JP2005097570A - Low frictional sliding member and low frictional sliding mechanism by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low frictional sliding member having a more excellent low shearing force than that of MoS<SB>2</SB>, and a low frictional sliding mechanism by using the same. <P>SOLUTION: This low frictional sliding member is provided by being equipped with a hard carbon thin membrane on at least a part of its sliding surface and forming a tribo-film having an ether, oxide and alcohol on sliding by intervening an organic oxygen-containing compound on the hard carbon thin membrane. The tribo-film is formed in a range of within 10 nm depth from the sliding surface of the hard carbon thin membrane. By using such the low frictional sliding member, the low frictional sliding mechanism is obtained by intervening the organic oxygen-containing compound on the sliding surface composed of the low frictional sliding members each other or the low frictional sliding member with a metal member. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a low-friction sliding member and a low-friction sliding mechanism using the same, and more specifically, a low-friction sliding member excellent in low-friction characteristics of a sliding surface and a low-friction sliding using the same. Regarding the mechanism.

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.
As for 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 sliding materials and lubricants 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 for lubricating oil, for example, fuel-saving measures for engines, include: (1) Reducing viscosity resistance in the fluid lubrication region and agitation resistance in the engine by reducing viscosity; (2) Optimal friction modifier and various types Mixing by blending additives and reducing friction loss under the boundary lubrication region 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.

One of these reasons is that because DLC is chemically inert, the tribo film made of low shear MoS ₂ formed on the sliding surface of steel is not formed on the DLC surface. ing.

The present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a low friction sliding member having a low shear force superior to MoS ₂ and a low friction using the same. It is to provide a sliding mechanism.

  As a result of intensive studies to solve the above problems, the present inventors have formed a very thin tribo film having a predetermined functional group when slid in the presence of an organic oxygen-containing compound. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

According to the present invention, when it is slid in the presence of an organic oxygen-containing compound, an extremely thin tribo film having a predetermined functional group is formed, and therefore, a low shear force superior to MoS ₂ is achieved. A low-friction sliding member having a low-friction sliding mechanism using the same can be provided.

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

The low friction sliding member of the present invention includes a hard carbon thin film on at least a part of the sliding surface. An example of such a hard carbon thin film is a thin film made of a DLC (diamond-like carbon) material. This DLC is amorphous mainly composed of carbon elements, and the bonding form between carbons consists of both a diamond structure (SP ³ bond) and a graphite bond (SP ² bond). 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 particular, from the viewpoint of exerting a significant friction reducing effect, a material having a smaller hydrogen content is preferred, and an a-C-based material having a hydrogen content of 10% or less in atomic ratio and further not containing hydrogen is used. preferable.
As a method for forming the hard carbon thin film, typically, ion plating, magnetron sputtering, or the like can be appropriately employed.

Also, a tribo film having functional groups related to ether, oxide or alcohol, and any combination thereof is formed on the surface of the hard carbon thin film by friction when sliding with an organic oxygen-containing compound interposed. Is done. Here, the “tribo film” refers to a film formed with a chemical reaction during friction. FIG. 1 shows a schematic diagram of a tribofilm.
Furthermore, it is preferable that the tribofilm is formed within a depth of 10 nm or less from the sliding surface of the hard carbon thin film. As a result, the friction coefficient of the sliding contact portion can be lowered.
Furthermore, the tribofilm should have lower friction properties than tribofilms that do not have functional groups related to ether, oxide or alcohol, and any combination thereof.

Further, the surface roughness Ra of the hard carbon thin film is preferably 0.1 μm or less, and 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 surface hardness of the hard carbon thin film is preferably a microvickers hardness (10 g load) of Hv 1000 to 3500 and a film thickness of 0.3 to 2.0 μm. Note that if the surface hardness and thickness are out of the above ranges, they will be easily worn if the Hv is less than 1000 and the thickness is less than 0.3 μm, and conversely, if the surface hardness and the thickness exceed 2.0 μm, they will be easily peeled off.

  In the low friction sliding member of the present invention, examples of the constituent material other than the hard carbon thin film 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, non-metallic materials such as resin, plastic and carbon can also 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).

  In addition, the metal material subjected to various coatings is not particularly limited, but specifically, various metal materials such as iron-based materials, aluminum-based materials, magnesium-based materials, titanium-based materials, etc. , CrN or the like, or a metal-based material having a thin film coating on the surface of the DLC material or the like, among which a metal material coated with the DLC material is preferable. Further, the DLC material is more preferably aC-based diamond-like carbon containing no hydrogen.

Next, the low friction sliding mechanism of the present invention will be described in more detail.
Such a low friction sliding mechanism is formed using the above-described low friction sliding member. Specifically, it has one or both of a sliding surface constituted by using two or more of the low friction sliding members and a sliding surface formed by the low friction sliding member and the metal member. In addition, an organic oxygen-containing compound is interposed on the sliding surface.
With such a configuration, an extremely thin tribo film is formed on the friction surface, and an excellent low shearing force is exhibited.

Here, as the metal member, for example, the iron-based member, the aluminum-based member, the magnesium-based member, or the titanium-based member can be used, and the surface thereof may be coated with TiN, CrN, or DLC material. .
Moreover, when using an iron-type member, the surface hardness is Rockwell hardness and it is desirable that it 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. If the surface hardness is less than HRC45, it may be buckled and peeled easily under high surface pressure.
Furthermore, when using an aluminum-based member, the surface hardness is desirably Brinell hardness _H B 80 to 130. If the surface hardness of the aluminum-based material is less than H _B 80, the aluminum-based material may be easily worn.
Furthermore, in the case of using a metal member coated with a thin film, particularly in the case of a metal member coated with a DLC material, the surface hardness is Hv 1000 to 3500 in terms of micro Vickers hardness (10 g load), and the DLC film thickness is 0. It is desirable to be 3 to 2.0 μm. When the surface hardness and thickness are less than Hv1000 and less than 0.3 μm, it tends to be worn away, and conversely, when it exceeds Hv3500 and thickness of 2.0 μm, peeling may easily occur.

As the low friction sliding mechanism of the present invention, for example, a sliding part of an internal combustion engine such as a 4-cycle or 2-cycle engine (for example, a valve system, piston, piston ring, piston skirt, cylinder liner, connecting rod, crankshaft, bearing) , Bearings, metal, gears, chains, belts, oil pumps, etc.), drive system transmission mechanisms (eg gears, etc.), sliding parts of hard disk drives, etc. The sliding part is the target. In these sliding parts, DLC coating is applied to at least one sliding member, and the organic oxygen-containing compound is supplied, so that it is more lubricated than before, and extremely excellent low friction characteristics can be obtained. It is.
Further, as a preferred embodiment in the valve train of the internal combustion engine, a disk-shaped shim or lifter crown surface coated with DLC on the base of steel material, low alloy chilled cast iron, carburized steel or tempered carbon steel, and these Examples thereof include a sliding portion made of a cam lobe using materials according to any combination.

The organic oxygen-containing compound is not particularly limited as long as it is an organic compound containing oxygen in the molecule. For example, it may be an organic oxygen-containing compound composed of carbon, hydrogen and oxygen, and other elements such as nitrogen, sulfur, halogen (fluorine, chlorine, etc.), phosphorus, boron, metal, etc. in the molecule. It may be an organic oxygen-containing compound. In particular, from the viewpoint of further reducing the friction of the sliding surface formed by the sliding member, an organic oxygen-containing compound having a hydroxyl group and consisting of carbon, hydrogen and oxygen and a derivative thereof are preferable. Moreover, it is more preferable to have two or more hydroxyl groups. For the same reason as described above, an organic oxygen-containing compound having a low sulfur content or no sulfur is more preferable.
The “derivative” here is typically an organic oxygen-containing compound composed of carbon, hydrogen and oxygen, for example, a nitrogen-containing compound, a phosphorus-containing compound, sulfur or a sulfur-containing compound, a boron-containing compound, Examples thereof include compounds obtained by reacting halogen elements and halogen element-containing compounds, metal elements and metal-containing compounds (regardless of organic or inorganic), and are not particularly limited.

  More specifically, (I) alcohols, (II) carboxylic acids, (III) esters, (IV) ethers, (V) ketones, (VI) aldehydes, (VII) carbonates or these Derivatives, and mixtures according to any combination thereof may be mentioned.

  Here, (I) alcohols have 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)
-Alkylene oxide adducts of the above three alcohols (I-4)
-1 type, or 2 or more types of mixtures chosen from said 4 types of alcohol (I-5)

  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.

  Furthermore, the alkylene oxide adduct (I-4) is an alkylene oxide adduct of the above alcohols (I-1 to 3). Specifically, the alcohol has 2 to 6 carbon atoms, preferably carbon. Examples include those obtained by adding an alkylene oxide of 2 to 4 or a polymer or copolymer thereof and hydrocarbyl etherifying or hydrocarbyl esterifying a hydroxyl group of an alcohol. Examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene oxide, propylene oxide, 1,2-epoxybutane (α-butylene oxide), 2,3-epoxybutane (β-butylene oxide), and 1,2-epoxy-1 -Methylpropane, 1,2-epoxyheptane, 1,2-epoxyhexane and the like. Among these, ethylene oxide, propylene oxide, and butylene oxide are preferable, and ethylene oxide and propylene oxide are more preferable from the viewpoint of excellent low friction.

  When two or more types of alkylene oxide are used, the polymerization mode of the oxyalkylene group is not particularly limited, and may be random copolymerized or block copolymerized. Moreover, when adding an alkylene oxide to the polyhydric alcohol which has 2-6 hydroxyl groups, you may make it add to all the hydroxyl groups, and you may make it add only to one part hydroxyl group.

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

      R- (COOH) n (2)

And a compound having one 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)
・ Alkylene oxide adducts of alcohols or esters (III-5)
-Arbitrary mixture (III-6) 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). Specific examples of the aliphatic monocarboxylic acid include glycerol monooleate, glyceroldiolate, sorbitan monooleate, and sorbitandiolate.

Examples of the other ester (III-1) include fatty acid esters having a linear or branched hydrocarbon group having 1 to 5 carbon atoms or 31 to 40 carbon atoms, and fatty acids and fats having such hydrocarbon groups. Examples include esters composed of a group 1 monohydric alcohol or an aliphatic polyhydric alcohol.
Among these, those having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s can be used as a lubricating base oil, and can generally be distinguished from the fatty acid ester-based ashless friction modifier. Examples of these include, for example, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, and the like, preferably 3 to 40 carbon atoms, preferably 4 to 18 carbon atoms, Particularly preferably 4 to 12 trivalent or higher polyols, particularly trivalent or higher polyols having a neopentyl structure, and a monocarboxylic acid having 1 to 40 carbon atoms, preferably 4 to 18 carbon atoms, particularly preferably 6 to 12 carbon atoms. Examples thereof include polyol esters such as single esters or complex esters with one or more selected from acids and mixtures thereof, or those further added with alkylene oxide. These may be complete esters in which all hydroxyl groups or carboxyl groups are esterified, and may be partial esters in which some hydroxyl groups or carboxyl groups remain, but are preferably complete esters, and the hydroxyl group value is usually 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, particularly preferably 10 mgKOH / g or less.
Further, the kinematic viscosity at 100 ° C. of these lubricating base oils is preferably ² to 60 mm ² / s, particularly preferably 3 to 50 mm ² / s.

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. Of these, those having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s can be used as the lubricating base oil.

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. Of these, those having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s can be used as the lubricating base oil.

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). Of these, those having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s can be used as the lubricating base oil.

The alkylene oxide adduct (III-5) of alcohols or esters is one or more selected from the above-mentioned monovalent, divalent, or trivalent or higher alcohols (I-1 to 3). And those obtained by adding an alkylene oxide to the ester, and those obtained by adding an alkylene oxide to the above (III-1 to 4) ester. Of these, those having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s can be used as the lubricating base oil.

  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)
-A mixture of two or more selected from the above three ethers (IV-4)

  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).

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

      R- (CO-R ') n (5)

And a compound having one 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 an organic oxygen-containing compound represented by the formula: a compound having one 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.

  Examples of the derivatives of the organic oxygen-containing compounds I to VII include, for example, nitrogen-containing compounds, phosphorus-containing compounds, sulfur and sulfur-containing compounds, boron-containing compounds, halogen elements and halogen element-containing compounds. Although the compound etc. which are obtained by making a compound, a metal element, a metal containing compound, etc. (regardless of organic and inorganic) react are mentioned, It does not restrict | limit in particular in these. In addition, although the said compound used when obtaining a derivative | guide_body is normally used as an additive, even when used as a base oil, the effect is not specifically limited.

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. (These hydrocarbon groups may further have one or more groups or bonds selected from a hydroxyl group, a carboxyl group, a carbonyl group, an ester bond, an ether bond, carbon, An element other than hydrogen and oxygen, for example, nitrogen or sulfur (for example, a heterocyclic compound), halogen (fluorine, chlorine, etc.), phosphorus, boron, metal, etc. may be contained.
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. Moreover, when it has a hydroxyl group and a carboxyl group with the said hydrocarbon group, these content does not have a restriction | limiting in particular, However, It is preferable that it is 10-1000 ppm on the basis of the composition whole quantity.

  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 organic oxygen-containing compounds described above can be similarly used even if they are derivatives thereof. 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. And reaction products with sulfuric acid, nitric acid, boric acid, phosphoric acid and esters or metal salts of these acids, reaction products with metals, metal-containing compounds, or amine compounds.
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, aliphatic amines having an alkyl group or alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine A branched example) may be mentioned as a preferred example.
Among these organic oxygen-containing compound derivatives, carboxylic acid amides having 8 to 20 carbon atoms such as oleic acid amide are preferred examples.

  The organic oxygen-containing compound exhibits extremely excellent low friction property by being used alone (that is, 100%) on the sliding surface, but it may be used by adding lubricating oil or the like. . Further, even when used as an aqueous solution containing the organic oxygen-containing compound, a large friction reducing effect can be obtained.

  Specific examples of such lubricating oils include various mineral oils, synthetic oils, natural fats and oils, diluent oils, greases, waxes, hydrocarbon solvents, organic solvents other than hydrocarbons, water, and the like, and mixtures thereof. And a medium that is liquid, grease-like or wax-like at the sliding conditions and at room temperature. The content of the organic oxygen-containing compound contained in these media is not particularly limited, but usually the lower limit is 0.001%, preferably 0.05%, more preferably 0.1%. Yes, you may make it contain exceeding 3.0%. The upper limit is 100% as described above, preferably 50%, more preferably 20%, still more preferably 10%, particularly preferably 5%, and a small amount of about 0.1 to 2%. Even if it is added, excellent low friction characteristics can be exhibited.

  Further, it is particularly desirable to use a lubricating base oil as the lubricating 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 lubricant base oils include alkylnaphthalene, alkylbenzene, polybutene or hydrides thereof; poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; Examples thereof include esters having a kinematic viscosity of 1 to 100 mm ² / s; and mixtures thereof. Examples of the synthetic lubricating base oil other than the esters include poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof. In addition, as the esters, polyol esters are particularly preferable.

  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, for example, when the content of organic oxygenates (excluding esters as lubricating base oil) exceeds 2%, storage stability may be inferior, so solvent refining as necessary It is preferable to adjust the total aromatic content of the lubricating base oil (for example, 2% or more) by blending mineral oil, alkylbenzene, or the like, or to use esters together as the lubricating base oil. 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.

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. preferably at ^{3 mm} 2 / s or more, while its upper limit is preferably not more than ^{20mm 2 / s, 10mm 2 /} s or less, and preferably less, especially ^{8 mm} 2 / s. 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.

  Furthermore, 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 lubricating base oil having a high viscosity index, a composition having not only excellent low-temperature viscosity characteristics but also excellent friction reduction effects can be obtained.

  The above lubricating oil includes ashless dispersant, antiwear agent or extreme pressure agent, metallic detergent, antioxidant, viscosity index improver, ashless friction modifier, rust inhibitor, nonionic surfactant. , Demulsifiers, metal deactivators, antifoaming agents, and the like 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 above polybutenyl succinimide, a boron compound or an organic oxygen-containing compound is allowed to act on the compounds represented by the chemical formulas (1) and (2), thereby remaining amino groups and / or imino groups. Examples thereof include so-called boron-modified compounds or acid-modified compounds obtained by neutralizing or amidating part or all of the above. 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 organic oxygen-containing 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, undecyl. C1-C30 monocarboxylic acid such as acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid and eicosanoic acid, oxalic acid, phthalic acid, tri Examples thereof include polycarboxylic acids having 2 to 30 carbon atoms such as merit acid and pyromellitic acid, and anhydrides or ester compounds thereof, alkylene oxides having 2 to 6 carbon atoms, and hydroxy (poly) oxyalkylene carbonate.

In addition, although content in particular of the said polybutenyl succinimide and / or its derivative (s) is not restrict | limited, 0.1 to 15% is desirable and it is good that it is 1.0 to 12% more desirably. 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 organic oxygenated compounds on the sliding surface between the hard carbon thin film and various metal members (especially iron-based members) 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. In addition, the viscosity index improver can be contained alone or in any combination of two or more, but the content is usually 0.1 to 40.0% based on the lubricating oil composition. desirable.

Examples of other ashless friction modifiers include boric acid esters, metal friction modifiers such as 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 lubricating oil composition used in the present invention, the content is based on the total amount of the composition, and other friction modifiers, rust inhibitors, and demulsifiers are 0.01 to 5%. % And the metal deactivator can be appropriately selected from the range of 0.0005 to 1%.

  As described above, the low-friction sliding mechanism of the present invention lubricates the sliding surface combined with a predetermined sliding member, and can improve the low-friction characteristics of various sliding surfaces.

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

(Examples 1-9, Comparative Examples 1-3)
Disc disks and pins as shown in Table 1 were made using trial materials. At this time, as for the surface coating product, various materials were coated on the finished surface by PVD or CVD treatment so that the film thickness became about 1 μm.
In Examples 1, 2, and 4 to 9, in which a friction modifier was mixed with lubricating oil, PAO was used as a base oil, and 1% of various friction modifiers were added and prepared.

As shown in FIG. 2, as an example of a sliding mechanism, a friction evaluation test was performed using a pin-on-disk type single friction tester that presses three fixed pins against a disk disk that rotates in lubricating oil. The friction evaluation test conditions at this time are shown below.
<Single cam follower friction test conditions>
Friction modifier supply method: immersion Oil temperature: 80 ° C
Maximum Hertz pressure: 700 MPa (Table 1 Examples 1 to 5, Comparative Examples 1 and 3)
80 Mpa (Table 1, Examples 6 to 9, Comparative Example 2)
Disk rotation speed: 30 rpm (0.03 m / s)
Test time: 60 min

From Table 1, as a result of the friction evaluation test which concerns on Examples 1-9, all showed the outstanding low friction coefficient. For example, compared with the case where the combination of the steel materials of Comparative Example 1 used in a general gasoline engine and the combination of the steel of Comparative Example 2 and the aluminum alloy material are slid in the engine oil, about A friction reduction effect of 40% or more was obtained. In addition, the combination of the DLC material and the steel of this example showed a friction reduction effect of about 20% or more as compared with the case of sliding with a lubricating oil PAO not containing an organic oxygen-containing compound.
Moreover, there was no problem in the surface shape after the test, and the abrasion resistance was very excellent.
Furthermore, in Example 4 and Example 5, Example 5 using a DLC material containing 20 at% of hydrogen is Example 4 that contains only 10 at% of the hydrogen content or a-C system that does not substantially contain hydrogen. Compared to other examples using DLC, the friction reducing effect was clearly reduced.
Therefore, the low friction sliding mechanism that slides in the presence of the lubricating oil composition contained as a friction modifier in Examples 1 to 9 has a great friction reducing effect. Moreover, as a constituent material of the hard carbon thin film, an aC based DLC material was suitable.

As mentioned above, although it demonstrated in detail by the Example and comparative example of this invention, this invention is not limited to these, A various deformation | transformation is possible if it is in the summary of this invention.
For example, an effect can be expected for all of the machine sliding parts, and a remarkable friction reducing effect that directly leads to an improvement in engine fuel efficiency can be obtained.

It is the schematic which shows the tribo film formed after sliding. It is the schematic which shows an example of a pin on disk friction test.

Claims (10)

A low friction sliding member comprising a hard carbon thin film on at least a part of the sliding surface,
A tribofilm having at least one functional group selected from the group consisting of ether, oxide and alcohol is formed when sliding on the hard carbon thin film with an organic oxygen-containing compound interposed therebetween. A low friction sliding member.   The low-friction sliding member according to claim 1, wherein the tribofilm is formed within a depth of 10 nm or less from the sliding surface of the hard carbon thin film.   3. The low tribo film according to claim 1, wherein the tribo film has a lower friction characteristic than a tribo film having no at least one functional group selected from the group consisting of ether, oxide and alcohol. Friction sliding member.   The low friction sliding member according to any one of claims 1 to 3, wherein the base material of the hard carbon thin film is diamond-like carbon having a hydrogen content of 10 at% or less.   The low-friction sliding member according to any one of claims 1 to 4, wherein the base material of the hard carbon thin film is aC-based diamond-like carbon containing no hydrogen.   The low-friction sliding member according to any one of claims 1 to 5, wherein the hard carbon thin film has a surface roughness Ra of 0.1 µm or less.   The surface hardness of the hard carbon thin film is micro Vickers hardness (10 g load) Hv 1000 to 3500, and the film thickness is 0.3 to 2.0 μm. The low friction sliding member according to one of the items. A low friction sliding mechanism using the low friction sliding member according to any one of claims 1 to 7,
It has a sliding surface formed by the low friction sliding members and / or a sliding surface formed by the low friction sliding member and the metal member, and an organic oxygen-containing compound is interposed in the sliding surface. Low friction sliding mechanism.   The organic oxygen-containing compound is at least one selected from the group consisting of alcohols, carboxylic acids, ethers, esters, aldehydes, ketones, carbonates and derivatives thereof. The low friction sliding mechanism according to claim 8.   The low friction sliding mechanism according to claim 8 or 9, wherein a lubricating oil containing an organic oxygen-containing compound is interposed on the sliding surface.

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