JP2010077403A - Lubricating oil additive and lubricating oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-ash dispersant excellent in dispersibility of an insoluble deposit, sludge etc., generating in lubricating oils and small increases in viscosity of lubrication oil compositions. <P>SOLUTION: This lubricating oil additive comprises at least one selected from the group consisting of an oil-soluble polymer (L) represented by general formula (1), an oil-soluble polymer (M) represented by general formula (2) and an oil-soluble polymer (N) represented by general formula (3), and fulfills mathematical formula (1): (L'+M')/(L'+M'+N')≥0.80 wherein L' is the number of moles of the polymer (L), M' is that of the polymer (M) and N' is that of the polymer (N). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lubricating oil composition comprising a lubricating oil additive and a lubricating oil additive. More specifically, the present invention relates to a lubricating oil additive containing an oil-soluble polymer and a lubricating oil composition containing the same.

Lubricating oils for internal combustion engines (for example, gasoline engines, diesel engines and gas engines) and drive system lubricating oils (for example, gear oils, hydraulic oils, automatic transmission oils, continuously variable transmission oils and power steering oils for automobiles, etc.) If it is used for a long time, it will oxidize and deteriorate, and insoluble deposits such as sludge and suit will be generated in the lubricating oil. This insoluble deposit induces various problems such as contaminating and wearing the lubrication parts of the internal combustion engine and the drive train engine, and increasing the power loss. Therefore, in order to solve such problems, the lubricating oil is blended with additives such as an ashless dispersant that disperses the insoluble deposits in the lubricating oil. Examples of the ashless dispersant include succinimide-based dispersants. Compounds, succinic acid amides or boronated derivatives thereof (Patent Documents 1 to 3) and poly (meth) acrylate compounds (Patent Document 4) are disclosed. However, these ashless dispersants cannot maintain the dispersibility of insoluble deposits for a long period of time, and are therefore not sufficiently effective in suppressing the wear of lubricated parts of internal combustion engines and drive train engines, or increasing the power loss. It was.
Further, in recent years, further improvement in fuel economy and long life has been required for lubricating oil from the viewpoint of protecting the global environment. In particular, in the case of engine oil, insoluble deposits are dispersed in the lubricating oil. There is a need for improved performance of ashless dispersants. Therefore, as means for improving the performance of the ashless dispersant, increasing the amount of the ashless dispersant added, increasing the molecular weight of the ashless dispersant, etc. have been studied. Since it rises, there exists a problem that fuel-saving property falls.

Japanese Patent Application Laid-Open No. 07-251056 JP 09-176673 A JP 2005-162968 A JP 2002-145961 A

  The present invention has been made in view of the above problems, and an object of the present invention is to improve the dispersibility of insoluble deposits generated in lubricating oil such as sludge and to reduce the viscosity increase of the lubricating oil composition. It is to provide a powder.

式中、Ａは５００〜５，０００の数平均分子量を有する炭化水素系重合体（Ａ）の残基；Ｘは第一級アミノ基を１〜４個有する炭素数２〜２０の炭化水素基（Ｘ１）、第一級アミノ基を１又は２個及び第ニ級アミノ基を１〜１０個有する炭素数２〜２０の基（Ｘ２）、第一級アミノ基を１又は２個及び水酸基を１〜３個有する炭素数２〜２０の炭化水素基（Ｘ３）、及び第一級アミノ基を１又は２個及びチオール基を１〜３個有する炭素数２〜２０の炭化水素基（Ｘ４）からなる群から選ばれる少なくとも１種である。

式中、Ａ及びＸは一般式（１）におけるＡ及びＸと同様の基；Ｙは−Ｏ−又は−ＮＲ−で表される基であり、Ｒは水素原子、炭素数１〜１２のアルキル基、第一級アミノ基を１〜４個有する炭素数２〜２０の炭化水素基（Ｒ１）、第一級アミノ基を１又は２個及び第ニ級アミノ基を１〜１０個有する炭素数２〜２０の基（Ｒ２）、第一級アミノ基を１又は２個及び水酸基を１〜３個有する炭素数２〜２０の炭化水素基（Ｒ３）、及び第一級アミノ基を１又は２個及びチオール基を１〜３個有する炭素数２〜２０の炭化水素基（Ｒ４）からなる群から選ばれる少なくとも１種である。

式中、Ａ及びＸは一般式（１）におけるＡ及びＸと同様の基；Ｙは一般式（２）におけるＹと同様の基；Ｚは、第一級アミノ基を０〜４個有する炭素数２〜２０の炭化水素基（Ｚ１）、第一級アミノ基を０〜２個及び第ニ級アミノ基を１〜１０個有する炭素数２〜２０の炭化水素基（Ｚ２）、第一級アミノ基を０〜２個及び水酸基を１〜３個有する炭素数２〜２０の炭化水素基（Ｚ３）、及び第一級アミノ基を０〜２個及びチオール基を１〜３個有する炭素数２〜２０の炭化水素基（Ｚ４）からなる群から選ばれる少なくとも１種；ｍ及びｎはそれぞれ独立して０〜４の整数であり、２≦ｍ＋ｎ≦４の関係を満たす。 As a result of intensive studies by the inventor in order to solve the above-mentioned problems, the inventors have found that a polymer having a specific chemical structure exhibits an excellent effect as an ashless dispersant, and reached the present invention. That is, the present invention is an oil-soluble polymer (L) represented by the general formula (1), an oil-soluble polymer (M) represented by the general formula (2), and an oil represented by the general formula (3). A lubricating oil additive comprising at least one selected from the group consisting of soluble polymers (N), wherein the lubricating oil additive satisfies the following mathematical formula (1); And a lubricating oil composition comprising a base oil; and an alkenyl succinic anhydride (B) obtained by an ene reaction between a polyolefin (A1) having a vinylidene group and a number average molecular weight of 500 to 5,000 and maleic anhydride ) Is amidated, esterified or imidated with a ketimine compound (D) obtained by ketiminizing part or all of the primary amino group of the compound (C) having 1 to 4 primary amino groups. After obtaining ketimine compound (D1), ( A; 1) A method of manufacturing a lubricating oil additive, characterized in that it is obtained by hydrolyzing.
(L ′ + M ′) / (L ′ + M ′ + N ′) ≧ 0.80 (1)
In the formula, L ′ represents the number of moles of the oil-soluble polymer (L); M ′ represents the number of moles of the oil-soluble polymer (M); N ′ represents the number of moles of the oil-soluble polymer (N).

In the formula, A is a residue of a hydrocarbon polymer (A) having a number average molecular weight of 500 to 5,000; X is a hydrocarbon group having 2 to 20 carbon atoms having 1 to 4 primary amino groups. (X1), a group having 2 to 20 carbon atoms having 1 or 2 primary amino groups and 1 to 10 primary amino groups (X2), 1 or 2 primary amino groups and a hydroxyl group 1 to 2 hydrocarbon groups having 1 to 3 carbon atoms (X3) and 1 or 2 primary amino groups and 1 to 3 hydrocarbon groups having 1 to 3 carbon atoms (X4) Is at least one selected from the group consisting of

In the formula, A and X are the same groups as A and X in the general formula (1); Y is a group represented by —O— or —NR—, R is a hydrogen atom, and an alkyl having 1 to 12 carbon atoms. Group, 1 to 4 carbon atoms having 1 to 4 primary amino groups (R1), 1 or 2 primary amino groups, and 1 to 10 carbon atoms having secondary amino groups 2 to 20 groups (R2), 1 or 2 primary amino groups and 1 to 2 hydrocarbon groups (R3) having 1 to 3 hydroxyl groups, and 1 or 2 primary amino groups It is at least 1 sort (s) chosen from the group which consists of a C2-C20 hydrocarbon group (R4) which has 1-3 pieces and a thiol group.

In the formula, A and X are the same groups as A and X in the general formula (1); Y is the same group as Y in the general formula (2); Z is a carbon having 0 to 4 primary amino groups. A hydrocarbon group having 2 to 20 carbon atoms (Z1), 0 to 2 primary amino groups and 1 to 10 secondary amino groups having 2 to 20 carbon atoms (Z2), primary Carbon number 2 to 20 hydrocarbon group (Z3) having 0 to 2 amino groups and 1 to 3 hydroxyl groups, and carbon number having 0 to 2 primary amino groups and 1 to 3 thiol groups At least one selected from the group consisting of 2 to 20 hydrocarbon groups (Z4); m and n are each independently an integer of 0 to 4 and satisfy the relationship of 2 ≦ m + n ≦ 4.

  The lubricating oil composition of the present invention and the lubricating oil composition containing the lubricating oil additive are excellent in dispersibility of insoluble deposits such as sludge generated in the lubricating oil. Since the lubrication site can be kept clean and wear can be suppressed, the effect of suppressing an increase in power loss is excellent. Further, since the dispersibility of the insoluble deposit can be sufficiently expressed only by adding a small amount to the lubricant, the viscosity of the lubricant composition is not increased, and the fuel efficiency of the automobile can be improved.

  Examples of the hydrocarbon polymer (A) having a number average molecular weight (hereinafter abbreviated as Mn) in the general formula (1) of 500 to 5,000 include unsaturated hydrocarbon polymers. Unsaturated hydrocarbons include: (1) aliphatic unsaturated hydrocarbons [olefins having 2 to 36 carbon atoms (for example, ethylene, propylene, butene, isobutene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, triacenene and hexacosene) Triacene, etc.), alkadienes having 2 to 36 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.)], (2) alicyclic unsaturated hydrocarbons [ For example, cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene and ethylidenebicycloheptene, etc.], (3) aromatic group-containing unsaturated hydrocarbon (for example, styrene, α-methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, ethylstyrene, isop Pirusuchiren, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, vinyl naphthalene, divinyl benzene, divinyl toluene, divinyl xylene and trivinyl benzene), and the like. Of the unsaturated hydrocarbons, aliphatic unsaturated hydrocarbons are preferable from the viewpoint of solubility in the lubricating oil composition, and propylene, butene, isobutylene, butadiene, and isoprene are more preferable. The hydrocarbon polymer (A) may be a polymer obtained from only one kind of the unsaturated hydrocarbon or a copolymer obtained from two or more kinds. In the case of a copolymer, it may be a block polymer or a random polymer.

  The hydrocarbon-based polymer (A) may have a linear structure or a branched structure, but a branched structure is preferable from the viewpoint of solubility in the lubricating oil composition and lowering the viscosity of the lubricating oil composition.

  Specific examples of the hydrocarbon polymer (A) include polypropylene, polyisobutene, polybutadiene, ethylene-propylene copolymer, ethylene-butadiene copolymer, ethylene-cyclohexene copolymer, propylene-benzylstyrene copolymer, and styrene. -Vinyl naphthalene copolymer etc. are mentioned. Of these, polyisobutene, polybutadiene, polyisoprene, and an ethylene-propylene copolymer are preferable from the viewpoint of solubility in the lubricating oil composition and low viscosity of the lubricating oil composition, and ethylene is more preferable. -Propylene copolymer and polyisobutene, particularly preferred is polyisobutene.

The Mn of the hydrocarbon-based polymer (A) in the present invention is 500 to 5,000, and preferably 800 to 4,000 from the viewpoint of dispersibility of insoluble deposits and low viscosity of the lubricating oil composition. More preferred is 1,000 to 2,500. If the Mn of the hydrocarbon polymer (A) is less than 500, the dispersibility of the insoluble deposit is poor, and if it exceeds 5,000, the viscosity of the lubricating oil composition is undesirably high. The Mn of the hydrocarbon polymer (A) can be measured by gel permeation chromatography using polystyrene as a standard substance under the following conditions.
Apparatus: HLC-802A manufactured by Tosoh Corporation
Column: TSK gel GMH6 2 Measurement temperature: 40 ° C
Sample solution: 0.5 wt% tetrahydrofuran solution solution injection amount: 200 μl
Detector: Refractive index detector Standard material: Polystyrene

  The hydrocarbon polymer (A) preferably has a specific solubility parameter from the viewpoint of solubility in a lubricating oil. The range of the solubility parameter is preferably 7.0 to 9.0, and more preferably 7.1 to 8.5. In addition, the solubility parameter in this invention is Fedors method [Polym. Eng. Sci. 14 (2) 152, 1974].

  The residue of the hydrocarbon polymer (A) in the present invention means that the double bond at the terminal of the hydrocarbon polymer (A) formed by the ene reaction described below is rearranged to the allylic position, and the terminal This is a residue obtained by removing one hydrogen atom.

  X in the general formula (1) is a hydrocarbon group having 2 to 20 carbon atoms (X1) having 1 to 4 primary amino groups, 1 or 2 primary amino groups, and a secondary amino group. A group having 2 to 20 carbon atoms (X2) having 1 to 10 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms having 1 or 2 primary amino groups and 1 to 3 hydroxyl groups (X3), and a first group It is at least one selected from the group consisting of hydrocarbon groups (X4) having 2 to 20 carbon atoms having 1 or 2 primary amino groups and 1 to 3 thiol groups. Of these, (X1) and (X2) are preferable from the viewpoint of dispersibility of the insoluble deposit, and (X2) is more preferable.

  Examples of the hydrocarbon group having 2 to 20 carbon atoms having 1 to 4 primary amino groups (X1) include 2-aminoethyl group, 3-aminopropyl group, 1,2-diaminoethyl group, 1,8- Diamino n-octyl group, 1,10-diamino n-decyl group, 1,12-diamino n-dodecyl group, 2,3-diaminotoluyl group, 2,4-diaminotoluyl group, 1,2-diaminonaphthyl group, 4,4'-diaminodiphenyl group, 1,2,3-tri (2-aminoethyl) propyl group, 2,4,6-triaminopyrimidyl group and 2,4,5,6-tetraaminopyrim Examples thereof include a gill group.

  As the group having 2 to 20 carbon atoms (X2) having 1 or 2 primary amino groups and 1 to 10 secondary amino groups, a residue obtained by removing one primary amino group from diethylenetriamine, Residue obtained by removing one primary amino group from triethylenetetramine, residue obtained by removing one primary amino group from tetraethylenepentamine, and residue obtained by removing one primary amino group from pentaethylenehexamine A residue obtained by removing one primary amino group from hexaethyleneheptamine, a residue obtained by removing one primary amino group from undecaethylene dodecamine, and 3- (2-aminoethylamino) propylamine Examples thereof include a residue obtained by removing one primary amino group and a residue obtained by removing one primary amino group from 3,3′-diaminodipropylamine.

  Examples of the hydrocarbon group having 2 to 20 carbon atoms having 1 or 2 primary amino groups and 1 to 3 hydroxyl groups (X3) include 2-amino-1-hydroxyethyl group and 2- (2-aminoethyl group). Amino) -1-hydroxyethyl group, 2- (2-aminoethoxy) -1-hydroxyethyl group, 1-amino-2-hydroxy-n-butyl group, 1-amino-3-hydroxyphenyl group, 2-amino -1-hydroxy n-propyl group, 5-amino-1-hydroxy n-pentyl group, 1-amino-2-hydroxy-4-methyl n-pentyl group and 1,3-diamino-2-hydroxy n-propyl group Etc.

  Examples of the hydrocarbon group having 2 to 20 carbon atoms having 1 or 2 primary amino groups and 1 to 3 thiol groups (X4) include 2-amino-1-mercaptoethyl group and 2- (2-amino group). Ethylamino) -1-mercaptoethyl group, 2- (2-aminoethoxy) -1-mercaptoethyl group, 1-amino-2-mercapto-n-butyl group, 1-amino-3-mercaptophenyl group, 2- Amino-1-mercapto n-propyl group, 5-amino-1-mercapto n-pentyl group, 1-amino-2-mercapto-4-methyl n-pentyl group and 1,3-diamino-2-mercapto n-propyl Groups and the like.

  A and X in the general formula (2) are the same groups as A and X in the general formula (1), and preferred ranges thereof are also the same. Y is a group represented by —O— or —NR—, and R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a hydrocarbon having 2 to 20 carbon atoms having 1 to 4 primary amino groups. Group (R1), 1 or 2 primary amino groups and 1 to 10 secondary amino groups (R2) having 2 to 20 carbon atoms, 1 or 2 primary amino groups and hydroxyl group 1 to 2 hydrocarbon groups (R3) having 1 to 3 carbon atoms, and 1 to 2 carbon atoms and 1 to 2 hydrocarbon groups having 1 to 3 thiol groups (R4). At least one selected from the group consisting of: Of these, (R1) and (R2) are preferable from the viewpoint of dispersibility of the insoluble deposit, and (R2) is more preferable.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n -Heptyl group, isoheptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group and the like. Of these, alkyl groups having 2 to 4 carbon atoms are preferable from the viewpoint of dispersibility of insoluble deposits.

  As a C2-C20 hydrocarbon group (X1) having 1 to 4 primary amino groups, a 2-aminoethyl group, an 8-amino n-octyl group, an 18-aminooctadecyl group, 1,2- Diaminoethyl group, 1,8-diamino n-octyl group, 1,10-diamino n-decyl group, 1,12-diamino n-dodecyl group, 2,3-diaminotoluyl group, 2,4-diaminotoluyl group, 1,2-diaminonaphthyl group, 4,4′-diaminodiphenyl group, 1,2,3-tri (2-aminoethyl) propyl group, 2,4,6-triaminopyrimidyl group and 2,4,4 Examples include a 5,6-tetraaminopyrimidyl group.

  Examples of the group having 2 to 20 carbon atoms (R2) having 1 or 2 primary amino groups and 1 to 10 secondary amino groups include the same groups as the above (X2).

  Examples of the hydrocarbon group having 2 to 20 carbon atoms (R3) having 1 or 2 primary amino groups and 1 to 3 hydroxyl groups include the same groups as the above (X3).

  Examples of the hydrocarbon group having 2 to 20 carbon atoms (R4) having 1 or 2 primary amino groups and 1 to 3 thiol groups include the same groups as the above (X4).

  A and X in the general formula (3) are the same groups as A and X in the general formula (1), Y is the same group as Y in the general formula (2), and the preferred range is also the same.

  Z in the general formula (3) is a hydrocarbon group having 2 to 20 carbon atoms (Z1) having 0 to 4 primary amino groups, 0 to 2 primary amino groups, and a secondary amino group. A hydrocarbon group having 4 to 20 carbon atoms (Z2) having 1 to 10 carbon atoms, a hydrocarbon group having 2 to 20 carbon atoms having 1 to 2 primary amino groups and 1 to 3 hydroxyl groups (Z3), and It is at least one selected from the group consisting of C2-C20 hydrocarbon groups (Z4) having 0 to 2 primary amino groups and 1 to 3 thiol groups. Of these, (Z1) and (Z2) are preferable from the viewpoint of dispersibility of the insoluble deposit, and (Z1) is more preferable.

  Examples of the hydrocarbon group having 2 to 4 primary amino groups and having 2 to 20 carbon atoms (Z1) include ethylene, propylene, butene, hexene, 2-aminoethylene group, 1,2-diaminoethylene group, 1, 8-diamino n-octylene group, 1,10-diamino n-decylene group, 1,12-diamino n-dodecylene group, 2,3-diaminotoluylene group, 2,4-diaminotoluylene group, 1,2- Diaminonaphthylene group, 4,4′-diaminodiphenylene group, 1,2,3-tri (2-aminoethyl) propylene group, 2,4,6-triaminopyrimidylene group and 2,4,5, Examples include 6-tetraaminopyrimidylene group.

  The C2-C20 hydrocarbon group (Z2) having 0 to 2 primary amino groups and 1 to 10 secondary amino groups is a residue obtained by removing two primary amino groups from diethylenetriamine. Group, residue obtained by removing two primary amino groups from triethylenetetramine, residue obtained by removing two primary amino groups from tetraethylenepentamine, and two primary amino groups removed from pentaethylenehexamine A residue obtained by removing two primary amino groups from hexaethyleneheptamine, a residue obtained by removing two primary amino groups from undecaethylene dodecamine, and 3,3′-diaminodipropylamine Examples thereof include a residue obtained by removing two primary amino groups.

  As a C2-C20 hydrocarbon group (Z3) having 0 to 2 primary amino groups and 1 to 3 hydroxyl groups, a 2-hydroxypropylene group, a 2-amino-1-hydroxyethylene group, 2 -(2-aminoethylamino) -1-hydroxyethylene group, 2- (2-aminoethoxy) -1-hydroxyethylene group, 1-amino-2-hydroxy-n-butylene group, 1-amino-3-hydroxy Phenylene group, 2-amino-1-hydroxy n-propylene group, 5-amino-1-hydroxy n-pentylene group, 1-amino-2-hydroxy-4-methyl-n-pentylene group and 1,3-diamino- Examples include 2-hydroxy n-propylene group.

  Examples of the hydrocarbon group having 2 to 20 carbon atoms having 0 to 2 primary amino groups and 1 to 3 thiol groups (Z4) include 2-mercaptoethylene group, 3-mercaptopropyl group, 2-amino- 1-mercaptoethylene group, 2- (2-aminoethylamino) -1-mercaptoethylene group, 2- (2-aminoethoxy) -1-mercaptoethylene group, 1-amino-2-mercapto-n-butylene group, 1-amino-3-mercaptophenylene group, 2-amino-1-mercapto n-propylene group, 5-amino-1-mercapto n-pentylene group, 1-amino-2-mercapto-4-methyl-n-pentylene group And 1,3-diamino-2-mercapto n-propylene group and the like.

  M and n in the general formula (3) are each independently an integer of 0 to 4, and satisfy the relationship of 2 ≦ m + n ≦ 4. From the viewpoint of dispersibility of the insoluble deposit, m and n are each independently an integer of 0 to 2, and satisfy the relational expression 2 ≦ m + n ≦ 3.

The lubricating oil additive of the present invention is characterized by satisfying the mathematical formula (1). From the viewpoint of suppressing the increase in the viscosity of the lubricating oil, the lubricating oil additive preferably satisfies the mathematical formula (2), and more preferably the mathematical formula ( It satisfies 3).
(L ′ + M ′) / (L ′ + M ′ + N ′) ≧ 0.80 (1)
(L ′ + M ′) / (L ′ + M ′ + N ′) ≧ 0.85 (2)
(L ′ + M ′) / (L ′ + M ′ + N ′) ≧ 0.90 (3)
In the formula, L ′ represents the number of moles of the polymer (L); M ′ represents the number of moles of the polymer (M); N ′ represents the number of moles of the polymer (N). The L ′, M ′, and N ′ can be measured by gel permeation chromatography, and the same measurement conditions as those for measuring Mn of the hydrocarbon polymer (A) can be used.

  The oil-soluble polymers (L), (M) and (N) in the present invention are obtained by an ene reaction between a polyolefin (A1) having a vinylidene group and a Mn of 500 to 5,000 and maleic anhydride. The obtained alkenyl succinic anhydride (B) is a ketimine product (D) obtained by ketiminizing a part or all of the primary amino group of the compound (C) having 2 to 4 primary amino groups. A method of hydrolyzing (D1) after amidation, esterification or imidization to obtain a ketimine product (D1) is mentioned.

  Examples of the polyolefin (A1) having a vinylidene group and Mn of 500 to 5,000 include a polymer obtained by polymerizing the unsaturated hydrocarbon by the method described in JP-A-2006-232672, Specific examples include polypropylene, polyisobutene, polybutadiene, ethylene-propylene copolymer, ethylene-butadiene copolymer, ethylene-cyclohexene copolymer, propylene-benzylstyrene copolymer, and styrene-vinylnaphthalene copolymer. . Moreover, as (A1), a commercial item can also be used, for example, polyisobutene {"GlossopalV500" (made by BASF) and "Nissan polybutene 015N" [made by NOF Corporation] etc.] etc. are mentioned.

  Examples of the compound (C) having 2 to 4 primary amino groups include 2 to 4 amine compounds (C1) having 2 to 4 primary amino groups and 2 to 4 primary amino groups. C2-20 amine compound (C2) having 1-10 secondary and secondary amino groups, C2-20 amine having 2-4 primary amino groups and 1-3 hydroxyl groups Examples include compound (C3) and an amine compound (C4) having 2 to 4 primary amino groups and 1 to 3 thiol groups and having 1 to 3 carbon atoms. Among these, (C2) is preferable from the viewpoint of dispersibility of insoluble deposits.

  Examples of the C2-C20 amine compound (C1) having 2 to 4 primary amino groups include 1,2-diaminoethane, 1,8-diamino n-octane, 1,10-diamino n-decane, 1,12-diamino n-dodecane, 2,3-diaminotoluene, 2,4-diaminotoluene, 1,2-diaminonaphthalene, 4,4′-diaminodiphenyl, 1,2,3-tri (2-aminoethyl) ) Propylene, 2,4,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine and the like.

Examples of the C2-C20 amine compound (C2) having 2 to 4 primary amino groups and 1 to 10 secondary amino groups include compounds represented by the general formula (4).
^{_{H 2 N- (R 1 -NH)}} n -R 2 -NH 2 (4)
In the formula, R ¹ and R ² are each independently an alkylene group having 1 to 8 carbon atoms, and n is a number of 1 to 10.
Examples of the alkylene group having 1 to 8 carbon atoms include methylene group, ethylene group, 1,2- or 1,3-propylene group, 1,2-, 1,3-, 2,3- or 1,4-butylene group. 1,2-, 1,3-, 1,5-pentylene group, 2-methyl-1,2-butylene group, 2-methyl-1,3-butylene group, 3-methyl-1,3-butylene group 1,2-, 1,4- or 1,6-hexylene group, 2-methyl-1,5-pentylene group, 2,3-dimethyl-1,4-butylene group, 1,2-, 1, Examples thereof include linear or branched alkylene groups such as 6- or 1,8-octylene group, 2-ethyl-1,6-hexylene group and 2,4-dimethyl-1,6-hexylene group. Of these, preferred are alkylene groups having 2 and 3 carbon atoms.
n is a number from 1 to 10, preferably 2 to 4.

  Examples of the C2-C20 amino compound (C3) having 2 to 4 primary amino groups and 1 to 3 hydroxyl groups include 1,3-diamino-2-hydroxy n-propane and the like.

  Examples of the C2-C20 amino compound (C4) having 2 to 4 primary amino groups and 1 to 3 thiol groups include 1,3-diamino-2-mercapto-n-propane.

  The ene reaction can be carried out under ordinary reaction conditions. For example, polyolefin (A1) having a vinylidene group Mn of 500 to 5,000 and maleic anhydride are charged into a pressure-resistant reaction vessel, and the reaction temperature is 200 with stirring. Examples include a method in which an ene reaction is performed at ~ 250 ° C, a pressure of 0.1 to 1.2 MPa, and a reaction time of 1 to 50 hours. The charged molar ratio of (A1) to maleic anhydride is preferably 1: 1 to 1: 1.2 from the viewpoint of the reactivity of the ene reaction, and after the completion of the ene reaction, unreacted maleic anhydride is distilled under reduced pressure. It can be removed by leaving.

The amidation, esterification or imidation can be carried out under ordinary reaction conditions. For example, an alkenyl succinic anhydride (B) obtained by an ene reaction and a compound having 2 to 4 primary amino groups ( A ketimine product (D) obtained by ketiminizing part or all of the primary amino group of C) is charged into a reaction vessel, reaction temperature 100 to 250 ° C., pressure −0.1 to 1.2 MPa, reaction time 1 A method of carrying out stirring while allowing water generated by amidation, esterification or imidization (hereinafter abbreviated as generated water) to be removed from the reaction system under stirring for ˜50 hours. The charged molar ratio [(B) / (D)] of (B) and (D) is preferably 0.5 to 1.0 in the case of amidation and esterification, and preferably in the case of imidization. 0.8-1.0. In the case of esterification, it is preferable to use 0.05 to 0.5% by weight of catalyst based on the weight of (B) in order to promote the reaction. Examples of the catalyst include inorganic acids (for example, sulfuric acid and hydrochloric acid), organic sulfonic acids (for example, methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and the like) and organic metal compounds (for example, dibutyltin oxide, tetraisopropoxy). Titanate, bistriethanolamine titanate, potassium oxalate titanate, etc.). When a catalyst is used, the catalyst can be neutralized as necessary after completion of the esterification reaction and treated with an adsorbent to remove and purify the catalyst. Examples of the method for gradually removing the generated water out of the reaction system include the following methods.
(1) Using an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, etc.), the organic solvent and the generated water are azeotroped under reflux, and only the generated water is gradually removed from the reaction system. Method (2) A method in which a carrier gas (for example, air, nitrogen, helium, argon and carbon dioxide) is blown into the reaction system, and the produced water is gradually removed from the reaction system together with the carrier gas. (3) The pressure in the reaction system is reduced. In the case where an organic solvent is used in the method (1), the organic solvent can be gradually removed by reducing the pressure in the reaction system after completion of the ketimination reaction. .

  When the alkenyl succinic anhydride (B) and the compound (C) having 2 to 4 primary amino groups are reacted directly, there is no selectivity of the reaction between the primary amino groups. [(L ′ + M ′) / (L ′ + M ′ + N ′)] is about 0.6, which does not satisfy Formula (1). In addition, since the reaction product is a polymer compound, it is difficult to purify the product after the reaction. Therefore, in order to obtain the lubricating oil additive of the present invention satisfying the formula (1) using (C), at least one of the primary amino groups possessed by (C) is previously protected with a ketimine group or the like. It is necessary to restore the primary amino group after the reaction without participating in the reaction of (B) and (C).

式中、Ｒ³及びＲ⁴はそれぞれ独立して炭素数１〜８のアルキル基（例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、イソブチル基、ｔ−ブチル基、イソオクチル基、２−エチルヘキシル基及び１−フェニルエチル基等）である。 The ketimine product (D) obtained by ketiminizing part or all of the primary amino group of the compound (C) having 1 to 4 primary amino groups is the primary amino group of (C). It is a compound having a ketimine group obtained by a dehydration reaction (ketimination reaction) between a group and a ketone having 3 to 16 carbon atoms. The ketimine group is a group represented by the general formula (5).

In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, t-butyl group, isooctyl group, 2- An ethylhexyl group and a 1-phenylethyl group).

  The ketimination reaction can be carried out under normal reaction conditions. For example, the (C) and a ketone having 3 to 16 carbon atoms are charged into a pressure-resistant reaction vessel, and the reaction temperature is 100 to 140 ° C. and the pressure is −0.1 to 1. A method of ketiminating while gradually removing the water produced by the ketimination reaction with stirring at 2 MPa and a reaction time of 1 to 50 hours. Moreover, when ketiminizing all the primary amino groups which said (C) has, the number of all the primary amino groups x (1-2 mol) of C3-C16 ketone is charged. preferable. When a part of the primary amino group of (C) is ketiminized, the number of primary amino groups to be ketiminized among the primary amino groups × (1 to 2 mol) of 3 to 16 carbon atoms It is preferable to charge the ketone. After completion of the ene reaction, unreacted ketone having 3 to 16 carbon atoms can be removed by distillation under reduced pressure. Examples of the method of gradually removing the generated water out of the reaction system include the same methods as the amidation, esterification or imidation.

  The method of hydrolyzing (D1) after obtaining the ketimine product (D1) by amidation, esterification or imidation with the ketimine product (D) can be carried out under normal reaction conditions, for example (D1) And water are charged into a pressure-resistant reaction vessel, the reaction temperature is 50 to 150 ° C., the pressure is −0.1 to 0.5 MPa, and the reaction time is 1 to 20 hours. Is removed by distillation under reduced pressure. The amount of water used for the hydrolysis is preferably 2 to 500% by weight based on the total weight of (D1).

  The lubricating oil additive of the present invention can contain a diluent as necessary from the viewpoint of being easily dissolved in the base oil.

  Diluents include aliphatic solvents [aliphatic hydrocarbons having 6 to 12 carbon atoms (eg, hexane, heptane, cyclohexane, octane, decalin, kerosene, etc.)], aromatic solvents {aromatic solvents having 6 to 16 carbon atoms [ For example, toluene, xylene, ethylbenzene, aromatic mixed solvent having 9 carbon atoms (a mixture of trimethylbenzene and ethyltoluene, etc. and aromatic mixed solvent having 10 or 11 carbon atoms, etc.)}, mineral oil [for example, solvent refined oil, paraffin oil , Isoparaffin-containing high viscosity index oil, hydrocracking high viscosity index oil and naphthenic oil, etc.] and synthetic lubricating oils (hydrocarbon synthetic lubricating oil (poly α-olefin synthetic lubricating oil, etc.) and ester synthetic lubricating oil) Oil etc.].

  The addition amount of the diluent is preferably 10 to 80% by weight, more preferably 15 to 70% by weight, particularly preferably from the viewpoint of handling properties, based on the total weight of the lubricant additive and the diluent. Is from 20 to 60% by weight.

  The lubricating oil composition of the present invention comprises a lubricating oil additive and a base oil. Examples of base oils include solvent refined oils mainly composed of paraffin, isoparaffin, and naphthene, hydrotreated oil, hydrocracked oil, ester-based and poly-α-olefin-based synthetic oils, and these may be used alone or 2 More than one species may be used in combination.

Kinematic viscosity at 100 ° C. of the base oil is, preferred is 1 to 10 mm ² / s, more preferably is 1 to 8 mm ² / s, particularly preferred is 2 to 5 mm ² / s. When the kinematic viscosity of the base oil is 1 mm ² / s or more, the temperature rise during use is suppressed, the oil content is less evaporated, and oil film breakage and seizure are less likely to occur even when exposed to high pressure in the lubricated part. When the kinematic viscosity of the base oil is 10 mm ² / s or less, the viscosity resistance is small and the energy loss is small.

  The viscosity index of the base oil is preferably 80 or more, more preferably 100 to 250, and the pour point (JIS K2269) of the base oil is preferably −5 ° C. or less, and more preferably -10 to -70 ° C.

  The content of the lubricating oil additive in the lubricating oil composition is preferably 0.01 to 25% by weight and more preferably based on the total weight of the lubricating oil composition from the viewpoint of dispersibility of the insoluble deposit. Is 0.1 to 14% by weight, particularly preferably 0.5 to 8% by weight. Further, the total content of the oil-soluble polymers (L), (M) and (N) in the lubricating oil composition is preferably based on the total weight of the lubricating oil composition from the viewpoint of dispersibility of the insoluble deposit. Is 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 5% by weight.

  The lubricating oil composition of the present invention may further contain other components depending on its use and required performance.

Other components include antioxidants, oiliness agents, corrosion inhibitors, friction modifiers, antiwear agents, extreme pressure agents, rust inhibitors, and viscosity index improvers that have been used as conventionally known lubricating oil compositions. And pour point depressants and antifoaming agents. These may be used alone or in combination of two or more.
Although the compounding quantity of these additives is not specifically limited as long as there exists a predetermined effect, The example of each preferable compounding quantity based on the total weight of a lubricating oil composition is shown below.
The blending amount of the antioxidant is preferably 0 to 5% by weight, and more preferably 0.01 to 3% by weight. The blending amount of the oily agent is preferably 0 to 5% by weight, and more preferably 0.01 to 3% by weight. The blending amount of the antiwear agent, extreme pressure agent and friction modifier is preferably 0 to 10% by weight, and more preferably 0.01 to 5% by weight. The blending amount of the rust preventive is preferably 0 to 5% by weight, and more preferably 0.01 to 2% by weight. The blending amount of the viscosity index improver and the pour point depressant is preferably 0 to 15% by weight, more preferably 0.01 to 15% by weight, and particularly preferably 0.1 to 7% by weight. It is. The blending amount of the antifoaming agent is preferably 0 to 0.1% by weight, and more preferably 0.0005 to 0.01% by weight.

  The lubricating oil composition of the present invention includes gear oil (for industrial use and automobile use), transmission oil [automatic transmission oil (automatic transmission oil, toroidal CVT oil and belt CVT oil, manual transmission oil, etc.], traction oil, hydraulic oil, etc. (Hydraulic hydraulic oil, power steering oil, shock absorber oil, etc.) and engine oil (gasoline, diesel, etc.) can be used widely and suitably. Of these applications, transmission oils and engine oils are preferable, gasoline engine oils and diesel engine oils are more preferable, and gasoline engine oils for automobiles and low viscosity grades of diesel engine oils (0 W) are particularly preferable. And 5W), it is possible to extend the life of the lubricating oil and improve fuel economy.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified below, parts are parts by weight.

<Production Example 1> Production of a polyethylene-propylene copolymer having a vinylidene group 2 parts of a toluene solution of methylaluminoxane adjusted to 1.0 mol / L in a pressure-resistant reaction vessel equipped with a thermometer, a heating / cooling device and a stirrer, 0.6 parts of toluene solution of 0.0 mol / L diethylaluminum chloride and 180 parts of toluene were charged and stirred at room temperature for 10 minutes. Next, 200 parts of propylene monomer and 20 parts of a toluene solution of bis (cyclopentadienyl) zirconium dichloride adjusted to 10 mmol / L were charged, and the temperature was raised to 115 ° C. with stirring (pressure-resistant reactor pressure: 2.64 MPa). Ethylene having a pressure of 2.85 MPa was supplied to the pressure resistant reactor for 1 hour. During the supply of ethylene, the supply amount of ethylene was adjusted in order to keep the pressure at 2.85 MPa. After supplying ethylene for 1 hour, polymerization was further performed at 115 ° C. for 3 hours. Toluene was removed under reduced pressure at 20 mmHg for 1 hour to obtain 400 parts of an ethylene-propylene random copolymer having a vinylidene group [ethylene / propylene = 50/50 (weight ratio), Mn = 4,500].

<Example 1>
In a pressure-resistant reaction vessel equipped with a thermometer, a heating / cooling device and a stirrer, 1,300 parts (1.0 mol part) of polyisobutene (Mn = 1,300) “Glossopal V500” (BASF) and maleic anhydride 117.6 Parts (1.2 mol parts) were charged and the atmosphere was replaced with nitrogen, followed by an ene reaction at 210 ° C. for 24 hours. After cooling to 177 ° C., unreacted maleic anhydride was removed under reduced pressure at 10 mmHg for 1 hour to obtain 678 parts of polybutenyl succinic anhydride. Into a glass reaction vessel having a thermometer, a heating / cooling device, a stirrer, and a rectifying tower, 146 parts (1.0 mole part) of triethylenetetramine and 100 parts (1.0 mole part) of methyl isobutyl ketone were charged, 125 The ketimine reaction was carried out while dehydration at 8 ° C for 8 hours. After the reaction, unreacted triethylenetetramine and methylisobutylketone are removed using a rectifying column, and a mixed fraction of ketimine compound [triethylenetetramine: monoketiminate: diketiminate (mol%) = 15:60:25] 202 parts were obtained. In a reaction vessel having a thermometer, a heating / cooling device, a stirrer and a reflux condenser, 66 parts (0.28 mole part) of the monoketimine compound and 349.5 parts (0.25 mole) of the polyisobutenyl succinic anhydride Part) was heated to 150 ° C., and the imination reaction was carried out while dehydrating under reduced pressure (20 mmHg) for 2 hours at the same temperature. After cooling to 95 ° C, 72 parts of water was charged and hydrolyzed at 95 ° C for 2 hours. The temperature was raised to 120 ° C., and water and methyl isobutyl ketone were distilled off over 2 hours under reduced pressure (20 mmHg). After further raising the temperature to 200 ° C., triethylenetetramine formed as a by-product over 2 hours under reduced pressure (10 mmHg) was distilled. To obtain a lubricant additive (K-1) [(K-1) is represented by the oil-soluble polymer (L-1) represented by the general formula (1) and the general formula (3). In the general formula (1), A is a residue of polyisobutene, and X is a triethylenetetramine with one primary amino group removed. An oil-soluble polymer that is a residue. (N-1) is an oil-soluble heavy in which m = 0, n = 2 in the general formula (3), A is a residue of polyisobutene, and Z is a residue obtained by removing two primary amino groups from triethylenetetramine. Coalescence. ].

<Example 2>
Example 1 except that 1,300 parts of polyisobutene (Mn = 1,300) “GlossopalV500” (BASF) were changed to 580 parts of polyisobutene (Mn = 580) “Nissan Polybutene 015N” [manufactured by NOF Corporation]. In the same manner, lubricating oil additive (K-2) was obtained [(K-2) is an oil-soluble polymer (L-2) represented by general formula (1) and general formula (3). In the general formula (1), A represents a residue of polyisobutene, and X represents a primary amino group from triethylenetetramine. An oil-soluble polymer that is the residue removed. (N-2) is an oil-soluble heavy in which m = 0, n = 2 in formula (3), A is a residue of polyisobutene, and Z is a residue obtained by removing two primary amino groups from triethylenetetramine. Coalescence. ].

<Example 3>
1,300 parts of polyisobutene (Mn = 1,300) “Glossopal V500” (manufactured by BASF) 4,500 parts of an ethylene-propylene random copolymer (Mn = 4,500) having a vinylidene group obtained in Production Example 1 Except having changed to (1.0 mol part), it carried out similarly to Example 1, and obtained the lubricating oil additive (K-3) [(K-3) is oil represented by General formula (1). A soluble polymer (L-3) and an oil-soluble polymer (N-3) represented by the general formula (3), wherein (L-3) is a residue of polyisobutene in the general formula (1). An oil-soluble polymer in which the group X is a residue obtained by removing one primary amino group from triethylenetetramine. (N-3) is an oil-soluble heavy in which m = 0, n = 2 in the general formula (3), A is a residue of polyisobutene, and Z is a residue obtained by removing two primary amino groups from triethylenetetramine. Coalescence. ].

<Example 4>
Into a glass reaction vessel having a thermometer, a heating / cooling device, a stirrer, and a rectifying tower, 189 parts (1.0 mole part) of tetraethylenepentamine and 150 parts (1.5 mole part) of methyl isobutyl ketone were charged, The ketimine reaction was performed while dehydrating at 125 ° C. for 8 hours. After the reaction, unreacted tetraethylenepentamine and methyl isobutyl ketone are removed using a rectifying column, and a mixed fraction of ketimine compound [tetraethylenepentamine: monoketiminate: diketiminate (mol%) = 5:45: 50] 298 parts were obtained. In a separate reaction vessel, 208 parts (0.68 mole part) of the mixed fraction of the ketiminate and 349.5 parts (0.25 mole part) of the polyisobutenyl succinic anhydride obtained in Example 1 were placed. The mixture was heated up to 150 ° C., and amidation and imination reaction were carried out while dehydrating under reduced pressure (20 mmHg) for 2 hours at the same temperature. After cooling to 95 ° C, 72 parts of water was charged and hydrolyzed at 95 ° C for 2 hours. Water and methyl isobutyl ketone were distilled off over 2 hours under reduced pressure (20 mmHg) by raising the temperature to 120 ° C., and after further raising the temperature to 200 ° C., tetraethylenepentamine formed as a by-product over 2 hours under reduced pressure (10 mmHg) Distilling to obtain a lubricating oil additive (K-4) [(K-4) is represented by the oil-soluble polymer (L-4) represented by the general formula (1) and the general formula (3). In the general formula (1), A represents a residue of polyisobutene, and X represents a primary amino group from tetraethylenepentamine. An oil-soluble polymer that is the residue removed. (N-4) is oil-soluble heavy in which m = 0, n = 2 in formula (3), A is a residue of polyisobutene, and Z is a residue obtained by removing two primary amino groups from triethylenetetramine. Coalescence. ].

<Example 5>
A glass reaction vessel having a thermometer, a heating / cooling device, a stirrer, and a rectifying tower was charged with 90 parts (1.0 mol part) of 2-hydroxypropylenediamine and 100 parts (1.0 mol part) of methyl isobutyl ketone. The ketimine reaction was performed while dehydrating at 125 ° C. for 8 hours. After the reaction, unreacted 2-hydroxypropylene diamine and methyl isobutyl ketone are removed using a rectifying column, and a mixed fraction of ketiminate [2-hydroxypropylenediamine: monoketiminate: diketiminate (mol%) = 5: 45:50] 298 parts were obtained. In a separate reaction vessel, 59 parts (0.28 mol) of the mixed fraction of the ketimine compound and 349.5 parts (0.25 mol) of the polyisobutenyl succinic anhydride obtained in Example 1 were placed. Then, the temperature was raised to 150 ° C., and esterification and imination were performed while dehydrating at the same temperature for 2 hours under reduced pressure (20 mmHg). After cooling to 95 ° C, 72 parts of water was charged and hydrolyzed at 95 ° C for 2 hours. Water and methyl isobutyl ketone were distilled off over 2 hours under reduced pressure (20 mmHg) by raising the temperature to 120 ° C., and after further raising the temperature to 200 ° C., tetraethylenepentamine formed as a by-product over 2 hours under reduced pressure (10 mmHg) Distilling to obtain a lubricating oil additive (K-5) [(K-5) is represented by the oil-soluble polymer (L-5) represented by the general formula (1) and the general formula (2). The oil-soluble polymer (M-5) and the oil-soluble polymer (N-5) represented by the general formula (3) are contained, and (L-5) is represented by A in the general formula (1). An oil-soluble polymer in which a residue of polyisobutene, X is a residue obtained by removing one primary amino group from 2-hydroxypropylenediamine. (M-5) is an oil-soluble polymer in which A in the general formula (2) is a residue of polyisobutene, X is a residue obtained by removing a hydroxyl group from 2-hydroxypropylenediamine, and Y is a group represented by -O-. . (N-5) is a mixture of three types, m = 1, n = 1 in the general formula (3), A is a residue of polyisobutene, Y is a group represented by -O-, and Z is 2 -An oil-soluble polymer (N-5-1) which is a residue obtained by removing one hydroxyl group and one primary amino group from hydroxypropylenediamine. In General Formula (3), m = 1, n = 2, A is a residue of polyisobutene, Y is a group represented by —O—, and Z is a hydroxyl group and a primary amino group from 2-hydroxypropylenediamine. An oil-soluble polymer (N-5-2) which is a residue obtained by removing two. In the general formula (3), m = 0, n = 2, A is a residue of polyisobutene, and Z is a residue obtained by removing two primary amino groups from 2-hydroxypropylenediamine (N- 5-3). ].

<Comparative Example 1>
Into a glass reaction vessel having a thermometer, a heating / cooling device, a stirrer, and a rectifying tower, 189 parts (1.0 mole part) of tetraethylenepentamine and 50 parts (0.5 mole part) of methyl isobutyl ketone were charged, The ketimine reaction was performed while dehydrating at 125 ° C. for 8 hours. After the reaction, unreacted methyl isobutyl ketone is removed using a rectifying column, and a mixed fraction of tetraethylenepentamine and ketiminate [tetraethylenepentamine: monoketiminate: diketiminate (mol%) = 35:64: 1] part was obtained. In another reaction vessel, 60.8 parts (0.25 mole part) of the mixed fraction of the ketiminate and 405.4 parts (0.29 mole part) of the polyisobutenyl succinic anhydride obtained in Example 1 were used. ), The temperature was raised to 150 ° C., and amidation and imination reaction were performed while dehydrating at that temperature for 2 hours under reduced pressure (20 mmHg). After cooling to 95 ° C, 72 parts of water was charged and hydrolyzed at 95 ° C for 2 hours. The temperature was raised to 120 ° C., and water and methyl isobutyl ketone were distilled off over 2 hours under reduced pressure (20 mmHg). After further raising the temperature to 200 ° C., triethylenetetramine formed as a by-product over 2 hours under reduced pressure (10 mmHg) was distilled. Leaving a lubricating oil additive (H-1).

<Comparative Example 2>
In a glass reaction vessel having a thermometer, a heating / cooling device, a stirrer, and a rectifying tower, 189 parts (1.0 mol part) of tetraethylenepentamine and the polyisobutenyl succinic anhydride obtained in Example 1 were used. 2097 parts (1.5 mol parts) were charged, the temperature was raised to 150 ° C., and amidation and iminization reactions were carried out while dehydrating at the same temperature for 2 hours under reduced pressure (20 mmHg). After cooling to 95 ° C, 72 parts of water was charged and hydrolyzed at 95 ° C for 2 hours. The temperature was raised to 120 ° C., and water and methyl isobutyl ketone were distilled off over 2 hours under reduced pressure (20 mmHg). After further raising the temperature to 200 ° C., triethylenetetramine formed as a by-product over 2 hours under reduced pressure (10 mmHg) was distilled. Leaving a lubricating oil additive (H-2).

<Examples 6 to 10 and Comparative Examples 3 and 4>
Minerals using 10 parts of oil-soluble polymers (K-1) to (K-5) and (H-1) and (H-2) obtained in Examples 1 to 5 and Comparative Examples 1 and 2 as a base oil Oil (“YUBASE3”: manufactured by SK Corporation) is dissolved in 90 parts, and the lubricating oil compositions (P-1) to (P-5) of the present invention and the comparative lubricating oil compositions (Q-1) and (Q -2) was obtained. Table 1 shows the results of the following carbon black dispersibility test, hot tube cleanliness test, and viscosity measurement for these lubricating oil compositions.

<Carbon black dispersibility test>
In a 200 mL container, 1.5 g of carbon black “MB-100” [Mitsubishi Chemical Corporation] and the lubricating oil compositions (P-1) to (P-5) and (Q-1), (Q-2) 48.5 g was added and mixed with a homogenizer at 29,000 ± 1,000 rpm for 10 minutes to obtain a carbon black dispersion sample. Also, put 50 mg of carbon black dispersion sample and 50 mL of xylene in a 70 mL glass container, cover the container, shake vigorously 10 times, and leave it at room temperature for 7 days. Was evaluated visually.
◎: There is no sediment… Dispersibility is very good ○: There is a very small amount of sediment… Dispersibility is good ×: There is a large amount of sediment… Dispersibility is poor

<Hot tube cleanliness test>
In accordance with JPI-5S-55-99 ("Japan Petroleum Institute Petroleum Test Standards" engine oil hot tube test method), lubricating oil compositions (P-1) to (P-5) in a glass tube having an inner diameter of 2 mm. ) And comparative lubricating oil compositions (Q-1) and (Q-2), respectively, at 0.3 ml / hour and air at 10 ml / second for 16 hours while keeping the temperature of the glass tube at 250 ° C. The color of the deposit in the tube was compared with the color sample to evaluate the cleanliness. The larger the number, the better the cleanliness.

<Method for measuring viscosity of lubricating oil composition>
The kinematic viscosity at 40 ° C. was measured by the method of JIS-K-2283.

  Lubricating oil additives and lubricating oil compositions of the present invention include drive system lubricating oils [for gear equipment (manual transmission oil and differential oil, etc.), automatic transmission oil (automatic transmission oil, Belt CVT oil, toroidal CVT oil, etc.)], hydraulic oil [mechanical hydraulic oil, power steering oil, shock absorber oil, etc.] and engine oil [gasoline, diesel, etc.].

Claims (5)

Oil-soluble polymer (L) represented by general formula (1), oil-soluble polymer (M) represented by general formula (2), and oil-soluble polymer (N) represented by general formula (3) A lubricating oil additive comprising at least one selected from the group consisting of: a lubricating oil additive satisfying the following mathematical formula (1):
(L ′ + M ′) / (L ′ + M ′ + N ′) ≧ 0.80 (1)
[Wherein, L ′ represents the number of moles of the oil-soluble polymer (L); M ′ represents the number of moles of the oil-soluble polymer (M); N ′ represents the number of moles of the oil-soluble polymer (N). ]

[Wherein A is a residue of a hydrocarbon polymer (A) having a number average molecular weight of 500 to 5,000; X is a hydrocarbon having 2 to 20 carbon atoms having 1 to 4 primary amino groups; Group (X1), 1 to 2 primary amino groups and 1 to 10 secondary amino groups (X2) having 2 to 20 carbon atoms, 1 or 2 primary amino groups and hydroxyl group 2 to 20 hydrocarbon group (X3) having 1 to 3 carbon atoms, and 1 or 2 primary amino group and 1 to 2 hydrocarbon group having 1 to 3 carbon atoms (X4). At least one selected from the group consisting of: ]

[Wherein, A and X are the same groups as A and X in the general formula (1); Y is a group represented by —O— or —NR—, R is a hydrogen atom, and has 1 to 12 carbon atoms. An alkyl group, a hydrocarbon group having 2 to 20 carbon atoms (R1) having 1 to 4 primary amino groups, 1 or 2 primary amino groups, and carbon having 1 to 10 secondary amino groups 2 to 20 groups (R2), 1 or 2 primary amino groups and 1 to 3 hydrocarbon groups (R3) having 1 to 3 hydroxyl groups, and 1 or 1 primary amino group It is at least 1 sort (s) chosen from the group which consists of a C2-C20 hydrocarbon group (R4) which has 2 and 1-3 thiol groups. ]

Wherein A and X are the same groups as A and X in the general formula (1); Y is the same group as Y in the general formula (2); Z has 0 to 4 primary amino groups A hydrocarbon group having 2 to 20 carbon atoms (Z1), a hydrocarbon group having 2 to 20 carbon atoms (Z2) having 0 to 2 primary amino groups and 1 to 10 secondary amino groups; C2-C20 hydrocarbon group (Z3) having 0 to 2 primary amino groups and 1 to 3 hydroxyl groups, and carbon having 0 to 2 primary amino groups and 1 to 3 thiol groups At least one selected from the group consisting of a hydrocarbon group (Z4) of 2 to 20; m and n are each independently an integer of 0 to 4, and satisfy the relationship of 2 ≦ m + n ≦ 4. ]   The oil-soluble polymers (L), (M) and (N) are alkenyl anhydrides obtained by an ene reaction between a polyolefin (A1) having a vinylidene group and a number average molecular weight of 500 to 5,000 and maleic anhydride. Amidation and esterification of succinic acid (B) with ketimine compound (D) obtained by ketiminizing part or all of the primary amino group of compound (C) having 2 to 4 primary amino groups The lubricating oil additive according to claim 1, which is an oil-soluble polymer obtained by hydrolyzing (D1) after obtaining a ketimine product (D1) by crystallization or imidization. The lubricating oil additive according to claim 1 or 2, wherein the compound (C) is an amine compound represented by the general formula (4).
^{_{H 2 N- (R 1 -NH)}} n -R 2 -NH 2 (4)
[In formula, R < ¹ > and R < ² > is respectively independently a C1-C8 alkylene group, and n is a number of 1-10. ]   A lubricating oil composition comprising the lubricating oil additive according to any one of claims 1 to 3 and a base oil.   An alkenyl succinic anhydride (B) obtained by an ene reaction between a polyolefin (A1) having a vinylidene group and a number average molecular weight of 500 to 5,000 and maleic anhydride has 2 to 4 primary amino groups. After amidation, esterification or imidation with a ketimine compound (D) obtained by ketiminization of part or all of the primary amino group of compound (C) to obtain ketiminate (D1), (D1) The method for producing a lubricating oil additive according to claim 1, wherein the lubricating oil additive is obtained by hydrolysis.