from the viewpoint of exerting a higher friction reduction effect. It is more preferable that it is 0.06% or less, and it is particularly preferable that zinc dithiophosphate is not contained. When the content of zinc dithiophosphate exceeds 0.1% in terms of phosphorus element, excellent friction reducing effect of the oxygen-containing organic compound (C) on the sliding surface between the DLC member and various metal materials, particularly iron-based materials May be disturbed.

Further, the zinc dithiophosphate is not particularly limited and can be produced by employing any conventional method. Specifically, for example, alcohol or phenol having a hydrocarbon group corresponding to R ⁴ , R ⁵ , R ⁶ and R ⁷ in the chemical formula (3) is reacted with niline pentasulfide to form dithiophosphoric acid, It can be synthesized by neutralizing with zinc oxide. In addition, it cannot be overemphasized that the structure of the said zinc dithiophosphate differs according to the raw material alcohol etc. to be used.
Other antiwear agents or extreme pressure agents include disulfides, sulfurized fats and oils, sulfurized olefins, phosphate esters, thiophosphate esters, and phosphite esters containing 1 to 3 hydrocarbon groups having 2 to 20 carbon atoms. , Thiophosphite esters and amine salts thereof.

As the metallic detergent, any compound usually used as a metallic detergent for lubricating oil can be used. For example, alkali metal or alkaline earth metal sulfonates, phenates, salicylates, naphthenates, and the like can be used alone or in combination. Here, examples of the alkali metal include sodium (Na) and potassium (K), and examples of the alkaline earth metal include calcium (Ca) and magnesium (Mg). Specific preferred examples include Ca or Mg sulfonates, phenates and salicylates.
In addition, the total base number and addition amount of these metal detergents can be arbitrarily selected according to the required performance of the lubricating oil. Usually, it is 0-500 mgKOH / g by the perchloric acid method, Preferably it is 150-400 mgKOH / g, The addition amount is 0.1 to 10% normally based on the composition whole quantity basis.

  As the antioxidant, any compound usually used as an antioxidant for lubricating oils can be used. For example, 4,4-methylenebis (2,6-di-tert-butylphenol) and octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3-methyl- Phenol antioxidants such as 5-tert-butyl-4-hydroxyphenyl) propionate, amine antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine and alkyldiphenylamine, and any combination thereof. Such a mixture is mentioned. Moreover, the addition amount of this antioxidant is 0.01 to 5% normally on the basis of the total amount of the composition.

Specific examples of the viscosity index improver include so-called non-dispersion type viscosity index improvers such as various methacrylic acids or copolymers and hydrogenated products thereof, and various methacrylic compounds containing nitrogen compounds. Examples thereof include a so-called dispersion type viscosity index improver obtained by copolymerizing an acid ester. Further, non-dispersed or dispersed ethylene-α-olefin copolymers (for example, propylene, 1-butene, 1-pentene, etc.) and hydrides thereof, polyisobutylene and hydrogenated products thereof, styrene- Examples thereof include diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes.
The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is, for example, 5,000 to 1,000,000, preferably 100,000 to 800,000 for dispersed and non-dispersed polymethacrylates, 800 to 5,000 for polyisobutylene or a hydride thereof, ethylene- The α-olefin copolymer and its hydride have a value of 800 to 300,000, preferably 10,000 to 200,000. Moreover, although this viscosity index improver can be contained individually or in combination of multiple types, it is desirable for the content to be 0.1 to 40.0% based on the composition.

Examples of the friction modifier other than (C) and (D) include metal friction modifiers such as boric acid ester, molybdenum dithiophosphate, molybdenum dithiocarbamate, and molybdenum disulfide.
Examples of the rust inhibitor include alkyl benzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
Furthermore, examples of the nonionic surfactant and demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether and polyoxyethylene alkyl naphthyl ether. .
Furthermore, examples of the metal deactivator include imidazoline, pyrimidine derivatives, thiadiazole, benzotriazole, and thiadiazole.
Examples of the antifoaming agent include silicone, fluorosilicone, and fluoroalkyl ether.
In addition, when these additives are contained in the low friction agent composition used in the present invention, the content is based on the total amount of the composition, the friction modifier other than (C) and (D), the rust inhibitor, and The demulsifier can be appropriately selected from the range of 0.01 to 5%, and the metal deactivator can be appropriately selected from the range of 0.0005 to 1%.

Next, the friction reducing method of the present invention will be described in detail.
Such a friction reducing method includes a DLC-coated sliding member (A) formed by coating diamond-like carbon, a coating material formed by coating a metal material, a non-metal material, or a thin film on these surfaces, and any combination thereof. The low friction agent composition is interposed on the sliding surface formed by the sliding member (B) using the material according to the present invention, and the oxygen-containing organic compound (C) and the aliphatic amine compound are present on the sliding surface. At least one selected from the group consisting of (D) is supplied. Thereby, the low friction characteristic of various sliding surfaces can be improved.

Next, the manual transmission of the present invention will be described in detail.
A manual transmission according to the present invention uses the above-described low friction sliding mechanism, and slides formed by coating diamond-like carbon on at least one sliding surface of members that slide with each other in the presence of a low friction agent composition. Provide the site. As a result, the friction coefficient of the sliding part is reduced, the seizure resistance and the wear resistance are improved, and the sliding resistance of each part is small, which contributes to the improvement of the fuel consumption of the automobile.

  FIG. 1 is a cross-sectional view showing an example of a sliding part in an automobile manual transmission according to the present invention. The manual transmission 1 according to the present invention is rotated by two ball bearings 2a and 2b in a clutch housing. An input shaft 3 that is freely supported and a main shaft 5 that is rotatably supported by a roller bearing 4a and a ball bearing 4b are provided. The input shaft 3 includes a third speed input gear 3a and a fourth speed input gear 3b. Are rotatably fitted via needle bearings 2c and 2d, respectively, and the fifth speed input gear 3c is fixed.

  On the other hand, the main shaft 5 has a first speed main gear 5a meshed with a gear 3d formed on the input shaft 3 by a needle bearing 4c, and a second speed main gear 5b meshed with a gear 3e of the input shaft 3 is a second speed bush. The needle bearings 4d attached via 6a are respectively rotatably fitted. Further, a 5-speed main gear 5c meshing with the 5-speed input gear 3c of the input shaft 3 is rotatably fitted to the main shaft 5 by a needle bearing 4e attached via a 5-speed bush 6b.

  In the manual transmission 1 according to the present invention, the sliding portion between the input shaft 3 and the needle bearing 2c of the third speed input gear 3a and the sliding between the input shaft 3 and the needle bearing 2d of the fourth speed input gear 3b. A hard carbon thin film can be coated on the surface of the moving part on the side of the input shaft 3. Of course, a hard carbon thin film may be coated on the surfaces of the needle bearings 2c and 2d, or a hard carbon film may be formed on both of them.

  As for the main shaft 5, the surface of the main shaft 5 at the sliding portion between the main shaft 5 and the needle bearing 4c of the first speed main gear 5a, the sliding between the second speed bush 6a of the main shaft 5 and the needle bearing 4d. The hard carbon thin film can be coated on the surface of the bushes 6a and 6b at the site and the sliding site between the 5-speed bush 6b and the needle bearing 4e. In this case as well, it is possible to form a hard carbon coating on both the surface of the needle bearing 4c, 4d or 4e, or on the sliding surfaces which are in sliding contact with each other.

Note that the inner peripheral surfaces of the third speed input gear 3a, the fourth speed input gear 3b, the first speed main gear 5a, the second speed main gear 5b, and the fifth speed main gear 5c that are in sliding contact with the needle bearings 2c, 2d, 4c, 4d, and 4e are rigid. It is also desirable if necessary to form a carbon coating.
In the above description, the three-speed input gear 3a and the fourth-speed input gear 3b of the input shaft 3 and the first five-speed main gear 5a and the second-speed main gear 5b and the fifth-speed main gear 5c of the main shaft 5 Although an example in which a hard carbon thin film is formed is shown, other sliding parts, for example, ball bearings 2a, 2b, 4b that rotatably support the input shaft 3 and the main shaft 5 and each sliding part of the roller bearing 4a are provided. A hard carbon thin film may be formed.
Furthermore, the low friction agent composition for a manual transmission to be used exhibits extremely excellent low friction characteristics when used on a sliding surface with a hard carbon thin film such as DLC. Metal detergents, antioxidants, viscosity index improvers, other ashless friction modifiers, other ashless dispersants, antiwear or extreme pressure agents, and rust inhibitors for the purpose of enhancing the performance required as hydraulic oil A nonionic surfactant, a demulsifier, a metal deactivator, an antifoaming agent, etc. can be blended singly or in combination of a plurality of types to enhance the required performance.

Next, the final reduction gear of the present invention will be described in detail.
The final reduction gear of the present invention uses the above-mentioned low friction sliding mechanism, and a sliding formed by coating diamond-like carbon on at least one sliding surface of members that slide with each other in the presence of the low friction agent composition. Provide the site. As a result, the friction coefficient of the sliding part is reduced, the seizure resistance and the wear resistance are improved, and the sliding resistance of each part is small, which contributes to the improvement of the fuel consumption of the automobile.

  FIG. 2 is a cross-sectional view showing an example of a sliding portion in the automobile final reduction gear according to the present invention. The final reduction gear 20 according to the present invention is provided with a drive pinion at a tip portion in a differential carrier (reduction gear box) 22. Drive shaft 23 provided with 23a, ring gear 25a meshing with drive pinion 23a are fixed, and differential case 25 is rotatably supported by differential carrier 22 via side bearing 24, and is rotatably held inside differential case 25 The two side gears 26 and two pinion mate gears 28 that are rotatably supported by the pinion mate shaft 27 in the differential case 25 and mesh with the side gears 26, respectively. The roller bearing 29 is rotatably supported by the differential carrier 22 and is connected to the propeller shaft. .

In the final speed reducer 20, when the propeller shaft rotates, the rotation is transmitted to the differential case 25 via the drive pinion 23a and the ring gear 25a. However, when the vehicle goes straight, the differential case 25 moves to the side gear 26 and the pinion mate gear. 28 and the left and right drive wheel axles rotate at the same speed.
On the other hand, when the vehicle approaches a curve, the resistance of the inner axle increases, so the side gear 26 and the pinion mate gear 28 rotate in the differential case 5 respectively, and the inner axle rotates slowly, and the outer axle rotates accordingly. The speed is increased, enabling the vehicle to turn smoothly.

  Here, as the sliding member in the final reduction gear 20, for example, the rollers 24 a and the inner race 24 b of the side bearing 24, the differential case 25, the side gear 26, the pinion mate shaft 27, the pinion mate gear 28, and the differential case 25 and the side gear 26 are used. A washer 30 that adjusts the backlash by interposing between the roller 24a and the inner race 24b of the side bearing 24, between the inner surface of the differential case 25 and the side gear 26, and the inner surface of the differential case 25. Low friction between the washer 30, between the back surface of the side gear 26 and the washer 30, between the outer peripheral surface of the pinion mate shaft 27 and the pinion mate gear 28, and between the back surface of the pinion mate gear 28 and the inner surface of the differential case 25. Sliding on each other in the presence of the agent composition One sliding surface at these sliding portions, for example, the end surface of the roller 24a in the side bearing 24, the inner surface of the differential case 25, the outer peripheral surface of the pinion mate shaft 27, the back surface of the pinion mate gear 28, the washer. A hard carbon thin film can be coated on both sides of 30. Of course, the other sliding surface of these sliding surfaces may be covered, or a hard carbon film may be formed on both of these sliding surfaces.

  Further, a hard carbon thin film may be formed on one or both of the sliding parts other than the above, for example, the end face of the roller 29a and the outer peripheral face of the inner race 29b in the roller bearing 29 supporting the drive shaft 23.

  Furthermore, the low friction agent composition for the final reduction gear to be used exhibits extremely excellent low friction characteristics when used on a sliding surface with a hard carbon thin film such as DLC. Metal detergents, antioxidants, viscosity index improvers, other ashless friction modifiers, other ashless dispersants, antiwear or extreme pressure agents, and rust inhibitors for the purpose of enhancing the performance required as hydraulic oil A nonionic surfactant, a demulsifier, a metal deactivator, an antifoaming agent, etc. can be blended singly or in combination of a plurality of types to enhance the required performance.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in full detail, this invention is not limited to these Examples.

1. Low friction sliding mechanism (sliding member)
As an example of the sliding member, a pin-on-disk friction test piece as shown in FIG. 3 was produced. This unit test piece is composed of three pins and a disc (disk), and is made using a sliding member obtained by the following method.
-Pin material After the SUJ2 heat-treated material was polished into a predetermined pin shape, the pins were finished to various surface roughnesses (Ra 0.2 μm or less) by polishing using a wrapping tape.
-Disc material A disc-shaped material made of SUJ2 heat treatment material and AC2A material was subjected to a predetermined aging coin treatment, and then the sliding surface with the pin was polished to have various surface roughnesses.
-Surface treatment The following materials (1) to (3) were coated on the surface of the pin material or disk material finished as described above by PVD treatment or CVD treatment using graphite as a target so as to have various film thicknesses. . The coated surface was further finished to various surface roughnesses (Ra 0.1 μm or less) by polishing with a wrapping tape.
(1) aC (PVD treatment)
(2) DLC (a-C: H) (CVD process)
(3) CrN
These sliding members are shown in Table 1.

(Preparation of low friction agent composition)
・ Sample oil 1
1-decene oligomer hydride (100 ° C. kinematic viscosity: 3.9 mm ² / s, viscosity index: 124, total aromatic content: 0.0%) was used as the lubricating base oil, and oleyl was used as the oxygen-containing organic compound. 1.0% alcohol and 13.0% other additives (ashless dispersant: polybutenyl succinimide (nitrogen content: 1.2%)) 5.0%, metallic detergent: 0.5% of calcium sulfonate (total base number: 300 mg KOH / g, calcium content: 12.0%) and 0.8% of calcium phenate (total base number: 255 mg KOH / g, calcium content: 9.2%) 9%) and a viscosity index improver, an antioxidant, an extreme pressure agent, a rust inhibitor, a demulsifier, a nonionic surfactant, a metal deactivator, an antifoaming agent, and the like.
・ Sample oil 2
It was prepared by repeating the same operation as Sample 1 except that 13.0% of other additives were not blended.
・ Sample oil 3
It was prepared by repeating the same operation as Sample 1 except that oleic acid was used as the oxygen-containing organic compound.
・ Sample oil 4
It was prepared by repeating the same operation as Sample 1 except that 0.5% oleyl alcohol and 0.5% oleic acid were used as the oxygen-containing organic compound.
・ Sample oil 5
Hydrocracked mineral oil (100 ° C. kinematic viscosity: 5.0 mm ² / s, viscosity index: 120, total aromatic content: 5.5%) as the lubricating base oil, oleic acid amide 1 as the oxygen-containing organic compound It was prepared by repeating the same operation as Sample 1 except that 0.0% was added.
・ Sample oil 6
A commercial engine oil having a kinematic viscosity at 100 ° C. of 10.2 mm ² / s was used.
・ Sample oil 7
It was prepared by repeating the same operation as Sample 5 except that 1.0% of molybdenum dithiocarbamate was added instead of oleic acid amide.
・ Sample oil 8
Glycerol (Glycerol Anhydrous: 1,2,3-Propanetriol, Fluka (manufactured by Sigma Aldrich Japan Co., Ltd.)) was used alone (100%).
・ Sample oil 9
Triester (KAOLUBE KSL-268) of trimethylolpropane and i-C8, n-C8, C10, C11 fatty acid mixture was used alone (100%).
・ Sample oil 10
The same procedure as in Sample 5 was repeated except that 1.0% of glycerol monooleyl ether was added as the oxygen-containing organic compound.
Sample oil 11
Glycerol mono-2-ethylhexyl ether was used alone (100%).
Table 2 shows the compositions of these low friction agent compositions and their sample properties.

(Examples 1 to 13)
As shown in Table 1, each sliding member is combined, and each low friction agent composition (sample oils 1 to 5, 8 to 11) described in Table 1 is used to produce a low friction sliding mechanism. The following pin-on-disk friction test was conducted. The results are shown in Table 1.

[Pin-on-disk friction test]
Maximum hertz pressure: 80 MPa
Disk rotation speed: 30 rpm
Oil supply method: Oil bath Supply oil temperature: 80 ° C
Test time: 60 min

(Comparative Examples 1-4)
In the same manner as in the examples, each sliding member was combined, and each low friction agent composition (sample oil 1, 2, 6, 7) described in Table 1 was used to prepare a low friction sliding mechanism. The pin-on-disk friction test was conducted. The results are shown in Table 1.

From Table 1, it turns out that the combination of the base material and sample oil which were obtained in Examples 1-13 shows the outstanding low friction coefficient. For example, as compared with Comparative Example 1 using a combination of a base material and a sample oil 6 used in a general gasoline engine, these exhibited a friction reduction effect of about 50 to 70%.
Moreover, it turns out that the hydroxyl group in a low friction agent composition is excellent in the friction reduction effect from the result of Examples 6-8.
Furthermore, it can be seen from the results of Examples 10 and 11 that the compound having an alcoholic hydroxyl group is excellent in the friction reducing effect.
In addition, the test pieces obtained in Examples 1 to 11 had no problem in the surface shape after the test, were very excellent in wear resistance, and exhibited stable low friction characteristics.

  Here, the combination of the test piece base material and the low friction agent composition of Reference Example 1 is most effective for the sliding surface between the steel material that has been subjected to chromium nitride treatment on one side and the steel material as the low friction agent composition. This is a combination of organic molybdenum. As a result, the coefficient of friction is as low as about 0.06. It is presumed that this is a reduction in friction due to the formation of a molybdenum disulfide coating on the sliding surface, in the same way that the mechanism has been studied in each direction. In the present invention, this low friction is one standard, and it can be seen that the low friction characteristics in the above-described embodiments are very excellent.

Moreover, the combination of the test piece base material and low friction agent composition of Comparative Example 1 is general bearing steel and engine oil. As a result, the friction coefficient exceeds 0.1 and the friction characteristics are inferior. This can be presumed to be because the mechanism showing the low friction behavior suggested in this patent is not sufficiently acting.
On the other hand, Comparative Example 2 is a combination of a steel material subjected to diamond-like carbon treatment on one side and a sample oil blended with an organic molybdenum compound, but the friction coefficient is as high as about 0.1, and the effect as in Example 2 is obtained. I can't. This is presumably because the friction reducing mechanism is different from the sliding surface between conventional steel materials.
Further, Comparative Example 3 and Comparative Example 4 are applied to the steel material obtained by performing chromium nitride treatment on the base material used in Comparative Example 2 and the sample oil used in the example, that is, the steel material obtained by subjecting one side to diamond-like carbon treatment. In this case, it is a combination with a sample oil that has a low friction effect. As a result, the coefficient of friction showed a value exceeding 0.1. This is presumed to be because the metal material and sample oil shown in this patent are a different combination and do not lead to low friction.

  In addition, the combination of the test piece base material and the low friction agent composition of Reference Example 1 is most effective for a sliding surface between a steel material subjected to chromium nitride treatment on one side and a conventional steel material as a low friction agent composition. This is a combination with the sample oil 7 containing the organic molybdenum. As a result, the coefficient of friction is as low as about 0.05. This is presumed to be a reduction in friction due to the formation of a molybdenum disulfide film on the sliding surface, in the same way as the mechanism has been studied.

2. As shown in FIG. 4, a cylinder-on-disk single-piece reciprocating friction test was performed using a cylindrical test piece 11 as a sliding test piece and a disk-like test piece 12 as a counterpart test piece. The coefficient of friction was measured under

[1] Friction test conditions Test equipment: Cylinder-on-disk single-reciprocating friction tester Sliding side test piece: φ15 × 22 mm cylindrical test piece Opposite side test piece: φ24 × 7.9 mm disc-shaped test piece Load: 400 N (sliding Side test piece pressing load)
Amplitude: 3.0 mm
Frequency: 50Hz
Test temperature: 80 ° C
Measurement time: 30 minutes

[2] Production of cylindrical test piece (sliding side) Cylindrical test piece 11 which is a sliding side test piece is machined to the above dimensions using SUJ2 steel specified as a high carbon chromium bearing steel in JIS G4805. After that, the surface roughness Ra was finished to 0.04 μm.

[3] Preparation of disk-shaped test piece (sliding mating side) Using SUJ2 steel, the disk-shaped test piece 12 which is the mating test piece is machined to the above dimensions, and the surface roughness Ra of the upper sliding surface is obtained. After finishing to 0.05 μm, the amount of hydrogen atoms on this surface is 0.5 atomic% or less, Knoop hardness Hk = 2170 kg / mm ² , surface roughness Ry = 0 by PVD arc ion ion plating method. A 0.03 μm DLC thin film was formed to a thickness of 0.5 μm. In addition, what did not coat | cover the DLC thin film was used for the comparative example.

[4] Preparation of low friction agent composition for manual transmission As a low friction agent composition for manual transmission, mineral oil or synthetic oil (PAO: polyalphaolefin (1-octene oligomer)) as a base oil, SP system ( S and P containing mineral or thiophosphate amine salt 0.5% by mass), ZnDTP (zinc dithiolate) -based extreme pressure agent (1.5% by mass as compound), antiwear agent, fatty acid ester-based or A combination of aliphatic amine friction modifiers was prepared.

[5] Test results The above-mentioned cylindrical test piece, disk-shaped test piece, and low friction agent composition for manual transmission were combined as shown in Table 3, and the friction coefficient was measured according to the above procedure. The result is shown in FIG.

  As is clear from the results of FIG. 5, in the example using the disk-shaped test piece in which the DLC thin film was formed on the upper sliding surface, compared to the comparative example using the disk-shaped test piece without the DLC thin film, It was confirmed that the coefficient of friction was significantly reduced.

3. Final reducer As shown in FIG. 4, a cylinder-on-disk reciprocating friction test was performed using a cylindrical specimen 11 as a sliding specimen and a disk specimen 12 as a counterpart specimen. The coefficient of friction was measured under
[1] Friction test conditions Test equipment: Cylinder-on-disk single-reciprocating friction tester Sliding side test piece: φ15 × 22 mm cylindrical test piece Opposite side test piece: φ24 × 7.9 mm disc-shaped test piece Load: 400 N (sliding Side test piece pressing load)
Amplitude: 3.0 mm
Frequency: 50Hz
Test temperature: 80 ° C
Measurement time: 30 minutes

[2] Production of cylindrical test piece (sliding side) Cylindrical test piece 11 which is a sliding side test piece is machined to the above dimensions using SUJ2 steel specified as a high carbon chromium bearing steel in JIS G4805. After that, the surface roughness Ra was finished to 0.04 μm.

[3] Preparation of disk-shaped test piece (sliding mating side) Using SUJ2 steel, the disk-shaped test piece 12 which is the mating test piece is machined to the above dimensions, and the surface roughness Ra of the upper sliding surface is obtained. After finishing to 0.05 μm, the amount of hydrogen atoms on this surface is 0.5 atomic% or less, Knoop hardness Hk = 2170 kg / mm ² , surface roughness Ry = 0 by PVD arc ion ion plating method. A 0.03 μm DLC thin film was formed to a thickness of 0.5 μm. In addition, what did not coat | cover the DLC thin film was used for the comparative example.

[4] Preparation of a low friction agent composition for a final reduction gear As a low friction agent composition for a final reduction gear, a mineral oil or a synthetic oil (PAO: polyalphaolefin (1-octene oligomer)) as a base oil, and an S system ( 4 mass% as a compound), SP system (1.5 mass% as a compound), borate extreme pressure agent (3 mass% as a compound), an antiwear agent, and a fatty acid ester friction modifier. Prepared.

[5] Test Results The above-mentioned cylindrical test piece, disk-shaped test piece, and low friction agent composition for final reduction gear were combined as shown in Table 4, and the friction coefficient was measured according to the above procedure. The result is shown in FIG.

  As is clear from the results of FIG. 6, in the example using the disk-shaped test piece in which the DLC thin film was formed on the upper sliding surface, compared to the comparative example using the disk-shaped test piece without the DLC thin film, It was confirmed that the coefficient of friction was significantly reduced.

As mentioned above, although this invention was demonstrated in detail by the Example and the comparative example, this invention is not limited to these, A various deformation | transformation is possible if it is in the summary of this invention.
For example, it can also be used for gear sliding members used in industrial machines.

It is a section explanatory view which illustrates a sliding part which coats a hard carbon thin film in a manual transmission of the present invention. It is sectional explanatory drawing which illustrates the sliding site | part which coat | covers a hard carbon thin film in the final reduction gear of this invention. It is the schematic which shows an example of a pin on disk friction test. It is a perspective view which shows the cylinder-on-disk single-piece | unit reciprocating friction test point used for the abrasion test in the Example of this invention. It is a graph which compares and shows the measurement result of the friction coefficient by the cylinder on disk single-piece | unit reciprocating friction test shown in FIG. It is a graph which compares and shows the measurement result of the friction coefficient by the cylinder on disk single-piece | unit reciprocating friction test shown in FIG.

Explanation of symbols

1 Manual transmission 2c 3 speed needle bearing (sliding part)
2d 4-speed needle bearing (sliding part)
3 Input shaft (sliding part)
4c 1-speed needle bearing (sliding part)
4d 2-speed needle bearing (sliding part)
4e 5-speed needle bearing (sliding part)
5 Main shaft (sliding part)
6a 2-speed bush (sliding part)
6b 5 speed bush (sliding part)
11 Cylinder-shaped specimen 12 Disc-shaped specimen 20 Final reduction gear 23 Drive shaft 24a Side bearing roller (sliding member)
24b Side bearing inner race (sliding member)
25 Differential case (sliding member)
26 Side gear (sliding member)
27 Pinion mate shaft (sliding member)
28 Pinion mate gear (sliding member)
29 Roller bearing 30 Washer (sliding member)

Claims (13)

A low friction sliding mechanism in which a low friction agent composition is interposed on a sliding surface formed by a DLC coating sliding member (A) and a sliding member (B),
The DLC coating sliding member (A) is formed by coating a substrate with diamond-like carbon,
The sliding member (B) is made of at least one material selected from the group consisting of a metal material, a non-metal material, and a coating material having a thin film coated on the surface thereof,
The low-friction agent composition contains at least one selected from the group consisting of an oxygen-containing organic compound (C) and an aliphatic amine-based compound (D). mechanism.   In the sliding member (B), the metal material is at least one material selected from the group consisting of iron-based materials, aluminum alloy materials, and magnesium alloy-based materials, and the coating material includes DLC, TiN, and The low-friction sliding mechanism according to claim 1, wherein the low-friction sliding mechanism is formed by coating a thin film of at least one material selected from the group consisting of CrN.   The low friction sliding mechanism according to claim 1 or 2, wherein the coated DLC has a hydrogen content of 20 atomic% or less.   The low friction sliding mechanism according to claim 1 or 2, wherein the coated DLC has a hydrogen content of 10 atomic% or less.   The low friction sliding mechanism according to claim 1, wherein the coated DLC has a hydrogen content of 0.5 atomic% or less.   The low friction sliding mechanism according to claim 1 or 2, wherein the coated DLC is made of a-C-based diamond-like carbon not containing hydrogen.   The oxygen-containing organic compound (C) is at least one selected from the group consisting of alcohols, carboxylic acids, esters, ethers, ketones, aldehydes, carbonates and derivatives thereof. The low-friction sliding mechanism according to claim 1, wherein the low-friction sliding mechanism is characterized.   The low oxygen friction compound according to any one of claims 1 to 7, wherein the oxygen-containing organic compound (C) is contained in an amount of 0.05 to 3.0% based on the total amount of the low friction agent. Moving mechanism.   The aliphatic amine compound (D) has a hydrocarbon group having 6 to 30 carbon atoms and is contained in an amount of 0.05 to 3.0% based on the total amount of the low friction agent. The low friction sliding mechanism as described in any one of -8. A DLC coating sliding member (A) coated with diamond-like carbon, and at least one material selected from the group consisting of a metallic material, a non-metallic material, and a coating material obtained by coating a thin film on these surfaces. On the sliding surface formed by the sliding member (B) used,
Friction reduction characterized by supplying a low-friction agent composition containing at least one selected from the group consisting of an oxygen-containing organic compound (C) and an aliphatic amine-based compound (D) for lubrication Method. A low friction agent composition for use in the low friction sliding mechanism according to any one of claims 1 to 9 or the friction reducing method according to claim 10,
A low friction agent composition comprising at least one selected from the group consisting of an oxygen-containing organic compound (C) and an aliphatic amine compound (D).   A manual transmission using the low friction sliding mechanism according to any one of claims 1 to 9.   A final reduction gear using the low friction sliding mechanism according to any one of claims 1 to 9.

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