JPH0762371A - Lubricant additive, lubricant additive composition and lubricating oil composition - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Lubricant additive (ashless detergent) useful for oil for diesel engines and methanol engines that comply with future emission regulations, high temperature stability (high temperature detergency) (EN) Provided are an additive composition for lubricants, which is excellent as an ashless detergent dispersant having a fine particle dispersing action, and a lubricating oil composition containing the additive for lubricants. [Structure] General formulas (I) and (II) [For example, (hexylhydroxybenzoic acid) hexylphenyl ester] [For example, (hexyl hydroxynaphthoic acid) hexyl phenyl ester] represented by a substituted hydroxyaromatic carboxylic acid ester derivative, at least one lubricant additive, and (a) this lubricant additive And an additive composition for a lubricant containing (b) an ashless dispersant, and a lubricating oil composition comprising a lubricant base oil containing the additive for a lubricant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for lubricants, an additive composition for lubricants and a lubricating oil composition, and more specifically, a lubricant useful as an excellent ashless detergent and antiwear agent. Additives for lubricants, engine oils that comply with strict exhaust gas regulations in the future, and especially additive compositions for lubricants that have excellent high-temperature stability and fine particle dispersibility that can be used for diesel engine oils and methanol engine oils, and the lubricants The present invention relates to a lubricating oil composition containing an additive for oil.

[0002]

2. Description of the Related Art Conventional ashless dispersants generally include succinimide type and hydroxybenzylamine type.
It is widely used as an additive for gasoline, diesel engine oil, etc. with an emphasis on its remarkable fine particle dispersing action. Further, these are recognized as synergistic effects with zinc dialkyldithiophosphate and metal type detergents, and are one of the extremely important additives for lubricants. However, in recent years, it has been frequently pointed out that the stability at high temperatures (high-temperature cleanability) is not sufficient.

Conventional lubricating oils for internal combustion engines are usually ashless dispersants such as base oil and polybutenyl succinimide, metal type detergents such as alkaline earth metal sulfonates and phenates, and zinc alkyldithiophosphates. However, there is a problem that the metal components in the additive components are generated as oxides or sulfates by combustion, which contributes to environmental pollution. In recent years, among internal combustion engines, especially diesel engines, particulates and NO _x
Environmental pollution control by exhaust gas regulations has become an important issue. There is an exhaust gas purification device such as a particulate trap and a NO _x removal catalyst as a countermeasure for these, but in the conventional internal combustion engine lubricating oil, there is a problem of blockage due to metal oxides and sulfides generated by combustion,
There is a demand for a lubricating oil for an internal combustion engine that can minimize the emission of these metal oxides and sulfides.

Further, a methanol engine has been attracting attention as one means for solving future exhaust gas countermeasures. In a diesel engine, light oil is sprayed into the engine by an injection pump, but the lubrication inside the pump is self-lubrication by the light oil itself. On the other hand, in a methanol engine, since the lubricity of methanol itself is low, engine oil is usually injected into the injection pump. In that case,
Due to poor compatibility between methanol and engine oil, additives precipitate in methanol, and in particular, metal-type detergents have the problem that metal components such as calcium clog nozzle injection ports. There is a demand for a lubricating oil for internal combustion engines that minimizes the above. As measures against such future exhaust gas, for example, for lubricating base oil,
(3,5-di-t-butyl-4-hydroxyphenyl)
An ashless lubricating oil composition containing an alkyl carboxylic acid ester, a succinimide-based ashless dispersant and an ashless antioxidant has been proposed (JP-A-4-353598). However, this composition has a problem that the high temperature stability (high temperature detergency) cannot be sufficiently satisfied.

On the other hand, US Pat. No. 4,098,708 proposes esters of alkyl-substituted hydroxyaromatic carboxylic acids having at least about 10 carbon atoms and derivatives thereof as dispersants for lubricating oils and fuel oils. Then, monohydric or polyhydric hydrocarbon alcohols are listed as suitable alcohol components of the ester, and specific examples thereof include substituted phenols such as cresol. However, also in the case of this ester, similarly, the high temperature stability is not sufficiently satisfactory.

[0006]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art and meets the future emission regulations, and is particularly useful for diesel engine oil and methanol engine oil. And an additive composition for a lubricant as an antiwear agent, an additive composition as an ashless detergent dispersant having excellent high temperature stability (high temperature detergency) and having a fine particle dispersing action, and an additive for the lubricant An object is to provide a lubricating oil composition containing the same.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have found that an additive for a lubricant comprising a specific substituted hydroxyaromatic carboxylic acid ester derivative is ashless. Useful as a mold detergent and antiwear agent, and by adding the lubricant additive to a conventional ashless dispersant, it has excellent high-temperature stability (high-temperature detergency) and fine particle dispersion action. It has been found that an additive composition for a lubricant, which is useful as an ashless-type detergent dispersant, can be obtained. The present invention has been completed based on such findings. That is, the present invention has the general formula (I)

[0008]

[Chemical 5]

[In the formula, R ¹ and R ² each represent an organic group having 6 or more carbon atoms, which may be the same or different, and a, b, c, d and e are each 1
≦ a ≦ 3,1 ≦ b ≦ 3,0 ≦ c ≦ 3,1 ≦ d ≦ 3,1 ≦
e ≦ 3, 3 ≦ (a + b + e) ≦ 6 and 1 ≦ (c + d) ≦
An integer that satisfies the relationship of 5 is shown. Further, when R ¹ and R ² are a plurality, the plurality of R ¹ and R ² may be different even in the same in each. ] And general formula (II)

[0010]

[Chemical 6]

[Wherein R³, R^FourAnd R^Five Respectively
Indicates an organic group having 6 or more carbon atoms, which are identical to each other
May be different, f, g, h, i, j, k and m
Are 0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g), respectively.
≦ 3,0 ≦ h ≦ 4,0 ≦ i ≦ 3,1 ≦ (h + i) ≦ 6
0 ≦ j ≦ 3, 1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g +
h + i + m) ≦ 8 and 1 ≦ (j + k) ≦ 5
Indicates an integer. Also, R ³, R^FourAnd R^Five If there are multiple
If more than one R³, R^FourAnd R^Five In each
It may be the same or different. ] The substitution represented by
Selected from hydroxy aromatic carboxylic acid ester derivatives
Providing at least one additive for lubricants
And (a) is represented by the above general formulas (I) and (II).
Of substituted hydroxyaromatic carboxylic acid ester derivatives
At least one selected from the above and (b) an ashless dispersant
To provide an additive composition for lubricants containing
is there. Further, the present invention is based on the above general formula for a lubricating base oil.
Substituted hydroxyaromatic cals represented by (I) and (II)
At least one selected from boric acid ester derivatives
The present invention also provides a lubricating oil composition containing
It The lubricant additive of the present invention has the general formulas (I) and (I
I)

[0012]

[Chemical 7]

It comprises at least one selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by: and is useful as an ashless detergent replacing a metal detergent and as an antiwear agent. is there.

In the above general formulas (I) and (II), R
¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an organic group having 6 or more carbon atoms. Examples of the organic group having 6 or more carbon atoms include a hydrocarbon group having 6 to 7,000 carbon atoms, and more preferably 8 to 225 carbon atoms. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group and an aralkyl group, which have a non-hydrocarbon substituent and a hetero atom in the chain or ring. Good. Specifically, hydrocarbon groups such as hexyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, triacontyl group, and groups derived from olefin polymers such as polyethylene, polypropylene, and polybutene can be used. Can be mentioned. When a low-viscosity substituted hydroxyaromatic carboxylic acid ester derivative is desired,
It is preferable that R ¹ , R ² , R ³ , R ⁴ and R ⁵ are substantially linear hydrocarbon groups. The R ¹ and R ² are
They may be the same or different, and R
³ , R ⁴ and R ⁵ may be the same or different from each other.

In the above general formula (I), a, b, c,
d and e are 1 ≦ a ≦ 3, 1 ≦ b ≦ 3, 0 ≦ c, respectively.
≦ 3,1 ≦ d ≦ 3,1 ≦ e ≦ 3,3 ≦ (a + b + e) ≦
6 and an integer satisfying the relationship of 1 ≦ (c + d) ≦ 5.
When b is 2 or 3, a plurality of R ¹ may be the same or different, and when d is 2 or 3, a plurality of R ² may be the same or different.

Further, in the above general formula (II), f,
g, h, i, j, k, and m are 0 ≦ f ≦ 3, 0, respectively.
≦ g ≦ 3,1 ≦ (f + g) ≦ 3,0 ≦ h ≦ 4,0 ≦ i ≦
3, 1 ≤ (h + i) ≤ 6, 0 ≤ j ≤ 3, 1 ≤ k ≤ 3, 1
≦ m ≦ 3,3 ≦ (f + g + h + i + m) ≦ 8 and 1 ≦
An integer satisfying the relationship of (j + k) ≦ 5 is shown. h is a few
Or 4, the plural R ^{3 s} may be the same or different, and when i is 2 or 3, the plural R ^{4 s} may be the same or different. When k is 2 or 3, plural R ^{5 s} may be the same or different.

Specific examples of the substituted hydroxyaromatic carboxylic acid ester derivative represented by the above general formula (I) include:
(Hexylhydroxybenzoic acid) hexylphenyl ester, (hexylhydroxybenzoic acid) dodecylphenyl ester, (octylhydroxybenzoic acid) octylphenyl ester, (nonylhydroxybenzoic acid) nonylphenyl ester, (nonylhydroxybenzoic acid) hexadecylphenyl ester , (Dodecylhydroxybenzoic acid) nonylphenyl ester, (dodecylhydroxybenzoic acid) dodecylphenyl ester, (dodecylhydroxybenzoic acid) hexadecylphenyl ester,
(Hexadecylhydroxybenzoic acid) hexylphenyl ester, (hexadecylhydroxybenzoic acid) dodecylphenyl ester, (hexadecylhydroxybenzoic acid) hexadecylphenyl ester, (eicosylhydroxybenzoic acid) eicosylphenyl ester, (C11 ~ 15 mixed alkyl hydroxybenzoic acid) mixed alkyl phenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, derived from polybutene having a weight average molecular weight of 400 or more] Group] hydroxybenzoic acid) dodecylphenyl ester, (long-chain alkyl [for example, group derived from polydecene having 30 or more carbon atoms, weight average molecular weight 400
The group derived from polybutene mentioned above] hydroxybenzoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyl hydroxy) Benzoic acid) hexylhydroxyphenyl ester, (octylhydroxybenzoic acid) octylhydroxyphenyl ester, (dodecylhydroxybenzoic acid) nonylhydroxyphenyl ester, (dodecylhydroxybenzoic acid) dodecylhydroxyphenyl ester, (hexadecylhydroxybenzoic acid) dodecylhydroxy Phenyl ester, (hexadecyl hydroxybenzoic acid) hexadecyl hydroxyphenyl ester,
(Eicosyl hydroxybenzoic acid) Eicosyl hydroxyphenyl ester, (C11-11 mixed alkyl hydroxybenzoic acid) C11-15 mixed alkyl hydroxyphenyl ester, (long-chain alkyl [for example, having 30 or more carbon atoms Group derived from polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] hydroxybenzoic acid) dodecyl hydroxyphenyl ester, (long-chain alkyl [eg, group derived from polydecene having 30 or more carbon atoms, weight average Group derived from polybutene having a molecular weight of 400 or more] hydroxybenzoic acid) long-chain alkyl [for example, group derived from polydecene having a carbon number of 30 or more, group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (Hexyldihydro Cybenzoic acid) hexylphenyl ester, (nonyldihydroxybenzoic acid) nonylphenyl ester, (nonyldihydroxybenzoic acid) dodecylphenyl ester, (dodecyldihydroxybenzoic acid) nonylphenyl ester, (dodecyldihydroxybenzoic acid) dodecylphenyl ester, (hexa) Decyldihydroxybenzoic acid) hexadecylphenyl ester, (eicosyldihydroxybenzoic acid) hexadecylphenyl ester, (eicosyldihydroxybenzoic acid) eicosylphenyl ester, (C11-15)
Mixed alkyldihydroxybenzoic acid) having 11 to 1 carbon atoms
5, mixed alkyl phenyl ester, (long chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) dodecyl phenyl ester, (long chain Alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid)
Long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyldihydroxybenzoic acid) hexylhydroxyphenyl ester, (nonyldihydroxybenzoic acid ) Nonylhydroxyphenyl ester, (nonyldihydroxybenzoic acid)
Dodecyl hydroxyphenyl ester, (dodecyl dihydroxybenzoic acid) nonyl hydroxyphenyl ester, (dodecyl dihydroxybenzoic acid) dodecyl hydroxyphenyl ester, (hexadecyl dihydroxybenzoic acid) hexadecyl hydroxyphenyl ester,
(Eicosyl dihydroxybenzoic acid) hexadecyl hydroxyphenyl ester, (Eicosyl dihydroxybenzoic acid) eicosyl hydroxyphenyl ester, (mixed alkyldihydroxybenzoic acid having 11 to 15 carbon atoms)
Mixed alkyl hydroxyphenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) dodecyl hydroxy Phenyl ester, (long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxybenzoic acid) long-chain alkyl [eg, having 30 or more carbon atoms Groups derived from polydecene,
A group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester and the like.

On the other hand, specific examples of the substituted hydroxyaromatic carboxylic acid ester derivative represented by the above general formula (II) include (hexylhydroxynaphthoic acid) hexylphenyl ester, (hexylhydroxynaphthoic acid) hexadecylphenyl ester, (Nonylhydroxynaphthoic acid) nonylphenyl ester, (dodecylhydroxynaphthoic acid) dodecylphenyl ester, (hexadecylhydroxynaphthoic acid) hexadecylphenyl ester, (dodecylhydroxynaphthoic acid) eicosylphenyl ester, (eicosylhydroxynaphthoic acid) Eicosyl phenyl ester, (mixed alkyl hydroxynaphthoic acid having 11 to 15 carbon atoms) Mixed alkyl phenyl ester having 11 to 15 carbon atoms, (long-chain alkyl [for example, 30 or more carbon atoms Group derived from polydecene, group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) dodecylphenyl ester, (long-chain alkyl [eg, group derived from polydecene having a carbon number of 30 or more, weight average molecular weight Group derived from polybutene of 400 or more] hydroxynaphthoic acid) long-chain alkyl [eg group derived from polydecene having 30 or more carbon atoms, group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyl (Hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (octyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) hexadecyl hydro Xyphenyl ester, (hexadecyl hydroxynaphthoic acid) hexadecyl hydroxyphenyl ester, (hexadecyl hydroxynaphthoic acid) eicosyl hydroxyphenyl ester, (mixed alkyl hydroxynaphthoic acid having 11 to 15 carbon atoms) mixed having 11 to 15 carbon atoms Alkyl hydroxyphenyl ester, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) dodecyl hydroxyphenyl ester, (long-chain alkyl [For example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxynaphthoic acid) long-chain alkyl [eg, derived from polydecene having 30 or more carbon atoms] Group, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester, (hexyldihydroxynaphthoic acid) hexylphenyl ester, (hexyldihydroxynaphthoic acid) hexadecylphenyl ester, (nonyldihydroxynaphthoic acid) nonylphenyl ester , (Dodecyldihydroxynaphthoic acid) dodecylphenyl ester, (dodecyldihydroxynaphthoic acid) eicosylphenyl ester,
(Hexadecyldihydroxynaphthoic acid) hexadecyl phenyl ester, (Eicosyl dihydroxynaphthoic acid) eicosyl phenyl ester, (C 11-15)
Mixed alkyldihydroxynaphthoic acid) having 11 to 11 carbon atoms
15 mixed alkyl phenyl esters, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecylphenyl ester, (long-chain Alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms] , A group derived from polybutene having a weight average molecular weight of 400 or more] phenyl ester, (hexyldihydroxynaphthoic acid) dodecylhydroxyphenyl ester, (octyldihydroxynaphthoic acid) dodecylhydroxyphenyl ester, (dodecyldihydroxynaphthoic acid) Decyl-hydroxyphenyl ester, (dodecyl dihydroxy naphthoic acid) hexadecyl-hydroxyphenyl ester, (hexadecyl dihydroxy-naphthoic acid) hexadecyl-hydroxyphenyl ester, (hexadecyl-dihydroxy-naphthoic acid) eicosyl hydroxyphenyl ester, (carbon number 11 to 15
Mixed alkyldihydroxynaphthoic acid) having 11 to 11 carbon atoms
15 mixed alkyl hydroxyphenyl esters, (long-chain alkyl [for example, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) dodecyl hydroxyphenyl ester, ( Long-chain alkyl [eg, a group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] dihydroxynaphthoic acid) long-chain alkyl [eg,
A group derived from polydecene having 30 or more carbon atoms, a group derived from polybutene having a weight average molecular weight of 400 or more] hydroxyphenyl ester and the like. Among these substituted hydroxyaromatic carboxylic acid ester derivatives, one of general formula (III) or (III ′)

[0019]

[Chemical 8]

[In the general formula (III), R ¹ , R ² , b, d and e are the same as above, and the sum of b and e is 2-5. In the general formula (III ′), R ³ , R ⁴ , R ⁵ , h, k
And m are the same as above, n is 0, 1 or 2, the sum of h and n is 1 to 6, the sum of h, m and n is 2 to 7.
Is. ] The compound represented by these is suitable. The lubricant additive of the present invention may be composed of one kind of the compound represented by the general formula (I) or may be composed of two or more kinds. The compound represented by the general formula (II) may be composed of one kind or two or more kinds. Further, it may be composed of one or more compounds represented by the general formula (I) and one or more compounds represented by the general formula (II). The method for producing the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (I) is not particularly limited,
For example, the general formula (IV)

[0021]

[Chemical 9]

[In the formula, R ¹ , a, b and e are the same as above. ] At least one of the organic group-substituted hydroxybenzenecarboxylic acids represented by the general formula (V)

[0023]

[Chemical 10]

[In the formula, R ² , c and d are the same as above. ] The substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (I) can be obtained by reacting with at least one of the organic group-substituted phenols represented by

On the other hand, the method for producing the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (II) is not particularly limited.

[0026]

[Chemical 11]

[In the formula, R ³ , R ⁴ , f, g, h, i and m are the same as above. ] At least one of the organic group-substituted hydroxynaphthalenecarboxylic acid represented by the general formula (VII)

[0028]

[Chemical 12]

[In the formula, R ⁵ , j and k are the same as above. ] The substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (II) can be obtained by reacting with at least one of the organic group-substituted phenols represented by In these reactions, the organic group-substituted hydroxyaromatic carboxylic acid and the organic group-substituted phenol are usually used in a molar ratio of 1: 0.01 to 1: 1.
4, preferably 1: 0.2 to 1: 3, more preferably 1:
It is in the range of 1 to 1: 3, most preferably 1: 1 to 1: 1.5. The reaction temperature is usually selected in the range of 100 to 300 ° C, preferably 150 to 250 ° C. This reaction may be carried out without a catalyst or may be carried out in the presence of an acid or alkali catalyst. In carrying out this reaction, a solvent such as a hydrocarbon oil can be used.
The above-mentioned organic group-substituted hydroxyaromatic carboxylic acid can be produced by various methods, and as an example, it can be obtained by a known Kolbe-Schmidt reaction from an organic group-substituted phenol or an alkali metal salt of naphthol and carbon dioxide. It can be produced by hydrolyzing the product.

Next, the additive composition for lubricants of the present invention is
The component (a) contains a lubricant additive comprising at least one selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formulas (I) and (II), and (b) It contains an ashless type dispersant as an ingredient and has excellent high temperature stability (high temperature detergency),
It is also used as an ashless detergent dispersant having a fine particle dispersing action.

Regarding the ashless dispersant of the component (b),
There is no particular limitation, and conventionally known substances such as carboxylic acid imide type, carboxylic acid ester type, and hydroxybenzylamine type can be used alone or in combination.
The preferred acid site of the carboxylic acid imide type and the carboxylic acid ester type is succinic acid and has a molecular weight of 2 in the molecular structure.
Those having a hydrocarbon group of 00 or more are suitable. The hydrocarbon group is an alkyl group or an alkenyl group, and may have a non-hydrocarbon substituent and a hetero atom in the chain or ring.

The above-mentioned carboxylic acid imide type and carboxylic acid ester type include (1) at least 1
Organic nitrogen compounds having one —NH— group, for example, reaction products with amines, ureas, hydrazines, etc., and (2) reaction products with hydroxy compounds such as phenols and alcohols. In addition, the reaction product of the carboxylic acid derivative and the reactive metal or the reactive metal compound may be contained in the range not affecting. In addition, these post-treatment products are also useful. Examples of the post-treatment agent include sulfur and sulfur compounds, urea, thiourea, guanidine, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds, etc. Details of the carboxylic acid imide type and the carboxylic acid ester type are described in JP-B-3-60876). On the other hand, the hydroxybenzylamine type is
For example, hydrocarbon-substituted phenols such as sulfur-bridged phenol and methylene-bridged phenol, formaldehyde, and a nitrogen compound having at least two —NH— groups,
For example, it is a reaction product with a polyamine.

In the lubricant additive composition of the present invention, the component (a) is selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formulas (I) and (II). The mixing ratio of at least one lubricant additive and the ashless dispersant as the component (b) is
10:90 to 99: 1 by weight, preferably 15:85
It is preferably in the range of 75:25. The lubricating oil composition of the present invention comprises, based on the lubricating base oil, (a) at least one selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formulas (I) and (II). And optionally (b) containing the above ashless dispersant. The components (a) and (b) are preferably blended in a proportion of 1 to 30% by weight, preferably 2 to 20% by weight, based on the total amount of the lubricating oil composition, with respect to the base oil.

As the lubricating base oil, a mineral oil, a synthetic oil or a combination thereof is used. The mineral oil may be a fraction of a paraffinic mineral oil, a naphthenic mineral oil, an aromatic mineral oil, or the like, and may be one that has undergone any refining method such as solvent refining, hydrorefining or hydrocracking. As the synthetic oil, polyphenyl ether, polyvinyl ether, hydrogenated products thereof, alkylbenzene, alkylnaphthalene, ester-based, polyglycol-based or polyolefin-based synthetic oils and the like can be used. The lubricating oil fraction has a kinematic viscosity (100 ° C.) of usually 1 to 50 cSt, preferably 3 to
It is in the range of 10 cSt.

As the ester-based synthetic oil, an ester of a monobasic acid or a dibasic acid and an alcohol, for example, a dibasic acid having 6 to 16 carbon atoms and a linear or branched alcohol having 5 to 20 carbon atoms is used. A synthetic oil composed of an ester obtained by the reaction can be used. In particular, adipic acid ester, sebacic acid ester, azelaic acid ester, trimethylolpropane ester, trimethylolethane ester, pentaerythritol ester, neopentyl glycol ester and the like are preferable. Polyolefin synthetic oils include ethylene, propylene, butylene,
Liquid products obtained by low polymerization or copolymerization of lower olefins such as octene, decene and dodecene, mixtures thereof and hydrotreated products thereof are suitable. In addition, complex ester composed of dibasic acid, glycol and monobasic acid and α-
An olefin / dibasic acid copolymer ester can also be used. In the lubricating oil composition of the present invention, as the base oil, one of the above mineral oils may be used, two or more of them may be used in combination, and one of the above synthetic oils may be used of two or more thereof. You may use in combination. further,
One or more mineral oils and one or more synthetic oils may be used in combination.

In the lubricating oil composition of the present invention, in addition to the above-mentioned additive composition for lubricants, various types conventionally used in conventional lubricating oil compositions, if desired, within a range not impairing the object of the present invention. Additives such as antioxidants, rust preventives, defoamers, viscosity index improvers, pour point depressants, antiwear agents, demulsifiers, and metallic detergents can be added in appropriate amounts. The lubricating oil composition of the present invention can be used, for example, as a lubricating oil for internal combustion engines, gear oil, bearing oil, transmission fluid, shock absorber oil, industrial lubricating oil, etc. It is useful as a lubricating oil composition (for methanol engines, etc.).

[0037]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Reference Example 1 In a 2 liter autoclave, polybutene (Mw: 9
87) 1100 g, cetyl bromide 6.4 g (0.021 mol)
And 115 g (1.2 mol) of maleic anhydride were added, the atmosphere was replaced with nitrogen, and the mixture was reacted at 240 ° C. for 5 hours. 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 the mixture was filtered. The yield of the obtained polybutenyl succinic anhydride was 1099 g. In a 2 liter separable flask, 500 g of the obtained polybutenyl succinic anhydride and tetraethylene pentamine (TEP
A: manufactured by Tosoh Corporation) 64 g (0.34 mol) and mineral oil 3
00 g was added and the mixture was reacted at 150 ° C. for 2 hours under a nitrogen stream. The temperature was raised to 200 ° C., unreacted TEPA and generated water were distilled off under reduced pressure, the temperature was lowered to 140 ° C., and filtration was performed. The yield of the obtained polybutenyl succinimide was 784 g. 5
In a 00 ml separable flask, 240 g of the above polybutenyl succinimide and 28 g of boric acid were placed and reacted at 150 ° C. for 4 hours under a nitrogen stream. The produced water was distilled off under reduced pressure at 150 ° C, the temperature was lowered to 140 ° C, and the mixture was filtered. The yield of the obtained reaction product was 231 g.

Example 1 A hexadecylphenol (1-
319 g (1 mol) of a reaction product of hexadecene and phenol and 200 g of xylene were added and stirred to be uniform. Heated to 70 ° C, 48 wt% NaOH aqueous solution 80
g was added and xylene was refluxed for 2 hours under a nitrogen stream to distill off water. Transfer the reaction solution to a 1 liter autoclave,
It was pressurized to 10 kg / cm ² G with carbon dioxide and reacted at 155 ° C. for 1 hour. The temperature was lowered to 80 ° C., the mixture was transferred to a 2 liter flask, 120 g of xylene was added, and the mixture was stirred so as to be uniform. Further, 250 g of 20 wt% sulfuric acid was added over 30 minutes and the reaction was carried out for 1 hour. The reaction solution was washed with water, phase-separated, and then filtered to remove xylene. The yield of the obtained reaction product was 312 g. In a 500 ml flask, 300 g of the obtained reaction product and 100 g of hexadecylphenol were placed, and the temperature was 250 ° C. under a nitrogen stream.
The reaction was carried out for 5 hours at 250 ° C., and the produced water and hexadecylphenol were distilled off under reduced pressure at 250 ° C. The yield of the obtained reaction product was 195 g.

This product is a mixture of compounds represented by the following formulas (VIII) and (IX), based on the results of electrolytic desorption / ionization mass spectrometry, proton nuclear magnetic resonance spectroscopy, and carbon-13 nuclear magnetic resonance spectroscopy. Was confirmed. From the results of liquid chromatographic analysis (detector: differential refractometer), the ratio of the compounds represented by formulas (VIII) and (IX) is
It was confirmed that the compound of formula (VIII) was 78 area% and the compound of formula (IX) was 22 area%. The results of electrolytic desorption / ionization mass spectrometry, proton nuclear magnetic resonance spectroscopy, and carbon-13 nuclear magnetic resonance spectroscopy of the compound represented by the formula (VIII) collected by liquid chromatography are shown in FIG. 1, FIG. 2 and FIG. 3 shows. Formula (VIII): (hexadecylhydroxybenzoic acid) hexadecylphenyl ester

[0040]

[Chemical 13]

Formula (IX): (hexadecylhydroxyphthalic acid) bis (hexadecylphenyl) ester

[0042]

[Chemical 14]

Example 2 The procedure of Example 1 was repeated, except that dodecylphenol (a reaction product of 1-dodecene and phenol) was used in place of hexadecylphenol. This product was a mixture of compounds represented by the following formulas (X) and (XI).

[0044]

[Chemical 15]

Example 3 The procedure of Example 1 was repeated, except that a mixture of dodecylphenol and dinonylphenol (a reaction product of a propylene oligomer and phenol) was used instead of hexadecylphenol. . This product was a mixture of compounds represented by the following formulas (XII) and (XIII).

[0046]

[Chemical 16]

Example 4 The procedure of Example 1 was repeated, except that nonylphenol (a reaction product of a propylene oligomer and phenol) was used in place of hexadecylphenol. This product was a mixture of compounds represented by the following formulas (XIV) and (XV).

[0048]

[Chemical 17]

Examples 5 to 8 Preparation of additive composition for lubricant (ashless detergent dispersant) 75% by weight of ashless dispersant (boric acid-treated polybutenyl succinimide) obtained in Reference Example 1 And the substituted hydroxyaromatic carboxylic acid ester derivative 25 obtained in Examples 1 to 4
% By weight to prepare an additive composition for lubricant.

Examples 9-12 Preparation of Lubricating Oil Compositions 10% by weight of the additive composition for lubricants of Examples 5-8 (substituted hydroxy aroma) was added to mineral oil of 500 neutral fraction, based on the total amount of the lubricating oil composition. Group carboxylic acid ester derivatives 2.
5% by weight and ashless dispersant 7.5% by weight) were mixed to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the following hot tube test. The results are shown in Table 1. (Hot tube test condition) 16 ml of test oil 0.3 ml / hr and 10 ml / min of air in a glass tube having an inner diameter of 2 mm while keeping the temperature of the glass tube at 310 ° C.
I kept running for hours. The lacquer attached to the glass tube and the color sample were compared, and a rating of 10 points for transparent and a score of 0 for black were given, and the weight of the lacquer attached to the glass tube was measured. The higher the score and the lower the lacquer weight, the higher the performance.

Comparative Example 1 The procedure of Example 1 was repeated, except that dodecylphenol (a reaction product of propylene oligomer and phenol) was used in place of hexadecylphenol.
Further purification was performed to obtain 5-dodecylsalicylic acid. This 5
-Dodecyl salicylic acid and p-cresol were reacted in the same manner as in Example 1. This product has the following formula (XVI)
Was a compound represented by.

[0052]

[Chemical 18]

Next, in mineral oil of 500 neutral fraction,
Based on the total amount of the lubricating oil composition, 2.5% by weight of the above compound and 7.5% by weight of the ashless dispersant of Reference Example 1 were blended to prepare a lubricating oil composition, and its performance was evaluated by a hot tube test. Was evaluated. The results are shown in Table 1.

Comparative Example 2 Comparative Example 1 except that salicylic acid was used in place of 5-dodecylsalicylic acid and hexadecylphenol (a reaction product of 1-hexadecene and phenol) was used in place of p-cresol in Comparative Example 1. It carried out similarly to.
This product was a compound represented by the following formula (XVII).

[0055]

[Chemical 19]

Next, a lubricating oil composition was prepared using the above compound in the same manner as in Comparative Example 1, and its performance was evaluated by a hot tube test. The results are shown in Table 1.

Comparative Example 3 A lubricating oil composition was prepared in the same manner as in Comparative Example 1 using the compound represented by the following formula (XVIII), and its performance was evaluated by a hot tube test. The results are shown in Table 1.

[0058]

[Chemical 20]

Comparative Example 4 A lubricating oil composition was prepared in the same manner as in Comparative Example 1 using the compound represented by the following formula (XIX), and its performance was evaluated by a hot tube test. The results are shown in Table 1.

[0060]

[Chemical 21]

Comparative Examples 5 and 6 In Comparative Example 1, the metal type detergents of overbased calcium phenate and overbased calcium salicylate were used instead of the compound represented by the formula (XVI), respectively. A lubricating oil composition was prepared in the same manner as in Comparative Example 1,
The performance was evaluated by a hot tube test. The results are shown in Table 1.

[0062]

[Table 1]

As can be seen from Table 1, examples using a lubricant additive composition comprising a lubricant additive comprising the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention and an ashless dispersant were used. The lubricating oil compositions of 9 to 12 were substituted or unsubstituted hydroxy aromatic ester derivatives of Comparative Examples 1 to 3 and octadecyl-3- (3,5-di- of Comparative Example 4).
In comparison with the lubricating oil composition using t-butyl-4-hydroxyphenyl) propionate, the overbased calcium phenate and the overbased calcium salicylate of the metal type detergents of Comparative Examples 5 and 6, hot tube test was performed. It showed good results and excellent high-temperature stability (high-temperature detergency).

Examples 13 and 14 Preparation of Lubricating Oil Composition 5% by weight of the substituted hydroxyaromatic carboxylic acid ester derivative obtained in Examples 1 and 2 was added to a mineral oil of 150 neutral fraction based on the total amount of the lubricating oil composition. Was blended to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the following shell four-ball test. The results are shown in Table 2. (Shell four-ball test) According to ASTM D-2783,
The amount of shell wear (mm) was determined by measuring under conditions of a load of 30 kg, an oil temperature of 75 ° C., and a time of 60 minutes.

Comparative Example 7 Mineral oil of 150 neutral fractions was evaluated by the shell four-ball test. The results are shown in Table 2.

[0066]

[Table 2]

From Table 2, it can be seen that the lubricant additive of the present invention has excellent wear characteristics.

Example 15 262 g of p-dodecylphenol (reaction product of propylene oligomer and phenol) was placed in a 1-liter flask.
(1.0 mol) and xylene (262 g) were added and stirred to be uniform. The mixture was heated to 70 ° C., 80 g of a 48 wt% sodium hydroxide aqueous solution was added, and xylene was refluxed for 2 hours under a nitrogen stream to distill off water. The reaction solution was transferred to a 1 liter autoclave, pressurized with carbon dioxide to 10 kg / cm ² G and reacted at 155 ° C. for 1 hour. Cool down to 80 ℃,
Transferred to a 1 liter flask and stirred. Further, 250 g of a 20 wt% sulfuric acid aqueous solution was added dropwise over 30 minutes, and the reaction was carried out for 1 hour. The reaction solution was washed with water, phase-separated, and then filtered to remove xylene. The yield was 257g. Furthermore, it refine | purified and obtained 5-dodecyl salicylic acid. In a 500 ml flask, 110 g of 5-dodecylsalicylic acid and 100 g of dodecylcatechol (a reaction product of a propylene oligomer and catechol) were added, and 2
The reaction was carried out at 50 ° C. for 5 hours, and the produced water and unreacted substances were distilled off under reduced pressure at 250 ° C. This product was mainly composed of a compound represented by the following formula (XX). Formula (XX): (5-dodecyl-2-hydroxybenzoic acid)
Dodecyl-2-hydroxyphenyl ester

[0069]

[Chemical formula 22]

Example 16 The procedure of Example 15 was repeated except that dodecylcatechol was used instead of p-dodecylphenol. This product was mainly composed of a compound represented by the following formula (XXI). Formula (XXI): (dodecyl-2,3-dihydroxybenzoic acid) dodecyl-2-hydroxyphenyl ester

[0071]

[Chemical formula 23]

Example 17 In Example 15, except that 4-dodecyl-1-naphthol was used instead of p-dodecylphenol and p-dodecylphenol was used instead of dodecylcatechol.
It carried out like Example 15. This product was mainly composed of a compound represented by the following formula (XXII). Formula (XXII): (4-dodecyl-1-hydroxy-2-naphthoic acid) 4-dodecylphenyl ester

[0073]

[Chemical formula 24]

Examples 18 to 20 Preparation of Additive Composition for Lubricants (Ashless Detergent Dispersant) 75% by weight of the ashless dispersant (boric acid-treated polybutenylsuccinimide) obtained in Reference Example 1 And 25% by weight of the substituted hydroxyaromatic carboxylic acid ester derivative obtained in Examples 15 to 17 were mixed to prepare an additive composition for lubricant.

Examples 21-23 Preparation of Lubricating Oil Compositions In mineral oil of 500 neutral fraction, 10% by weight of the additive composition for lubricants of Examples 18-20 (substituted hydroxyaromatic) based on the total amount of lubricating oil composition. Carboxylic acid ester derivative
2.5% by weight and ashless dispersant 7.5% by weight) were blended to prepare a lubricating oil composition. The performance of this lubricating oil composition was evaluated by the same hot tube test as in Examples 9-12. The results are shown in Table 3.

[0076]

[Table 3]

[0077]

INDUSTRIAL APPLICABILITY The additive for lubricants comprising the specific substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is useful as an excellent ashless detergent and antiwear agent, and is useful as an engine oil for internal combustion engines and gears. It can be used as oil, bearing oil, shock absorber oil and industrial lubricating oil. A lubricant additive composition containing the lubricant additive and an ashless dispersant is excellent in high temperature stability (high temperature detergency), has fine particle dispersibility, and is a lubricating oil. It is useful as an excellent ashless type detergent-dispersant for use. Therefore, the lubricating oil composition of the present invention can be made ashless, and is particularly useful as a diesel engine oil and a methanol engine oil that comply with future emission regulations.

[Brief description of drawings]

FIG. 1 is a chart showing the result of electrolytic desorption / ionization mass spectrometry of (hexadecylhydroxybenzoic acid) hexadecylphenyl ester obtained in Example 1.

FIG. 2 is a chart showing the results of proton nuclear magnetic resonance spectroscopy of (hexadecylhydroxybenzoic acid) hexadecylphenyl ester obtained in Example 1.

FIG. 3 is the carbon of hexadecylphenyl ester of (hexadecylhydroxybenzoic acid) obtained in Example 1.
13 is a chart showing the results of 13 nuclear magnetic resonance spectroscopy.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masahisa Goto 24, Anezaki Kaigan, Ichihara, Chiba 4 Idemitsu Kosan Co., Ltd.

Claims (5)

[Claims] 1. A compound represented by the general formula (I):[In the formula, R¹And R²Are organics each having 6 or more carbon atoms
Represents a group, which may be the same or different
, A, b, c, d and e are 1 ≦ a ≦ 3, 1 respectively.
≦ b ≦ 3,0 ≦ c ≦ 3,1 ≦ d ≦ 3,1 ≦ e ≦ 3,3 ≦
The relationship of (a + b + e) ≦ 6 and 1 ≦ (c + d) ≦ 5 is satisfied.
Indicates the integer to add. Also, R¹And R²If there are multiple
Are multiple R¹And R²Are the same in each
Or they may be different. ] And general formula (II)[In the formula, R³, R^FourAnd R^Five Each has 6 or more carbon atoms
, Which are the same or different
, F, g, h, i, j, k and m are respectively
0 ≦ f ≦ 3, 0 ≦ g ≦ 3, 1 ≦ (f + g) ≦ 3, 0 ≦ h
≦ 4,0 ≦ i ≦ 3,1 ≦ (h + i) ≦ 6,0 ≦ j ≦ 3
1 ≦ k ≦ 3, 1 ≦ m ≦ 3, 3 ≦ (f + g + h + i + m)
Indicates an integer that satisfies the relations ≦ 8 and 1 ≦ (j + k) ≦ 5.
You Also, R ³, R^FourAnd R^Five If there are multiple
R³, R^FourAnd R^Five Are the same in each
Or they may be different. ] A substituted hydroxy represented by
A small amount selected from among aromatic carboxylic acid ester derivatives
At least one additive for lubricants. 2. A substituted hydroxyaromatic carboxylic acid ester derivative has the general formula (III): [In the formula, R ¹ and R ² each represent an organic group having 6 or more carbon atoms, and they may be the same or different, and b, d and e are 1 ≦ b ≦ 3, 1 ≦, respectively. d ≦
3, an integer that satisfies the relationship of 1 ≦ e ≦ 3 and 2 ≦ (b + e) ≦ 5. Further, when R ¹ and R ² are a plurality, the plurality of R ¹ and R ² may be different even in the same in each. ] Or general formula (III ') [In the formula, R ³ , R ⁴ and R ⁵ each represent an organic group having 6 or more carbon atoms, and they may be the same or different, and h, n, k and m are each 0 ≦ h. ≦ 4
0 ≦ n ≦ 2, 1 ≦ (h + n) ≦ 6, 1 ≦ k ≦ 3, 1 ≦ m
An integer that satisfies the relationship of ≦ 3 and 2 ≦ (h + n + m) ≦ 7 is shown. Further, if R ^3, R ⁴ and R ⁵ have more than one plurality of R ^3, R ⁴ and R ⁵ may be different even in the same in each. ] The lubricant additive according to claim 1, which is represented by: 3. A method comprising (a) at least one selected from the substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formulas (I) and (II) and (b) an ashless dispersant. Additive composition for lubricant. 4. A lubricating oil composition comprising a lubricating base oil and at least one selected from substituted hydroxyaromatic carboxylic acid ester derivatives represented by the general formulas (I) and (II). . 5. A lubricating oil composition for an internal combustion engine.
The lubricating oil composition described.