JP6045905B2 - Lubricating additive - Google Patents

Description

  The present invention relates to a lubricating additive used for lubricating oil and fuel oil, and more particularly to a lubricating additive suitably used as an additive for lubricating oil for internal combustion engines.

  In recent years, in order to reduce energy loss and carbon dioxide emission while driving a car, it has been studied to improve the fuel efficiency of the car. As measures to improve the fuel efficiency of automobiles, the weight of automobile bodies has been reduced. However, lubricating oils are also required to contribute to fuel efficiency. Further improvement of friction reduction characteristics by oil is being studied.

  Conventionally, boric acid based additives for lubrication are known as additives having wear reduction characteristics and lubrication characteristics. For example, in Patent Document 1, an organic borate ester is blended in a lubricating oil composition together with a 1,3,4-thiadiazole compound, dithiocarbamate, and a non-sulfur molybdenum compound, and exhibits synergistic anti-wear properties together with these compounds. Is described. The organic borate ester used in Patent Document 1 is a reaction product obtained by reacting fatty oil and diethanolamine and then reacting with boric acid.

  Patent Document 2 discloses a lubricating oil composition containing a boric acid-containing succinimide-based ashless dispersant that improves friction characteristics and abrasion resistance between a belt and a pulley. Patent Document 3 discloses that an amine compound borate, boric acid ester, or boric acid amide is added to the lubricating oil composition as an additive for improving the cleanliness of the lubricating oil. Furthermore, Patent Document 4 discloses that bis (2-hydroxyethyl) oleamide boride as a friction modifier is added to the lubricating oil composition.

JP-T-2006-502287 JP 2006-206924 A Japanese Patent Laid-Open No. 7-197062 U.S. Pat. No. 4,389,322

As described above, boron compounds are known to exhibit a relatively high friction coefficient, although they are excellent in wear reduction characteristics and cleanliness. However, in order to achieve further fuel economy in engine oil, diesel engine oil, etc., an additive that lowers the friction coefficient of lubricating oil or fuel oil is required.
The present invention has been made in view of the above problems, and is a lubricant additive or fuel oil additive that has excellent wear resistance and can reduce the coefficient of friction of a lubricant, fuel oil, or the like. The purpose is to provide.

As a result of intensive studies, the inventors of the present invention have reduced the coefficient of friction of a lubricating oil or the like when a compound obtained by heating and stirring an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative at a predetermined temperature. I found that it was possible. Further, the present inventors have found that the compound obtained by heating and stirring contains a relatively large amount of tricoordinate boron-containing compound, and the tricoordinate boron-containing compound has a friction coefficient such as lubricating oil or fuel oil. It has been found that it is excellent in the effect of lowering and is optimal as a lubricating additive.
The present invention has been obtained based on the above findings and provides the following (1) to (14).
(1) A lubricating additive obtained by heating and stirring an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative at a temperature of 100 ° C. or higher and 150 ° C. or lower.
(2) The organic compound has an amine compound (A), an amide compound (B) having a hydroxyl group, an imide compound (C) having an amino group, an ester compound (D) having a hydroxyl group, and a hydroxyl group. The lubricating additive according to (1) above, which is at least one compound selected from the alcohol compounds (E).

(3) The lubricating additive according to (1), wherein the amine compound (A) is at least one compound selected from the compounds represented by the following general formulas (A1) to (A5).
(In the formulas (A1) to (A5), R ₁ , R ₁₀ , R ₁₁ , R ₁₆ , R ₂₉ and R ₄₇ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₁₀ and R ₁₁ may be the same as each other. R _{2 to} R ₉ , R _{12 to} R ₁₅ , R _{17 to} R ₂₈ , R _{30 to} R ₄₅ , and R _{48 to} R ₄₉ may be a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms. A, b, c, e, f, g, j, k, w, m are each an integer of 0-20, and d, h, i are respectively An integer of 1-6, a + b = 1-20, e + f + g = 0-20, j + k + w + m = 0-20.)

(4) The lubricant additive according to (1), wherein the amide compound (B) is at least one compound selected from the compounds represented by the following general formulas (B1) and (B2).

(In the formulas (B1) and (B2), R ₅₁ , R ₆₁ and R ₆₂ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₆₁ and R ₆₂ may be the same as or different from each other. R _{52 to} R ₅₉ and R _{63 to} R ₆₆ are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different from each other, n is an integer of 0 to 20, and o, p Each represents an integer of 1 to 20.)

(5) The lubricant additive according to (1), wherein the imide compound (C) is at least one compound selected from compounds represented by the following general formula (C1).
(In Formula (C1), _R69 is a hydrocarbon group having 20 to 150 carbon atoms, and s is an integer of 0 to 5).

(6) The lubricating additive according to (1), wherein the ester compound (D) is at least one compound selected from the compounds represented by the following general formulas (D1) and (D2).

(In the formulas (D1) and (D2), R ₈₁ and R ₁₀₁ are each a hydrocarbon group having 1 to 32 carbon atoms, and R _{82 to} R ₈₅ and R _{102 to} R ₁₀₆ are each a hydrogen atom or a carbon number. 1 to 18 hydrocarbon groups, which may be the same or different from each other, and r represents an integer of 1 to 20.)

(7) The lubricating additive according to (1), wherein the alcohol compound (E) is at least one compound selected from compounds represented by the following general formulas (E1) to (E3).

(In the formulas (E1) to (E3), R ₇₁ , R ₉₁ and R ₁₁₁ are each a hydrocarbon group having 1 to 32 carbon atoms, R _{72 to} R ₇₅ , R _{92 to} R ₉₈ , R _{112 to} R ₁₁₈ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different from each other, and q represents an integer of 0 to 20.)

(8) When BF ₃ · OEt ₂ is used as an external standard (0 ppm) and ¹¹ B-NMR measurement is performed in deuterated chloroform, the peak of chemical shift 5-25 ppm with respect to the integrated value of peak of chemical shift -10-25 ppm The additive for lubrication according to any one of the above (1) to (7), wherein the ratio of the integral values is 0.47 or more.
(9) The lubricating additive according to any one of (1) to (8), wherein a molar ratio of the organic compound to boric acid or a boric acid derivative is 1: 0.01 to 1:10.
(10) The lubricating additive according to any one of (1) to (9), wherein the temperature is 100 ° C. or higher and 130 ° C. or lower.
(11) The lubricating additive according to any one of (1) to (10), which is a friction modifier for lubrication.
(12) A method for producing a lubricating additive, wherein an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative are heated and stirred at a temperature of 100 ° C. or higher and 150 ° C. or lower to obtain a lubricating additive.
(13) A friction modifier for lubrication containing a tricoordinate boron-containing compound in a molar ratio of 0.47 or more with respect to the total amount of tricoordinate and tetracoordinate boron-containing compounds.
(14) Tricoordinate boron obtained by mixing an organic compound having a hydroxyl group or an amino group with boric acid or a boric acid derivative with respect to the total amount of tricoordinate and tetracoordinate boron-containing compounds. The additive for lubrication whose amount of a containing compound is 0.47 or more by molar ratio.

  If the lubricating additive of the present invention is used, the friction coefficient of lubricating oil, fuel oil, etc. can be lowered.

Hereinafter, the present invention will be described in more detail.
<Lubricant additive>
The lubricating additive of the present invention is a boron-containing compound obtained by heating and stirring (mixing) an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative at 100 ° C. or more and 150 ° C. or less. In addition, the obtained boron-containing compound includes a state in which boric acid or a boric acid derivative is dispersed without being bonded to a compound having a hydroxyl group or an amino group.
The lubricating additive of the present invention is blended in lubricating oil or fuel oil, etc. to reduce their friction coefficient and to exhibit excellent wear resistance characteristics, and is suitably used as a lubricating friction modifier. It is what is done.

  Examples of the organic compound having a hydroxyl group or amino group include an amine compound (A), an amide compound (B) having a hydroxyl group, an imide compound (C) having an amino group, and an ester compound having a hydroxyl group (D ) And at least one compound selected from alcohol compounds (E) having a hydroxyl group.

Hereinafter, the compounds (A) to (E) will be described in detail.
[Amine compound (A)]
The amine compound (A) is an amine compound (a1) having one or more hydroxyl groups and one or more amino groups, an amine compound (a2) having two or more amino groups, or an amine having only one amino group A compound (a3) etc. are mentioned.
Among the above, as the amine compound (a1), more specifically, compounds represented by the following general formulas (A1) and (A2) can be mentioned, and as the amine compound (a1) or the amine compound (a2), The compound represented by general formula (A3) or (A4) is mentioned. Moreover, as an amine compound (a3), the compound represented by the following general formula (A5) is mentioned.

In formulas (A1) to (A5), R ₁ , R ₁₀ , R ₁₁ , R ₁₆ , R ₂₉ and R ₄₇ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₁₀ and R ₁₁ are the same as each other. But it may be different. Such a hydrocarbon group may be saturated or unsaturated, may be aliphatic or aromatic, may be linear, branched or cyclic, for example, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, Or an aromatic hydrocarbon group is mentioned.
Specific examples of the hydrocarbon group include methyl, ethyl, propyl, butyl, butenyl, hexyl, hexenyl, octyl, octenyl, 2-ethylhexyl, nonyl, decyl, undecyl. Group, decenyl group, dodecyl group, dodecenyl group, tridecyl group, tetradecyl group, tetradecenyl group, pentadecyl group, hexadecyl group, hexadecenyl group, heptadecyl group, octadecyl group, octadecenyl group, stearyl group, isostearyl group, oleyl group, linol group , Nonadecyl group, icosyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl , Decene trimer group, polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group and other aliphatic hydrocarbon groups, phenyl group, methylphenyl group, ethylphenyl Groups, aromatic hydrocarbon groups such as dimethylphenyl group, propylphenyl group, trimethylphenyl group, butylphenyl group and naphthyl group.
The hydrocarbon group is preferably a hydrocarbon group having 4 to 22 carbon atoms, and more preferably a hydrocarbon group having 6 to 18 carbon atoms.

R _{2 to} R ₉ , R _{12 to} R ₁₅ , R _{17 to} R ₂₈ , R _{30 to} R ₄₅ , R _{48 to} R ₄₉ are a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or an ether bond or an ester bond. These are oxygen-containing hydrocarbon groups that may be the same or different from each other, but are preferably hydrogen atoms or hydrocarbon groups.
The hydrocarbon group may be saturated or unsaturated, aliphatic or aromatic, linear, branched or cyclic, for example, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic group Group hydrocarbon group. More specifically, methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, decenyl group, Dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linole, cyclopentyl, cyclohexyl Group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, aliphatic hydrocarbon group such as trimethylcyclohexyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group Group, propylphenyl group, trimethylphenyl group, butylphenyl group, an aromatic hydrocarbon group and a naphthyl group.
As this hydrocarbon group, a C1-C18 thing is preferable, A C1-C16 thing is more preferable, A C1-C12 thing is especially preferable.
Examples of the oxygen-containing hydrocarbon group containing an ether bond or an ester bond are those having 1 to 18 carbon atoms, such as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, t-butoxymethyl group, hexyloxymethyl group, octyloxymethyl group, 2-ethylhexyloxymethyl group, decyloxymethyl group, dodecyloxymethyl group, 2-butyloctyloxymethyl group, tetradecyloxymethyl group, hexadecyloxy group Methyl group, 2-hexyldecyloxymethyl group,
Allyloxymethyl group, phenoxy group, benzyloxy group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxypropyl group, ethoxypropyl group, (2-methoxyethoxy) propyl group , (1-methyl-2-methoxy) propyl group, acetyloxymethyl group, propanoyloxymethyl group, butanoyloxymethyl group, hexanoyloxymethyl group, octanoyloxymethyl group, 2-ethylhexanoyloxymethyl group Decanoyloxymethyl group, dodecanoyloxymethyl group, 2-butyloctanoyloxymethyl group, tetradecanoyloxymethyl group, hexadecanoyloxymethyl group, 2-hexyldodecanoyloxymethyl group, benzoyloxymethyl group, etc. Can be mentioned .

Moreover, a, b, c, e, f, g, j, k, w, m each represents an integer of 0-20, d, h, i each represents an integer of 1-6, and a + b = 1-20, e + f + g = 0-20, j + k + w + m = 0-20.
(A + b) is preferably 1 to 12, more preferably 1 to 10. C, (e + f + g), and (j + k + w + m) are each preferably 0 to 12, more preferably 0 to 7. d, h, and i are each preferably 2-4.

In the general formula (A1), all of R _{2 to} R ₅ and R _{6 to} R ₉ are hydrogen atoms, or R _{2 to} R ₄ and R _{6 to} R ₈ are all hydrogen atoms and R ₅ and It is preferable that one or both of R ₉ is a hydrocarbon group.
In the general formula (A2), it is preferable that all of R _{12 to} R ₁₄ are hydrogen atoms, and R ₁₅ is a hydrogen atom or a hydrocarbon group.
In the general formula (A3), each of e, f and g is 1 or more, and R _{17 to} R ₂₈ are preferably all hydrogen atoms, more preferably all of e, f and g are 1. Of course, in general formula (A3), all of e, f, and g are 0, and it does not need to have a hydroxyl group.
Moreover, in general formula (A4), it is preferable that j, k, w, and m are all 0. Furthermore, in the general formula (A5), R ₄₇ is preferably an alkyl group, and at least one of R ₄₈ and R ₄₉ may be a hydrocarbon group, and the hydrocarbon group is an alkyl group. preferable.

Specific compounds of the general formula (A1) include octylethanolamine, decylethanolamine, dodecylethanolamine, tetradecylethanolamine, hexadecylethanolamine, stearylethanolamine, oleylethanolamine, coconut oil ethanolamine, palm oil. An amine compound having one 2-hydroxyalkyl group such as hydroxyethyl group exemplified by ethanolamine, rapeseed oil ethanolamine, beef tallow ethanolamine and the like; octyldiethanolamine, decyldiethanolamine, dodecyldiethanolamine, tetradecyldiethanolamine, hexadecyldiethanolamine, Stearyl diethanolamine, oleyl diethanolamine, coconut oil diethanolamine, palm oil diethanolamine Rapeseed oil diethanolamine, beef tallow diethanolamine, 1- [cyclohexyl (2-hydroxyethyl) amino] dodecan-2-ol, N, N-bis (2-hydroxydodecyl) -N-cyclohexylamine, 1- [N- (2 -Hydroxyethyl) anilino] dodecan-2-ol, N, N-bis (2-hydroxydodecyl) -N-octylamine, N, N-bis (2-hydroxypropyl) -N-oleylamine, N, N-bis (2-hydroxydodecyl) -amine compounds having two 2-hydroxyalkyl groups exemplified by aniline and the like; polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene dodecylamine, polyoxyethylene tetradecylamine, Polyoxyethylene hexadecylami , Polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene beef tallow amine, polyoxyethylene coconut oil amine, polyoxyethylene palm oil amine, polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine, ethylene oxide And amine compounds having a polyalkylene oxide structure such as propylene oxide stearylamine.
Moreover, as a commercial item of the compound shown by general formula (A1), Amit 105, Amit 308, Amit 320 (above, Kao Corporation make), Nimine L-202, Nimeen L-207, Nimine S-202, Nymin S-204, Nymeen S-210, Nymeen S-215, Nymeen S-220, Nymeen T2-202, Nymeen T2-206, Nymeen T2-210, Nymeen T2-230, Nymeen T2-260, Nymeen DT-203, Nymeen DT-208 (above, manufactured by NOF Corporation), Kawasoft EP59S (Kawaken Fine Chemical), Esomin T / 15, Esomin S / 15, Esomin O / 15 (above, manufactured by Lion Corporation) and the like are available.

  Specific examples of the general formula (A2) include, for example, N-methyl-octylethanolamine, N-methyl-decylethanolamine, N-methyl-dodecylethanolamine, N-methyl-tetradecylethanolamine, N- Methyl-hexadecylethanolamine, N-methyl-stearylethanolamine, N-methyl-oleylethanolamine, N-methyl-coconut oil ethanolamine, N-methyl-palm oil ethanolamine, N-methyl-rapeseed oil ethanolamine, Alkylamine compounds having one 2-hydroxyalkyl group such as hydroxyethyl group exemplified by N-methyl-tallow ethanolamine; polyoxyethylene N-methyl-decylamine, polyoxyethylene N-methyl-dodecylamine, poly Oxyethylene Alkylamines having a polyalkylene oxide structure exemplified by N-methyl-tetradecylamine, polyoxyethylene N-methyl-hexadecylamine, polyoxyethylene N-methyl-stearylamine, polyoxyethylene N-methyl-oleylamine and the like Compounds.

Specific compounds of the general formula (A3) include, as the amine compound (a2) having two or more amino groups, for example, N-lauryl-1,3-diaminopropane, N-stearyl-1,3-diaminopropane, Alkyl such as N-oleyl-1,3-diaminopropane, N-coconut oil alkyl-1,3-diaminopropane, N-tallow alkyl-1,3-diaminopropane, N-cured tallow-1,3-diaminopropane Or an alkenyl diamine etc. are mentioned.
Commercially available alkyl or alkenyl diamines include Duomin CD, Duomin T, Duomin HT Flakes (above, Lion Corporation) Nissan Amine DT, Nissan Amine DT-H, Nissan Amine DOB-R (above, NOF Corporation) ) Etc. are commercially available.

  In addition, specific compounds of the general formula (A3) include tris (2-hydroxyethyl) laurylpropylenediamine, tris (1) as a compound (a1) having one or more hydroxy groups and one or more amino groups. 2-hydroxyethyl) stearylpropylenediamine, tris (2-hydroxyethyl) oleylpropylenediamine, tris (2-hydroxyethyl) coconut oil propylenediamine, tris (2-hydroxyethyl) palm oil propylenediamine, tris (2-hydroxyethyl) ) Diamine compounds having three 2-hydroxyalkyl groups such as 2-hydroxyethyl groups exemplified by beef tallow propylene diamine; polyoxyethylene lauryl propylene diamine, polyoxyethylene stearyl propylene diamine, polyoxyethylene Yl propylenediamine, polyoxyethylene coconut oil propylene diamine, polyoxyethylene palm oil propylene diamine, diamine compounds having a polyalkylene oxide structure illustrated polyoxyethylene beef tallow propylene diamine, and the like. Further, Esododumin T / 13, Esododumine T / 25 (above, manufactured by Lion Corporation), Naimine DT-203, Naimine DT-208 (above, manufactured by NOF Corporation) and the like are commercially available.

  Specific compounds represented by the general formula (A4) include, for example, lauryl dipropylene triamine, stearyl dipropylene triamine, oleyl dipropylene triamine, coconut oil alkyldipropylene triamine as the compound (a2) having two or more amino groups. Alkyl or alkenyltriamines such as palm oil alkyldipropylenetriamine, beef tallow alkyldipropylenetriamine, hardened beef tallowalkyldipropylenetriamine, and the like, and triamine Y12D, triamine T (above, manufactured by Lion Co., Ltd.) and the like are available as commercial products it can.

  In addition, the compound represented by the general formula (A5) is an amine compound (a3) having only one amino group, such as hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, or Primary amines such as oleylamine; secondary amines such as dihexylamine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dioleylamine: trihexylamine, trioctylamine, tridecyl Examples include amines having about 6 to 18 carbon atoms such as tertiary amines such as amine, tridodecylamine, tritetradecylamine, trihexadecylamine, trioctadecylamine, and trioleylamine. Is, secondary or tertiary amines are preferred, more preferably a tertiary amine.

  Of the amine compounds (A) described above, the amine compound (amino alcohol compound) (a1) having a hydroxyl group and an amino group is the total number of carbon atoms of the hydrocarbon group in consideration of solubility in the lubricating base oil. Is preferably 12 or more. Moreover, the compound shown by general formula (A1) is preferable from a viewpoint which can make the solubility with respect to lubricating base oil, and a friction coefficient lower among the said amine compounds (A).

The amine compound (amino alcohol compound) (a1) having a hydroxyl group and an amino group includes a compound (Aa) having at least one of a primary amino group and a secondary amino group, and a compound (Ae) having an epoxy group. ) Is preferably obtained.
Specific examples of the compound (Aa) having at least one of a primary amino group and a secondary amino group include a primary amine or a secondary amine, and the primary amine has a total carbon number of 1 or more. It preferably has 32 or less hydrocarbon groups, and may further contain an oxygen atom. The secondary amine preferably has a hydrocarbon group having 2 to 40 carbon atoms in total, and may further contain an oxygen atom.
In the primary amine or the secondary amine, if the total carbon number of the hydrocarbon group is not less than the above lower limit, the amino alcohol compound obtained from the primary amine or the secondary amine is sufficiently dissolved in the lubricating base oil. If it is less than the above upper limit, a high base number amino alcohol compound can be obtained.

  The hydrocarbon group possessed by the primary amine and the secondary amine may be saturated or unsaturated, may be aliphatic or aromatic, and may be linear, branched or cyclic. Specifically, methyl, ethyl, propyl, butyl, butenyl, hexyl, hexenyl, octyl, octenyl, 2-ethylhexyl, nonyl, decyl, undecyl, decenyl, dodecyl Group, dodecenyl group, tridecyl group, tetradecyl group, tetradecenyl group, pentadecyl group, hexadecyl group, hexadecenyl group, heptadecyl group, octadecyl group, octadecenyl group, stearyl group, isostearyl group, oleyl group, linole group, nonadecyl group, icosyl group Eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, decentrimer , Polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group and other aliphatic hydrocarbon groups, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl Groups, aromatic hydrocarbon groups such as a trimethylphenyl group, a butylphenyl group, and a naphthyl group.

Specific examples of primary amines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 2-ethylhexylamine, 2-decyltetra Examples include decylamine, oleylamine, ethanolamine, propanolamine, octadecyloxyethylamine, 3- (2-ethylhexyloxy) propylamine, 12-hydroxystearylamine, cyclohexylamine, and aniline.
Specific examples of secondary amines include dimethylamine, diethylamine, dibutylamine, dihexylamine, dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, di-2-ethylhexylamine, di- Mention may be made of oleylamine, methylstearylamine, ethylstearylamine, methyloleylamine, diethanolamine, dipropanolamine, 2-butylaminoethanol, hexylaminoethanol, phenylaminoethanol, cyclohexylethanolamine. In addition, cyclic secondary amines such as piperidine, piperazine and morpholine can also be mentioned.

  The compound (Ae) having an epoxy group is preferably a compound in which an epoxy group and a hydrocarbon group are directly bonded, and the hydrocarbon group may be saturated or unsaturated, and may be aliphatic or aromatic. It may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic hydrocarbon group. More specifically, the hydrocarbon group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a hexenyl group, an octyl group, an octenyl group, a decyl group, a decenyl group, a dodecyl group, and a dodecenyl group. , Tetradecyl group, tetradecenyl group, hexadecyl group, hexadecenyl group, octadecyl group, octadecenyl group, isostearyl group, decene trimer group, polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl Aliphatic hydrocarbon groups such as phenyl groups, phenyl groups, methylphenyl groups, ethylphenyl groups, dimethylphenyl groups, propylphenyl groups, trimethylphenyl groups, butylphenyl groups, naphthyl groups, etc. It is.

  Specific examples of the compound (Ae) having an epoxy group include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2 -Epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxydodecane, 1,2 -Epoxytetradecene, 1,2-epoxyhexadecene, 1,2-epoxyoctadecene, 1,2-epoxy-2-octyldodecane and the like.

The amino alcohol compound is preferably a compound obtained by reacting the amine compound (Aa) and the epoxy compound (Ae) in a ratio (molar ratio) of 1: 0.7 to 1:12. More preferably, the compound is obtained by reacting at a ratio of 10: 1 to 10: 1.
The reaction of the amine compound (Aa) and the epoxy compound (Ae) is preferably performed at a temperature of about 50 ° C. to 250 ° C., more preferably about 80 ° C. to 200 ° C.

[Amide compound (B)]
The amide compound (B) having a hydroxyl group is an amide alcohol compound having one or more amide groups in the molecule and one or more hydroxyl groups in the molecule, and is represented by the following general formula (B1) or general formula (B2): It is preferable that it is a compound shown by these.

In the formulas (B1) and (B2), R ₅₁ , R ₆₁ and R ₆₂ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₆₁ and R ₆₂ may be the same as or different from each other.
The hydrocarbon group for R ₅₁ , R ₆₁ , and R ₆₂ may be saturated or unsaturated, aliphatic or aromatic, linear, branched, or cyclic, such as an alkyl group or an alkenyl group. Examples thereof include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Specifically, methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, decenyl group, dodecyl group Group, dodecenyl group, tridecyl group, tetradecyl group, tetradecenyl group, pentadecyl group, hexadecyl group, hexadecenyl group, heptadecyl group, octadecyl group, octadecenyl group, stearyl group, isostearyl group, oleyl group, linole group, nonadecyl group, icosyl group Eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, decentrimer , Polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, aliphatic hydrocarbon group such as trimethylcyclohexyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl Groups, aromatic hydrocarbon groups such as propylphenyl group, trimethylphenyl group, butylphenyl group and naphthyl group.
Here, the carbon number of the hydrocarbon groups R ₅₁ and R ₆₁ is preferably 4 to 22, 6 to 18 is more preferable. The number of carbon atoms of the hydrocarbon group R ₆₂ is preferably 1 to 18, more preferably 1 to 10, 1 to 4 are particularly preferred.

R _{52 to} R ₅₉ and R _{63 to} R ₆₆ are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same as or different from each other. The hydrocarbon group may be saturated or unsaturated, aliphatic or aromatic, linear, branched or cyclic, for example, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic group A hydrocarbon group is mentioned. More specifically, methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, decenyl group, Dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linole, cyclopentyl, cyclohexyl Group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, aliphatic hydrocarbon group such as trimethylcyclohexyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group Group, propylphenyl group, trimethylphenyl group, butylphenyl group, and aromatic hydrocarbon groups such as a naphthyl group.
Examples of the hydrocarbon group _{R 52 ~R 59, R 63 ~R} 66, preferably has 1 to 16 carbon atoms, more preferably those having 1 to 12 carbon atoms, particularly preferably from 1 to 10 carbon atoms.

  Here, n shows the integer of 0-20, o and p show the integer of 1-20, respectively. Moreover, n + o = 1-20 is shown. In addition, (n + o) and p are each preferably 1 to 12, more preferably 1 to 10.

In the general formula (B1), all of R _{52 to} R ₅₅ and R _{56 to} R ₅₉ are hydrogen atoms, or R _{52 to} R ₅₄ and R _{56 to} R ₅₈ are all hydrogen atoms and R ₅₅ , One or both of R ₅₉ are preferably a hydrocarbon group.
In general formula (B2), it is preferable that all of R _{63 to} R ₆₅ are hydrogen atoms, and R ₆₆ is a hydrogen atom or a hydrocarbon group.

Specific compounds of the general formula (B1) include octyl diethanolamide, decyl diethanolamide, dodecyl diethanolamide, stearyl diethanolamide, oleyl diethanolamide, coconut oil fatty acid diethanolamide, palm oil fatty acid diethanolamide, rapeseed oil fatty acid diethanolamide. And fatty acid dialkanolamides such as fatty acid diethanolamide exemplified by beef tallow fatty acid diethanolamide.
These fatty acid dialkanolamides are known as Starhome F, Starhome T, Starhome FK, Starhome DL, Starhome DF-1, Starhome DF-2, Starhome DF-4, Starhome DFC, Starhome DO, Starhome Home DOS (above, manufactured by NOF Corporation), Amizole CDE, Amizole FDE, Amizole KD-1, Amizole KD-3, Amizole CD, Amizole FD, Amizole CDC, Amizole M, Amizole LDE, Amizole LMDE, Amizole MDE, Amizole SDE, amizole SDHE, amizole ODE, amizole ODHE (manufactured by Kawaken Fine Chemical Co., Ltd.), polynon DAO, polynon DAL-C, polynon DAT (manufactured by Shoei Pharmaceutical Co., Ltd.) and the like are commercially available.
Specific compounds represented by the general formula (B1) include polyoxyethylene octanoic acid amide, polyoxyethylene decanoic acid amide, polyoxyethylene lauric acid amide, polyoxyethylene myristic acid amide, polyoxyethylene palmitic acid amide. , Polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide, polyoxyethylene coconut oil fatty acid amide, polyoxyethylene palm oil fatty acid amide, polyoxyethylene rapeseed oil fatty acid amide, polyoxyethylene beef tallow fatty acid amide, etc. Examples include fatty acid amides having a polyalkylene oxide structure such as polyoxyalkylene fatty acid amide, and these are usually monoalkanolamides in which only one of n and o is 1 or more, It may be a di-alkanolamides any of o is 1 or more, or a mixture thereof.

  Specific compounds of the general formula (B2) include N-methyl-octylethanolamide, N-methyl-decylethanolamide, N-methyl-dodecylethanolamide, N-methyl-oleylethanolamide, coconut oil fatty acid N- Fatty acid N-alkyl monoalkanolamides such as fatty acid N-alkylethanolamides exemplified by methylethanolamide, palm oil fatty acid N-methylethanolamide, rapeseed oil fatty acid N-methylethanolamide, beef tallow fatty acid N-methylethanolamide, etc. Can be mentioned. Fatty acid N-alkyl monoalkanol amides are: Esomide HT / 15, Esomide HT / 60, Esomide O / 15 (above, manufactured by Lion Co., Ltd.), Amizole CME, Amizole SME, Amizole PCME, Amizole PLME-A, Amidette 2C, Amidette 5C, Amidette 10C, Amidette 2L-Y, Aminex HO (manufactured by Kawaken Fine Chemical Co., Ltd.), Stahome MF pellets, Stahome LIPA (manufactured by NOF Corporation), Aminone C-11S (manufactured by Kao Corporation) ) Is commercially available.

  Of the amide compounds (B), the compound represented by the general formula (B2) is preferable from the viewpoint of reducing the friction coefficient.

[Imide compound (C)]
The imide compound (C) has one or more imide groups in the molecule, and is preferably a succinimide. Examples of the succinimide include compounds represented by the following general formula (C1).

In the formula (C1), R ₆₉ is a hydrocarbon group having 20 to 150 carbon atoms, which may be saturated or unsaturated, aliphatic or aromatic, linear or branched, For example, an alkenyl group or an alkyl group can be mentioned. Moreover, s is an integer of 0-5.
As the alkenyl group or alkyl group having 20 to 150 carbon atoms, a polymer or copolymer of monoolefin or diolefin having 2 to 16 carbon atoms or a hydrogenated product thereof is usually used. Specific examples of the monoolefin include ethylene, propylene, butene, butadiene, decene, dodecene, hexadecene and the like. Among these monoolefins, in the present invention, butene is particularly preferred from the viewpoint of improving the cleanliness at high temperature and being easily available, and is a polybutenyl group which is a polymer thereof, and an alkyl group obtained by hydrogenating it. Hydrogenated polybutenyl groups are preferred. By setting the carbon number of the alkenyl group or alkyl group to 20 or more, the alkenyl group or the alkyl group can be sufficiently dissolved in a lubricating base oil and the like, and the dispersibility, which is the original function of succinimide, can also be exhibited. Moreover, it can prevent that a viscosity becomes high by setting it as 150 or less.

In the succinimide represented by the general formula (C1), an alkene having 20 to 150 carbon atoms and maleic anhydride are reacted under the conditions of a reaction temperature of 50 to 280 ° C., and the following general formula (C2): It can be obtained by heating and stirring the polyamine represented at a reaction temperature of 50 to 250 ° C.
At this time, the molar ratio of alkene having 20 to 150 carbon atoms and maleic anhydride can be adjusted at a ratio of 1: 5 to 5: 1, and the ratio of alkenyl succinic anhydride to polyamine (D2) is 1: 5. It can be adjusted at a ratio of ˜5: 1.

(In general formula (C2), t is an integer of 0 to 5.)

  Examples of the polyamine (C2) include, for example, ethylenediamine, propanediamine, butanediamine, alkylenediamine such as N-methyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, and diethylenetriamine, Examples include polyalkylene polyamines such as triethylenetetramine and tetraethylenepentamine, and polyalkylene polyamines having cyclic alkylene amines such as aminoethylpiperazine.

[Ester compound (D)]
The ester compound (D) is a compound having one or more hydroxyl groups in the molecule, and examples thereof include compounds represented by the following general formula (D1) or (D2).

In the formulas (D1) and (D2), R ₈₁ and R ₁₀₁ are each a hydrocarbon group having 1 to 32 carbon atoms. Such a hydrocarbon group may be saturated or unsaturated, and may be aliphatic or aromatic. It may be a straight chain, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic hydrocarbon group.
Examples of the hydrocarbon group represented by R ₈₁ and R ₁₀₁ include methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, Undecyl, decenyl, dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linole Group, nonadecyl group, icosyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacon group Group, decene trimer group, polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group and other aliphatic hydrocarbon groups, phenyl group, methylphenyl group, Examples thereof include aromatic hydrocarbon groups such as ethylphenyl group, dimethylphenyl group, propylphenyl group, trimethylphenyl group, butylphenyl group, and naphthyl group.
Here, the carbon number of the hydrocarbon groups R ₈₁ and R ₁₀₁ is preferably 8 to 32, 12 to 24 is more preferable.

R _{82 to} R ₈₅ and R _{102 to} R ₁₀₆ are each a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same as or different from each other. Such hydrocarbon groups may be saturated or unsaturated. It may be aliphatic or aromatic, and may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic hydrocarbon group. More specifically, methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, decenyl group, Dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linole, cyclopentyl, cyclohexyl Group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, aliphatic hydrocarbon group such as trimethylcyclohexyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group And aromatic hydrocarbon groups such as propylphenyl group, trimethylphenyl group, butylphenyl group, naphthyl group, etc., and r represents an integer of 1-20, preferably 1-12, more preferably 1-10.
In the general formula (D1), all of R ₈₂ to R ₈₅ is a hydrogen atom, or R ₈₂ to R _84, but it is preferable that both R ₈₅ together with a hydrogen atom is a hydrocarbon group. In the general formula (D2), it is preferable that all of R ₁₀₂ to R ₁₀₆ is a hydrogen atom.

The compound represented by the general formula (D1) is obtained, for example, by a reaction between a fatty acid and an alkylene oxide.
Here, examples of the fatty acid for obtaining the compound represented by the general formula (D1) include lauric acid, myristic acid, palmitic acid, oleic acid, beef tallow fatty acid, coconut oil fatty acid and the like. Examples of the alkylene oxide include alkylene oxides having 2 to 12 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, octylene oxide, decylene oxide, and dodecylene oxide. Is mentioned.
Examples of the compound of the general formula (D1) include polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate. Moreover, the compound of general formula (D1) is nonion (L-2, L-4, S-2, S-4, S-6, S-10, S-15, S-15K, S-15.4. , O-2, O-3, O-4, O-5, O-6) (manufactured by Lion Corporation), Ionette series (MS-400, MS-1000, DL-200 and DS-4000, MO-400) , MO-600, DO-400, DO-600) (manufactured by Sanyo Chemical Industries, Ltd.) is commercially available.

Examples of the compound represented by the general formula (D2) include glycerol fatty acid monoesters such as glycerol monolaurate, glycerol monostearate, glycerol monomysterate, and glycerol monooleate.
The compound represented by the general formula (D2) includes, as commercially available products, UNIGURI GO-102R, UNIGURI GO-106, UNIGLY GL-106, UNIGLY GS-106 (manufactured by NOF Corporation), Ryoto Polyglycerester L- 10D, Ryoto-polyglyceryl ester L-7D, Ryoto-polyglycerol ester M-10D, Ryoto-polyglycerol ester M-7D, Ryoto-polyglycerol ester P-8D, Ryoto-polyglycerol ester SWA-20D, Ryoto-polyglycerol ester Ryoto-polyglycerol ester SWA-10D, Ryoto polyglycerester O-50D, Ryoto polyglycerester O-15D, Ryoto polyglycerate ER-60D (manufactured by Mitsubishi Chemical Foods Co., Ltd.), NIKKOL DGMO-CV, NIKKOL DGMO-90V, IKKOL Tetraglyn1-OV, NIKKOL Decaglyn1-OV, NIKKOL Decaglyn 1-LN, NIKKOL Decaglyn 5-HS, NIKKOL Decaglyn 5-OV, NIKKOL Decaglyn 7-OV, NIKKOL Decaglyn 10-OV, NIKKOL Decaglyn 10-MAC, NIKKOL Decaglyn PR- 20 (above, manufactured by Nikko Chemicals Co., Ltd.) can be obtained.

[Alcohol compound (E)]
The alcohol compound (E) is a compound having one or more hydroxyl groups in the molecule, and examples thereof include compounds represented by the following general formulas (E1), (E2), (E3) and the like.

In the general formulas (E1) to (E3), R ₇₁ , R ₉₁ and R ₁₁₁ are each a hydrocarbon group having 1 to 32 carbon atoms. Such hydrocarbon group may be saturated or unsaturated, It may be aliphatic or aromatic, and may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, or an aromatic hydrocarbon group. Examples of the hydrocarbon group in R ₇₁ , R ₉₁ and R ₁₁₁ include methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, Decyl, undecyl, decenyl, dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl Group, linole group, nonadecyl group, icosyl group, eicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, Triacontyl group, descent trimer group, polybutene group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group and other aliphatic hydrocarbon groups, phenyl group, methylphenyl group, Examples thereof include aromatic hydrocarbon groups such as ethylphenyl group, dimethylphenyl group, propylphenyl group, trimethylphenyl group, butylphenyl group, and naphthyl group.
As the hydrocarbon group for R ₇₁ , R ₉₁ and R _111, a hydrocarbon group having 8 to 24 carbon atoms is preferable, and a hydrocarbon group having 8 to 18 carbon atoms is more preferable.

R _{72 to} R ₇₅ , R _{92 to} R ₉₈ , and R _{112 to} R ₁₁₈ are each a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same as or different from each other. Such a hydrocarbon group may be saturated or unsaturated, may be aliphatic or aromatic, may be linear, branched or cyclic, for example, an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, Or an aromatic hydrocarbon group is mentioned. More specifically, methyl group, ethyl group, propyl group, butyl group, butenyl group, hexyl group, hexenyl group, octyl group, octenyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, decenyl group, Dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linole, cyclopentyl, cyclohexyl Group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, dimethylcyclohexyl group, aliphatic hydrocarbon group such as trimethylcyclohexyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group Group, propylphenyl group, trimethylphenyl group, butylphenyl group, an aromatic hydrocarbon group and a naphthyl group.
As this hydrocarbon group, a C1-C16 thing is preferable, A C1-C12 thing is more preferable, A C1-C10 thing is especially preferable.
Moreover, although q shows the integer of 0-20, Preferably it is 0-12, More preferably, it is 0-10.
In the general formula (E1), it is preferable that all of R _{72 to} R ₇₅ are hydrogen atoms, or any one is a hydrocarbon group and the other is a hydrogen atom. In the general formula (E2), A is preferably an oxygen atom, and any of R _{92 to} R ₉₈ is preferably a hydrogen atom. In general formula (E3), it is preferable that all of R _{112 to} R ₁₁₇ are hydrogen atoms, and R ₁₁₇ is a hydrocarbon group.

  The specific compound of the general formula (E1) is a compound having q of 0 and having one hydroxyl group in the molecule, such as hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, tetradecanol. , Pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, triacosanol, etc. Chain alkanols; hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadeceno Straight chain alkenols such as hexadecenol, pentadecenol, hexadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, eisenol, docosenol, tetracosenol, pentacosenol, hexacosenol, heptacosenol, heptacosenol, octacosenol, nonacosenol and triaconsenol; 2-ethylhexanol; 1-methylheptadecanol, 1-hexylheptanol, isodecanol, isotridecanol and other branched alkanols; isohexenol, 2-ethylhexenol, isotridecenol, 1-methylheptadecenol, 1-hexylheptenol And alcohol compounds such as branched alkenols such as isotridecenol and isooctadecenol.

Moreover, as a specific compound shown by General formula (E1) whose q is 1-20, the alkylene oxide adduct and styrene oxide adduct of said various alcohol compound are mentioned. Here, examples of the alkylene oxide include alkylene oxides having 2 to 12 carbon atoms. Specific examples include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, octylene oxide, decylene oxide, and dodecylene oxide. Can be mentioned.
The number of moles of alkylene oxide added is preferably 1-20, more preferably 1-10, and particularly preferably 1-7, per mole of alcohol. Within this range, the solubility in mineral oil is further improved.
The alkylene oxide may be added singly or in combination of two or more, and when mixed and added, the alkylene oxide may be in a block form, a random form, or a combination thereof. Specifically, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene / ethylene glycol (bonding mode of oxypropylene and oxyethylene: random), polyoxybutylene / ethylene glycol (bonding mode of oxypropylene and oxyethylene: Random), polyoxyethylene / polyoxypropylene / polyoxyethylene glycol (bonding mode of oxypropylene and oxyethylene: block).
Further, the carbon number of the alcohol compound (E) is preferably C12 to C30, preferably C12 to C24, and particularly preferably C12 to C18. When the carbon number is within these ranges, the solubility in mineral oil is good.

  Compounds represented by general formula (E1) in which q is 1 to 20 are commercially available as nonion (K-204, K-220, K-230), persoft (NK-60, NK-60C, NK- 100, NK-100C), nonion (P-208, P-210, P-213, E-202, E-202S, E-205, E-205S, E-212, E-215, E-230, S -202, S-207, S-215, S-220, EH-204, EH-208, ID-203, ID-206, ID-209, EAD-13, TA-405, TA-407, TA-409 TA-411, TA-412, TA-413, TA-415, TA-418) (above, manufactured by Lion Corporation), BLAUNON series (EL-1303, EN-1502, EN-905, EH) 2, EH-4, DAL-2, DAH-3, NDB-2040, DAP-1008, ELP-0809B, ELP-1608B, EHP-4, BPO-3), FINESURF series (NDB-800, IDEP-608, IDEP-604, IDEP-802, IDEP-560, IDEP-580, IDEP-9161, IDEP-5010, IDEP-9010, IDEP-7045, IDEP-7085, 5010, 7045, 7085, 9010, TDP-0108, TDP- 0109, TDP-0255, TDP-0633K, TDP-1033, TDP-1055), WONDERSURF series (100, 140, NDR-800, NDR-1000, NDR-1400, RL-80, RL-100, RL-80, RL 100, RL-140, ID-50, ID-70, ID-90, S-800, S-1000, S-1400 (above, manufactured by Aoki Yushi Kogyo Co., Ltd.), Lionol series (TDL-20, TDL) -30, TDL-50) (above, manufactured by Lion Corporation), New Pole Series (LB-285, LB-625, LB-1715, 50HB-100, 50HB-260, 50HB-400, 50B-2000, 50HB- 5100, PP-400) (manufactured by Sanyo Chemical Industries, Ltd.).

  Examples of the compound represented by the general formula (E2) include 3- (dodecyloxy) propane-1,2-diol, 3- (tetradecyloxy) propane-1,2-diol, 3- (hexadecyloxy) propane- 1,2-diol, 3- (octadecyloxy) propane-1,2-diol, 3- (oleyloxy) propane-1,2-diol, 1,2-dodecanediol, 1,2-tetradecanediol, 1, Examples include 2-hexadecanediol and 1,2-octadecanediol.

  Examples of the compound represented by the general formula (E3) include lauryl glycol hydroxypropyl ether, myristyl glycol hydroxypropyl ether, stearyl glycol hydroxypropyl ether, oleyl glycol hydroxypropyl ether, and the like. Moreover, as a commercial item of the compound shown by general formula (E3), Visco Safe LPE, Visco Safe LMPE (above, Kawaken Fine Chemical Co., Ltd. product) etc. are mentioned.

  Among the alcohol compounds (E), a compound represented by the general formula (E2) is preferable from the viewpoint of reducing the friction coefficient.

  Of the compounds (A) to (E), the friction can be reduced, and from the viewpoint of enhancing the wear resistance, the compounds (A) to (C) are preferable, and the compounds (A) or ( B) is more preferred.

  In addition, the boric acid derivatives include orthoboric acid, metaboric acid, tetraboric acid, boron oxide, boron trifluoride, boron tribromide, boron trichloride and other boron halides, trimethyl borate, triethyl borate, boron Examples thereof include boric acid esters such as tributyl acid, triisopropyl borate, and tributyl borate.

The lubricating additive according to the present invention was obtained by heating and stirring an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative at a temperature of 100 ° C. or higher and 150 ° C. or lower, for example, and reacting them. A boron-containing compound, usually containing a tri-coordinate boron-containing compound and a mixture of tetra-coordinate boron-containing compounds, but consisting only of a tri-coordinate boron-containing compound, Also good.
When the organic compound and boric acid are heated and stirred at a temperature higher than 150 ° C., the amount of tri-coordinate boron compound is reduced, the effect of reducing the friction coefficient is difficult to obtain, and the viscosity may increase. is there. In particular, when the amide compound (B) is treated at a high temperature, the friction coefficient tends to increase.
In addition, if heating and stirring is not performed at a temperature of 100 ° C. or higher, moisture generated by the dehydration reaction remains, and the remaining moisture causes fuel oil, lubricating oil, and the like to cause hydrolysis of other additives, thereby causing fuel oil. It promotes the deterioration of oil and lubricating oil, etc., causing unstable performance.

In the present invention, the organic compound having a hydroxyl group or amino group and boric acid are preferably heated and stirred for 30 minutes to 30 hours in the temperature range of 100 to 150 ° C., and heated and stirred for 30 minutes to 10 hours. More preferably.
In the present invention, the boron-containing compound of the present invention can be obtained by heating and stirring an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative at a temperature of 100 ° C. or higher and 130 ° C. or lower. preferable.

Specifically, in the present invention, first, an organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative are mixed and stirred and mixed at less than 100 ° C. (for example, around 80 ° C.). By dehydrating, borate and boric acid dispersions are obtained. Thereafter, the temperature is increased gradually or stepwise, and dehydrated while stirring and mixing within a temperature range of 100 to 150 ° C., preferably 100 to 130 ° C., thereby borate and borate esters. , Boric acid amide, and a boron-containing compound consisting of a dispersion of boric acid and a boric acid dehydration condensate, or a lubricating additive consisting of a mixture thereof.
In this operation, it is preferable to raise the temperature stepwise or gradually even in the temperature range of 100 to 150 ° C.
The heating and stirring of the organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative may be performed in the presence of a solvent, for example, an organic solvent such as hydrocarbon oil.
The timing of adding the solvent is not particularly limited, and may be added to the organic compound before mixing the boric acid or boric acid derivative with the organic compound, or added after mixing the boric acid or boric acid derivative with the organic compound. Also good. Moreover, after heating for a predetermined time in the temperature range of 100-150 degreeC, a solvent may be added and it may heat for a predetermined time further in the temperature range of 100-150 degreeC after that.
In addition, when stirring with heating, the pressure may be reduced to facilitate removal of moisture.
However, in the present invention, the organic compound having a hydroxyl group or amino group and boric acid or a boric acid derivative are mixed, heated and stirred, and heated to a temperature higher than 150 ° C. in a series of operations to obtain a lubricant additive. It is preferred that it is not heated to a temperature higher than 130 ° C. Thus, in the present invention, since it is not heated at a high temperature, a large amount of tricoordinate boron compounds can be generated.

  The lubricating additive is heated and stirred at a ratio of 1: 0.01 or more and 1:10 or less of the number of moles of the organic compound having a hydroxyl group or amino group and the number of moles of boric acid or boric acid derivative. The compound obtained by heating and stirring at a ratio of 1: 0.05 or more and 1: 8 or less is more preferable. Here, if the ratio of the number of moles is 1: 0.01 or more, a lubricating additive having a low friction coefficient and excellent wear resistance can be obtained. On the other hand, when the molar ratio is 1:10 or less, the solubility of the lubricating additive in the lubricating base oil and fuel oil can be improved.

The lubricating additive of the present invention has a high content of tricoordinate boron-containing compounds. Specifically, the tricoordinate boron-containing compound is the sum of tricoordinate and tetracoordinate boron-containing compounds. It is contained in a molar ratio of 0.47 or more with respect to the amount.
In the present invention, if the ratio of the tricoordinate boron-containing compound is less than 0.47, the friction coefficient of the lubricating oil or fuel oil containing the lubricating additive is increased, and the effects of the present invention cannot be obtained. .
Further, from the viewpoint of lowering the friction coefficient and lowering the viscosity of the lubricating oil or fuel oil, the ratio is preferably 0.50 or more, more preferably 0.55 or more, and 0 It is particularly preferable to be .65 or more. In addition, it exists in the tendency which can reduce a friction coefficient, so that the said ratio is large, and it is preferable that it is 1.0 or less.
The ratio of such a tricoordinate boron-containing compound and a tetracoordinate boron-containing compound can be measured by, for example, ¹¹ B-NMR measurement as a BF ₃ · OEt ₂ standard (0 ppm). In this ¹¹ B-NMR measurement, the peak of the tricoordinate boron-containing compound appears at 5 to 25 ppm, and the peak of the tetracoordinate boron-containing compound appears at −10 to 5 ppm. It is possible to calculate the ratio by calculating.

The lubricating additive of the present invention has a chemical shift peak of 5 to 25 ppm with respect to the integrated value of the chemical shift of -10 to 25 ppm when measured by ¹¹ B-NMR as BF ₃ · OEt ₂ standard (0 ppm). The ratio of the integral values is 0.47 or more and 1.0 or less.
In the ¹¹ B-NMR measurement using the BF ₃ · OEt ₂ standard (0 ppm), as described above, a tricoordinate peak appears at a chemical shift of −10 to 25 ppm. When it is 47 or more, the ratio of tricoordination in the lubricating additive increases, and the above-described effects of the present invention can be obtained. In addition, from the viewpoint of lowering the viscosity of the lubricating oil or fuel oil with a low friction coefficient, the ratio of the integrated values is preferably 0.50 or more, more preferably 0.55 or more, Most preferably, it is 0.65 or more. Further, the larger the ratio of the integral values, the smaller the friction coefficient tends to be, and it may be 1.0 or less.

Further, in a boron-containing compound (lubricant additive) obtained by acting an organic compound having an amino group and boric acid or a boric acid derivative, the ratio of the boron atom amount to the nitrogen atom amount contained in the compound (B / N ratio) ) Is preferably 0.6 or more on a mass basis, and more preferably 0.7 or more. Further, the B / N ratio is not particularly limited, but is preferably 2.0 or less, and more preferably 1.5 or less. By setting the B / N ratio to 0.6 or more, the lubricating oil composition can be appropriately reduced in friction.
In the lubricating additive, the boron atom content is preferably 0.1 to 3% by mass, more preferably 1 to 3% by mass.

  As described above, the lubricating additive of the present invention has a high effect of reducing the friction coefficient and has high wear resistance and can be suitably used as a friction modifier.

[Lubricant]
The lubricating additive of the present invention is used by being blended with hydrocarbon oil or synthetic oil which is a lubricating base oil.
In the lubricating oil composition obtained by blending the lubricating additive of the present invention with the lubricating base oil, the lubricating additive is usually 0.01% by mass or more and 50% by mass or less, preferably in the lubricating oil composition. It is blended in the range of 0.1 to 30% by mass, more preferably 0.1 to 10% by mass.
In addition, the lubricating oil composition contains antioxidants, antiwear agents, detergent dispersants, viscosity index improvers, fluidity, and the like, which are usually blended in the lubricating oil, as long as the effects of the lubricating additive of the present invention are not impaired. An improver, other friction modifiers and other additives may be added.
The lubricating base oil is not particularly limited as long as it is generally used as a base oil for lubricating oil, but preferably has a kinematic viscosity at 100 ° C. in the range of 1 mm ² / s to 50 mm ² / s. Those in the range of ² mm ² / s to 20 mm ² / s are more preferable. The pour point, which is an indicator of the low temperature fluidity of the base oil, is not particularly limited, but is usually preferably −10 ° C. or lower.

In addition, examples of the lubricating base oil include hydrocarbon oils and synthetic oils.
The hydrocarbon oil may be, for example, a lubricating base oil such as paraffinic mineral oil, naphthenic mineral oil, aromatic mineral oil, or a fraction of fuel oil such as gasoline, kerosene, light oil, solvent refining, hydrogenation, etc. Any purification method such as purification or hydrogenolysis can be used.
As the synthetic oil, poly α-olefins, polyphenyl ether, alkylbenzene, alkylnaphthalene, ester oil, glycol-based or polyolefin-based synthetic oil, and the like can be used. More specifically, poly-α-olefin, ethylene-α-olefin copolymer, polybutene, alkylbenzene, alkylnaphthalene, polyalkylene glycol, polyphenyl ether, alkyl-substituted diphenyl ether, polyol ester, dibasic acid ester, carbonate ester Synthetic oils such as silicone oil, fluorinated oil, GTL (Gas to Liquids), paraffinic mineral oil, naphthenic mineral oil, or refined mineral oils obtained by refining them can be used.

The lubricating additive of the present invention can lower the friction coefficient of the lubricating oil, and can further improve the wear resistance and viscosity. Therefore, the lubricating oil composition containing the lubricating additive can be expected to improve fuel efficiency compared to conventional gasoline engine oil.
The lubricating oil composition containing the lubricating additive of the present invention is suitably used as a lubricating oil for internal combustion engines such as gasoline engines, diesel engines, and two-cycle engines, as well as gear oils, bearing oils, and gear shifts. It is also suitably used as machine oil, shock absorber oil, or industrial lubricating oil.

[Fuel oil]
The above-described lubricating oil additive (boron-containing compound) of the present invention can also be used as a fuel oil additive to be added to fuel oil, and is used by being blended with fuel oil composed of hydrocarbon oil or the like. .
The fuel oil to which the lubricating additive (fuel oil additive) is added is not particularly limited, and examples thereof include gasoline, kerosene, light oil, heavy oil, and jet fuel.
In the fuel oil composition obtained by blending the lubricant additive of the present invention with the fuel oil, the lubricant additive is preferably 0.001% by mass or more and 1% by mass or less based on the total amount of the fuel oil composition. Preferably it is 0.01 mass% or more and 1.0 mass% or less.
The fuel oil composition includes a colorant, an antioxidant, a detergent, a metal deactivator, an octane number improver, a low temperature fluidity improver, and a lubricity, as long as the effects of the lubricating additive of the present invention are not impaired. You may mix | blend additives, such as an improver and a cetane number improver.
Since the fuel oil composition is blended with the lubricating additive of the present invention, the friction coefficient is reduced and the viscosity is lowered, so that fuel efficiency and combustion efficiency are improved as compared with conventional fuel oil compositions. be able to.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these examples. The lubricating additive was evaluated according to the following method.
(1) ¹¹ B-NMR
BF ₃ · OEt ₂ was used as an external standard (0 ppm), and measurement was performed in deuterated chloroform at a pulse width of 90 °.
(2) Friction characteristics (friction coefficient and wear width)
To the base oil A (kinematic viscosity at 100 ° C. = 11.01 mm ² / s, viscosity index = 105), 1.0% by mass of the boron-containing compounds of Examples and Comparative Examples were added and mixed uniformly. The friction coefficient and the wear width were measured with a disk-type reciprocating friction tester (TE77 Cameron print tester). The ball material was SUJ2, the ball diameter was 10 mm, and the disk material was SUJ2. The load was increased stepwise from 40N to 240N in steps of 40N while performing the test for 1800 seconds at a vibration frequency of 20Hz, an amplitude of 15.0mm, and a temperature of 80 ° C. And the friction coefficient in 80N load was calculated | required, and the wear width was measured after completion | finish of a test.
(3) Viscosity characteristics Viscosity was determined by measuring the viscosity at 100 ° C. (g / cm ³ · cP) using an acoustic viscometer eCuP manufactured by VECTRON INTERNATIONAL.
(4) Measurement of boron content and nitrogen content The boron content is a value measured according to ASTM D4951. The nitrogen content is a value measured according to JIS K2609.

Example A-1
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 267 g (0.75 mol) of stearyl diethanolamine (Nymene S-202), mineral oil A (100 ° C.) charge of kinematic viscosity = 4.12mm ² / s, viscosity index = 134) 40 g, under nitrogen stream, and heated to 70 to 80 ° C.. To this mixture, 43.3 g (0.60 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. The obtained mixture was subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to obtain 293.5 g of Boron-containing stearyl diethanolamine was obtained. This boron-containing stearyldiethanolamine had a boron content of 2.0 mass%, a nitrogen content of 3.1 mass%, and a boron atom / nitrogen atom mass ratio of 0.65.

Example A-2
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, polyoxyethylene stearylamine (a + b = 4) represented by the general formula (A1) (Nymin S-204) 435 g (0.98 mol) was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 43.3 g (0.60 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), thereby containing 433 g of boron. Polyoxyethylene stearylamine was obtained. The boron-containing polyoxyethylene stearylamine had a boron content of 1.7% by mass, a nitrogen content of 3.2% by mass, and a boron atom / nitrogen atom mass ratio of 0.53.

Example A-3
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, polyoxyethylene tallow amine (a + b = 5) (esomine) represented by the general formula (A1) T / 15) 382 g (0.80 mol) was charged and heated to 70 to 80 ° C. in a nitrogen stream. To this mixture, 49.5 g (0.80 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 90 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. By subjecting the obtained mixture to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), 433 g of boron-containing poly Oxyethylene beef tallow amine was obtained. This boron-containing polyoxyethylene beef tallow amine had a boron content of 1.7 mass%, a nitrogen content of 2.2 mass%, and a mass ratio of boron atom / nitrogen atom of 0.78.

Example A-4
Example A-3 except that polyoxyethylene stearylamine (a + b = 5) (esomine S / 15) represented by general formula (A1) was used instead of polyoxyethylene beef tallow amine (esomine T / 15) The reaction was carried out in the same manner to obtain boron-containing polyoxyethylene stearylamine. This boron-containing polyoxyethylene stearylamine had a boron content of 1.7% by mass and a nitrogen content of 1.8% by mass, and the mass ratio of boron atom / nitrogen atom was 0.95.

Example A-5
The same as Example A-3 except that polyoxyethylene oleylamine (a + b = 7) (esomine O / 17) represented by general formula (A1) was used instead of polyoxyethylene beef tallow amine (esomine T / 15) The reaction was carried out to obtain a boron-containing polyoxyethylene oleylamine. This boron-containing polyoxyethylene oleylamine had a boron content of 1.8% by mass.

Example A-6
Example A-3 except that instead of polyoxyethylene beef tallow amine (esomine T / 15), polyoxyethylene beef tallow amine (a + b = 10) (Nymeen T2-210) represented by general formula (A1) was used Reaction was similarly carried out to obtain a boron-containing polyoxyethylene tallow amine represented by the general formula (A1). This boron-containing polyoxyethylene beef tallow amine had a boron content of 1.4% by mass.

Example A-7
Example A-3 except that polyoxyethylene stearylamine (a + b = 10) (Nymine S-210) represented by the general formula (A1) was used instead of polyoxyethylene beef tallow amine (esomine T / 15) Reaction was similarly performed and the boron containing polyoxyethylene stearylamine shown by general formula (A1) was obtained. This boron-containing polyoxyethylene stearylamine had a boron content of 1.3% by mass.

Example A-8
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 114.6 g (0.80 mol) of N-cyclohexylethanolamine and 1,2-epoxide decane 147.5 g (0.80 mol) was charged, and the mixture was heated and stirred at 120 ° C. for 5 hours under a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 2 hours to give 1- [cyclohexyl (2-hydroxyethyl) amino] dodecane. 2-ol was obtained.
Under a nitrogen stream, 49.5 g (0.80 mmol) of boric acid was gradually added to the reaction product and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 90 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), so that 351 g of boron-containing 1 -[Cyclohexyl (2-hydroxyethyl) amino] dodecan-2-ol was obtained. The obtained boron-containing compound had a boron content of 2.3% by mass.

Example A-9
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 200.5 g (1.40 mol) of N-cyclohexylethanolamine and 1,2-epoxide decane 258.1 g (1.40 mol) was charged, and the mixture was heated and stirred at 120 ° C. for 5 hours under a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 2 hours to give 1- [cyclohexyl (2-hydroxyethyl) amino] dodecane. 2-ol was obtained.
Under a nitrogen stream, 43.3 g (0.70 mmol) of boric acid was gradually added to the reaction product, and the mixture was stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 158 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), thereby 609 g of boron-containing 1 -[Cyclohexyl (2-hydroxyethyl) amino] dodecan-2-ol was obtained. The obtained boron-containing compound had a boron content of 1.2% by mass.

Reference Example A-10
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 99.2 g (1.00 mol) of N-cyclohexylamine and 1,2-epoxide decane 368 were added. .6 g (2.00 mol) was charged, and the mixture was heated and stirred at 120 ° C. for 5 hours under a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 3 hours, and N, N-bis (2-hydroxydodecyl) -N— Cyclohexylamine was obtained.
Under a nitrogen stream, 61.8 g (1.00 mol) of boric acid was gradually added to the reaction product and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 113 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), so that 578 g of boron-containing N , N-bis (2-hydroxydodecyl) -N-cyclohexylamine was obtained. The obtained boron-containing compound had a boron content of 0.9% by mass.

Example A-11
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 109.7 g (0.80 mol) of 2- (phenylamino) ethanol and 1,2- 147.5 g (0.80 mol) of epoxide decane was charged, and heated and stirred at 120 ° C. for 5 hours under a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 3 hours to give 1- [N- (2-hydroxyethyl). Anilino] dodecan-2-ol was obtained.
Under a nitrogen stream, 49.5 g (0.80 mmol) of boric acid was gradually added to the reaction product and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Then, 113 g of mineral oil A was added and heated and stirred at 120 ° C. for 30 minutes to obtain 423 g of boron-containing 1- [N- (2-hydroxyethyl) anilino] dodecan-2-ol. The obtained boron-containing compound had a boron content of 1.9% by mass.

Reference Example A-12
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 192.0 g (1.40 mol) 2- (phenylamino) ethanol and 1,2- Epoxydodecane (258.1 g, 1.40 mol) was charged, and the mixture was heated and stirred at 120 ° C. for 5 hours under a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 3 hours, and 1- [N- (2-hydroxyethyl) Anilino] dodecan-2-ol was obtained.
Under a nitrogen stream, 43.3 g (0.70 mmol) of boric acid was gradually added to the reaction product, and the mixture was stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Then, 113 g of mineral oil A was added and heated and stirred at 120 ° C. for 30 minutes to obtain 589 g of boron-containing 1- [N- (2-hydroxyethyl) anilino] dodecan-2-ol. The obtained boron-containing compound had a boron content of 0.9% by mass.

Reference Example A-13
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube, and a nitrogen blowing tube, 93.1 g (1.00 mol) of aniline and 368.6 g of 1,2-epoxydodecane ( 2.00 mol) was added, and the mixture was heated and stirred at 120 ° C. for 5 hours in a nitrogen atmosphere, and further heated and stirred at 160 ° C. for 3 hours to obtain N, N-bis (2-hydroxydodecyl) -aniline.
Under a nitrogen stream, 61.8 g (1.00 mmol) of boric acid was gradually added to the reaction product and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Then, 113 g of mineral oil A was added and heated and stirred at 120 ° C. for 30 minutes to obtain 565 g of boron-containing N, N-bis (2-hydroxydodecyl) -aniline. The obtained boron-containing compound had a boron content of 0.9% by mass.

Example A-14
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, N, N ′, N′-Tris (2-hydroxyethyl) -N-tallow- 1,7-diaminopropane (esododumine T / 13) 57.7 g (0.15 mol) was charged and heated to 70 to 80 ° C. under a nitrogen stream. To this mixture, 9.3 g (0.15 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. The obtained mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), thereby 47.3 g of boron. Containing N, N ′, N′-tris (2-hydroxyethyl) -N-tallow-1,3-diaminopropane was obtained. The obtained boron-containing compound had a boron content of 2.7% by mass.

Example A-15
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 129.2 g (1.00 mol) of 1-octylamine and 1,2-epoxide decane 368 .6 g (2.00 mol) was charged, and the mixture was heated and stirred at 80 ° C. for 2 hours and 120 ° C. for 2 hours, and further heated and stirred at 160 ° C. for 12 hours, and N, N-bis (2 -Hydroxydodecyl) -N-octylamine was obtained.
Under a nitrogen stream, 61.8 g (1.00 mmol) of boric acid was gradually added to the reaction product and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Mineral oil A113g was added and it heat-stirred at 120 degreeC for 30 minutes. By subjecting the obtained mixture to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), 609 g of boron-containing N , N-bis (2-hydroxydodecyl) -N-octylamine was obtained. The obtained boron-containing compound had a boron content of 1.7 mass%, a nitrogen content of 2.1 mass%, and a mass ratio of boron atom / nitrogen atom was 0.79.

Example A-16
An autoclave equipped with a stirrer, a heating device, a thermometer and a pressure gauge was charged with 107.0 g (0.40 mol) of oleylamine and 46.5 g (0.80 mol) of propylene oxide, and at 80 ° C. for 2 hours under a nitrogen atmosphere. The mixture was stirred at 120 ° C. for 2 hours and 140 ° C. for 2 hours, and further stirred at 160 ° C. for 3 hours to obtain 150 g of N, N-bis (2-hydroxypropyl) -N-oleylamine. .
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, 150 g (0.39 mol) of N, N-bis (2-hydroxypropyl) -N-oleylamine was added. And heated to 70-80 ° C. under a nitrogen atmosphere. Under a nitrogen stream, 24.2 g (0.39 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 44 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), so that 178 g of boron-containing N , N-bis (2-hydroxypropyl) -N-oleylamine was obtained. The obtained boron-containing compound had a boron content of 2.1% by mass, a nitrogen content of 2.7% by mass, and a boron / nitrogen atom mass ratio of 0.77.

Example A-17
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 194.7 g of N-oleyl-1,3-diaminopropane (Nissan Amine DOB-R) (0.60 mol) was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 37.1 g (0.60 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Furthermore, it heated and stirred at 90-100 degreeC for 2 hours and 110 degreeC-120 degreeC for 3 hours, spin-dry | dehydrating. Thereafter, 60 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), so that 253 g of boron-containing N -Oleyl-1,3-diaminopropane was obtained. The obtained boron-containing compound had a boron content of 2.9% by mass.

Reference Example B-1
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 44.5 g (0.15 mol) of coconut oil fatty acid diethanolamide (Amizole CDE), It heated at 70-80 degreeC under nitrogen stream. To this mixture, 9.3 g (0.15 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, while dehydrating, the mixture was heated and stirred at 90 to 100 ° C. for 2 hours and at 110 to 120 ° C. for 3 hours to obtain 42.5 g of boron-containing coconut oil fatty acid diethanolamide. The obtained boron-containing compound had a boron content of 3.4% by mass.

Example B-2
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 29.7 g of a mixture of coconut oil fatty acid diethanolamide and coconut oil fatty acid glycerin (Amizole FDE), 100 ml of toluene was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 6.2 g (0.10 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, while dehydrating, the mixture was stirred at 90 to 100 ° C. for 2 hours and with heating under reflux for 3 hours. After filtration, toluene was distilled off over 3 hours while raising the temperature from 70 ° C. to 120 ° C. under reduced pressure using a vacuum evaporator to obtain 27.5 g of a boron-containing compound (heating stirring time at 100 to 120 ° C. : 2 hours). The obtained boron-containing compound had a boron content of 2.8% by mass, a nitrogen content of 4.2% by mass, and a mass ratio of boron atom / nitrogen atom was 0.67.

Example B-3
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 37.2 (0.10 mol) g of stearyl diethanolamide (Amizole SDE) and 100 ml of toluene were added. The mixture was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 6.2 g (0.10 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, while dehydrating, the mixture was stirred at 90 to 100 ° C. for 2 hours and with heating under reflux for 3 hours. After filtration, toluene was distilled off over 3 hours while raising the temperature from 70 ° C. to 120 ° C. under reduced pressure using a vacuum evaporator to obtain 30.0 g of boron-containing stearyl diethanolamide (heating at 100 to 120 ° C. Stirring time: 2 hours). This boron-containing stearyl diethanolamide had a boron content of 1.8% by mass, a nitrogen content of 3.8% by mass, and a boron atom / nitrogen atom mass ratio of 0.47.

Example B-4
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, a polyoxyethylene oleic acid amide represented by the general formula (B1) (n = 5, o = 0) (esomide O / 15) 48.8 (0.10 mol) g was charged and heated to 70 to 80 ° C under a nitrogen stream. To this mixture, 6.2 g (0.10 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, the mixture was stirred at 90-100 ° C. for 2 hours and at 110-120 ° C. for 8 hours while dehydrating. The obtained mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to obtain 40.5 g of boron. Containing polyoxyethylene oleic acid amide was obtained. This boron-containing polyoxyethylene oleic acid amide had a boron content of 2.2% by mass.

Example B-5
In a separable flask reaction vessel equipped with a stirrer, heating device, thermometer, Dean-Stark tube, Dimroth condenser tube and nitrogen blowing tube, polyoxyethylene coconut oil fatty acid monoethanolamide (n = 11, o = 0) (Nymid MF-210) 517.8 g was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 49.5 g (0.80 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, the mixture was stirred at 90-100 ° C. for 2 hours and at 110-120 ° C. for 8 hours while dehydrating. Mineral oil A90g was added and it heat-stirred at 120 degreeC. By subjecting the obtained mixture to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), 607 g of boron-containing poly Oxyethylene coconut oil fatty acid monoethanolamide was obtained. This boron-containing compound had a boron content of 1.4% by mass.

Example B-6
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 310.0 g of coconut oil fatty acid N-methylethanolamide (Aminone C-11S), It heated at 70-80 degreeC under nitrogen stream. To this mixture, 61.8 g (1.00 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, the mixture was stirred at 90-100 ° C. for 2 hours and at 110-120 ° C. for 8 hours while dehydrating. Thereafter, 68 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to give 356 g of boron-containing palm. Oil fatty acid N-methylethanolamide was obtained. The obtained boron-containing compound had a boron content of 2.9% by mass.

Reference Example B-7
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 310.0 g of coconut oil fatty acid N-methylethanolamide (Aminone C-11S), It heated at 70-80 degreeC under nitrogen stream. To this mixture, 61.8 g (1.00 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, while dehydrating, the mixture was heated and stirred at 90 to 100 ° C. for 2 hours, 110 to 120 ° C. for 1 hour, 130 to 140 ° C. for 1 hour, and 150 to 160 ° C. for 3 hours. Thereafter, 68 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The resulting mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retention particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to give 356 g of boron-containing palm. Oil fatty acid N-methylethanolamide was obtained. The obtained boron-containing compound had a boron content of 3.5% by mass.

Example C-1
550 g of polybutene (Mn: 960), 1.5 g of cetyl bromide and 59 g (0.6 mol) of maleic anhydride were placed in a 1 L autoclave, and the reaction was carried out at 240 ° C. for 5 hours after purging with nitrogen. The temperature was lowered to 215 ° C., unreacted maleic anhydride and cetyl bromide were distilled off under reduced pressure, the temperature was lowered to 140 ° C. and filtered. The yield of the obtained polybutenyl succinic anhydride was 550 g, and the saponification value was 86 mgKOH / g.
In a 500 mL separable flask, 200 g of polybutenyl succinic anhydride, 7.2 g (0.056 mol) of aminoethylpiperazine (AEP), 4.3 g (0.042 mol) of diethylenetriamine (DETA), triethylenetetraamine ( TETA) 6.1 g (0.042 mol) and 150 neutral mineral oil 100 g were added and reacted at 150 ° C. for 2 hours under a nitrogen stream. The temperature was raised to 200 ° C., and unreacted AEP, DETA and produced water were distilled off under reduced pressure. The yield of the obtained polybutenyl succinimide was 315 g, and the base value (hydrochloric acid method) was 30.8 mg KOH / g.
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 110 g of polybutenyl succinimide and heated to 70-80 ° C. under a nitrogen stream. did. To this mixture, 19.1 g (0.308 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, the mixture was heated and stirred at 90 to 100 ° C. for 2 hours and at 150 ° C. for 2 hours while dehydrating. The obtained mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), thereby containing 110 g of boron. Polybutenyl succinimide was obtained. This boron-containing polybutenyl succinimide had a boron content of 2.1 mass%, a nitrogen content of 2.1 mass%, and a boron atom / nitrogen atom mass ratio of 1.0.

Example C-2
A boron-containing polybutenyl succinimide was obtained in the same manner as in Example C-2 except that the amount of boric acid was changed to 13.6 g (0.220 mol). This boron-containing polybutenyl succinimide had a boron content of 1.5% by mass, a nitrogen content of 2.1% by mass, and a boron / nitrogen atom mass ratio of 0.7.

Reference Example D-1
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 285.2 g (0.80 mol) of glycerol monooleate under a nitrogen stream, Heated to 80 ° C. To this mixture, 49.5 g (0.80 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Thereafter, 54 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The obtained mixture was subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to obtain 345 g of boron-containing glycerol. Monooleate was obtained.

Reference Example D-2
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 286.9 g (0.80 mol) of glycerol monostearate under a nitrogen stream. Heated to ~ 80 ° C. To this mixture, 49.5 g (0.80 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Thereafter, 54 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The obtained mixture was subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.) to obtain 337 g of boron-containing glycerol. Monostearate was obtained.

Reference Example E-1
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 26.0 g (0.10 mol) of toluene (100 ml) of lauryl glycol hydroxypropyl ether (Bisco Safe LPE) was added. The mixture was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 6.2 g (0.10 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, while dehydrating, the mixture was stirred at 90 to 100 ° C. for 2 hours and with heating under reflux for 3 hours. After filtration, toluene was distilled off over 3 hours while raising the temperature from 70 ° C. to 120 ° C. under reduced pressure using a vacuum evaporator to obtain 26.7 g of boron-containing lauryl glycol hydroxypropyl ether (at 100 to 120 ° C. And stirring time: 2 hours).

Reference Example E-2
In a separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube, 253.2 g of 3- (hexadecyloxy) propane-1,2-diol (0. 80 mol) was charged and heated to 70-80 ° C. under a nitrogen stream. To this mixture, 49.5 g (0.80 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Thereafter, 54 g of mineral oil A was added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The obtained mixture is subjected to pressure filtration (pressure 4.0 kg / cm ² ) using a filter plate (NA-600, retained particle size 0.4 μm, manufactured by Advantech Toyo Co., Ltd.), thereby obtaining 337 g of boron-containing 3 -(Hexadecyloxy) propane-1,2-diol was obtained.

Comparative Example 1
In a 1 L autoclave, 100 g of polydecene (Mw: 2119), 0.14 g (0.0046 mmol) of cetyl bromide and 12 g (0.122 mol) of maleic anhydride were substituted with nitrogen and reacted at 248 ° C. for 5 hours. It was. The temperature was lowered to 215 ° C., unreacted maleic anhydride and cetyl bromide were distilled off under reduced pressure, and the temperature was lowered to 140 ° C. and filtered. The yield of the obtained polydecenyl succinic anhydride was 126.9 g, and the saponification value was 41.7 mgKOH / g.
In a 500 mL separable flask, 84 g of polydecenyl succinic anhydride obtained above, 4.1 g (0.032 mol) of aminoethylpiperazine (AEP), 2.4 g (0.024 mol) of diethylenetriamine (DETA) Then, 3.5 g (0.024 mol) of triethylenetetraamine (TETA) and 36 g of 150 neutral oil were added and reacted at 150 ° C. for 2 hours under a nitrogen stream. The temperature was raised to 200 ° C., and unreacted AEP, DETA and produced water were distilled off under reduced pressure. The yield of the obtained polydecenyl succinimide was 123 g, and the base value (hydrochloric acid method) was 37.9 mgKOH / g.
A separable flask reaction vessel equipped with a stirrer, a heating device, a thermometer, a Dean-Stark tube, a Dimroth condenser tube and a nitrogen blowing tube was charged with 110 g of polydecenyl succinimide and heated to 70-80 ° C. under a nitrogen stream. Heated. To this mixture, 19.1 g (0.308 mol) of boric acid was gradually added and stirred at 80 ° C. for 2 hours. Further, the mixture was heated and stirred at 90 to 100 ° C. for 2 hours and then at 150 to 160 ° C. for 2 hours while dehydrating. The obtained mixture was diluted with toluene, filtered under reduced pressure, and toluene was distilled off under reduced pressure to obtain 110 g of boron-containing polydecenyl succinimide. This boron-containing polydecenyl succinimide had a boron content of 2.5 mass%, a nitrogen content of 1.8 mass%, and a boron atom / nitrogen atom mass ratio of 1.4.

For the boron-containing compounds of Examples, Reference Examples, and Comparative Examples, ¹¹ B-NMR was measured, and friction characteristics (friction coefficient and wear width) were measured.
In Table 1, the integrated value of boron NMR is [integrated value of 5-25 ppm peak / integrated value of -10-25 ppm peak]. For all Examples, Reference Examples, and Comparative Examples, ¹¹ B-NMR shows a peak at 5 to 25 ppm and no peak was detected at -10 to 5 ppm or only one peak was observed. there were. Therefore, the following integral value indicates the molar ratio of the tricoordinate boron-containing compound to the total amount of the tricoordinate and tetracoordinate boron-containing compound.

As is apparent from Table 1, the friction coefficient was low in all examples, and the lubricating additive of each example was able to reduce the friction coefficient of the lubricating oil. On the other hand, in Comparative Example 1, the wear width was the same as that of the example and the wear resistance was relatively good, but the friction coefficient was high, and the lubricating oil could not be made to have a low friction coefficient.

  By blending the lubricating additive of the present invention with lubricating oil, fuel oil, etc., it is possible to provide lubricating oil, fuel oil, etc. with reduced friction and improved wear resistance.

Claims (13)

Borate of organic compounds having a hydroxyl group or an amino group, a boric acid ester, boric acid amide, and, at least one selected from any of a dispersion of boric acid and boric acid dehydration condensates, BF ₃ · When ¹¹ B-NMR measurement was performed as an OEt ₂ standard (0 ppm), the ratio of the integrated value of the chemical shift peak of 5 to 25 ppm to the integrated value of the chemical shift peak of 10 to 25 ppm was 0.47 or more and 1.0 or less. A lubricating additive,
While the boron atom content is 1 to 3% by mass,
The organic compound is at least one compound selected from an amine compound (A), an amide compound (B) having a hydroxy compound, and an imide compound (C) having an amino group,
The imide compound (C) is a lubricating additive which is at least one compound selected from compounds represented by the following general formula (C1) .
(In Formula (C1), _R69 is a hydrocarbon group having 20 to 150 carbon atoms, and s is an integer of 0 to 5). The lubricating additive according to claim 1, wherein the amine compound (A) is at least one compound selected from compounds represented by the following general formulas (A1) to (A5).
(In the formulas (A1) to (A5), R ₁ , R ₁₀ , R ₁₁ , R ₁₆ , R ₂₉ , R ₄₇ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₁₀ and R ₁₁ are R _{2 to} R ₉ , R _{12 to} R ₁₅ , R _{17 to} R ₂₈ , R _{30 to} R ₄₅ , and R _{48 to} R ₄₉ may be a hydrogen atom or a C 1-18 carbon atom. It is a hydrocarbon group and may be the same or different from each other, a, b, c, e, f, g, j, k, w, m each represents an integer of 0 to 20, and d, h, i are , Each represents an integer of 1-6, a + b = 1-20, e + f + g = 0-20, j + k + w + m = 0-20.) The organic compound is at least one compound selected from the compounds represented by the general formula (A1), a and b each represent an integer of 1, and R ₂ ~ R ₄ , R ₆ ~ R ₈ Are both hydrogen atoms and R ₅ And R ₉ The lubricating additive according to claim 2, wherein one or both of them are hydrocarbon groups. The lubricating additive according to claim 1, wherein the organic compound is an imide compound (C). The lubricating additive according to claim 1, wherein the amide compound (B) is at least one compound selected from compounds represented by the following general formulas (B1) and (B2).
(In the formulas (B1) and (B2), R ₅₁ , R ₆₁ and R ₆₂ are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₆₁ and R ₆₂ may be the same as or different from each other. R _{52 to} R ₅₉ and R _{63 to} R ₆₆ are a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different from each other, n represents an integer of 0 to 20, and o, p Each represents an integer of 1 to 20.) The lubricating additive according to any one of claims 1 to 5 , which is a lubricating friction modifier. An organic compound having a hydroxyl group or an amino group and boric acid or a boric acid derivative are mixed and dehydrated while stirring at less than 100 ° C., and then the temperature is increased within a temperature range of 100 ° C. to 150 ° C. In the method for producing a lubricating additive, which is heated and stirred and dehydrated to obtain a lubricating additive.
In a series of operations in which the organic compound and boric acid or a boric acid derivative are mixed and heated and stirred to obtain a lubricant additive, the organic compound is not heated to a temperature higher than 150 ° C.
Additives wherein the lubricant _is, when ¹¹ B-NMR measured as BF 3 · OEt ₂ standard (0 ppm), with respect to the integral value of the peak of the chemical shift -10～25Ppm, the integral value of the peak of a chemical shift 5~25ppm The ratio is 0.47 or more and 1.0 or less, and the boron atom content is 1 to 3% by mass,
The organic compound is at least one compound selected from an amine compound (A), an amide compound (B) having a hydroxy compound, and an imide compound (C) having an amino group,
The said imide compound (C) is a manufacturing method of the additive for lubrication which is at least 1 compound chosen from the compound represented by the following general formula (C1).

(In Formula (C1), _R69 is a hydrocarbon group having 20 to 150 carbon atoms, and s is an integer of 0 to 5). The method for producing a lubricating additive according to claim 7 , wherein a molar ratio of the organic compound to boric acid or a boric acid derivative is 1: 0.01 to 1:10 . 9. The method for producing a lubricating additive according to claim 7, wherein the temperature range is 100 ° C. or higher and 130 ° C. or lower, and is not heated to a temperature higher than 130 ° C. in the series of operations .   The method for producing a lubricating additive according to any one of claims 7 to 9, wherein the amine compound (A) is at least one compound selected from compounds represented by the following general formulas (A1) to (A5).
(In the formulas (A1) to (A5), R ₁ , R ₁₀ , R ₁₁ , R ₁₆ , R ₂₉ , R ₄₇ Are each a hydrocarbon group having 1 to 32 carbon atoms, and R ₁₀ , R ₁₁ May be the same as or different from each other. R ₂ ~ R ₉ , R ₁₂ ~ R ₁₅ , R ₁₇ ~ R ₂₈ , R ₃₀ ~ R ₄₅ , R ₄₈ ~ R ₄₉ Is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, which may be the same as or different from each other. a, b, c, e, f, g, j, k, w, m each represents an integer of 0 to 20, d, h, i each represents an integer of 1 to 6, and a + b = 1 to 20, e + f + g = 0-20, j + k + w + m = 0-20. ) The organic compound is at least one compound selected from the compounds represented by the general formula (A1), a and b each represent an integer of 1, and R ₂ ~ R ₄ , R ₆ ~ R ₈ Are both hydrogen atoms and R ₅ And R ₉ The method for producing a lubricating additive according to claim 10, wherein one or both of the hydrocarbon groups are hydrocarbon groups. The method for producing a lubricating additive according to any one of claims 7 to 9, wherein the organic compound is an imide compound (C). The method for producing a lubricating additive according to any one of claims 7 to 9, wherein the amide compound (B) is at least one compound selected from compounds represented by the following general formulas (B1) and (B2).
(In the formulas (B1) and (B2), R ₅₁ , R ₆₁ , R ₆₂ Is a hydrocarbon group having 1 to 32 carbon atoms, and R ₆₁ , R ₆₂ May be the same or different. R ₅₂ ~ R ₅₉ , R ₆₃ ~ R ₆₆ Is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, which may be the same as or different from each other. n shows the integer of 0-20, o and p show the integer of 1-20, respectively. )