JP2016117788A - Lubricant additive, and lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel lubricant additive that is used for an internal combustion engine, an automatic transmission, a bearing and others, and has the action to reduce friction resistance.SOLUTION: The present invention provides one or more compound represented by general formula (1) or (2).SELECTED DRAWING: None

Description

  The present invention relates to a lubricating oil additive and a lubricating oil composition.

  Lubricating oil is used for an internal combustion engine, an automatic transmission, a bearing, and the like in order to make the operation smooth. In general, various additives are blended in the lubricating oil in order to give the performance required for the lubricating oil. For example, ordinary engine oils are blended with lubricating oil additives such as antiwear agents, friction modifiers, metallic detergents, ashless dispersants and antioxidants.

  Among the lubricating oil additives, an additive having a function of reducing frictional resistance (friction modifier, which may be referred to as “FM” hereinafter) is an important component for reducing energy loss due to friction. Generally used FM can be classified into an organic molybdenum-based FM containing molybdenum and an oil-based agent-based FM that reduces friction by improving oiliness.

  As the organic molybdenum-based FM, MoDTC (molybdenum dithiocarbamate) and MoDTP (molybdenum dithiophosphate) are widely known (see, for example, Patent Document 1). Although these organomolybdenum FMs are excellent in the friction reduction effect at the initial stage of use, there is a limit to maintaining the friction reduction effect well over a long period of time. Moreover, since organic molybdenum type | system | group FM contains ash content, it becomes difficult to recycle used lubricating oil. Further, when used for lubricating an internal combustion engine, the exhaust gas purification device may be adversely affected. Therefore, there is a demand for reducing the amount of organic molybdenum FM added.

  On the other hand, according to the oil-based agent type FM, there is a possibility that the above-mentioned problems of the organic molybdenum type FM can be overcome. Therefore, the importance of the oil-based agent system FM is increasing from the viewpoint of environmental response (see, for example, Patent Documents 2 to 3).

JP 2013-133453 A JP 2009-235252 A JP 2006-257383 A

  The present invention provides a lubricating oil additive containing a novel ashless oil based friction modifier. Moreover, the lubricating oil composition containing this oil-based agent friction modifier is provided.

  The first aspect of the present invention is a lubricating oil additive containing one or more compounds represented by the general formula (1) or (2).

（一般式（１）において、Ｒは炭素数１以上の炭化水素含有基であり；Ｘ^１は、単結合、−ＣＯＮＨ−基、−ＮＨＣＯ−基、−ＮＨ−基、又は、１以上のヘテロ原子を有し該ヘテロ原子に結合した水素原子を有しない炭素数０〜１の結合基であり、該ヘテロ原子は酸素、窒素、及び硫黄からなる群から選ばれ；Ｘ^２は、単結合、又は、１以上のヘテロ原子を有し該ヘテロ原子に結合した水素原子を有しない炭素数０〜１の結合基であり、該ヘテロ原子は酸素、窒素、及び硫黄からなる群から選ばれ；Ｚは、−ＣＮ基、−ＣＯ_２ＣＨ_３基、−ＯＣＯＣＨ_３基、−ＯＣＯＮ（ＣＨ_３）_２基、又は、１以上のヘテロ原子及び該ヘテロ原子に結合した水素原子を有する炭素数０〜６の基であり、該ヘテロ原子は酸素、窒素、硫黄、及びリンからなる群から選ばれ；ａは０又は１であり；ｂは０又は１であり；ｃは０〜２の整数であり；ｃが１以上のとき、Ｙは−ＣＨ_２−基又は−ＯＣＨ_２ＣＨ_２−基である。）

(In General Formula (1), R is a hydrocarbon-containing group having 1 or more carbon atoms; X ¹ is a single bond, —CONH— group, —NHCO— group, —NH— group, or one or more hetero groups; A C 0-1 linking group having an atom and no hydrogen atom bonded to the heteroatom, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, and sulfur; X ² is a single bond, Or a linking group having 0 to 1 carbon atoms that has one or more heteroatoms and no hydrogen atoms bonded to the heteroatoms, and the heteroatoms are selected from the group consisting of oxygen, nitrogen, and sulfur; Z is, -CN group, _-CO 2 CH ₃ group, -OCOCH ₃ group, -OCON _{(CH 3) 2} group, or 0-6 carbon atoms having one or more hetero atoms and hydrogen atoms bonded to hetero atoms The heteroatoms from oxygen, nitrogen, sulfur, and phosphorus Selected from that group; a is 0 or 1; b is 0 or 1; c is an integer from 0 to 2; when c is 1 or more, Y is -CH ₂ - group or a -OCH ₂ CH ₂ - is a radical).

In the general formulas (1) and (2), the naphthalene skeleton has a first six-membered ring and a second six-membered ring. In the general formula (1), the first six-membered ring of the naphthalene skeleton is substituted with an R—X ¹ — (CH ₂ ) _a — group, and the second six-membered ring of the naphthalene skeleton is substituted with Z— (Y _{^{) c -X 2 - (CH 2}} ) b - groups are substituted, ^R-X 1 in the first six-membered ring - _{(CH 2) a} - Z in the substituted position and the second six-membered ring of the group The substitution position of the-(Y) _c -X ^2- (CH ₂ ) _b -group is arbitrary. In the general formula (2), both the R—X ¹ — (CH ₂ ) _a — group and the Z— (Y) _c —X ² — (CH ₂ ) _b — group are present on the first six-membered ring of the naphthalene skeleton. Is substituted, and the substitution position of the R—X ¹ — (CH ₂ ) _a — group and the Z— (Y) _c —X ² — (CH ₂ ) _b — group in the first six-membered ring is arbitrary. .

  The lubricating oil additive according to the first aspect of the present invention preferably contains a compound represented by the general formula (1).

  A second aspect of the present invention is a lubricating oil composition comprising (A) a lubricating base oil and (B) a lubricating oil additive according to the first aspect of the present invention.

  The lubricating oil composition according to the second aspect of the present invention is represented by the ashless dispersant, the antioxidant, the general formula (1) or (2), in addition to the component (A) and the component (B). At least one selected from friction modifiers, antiwear agents, metal detergents, viscosity index improvers, corrosion inhibitors, rust inhibitors, antiemulsifiers, metal deactivators, antifoaming agents and colorants May contain seed additives.

The lubricating oil additive according to the first aspect of the present invention acts as an ashless oil based friction modifier and can exhibit a good friction reducing effect under boundary lubrication conditions.
The lubricating oil composition according to the second aspect of the present invention is a lubricating oil composition containing an ashless oil-based friction modifier, and can exhibit a good friction reducing effect under boundary lubrication conditions.

It is a graph which shows the evaluation result of the friction characteristic of the lubricating oil composition which concerns on each Example and each comparative example.

  Hereinafter, the present invention will be described in detail. Unless otherwise specified, the notation “A to B” in the numerical range means “A or more and B or less”. In this notation, when a unit is attached to only the numerical value B, the unit is also applied to the numerical value A.

<1. Lubricating oil additive>
The lubricating oil additive according to the first aspect of the present invention comprises one or more compounds represented by the following general formula (1) or (2).

  In the general formulas (1) and (2), a is 0 or 1, and b is 0 or 1. The compounds represented by the general formula (1) or (2) all have one naphthalene skeleton.

  In the general formulas (1) and (2), R is a hydrocarbon-containing group having 1 or more carbon atoms, and typically a hydrocarbon group having 1 or more carbon atoms. However, as long as R has a hydrocarbon group, R may have one or more heteroatoms selected from oxygen, nitrogen, and sulfur in the molecular structure.

  Examples of the hydrocarbon group include an alkyl group (which may have a ring structure), an alkenyl group (the position of the double bond is arbitrary and may have a ring structure), an aryl group (alkyl A group or an alkenyl group), an arylalkyl group, an arylalkenyl group, and the like.

  Examples of the alkyl group include various linear or branched alkyl groups. Examples of the ring structure that the alkyl group may have include cycloalkyl groups having 5 to 7 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. When a chain hydrocarbon group is substituted in the ring structure, the substitution position on the ring structure is arbitrary.

  Examples of the alkenyl group include linear or branched alkenyl groups. Examples of the ring structure that the alkenyl group may have include a cycloalkenyl group having 5 to 7 carbon atoms, such as a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group, in addition to the above cycloalkyl group. When a chain hydrocarbon group is substituted in the ring structure, the substitution position on the ring structure is arbitrary.

  Examples of the aryl group include a phenyl group and a naphthyl group. Further, in the alkylaryl group, alkenylaryl group, arylalkyl group, and arylalkenyl group, the substitution position on the aromatic ring is arbitrary.

  The carbon number of R is 1 or more, usually 40 or less, and typically 30 or less. The carbon number of R is preferably 6 or more, more preferably 13 or more, and particularly preferably 15 or more. The hydrocarbon group for R is preferably an aliphatic hydrocarbon group, and more preferably a linear aliphatic hydrocarbon group.

In the general formulas (1) and (2), X ¹ represents a single bond, —CONH— group, —NHCO— group, —NH— group, or hydrogen having one or more heteroatoms and bonded to the heteroatoms. It is a C1-C1 bonding group which does not have an atom. For X ¹ , the “heteroatom” is selected from oxygen, nitrogen, and sulfur, typically oxygen or nitrogen. With respect to X ¹ , “a linking group having 0 to 1 carbon atoms that has one or more heteroatoms and no hydrogen atoms bonded to the heteroatoms” includes, for example, —O— group, —S— group, —S ( O) — group, —S (O) ₂ — group, —S (O) ₂ O— group, —OS (O) ₂ — group, —NCH ₃ — group, —C (O) — group, —OC ( O) -group, -C (O) O-group, and the like. As a preferred embodiment, in General Formulas (1) and (2), a is 0, and X ¹ is a single bond, —O— group, or —C (O) O— group.

In the general formulas (1) and (2), X ² is a single bond or a linking group having 0 to 1 carbon atoms that has one or more heteroatoms and does not have a hydrogen atom bonded to the heteroatoms. For X ² , the “heteroatom” is selected from oxygen, nitrogen, and sulfur, typically oxygen or nitrogen. With respect to X ² , “a linking group having 0 to 1 carbon atoms that has one or more heteroatoms and no hydrogen atoms bonded to the heteroatoms” is, for example, an —O— group, —S— group, —S ( O) — group, —S (O) ₂ — group, —S (O) ₂ O— group, —OS (O) ₂ — group, —NCH ₃ — group, —C (O) — group, —OC ( O) -group, -C (O) O-group, and the like. As a preferred embodiment, in the general formulas (1) and (2), b is 0, and X ² is a single bond, —O— group, or —OC (O) — group.

In the general formulas (1) and (2), Z represents a —CN group, —CO ₂ CH ₃ group, —OCOCH ₃ group, —OCON (CH ₃ ) ₂ group, or one or more heteroatoms and the heteroatoms. A group having 0 to 6 carbon atoms having a bonded hydrogen atom; For Z, the “heteroatom” is selected from oxygen, nitrogen, sulfur, and phosphorus, typically oxygen or nitrogen. When “the group having 0 to 6 carbon atoms having one or more heteroatoms and hydrogen atoms bonded to the heteroatoms” has two or more heteroatoms, there are one or more heteroatoms to which no hydrogen atoms are bonded. Also good. For Z, “a group having 0 to 6 carbon atoms having one or more heteroatoms and a hydrogen atom bonded to the heteroatoms” is, for example, an —OH group, —OCONH ₂ group, —OCONHR ′ group (where R ′ is a hydrocarbyl group). Group), —CO ₂ H group, —NH ₂ group, —NHR ′ group (where R ′ is a hydrocarbyl group), —NHCOR ′ group (where R ′ is a hydrocarbyl group), —CONH ₂ group, —CONHR ′ group ( Where R ′ is a hydrocarbyl group), —SH group, —SOH group, —S (O) H group, —S (O) OH group, —S (O) ₂ H group, —S (O) ₂ OH group, -OS _{(O) 2} H group, -P _{(OH) 2} group, -P (OR ') OH group (wherein R' is a hydrocarbyl radical), - PH (O) OH group, -P (O) (OH) R ′ group (where R ′ is a hydrocarbyl group), —OPH (OH) group, —OP (OH) R ′ group ( Where R ′ is a hydrocarbyl group), —P (O) (OH) ₂ group, —P (O) (OR ′) OH group (where R ′ is a hydrocarbyl group), —OP (OH) ₂ group, —OP ( OR ′) OH group (where R ′ is a hydrocarbyl group), —OPH (O) OH group, —OPH (O) OR ′ group (where R ′ is a hydrocarbyl group), —OP (O) (OH) R ′ group (Where R ′ is a hydrocarbyl group), —OP (O) (OH) ₂ group, —OP (O) (OR ′) OH group (where R ′ is a hydrocarbyl group), and the like. Regarding Z, the carbon number of “a group having 0 to 6 carbon atoms having one or more heteroatoms and a hydrogen atom bonded to the heteroatoms” is preferably 0 to 5, and more preferably 0 to 3.

In general formula (1) and (2), c is an integer of 0-2, Preferably it is 0 or 1, More preferably, it is 0. When c is 1 or more, Y is a —CH ₂ — group or —OCH ₂ CH ₂ — group, typically a —CH ₂ — group. Note that the compound represented by the general formula (1) preferably has no —O—O— bond.

As a preferable mode in the general formulas (1) and (2), b is 0, X ² is a single bond, c is 0, Z is a —OCOCH ₃ group, —OCON (CH ₃ ). ₂ groups, —OH group, —OCONH ₂ group, —OCONHR ′ group, —OS (O) ₂ H group, —OPH (OH) group, —OP (OH) R ′ group, —OP (OH) ₂ group, -OP (OR ') OH group, -OPH (O) OH group, -OPH (O) OR' group, -OP (O) (OH) R 'group, -OP (O) (OH) ₂ group, or The form which is -OP (O) (OR ') OH group can be illustrated.

In the general formulas (1) and (2), the naphthalene skeleton has a first six-membered ring and a second six-membered ring. In the general formula (1), the first six-membered ring of the naphthalene skeleton is substituted with an R—X ¹ — (CH ₂ ) _a — group, and the second six-membered ring of the naphthalene skeleton is substituted with Z— (Y _{^{) c -X 2 - (CH 2}} ) b - as long as the group is substituted, the substitution pattern of the naphthalene skeleton (i.e., ^R-X 1 in the first six-membered ring - _{(CH 2) a} - substituent groups The position and the substitution position of the Z— (Y) _c —X ² — (CH ₂ ) _b — group in the second six-membered ring) are not particularly limited. Preferred substitution patterns of the naphthalene skeleton in the general formula (1) include 1,5-substituted, 1,6-substituted (R—X ¹ — (CH ₂ ) _a — group and Z— (Y) _c —X ² —. Any of the (CH ₂ ) _b — groups may be substituted at the 1-position), 1,7-substituted (R—X ¹ — (CH ₂ ) _a — group and Z— (Y) _c —X ² — (CH ₂ ) _b -group may be substituted at the 1-position) and 2,6-substitution. In the general formula (2), both the R—X ¹ — (CH ₂ ) _a — group and the Z— (Y) _c —X ² — (CH ₂ ) _b — group are present on the first six-membered ring of the naphthalene skeleton. As long as is substituted, the substitution pattern of the naphthalene skeleton (ie, the R—X ¹ — (CH ₂ ) _a — group and the Z— (Y) _c —X ² — (CH ₂ ) in the first six-membered ring) The substitution position of the _b -group is not particularly limited. As a preferable substitution pattern of the naphthalene skeleton in the general formula (2), 1,4-substitution can be exemplified.

  The content of the compound represented by the general formula (1) or (2) in the lubricating oil additive of the present invention is not particularly limited. For example, it can be set to an amount that realizes a normal or preferable content of the component (B) in the lubricating oil composition of the present invention described later.

<2. Lubricating oil composition>
The lubricating oil composition according to the second aspect of the present invention comprises (A) a lubricating base oil and (B) one or more compounds represented by the above general formula (1) or (2) (hereinafter referred to as “ Naphthalene-based ashless friction modifier ”).

((A) Lubricating base oil)
The lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and mineral base oils and synthetic base oils used for ordinary lubricating oils can be used.

  Specifically, as the mineral base oil, the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Method to isomerize GTL WAX (gas-to-liquid wax) produced by one or more processes such as solvent dewaxing, hydrorefining, etc., or wax isomerized mineral oil, Fischer-Tropsch process, etc. The lubricating base oil produced in (1) can be exemplified.

  Synthetic lubricating oils include polyalphaolefins such as 1-octene oligomers and 1-decene oligomers or their hydrides, isobutene oligomers or their hydrides, paraffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate, di- 2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc., polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargo) Acid), polyoxyalkylene glycol, dialkyl diphenyl ether, polyphenyl ether and the like. Other examples include aromatic synthetic oils such as alkylnaphthalene, alkylbenzene, and aromatic esters, or mixtures thereof.

  In the lubricating oil composition of the present invention, a mineral base oil, a synthetic base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from these can be used as the lubricating base oil. Examples thereof include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.

The kinematic viscosity, NOACK evaporation amount, and viscosity index of the lubricating base oil in the lubricating oil composition of the present invention can be selected according to the application of the lubricating oil composition. For example, when the lubricating oil composition is for an internal combustion engine, the kinematic viscosity at 100 ° C. of the lubricating base oil can be set to, for example, 3.0 to 16.3 mm ² / s. For example, when the lubricating oil composition is used for a transmission, the kinematic viscosity at 100 ° C. of the lubricating base oil can be set to, for example, 3.5 to 25.0 mm ² / s.

((B) Naphthalene-based ashless friction modifier)
(B) The details of the compound represented by the general formula (1) or (2) are as already described for the lubricating oil additive according to the first aspect of the present invention. The content of the component (B) is not particularly limited, and the content of the compound represented by the above general formula (1) or (2) is, for example, 0.05 to the total amount of the lubricating oil composition. It can be 10% by weight. However, it is preferably 5% by weight or less. The preferable content range may vary depending on the use of the lubricating oil composition, but is preferably 0.1% by weight or more, and preferably 3% by weight or less.

(Other additives)
The lubricating oil composition according to the second aspect of the present invention comprises (C) an ashless dispersant, (D) an antioxidant, in addition to the above (A) lubricating base oil and (B) naphthalene-based ashless friction modifier. Agents, (E) friction modifiers other than the compounds represented by the above general formula (1) or (2), (F) antiwear or extreme pressure agent, (G) metal detergent, (H) viscosity index Improvers or pour point depressants, (I) corrosion inhibitors, (J) rust inhibitors, (K) metal deactivators, (L) demulsifiers, (M) antifoaming agents, and (N) colorants. It may further contain one or more additives selected from: The lubricant additive according to the first aspect of the present invention may contain one or more additives selected from (C) to (N) to form an additive package.

  (C) As an ashless dispersant, well-known ashless dispersants, such as a succinimide type ashless dispersant, can be used, for example. When the lubricating oil composition of the present invention contains an ashless dispersant, its content is usually 0.01% by weight or more based on the total amount of the lubricating oil composition, that is, the total amount of the lubricating oil composition is 100% by weight. The content is preferably 0.1% by weight or more. Moreover, it is 20 weight% or less normally, Preferably it is 10 weight% or less.

  (D) As antioxidant, well-known antioxidants, such as a phenolic antioxidant and an amine antioxidant, can be used (however, the compound represented by the said General formula (1) or (2) is used. except.). When the antioxidant is contained in the lubricating oil composition of the present invention, the content is usually 5.0% by weight or less, preferably 3.0% by weight or less, based on the total amount of the lubricating oil composition. Moreover, it is preferably 0.1% by weight or more, more preferably 0.5% by weight or more.

  (E) As the friction modifier other than the compound represented by the general formula (1) or (2), a known friction modifier can be used. Examples include oil based friction modifiers such as fatty acid esters and organic molybdenum friction modifiers. When these friction modifiers are contained in the lubricating oil composition of the present invention, the content is usually 0.05% by weight or more and 5% by weight or less based on the total amount of the lubricating oil composition.

  (F) As an antiwear agent or extreme pressure agent, a well-known antiwear agent or extreme pressure agent can be used. Examples include phosphorus compounds such as zinc dithiophosphate, and sulfur-containing compounds such as disulfides and sulfurized fats and oils (excluding compounds represented by the above general formula (1) or (2)). . When these lubricants are contained in the lubricating oil composition of the present invention, the content is usually 0.05% by weight or more and 5% by weight or less based on the total amount of the lubricating oil composition.

  (G) As a metallic detergent, a well-known metallic detergent can be used. Examples include alkali metal sulfonates, alkaline earth metal sulfonates, alkali metal phenates, alkaline earth metal phenates, alkali metal salicylates, alkaline earth metal salicylates, and combinations thereof. These metallic detergents may be overbased. When the metallic detergent is contained in the lubricating oil composition of the present invention, the content is not particularly limited. However, in the case of an automatic transmission or a continuously variable transmission, it is usually 0.01% by weight or more and 1.0% by weight or less in terms of the amount of metal element based on the total amount of the lubricating oil composition. In the case of an internal combustion engine, it is usually 0.01% by weight or more and 5% by weight or less in terms of the amount of metal element based on the total amount of the lubricating oil composition.

  As the (H) viscosity index improver or pour point depressant, known viscosity index improvers or pour point depressants can be used. Examples of viscosity index improvers are so-called non-dispersed viscosity index improvers such as polymers or copolymers of one or more monomers selected from various methacrylates, and hydrogenated products thereof; So-called dispersed viscosity index improvers copolymerized with various methacrylic esters containing nitrogen compounds; non-dispersed or dispersed ethylene-α-olefin copolymers and hydrogenated products thereof; polyisobutylene and hydrogenated products thereof; Examples thereof include hydrogenated styrene-diene copolymer; styrene-maleic anhydride ester copolymer; and polyalkylstyrene. When these viscosity index improvers are contained in the lubricating oil composition of the present invention, the content thereof is usually 0.1% by weight or more and 20% by weight or less based on the total amount of the lubricating oil composition. Examples of pour point depressants include polymethacrylate polymers. When the lubricating oil composition of the present invention contains a pour point depressant, the content thereof is usually 0.01% by weight or more and 1% by weight or less based on the total amount of the lubricating oil composition.

  (I) As a corrosion inhibitor, well-known corrosion inhibitors, such as a benzotriazole type compound, a tolyl triazole type compound, a thiadiazole type compound, and an imidazole type compound, can be used, for example. When these corrosion inhibitors are contained in the lubricating oil composition of the present invention, the content is usually 0.005 wt% or more and 5 wt% or less based on the total amount of the lubricating oil composition.

  (J) As a rust preventive agent, well-known rust preventive agents, such as petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester, can be used, for example. When these antirust agents are contained in the lubricating oil composition of the present invention, the content thereof is usually 0.005 wt% or more and 5 wt% or less based on the total amount of the lubricating oil composition.

  Examples of (K) metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles and derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2, Known metal deactivators such as 5-bisdialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile can be used. When these metal deactivators are contained in the lubricating oil composition of the present invention, the content is usually 0.005 wt% or more and 1 wt% or less based on the total amount of the lubricating oil composition.

  (L) As a demulsifier, well-known demulsifiers, such as a polyalkylene glycol type nonionic surfactant, can be used, for example. When the lubricating oil composition of the present invention contains an anti-emulsifier, the content thereof is usually 0.005% by mass or more and 5% by mass or less based on the total amount of the lubricating oil composition.

  (M) As an antifoamer, well-known antifoamers, such as silicone, fluorosilicone, and fluoroalkyl ether, can be used, for example. When these antifoaming agents are contained in the lubricating oil composition of the present invention, the content thereof is usually 0.0005 wt% or more and 1 wt% or less based on the total amount of the lubricating oil composition.

  (N) As a coloring agent, well-known coloring agents, such as an azo compound, can be used, for example.

Examples of the form of the lubricating oil additive and lubricating oil composition of the present invention include the following forms [1] to [43].
[1] A lubricating oil additive containing one or more compounds represented by the general formula (1) or (2).

（一般式（１）及び（２）において、Ｒは炭素数１以上の炭化水素含有基であり；
Ｘ^１は、単結合、−ＣＯＮＨ−基、−ＮＨＣＯ−基、−ＮＨ−基、又は、１以上のヘテロ原子を有し該ヘテロ原子に結合した水素原子を有しない炭素数０〜１の結合基であり、Ｘ^１の該ヘテロ原子は酸素、窒素、及び硫黄からなる群から選ばれ；
Ｘ^２は、単結合、又は、１以上のヘテロ原子を有し該ヘテロ原子に結合した水素原子を有しない炭素数０〜１の結合基であり、Ｘ^２の該ヘテロ原子は酸素、窒素、及び硫黄からなる群から選ばれ；
Ｚは、−ＣＮ基、−ＣＯ_２ＣＨ_３基、−ＯＣＯＣＨ_３基、−ＯＣＯＮ（ＣＨ_３）_２基、又は、１以上のヘテロ原子及び該ヘテロ原子に結合した水素原子を有する炭素数０〜６の基であり、Ｚの該ヘテロ原子は酸素、窒素、硫黄、及びリンからなる群から選ばれ；
ａは０又は１であり；ｂは０又は１であり；ｃは０〜２の整数であり；
ｃが１以上のとき、Ｙは−ＣＨ_２−基又は−ＯＣＨ_２ＣＨ_２−基である。）
［２］上記［１］において、Ｒが炭素数１以上の炭化水素基である形態。
［３］上記［１］又は［２］において、Ｒの炭素数が６以上である形態。
［４］上記［１］〜［３］のいずれかにおいて、Ｒの炭素数が１３以上である形態。
［５］上記［１］〜［４］のいずれかにおいて、Ｒの炭素数が１５以上である形態。
［６］上記［１］〜［５］のいずれかにおいて、Ｒの炭素数が４０以下である形態。
［７］上記［１］〜［６］のいずれかにおいて、Ｒの炭素数が３０以下である形態。
［８］上記［１］〜［７］のいずれかにおいて、Ｒが脂肪族炭化水素基である形態。
［９］上記［１］〜［８］のいずれかにおいて、Ｒが直鎖脂肪族炭化水素基である形態。
［１０］上記［１］〜［９］のいずれかにおいて、Ｘ^１が単結合、−ＣＯＮＨ−基、−ＮＨＣＯ−基、−ＮＨ−基、−Ｏ−基、−Ｓ−基、−Ｓ（Ｏ）−基、−Ｓ（Ｏ）_２−基、−Ｓ（Ｏ）_２Ｏ−基、−ＯＳ（Ｏ）_２−基、−ＮＣＨ_３−基、−Ｃ（Ｏ）−基、−ＯＣ（Ｏ）−基、又は−Ｃ（Ｏ）Ｏ−基である形態。
［１１］上記［１］〜［１０］のいずれかにおいて、Ｘ^１のヘテロ原子が酸素及び窒素から選ばれ、Ｘ^１は酸素および窒素以外のヘテロ原子を有しない形態。
［１２］上記［１］〜［１１］のいずれかにおいて、ａが０である形態。
［１３］上記［１］〜［１２］のいずれかにおいて、ａが０であり、Ｘ^１が単結合、−Ｏ−基、又は−Ｃ（Ｏ）Ｏ−基である形態。
［１４］上記［１］〜［１３］のいずれかにおいて、ｂが０である形態。
［１５］上記［１］〜［１４］のいずれかにおいて、ｃが０である形態。
［１６］上記［１］〜［１５］のいずれかにおいて、Ｘ^２が単結合、−Ｏ−基、−Ｓ−基、−Ｓ（Ｏ）−基、−Ｓ（Ｏ）_２−基、−Ｓ（Ｏ）_２Ｏ−基、−ＯＳ（Ｏ）_２−基、−ＮＣＨ_３−基、−Ｃ（Ｏ）−基、−ＯＣ（Ｏ）−基、又は−Ｃ（Ｏ）Ｏ−基である形態。
［１７］上記［１］〜［１６］のいずれかにおいて、Ｘ^２のヘテロ原子が酸素及び窒素から選ばれ、Ｘ^２は酸素および窒素以外のヘテロ原子を有しない形態。
［１８］上記［１］〜［１７］のいずれかにおいて、ｂが０であり、Ｘ^２が単結合、−Ｏ−基、又は−ＯＣ（Ｏ）−基である形態。
［１９］上記［１］〜［１８］のいずれかにおいて、Ｚが−ＣＮ基、−ＣＯ_２ＣＨ_３基、−ＯＣＯＣＨ_３基、−ＯＣＯＮ（ＣＨ_３）_２基、−ＯＨ基、−ＯＣＯＮＨ_２基、−ＯＣＯＮＨＲ’基、−ＣＯ_２Ｈ基、−ＮＨ_２基、−ＮＨＲ’基、−ＮＨＣＯＲ’基、−ＣＯＮＨ_２基、−ＣＯＮＨＲ’基、−ＳＨ基、−ＳＯＨ基、−Ｓ（Ｏ）Ｈ基、−Ｓ（Ｏ）ＯＨ基、−Ｓ（Ｏ）_２Ｈ基、−Ｓ（Ｏ）_２ＯＨ基、−ＯＳ（Ｏ）_２Ｈ基、−Ｐ（ＯＨ）_２基、−Ｐ（ＯＲ’）ＯＨ基、−ＰＨ（Ｏ）ＯＨ基、−Ｐ（Ｏ）（ＯＨ）Ｒ’基、−ＯＰＨ（ＯＨ）基、−ＯＰ（ＯＨ）Ｒ’基、−Ｐ（Ｏ）（ＯＨ）_２基、−Ｐ（Ｏ）（ＯＲ’）ＯＨ基、−ＯＰ（ＯＨ）_２基、−ＯＰ（ＯＲ’）ＯＨ基、−ＯＰＨ（Ｏ）ＯＨ基、−ＯＰＨ（Ｏ）ＯＲ’基、−ＯＰ（Ｏ）（ＯＨ）Ｒ’基、−ＯＰ（Ｏ）（ＯＨ）_２基、又は−ＯＰ（Ｏ）（ＯＲ’）ＯＨ基であり、Ｒ’がヒドロカルビル基であり、Ｚの炭素数が０〜６である形態。
［２０］上記［１］〜［１９］のいずれかにおいて、ｂが０であり、Ｘ^２が単結合であり、ｃが０であり、Ｚが−ＯＣＯＣＨ_３基、−ＯＣＯＮ（ＣＨ_３）_２基、−ＯＨ基、−ＯＣＯＮＨ_２基、−ＯＣＯＮＨＲ’基、−ＯＳ（Ｏ）_２Ｈ基、−ＯＰＨ（ＯＨ）基、−ＯＰ（ＯＨ）Ｒ’基、−ＯＰ（ＯＨ）_２基、−ＯＰ（ＯＲ’）ＯＨ基、−ＯＰＨ（Ｏ）ＯＨ基、−ＯＰＨ（Ｏ）ＯＲ’基、−ＯＰ（Ｏ）（ＯＨ）Ｒ’基、−ＯＰ（Ｏ）（ＯＨ）_２基、又は−ＯＰ（Ｏ）（ＯＲ’）ＯＨ基であり、Ｒ’がヒドロカルビル基であり、Ｚの炭素数が０〜６である形態。
［２１］上記［１］〜［２０］のいずれかにおいて、Ｚのヘテロ原子が酸素及び窒素から選ばれ、Ｚは酸素および窒素以外のヘテロ原子を有しない形態。
［２２］上記［１］〜［２１］のいずれかにおいて、Ｚの炭素数が０〜５である形態。
［２３］上記［１］〜［２２］のいずれかにおいて、Ｚの炭素数が０〜３である形態。
［２４］上記［１］〜［２３］のいずれかにおいて、上記一般式（１）で表される化合物および上記一般式（２）で表される化合物がいずれも−Ｏ−Ｏ−結合を有しない形態。
［２５］上記［１］〜［２４］のいずれかにおいて、ａが０であり、ｂが０であり、ｃが０であり、Ｘ^１が−Ｃ（Ｏ）Ｏ−基であり、Ｘ^２が単結合であり、Ｚが−ＯＨ基である形態。
［２６］上記［１］〜［２５］のいずれかにおいて、上記一般式（１）及び（２）におけるナフタレン骨格の置換パターンが、１，５−置換、１，６−置換（２つの置換基のいずれが１−位に置換していてもよい）、１，７−置換（２つの置換基のいずれが１−位に置換していてもよい）、２，６−置換、又は１，４−置換である形態。
［２７］上記［１］〜［２６］のいずれかにおいて、上記一般式（１）で表される１種以上の化合物を含有する形態。
［２８］（Ａ）潤滑油基油と、（Ｂ）上記［１］〜［２７］のいずれかにおける上記一般式（１）又は（２）で表される１種以上の化合物とを含有する、潤滑油組成物。
［２９］上記［２８］において、（Ｂ）成分として上記［１］〜［２６］のいずれかにおける上記一般式（１）で表される１種以上の化合物を含有する形態。
［３０］上記［２８］又は［２９］において、（Ｂ）成分の含有量が、上記一般式（１）又は（２）で表される化合物の含有量として、潤滑油組成物全量基準で０．０５〜１０重量％である形態。
［３１］上記［２８］〜［３０］のいずれかにおいて、（Ｂ）成分の含有量が、上記一般式（２）で表される化合物の含有量として、潤滑油組成物全量基準で５重量％以下である形態。
［３２］上記［２８］〜［３１］のいずれかにおいて、（Ｂ）成分の含有量が、上記一般式（２）で表される化合物の含有量として、潤滑油組成物全量基準で０．１重量％以上である形態。
［３３］上記［２８］〜［３２］のいずれかにおいて、（Ａ）潤滑油基油の１００℃における動粘度が３．０〜２５．０ｍｍ^２／ｓである形態。
［３４］上記［２８］〜［３３］のいずれかにおいて、内燃機関用潤滑油組成物であって、（Ａ）潤滑油基油の１００℃における動粘度が３．０〜１６．３ｍｍ^２／ｓである形態。
［３５］上記［２８］〜［３３］のいずれかにおいて、変速機油組成物であって、（Ａ）潤滑油基油の１００℃における動粘度が３．５〜２５．０ｍｍ^２／ｓである形態。
［３６］上記［２８］〜［３５］のいずれかにおいて、無灰分散剤、酸化防止剤、上記一般式（１）又は（２）で表される化合物以外の摩擦調整剤、摩耗防止剤、極圧剤、金属系清浄剤、粘度指数向上剤、流動点降下剤、腐食防止剤、防錆剤、金属不活性化剤、抗乳化剤、消泡剤及び着色剤から選ばれる１種以上の添加剤をさらに含む形態。
［３７］上記［２８］〜［３６］のいずれかにおいて、無灰分散剤を組成物全量基準で０．０１〜２０重量％含む形態。
［３８］上記［２８］〜［３７］のいずれかにおいて、酸化防止剤（ただし上記一般式（１）又は（２）で表される化合物を除く。）を組成物全量基準で０．１〜５．０重量％含む形態。
［３９］上記［２８］〜［３８］のいずれかにおいて、上記一般式（１）又は（２）で表される化合物以外の摩擦調整剤を組成物全量基準で０．０５〜５重量％含む形態。
［４０］上記［２８］〜［３９］のいずれかにおいて、摩耗防止剤または極圧剤（ただし上記一般式（１）又は（２）で表される化合物を除く。）を組成物全量基準で０．０５〜５重量％含む形態。
［４１］上記［２８］〜［４０］のいずれかにおいて、金属系清浄剤を金属元素換算量で潤滑油組成物全量に対して０．０１〜１．０重量％含む形態。
［４２］上記［４１］において、自動変速機または無段変速機の潤滑に用いられる形態。
［４３］上記［２８］〜［４０］のいずれかにおいて、金属系清浄剤を金属元素換算量で潤滑油組成物全量に対して０．０１〜５．０重量％含む形態。
［４４］上記［４３］において、内燃機関の潤滑に用いられる形態。

(In the general formulas (1) and (2), R is a hydrocarbon-containing group having 1 or more carbon atoms;
X ¹ is a single bond, a —CONH— group, a —NHCO— group, a —NH— group, or a bond having 0 to 1 carbon atoms that has one or more heteroatoms and does not have a hydrogen atom bonded to the heteroatoms. The hetero atom of X ¹ is selected from the group consisting of oxygen, nitrogen, and sulfur;
X ² is a single bond or a C 0-1 linking group having one or more hetero atoms and no hydrogen atom bonded to the hetero atom, and the hetero atom of X ² is oxygen, nitrogen, And selected from the group consisting of sulfur;
Z represents a —CN group, —CO ₂ CH ₃ group, —OCOCH ₃ group, —OCON (CH ₃ ) ₂ group, or one or more heteroatoms and a hydrogen atom bonded to the heteroatoms having 0 to 0 carbon atoms. 6 wherein the heteroatom of Z is selected from the group consisting of oxygen, nitrogen, sulfur, and phosphorus;
a is 0 or 1; b is 0 or 1; c is an integer from 0 to 2;
When c is 1 or more, Y is a —CH ₂ — group or a —OCH ₂ CH ₂ — group. )
[2] In the above [1], R is a hydrocarbon group having 1 or more carbon atoms.
[3] In the above [1] or [2], R has 6 or more carbon atoms.
[4] In any one of the above [1] to [3], the carbon number of R is 13 or more.
[5] In any one of the above [1] to [4], the carbon number of R is 15 or more.
[6] The form in which the carbon number of R is 40 or less in any one of the above [1] to [5].
[7] In any one of the above [1] to [6], the carbon number of R is 30 or less.
[8] The form in which R is an aliphatic hydrocarbon group in any one of the above [1] to [7].
[9] The form in which R is a linear aliphatic hydrocarbon group in any one of the above [1] to [8].
[10] In any one of the above [1] to [9], X ¹ is a single bond, —CONH— group, —NHCO— group, —NH— group, —O— group, —S— group, —S ( O) — group, —S (O) ₂ — group, —S (O) ₂ O— group, —OS (O) ₂ — group, —NCH ₃ — group, —C (O) — group, —OC ( A form that is an O)-group or a -C (O) O- group.
[11] In any of the above [1] to [10], heteroatoms ^{X 1} is selected from oxygen and nitrogen, ^{X 1} does not have the form a heteroatom other than oxygen and nitrogen.
[12] The form in which a is 0 in any one of the above [1] to [11].
[13] The form in which in any one of the above [1] to [12], a is 0 and X ¹ is a single bond, an —O— group, or a —C (O) O— group.
[14] The form in which b is 0 in any one of the above [1] to [13].
[15] The form in which c is 0 in any one of the above [1] to [14].
[16] In any one of the above [1] to [15], X ² is a single bond, —O— group, —S— group, —S (O) — group, —S (O) ₂ — group, — S (O) ₂ O— group, —OS (O) ₂ — group, —NCH ₃ — group, —C (O) — group, —OC (O) — group, or —C (O) O— group. Some form.
[17] In any of the above [1] to [16], heteroatoms ^{X 2} is selected from oxygen and nitrogen, ^{X 2} does not have the form a heteroatom other than oxygen and nitrogen.
[18] The form in which b is 0 and X ² is a single bond, an —O— group, or an —OC (O) — group in any one of the above [1] to [17].
A method according to any one of [19] above [1] ~ [18], Z is a -CN group, _-CO 2 CH ₃ group, -OCOCH ₃ group, -OCON _{(CH 3) 2} group, -OH group, -OCONH ₂ Group, —OCONHR ′ group, —CO ₂ H group, —NH ₂ group, —NHR ′ group, —NHCOR ′ group, —CONH ₂ group, —CONHR ′ group, —SH group, —SOH group, —S (O ) H group, -S (O) OH groups, -S _{(O) 2} H group, -S _(O) 2 OH group, -OS _{(O) 2} H group, -P _{(OH) 2} group, -P ( OR ′) OH group, —PH (O) OH group, —P (O) (OH) R ′ group, —OPH (OH) group, —OP (OH) R ′ group, —P (O) (OH) ₂ groups, -P (O) (OR ') OH group, -OP (OH) ₂ group, -OP (OR') OH group, -OPH (O) OH group, -OPH (O) OR 'group,- OP (O) (OH ) R ′ group, —OP (O) (OH) ₂ group, or —OP (O) (OR ′) OH group, R ′ is a hydrocarbyl group, and Z has 0 to 6 carbon atoms .
[20] In any one of the above [1] to [19], b is 0, X ² is a single bond, c is 0, Z is a —OCOCH ₃ group, —OCON (CH ₃ ) _2. Group, —OH group, —OCONH ₂ group, —OCONHR ′ group, —OS (O) ₂ H group, —OPH (OH) group, —OP (OH) R ′ group, —OP (OH) ₂ group, — OP (OR ′) OH group, —OPH (O) OH group, —OPH (O) OR ′ group, —OP (O) (OH) R ′ group, —OP (O) (OH) ₂ group, or — A form in which it is an OP (O) (OR ′) OH group, R ′ is a hydrocarbyl group, and Z has 0 to 6 carbon atoms.
[21] In any one of the above [1] to [20], the hetero atom of Z is selected from oxygen and nitrogen, and Z does not have a hetero atom other than oxygen and nitrogen.
[22] The form in which the carbon number of Z is 0 to 5 in any one of the above [1] to [21].
[23] The form in which the carbon number of Z is 0 to 3 in any one of the above [1] to [22].
[24] In any one of the above [1] to [23], each of the compound represented by the general formula (1) and the compound represented by the general formula (2) has an —O—O— bond. No form.
[25] In any one of the above [1] to [24], a is 0, b is 0, c is 0, X ¹ is a —C (O) O— group, and X ² Is a single bond and Z is an —OH group.
[26] In any one of the above [1] to [25], the substitution pattern of the naphthalene skeleton in the general formulas (1) and (2) is 1,5-substituted, 1,6-substituted (two substituents 1 may be substituted at the 1-position), 1,7-substituted (any of the two substituents may be substituted at the 1-position), 2,6-substituted, or 1,4 A form that is a substitution.
[27] A form containing one or more compounds represented by the general formula (1) in any one of the above [1] to [26].
[28] Contains (A) a lubricating base oil and (B) one or more compounds represented by the above general formula (1) or (2) in any one of the above [1] to [27]. , Lubricating oil composition.
[29] A form in which the above [28] contains one or more compounds represented by the general formula (1) in any one of the above [1] to [26] as the component (B).
[30] In the above [28] or [29], the content of the component (B) is 0 on the basis of the total amount of the lubricating oil composition as the content of the compound represented by the general formula (1) or (2). A form that is from 05 to 10% by weight.
[31] In any one of the above [28] to [30], the content of the component (B) is 5% based on the total amount of the lubricating oil composition as the content of the compound represented by the general formula (2). % Form or less.
[32] In any one of the above [28] to [31], the content of the component (B) is 0.00 on the basis of the total amount of the lubricating oil composition as the content of the compound represented by the general formula (2). A form that is 1% by weight or more.
[33] In any one of the above [28] to [32], (A) the kinematic viscosity at 100 ° C. of the lubricating base oil is 3.0 to 25.0 mm ² / s.
[34] The lubricating oil composition for internal combustion engines according to any one of [28] to [33], wherein (A) the lubricating oil base oil has a kinematic viscosity at 100 ° C. of 3.0 to 16.3 mm ² / A form that is s.
[35] The transmission oil composition according to any one of [28] to [33], wherein (A) the lubricating base oil has a kinematic viscosity at 100 ° C. of 3.5 to 25.0 mm ² / s. Form.
[36] In any one of the above [28] to [35], an ashless dispersant, an antioxidant, a friction modifier other than the compound represented by the general formula (1) or (2), an antiwear agent, an electrode One or more additives selected from pressure agents, metal detergents, viscosity index improvers, pour point depressants, corrosion inhibitors, rust inhibitors, metal deactivators, demulsifiers, antifoaming agents and colorants The form which further contains.
[37] A form containing the ashless dispersant in an amount of 0.01 to 20% by weight based on the total amount of the composition according to any one of [28] to [36].
[38] In any one of the above [28] to [37], an antioxidant (excluding the compound represented by the general formula (1) or (2)) is added in an amount of 0.1 to 0.1 on the basis of the total amount of the composition. Form containing 5.0% by weight.
[39] In any one of the above [28] to [38], a friction modifier other than the compound represented by the general formula (1) or (2) is included in an amount of 0.05 to 5% by weight based on the total amount of the composition. Form.
[40] In any one of the above [28] to [39], the antiwear agent or extreme pressure agent (excluding the compound represented by the general formula (1) or (2)) is based on the total amount of the composition. Form containing 0.05 to 5% by weight.
[41] A form comprising the metal detergent in an amount of 0.01 to 1.0% by weight in terms of metal element based on the total amount of the lubricating oil composition in any one of [28] to [40].
[42] The form used in [41] above for lubricating an automatic transmission or a continuously variable transmission.
[43] In any one of the above [28] to [40], the metallic detergent is contained in an amount of 0.01 to 5.0% by weight in terms of a metal element with respect to the total amount of the lubricating oil composition.
[44] The form used in the above [43] for lubricating an internal combustion engine.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. The following examples are intended to illustrate the present invention and are not intended to limit the present invention.

<Production example>
Naphthalene-based friction modifiers L1 to L5 according to the first aspect of the present invention and friction modifiers C1 and C2 that are outside the scope of the present invention were produced.

(Production Example 1)
According to the following procedure, in the above general formula (1), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, X ² is a single bond, Z Is a —OH group, a = 0, b = 0, c = 0, and a naphthalene-based friction modifier L1 in which the substitution pattern for the naphthalene skeleton is 1,5-substitution was produced.

After adding 31 mmol (5.00 g) of 1,5-naphthalenediol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 ml of pyridine to the eggplant flask, the inside was replaced with nitrogen. From the dropping funnel, 31 mmol (9.40 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at room temperature. After dropping, the mixture was heated to reflux for 1 hour. Thereafter, the produced pyridine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. 200 ml of toluene was added to the obtained solid, and residual pyridine was removed azeotropically with toluene by a rotary evaporator. The pyridine removal operation was repeated three times, and then purified by silica gel column chromatography to obtain 4.83 g of the target compound (formula (L1) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 2)
According to the following procedure, in the above general formula (1), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, X ² is a single bond, Z A naphthalene-based friction modifier L2 in which is an —OH group, a = 0, b = 0, c = 0, and an isomer mixture of compounds in which the substitution pattern for the naphthalene skeleton is 2,5-substitution. Manufactured.

After adding 62 mmol (10.00 g) of 1,6-naphthalenediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 50 ml of pyridine and 50 ml of tetrahydrofuran to the eggplant flask, the inside was purged with nitrogen. 12 mmol (3.76 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel while stirring at room temperature. After dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, the produced pyridine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. 200 ml of toluene was added to the obtained solid, and residual pyridine was removed azeotropically with toluene by a rotary evaporator. The pyridine removal operation was repeated three times, and then purified by silica gel column chromatography to obtain 3.00 g of the target compound (formula (L2) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 3)
According to the following procedure, in the above general formula (1), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, X ² is a single bond, Z A naphthalene-based friction modifier L3 in which is an —OH group, a = 0, b = 0, c = 0, and an isomer mixture of compounds in which the substitution pattern for the naphthalene skeleton is 1,7-substitution. Manufactured.

To the eggplant flask, 44 mmol (7.00 g) of 1,7-naphthalenediol (Tokyo Kasei Kogyo Co., Ltd.), 100 mL of tetrahydrofuran, and 20 mL of triethylamine were added, and the interior was purged with nitrogen. To the dropping funnel, 44 mmol (13.15 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 mL of tetrahydrofuran were added and added dropwise with stirring at room temperature. After dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, the produced triethylamine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. The obtained solid was purified by silica gel column chromatography to obtain 6.00 g of the desired compound (formula (L3) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 4)
According to the following procedure, in the above general formula (1), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, X ² is a single bond, Z Is a —OH group, a = 0, b = 0, c = 0, and a naphthalene-based friction modifier L4 having a substitution pattern of 2,6-substitution with respect to the naphthalene skeleton was produced.

After adding 44 mmol (7.00 g) of 2, 6-naphthalenediol (Tokyo Chemical Industry Co., Ltd.) and 100 ml of pyridine to the eggplant flask, the inside was purged with nitrogen. From the dropping funnel, 44 mmol (13.24 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at room temperature. After dropping, the mixture was heated to reflux for 1 hour. Thereafter, the produced pyridine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. 200 ml of toluene was added to the obtained solid, and residual pyridine was removed azeotropically with toluene by a rotary evaporator. After the pyridine removal operation was repeated three times, the obtained solid was dissolved in 200 ml of methanol, and the insoluble matter was removed by filtration. The solvent of the filtrate was removed by a rotary evaporator, and the obtained solid was purified by silica gel column chromatography to obtain 5.92 g of the target compound (the above formula (L4)). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 5)
According to the following procedure, in the above general formula (2), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, X ² is a single bond, and Z Is a —OH group, a = 0, b = 0, c = 0, and a naphthalene-based friction modifier L5 in which the substitution pattern for the naphthalene skeleton is 1,4-substitution was produced.

To the eggplant flask, 44 mmol (7.00 g) of 1,4-naphthalenediol (Tokyo Chemical Industry Co., Ltd.) and 100 ml of pyridine were added, and the interior was purged with nitrogen. From the dropping funnel, 44 mmol (13.24 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at room temperature. After dropping, the mixture was heated to reflux for 1 hour. Thereafter, the produced pyridine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. 200 ml of toluene was added to the obtained solid, and residual pyridine was removed azeotropically with toluene by a rotary evaporator. The pyridine removal operation was repeated three times, and then purified by silica gel column chromatography to obtain 4.33 g of the target compound (formula (L5) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 6)
According to the following procedure, in the above general formula (1) or (2), R is a cis-8-heptadecen-1-yl group, X ¹ is a —C (O) O— group, and a = 0. The R—X ¹ — (CH ₂ ) _a — group of the embodiment has the 2-position of the naphthalene skeleton, but does not have the — (CH ₂ ) _b —X ² — (Y) _c —Z group. A friction modifier C1 that is out of range was produced.

To the eggplant flask, 35 mmol (5.00 g) of 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 ml of pyridine were added, and the inside was replaced with nitrogen. From the dropping funnel, 35 mmol (10.44 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at room temperature. After dropping, the mixture was heated to reflux for 1 hour. Thereafter, the produced pyridine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. 200 ml of toluene was added to the obtained solid, and residual pyridine was removed azeotropically with toluene by a rotary evaporator. The pyridine removal operation was repeated three times, and then purified by silica gel column chromatography to obtain 10.04 g of the target compound (formula (C1) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

(Production Example 7)
According to the following procedure, the substitution pattern for the naphthalene skeleton in the above general formula (1) is 1,7-substitution, R is a cis-8-heptadecen-1-yl group, and X ¹ is —C (O) O. - group, a a = 0, a b = 0, ^{X 2} is -OC (O) - is a group, - _(Y) c -Z groups cis-8- heptadecene-1-yl group Therefore, friction modifier C2 which is outside the scope of the present invention was produced.

To the eggplant flask, 44 mmol (7.00 g) of 1,7-naphthalenediol (Tokyo Kasei Kogyo Co., Ltd.), 100 mL of tetrahydrofuran, and 20 mL of triethylamine were added, and the interior was purged with nitrogen. To the dropping funnel, 44 mmol (13.15 g) of oleic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 mL of tetrahydrofuran were added and added dropwise with stirring at room temperature. After dropping, the mixture was stirred at room temperature for 1 hour. Thereafter, the produced triethylamine hydrochloride was removed by filtration, and the solvent of the filtrate was removed by a rotary evaporator. The obtained solid was purified by silica gel column chromatography to obtain 8.67 g of the target compound (formula (C2) above). Progress of the reaction was confirmed by ¹ H-NMR spectrum.

<Examples 1-5 and Comparative Examples 1-3>
As shown in Table 1, lubricating oil compositions of the present invention (Examples 1 to 5) and comparative lubricating oil compositions (Comparative Examples 1 to 3) were prepared. In Table 1, the unit “wt.%” Means weight%.

(Evaluation method)
The friction characteristics of each of the prepared lubricating oil compositions were evaluated. The friction characteristics were measured using a cylinder-on-disk reciprocating friction tester (SRV manufactured by Optimol) with a load of 700 N, a surface pressure (maximum hertz pressure) of 0.4 GPa, a vibration frequency of 10 Hz, an amplitude of 1 mm, a temperature of 100 ° C., and a test time of 60. The friction coefficient was measured under the condition of minutes, and evaluation was performed by calculating an average friction coefficient obtained by averaging the friction coefficients of 30 to 60 minutes of the test time. This measurement condition corresponds to the boundary lubrication condition. A graph plotting the measured coefficient of friction for each lubricating oil composition is shown in FIG.

FIG. 1 is a graph comparing the test results of Examples 1 to 5 and Comparative Examples 1 to 3. The lubricating oil of Comparative Example 3 consists only of base oil. The friction reducing effect of the lubricating oil composition is evaluated by comparing the friction coefficient of the lubricating oil of Comparative Example 3.
As shown in FIG. 1, the lubricating oil compositions of Examples 1 to 5 showed a good friction reducing effect.
The lubricating oil composition of Comparative Example 1 containing the compound C1 having no — (CH ₂ ) _b —X ² —Z group in the general formula (1) or (2), and the requirement for Z in the general formula (1) The lubricating oil composition of Comparative Example 2 containing the compound C2 that does not satisfy the condition was inferior in the friction reducing effect than the lubricating oil compositions of Examples 1 to 5.

  From the above test results, it was shown that according to the lubricating oil additive of the present invention, an ashless oil-based friction modifier having an excellent friction reducing effect can be provided.

  The lubricating oil additive and lubricating oil composition of the present invention can be suitably used for lubricating various machines, and in particular, can be suitably used for lubricating internal combustion engines and transmissions.

Claims (4)

A lubricating oil additive comprising one or more compounds represented by formula (1) or (2).

(In the general formulas (1) and (2), R is a hydrocarbon-containing group having 1 or more carbon atoms;
X ¹ is a single bond, a —CONH— group, a —NHCO— group, a —NH— group, or a bond having 0 to 1 carbon atoms that has one or more heteroatoms and does not have a hydrogen atom bonded to the heteroatoms. The hetero atom of X ¹ is selected from the group consisting of oxygen, nitrogen, and sulfur;
X ² is a single bond or a C 0-1 linking group having at least one hetero atom and no hydrogen atom bonded to the hetero atom, and the hetero atom of X ² is oxygen, nitrogen, And selected from the group consisting of sulfur;
Z represents a —CN group, —CO ₂ CH ₃ group, —OCOCH ₃ group, —OCON (CH ₃ ) ₂ group, or one or more heteroatoms and a hydrogen atom bonded to the heteroatoms having 0 to 0 carbon atoms. 6 wherein the heteroatom of Z is selected from the group consisting of oxygen, nitrogen, sulfur, and phosphorus;
a is 0 or 1; b is 0 or 1; c is an integer from 0 to 2;
When c is 1 or more, Y is a —CH ₂ — group or a —OCH ₂ CH ₂ — group. )   The lubricating oil additive according to claim 1, comprising at least one compound represented by the general formula (1). (A) a lubricating base oil;
(B) A lubricating oil composition comprising the lubricating oil additive according to claim 1 or 2. Ashless dispersant, antioxidant, friction modifier other than the compound represented by the general formula (1) or (2), antiwear agent, extreme pressure agent, metallic detergent, viscosity index improver, pour point depressant Further comprising one or more additives selected from agents, corrosion inhibitors, rust inhibitors, metal deactivators, demulsifiers, antifoaming agents and colorants,
The lubricating oil composition according to claim 3.

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