JPH07165671A - Substituted hydroxy-aromatic carboxylic acid ester derivative and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new compound useful as an ashless type cleaning agent excellent in high-temperature stability (high-temperature cleaning properties). CONSTITUTION:This compound is expressed by formula I to III {(x) and (y) are each 1-3; R<1> and R<2> are each a 9-20C alkyl; (m) is 1-2; (n) is 0-2; [(m)+(n)] is 2-4; (o) and (p) are each 1-3; (q), (r) and (s) are each 0-2; [(q)+(r)] is 1-2; (t) and (u) are each 0-3; [(t)+(u)] is 1-3; (w) is 1-3}, e.g. bis(hexadecylphenyl) (hexadecylhydroxybenzenedicarboxylate). The compound expressed by formula I is obtained by reacting an alkyl group-substituted salicylic acid expressed by formula IV with an alkyl group-substituted phenol expressed by formula V as necessary, in the presence of a catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a substituted hydroxyaromatic carboxylic acid ester derivative and a method for producing the same.
More specifically, the present invention relates to a substituted hydroxyaromatic carboxylic acid ester derivative useful as an ashless-type detergent excellent in high-temperature stability, which is an alternative to conventional metal-type detergents, and a method for efficiently producing the ester derivative.

[0002]

2. Description of the Related Art Conventional ashless dispersants generally include succinimide type and hydroxybenzylamine type (Mannich bases), and their remarkable fine particle dispersing action is emphasized in gasoline and diesel engine oils. It is widely used as an additive for 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 sulfonates and phenates of alkaline earth metals, and zinc alkyldithiophosphate. 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. Recently, among the internal combustion engine, in particular, environmental pollution measures have become an important issue due to exhaust gas regulations, such as particulate and NO _X in the diesel engine. Exhaust gas purifiers such as particulate traps and NO _x removal catalysts are available as countermeasures against these problems, but conventional lubricating oils for internal combustion engines have a problem of blockage due to metal oxides and sulfides produced by combustion. There is a demand for a lubricating oil for an internal combustion engine that can minimize the emission of 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 the case of a methanol engine, since the lubricity of methanol itself is low, engine oil is usually injected into the injection pump. In that case, since the compatibility between methanol and engine oil is poor, the additive is precipitated in methanol, in particular, in the metal detergent, there is a problem that metal components such as calcium clog the nozzle injection port, Lubricating oils for internal combustion engines that minimize these metal components are required. As measures against such future exhaust gas, for example, (3,5-di-t-butyl-4-hydroxyphenyl) carboxylic acid alkyl ester and succinimide ashless dispersant are used for lubricating base oils. And an ashless lubricating oil composition containing an ashless antioxidant has been proposed (JP-A-4-35359).
No. 8). However, this composition has a problem that the high temperature stability (high temperature detergency) cannot be sufficiently satisfied. On the other hand, U.S. Pat. No. 4,098,708 proposes esters of alkyl-substituted hydroxyaromatic carboxylic acids having at least about 10 carbon atoms and their derivatives as dispersants for lubricating oils and fuel oils. And, as a suitable alcohol component of the ester, monohydric or polyhydric hydrocarbon alcohols are listed,
Specific examples thereof include substituted phenols such as cresol. However, also in the case of this ester, similarly, the high temperature stability (high temperature detergency) is not sufficiently satisfactory. And East German Patent No. 2689
In the specification of No. 33, a method for producing an alkylphenol ester of an alkyl-substituted hydroxyaromatic carboxylic acid having 1 to 14 carbon atoms is proposed. In the examples, an isobutyl group, an ethylphenyl group and the like are mentioned as specific alkyl groups of the ester. Furthermore, C
A. Re. No. 19310-46-4 has a 5-
(1,1,3,3-tetramethylbutyl) salicylic acid p
-(1,1,3,3-Tetramethylbutyl) phenyl ester has been proposed. However, also in the case of these esters having 8 or less carbon atoms, similarly, the high temperature stability (high temperature detergency) is not sufficiently satisfactory.

[0005]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art and is suitable for diesel engine oils and methanol engine oils, which are suitable for future exhaust gas regulations and are suitable for high temperature stability. It was made for the purpose of providing a substituted hydroxyaromatic carboxylic acid ester derivative useful as an additive for a lubricant (ashless detergent) excellent in (high temperature detergency), and a method for efficiently producing the ester derivative. It is a thing.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a specific alkyl group-substituted salicylic acid, alkyl group-substituted hydroxybenzoic acid or alkyl group-substituted hydroxynaphthoic acid is , A substituted hydroxyaromatic carboxylic acid ester derivative obtained by reacting with a specific alkyl group-substituted hydroxybenzene is a novel compound and is an additive for lubricants (ashless, which is excellent in high temperature stability (high temperature detergency)). It was found to be useful as a mold detergent). The present invention has been completed based on such findings. That is, the present invention has the general formula (I)

[0007]

[Chemical 10] [In the formula, x and y are integers satisfying 1 ≦ x ≦ 3 and 1 ≦ y ≦ 3, respectively, and R ¹ and R ² have 9 to ² carbon atoms.
0 alkyl groups, which may be the same or different from each other, in the case of 2 ≦ x ≦ 3 and 2 ≦ y ≦ 3, R ^{1 s} and R ^{2 s} are the same. Or they may be different. ], General formula (II)

[0008]

[Chemical 11] [Wherein, m, n, o and p are 1 ≦ m ≦ 2 and 0 ≦, respectively.
n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ o ≦ 3, 1 ≦ p ≦ 3
And R ¹ and R ² have 9 to 9 carbon atoms.
20 alkyl groups, which may be the same or different from each other, in the case of 2 ≦ o ≦ 3 and 2 ≦ p ≦ 3, R ^{1 s} and R ^{2 s} are the same. Or they may be different. ] Or general formula (III)

[0009]

[Chemical 12] [In the formula, q, r, s, t, u, and w are each 0 ≦ q
≦ 2, 0 ≦ r ≦ 2, 1 ≦ (q + r) ≦ 2, 0 ≦ s ≦ 2,
0 ≦ t ≦ 3, 0 ≦ u ≦ 3, 1 ≦ (t + u) ≦ 3, 1 ≦ w
Is an integer satisfying ≦ 3, and R ¹ and R ² represent an alkyl group having 9 to 20 carbon atoms, which may be the same or different from each other, 2 ≦ (t + u) ≦ 3 2 ≦
When w ≦ 3, R ^{1 s} and R ^{2 s} may be the same or different. ] A substituted hydroxyaromatic carboxylic acid ester derivative represented by the following is provided. In addition, the present invention also has the general formula (IV)

[0010]

[Chemical 13] [In the formula, x is an integer satisfying 1 ≦ x ≦ 3, and R ¹ represents an alkyl group having 9 to 20 carbon atoms. ] And an alkyl group-substituted salicylic acid represented by the general formula (V)

[0011]

[Chemical 14] [In the formula, y is an integer satisfying 1 ≦ y ≦ 3, and R ² represents an alkyl group having 9 to 20 carbon atoms. ] Reacting with an alkyl group-substituted phenol represented by the formula (VI) without catalyst or in the presence of a catalyst.

[0012]

[Chemical 15] [In the formula, m and o are integers satisfying 1 ≦ m ≦ 2 and 1 ≦ o ≦ 3, respectively, and R ¹ represents an alkyl group having 9 to 20 carbon atoms. ] An alkyl group-substituted hydroxybenzoic acid represented by the general formula (VII)

[0013]

[Chemical 16] [In the formula, n and p are integers satisfying 0 ≦ n ≦ 2 and 1 ≦ p ≦ 3, respectively, and R ² represents an alkyl group having 9 to 20 carbon atoms. ] Reacting with an alkyl group-substituted hydroxybenzene represented by the following, in the absence of a catalyst or in the presence of a catalyst,
Alternatively, the general formula (VIII)

[0014]

[Chemical 17] [In the formula, q, r, t, and u are 0 ≦ q ≦ 2 and 0 ≦, respectively.
r ≦ 2, 1 ≦ (q + r) ≦ 2, 0 ≦ t ≦ 3, 0 ≦ u ≦
3, an integer satisfying 1 ≦ (t + u) ≦ 3, R ¹ represents an alkyl group having 9 to 20 carbon atoms, and 2 ≦ (t + u) ≦ 3.
In the case of, R ^{1 s} may be the same or different. ] An alkyl group-substituted hydroxynaphthoic acid represented by the general formula (IX)

[0015]

[Chemical 18] [In the formula, s and w are integers satisfying 0 ≦ s ≦ 2 and 1 ≦ w ≦ 3, respectively, and R ² represents an alkyl group having 9 to 20 carbon atoms. ] The substituted hydroxyaromatic carvone represented by the above general formula (I), (II) or (III), which is characterized by reacting with an alkyl group-substituted hydroxybenzene represented by It also provides a method for producing an acid ester derivative. Hereinafter, the present invention will be described in detail.

The substituted hydroxyaromatic carboxylic acid ester derivative of the present invention has the general formula (I)

[Chemical 19] General formula (II)

[0017]

[Chemical 20] Or the general formula (III)

[0018]

[Chemical 21] It is represented by.

In the above general formulas (I), (II) and (III), R ¹ and R ² each represent an alkyl group having 9 to 20 carbon atoms, preferably an alkyl group having 9 to 18 carbon atoms. May be the same as or different from each other, and when there are a plurality of R ¹ and R ² , R ^1's and R ²
They may be the same or different.
Here, examples of the alkyl group having 9 to 20 carbon atoms include hydrocarbon groups such as nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, eicosyl group, and olefin polymers (eg, polyethylene, polypropylene, polybutene). And the like). The alkyl group having 9 to 20 carbon atoms may be a linear hydrocarbon group or a branched hydrocarbon group, but when a low viscosity carboxylic acid ester derivative is desired, , R ¹ and R ² are preferably substantially linear hydrocarbon groups. In the general formula (I), x and y are 1 ≦ x ≦ 3, 1 ≦ y ≦ 3,
Preferably, it is an integer satisfying 1 ≦ x ≦ 2, 1 ≦ y ≦ 2, and in the general formula (II), m, n, o and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦, respectively. (M + n) ≦ 4
1 ≦ o ≦ 3, 1 ≦ p ≦ 3, preferably 1 ≦ m ≦ 2, 0 ≦
n ≦ 1,2 ≦ (m + n) ≦ 3,1 ≦ o ≦ 2,1 ≦ p ≦ 2
Is an integer that satisfies the following formula, and in the general formula (III), q,
r, s, t, u and w are 0 ≦ q ≦ 2 and 0 ≦ r, respectively.
≦ 2,1 ≦ (q + r) ≦ 2,0 ≦ s ≦ 2,0 ≦ t ≦ 3
0 ≦ u ≦ 3, 1 ≦ (t + u) ≦ 3, 1 ≦ w ≦ 3, preferably 0 ≦ q ≦ 2, 0 ≦ r ≦ 2, 1 ≦ (q + r) ≦ 2,0
≦ s ≦ 1,0 ≦ t ≦ 2,0 ≦ u ≦ 2,1 ≦ (t + u) ≦
2, an integer that satisfies 1 ≦ w ≦ 2. And 2 ≦ (t
+ U) ≦ 3, 2 ≦ w ≦ 3, R ^{1 s} and R ^{2 s} may be the same or different.

The substituted hydroxy group represented by the above general formula (I)
Specific examples of the cyaromatic carboxylic acid ester derivative include:
(Hexadecyl salicylic acid) Hexadecyl phenyl ester
Tell, (tetradecylsalicylic acid) tetradecylpheni
Luester, (dodecyl salicylic acid) dodecyl phenyl
Ester, (decyl salicylic acid) decyl phenyl ester
Nonylphenyl (nonylsalicylic acid) ester,
(Hexadecyl salicylic acid) nonyl phenyl ester,
(Mixed C₁₁~ C₁₅) Alkyl salicylic acid (mixed C ₁₁~ C
₁₅) Alkyl phenyl ester, (mixed C₁₁~ C₁₅)
Rukylsalicylic acid hexadecyl phenyl ester, (mixed
Combined C₁₁~ C₁₅) Dodecyl phenyl alkylsalicylate
Stell, (mixed C₁₁~ C₁₅) Decyl alkylsalicylate
Phenyl ester, (mixed C₁₁~ C₁₅) Alkyl salici
Acid nonyl phenyl ester etc. are mentioned.

The substituted hydroxy group represented by the above general formula (II)
Specific examples of the cyaromatic carboxylic acid ester derivative include:
(Hexadecyl salicylic acid) Hexadecyl hydroxyphenyl
Phenyl ester, (tetradecyl salicylic acid) tetrade
Syl hydroxyphenyl ester, (dodecyl salicyl
Acid) dodecyl hydroxyphenyl ester, (decylsa
(Lycylic acid) decyl hydroxyphenyl ester, (Noni
Lusalicylic acid) nonyl hydroxyphenyl ester,
(Hexadecyl salicylate) nonyl hydroxyphenyl
Ester, (mixed C₁₁~ C₁₅) Alkyl salicylate hex
Sadecyl hydroxyphenyl ester, (mixed C₁₁~ C
₁₅) Dodecyl hydroxyphenyl alkylsalicylate
Stell, (mixed C₁₁~ C₁₅) Decyl alkylsalicylate
Hydroxyphenyl ester, (mixed C₁₁~ C₁₅) Al
Kirsalicylic acid nonyl hydroxyphenyl ester,
(Hexadecyldihydroxybenzoic acid) Hexadecyl
Phenyl ester, (tetradecyl dihydroxy benzoate
Acid) tetradecyl phenyl ester, (dodecyl dihydride
Roxybenzoic acid) dodecyl phenyl ester, (decyl
Dihydroxybenzoic acid) decyl phenyl ester, (no
Nyldihydroxybenzoic acid) nonylphenyl ester,
(Hexadecyldihydroxybenzoic acid) nonylphenyl
Ester, hexadecyldihydroxybenzoic acid (mixed C
₁₁~ C₁₅) Alkyl phenyl ester, dodecyl dihydride
Roxybenzoic acid (mixed C₁₁~ C₁₅) Alkylphenyl
Stell, decyldihydroxybenzoic acid (mixed C₁₁~
C₁₅) Alkylphenyl ester, nonyldihydroxy
Benzoic acid (mixed C₁₁~ C₁₅) Alkyl phenyl ester
Hexadecyl (hexadecyldihydroxybenzoic acid)
L-hydroxyphenyl ester, (tetradecyl dihydride
Roxybenzoic acid) tetradecyl hydroxyphenyl es
Tell, (dodecyldihydroxybenzoic acid) dodecyl hydride
Roxyphenyl ester, (decyldihydroxybenzoic acid
Acid) decyl hydroxyphenyl ester, (nonyldihi)
(Droxybenzoic acid) nonyl hydroxyphenyl ester
Nonyl hydrate (hexadecyldihydroxybenzoic acid)
Roxyphenyl ester, hexadecyldihydroxy ammonium
Benzoic acid (mixed C₁₁~ C₁₅) Alkyl hydroxyphenyl
Ester, dodecyldihydroxybenzoic acid (mixed C₁₁~
C₁₅) Alkyl hydroxyphenyl ester, decyldi
Hydroxybenzoic acid (mixed C₁₁~ C₁₅) Alkylhydro
Xyphenyl ester, nonyldihydroxybenzoic acid
(Mixed C₁₁~ C ₁₅) Alkyl hydroxyphenyl ester
And the like.

Specific examples of the substituted hydroxyaromatic carboxylic acid ester derivative represented by the above general formula (III) include:
(Hexadecylhydroxynaphthoic acid) hexadecylphenyl ester, (tetradecylhydroxynaphthoic acid) tetradecylphenyl ester, (dodecylhydroxynaphthoic acid) dodecylphenyl ester, (decylhydroxynaphthoic acid) decylphenyl ester, (nonylhydroxynaphthoic acid) Nonyl phenyl ester,
(Hexadecylhydroxynaphthoic acid) nonylphenyl ester, hexadecylhydroxynaphthoic acid (mixed C
₁₁ -C ₁₅₎ alkylphenyl ester, dodecyl hydroxynaphthoic acid (mixed C ₁₁ -C ₁₅₎ alkylphenyl ester, decyl hydroxynaphthoic acid (mixed C ₁₁ ~
C ₁₅ ) alkylphenyl ester, nonylhydroxynaphthoic acid (mixed C ₁₁ -C ₁₅ ) alkylphenyl ester, (hexadecyldihydroxynaphthoic acid) hexadecylphenyl ester, (tetradecyldihydroxynaphthoic acid) tetradecylphenyl ester, (dodecyldihydroxy) Naphthoic acid) dodecyl phenyl ester,
(Decyldihydroxynaphthoic acid) decylphenyl ester, (nonyldihydroxynaphthoic acid) nonylphenyl ester, (hexadecyldihydroxynaphthoic acid)
Nonylphenyl ester, hexadecyldihydroxynaphthoic acid (mixed C _{11 to} C ₁₅ ) Alkylphenyl ester, dodecyldihydroxynaphthoic acid (mixed C ₁₁ to C ₁₅ )
C ₁₅₎ alkyl phenyl ester, decyl dihydroxy naphthoic acid (mixed C ₁₁ -C ₁₅₎ alkylphenyl ester, nonyl dihydroxy naphthoic acid (mixed C ₁₁ -C ₁₅₎
Alkyl phenyl ester, (hexadecyl hydroxynaphthoic acid) hexadecyl hydroxyphenyl ester, (tetradecyl hydroxynaphthoic acid) tetradecyl hydroxyphenyl ester, (dodecyl hydroxynaphthoic acid) dodecyl hydroxyphenyl ester,
(Decylhydroxynaphthoic acid) decylhydroxyphenyl ester, (nonylhydroxynaphthoic acid) nonylhydroxyphenyl ester, (hexadecylhydroxynaphthoic acid) nonylhydroxyphenyl ester, hexadecylhydroxynaphthoic acid (mixed C ₁₁ -C ₁₅ ) alkyl hydroxyphenyl Ester, dodecyl hydroxynaphthoic acid (mixed C _{11 to} C ₁₅ ) Alkyl hydroxyphenyl ester, decyl hydroxynaphthoic acid (mixed C
₁₁ -C ₁₅₎ alkyl-hydroxyphenyl ester, nonyl hydroxynaphthoic acid (mixed C ₁₁ -C ₁₅₎ such as an alkyl-hydroxyphenyl ester.

The substituted hydroxyaromatic carboxylic acid ester derivative of the present invention having such a structure is a novel compound, and is an ashless detergent which is excellent in high temperature stability (high temperature detergency) in place of a metal detergent. And is suitable for use as an additive for lubricants of engine oils that meet strict exhaust gas regulations in the future, especially diesel engine and methanol engine oils.

Next, the substituted hydroxyaromatic carboxylic acid ester derivative according to the present invention can be produced by various methods. However, the substituted hydroxyaromatic carboxylic acid ester derivative having excellent performance as an additive for lubricants, etc. In order to obtain the derivative, it is preferable to produce it by the following method. That is, the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (I) of the present invention has the general formula (I
V)

[0025]

[Chemical formula 22]

[In the formula, R ¹ and x are the same as defined above. ] And an alkyl group-substituted salicylic acid represented by the general formula (V)

[0027]

[Chemical formula 23] [In the formula, R ² and y are the same as defined above. ] The alkyl group-substituted phenol represented by the above formula can be produced by reacting with or without a catalyst. Further, the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (II) of the present invention has the general formula (VI)

[0028]

[Chemical formula 24] [In the formula, R ¹ , m and o are the same as defined above. ] An alkyl group-substituted hydroxybenzoic acid represented by the general formula (VI
I)

[0029]

[Chemical 25] [In the formula, R ² , n and p are the same as defined above. ] It can manufacture by making the alkyl group substituted hydroxybenzene represented by these react with or without a catalyst. Further, the substituted hydroxyaromatic carboxylic acid ester derivative represented by the general formula (III) of the present invention is
General formula (VIII)

[0030]

[Chemical formula 26] [In the formula, R ¹ , q, r, t, and u are the same as described above. ] An alkyl group-substituted hydroxynaphthoic acid represented by the general formula (IX)

[0031]

[Chemical 27] [In the formula, R ² , s and w are the same as defined above. ] It can manufacture by making the alkyl group substituted hydroxybenzene represented by these react with or without a catalyst. In these reactions, the alkyl group-substituted salicylic acid, the alkyl group-substituted hydroxybenzoic acid or the alkyl group-substituted hydroxynaphthoic acid, and the alkyl group-substituted hydroxybenzene are used in a molar ratio of 1: 0.
The range of 01 to 1: 3, preferably 1: 0.2 to 1: 1.5 is desirable. The reaction temperature is usually 100 to 300 ° C.
It is preferably selected in the range of 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. When carrying out this reaction,
Solvents such as hydrocarbon oils and the like can be used. The above-mentioned alkyl group-substituted salicylic acid, alkyl group-substituted hydroxybenzoic acid or alkyl group-substituted hydroxynaphthoic acid are known from, for example, alkyl group-substituted phenol, alkyl group-substituted hydroxybenzene or alkyl metal-substituted naphthol alkali metal salts and carbon dioxide. The product obtained by the Kolbe-Schmidt reaction can be produced by hydrolysis.

As the alkyl group-substituted salicylic acid,
Examples thereof include nonylsalicylic acid, decylsalicylic acid, dodecylsalicylic acid, hexadecylsalicylic acid, octadecylsalicylic acid, eicosylsalicylic acid and the like.
As the alkyl group-substituted hydroxybenzoic acid, for example,
Dodecyl-2,3-dihydroxybenzoic acid, dodecyl-
2,4-dihydroxybenzoic acid, dodecyl-3,4-dihydroxybenzoic acid, nonyl-2,3-dihydroxybenzoic acid, hexadecyl-2,3-dihydroxybenzoic acid, octadecyl-2,3-dihydroxybenzoic acid, etc. Can be mentioned. Examples of the alkyl group-substituted hydroxynaphthoic acid include nonylhydroxynaphthoic acid, decylhydroxynaphthoic acid, dodecylhydroxynaphthoic acid, hexadecylhydroxynaphthoic acid and octadecylhydroxynaphthoic acid.

As the alkyl group-substituted hydroxybenzene, for example, nonylphenol, decylphenol, dodecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, nonyldihydroxybenzene, decyldihydroxybenzene,
Dodecyldihydroxybenzene, hexadecyldihydroxybenzene, octadecyldihydroxybenzene, eicosyldihydroxybenzene and the like can be mentioned. The position of the alkyl group in the alkyl group-substituted salicylic acid, the alkyl group-substituted hydroxybenzoic acid, the alkyl group-substituted hydroxynaphthoic acid and the alkyl group-substituted hydroxybenzene is not particularly limited.

The above general formula (I), (II) or (II of the present invention
The substituted hydroxyaromatic carboxylic acid ester derivative represented by I) is useful as an ashless detergent as described above. For example, the ester derivative is used as the component (A), and the component (B) is added thereto. As an ashless type dispersant, it is possible to prepare an additive composition for a lubricant which is excellent in high temperature stability (high temperature detergency) and has a fine particle dispersing action and which is suitable as an ashless type detergent dispersant. it can. Here, the ashless dispersant of the component (B) is not particularly limited, and conventionally known ones, for example, carboxylic acid imide type, carboxylic acid ester type or hydroxybenzylamine type, may be used alone or in combination. Can be used. The preferred acid site of the carboxylic acid imide type and the carboxylic acid ester type is succinic acid, and a carboxylic acid having a hydrocarbon group having a molecular weight of 200 or more in the molecular structure is suitable. Further, 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 are (1)
An organic nitrogen compound having at least one -NH- group,
For example, it is a reaction product with an amine, urea, hydrazine or the like, or (2) a reaction product with a hydroxy compound such as phenols or 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 and phosphorus compounds. For details of the carboxylic acid imide type and carboxylic acid ester type of
No. 60876. ).

On the other hand, the hydroxybenzylamine system includes, 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 additive composition for a lubricant using the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention, the ester derivative represented by the general formula (I), (II) or (III) which is the component (A) is used. The mixing ratio with the ashless dispersant which is the component (B) is 10:90 to 99: 1 by weight, preferably 15:90.
It is preferably in the range of 85 to 75:25.

Further, with respect to the base oil consisting of mineral oil and / or synthetic oil, as the component (A), the above-mentioned general formula (I),
A substituted hydroxyaromatic carboxylic acid ester derivative represented by (II) or (III) is further contained, and if necessary, the ashless type dispersant is further contained as the component (B). A lubricating oil composition suitable for engines and the like can be prepared. It is desirable that the component (A) and the component (B) that is optionally used be blended in a proportion of 1 to 30% by weight, preferably 2 to 20% by weight, based on the base oil. Here, the mineral oil used as the base oil may be any fraction such as paraffinic mineral oil, naphthenic mineral oil, and aromatic mineral oil, which has been subjected to any refining method such as solvent refining, hydrorefining or hydrocracking. Anything can be used. Further, as the synthetic oil, polyphenyl ether, alkylbenzene, alkylnaphthalene, ester-based, glycol-based or polyolefin-based synthetic oil can be used. The kinematic viscosity (100 ° C.) of the lubricating oil fraction is usually 1 to 50 cSt, preferably 3 to 1
It is in the range of 0 cSt.

Examples of the ester-based synthetic oil include esters of alcohols with monobasic acids or dibasic acids, for example,
A synthetic oil composed of an ester obtained by reacting a dibasic acid having 6 to 16 carbon atoms with a linear or branched alcohol having 5 to 20 carbon atoms 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. And
Examples of the polyolefin synthetic oil include liquid products obtained by low polymerization or copolymerization of lower olefins such as ethylene, propylene, butylene, octene, decene, and dodecene.
Mixtures thereof and hydrofinished products thereof are suitable. Further, a complex ester composed of a dibasic acid, glycol and a monobasic acid, or an α-olefin / dibasic acid copolymer ester can also be used.

In the lubricating oil composition using the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention, as the base oil, one of the above mineral oils may be used, or two or more thereof may be used in combination. Further, the synthetic oil may be used alone or in combination of two or more kinds. Further, one or more of the mineral oil and one or more of the synthetic oil may be used in combination. In the above-mentioned lubricating oil composition, in addition to the above-mentioned components, if necessary, various additive components commonly used in conventional lubricating oil compositions, for example, antioxidants, rust preventive agents,
An appropriate amount of antifoaming agent, viscosity index improver, pour point depressant, antiwear agent, demulsifier, metallic detergent, etc. can be added. The lubricating oil composition using the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is used, for example, as a lubricating oil for internal combustion engines, gear oils, bearing oils, transmission fluids, shock absorber oils, industrial lubricating oils, etc. I can, but
In particular, it is useful as a lubricating oil composition for internal combustion engines (such as diesel engines and methanol engines).

[0039]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. 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. Then
In a 2 liter separable flask, 500 g of the obtained polybutenyl succinic anhydride, 64 g (0.34 mol) of tetraethylenepentamine [TEPA: manufactured by Tosoh Corp.] and 300 g of mineral oil were placed, and the mixture was heated at 150 ° C. under a nitrogen stream at 2 ° C. Reacted for hours. 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. Further, 240 g of the obtained polybutenyl succinimide and 28 g of boric acid were placed in a 500 ml separable flask 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. Wash this reaction solution with water,
After phase separation, xylene was distilled off by filtration. The yield of the obtained reaction product was 312 g. Then, 300 g of the obtained reaction product and 100 g of hexadecylphenol were put into a 500 ml flask, and the mixture was heated to 250 g under a nitrogen stream.
The reaction was carried out at 5 ° C for 5 hours, 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 (X) and (XI), 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 the formulas (X) and (XI) is
It was confirmed that the compound of the formula (X) was 78 area% and the compound of the formula (XI) 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 formula (X) collected by liquid chromatography are shown in FIG. 1, FIG. 2, and FIG. 3 shows. Formula (X): (hexadecyl salicylic acid) hexadecyl phenyl ester

[0042]

[Chemical 28]

Formula (XI): (hexadecylhydroxybenzenedicarboxylic acid) bis (hexadecylphenyl) ester

[0044]

[Chemical 29]

Example 2 Example 1 was repeated except that a mixed alkylphenol having a carbon number of 11, 12, 13, 14, 15 (reaction product of propylene oligomer and phenol) was used in place of hexadecylphenol. It carried out similarly to.
This product is a mixture represented by the following formula (XII) (wherein R ¹ and R ² represent an alkyl group having 11 to 15 carbon atoms) from a compound separated by liquid chromatography. It was Then, the result of the electrolytic desorption / ionization mass spectrometry is
As shown in FIG. Formula (XII) :( mixed C ₁₁ -C ₁₅₎ alkyl salicylic acid (mixed C ₁₁ -C ₁₅₎ alkylphenyl ester

[0046]

[Chemical 30]

Example 3 The procedure of Example 1 was repeated, except that nonylphenol (a reaction product of a propylene oligomer and phenol) was used instead of hexadecylphenol. This product was a compound represented by the following formula (XIII) from the compound collected by liquid chromatography. The results of electrolytic desorption / ionization mass spectrometry, proton nuclear magnetic resonance spectroscopy, and carbon-13 nuclear magnetic resonance spectroscopy are shown in FIGS. 5, 6 and 7, respectively. Formula (XIII): (5-nonylsalicylic acid) p-nonylphenyl ester

[0048]

[Chemical 31]

Example 4 Example 1 was repeated except that a mixed alkylphenol having 11, 12, 13, 14, 15 carbon atoms (reaction product of propylene oligomer and phenol) was used instead of hexadecylphenol. In the same manner as above, the reaction product was purified to obtain an alkylsalicylic acid (the alkyl group has 11 to 15 carbon atoms). This alkylsalicylic acid was reacted with dodecylcatechol (a reaction product of 1-dodecene and catechol) in the same manner as in Example 1 to obtain a product. This product was a mixture represented by the following formula (XIV) (in the formula, R ¹ represents an alkyl group having 11 to 15 carbon atoms) from the compound separated by liquid chromatography. And the result of electrolytic desorption ionization mass spectrometry is shown in FIG. Formula (XIV) :( mixed C ₁₁ -C ₁₅₎ alkyl salicylic acid dodecyl-2-hydroxyphenyl ester

[0050]

[Chemical 32]

Example 5 The procedure of Example 1 was repeated except that dodecylcatechol (a reaction product of 1-dodecene and catechol) was used instead of hexadecylphenol, and the reaction product was purified. To give dodecyl-2,3-dihydroxybenzoic acid. This dodecyl-2,3-dihydroxybenzoic acid and a mixed alkylphenol having a carbon number of 11, 12, 13, 14, 15 (reaction product of propylene oligomer and phenol) were reacted in the same manner as in Example 1 to obtain a product. It was This product is obtained by the following formula (XV) (wherein R ² is a carbon number of 11 to 11) from a compound collected by liquid chromatography.
15 represents an alkyl group. ) Was a mixture represented by. Then, the result of the electrolytic desorption / ionization mass spectrometry is shown in FIG.
Shown in. Formula (XV): dodecyl-2,3-dihydroxybenzoic acid (mixed C ₁₁ -C ₁₅₎ alkylphenyl ester

[0052]

[Chemical 33]

Example 6 Example 6 was repeated except that dodecyl-1-naphthol (a reaction product of 1-dodecene and 1-naphthol) was used in place of hexadecylphenol. The reaction was purified to dodecyl-1-hydroxy-
2-Naphthoic acid was obtained. This dodecyl-1-hydroxy-2-naphthoic acid and carbon numbers 11, 12, 13, 14, 1
The mixed alkylphenol of 5 (reaction product of propylene oligomer and phenol) was reacted in the same manner as in Example 1 to obtain a product. This product is obtained by the following formula (XVIa) and / or formula from the compound collected by liquid chromatography.
(XVIb) (in the formula, R ² represents an alkyl group having 11 to 15 carbon atoms). The result of the electrolytic desorption / ionization mass spectrometry is shown in FIG. Formula (XVIa): dodecyl-1-hydroxy-2-naphthoic acid (mixed C ₁₁ -C ₁₅ ) alkylphenyl ester

[0054]

[Chemical 34] Formula (XVIb): dodecyl-1-hydroxy-2-naphthoic acid (mixed C ₁₁ -C ₁₅₎ alkylphenyl ester

[0055]

[Chemical 35]

Comparative Example 1 The procedure of Example 1 was repeated except that dodecylphenol (a reaction product of a propylene oligomer and phenol) was used in place of hexadecylphenol, and further purified to give 5-dodecyl. Salicylic acid was obtained. This 5-dodecylsalicylic acid and p-cresol were reacted in the same manner as in Example 1. This product has the formula (X
It was the compound represented by VII).

[0057]

[Chemical 36]

Comparative Example 2 5-octylsalicylic acid and p-octylphenol were reacted in the same manner as in Example 1. This product is
It was a compound represented by the following formula (XVIII).

[0059]

[Chemical 37]

Comparative Example 3 5-t-butylsalicylic acid and pt-butylphenol were reacted in the same manner as in Example 1. This product was a compound represented by the following formula (XIX).

[0061]

[Chemical 38]

Application Examples 1 to 9 (1) Preparation of Additive Composition for Lubricants (Ashless Detergent Dispersant) Ashless dispersant obtained in Reference Example 1 (boric acid-treated polybutenyl succinimide) 75% by weight and the formulas (X), (XII), (XIII) and (XI obtained in Examples 1 to 6 and Comparative Examples 1 to 3).
V), (XV), (XVI), (XVII), (XVIII) and 25% by weight of each substituted hydroxyaromatic carboxylic acid ester derivative represented by (XIX), and an additive composition for lubricant Was prepared.

(2) Preparation of Lubricating Oil Composition To the mineral oil of 500 neutral fraction, 10% by weight of the additive composition for lubricant obtained in the above (I) (2.5% by weight of phenol ester derivative, ashless) A mold dispersant (7.5% by weight) was blended 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 Conditions] Test oil 0.3 ml / hr, air 10 in a glass tube with an inner diameter of 2 mm.
The flow of milliliter / min was continued for 16 hours while maintaining the temperature of the glass tube at 310 ° C. 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,
In addition, the smaller the lacquer weight, the higher the performance.

[0065]

[Table 1]

As can be seen from Table 1, Application Example 1 using a lubricant additive composition comprising the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention and an ashless dispersant.
The lubricating oil compositions of Nos. 6 to 6 show better results in the hot tube test than the lubricating oil compositions of Application Examples 7 to 9 using the ester derivative of Comparative Example, and have excellent high-temperature stability (high-temperature detergency). ) Had.

[0067]

INDUSTRIAL APPLICABILITY The substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is a novel compound and is useful as an ashless detergent excellent in high temperature stability (high temperature detergency). An additive composition for a lubricant comprising the ester derivative and an ashless dispersant has excellent high temperature stability (high temperature detergency),
It is also suitable as an ashless detergent dispersant having a fine particle dispersing action. Further, the lubricating oil composition using the substituted hydroxyaromatic carboxylic acid ester derivative of the present invention is preferably used as an ashless type, particularly in diesel engine oil and methanol engine oil that comply with future emission regulations.

[Brief description of drawings]

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

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

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

FIG. 4 is a chart showing the results of electrolytic desorption / ionization mass spectrometry of the (mixed C _{11 to} C ₁₅ ) alkylsalicylic acid (mixed C _{11 to} C ₁₅ ) alkylphenyl ester obtained in Example 2.

FIG. 5: (5-nonylsalicylic acid) obtained in Example 3
It is a chart which shows the electrolytic desorption ionization mass spectrometry result of p-nonyl phenyl ester.

FIG. 6 (5-nonylsalicylic acid) obtained in Example 3
It is a chart which shows the proton nuclear magnetic resonance spectroscopy result of p-nonyl phenyl ester.

FIG. 7: (5-nonylsalicylic acid) obtained in Example 3
It is a chart which shows the carbon-13 nuclear magnetic resonance spectroscopy result of 5-nonyl phenyl ester.

FIG. 8 is a chart showing the results of electrolytic desorption / ionization mass spectrometry of the (mixed C _{11 to} C ₁₅ ) alkylsalicylic acid-dodecyl-2-hydroxyphenyl ester obtained in Example 4.

FIG. 9: Dodecyl-2,3-dihydride obtained in Example 5
Roxybenzoic acid (mixed C₁₁~ C ₁₅) Alkylphenyl
Chart showing the results of electrolytic desorption / ionization mass spectrometry of Stell
Is.

10 is a chart showing the results of electrolytic desorption / ionization mass spectrometry of the dodecyl-1-hydroxy-2-naphthoic acid (mixed C ₁₁ -C ₁₅ ) alkylphenyl ester obtained in Example 6. FIG.

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

Claims (4)

[Claims] 1. A compound represented by the general formula (I): [In the formula, x and y are integers satisfying 1 ≦ x ≦ 3 and 1 ≦ y ≦ 3, respectively, and R ¹ and R ² have 9 to ² carbon atoms.
0 alkyl groups, which may be the same or different from each other, in the case of 2 ≦ x ≦ 3 and 2 ≦ y ≦ 3, R ^{1 s} and R ^{2 s} are the same. Or they may be different. ], General formula (II) [Wherein, m, n, o and p are 1 ≦ m ≦ 2 and 0 ≦, respectively.
n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ o ≦ 3, 1 ≦ p ≦ 3
And R ¹ and R ² have 9 to 9 carbon atoms.
20 alkyl groups, which may be the same or different from each other, in the case of 2 ≦ o ≦ 3 and 2 ≦ p ≦ 3, R ^{1 s} and R ^{2 s} are the same. Or they may be different. ] Or general formula (III): [In the formula, q, r, s, t, u, and w are each 0 ≦ q
≦ 2, 0 ≦ r ≦ 2, 1 ≦ (q + r) ≦ 2, 0 ≦ s ≦ 2,
0 ≦ t ≦ 3, 0 ≦ u ≦ 3, 1 ≦ (t + u) ≦ 3, 1 ≦ w
Is an integer satisfying ≦ 3, and R ¹ and R ² represent an alkyl group having 9 to 20 carbon atoms, which may be the same or different from each other, 2 ≦ (t + u) ≦ 3 2 ≦
When w ≦ 3, R ^{1 s} and R ^{2 s} may be the same or different. ] The substituted hydroxy aromatic carboxylic acid ester derivative represented by these. 2. A compound represented by the general formula (IV): [In the formula, x is an integer satisfying 1 ≦ x ≦ 3, and R ¹ represents an alkyl group having 9 to 20 carbon atoms. And an alkyl group-substituted salicylic acid represented by the following general formula (V): [In the formula, y is an integer satisfying 1 ≦ y ≦ 3, and R ² represents an alkyl group having 9 to 20 carbon atoms. ] The method for producing a substituted hydroxyaromatic carboxylic acid ester derivative according to claim 1, which comprises reacting with an alkyl group-substituted phenol represented by the following formula in the absence of a catalyst or in the presence of a catalyst. 3. A compound represented by the general formula (VI): [In the formula, m and o are integers satisfying 1 ≦ m ≦ 2 and 1 ≦ o ≦ 3, respectively, and R ¹ represents an alkyl group having 9 to 20 carbon atoms. ] And an alkyl group-substituted hydroxybenzoic acid represented by the following general formula (VII) [In the formula, n and p are integers satisfying 0 ≦ n ≦ 2 and 1 ≦ p ≦ 3, respectively, and R ² represents an alkyl group having 9 to 20 carbon atoms. ] The method for producing a substituted hydroxyaromatic carboxylic acid ester derivative according to claim 1, which comprises reacting the alkyl group-substituted hydroxybenzene represented by the following with or without a catalyst. 4. A compound represented by the general formula (VIII):[In the formula, q, r, t, and u are 0 ≦ q ≦ 2 and 0 ≦, respectively.
r ≦ 2, 1 ≦ (q + r) ≦ 2, 0 ≦ t ≦ 3, 0 ≦ u ≦
3, an integer satisfying 1 ≦ (t + u) ≦ 3, and R ¹Is
Indicates an alkyl group having 9 to 20 carbon atoms, 2 ≦ (t + u) ≦
In case of 3, R¹Even though they are the same, they are different
Good. ] Alkyl group-substituted hydroxynaphtho represented by
Ethyl acid and the general formula (IX)[In the formula, s and w are 0 ≦ s ≦ 2 and 1 ≦ w ≦ 3, respectively.
Is an integer that satisfies R²Is an alkyl group having 9 to 20 carbon atoms
Indicates. ] An alkyl group-substituted hydroxybenze represented by
Reaction with a catalyst in the absence of a catalyst or in the presence of a catalyst.
The substituted hydroxyaromatic carbo according to claim 1, characterized in that
Method for producing acid ester derivative.