JP6582021B2 - Friction modifier and lubricating oil composition - Google Patents

Description

  The present invention relates to a friction modifier and a lubricating oil composition containing the friction modifier.

  Lubricating oils and hydraulic oils used in automobiles and the like have recently been reduced in viscosity due to the pursuit of fuel efficiency. Low viscosity reduces frictional resistance in the fluid lubrication area and improves fuel efficiency, but wear tends to occur under high pressure in the mixed lubrication area and boundary lubrication area, and a friction modifier is used to prevent such wear. It is common. Friction modifiers that improve fuel efficiency are mainly classified into four types, which are oil-based improvers that form an oil film on the friction surface under low load and reduce friction and wear, and secondary compounds on the friction surface. An anti-wear agent that forms a protective film to prevent wear, an extreme pressure agent that prevents seizure and scuffing in extreme pressure lubrication, and a friction control that controls the coefficient of friction by physically and chemically adsorbing to the friction surface. It is an agent.

Currently used friction modifiers are long chain fatty acid esters and fatty acid amides as oiliness improvers, phosphate esters and zinc dithiophosphate as antiwear agents, organic sulfur, organic halogen compounds and friction control agents as extreme pressure agents. Examples thereof include organic molybdenum compounds.
Polymeric friction modifiers include α-olefin and fumaric acid ester copolymers (Patent Document 1), hydroxyl group-containing acrylic acid ester copolymers (Patent Document 2), hydrophilic polymer units and polyolefins. Polyester having a unit (Patent Document 3), Methacrylate copolymer having a block structure composed of a polar segment unit and a hydrophobic segment unit (Patent Document 4), Phosphorus functionalized methacrylate copolymer (Patent) Document 5) is known.

  However, the above polymer friction modifier has a problem that the friction reducing effect is not yet sufficient.

Japanese Patent No. 3730660 Japanese Patent No. 5822706 Japanese Patent No. 5684842 Japanese Patent No. 4686444 Special table 2014-518925 gazette

  An object of the present invention is to provide a friction modifier having an excellent friction reducing effect; a lubricating oil composition containing the friction modifier.

As a result of intensive studies, the present inventors have arrived at the present invention. That is, the present invention provides at least one monomer selected from the group consisting of the monomer (a1) represented by the following general formula (1) and the monomer (a2) represented by the following general formula (2). A friction modifier comprising a (co) polymer (A) having the body (a) as an essential constituent monomer , wherein the polymer (A) is a monomer represented by the following general formula (3) It is a friction modifier which is a copolymer having (b) as a constituent monomer .

[In the formulas (1) and (2), A ¹ is a monovalent radical polymerizable group, and A ² is a divalent radical polymerizable group. -X ¹ -, - ^{X 2} - and -X ³ - is a group represented by each independently -O- or -NH-, a plurality of the formula ^{(2) -X 1 -, -} X 2 - and -X 3 ^- may be the same or different. R ¹ is an alkylene group having 1 to 4 carbon atoms. R ² is each independently an alkylene group having 2 to 20 carbon atoms, and a plurality of R ¹ may be the same or different. R ³ is a hydrogen atom, an alkyl group having 1 to 44 carbon atoms, an acyl group having 2 to 45 carbon atoms, a phenyl group or a benzoyl group which may be substituted with an alkyl group having 1 to 44 carbon atoms. The two R ³ groups in) may be the same or different. p, q and r are each an integer of 1 to 100.
In Formula (3), R ⁴ is a hydrogen atom or a methyl group; —X ⁴ — is a group represented by —O— or —NH—; R ⁵ is a linear or branched alkyl group having ⁵ to 44 carbon atoms. . ]

  The lubricating oil composition containing the friction modifier of the present invention has the effect of being excellent in reducing friction in the effective temperature range.

  The friction modifier of the present invention is one or more selected from the group consisting of a monomer (a1) represented by the following general formula (1) and a monomer (a2) represented by the following general formula (2). A friction modifier containing the (co) polymer (A) having the monomer (a) as an essential constituent monomer and a lubricating oil composition containing the friction modifier. The (co) polymer means a copolymer or a polymer.

A ¹ in the general formula (1) is a monovalent radical polymerizable group, and specifically, a vinyl group, a (meth) acryloyl group, or the like.
A ² in the general formula (2) is a divalent radical polymerizable group, and specifically, a divalent residue obtained by removing a hydroxyl group from two carboxyl groups of fumaric acid and maleic acid.
Among these monomers (a), from the viewpoint of reducing friction, A ¹ in the general formula (1) is preferably (a1) of a vinyl group and a (meth) acryloyl group, and more preferably (meth) acryloyl. It is a group.

Formula (1) and in the general formula ^{(2) -X 1 -, -} X 2 - and -X ³ - is a group represented by each independently -O- or -NH-, equation (2) The plurality of —X ¹ —, —X ² —, and —X ³ — may be the same or different.
These -X ^1- , -X ² -and -X ³ -are preferably -O- from the viewpoint of friction reduction.

^{R 1} Formula (1) in the general formula (2) is an alkylene group having 1 to 4 carbon atoms.
Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a 1,2- and 1,3-propylene group, and a 1,2-, 1,3- and 1,4-butylene group. Of these, ethylene groups and 1,2- and 1,3-propylene groups are preferable from the viewpoint of reducing friction, and ethylene groups are more preferable.

P in the general formula (1) and q and r in the general formula (2) are each a number of 1 to 100, preferably from an integer of 1 to 70, more preferably 1 from the viewpoint of friction reduction and base oil solubility. An integer of ˜40, particularly preferably an integer of 1-20. A plurality of (—C (═O) —R ² —X ³ —) may be the same or different.

A plurality of R ² in general formulas (1) and (2) are each independently an alkylene group having 2 to 20 carbon atoms, plurality of R ¹ may be the same or different.
Specifically, as the alkylene group having 1 to 20 carbon atoms, ethylene group, isopropylene group, 1,2- or 1,3-propylene group, isobutylene group, 1,2-, 1,3- or 1, 4-butylene group, isopentylene group, 1,2-, 1,3-, 1,4- or 1,5-pentylene group, isohexylene group, 1,2-, 1,3-, 1,4-, 1, 5- or 1,6-hexylene group, isoheptylene group, 1,2-, 1,3-, 1,4-, 1,5-, 1,6- or 1,7-heptylene group, isooctylene, 1,8 -Octylene group, isononylene group, 1,9-nonylene group, isodecylene group, 1,10-decylene group, isoundecylene group, 1,11-undecylene group, isododecylene group, 1,12-dodecylene group, isotridecylene group, 1, 13-tridecylene group, a Tetradecylene group, 1,14-tetradecylene group, isopentadecylene group, 1,15-pentadecylene group, isohexadecylene group, 1,16-hexadecylene group, isoheptadecylene group, 1,17-heptadecylene group, iso Examples include an octadecylene group, a 1,18-isooctadecylene group, an isonononadecylene group, a 1,19-isononadecylene group, an isoeicosylene group, and a 1,20-eicosylene group.
R ² is preferably an alkylene group having 2 to 17 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, particularly preferably an alkylene group having 1 to 13 carbon atoms, and most preferably 1 carbon atom from the viewpoint of reducing friction. -10 alkylene groups.

R ³ in the general formulas (1) and (2) may be substituted with a hydrogen atom, an alkyl group having 1 to 44 carbon atoms, an acyl group having 2 to 45 carbon atoms, or an alkyl group having 1 to 44 carbon atoms. It is a good phenyl group or benzoyl group, and two R ³ in the formula (2) may be the same or different.

  Specific examples of the linear or branched alkyl group having 1 to 44 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, Isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, 2-ethyldodecyl group, n-pentadecyl group 2-methyltetradecyl group, n-hexadecyl group, isohexadecyl group, n-heptadecyl group, isoheptadecyl group, 2-ethylpentadecyl group, 2-octylnonyl group, 2- (3-methylhexyl) -7- Methyl-nonyl group, n-octadecyl group, isooctadecyl group, 2-hexylundecyl group, 2-ethylheptade Group, 1-hexyltridecyl group, n-icosyl group, 2-octylundecyl group, isoicosyl group, 1-undecyldodecyl group, 1-octylpentadecyl group, 2-decyltridecyl group, n-tetricosyl group, 2 -Decyltetradecyl group, 2-dodecylpentadecyl group, 2-heptylukosyl group, 2-dodecylhexadecyl group, n-triacontyl group, 2-tetradecyloctadecyl group, n-hexatriacontyl group, n-tetracontyl group, From an oxo alcohol obtained from a 2-ethyltetracontyl group and an olefin [for example, propylene oligomer (2 to 14 mer), ethylene / propylene oligomer (2 to 20 mer), isobutene oligomer (2 to 10 mer, etc.)] Examples thereof include a residue excluding a hydroxyl group.

Among these R ³ , from the viewpoint of reducing friction, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, or an alkyl group having 1 to 12 carbon atoms may be substituted. Good phenyl or benzoyl group.

The monomer (a) preferably has a specific solubility parameter (hereinafter sometimes abbreviated as SP value) from the viewpoint of solubility in lubricating oil.
The range of the SP value is preferably 9.0 to 12.5 (cal / cm ³ ) ^1/2 , more preferably 9.3 to 12.3 (cal / cm ³ ) ^1/2 , especially Preferably it is 9.5 to 12.0 (cal / cm < ³ >) < ^1/2 >.
The SP value in the present invention is a value calculated by the method described in the Fedors method (Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154).

  In addition, when using together 2 or more types of monomers, SP value of this monomer (a) calculates SP value of each of several monomer which comprises (a) by the said method, The SP value of each monomer (a) is an arithmetic average value based on the molar fraction of the constituent monomer units.

The number average molecular weight (hereinafter abbreviated as Mn) of the monomer (a) is preferably 150 to 20,000, more preferably 150 to 10,000, and particularly preferably 150 to 7 from the viewpoint of friction reduction. 1,000, most preferably 150 to 4,000. In addition, the Mn of (a) and the weight average molecular weight (hereinafter abbreviated as Mw) of the (co) polymer (A) described later can be measured by gel permeation chromatography under the following conditions.
<Measurement conditions of Mn in (a) and Mw in (A)>
Apparatus: “HLC-802A” [manufactured by Tosoh Corporation]
Column: Two “TSK gel GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

The monomer (a) is preferably a lactone adduct end OH, a lactone adduct end OR ³ , a lactam adduct end NH, or the like from the viewpoint of reducing friction.
These monomers (a) can be obtained by a known production method.

Lactone adduct terminal OH:
Examples thereof include a method obtained by ring-opening addition of a lactone to hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA). The reaction temperature for the ring-opening addition reaction of lactone with hydroxyethyl acrylate ester (HEA) or hydroxyethyl methacrylate ester (HEMA) is preferably 80 to 150 ° C., more preferably 100 ° C. from the viewpoint of reaction time. ~ 140 ° C. The reaction time is preferably 2 to 24 hours, more preferably 3 to 10 hours. The reaction is mainly carried out in the presence of a catalyst.
The catalyst for the reaction may be a known catalyst such as p-toluenesulfonic acid, tetrapropyl titanate, stannous octoate and the like. The amount of the catalyst used is preferably 0.01 to 5% by mass, more preferably 0.03 to 0.5% by mass, based on the amount of the reaction product. After completion of the ring-opening addition reaction, the catalyst is desirably treated by adsorption, filtration and removal using an adsorbent, neutralization to inactivate the catalyst, or the like.

Lactone adduct terminal OR ³ :
The reaction temperature for the esterification reaction of the compound (a-1) and the carboxylic acid is preferably 80 to 150 ° C., more preferably 90 to 130 ° C. from the viewpoint of reaction time and prevention of polymerization of (meth) acrylic acid. ° C. In the esterification reaction, the reaction pressure may be reduced for the purpose of removing generated water. A preferable reaction pressure is preferably 0.007 to 0.095 MPa, more preferably 0.01 to 0.092 MPa from the viewpoint of reaction time and polymerization prevention. The reaction time is preferably 2 to 24 hours, more preferably 3 to 10 hours. The esterification reaction is desirably performed in the presence of a catalyst.
The catalyst for the esterification reaction may be a known catalyst, and examples thereof include sulfuric acid and p-toluenesulfonic acid. A solvent may be used for the esterification reaction, and examples of the solvent include water-insoluble solvents having a boiling point of 150 ° C. or lower, such as cyclohexane and toluene.

Lactam adduct terminal NH:
Examples thereof include a method obtained by ring-opening addition of lactam to hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylic acid ester (HEMA). The reaction temperature for the ring-opening addition reaction of lactam to hydroxyethyl acrylate ester (HEA) or hydroxyethyl methacrylate ester (HEMA) is preferably 80 to 150 ° C., more preferably 100 ° C. from the viewpoint of reaction time. ~ 140 ° C. The reaction time is preferably 2 to 24 hours, more preferably 3 to 10 hours. The reaction is mainly carried out in the presence of a catalyst.
The catalyst for the above reaction may be a known catalyst, such as tetrapropyl titanate and stannous octoate. The amount of the catalyst used is preferably 0.01 to 5% by mass, more preferably 0.03 to 0.5% by mass, based on the amount of the reaction product. After completion of the ring-opening addition reaction, the catalyst is desirably treated by adsorption, filtration and removal using an adsorbent, neutralization to inactivate the catalyst, or the like.

  Specific examples of the lactone adduct terminal OH include hydroxypolyacetolactone mono (meth) acrylate (addition of 1 to 100 mol of α-acetolactone), hydroxypolypropiolactone mono (meth) acrylate (β-propiolactone 1 To 100 mol addition), hydroxypolybutyrolactone mono (meth) acrylate (1 to 100 mol addition of γ-butyrolactone), hydroxypolyvalerolactone mono (meth) acrylate (1 to 100 mol addition of δ-valerolactone), hydroxypoly Caprolactone mono (meth) acrylate (1 to 100 mol of ε-caprolactone added).

Specific examples of the lactone adduct terminal OR ³ include alkyl ester polyacetolactone mono (meth) acrylate having 1 to 44 carbon atoms (addition of 1 to 100 mol of α-acetolactone), alkyl ester polypropylene having 1 to 44 carbon atoms. Olactone mono (meth) acrylate (addition of 1 to 100 mol of β-propiolactone), alkyl ester polybutyrolactone mono (meth) acrylate having 1 to 44 carbon atoms (addition of 1 to 100 mol of γ-butyrolactone), carbon number 1 to 44 alkyl ester polyvalerolactone mono (meth) acrylate (addition of 1 to 100 mol of δ-valerolactone), C1 to 44 alkyl ester polycaprolactone mono (meth) acrylate (1 to 100 of ε-caprolactone) Molar addition).

  Specific examples of the lactam adduct terminal NH include aminopolypropiolactam mono (meth) acrylate (addition of 1 to 100 mol of β-propiolactam), aminopolybutyrolactam mono (meth) acrylate (γ-butyrolactam 1 To 100 mol addition), and aminopolyvalerolactam mono (meth) rate (1 to 100 mol addition of δ-valerolactam).

Among the monomers (a), from the viewpoint of friction reduction, lactone adduct terminal OH and lactone adduct terminal OR ³ are preferable, lactone adduct terminal OH is more preferable, and lactone 1 to 20 is particularly preferable. It is a molar adduct.

  Monomer (a) is a spectrum obtained by nuclear magnetic resonance analysis (13C-NMR), wherein the peak total area M1 between the chemical shift 170-180 ppm relative to the total area of all peaks and the chemical shift 160-170 ppm. The ratio M1 / M2 of the total area M2 of the peaks is 0.01 or more.

  M1 / M2 needs to be 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, particularly preferably 0.04 or more, and most preferably 0.05 or more. M1 / M2 is preferably 200 or less, more preferably 180 or less, particularly preferably 150 or less, and most preferably 130 or less. When M1 / M2 is less than 0.01, not only the required frictional reduction cannot be obtained, but also fuel economy may be deteriorated. Moreover, when M1 / M2 exceeds 200, there exists a possibility that required friction reduction may not be obtained, and there exists a possibility that solubility and storage stability may deteriorate.

  In addition, the total area (M1) of the peak between chemical shift 170-180 ppm with respect to the total area of all the peaks is a specific carbonyl structure of (meth) acrylate with respect to the total integrated intensity of all the carbons measured by 13C-NMR. Means the ratio of the integrated intensity derived from. The total peak area (M2) between chemical shifts 160-170 ppm relative to the total area of all peaks is derived from the specific carbonyl structure of (meth) acrylates relative to the total integrated intensity of all carbons as measured by 13C-NMR. It means the ratio of the integrated intensity.

  M1 / M2 means the ratio of a specific carbonyl structure of (meth) acrylate, but other methods may be used as long as equivalent results are obtained. In the 13C-NMR measurement, 0.1 g of a sample diluted with 2 ml of deuterated chloroform was used as a sample, the measurement temperature was room temperature, the resonance frequency was 100 MHz, and the measurement method was a decoupling method with a reverse gate. It was used.

From the above analysis,
(A) Sum of integral intensities of chemical shift 160-180 ppm (sum of integral intensities due to all carbons of hydrocarbons), and (b) Sum of integral intensities of chemical shifts 170-180 ppm (caused by specific carbonyl structures) Total integrated intensity)
(C) Total integrated intensity of chemical shifts 160-170 ppm (total integrated intensity due to specific carbonyl structure)
Were measured, and the ratio (%) of (b) when (a) was set to 100% was calculated as M1. Similarly, the ratio (%) of (c) when (a) was set to 100% was calculated and set as M2.

  The (co) polymer (A) in the present invention preferably contains a monomer (b) represented by the following general formula (3) as a constituent monomer from the viewpoint of friction reduction.

[R ⁴ is a hydrogen atom or a methyl group; —X ⁴ — is a group represented by —O— or —NH—; R ⁵ is a linear or branched alkyl group having ⁵ to 44 carbon atoms. ]

—X ⁴ — in the general formula (3) is a group represented by —O— or NH—, and among these, —O— is preferable from the viewpoint of friction reduction.

R ⁴ in the general formula (3) is a hydrogen atom or a methyl group, and among these, a methyl group is preferable from the viewpoint of the effect of improving the viscosity index.

R ⁵ in the general formula (3) is a linear or branched alkyl group having 5 to 44 carbon atoms. Specifically, pentyl group, hexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, Isododecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, 2-ethyldodecyl group, n-pentadecyl group, 2-methyltetradecyl group, n-hexadecyl group, isohexadecyl group, n-heptadecyl group, isoheptadecyl group Group, 2-ethylpentadecyl group, 2-octylnonyl group, 2- (3-methylhexyl) -7-methyl-nonyl group, n-octadecyl group, isooctadecyl group, 2-hexylundecyl group, 2-ethyl Heptadecyl, 1-hexyltridecyl, n-icosyl, 2-octylundecyl, iso Sil group, 1-undecyl dodecyl group, 1-octyl pentadecyl group, 2-decyl tridecyl group, n-tetricosyl group, 2-decyl tetradecyl group, 2-dodecyl pentadecyl group, 2-heptylukosyl group, 2-dodecyl hexa group Decyl group, n-triacontyl group, 2-tetradecyloctadecyl group, n-hexatriacontyl group, n-tetracontyl group, 2-ethyltetracontyl group and olefin [for example, propylene oligomer (2-14 mer), ethylene / A residue obtained by removing a hydroxyl group from an oxo alcohol obtained from a propylene oligomer (2 to 20 mer) and an isobutene oligomer (2 to 10 mer)].

R ⁵ is preferably a linear or branched alkyl group having 10 to 34 carbon atoms, more preferably an alkyl group having 12 to 32 carbon atoms, and particularly preferably an alkyl group having 16 to 32 carbon atoms. Most preferred are linear alkyl groups having 16 to 22 carbon atoms and branched alkyl groups having 18 to 32 carbon atoms.

  The polymer (A) in the present invention is a copolymer further comprising (meth) acrylic acid alkyl ester (c) whose alkyl group is a linear alkyl group having 1 to 4 carbon atoms as a constituent monomer. Also good.

Examples of (meth) acrylic acid alkyl ester (c) in which the alkyl group is a linear alkyl group having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. And n-butyl (meth) acrylate.
Among (c), preferred are (meth) acrylic acid esters having a linear alkyl group having 1 to 3 carbon atoms, and more preferred are methyl (meth) acrylate and ethyl (meth) acrylate, Particularly preferred is methyl (meth) acrylate.

The polymer (A) comprises a monomer (a) and a nitrogen atom-containing monomer (d) other than the monomer (b), a hydroxyl group-containing monomer (e), and a phosphorus atom-containing monomer (f). A copolymer having at least one selected from the group consisting of as constituent monomers may also be used.
As the nitrogen atom-containing monomer (d) used together with the monomer (a) [excluding the monomer (a) and the monomer (b)], the following monomers (d1) to (d4) ).

Amide group-containing monomer (d1):
(Meth) acrylamide, monoalkylamino (meth) acrylamide [nitrogen atom having one alkyl group having 1 to 4 carbon atoms bonded thereto; for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Isopropyl (meth) acrylamide and Nn- or isobutyl (meth) acrylamide, etc.], monoalkylaminoalkyl (meth) acrylamide [aminoalkyl group in which one alkyl group having 1 to 4 carbon atoms is bonded to the nitrogen atom (carbon number 2-6); for example N-methylaminoethyl (meth) acrylamide, N-ethylaminoethyl (meth) acrylamide, N-isopropylamino-n-butyl (meth) acrylamide and Nn- or isobutylamino- n-butyl (meth) acrylamide etc.], dialkyl Mino (meth) acrylamide [nitrogen atom having two alkyl groups having 1 to 4 carbon atoms bonded; for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (Meth) acrylamide and N, N-di-n-butyl (meth) acrylamide, etc.], dialkylaminoalkyl (meth) acrylamide [aminoalkyl group in which two alkyl groups having 1 to 4 carbon atoms are bonded to a nitrogen atom (carbon Having 2 to 6); for example, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and N, N-di -N-butylaminobutyl (meth) acrylamide etc.], N-vinylcarboxylic acid amide [ - vinyl formamide, N- vinyl acetamide, include those having a N- vinyl -n- or isopropionyl and N- vinyl-hydroxyacetamide etc.] amide groups only on the nitrogen atom and the like.

Nitro group-containing monomer (d2):
4-nitrostyrene etc. are mentioned.

Monomers containing primary to tertiary amino groups (d3):
Primary amino group-containing vinyl monomer {alkenylamine having 3 to 6 carbon atoms [(meth) allylamine, crotylamine, etc.], aminoalkyl (2 to 6 carbon atoms) (meth) acrylate [aminoethyl (meth) acrylate, etc.] }; Secondary amino group-containing vinyl monomer {monoalkylaminoalkyl (meth) acrylate [having an aminoalkyl group (2 to 6 carbon atoms) in which one alkyl group having 1 to 6 carbon atoms is bonded to a nitrogen atom] For example, t-butylaminoethyl (meth) acrylate and methylaminoethyl (meth) acrylate, etc.], C 6-12 dialkenylamine [di (meth) allylamine, etc.}}; tertiary amino group-containing vinyl monomer {Dialkylaminoalkyl (meth) acrylate [Aminoalkyl having two alkyl groups having 1 to 6 carbon atoms bonded to a nitrogen atom] Having a sulfur group (2 to 6 carbon atoms); for example, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, etc.], alicyclic (meth) acrylate having a nitrogen atom [morpholinoethyl (meth) acrylate, etc. ], Aromatic vinyl monomers [N, N-diphenylaminoethyl (meth) acrylamide, N, N-dimethylaminostyrene, 4-vinylpyridine, 2-vinylpyridine, N-vinylpyrrole, N-vinylpyrrolidone and N-vinylthiopyrrolidone etc.], and their hydrochlorides, sulfates, phosphates or lower alkyl (C 1-8) monocarboxylic acids (such as acetic acid and propionic acid) salts.

Nitrile group-containing monomer (d4):
Examples include (meth) acrylonitrile.

  Among the nitrogen atom-containing vinyl monomers (d), (d1) and (d3) are preferable, and N, N-diphenylaminoethyl (meth) acrylamide and dimethylaminoethyl (meth) acrylamide are more preferable. , Diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

Specific examples of the hydroxyl group-containing monomer (e) used in combination with the monomer (a) include the following.
Hydroxyl group-containing aromatic monomer (p-hydroxystyrene and the like), hydroxyalkyl (2 to 6 carbon atoms) (meth) acrylate [2-hydroxyethyl (meth) acrylate, and 2- or 3-hydroxypropyl (meth) acrylate Etc.], mono- or di-hydroxyalkyl (1 to 4 carbon atoms) substituted (meth) acrylamide [N, N-dihydroxymethyl (meth) acrylamide, N, N-dihydroxypropyl (meth) acrylamide, N, N-di -2-hydroxybutyl (meth) acrylamide etc.], vinyl alcohol, C3-C12 alkenol [(meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-octenol and 1-undecenol etc.], carbon number 4 to 12 alkene monools or alkene diols [ -Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol and the like], hydroxyalkyl (C1-6) alkenyl (C3-10) ether (2-hydroxyethyl) Propenyl ether, etc.), polyhydric (3-8 valent) alcohols (glycerin, pentaerythritol, sorbitol, sorbitan, diglycerin, saccharides, sucrose, etc.) alkenyl (3 to 10 carbon atoms) ether or (meth) acrylate [sucrose ( Meta) allyl ether and the like] and the like.

  Examples of the phosphorus atom-containing monomer (f) used in combination with the monomer (a) include the following monomers (f1) to (f2).

Phosphate group-containing monomer (f1):
(Meth) acryloyloxyalkyl (2 to 4 carbon atoms) phosphoric acid ester [(meth) acryloyloxyethyl phosphate and (meth) acryloyloxyisopropyl phosphate] and phosphoric acid alkenyl ester [vinyl phosphate, allyl phosphate, Propenyl phosphate, isopropenyl phosphate, butenyl phosphate, pentenyl phosphate, octenyl phosphate, decenyl phosphate, dodecenyl phosphate, etc.].

Phosphono group-containing monomer (f2):
(Meth) acryloyloxyalkyl (2 to 4 carbon atoms) phosphonic acid [(meth) acryloyloxyethylphosphonic acid etc.] and alkenyl (2 to 12 carbon atoms) phosphonic acid [vinyl phosphonic acid, allyl phosphonic acid and octenyl phosphonic acid Etc.].

  Of the phosphorus atom-containing monomers (f), (f1) is preferred, (meth) acryloyloxyalkyl (2 to 4 carbon atoms) phosphate is more preferred, and (meth) is particularly preferred. ) Acryloyloxyethyl phosphate.

  In addition to the monomers (a) to (f), the polymer (A) may contain the following monomers (g) to (n) as constituent monomers.

Alkoxyalkyl ether monomer (g);
Methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyheptyl (meth) acrylate, methoxyhexyl (meth) acrylate, methoxypentyl (meth) acrylate, methoxyoctyl (meth) acrylate, ethoxy Ethyl (meth) acrylate, ethoxypropyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyheptyl (meth) acrylate, ethoxyhexyl (meth) acrylate, ethoxypentyl (meth) acrylate, ethoxyoctyl (meth) acrylate, propoxymethyl ( (Meth) acrylate, propoxyethyl (meth) acrylate, propoxypropyl (meth) acrylate, propoxybutyl (meth) acrylate Relate, propoxyheptyl (meth) acrylate, propoxyhexyl (meth) acrylate, propoxypentyl (meth) acrylate, propoxyoctyl (meth) acrylate, butoxymethyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxypropyl (meth) acrylate , Butoxybutyl (meth) acrylate, butoxyheptyl (meth) acrylate, butoxyhexyl (meth) acrylate, butoxypentyl (meth) acrylate, butoxyoctyl (meth) acrylate, and the like.
Among the monomers (g), methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and butoxyethyl (meth) acrylate are preferable.

Aliphatic hydrocarbon monomer (h):
Alkenes having 2 to 20 carbon atoms (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.) and alkadienes having 4 to 12 carbon atoms (butadiene, isoprene, 1,4-pentadiene, 1 , 6-heptadiene and 1,7-octadiene).

Alicyclic hydrocarbon monomer (i):
Examples include cyclohexene, (di) cyclopentadiene, pinene, limonene, vinylcyclohexene, and ethylidenebicycloheptene.

Aromatic hydrocarbon monomer (j):
Styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 4-butylstyrene, 4-phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, indene, 4 -Crotylbenzene, 2-vinylnaphthalene and the like.

Vinyl esters, vinyl ethers, vinyl ketones (k):
Vinyl esters of saturated fatty acids having 2 to 12 carbon atoms (such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl octoate), alkyl, aryl or alkoxyalkyl vinyl ethers having 1 to 12 carbon atoms (methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether) Butyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, vinyl-2-methoxyethyl ether and vinyl-2-butoxyethyl ether) and alkyl or aryl vinyl ketones having 1 to 8 carbon atoms (methyl vinyl ketone, ethyl vinyl ketone and Phenyl vinyl ketone, etc.).

Epoxy group-containing monomer (l):
Examples thereof include glycidyl (meth) acrylate and glycidyl (meth) allyl ether.

Halogen element-containing monomer (m):
Examples thereof include vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride and halogenated styrene (dichlorostyrene and the like).

Unsaturated polycarboxylic acid ester (n):
Alkyl, cycloalkyl or aralkyl ester of unsaturated polycarboxylic acid [alkyl diester having 1 to 8 carbon atoms of unsaturated dicarboxylic acid (such as maleic acid, fumaric acid and itaconic acid) (dimethyl maleate, dimethyl fumarate, diethyl maleate) And dioctyl maleate)] and the like.

The proportion of the monomer (a) constituting the polymer (A) is preferably 2 to 90% by weight, more preferably 10 to 80% by weight based on the weight of (A) from the viewpoint of friction reduction. %, More preferably 15 to 70% by weight, particularly preferably 20 to 60% by weight, and most preferably 25 to 55% by weight.
The proportion of (b) constituting (A) is preferably 10 to 98% by weight, more preferably 20 to 90% by weight based on the weight of (A), from the viewpoints of friction reduction and base oil solubility. %, More preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight.
The proportion of (c) constituting (A) is preferably 0 to 50% by weight, more preferably 0 to 45% by weight, particularly preferably from the viewpoint of friction reduction, based on the weight of (A). 2 to 40% by weight.
The total content of (d) to (f) constituting (A) is preferably 0 to 20% by weight, more preferably 1 to 20% by weight based on the weight of (A), from the viewpoint of friction reduction. 15% by weight, particularly preferably 2 to 10% by weight.
The total content of (g) to (n) constituting (A) is preferably 0 to 10% by weight, more preferably 1 to 10% by weight based on the weight of (A) from the viewpoint of friction reduction. 7% by weight, particularly preferably 2 to 5% by weight.

The SP value of (A) is preferably 8.5 to 11.5 (cal / cm ³ ) ^1/2 , and more preferably 8.7 to from the viewpoint of the effect of improving the viscosity index and the low temperature viscosity of the lubricating oil composition. 11.0 ((cal / cm ³ ) ^1/2 , more preferably 8.9 to 10.5 (cal / cm ³ ) ^1/2 , particularly preferably 9.2 to 10.2 (cal / cm ³ ) ^1/2 .

In addition, the SP value of (A) in the case of a copolymer composed of two or more monomers is calculated by the above method for the SP values of all the monomers constituting (A), respectively. Is an arithmetic average value calculated based on the mole fraction of the constituent monomer units. The SP value of (A) can be adjusted to 8.5 to 11.5 (cal / cm ³ ) ^1/2 by appropriately adjusting the SP value and mole fraction of the monomer used.

The absolute value (ΔSP) of the difference between the SP value of the polymer (A) and the SP value of the base oil is preferably 0.5 to 3.2 (cal from the viewpoint of improving the viscosity index and solubility in the lubricating oil. / Cm ³ ) ^1/2 , more preferably 0.6 to 2.5 (cal / cm ³ ) ^1/2 , particularly preferably 0.6 to 2.1 (cal / cm ³ ) ^1/2 . Yes, most preferably 0.7 to 1.7 (cal / cm ³ ) ^1/2 .
If the absolute value of the difference is less than 0.5 (cal / cm ³ ) ^1/2 , the friction reducing effect is low, and if it exceeds 3.2 (cal / cm ³ ) ^1/2 , the solubility in the base oil decreases.

  Mw of (A) is preferably 5,000 to 2,000,000, more preferably 7,000 to 1,000,000, from the viewpoint of the effect of improving the viscosity index and the low temperature viscosity of the lubricating oil composition. Particularly preferably 10,000 to 600,000, most preferably 15,000 to 500,000.

(A) can be obtained by a known production method, and specifically includes a method obtained by solution polymerization of the above monomer in a solvent in the presence of a polymerization catalyst.
Examples of the solvent include toluene, xylene, alkylbenzene having 9 to 10 carbon atoms, methyl ethyl ketone, ethyl acetate, 2-propanol and mineral oil.
Polymerization catalysts include azo catalysts (azobisisobutyronitrile, azobisvaleronitrile, etc.), peroxide catalysts (benzoyl peroxide, cumyl peroxide, lauryl peroxide, etc.) and redox catalysts (benzoyl peroxide). And a mixture of a tertiary amine and the like. Furthermore, if necessary, a known chain transfer agent (such as an alkyl mercaptan having 2 to 20 carbon atoms) can also be used.
The polymerization temperature is preferably 25 to 140 ° C, more preferably 50 to 120 ° C. In addition to the above solution polymerization, (A) can be obtained by bulk polymerization, emulsion polymerization or suspension polymerization.
When (A) is a copolymer, the polymerization form may be either a random addition polymer or an alternating copolymer, and may be either a graft copolymer or a block copolymer.

  The lubricating oil composition of the present invention comprises the friction modifier of the present invention and a base oil. Base oils include mineral oils (solvent refined oils, paraffin oils, high viscosity index oils containing isoparaffins, high viscosity index oils obtained by hydrocracking isoparaffins, naphthenic oils, etc.), synthetic lubricating oils (hydrocarbon synthetic lubricating oils) (Poly-α-olefin-based synthetic lubricating oil, etc.) and ester-based synthetic lubricating oil, etc.] and mixtures thereof. Of these, preferred are mineral oils and ester-based synthetic lubricating oils, and more preferred are mineral oils.

(Measured by JIS-K2283) kinematic viscosity at 100 ° C. of the base oil is preferably from the viewpoint of the viscosity index improving effect is 1 to 15 mm ² / s, more preferably from 2 to 5 mm ² / s.
The viscosity index (measured according to JIS-K2283) of the base oil is preferably 90 or more, more preferably 100 or more, from the viewpoint of the effect of improving the viscosity index.

  The cloud point (measured according to JIS-K2269) of the base oil is preferably −5 ° C. or lower, more preferably −15 ° C. or lower. When the cloud point of the base oil is within this range, the low temperature viscosity of the lubricating oil composition is good.

  The content of the friction modifier in the lubricating oil composition of the present invention is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, based on the weight of the base oil. Preferably it is 0.1 to 10 weight%.

  The lubricating oil composition of the present invention includes gear oil (differential oil and industrial gear oil, etc.), MTF, transmission oil [ATF and belt-CVTF, etc.], traction oil (toroidal-CVTF, etc.), shock absorber oil, power steering It is suitably used for oil, hydraulic oil (such as construction machine hydraulic oil and industrial hydraulic oil) and engine oil. Of these, gear oil, MTF, transmission oil, traction oil and engine oil are preferable, and differential oil, MTF, ATF, belt-CVTF and engine oil are more preferable, and MTF and ATF are particularly preferable. , Belt-CVTF and engine oil.

The lubricating oil composition of the present invention may contain various additives. The following are mentioned as an additive.
(1) Viscosity index improver:
(C1-7) alkyl (meth) acrylate / (C8-40) linear or branched alkyl (meth) acrylate copolymer, dispersion monomer (amine monomer, etc.) / (C1-7) alkyl (meth) acrylate / (C8 -40) linear or branched alkyl (meth) acrylate copolymer, hydroxy group-containing monomer / (C1-7) alkyl (meth) acrylate / (C8-40) linear or branched alkyl (meth) acrylate copolymer, Comb polymer [(C1-7) alkyl (meth) acrylate / (C8-40) linear or branched alkyl (meth) acrylate / polyolefin macromonomer], ethylene / (C1-18) alkyl (meth) acrylate copolymer, Polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene / ma Ynoic acid ester copolymer, styrene / isoprene hydrogenated copolymers and the like;
(2) Detergent:
Basic, overbased or neutral metal salts [overbased or alkaline earth metal salts of sulfonates (such as petroleum sulfonates, alkylbenzene sulfonates and alkylnaphthalene sulfonates)], salicylates, phenates, naphthenates , Carbonates, phosphonates and mixtures thereof;
(3) Dispersant:
Succinimides (bis- or mono-polybutenyl succinimides), Mannich condensation products, borates and the like;
(4) Antioxidant:
Hindered phenols and aromatic secondary amines, etc .;
(5) Oiliness improver:
Long chain fatty acids and their esters (such as oleic acid and oleic acid esters), long chain amines and their amides (such as oleylamine and oleylamide), etc .;
(6) Friction and wear modifier:
Molybdenum and zinc compounds (such as molybdenum dithiophosphate, molybdenum dithiocarbamate and zinc dialkyldithiophosphate);
(7) Extreme pressure agent:
Sulfur compounds (mono or disulfides, sulfoxides and sulfur phosphide compounds), phosphide compounds and chlorinated compounds (chlorinated paraffins, etc.);
(8) Antifoaming agent:
Silicon oil, metal soap, fatty acid ester and phosphate compound, etc .;
(9) Demulsifier:
Quaternary ammonium salts (tetraalkylammonium salts, etc.), sulfated oils and phosphates (polyoxyethylene-containing nonionic surfactant phosphates, etc.);
(10) Corrosion inhibitor:
Nitrogen atom-containing compounds (benzotriazole and 1,3,4-thiodiazolyl-2,5-bisdialkyldithiocarbamate, etc.) and the like;
(11) Pour point effect agent:
Polyalkyl methacrylate, polyalkyl acrylate, polyalkyl styrene, polyvinyl acetate and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

<Production Example 1> [Production of monomer (a-1)]
In a reaction vessel equipped with a temperature controller, a vacuum stirring blade, a decompressor, a Dimroth condenser, a fractionation pipe, a distillate receiving flask, a nitrogen inlet and an outlet, 2-hydroxyethyl methacrylate (HEMA) 260.3 Parts by weight (2.0 mol parts), 1141.4 parts by weight of ε-caprolactone (10.0 mol parts), 3.7 parts by weight (0.03 mol parts) of hydroquinone monomethyl ether, butyl tris (2-ethylhexanoyloxy) ) 0.27 part by weight of tin was added, and the temperature was raised to 115 ° C. with stirring while passing air. Subsequently, reaction was performed at 115 degreeC for 8 hours, and distillate water was isolate | separated. Furthermore, it cooled to 25 degreeC and confirmed the esterification reaction product by 1H-NMR (yield 98 mol%).
(A-1) is a monomer represented by A in formula (1), A is a methacryloyl group, R ¹ is an ethylene group, p = 5, R ² = pentylene group, R ³ is a hydrogen atom, and SP value Is 10.8.

<Production Example 2> [Production of monomer (a-2)]
In a reaction vessel equipped with a temperature controller, a vacuum stirring blade, a decompressor, a Dimroth condenser, a fractionation tube, a distillate receiving flask, a nitrogen inlet and an outlet, 520.8 parts by weight of lauric acid, (a- 1) 711.0 parts by weight, 3.7 parts by weight of hydroquinone monomethyl ether (0.03 mol part), 300 parts by weight of toluene and 20.7 parts by weight of paratoluenesulfonic acid were added, and the temperature was raised to 115 ° C. with stirring. . Next, an esterification reaction was performed at 115 ° C. for 8 hours, and distillate water was separated. Furthermore, it cooled to 25 degreeC and confirmed the esterification reaction product by 1H-NMR (yield 98 mol%). 200 parts by weight of a 10% by weight sodium hydroxide aqueous solution was added and stirred to sufficiently neutralize paratoluenesulfonic acid. The supernatant was collected with a separatory funnel, heated to 120 ° C., and toluene was removed at the same temperature under reduced pressure (0.027 to 0.040 MPa) over 2 hours to obtain (a-2).
(A-2) is a monomer represented by A in the general formula (1), a methacryloyl group, R ¹ is an ethylene group, p = 5, R ² = pentylene group, and R ³ is a C12 lauryl group. The SP value is 9.7.

<Production Example 3> [Production of monomer (a-3)]
In a reaction vessel equipped with a temperature controller, a vacuum stirring blade, a decompressor, a Dimroth condenser, a fractionation pipe, a distillate receiving flask, a nitrogen inlet and an outlet, 2-hydroxyethyl acrylate (HEA) 232.2 Parts by weight (2.0 mol parts), ε-caprolactone 2282.8 parts by weight (20.0 mol parts), hydroquinone monomethyl ether 3.7 parts by weight (0.03 mol parts), butyl tris (2-ethylhexanoyloxy) ) 0.27 part by weight of tin was added, and the temperature was raised to 115 ° C. with stirring while passing air. Subsequently, reaction was performed at 115 degreeC for 8 hours, and distillate water was isolate | separated. Furthermore, it cooled to 25 degreeC and confirmed the esterification reaction product by 1H-NMR (yield 98 mol%).
(A-3) is a monomer in which A in the general formula (1) is an acryloyl group, R ¹ is an ethylene group, p = 10, R ² = pentylene group, R ³ is a hydrogen atom, and SP value Is 10.5.

<Examples 1-12, Comparative Examples 1-7>
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a nitrogen introduction tube, 185 parts by weight of ethyl acetate, 100 parts by weight of various monomer compounds listed in Tables 1 and 2, 2, 2′- Charge 0.5 parts by weight of azobis (2,4-dimethylvaleronitrile) and 0.2 parts by weight of 2,2′-azobis (2-methylbutyronitrile) and perform nitrogen substitution (gas phase oxygen concentration 100 ppm). Then, the temperature was raised to 76 ° C. with stirring in a sealed state, and a polymerization reaction was performed at the same temperature for 6 hours.
Mineral oil [SP value: 8.3 (cal / cm ³ ) ^1/2 , kinematic viscosity at 100 ° C .: 4.2 mm ² / s, viscosity index: 122] 43 parts by weight are added, and the temperature is raised to 120 to 130 ° C. Thereafter, unreacted monomers and ethyl acetate were removed over 2 hours at the same temperature under reduced pressure (0.027 to 0.040 MPa), and the copolymers (A-1) to (A-12) of the present invention were removed. ), Friction modifiers (R-1) to (R-12) of Examples 1 to 12 containing (H-1) to (H-7) for comparison, and Comparative Examples 1 to 7 Comparative samples (S-1) to (S-7) were obtained.

The various monomers described in Tables 1 and 2 are as described below.
(A-4): ε-caprolactone 1 mol adduct of HEMA (SP value 11.9)
(A-5): ε-caprolactone 20 mol adduct of HEMA (SP value 10.3)
(A-6): terminal butyl ester of ε-caprolactone 4-mol adduct of HEMA (SP value 9.9)
(A-7): ε-caprolactone 2-mol adduct of HEA (SP value 11.5)
(A-8): HEA ε-caprolactone 14 mol adduct (SP value 10.4)
(A-9): Terminal butyl ester of HEA ε-caprolactone 7 mol adduct (SP value 10.4)
(B-1): dodecyl methacrylate (b-2): dodecyl methacrylate-pentadecyl (b-3): n-hexadecyl methacrylate (b-4): n-octadecyl methacrylate (b-5): methacrylic acid 2-decyltetradecyl (b-6): 2-dodecylhexadecyl methacrylate (b-7): 2-tetradecyloctadecyl methacrylate (b-8): dodecyl acrylate (b-9): acrylic acid n -Octadecyl (c-1): Methyl methacrylate (c-2): Butyl methacrylate (d-1): N, N-dimethylaminoethyl methacrylate (e-1): 2-hydroxyethyl acrylate (e-2 ): 2-hydroxyethyl methacrylate (e-3): 2-hydroxyisobutyl methacrylate

<Examples 13-24, Comparative Examples 8-14>
The friction modifiers (R-1) to (R-12) obtained in Examples 1 to 12 and the comparative samples (S-1) to (S-7) obtained in Comparative Examples 1 to 7 are shown below. The base oil is added at 1% by weight with respect to the weight of the base oil (addition amount is in solids), and the blending ratio of the base oils 1 to 4 is adjusted so that the kinematic viscosity at 100 ° C. is 7.0 mm. ² / s to obtain lubricating oil compositions (V-1) to (V-12) and (W-1) to (W-7).

(1) Base Oil 1: kinematic viscosity ^{4.2mm 2 /s(100℃),19.6mm 2 / s (40} ℃), mineral oil viscosity index = 122, SP value 8.30 (cal / ^cm 3) ^1/2 .
(2) Base Oil 2: kinetic viscosity ^{6.4mm 2 /s(100℃),35.5mm 2 / s (40} ℃), mineral oil viscosity index = 132, SP value 8.30 (cal / ^cm 3) ^1/2 .
(3) Base Oil 3: kinetic viscosity ^{7.6mm 2 /s(100℃),47.0mm 2 / s (40} ℃), mineral oil viscosity index = 128, SP value 8.30 (cal / ^cm 3) ^1/2 .
(4) Base Oil 4: kinematic viscosity ^{2.2mm 2 /s(100℃),7.6mm 2 / s (40} ℃), mineral oil viscosity index = 105, SP value 8.30 (cal / ^cm 3) ^1/2 .

The friction evaluation of the lubricating oil compositions (V-1) to (V-12) and (W-1) to (W-7) was measured by the following method.
<Friction evaluation>
Equipment: PCS Instruments MTM-2
Disc: MTM polished disc (standard) (0.01 micron)
Ball: Drilled 3/4 AISI 52100 precision steel ball
Speed: 10 mm / s to 3,000 mm / s
Temperature: 80 ° C, 100 ° C, 135 ° C
Sliding / rolling ratio: 50%
Load: 30N
As a result of the friction evaluation, a Stribeck curve is obtained, and the friction coefficient at speeds of 10, 100, and 1,000 mm / s at each temperature is used as a measurement result.

  As is clear from the results of Tables 3 and 4, the lubricating oil compositions (Examples 13 to 24) containing the friction modifier of the present invention were compared with the lubricating oil compositions of Comparative Examples 8 to 14. High friction reduction effect.

<Examples 25 to 27 and Comparative Examples 15 and 16>
In a stainless steel container equipped with a stirrer, the number of parts described in Table 5 is set so that the HTHS viscosity at 150 ° C. of the lubricating oil composition obtained by the following composition is 2.60 ± 0.05 (mm ² / s). The general viscosity index improver 1 (polymethacrylate), the viscosity index improver 2 (olefin copolymer), and the friction modifier (R-5) of the present invention obtained in Example 5 were converted into solids. 1% by weight, 10 parts by weight of a commercially available performance additive, mineral oil [SP value: 8.3 (cal / cm ³ ) ^1/2 , kinematic viscosity at 100 ° C .: 4.2 mm ² / s, viscosity index : 122] to obtain lubricating oil compositions (Y1) to (Y3) of Examples 25 to 27 and Comparative Examples 15 and 16 (T1) and (T2).
Table 5 shows the friction evaluation of the lubricating oil compositions (Y1) to (Y3) and (T1) and (T2).
The above-mentioned commercially available performance additives include metal detergents (TBN 300 mg KOH / g calcium sulfonate), ashless dispersant (succinimide), antiwear agent (phosphoric acid), antioxidant (diphenylamine). , A metal deactivator (thiadiazole), and a sulfur-based additive (sulfurized ester).

As is apparent from the results in Table 5, the lubricating oil compositions (Examples 25 to 27) containing the friction modifier (R-5) of the present invention were lubricated with (R-5) not added. Compared to oil compositions (Comparative Examples 15 and 16), the friction reducing effect is high.

Lubricating oil compositions containing the friction modifier of the present invention include drive system lubricating oil (MTF, differential gear oil, ATF, belt-CVTF, etc.), hydraulic oil (mechanical hydraulic oil, power steering oil, and shock absorber). Oil), engine oil (gasoline, diesel, etc.) and traction oil.

Claims (14)

One or more monomers (a) selected from the group consisting of a monomer (a1) represented by the following general formula (1) and a monomer (a2) represented by the following general formula (2): A friction modifier containing a (co) polymer (A) as an essential constituent monomer , wherein the polymer (A) further constitutes a monomer (b) represented by the following general formula (3) A friction modifier that is a copolymer as a monomer .

[In the formulas (1) and (2), A ¹ is a monovalent radical polymerizable group, and A ² is a divalent radical polymerizable group. -X ¹ -, - ^{X 2} - and -X ³ - is a group represented by each independently -O- or -NH-, a plurality of the formula ^{(2) -X 1 -, -} X 2 - and -X 3 ^- may be the same or different. R ¹ is an alkylene group having 1 to 4 carbon atoms. R ² is each independently an alkylene group having 2 to 20 carbon atoms, and a plurality of R ¹ may be the same or different. R ³ is a hydrogen atom, an alkyl group having 1 to 44 carbon atoms, an acyl group having 2 to 45 carbon atoms, a phenyl group or a benzoyl group which may be substituted with an alkyl group having 1 to 44 carbon atoms. The two R ³ groups in) may be the same or different. p, q and r are each an integer of 1 to 100.
In Formula (3), R ⁴ is a hydrogen atom or a methyl group; —X ⁴ — is a group represented by —O— or —NH—; R ⁵ is a linear or branched alkyl group having ⁵ to 44 carbon atoms. . ] Friction modifier of claim 1 solubility parameter 9.0~12.5 (cal ^/ cm ³⁾ is ^1/2 of the monomer (a). The friction modifier according to claim 1 or 2, wherein R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The friction modifier according to any one of claims 1 to 3, wherein A ^{1 in the} general formula (1) is a (meth) acryloyl group. Formula (1) in ^-X 1 -, - ^{X 2} -, or -X ³ - friction modifier according to claim 1 is a group represented by -O-. The polymer (A) is a copolymer containing 2 to 90% by weight of (a) and 10 to 98% by weight of (b) based on the weight of (A) as a constituent monomer of (A). The friction modifier in any one of Claims 1-5 . The polymer (A) is a copolymer further comprising a (meth) acrylic acid alkyl ester (c) whose alkyl group is a linear alkyl group having 1 to 4 carbon atoms as a constituent monomer. 6. The friction modifier according to any one of 6 . The friction modifier according to any one of claims 1 to 7 , wherein the polymer (A) has a weight average molecular weight of 5,000 to 2,000,000. The solubility parameter of a polymer (A) is 8.5-11.5 (cal / cm < ³ >) < ^1/2 >, The friction modifier in any one of Claims 1-8 . The polymer (A) further comprises a nitrogen atom-containing monomer (d) [excluding the monomer (a) and the monomer (b)], a hydroxyl group-containing monomer other than the monomer (a) ( The friction modifier according to any one of claims 1 to 9 , which is a copolymer having at least one selected from the group consisting of e) and a phosphorus atom-containing monomer (f) as a constituent monomer. A lubricating oil composition comprising the friction modifier according to any one of claims 1 to 10 and a base oil. The lubricating oil composition according to claim 11 , wherein the absolute value of the difference between the solubility parameter of the polymer (A) and the solubility parameter of the base oil is 0.5 to 3.2. Further selected from the group consisting of viscosity index improvers, detergents, dispersants, antioxidants, oiliness improvers, friction and wear modifiers, extreme pressure agents, antifoaming agents, demulsifiers, corrosion inhibitors and pour point effect agents. claim 1 comprising one or more additives 1 or 1 2 to the lubricating oil composition. A 100 ° C. kinematic viscosity of 1 to 15 mm ² / s of the base oil, and lubricating oil composition according to any one of claims 1 1 to 1 3 base oil of a viscosity index of 90 or more.