JPH07316576A - Lubricating oil additive for diesel engine and lubricating oil composition - Google Patents

Abstract

PURPOSE:To obtain an additive capable of improving cleanness of lubricating oil and extending working life of the oil, consisting of a specific aminoalcohol, having function to disperse water-contg. calcium sulfate into oil. CONSTITUTION:This additive consists of an aminoalcohol having in the molecule both amino and hydroxyl groups with the hydroxyl group on the C-atom at beta-site based on the N-atom and produced by epoxy ring opening reaction between (A) an amine compound of pref. formula I, II or III [R1 R3 are each (OH)-contg. 1-2C alkyl, alkenyl, aryl, or aralkyl; R4, R5 and R7 to R9 are each H, a 1-22C alkyl, alkenyl, aryl or aralkyl; R6 is a 2-4C alkylene; (n) is 0-20] and (B) an epoxy compound such as 1,2-epoxypropanol, glycerin monoglycidyl ether, trimethylolpropane monoglycidyl ether, bisphenol A monoglycidyl ether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating oil additive and a lubricating oil composition for land and marine diesel engines. More specifically, it relates to a lubricating oil additive for a diesel engine, which improves the cleanliness of the lubricating oil and extends the life of the lubricating oil, and a lubricating oil composition containing the additive.

[0002]

2. Description of the Related Art In recent years, piston / cylinder engines ranging from diesel engines for land use to ships and power generation are required to have high output and low fuel consumption, and maintenance-free. Is required. Above all, the cleaning function of the engine oil around the piston and the friction part keeps each function of the oil normal, which leads to a longer life.

However, in the present situation, diesel engines do not satisfy the above-mentioned requirements because of the influence of fuel gas and deterioration of the oil cleaning function. That is, for a ship and an engine for power generation, a low-quality fuel containing a large amount of petroleum distillation residue is used for cost reduction. Since the low-quality fuel contains a large amount of sulfur compounds, the combustion gas contains a large amount of sulfur oxides and also contains nitrogen oxides. These sulfur oxides and nitrogen oxides condense in the engine to form sulfuric acid and nitric acid, accelerate the formation of dirt components (sludge) in the oil, and aggregate and adhere. That is, when sulfuric acid or nitric acid is mixed into engine oil, deterioration of the oil is promoted, unburned products (soot) are aggregated, and corrosion is also increased, so that contaminant components are accumulated in the piston groove / bearing portion. As a result, the energy transmission parts such as the piston ring and the bearing friction part are damaged, causing serious troubles.

Further, in the case of land-based diesel engines, EGR (Exhaust Gas Recirculation) is required due to the recent exhaust gas regulations.
The method is beginning to be adopted. Therefore, the inside of the engine is more easily affected by the combustion gas, the oxidative deterioration of the oil in the combustion gas atmosphere as described above progresses, and the accumulation of sludge in the piston groove / bearing portion is accelerated.

That is, it has been confirmed to date that the mixing of these acidic substances into the lubricating oil accelerates the deterioration of the lubricating oil and significantly reduces the respective functions of the lubricating oil. Therefore, the current situation is that the frequency of replacement or replenishment of the lubricating oil eventually increases. In particular, the function of the lubricating oil, which decreases due to the mixing of acidic substances, is the cleaning function inside the engine, and the mixed contaminants such as lubricating oil deterioration products, combustion products, and abrasion powder accumulate around the piston and the cylinder liner periphery, Wear of the sliding parts becomes more severe. As a result, a normal compression ratio cannot be finally obtained, which affects navigation and driving.

Conventionally, for the production of such an acidic substance, an additive called a metallic detergent is used in the lubricating oil to neutralize the acidic substance produced in the engine and oxidize the lubricating oil. Taking measures to reduce deterioration (Journal of Japan Petroleum Institute Vo
L.35, No.1, 1992 Development of overbased sulfurized phenates and sulfurized salicylates). That is, as will be described later, the metal-based detergent is dissolved or dispersed in the lubricating oil in the state of a carboxylate / sulfonate / phenolate or carbonate of an alkaline earth metal such as calcium or magnesium to form a lubricant It neutralizes the mixed acidic substances.

However, since the metal-based detergent contains a metal such as calcium, the metal-based detergent has a high ash content and has a drawback of accumulating a residue in a high temperature region from the combustion chamber to the side wall of the piston. In addition, sulfates (calcium sulfate, etc.) and nitrates (calcium nitrate, etc.) formed from metal-based detergents and acidic substances absorb water and adhere to the piston ring, piston groove, and other peripheral parts. These sulfates, nitrates and the like that have absorbed water still tend to agglomerate the soot, which is an unburned substance, at high temperatures (150 to 300 ° C.), leaving the problem of facilitating the formation of soot stains.

In the lubricating oil composition of a diesel engine, succinic acid and poly with succinic acid substituted with long-chain alkyl described in JP-A-52-102892 and JP-A-61-257968 are used as an ashless dispersant. The alkylene polyamine reactant and its derivative may be used (added). Such an ashless dispersant is excellent in the effect of dispersing an inorganic substance containing no water in oil. However, the present situation is that the effect of dispersing inorganic substances that have absorbed water (water generated during combustion) in oil is very poor. From the above, there is still no satisfactory diesel engine lubricating oil additive and diesel engine lubricating oil composition that can sufficiently cope with the environmental deterioration in the engine due to "use of low quality fuel" and "exhaust gas regulation". The current situation is that it has not been done.

[0009]

Therefore, the present invention is
To provide a lubricating oil composition for a diesel engine, which can improve the cleanability of a lubricating oil for a diesel engine for land use and a ship, and thereby prolong the life of the lubricating oil, and a lubricating oil composition containing the same. The purpose is.

[0010]

Under the circumstances, the inventors of the present invention have earnestly studied the deterioration of the diesel engine lubricating oil and the contamination of the piston and the cylinder liner around the cylinder liner due to the mixing of the acidic substance. It was found that the soot-like stain formed on the part was formed by the absorption of water by an inorganic salt such as calcium sulfate. Furthermore, 1
When amino alcohols obtained by a ring-opening reaction of a primary amine or a secondary amine with an epoxy compound are added to a lubricating oil, the dispersing function of calcium sulfate containing water mixed in the lubricating oil is dramatically improved, and the lubricating oil The function of dispersing dirt components such as soot, sludge, etc. in oil is enhanced, the detergency is dramatically improved, the addition amount of metallic detergent can be reduced, and the life of lubricating oil is extended. It was found that the present invention can be achieved, and further research was conducted to complete the present invention.

That is, the gist of the present invention is to use water-containing calcium sulfate in oil, which has an amino group and a hydroxyl group in the molecule, and the hydroxyl group exists on the carbon atom at the β-position from the nitrogen atom. The present invention relates to a diesel engine lubricating oil additive comprising one or more amino alcohols having a dispersing function, and a diesel engine lubricating oil composition added with the diesel engine lubricating oil additive.

The present invention will be described in detail below. The diesel engine lubricating oil additive of the present invention has an amino group and a hydroxyl group in the molecule, and the hydroxyl group is present on the carbon atom at the β-position from the nitrogen atom. It is composed of one or more amino alcohols having a function of medium dispersion. These amino alcohols are epoxy ring-opening reaction products of an amine compound having one or more primary amino groups and / or secondary amino groups and a compound having an epoxy group.

(1) Amine Compound The amine compound as referred to in the present invention includes primary and / or secondary amine compounds.
An amine compound having one or more primary amino groups, 29
Those having a molecular weight of ˜2500 are preferably used.
Specifically, primary amines, secondary amines described below,
And polyalkylene polyamines. As the primary amine, a compound represented by the general formula (I)

[0014]

[Chemical 16]

Examples thereof include those having the structure shown in. In the formula, R ₁ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. The term "may have a hydroxyl group" as used herein corresponds to any substituent of an alkyl group, an alkenyl group, an aryl group, and an aralkyl group (the same applies hereinafter in the present specification. Is the same in the definition of). The number of carbon atoms of the aryl group or aralkyl group is up to 22 (this definition is the same in the following).

As the compound represented by the general formula (I),
Specifically, for example, monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, monolaurylamine, monomyristylamine, monopalmitylamine, monostearyl. Amine, monooleylamine, monobehenylamine,
Monophenylamine, mononaphthylamine, monobenzylamine, monoethanolamine, monopropanolamine, vinylamine, 1-propenylamine, 1,3-
Butadienylamine and the like can be mentioned. Particularly preferred amines have 2 to 18 carbon atoms, depending on the type of epoxy compound used in the reaction.

The secondary amine has the general formula (II)

[0018]

[Chemical 17]

Those having a structure represented by In the formula, R ₂ and R ₃ may be the same or different and each may have a hydroxyl group, and is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or Indicates an aralkyl group.

As the compound represented by the general formula (II),
Specifically, for example, dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylisopropylamine, dibutylamine, dihexylamine, dioctylamine, dilaurylamine, dimyristylamine, dipalmitylamine, distearylamine, dioleylamine. , Dibehenylamine, diphenylamine, dibenzylamine, di2-ethylhexylamine, diethanolamine, dipropanolamine and the like.
Particularly preferred amines are those having 2 to 18 carbon atoms, which vary depending on the type of epoxy compound used in the reaction.

The polyalkylene polyamine having a primary and / or secondary amino group is represented by the general formula (III)

[0022]

[Chemical 18]

Examples thereof include those having the structure shown in. In the formula, R ₄ , R ₅ , R ₇ , R ₈ and R ₉ may be the same or different and each is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or An aryl group or an aralkyl group is shown. R ₆ represents an alkylene group having 2 to 4 carbon atoms. Moreover, n shows 0-20. As the compound represented by the general formula (III), specifically, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, propylenediamine, dipropylenetriamine, tripropylenetetramine, Pentapropylenehexamine, Butylenediamine, Dibutylenetriamine, Tributylenetetramine, Tetrabutylenepentamine, Pentabutylenehexamine, Monostearylpropylenediamine, Monooleylpropylenediamine, Monopalmitylpropylenediamine, Monolaurylpropylenediamine, Monostearylethylenediamine, Mono Oleyl ethylenediamine,
Examples include monolauryl ethylenediamine. Particularly preferred polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, monostearylpropylenediamine and oleylpropylenediamine. When the polyamine has a high molecular weight, the synthetic product becomes very viscous and a special solvent is required, which is economically unfavorable. Therefore, n is preferably about 0 to 20, and a particularly preferable range is 0 to 6.

(2) Epoxy compound As the epoxy compound used in the synthesis of the amino alcohol of the present invention, (A) one having one epoxy group in the molecule, (B) two to four epoxies in the molecule The thing having a group is mentioned. Further, as the epoxy group, those having a 1,2-epoxy group are preferable from the viewpoint that the solubility of the resulting amino alcohol in oil and the orientation to stains are good. (A) One having one epoxy group in the molecule As the compound having an epoxy group, the adsorptivity of the resulting aminoalcohol to the stain becomes strong,
Those having a hydroxyl group in the molecule are preferable. Examples of such an epoxy compound having a hydroxyl group include 1,2-epoxypropanol, glycerin monoglycidyl ether, trimethylolpropane monoglycidyl ether, pentaerythritol monoglycidyl ether, ethylene glycol monoglycidyl ether, and bisphenol A monoglycidyl ether. , Propylene glycol monoglycidyl ether and the like. When this compound is used, it does not dissolve in oil unless it is reacted with a relatively long-chain amine compound.

As a paraffin-based epoxy compound,
General formula (XVI)

[0026]

[Chemical 19]

Those having a structure represented by In the formula, A ₁₆ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. Specific examples of the compound represented by the general formula (XVI) include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxyoctane, 1,2-epoxydecane, and 1,2-epoxydecane. Epoxy dodecane, 1,2-epoxy tetradecane, 1,2-epoxy hexadecane, 1,2-epoxy octadecane,
1,2-epoxy eicosane and the like can be mentioned.

As the ether-based epoxy compound, a compound represented by the general formula (XVII)

[0029]

[Chemical 20]

Those having a structure represented by In the formula, A ₁₇ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. Specific examples of the compound represented by the general formula (XVII) include ethyl glycidyl ether, propyl glycidyl ether, octyl glycidyl ether, 2 ethylhexyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, palmityl glycidyl ether, stearyl glycidyl ether. Ether, oleyl glycidyl ether,
Examples thereof include behenyl glycidyl ether, phenol glycidyl ether, octylphenol glycidyl ether, nonylphenol glycidyl ether and the like.

As the ester-based epoxy compound, a compound represented by the general formula (XVIII)

[0032]

[Chemical 21]

Those having a structure represented by In the formula, A ₁₈ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. These groups may have a hydroxyl group.

Specific examples of the compound represented by the general formula (XVIII) include acetic acid glycidyl ester, methacrylic acid glycidyl ester, 2-ethylhexyl acid glycidyl ester, caprylic acid glycidyl ester, lauric acid glycidyl ester, myristic acid glycidyl ester. Examples thereof include ester, glycidyl palmitate, glycidyl stearate, glycidyl oleate, and glycidyl behenate.

(B) Having 2 to 4 epoxy groups in the molecule As a compound having 2 to 4 epoxy groups in the molecule,
Amino acids having 4 to 30 carbon atoms are preferably used from the viewpoint that the obtained amino alcohol has a high function of dispersing dirt in oil. First, diglycidyl ether is mentioned as a compound which has two epoxy groups in a molecule. This compound has a high molecular weight when reacted with polyamines,
It can be used in the synthesis of the amino alcohol of the present invention by reacting with a secondary amine. When reacted with a primary amine, a reaction product excellent in the function of dispersing calcium sulfate containing water in oil is obtained by reacting with a primary amine in an equimolar amount with the epoxy group of the epoxy compound. be able to.

A compound having 2 to 4 epoxy groups in the molecule used for the synthesis of the amino alcohol of the present invention like diglycidyl ether, and can be used without being polymerized by reacting with a secondary amine. As, for example, glycerin triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, pentaerythritol tetraglycidyl ether,
Pentaerythritol triglycidyl ether, pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, propylene glycol diglycidyl ether, tartaric acid diglycidyl ester, succinic acid diglycidyl ester, malic acid diglycidyl ester, maleic acid diester Examples thereof include glycidyl ester, citric acid triglycidyl ester and trimellitic acid triglycidyl ester. Since these compounds have a high molecular weight when reacted with polyamines, the excellent additive of the present invention can be obtained by reacting with a secondary amine.

(3) Amino Alcohol of the Present Invention The amino alcohol of the present invention is obtained by an epoxy ring-opening reaction of the above amine compound and a compound having an epoxy group. There are many things. A: Amino alcohol obtained by using a compound having one epoxy group in the molecule 1) Compound a represented by the general formula (XIX) and compound b represented by the general formula (XX) are a primary monoamine and 1 , 2
An amino alcohol obtained by reacting one of the hydroxyl groups of a polyhydric alcohol such as epoxy propanol or glycerin monoglycidyl ether, pentaerythritol monoglycidyl ether with glycidyl etherification. In the formula, A ₁₉ and A _{20, which} may be the same or different, each represents a hydrogen atom or a polyhydric alcohol residue, and A ₂₁ represents a hydrogen atom or a polyhydric alcohol residue. Both R ₃₇ and R ₃₈ have 6 carbon atoms.
~ 22 are linear or branched alkyl or alkenyl groups, or aryl or aralkyl groups. When the number of carbon atoms is less than 6, the solubility in oil becomes low, which causes a problem in use. Compound a is obtained by reacting 1 mol of a primary amine with 2 mol of 1,2-epoxypropanol or glycerin monoglycidyl ether, pentaerythritol monoglycidyl ether, etc., in which one of the hydroxyl groups of a polyhydric alcohol is glycidyl etherified. Can be easily obtained. When R ₃₇ is an alkyl group, it preferably has 8 to 18 carbon atoms, and more preferably 10 to 18 carbon atoms.

[0038]

[Chemical formula 22]

In the compound b, one hydroxyl group of a polyhydric alcohol such as 1,2-epoxypropanol or glycerin monoglycidyl ether or pentaerythritol monoglycidyl ether is glycidyl etherified with respect to 1 mol of a primary amine. It can be obtained by reacting 1 mol of the compound, but in this case, it becomes a mixture with the compound a. When R ₃₈ is an alkyl group, it preferably has 8 to 16 carbon atoms, and more preferably 10 to 16 carbon atoms.

[0040]

[Chemical formula 23]

2) The compound c represented by the general formula (XXI) is a secondary monoamine and 1,2-epoxypropanol or glycerin monoglycidyl ether, one of the hydroxyl groups of a polyhydric alcohol such as pentaerythritol tetraglycidyl ether is glycidyl ether. It is an amino alcohol obtained by the reaction with a compound that has been converted.
A ₂₂ represents a hydrogen atom or a polyhydric alcohol residue.
R ₃₉ and R ₄₀ may be the same or different and each represents a linear or branched alkyl group or alkenyl group which may have a hydroxyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. . However, the number of alkyl carbon atoms of R ₃₉ + R ₄₀ is 6 or more (especially 6
To 44) are preferable. If the number of carbon atoms is less than 6, the solubility in oil will be low. Therefore, even if the number of carbon atoms of R ₃₉ is 1, but that of R ₄₀ is 6 or more, it can be preferably used. The preferred number of carbon atoms in the alkyl group of compound c is
R ₃₉ + R ₄₀ is 10 to 30, and more preferably 10
~ 24.

[0042]

[Chemical formula 24]

3) Compound d represented by the general formula (XXII)
Is a polyalkylene polyamine containing primary and secondary amines and one of the hydroxyl groups of a polyhydric alcohol such as 1,2-epoxypropanol or glycerin monoglycidyl ether, pentaerythritol tetraglycidyl ether, etc. being glycidyl etherified. Is an amino alcohol obtained by the reaction of R ₄₁ + R ₄₃ +
The sum of the number of carbon atoms of R ₄₄ + R ₄₅ is 6 or more (especially 6 to 88)
Is used. If the number of carbon atoms is less than that, the solubility in oil is low, which causes a problem in use. A ₂₃ represents a hydrogen atom or a polyhydric alcohol residue. R ₄₁ , R ₄₃ , R ₄₄ and R ₄₅ may be the same or different and each is a hydrogen atom or HOCH ₂ CH.
(OH) CH ₂ — group, a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an aryl group or an aralkyl group. Also, R ₄₂
Represents an alkylene group having 2 to 4 carbon atoms, and the repeating number n is 0 to 20. If it exceeds 20, the viscosity at the time of synthesis increases and the solvent dilution rate increases, which is economically disadvantageous. The preferred number of carbon atoms of the alkyl group (R ₄₁ , R ₄₃ , R ₄₄ , R ₄₅ ) of the compound d is 10 to 30 for R ₄₁ + R ₄₃ + R ₄₄ + R _45.
And the preferred number of carbon atoms of R ₄₂ is 2. Also,
n is preferably 0 to 4.

[0044]

[Chemical 25]

4) The compound e represented by the general formula (IV) and the compound f represented by the general formula (V) are reaction products of a primary monoamine and a paraffin epoxy compound (general formula (XVI)). In the formula, A ₁ and A ₂ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. R ₁₀ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. A ₃ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group. R ₁₁ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or aralkyl group.

If the total number of carbon atoms of R ₁₀ , A ₁ and A _{2 in} the compound e and the total number of carbon atoms of R ₁₁ and A _{3 in} the compound f are 6 or more (especially 6 to 62) respectively, it is compared with the oil. It is soluble and can be used advantageously in the present invention. The total number of carbon atoms of compound e is preferably 10 to 30, and more preferably 10 to 24. Further, the total number of carbon atoms of the compound f is preferably 10 to 24, more preferably 10 to 20.

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

5) The compound g represented by the general formula (VI) is a reaction product of a secondary monoamine and a paraffinic epoxy compound (general formula (XVI)). R ₁₂ and R ₁₃ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. Show. A ₄ has 1 carbon atom
~ 22 are linear or branched alkyl or alkenyl groups, or aryl or aralkyl groups. The preferred number of carbon atoms of A ₄ + R ₁₂ + R ₁₃ of the compound g is 6 to 64, preferably 10 to 30, and more preferably 10 to 24.

[0050]

[Chemical 28]

6) The compound h represented by the general formula (VII) is a reaction product of a polyalkylene polyamine containing primary and secondary amines and a paraffin epoxy compound (general formula (XVI)). In the formula, A ₅ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₁₄ , R
₁₆ , R ₁₇ and R ₁₈ may be the same or different and each is an A ₅ —CH (OH) CH ₂ — group, a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, Alternatively, it represents an aryl group or an aralkyl group. R ₁₅ represents an alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms. Also, n is 0
20 is shown, and preferably 0-4. If it exceeds 20, the viscosity at the time of synthesis increases and the solvent dilution rate increases, which is economically disadvantageous. The total number of carbon atoms of R ₁₄ , R ₁₆ , R ₁₇ , R ₁₈ , and A ₅ is preferably 6 or more (particularly 6 to 86 + 22n), and more preferably 10 to 30. R ₁₄ ,
R ₁₆ , R ₁₇ , and R ₁₈ may react with an epoxy compound.

[0052]

[Chemical 29]

7) Compound i represented by the general formula (VIII)
And a compound j represented by the general formula (IX) is a reaction product of a secondary monoamine and an ether type epoxy compound (general formula (XVII)). In the general formula (VIII), A ₆ and A ₇ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. R ₁₉ is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group,
Alternatively, it represents an aryl group or an aralkyl group. However,
The number of carbon atoms of R ₁₉ + A ₆ + A ₇ is 6 or more (especially 6 to 6).
6), preferably 10 to 30, and more preferably 10 to 24.

[0054]

[Chemical 30]

In the general formula (IX), A ₈ has 1 to 2 carbon atoms.
2 represents a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group. R
₂₀ is a carbon atom which may have a hydroxyl group 1
~ 22 are linear or branched alkyl or alkenyl groups, or aryl or aralkyl groups. However, the number of carbon atoms of R ₂₀ + A ₈ is 6 or more (especially 6 to
44), preferably 10 to 30, and more preferably 10 to 24. )

[0056]

[Chemical 31]

8) The compound k represented by the general formula (X) is a reaction product of a secondary monoamine and an ether type epoxy compound (general formula (XVII)). In the formula, A ₉ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. R ₂₁ and R ₂₂ may be the same or different and each represents an alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. However, A ₉
The number of carbon atoms of + R ₂₁ + R ₂₂ is 6 or more (particularly 6 to 66), preferably 10 to 30, and more preferably 10 to 24.

[0058]

[Chemical 32]

9) The compound l represented by the general formula (XI) is a polyalkylene polyamine having a primary and / or secondary amine and an ether type epoxy compound (the general formula (XVII)).
It is a reaction product of. In formula (XI), A ₁₀ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₂₃ , R ₂₅ , R ₂₆ and R ₂₇ may be the same or different and each is A ₁₀ —O—CH (OH) CH.
_{A 2} -group, a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group is shown. However, A ₁₀ + R ₂₃ +
The number of carbon atoms of R ₂₅ + R ₂₆ + R ₂₇ is 6 or more (especially 6 to 86).
+ 22n), preferably 10 to 30. R ₂₄
Represents an alkylene group having 2 to 4 carbon atoms, preferably 2. n shows 0-20, Preferably it is 0-4.

[0060]

[Chemical 33]

10) Compound m represented by the general formula (XII)
The compound n represented by the general formula (XIII) is a reaction product of a primary amine and an ester epoxy compound (general formula (XVIII)). In the general formula (XII), A ₁₁ and A
_12's may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₂₈ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. However, A ₁₁
The number of carbon atoms of + A ₁₂ + R ₂₈ is 6 or more (particularly 6 to 66), preferably 10 to 30, and more preferably 1
0 to 24.

[0062]

[Chemical 34]

In the general formula (XIII), A ₁₃ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or aralkyl group. R ₂₉ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. However, A ₁₃ + R ₂₉
Has 6 or more (particularly 6 to 44) carbon atoms, preferably 10 to 25, and more preferably 10 to 22.

[0064]

[Chemical 35]

11) Compound o represented by the general formula (XIV)
Is a reaction product of a secondary amine and an ester-based epoxy compound (general formula (XVIII)). In the formula, A ₁₄ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₃₀ and R ₃₁ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. Show. However, A
_The number of carbon atoms of ₁₄ + R ₃₀ + R ₃₁ is 6 or more (especially 6 to 66).
And preferably 10 to 30, and more preferably 10 to 24.

[0066]

[Chemical 36]

12) Compound p represented by the general formula (XV)
Is a polyalkylene polyamine having a primary and / or secondary amino group and an ester epoxy compound (general formula (XVII
I)) reaction product. In the formula, A ₁₅ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₃₂ , R ₃₄ , R
₃₅ and R ₃₆ may be the same or different and each is A _{15
-C (O) OCH 2 -CH (} OH) CH 2 - group shown, a hydrogen atom, a linear or branched alkyl or alkenyl group or an aryl group or an aralkyl group, of 1 to 22 carbon atoms. However, A ₁₅ + R ₃₂ + R ₃₄ + R ₃₅ + R
_The number of carbon atoms of ₃₆ is 6 or more (particularly 6 to 88 + 22n), and preferably 10 to 30. R ₃₃ has 2 carbon atoms
~ 4 alkylene group is shown, n is 0-20, preferably 0-4.

[0068]

[Chemical 37]

B: Amino alcohol obtained by using a compound having 2 to 4 epoxy groups in the molecule The reaction product of a compound having 2 to 4 epoxy groups in the molecule with a secondary amine is the present invention. It is particularly useful as an additive for. Examples of such epoxy compounds include glycidyl ether compounds of polyhydric alcohols and glycidyl esters such as dibasic acids and tribasic acids. By reacting such an epoxy compound with a secondary amine, a compound having good dispersibility in oil such as hydrous calcium sulfate can be obtained. However, in order to ensure solubility in oil, the total number of alkyl carbon atoms in the secondary amine is preferably 6 or more.
As a reaction product of the above-mentioned epoxy compound and a secondary amine, all epoxy groups in the molecule may react with the amine compound, and a partial reaction product or a partial reaction after leaving a part of the epoxy groups may occur. A compound in which an epoxy group is opened to generate a hydroxyl group can also be used as the additive of the present invention.

The reaction products of a compound having 2 to 4 epoxy groups in the molecule and a secondary amine, which are particularly useful in the present invention, are exemplified below. 1) First, the compound q represented by the general formula (XXIII) is a reaction product of a secondary amine and glycerin triglycidyl ether. In the formula, R ₄₆ and R _{47, which} may be the same or different, each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, R ₄₆ + R ₄₇
Has 6 or more (particularly 6 to 132) carbon atoms. Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0071]

[Chemical 38]

2) Compound r represented by the general formula (XXIV)
Is a partial reaction product of a secondary amine and glycerin triglycidyl ether. In the formula, R ₄₈ and R ₄₉ may be the same or different and each is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms,
Alternatively, it represents an aryl group or an aralkyl group. However, the number of carbon atoms of R ₄₈ + R ₄₉ is 6 or more (especially 6 to 8).
8). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0073]

[Chemical Formula 39]

3) Compounds represented by the general formula (XXV)
Is a reaction product of a secondary amine and pentaerythritol tetraglycidyl ether. In the formula, R ₅₀ , R
₅₁ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₅₀ + R ₅₁ is 6 or more (particularly 6 to 176). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0075]

[Chemical 40]

4) Compound t represented by the general formula (XXVI)
Is a reaction product of a secondary amine and pentaerythritol diglycidyl ether. In the formula, R ₅₂ and R ₅₃ may be the same or different and each has 1 to 2 carbon atoms.
2 represents a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₅₂ + R ₅₃ is 6 or more (especially 6 to 8).
8). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0077]

[Chemical 41]

5) Compound u represented by the general formula (XXVII)
Is a reaction product of a secondary amine and trimethylolpropane triglycidyl ether. In the formula, R ₅₄ , R
_{55, which} may be the same or different, each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₅₄ + R ₅₅ is 6 or more (particularly 6 to 132). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0079]

[Chemical 42]

6) The compound v represented by the general formula (XXVIII) is a reaction product of a secondary amine and ethylene glycol diglycidyl ether. In the formula, R ₅₆ and R ₅₇ may be the same or different and each has 1 to 2 carbon atoms.
2 represents a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₅₆ + R ₅₇ is 6 or more (especially 6 to 8).
8). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0081]

[Chemical 43]

7) Compound w represented by the general formula (XXIX)
Is a reaction product of a secondary amine and propylene glycol diglycidyl ether. In the formula, R ₅₈ and R ₅₉ may be the same or different and each has 1 to 2 carbon atoms.
2 represents a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₅₈ + R ₅₉ is 6 or more (especially 6 to 8).
8). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0083]

[Chemical 44]

8) Compound x represented by the general formula (XXX)
Is a reaction product of a secondary amine and diglycidyl ether. In the formula, R ₆₀ and R _{61, which} may be the same or different, each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, the number of carbon atoms of R ₆₀ + R ₆₁ is 6 or more (particularly 6 to 88). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0085]

[Chemical formula 45]

9) Compound y represented by the general formula (XXXI)
Is a reaction product of a secondary amine and bisphenol A diglycidyl ether. In the formula, R ₆₂ and R ₆₃ may be the same or different and each is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms,
Alternatively, it represents an aryl group or an aralkyl group. However, the number of carbon atoms of R ₆₂ + R ₆₃ is 6 or more (especially 6 to 8).
8). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0087]

[Chemical formula 46]

10) The compound z represented by the general formula (XXXII) is a reaction product of a secondary amine and tartaric acid diglycidyl ester. In the formula, R ₆₄ and R _{65, which} may be the same or different, each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, R ₆₄ +
The number of carbon atoms of R ₆₅ is 6 or more (particularly 6 to 88).
Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0089]

[Chemical 47]

11) The compound α represented by the general formula (XXXIII) is a reaction product of a secondary amine and malic acid diglycidyl ester. In the formula, R ₆₆ and R ₆₇ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, R
_The number of carbon atoms of ₆₆ + R ₆₇ is 6 or more (particularly 6 to 88). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0091]

[Chemical 48]

12) The compound β represented by the general formula (XXXIV) is a reaction product of a secondary amine and succinic acid diglycidyl ester. In the formula, R ₆₈ and R ₆₉ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, R ₆₈
The number of carbon atoms of + R ₆₉ is 6 or more (particularly 6 to 88). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0093]

[Chemical 49]

13) The compound γ represented by the general formula (XXXV) is a reaction product of a secondary amine and citric acid triglycidyl ester. In the formula, R ₇₀ and R _{71, which} may be the same or different, each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. However, R
_The number of carbon atoms of ₇₀ + R ₇₁ is 6 or more (particularly 6 to 132). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0095]

[Chemical 50]

14) The compound δ represented by the general formula (XXXVI) is a reaction product of a secondary amine and trimellitic acid triglycidyl ester. In the formula, R ₇₂ and R ₇₃ may be the same or different and each has 1 to 22 carbon atoms.
Is a linear or branched alkyl group or alkenyl group, or an aryl group or aralkyl group. However, the number of carbon atoms of R ₇₂ + R ₇₃ is 6 or more (especially 6 to 1).
32). Further, in the synthesis of this compound, secondary amines having different numbers of alkyl carbon atoms may be used.

[0097]

[Chemical 51]

The amino alcohols described above are suitable examples for use in the present invention, but the present invention is not limited thereto. Further, by adding these amino alcohols to the lubricating oil for diesel engines, the dispersion function of calcium sulfate containing water in oil is improved. These amino alcohols, depending on the usage,
That is, it is possible to use two or more kinds in combination depending on the water content of the inorganic substance.

Such amino alcohol can be produced, for example, according to the following reactions. In the formula, R has 1 to 22 carbon atoms which may have a hydroxyl group.
A linear or branched alkyl group or alkenyl group, an aryl group or an aralkyl group, R'is a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, Represents a number from 0 to 20, and m represents a number from 1 to 24.
However, the total number of carbon atoms of R and R ′ is 6 or more.

[0100]

[Chemical 52]

[0101]

[Chemical 53]

[0102]

[Chemical 54]

[0103]

[Chemical 55]

[0104]

[Chemical 56]

[0105]

[Chemical 57]

[0106]

[Chemical 58]

[0107]

[Chemical 59]

[0108]

[Chemical 60]

The above synthetic reaction can be carried out as follows. First, a primary amine or secondary amine as a raw material is stirred at a temperature of 80 ° C. or lower, preferably room temperature or lower, and an epoxy compound is added dropwise. This reaction does not require a catalyst. Here, when the raw material amine or the raw material epoxy compound is a solid, it can be used by dissolving it in a solvent such as ethanol, toluene, xylene or hexane.
The dropping rate of the epoxy compound is not particularly limited and may be adjusted so that the temperature falls within the above range. After the dropping of the epoxy compound, aging is carried out for 3 to 8 hours, and then, when a solvent is used, this is removed (topping separation) by reduced pressure or the like to obtain an amino alcohol. This synthetic method, conditions, etc. are similarly applicable to the reaction of primary amine, secondary amine or polyalkylene polyamine with all epoxy compounds described in this specification.

In the amino alcohol of the present invention thus obtained, all the hydroxyl groups obtained by opening the epoxy ring are present on the carbon atom at the β-position from the nitrogen atom. Therefore, this hydroxyl group is conjugated with a nitrogen atom and becomes an adsorption group having an effective chelating effect on metal salt stains, and disperses stain components in oil. In addition, since the amino alcohol of the present invention needs to be dissolved in a lubricating oil for diesel engines, a group (R) in which a nitrogen atom of a primary amine or a secondary amine as a raw material is substituted and an epoxy ring of an epoxy compound are substituted. It is preferable that the total number of carbon atoms of the group (R ′) and the group (R ′) is 6 or more. The amino alcohol of the present invention can be used in the range of 0.1 to 10% by weight with respect to the diesel engine lubricating oil, and preferably by adding 0.2 to 3.0% by weight, the sludge dispersion of the diesel engine lubricating oil can be improved. Easy and distributed
Improve the cleaning effect. If the addition amount is less than 0.1% by weight, the dispersing effect is reduced, and if it exceeds 10% by weight, there is no corresponding effect and it is uneconomical.

The ring-opening reaction product of an epoxy compound and a primary or secondary amine may be used as a rust preventive for lubricating oils (JP-A-61-225154 and JP-A-62-125154). 270697). However, the lubricating oil additive for diesel engines of the present invention has a function of dispersing calcium sulfate containing water in oil,
It has completely different properties from the rust preventive agent, and the following chemical structure is essential and exhibits the above functions. That is,
The amino alcohol of the present invention is an epoxy compound and a primary,
All of the hydroxyl groups formed by the reaction with the secondary amine are characterized by being present on the carbon atom at the β-position from the nitrogen atom. As described above, this hydroxyl group becomes an adsorption group that is conjugated with the nitrogen atom and has an effective chelating effect on metal salt stains, effectively functions as a trap for inorganic salts such as calcium sulfate, and disperses stain components in oil. To do. Due to this property, the purpose of effective dispersion of the inorganic salt can be achieved by dissolving these compounds in oil. On the other hand, the rust preventive effect is that the ring-opening reaction product of the epoxy compound and the primary or secondary amine is adsorbed on the metal wall as a whole molecule to exert the rust preventive effect. Although it is completely different from the effect of dispersion in oil by adsorption, it is particularly required that the characteristic positional relationship between the hydroxyl group and the nitrogen atom in the present invention is particularly required in the compound effective for the rust preventive effect. In addition, it is pointed out that the action is enhanced when there are two or more characteristic structures between the hydroxyl group and the nitrogen atom in one molecule, and that it is also useful as a rust preventive agent. Absent. Therefore, it is understood that the rust prevention effect requires a structure in which the entire molecule including one such structure is integrated.

The amino alcohol of the present invention can be used alone as a lubricating oil additive for diesel engines of the present invention, but by further using a metal-based detergent in combination, a lubricating oil composition for diesel engines of the present invention can be obtained. It can also be used. The metal-based detergent is not particularly limited as long as it has been conventionally used as a lubricating oil additive for diesel engines, and examples thereof include petroleum sulfonic acid (hereinafter referred to as petroleum sulfonate-based metal detergent) and synthetic sulfonic acid. , A neutral salt of an alkaline earth metal salt of an organic acid such as an alkylphenol sulfide polymer (hereinafter abbreviated as a phenate metal detergent), an alkyl salicylic acid (hereinafter referred to as a salicylate metal detergent), or an alkaline earth An overbased compound containing a carbonate of a similar metal may be mentioned. The amount of the metallic detergent compounded varies depending on the type of fuel used, but is usually 0.5 to 50% by weight, 5.0 to 50% by weight in the lubricating oil for diesel engines for ships, and 0 for land. It is preferably from 0.5 to 10% by weight.

The lubricating oil additive of the present invention can be further mixed with a base oil together with an ashless dispersant and an extreme pressure lubricant to give the lubricating oil composition for diesel engines of the present invention.

The base oil used in the lubricating oil composition for diesel engines of the present invention is not particularly limited, and examples thereof include those usually used as base oils, but generally 20 to 250 mm ² / sec, 40 Mineral oils or synthetic oils at ° C are preferred. Here, the mineral oil refers to paraffinic hydrocarbons, aromatic hydrocarbons, or a mixture thereof, and examples of synthetic oils include poly α-olefins, esters, polyglycols, and the like.

The ashless dispersant used in the diesel engine lubricating oil composition of the present invention is not particularly limited, and conventionally known ones can be used, but carboxylic acid compounds and amide compounds of amines can be used. Commonly used alkenyl succinimide is a typical example. Examples of the carboxylic acid compound used here include polyolefin maleic anhydride derivatives and fatty acids, and examples of the amines include polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. The ashless dispersant is preferably added in the lubricating oil composition in an amount of 0.1 to 10% by weight, and a relatively large amount needs to be added in order to ensure high detergency.

The extreme pressure lubricant used in the diesel engine lubricating oil composition of the present invention is not particularly limited.
Although conventionally known compounds can be used, for example, zinc dialkyldithiophosphate, zinc alkylphosphate, alkaline earth metal salt of alkylphosphate, alkylphosphate ester,
Fatty acids and the like can be mentioned. Such extreme pressure lubricant is preferably blended in the lubricating oil composition for diesel engines in an amount of 0.01 to 5% by weight.

The lubricating oil composition for diesel engines of the present invention has a molecular weight of 10,000 to 100,000 and a lauryl methacrylic acid ester copolymer, depending on the characteristics required in the region and conditions of use, as long as the effects of the present invention are not impaired. A flow effect agent / viscosity index improver having a basic skeleton, an antioxidant such as tertiary butyl paracresol, a metal deactivator such as triphenylphosphite, and a viscosity of 10 cSt to 100,000 cS.
A dimethylsilicon-based antifoaming agent at t / 25 ° C. can be blended.

[0118]

EXAMPLES 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.

Example 1 The cleanliness of the lubricating oil composition was evaluated using the hot tube tester shown in FIG. That is, lubricating oil and air that had been deteriorated in advance were inserted into a glass tube heated to a constant temperature, and the state of adhesion of dirt components due to deterioration of the lubricating oil was observed and evaluated as a lacquer rating. <Setting conditions> Oil insertion amount: 6 ml / 16 hours Air insertion amount: 10 ml / min Heating part temperature: 280 to 320 ° C. <Lubricant oil treatment method> Acidic substances (sulfuric acid) mixed in during actual operation, combustion generation Assuming materials and abrasion powder, each lubricating oil was pretreated under the following conditions. That is, carbon black, iron powder, and sulfuric acid were added at the following ratio at a lubricating oil temperature of 100 ° C.
What was stirred and mixed for 10 minutes was used as a test oil. Carbon black: 0.2% by weight of lubricating oil 5 μm or less iron powder: 0.05% by weight of lubricating oil Sulfuric acid: 0.8% by weight of lubricating oil

<Evaluation Method> The glass tube after the 16-hour test is compared with a predetermined standard color to give an evaluation score of 1 to 10. Evaluation point 1: The glass tube has the most stains and is discolored to black (black carbonization) Evaluation point 5: The stains on the glass tube is medium and discolored to pale yellow Evaluation point 10: The stains on the glass tube The glass tube with the smallest number and almost the same state as the original glass tube has a higher evaluation point, indicating that the cleanliness is better. <Lubricating oil composition> A mixture of the amino alcohol of the present invention shown in Tables 2 to 4 and other components in the composition shown in Table 1 was used as a test oil.

[0121]

[Table 1]

* 1: The compounds are shown in Tables 2-4. * 2: Using the products with the following alkalinity, the alkalinity of the lubricating oil composition was adjusted to 30 TBN or 15 TBN. b1: salicylate-based detergent = 200 TBN TBN (total base number): 1 TBN corresponds to 1 KOHmg / g in an industry unit showing an alkali number. b2: Phenate-based detergent = 170 TBN b3: Petroleum sulfonate-based detergent = 227 TBN * 3: Polybutenyl succinimide (bis type) * 4: Zinc dithiophosphate (primary type) * 5: Natural mineral oil (120 cSt / 40) (° C.) (paraffin-based) All the above raw materials are commercial products.

[0123]

[Table 2]

[0124]

[Table 3]

[0125]

[Table 4]

<Results> The results are shown in Tables 5 and 6.

[0127]

[Table 5]

[0128]

[Table 6]

It can be seen that the detergency of the lubricating oil containing the amino alcohol of the present invention is all improved. Particularly, the cleanliness in the high temperature part (300 to 320) was remarkably improved.
Further, the cleaning effect of the amino alcohol of the present invention is effectively recognized regardless of the kind of the metal-based detergent, and the addition amount of the metal-based detergent or the ashless dispersant can be reduced.

Example 2 4-cylinder diesel engine SD- manufactured by Nissan Motor Co., Ltd.
22 was used to evaluate the cleanliness of the piston. The fuel used was a mixture of heavy oil A / light oil (1: 1) and DBDS
The sulfur concentration in the fuel was adjusted to be equivalent to C heavy oil (3%) with (di-t-butyldisulfide). The detailed experimental conditions and engine types used are described below. <Engine used> Type: 4-cycle, 4-cylinder, water-cooled diesel engine Displacement: 2.2 liters Combustion method: Sub-chamber type Bore x Stroke: 80 x 83.6 mm Compression ratio: 22.2 <Engine test conditions> Engine test Time: 100 hours Engine speed: 3000 rpm Fuel: A heavy oil / light oil (1: 1) + DBDS (S = 3%)

<Evaluation site of cleanliness and evaluation criteria> Evaluation site of cleanliness: piston land (TOP, 2nd, 3rd
(Refer to Fig. 2) Cleanliness evaluation criteria: The dirt condition of the piston land is classified and evaluated as follows F: Carbon adhered (almost all) E: Carbon adhered (piston circumferential direction 1/3) Adhesion over the area) D: Carbon adhering (Adhesion under 1/3 area in the piston circumferential direction) C: Discolored light yellow (discolored over 1/3 area in the piston circumferential direction) B: Discolored light yellow (piston (Discoloration at 1/3 area or less in the circumferential direction) A: No discoloration <Test oil> The test oils shown in Table 7 were used. The test oils (72, 73, 78, 79, 80, 84) were prepared in Example 3 described later.

<Results> The results are shown in Table 7. As is clear from these results, it was found that the lubricating oil composition of the present invention to which the amino alcohol was added markedly improved the cleanliness of the piston. Since the combustion gas directly participates in the piston land portion, carbon dirt is generally likely to accumulate. Therefore, regarding the cleanliness of the piston, dirt on the lower part (2nd part, 3rd part) is regarded as important. It can be seen that the lubricating oil composition of the present invention is very effective especially in the 2nd land portion and the 3rd portion. The effect of this piston cleanliness is that the addition amount of the amino alcohol of the present invention is 0.5%.
Was well accepted.

[0133]

[Table 7]

Example 3 The dispersion effect in water of calcium sulfate absorbing water was tested. The test method was a lubricating oil composition (Table 8) prepared by adding 30 TBN with a metallic detergent (calcium salicylate).
The test oil described in 12) was used to observe the dispersion state of calcium sulfate. That is, sulfuric acid diluted to 60% with water was added to the test oil, and the mixture was stirred for a certain period of time and the dispersion state of the produced calcium sulfate was visually observed and judged. Calcium sulfate produced by mixing sulfuric acid has a property of absorbing a large amount of water, and it is easy to use calcium sulfate (theoretical water ≈3.63 mol / CaSO ₄ 1 mol) that has absorbed water by using sulfuric acid diluted with water beforehand. To form.

<Test conditions> 1) 50 g of test oil was sampled in a test tube having an inner diameter of 30 mm, and sulfuric acid previously diluted with water to 60% was diluted with 9 TBN (KOHmg /
g) Add a neutralizing amount (0.65 g / 50 goil). 2) Next, the temperature is raised to 50 ° C. and the stirrer (flat stirrer 1
20 mm × 18 mm) and stir for 10 minutes. 3) After completion of stirring, the mixture was allowed to stand at a temperature of 50 ° C. for 30 minutes, and then the dispersion state of calcium sulfate in oil was visually judged.

<Evaluation Method> A: Calcium sulfate is in a state of being dispersed in oil without adhering to or precipitating on the container wall. B: A dispersion state in which a part (about 1/3) of calcium sulfate adheres and precipitates on the container wall. C: A dispersed state in which more than half of the calcium sulfate adhered / precipitated on the container wall. D: A state of dispersion in which all of the calcium sulfate adhered / precipitated to the container wall.

<Results> The obtained results are shown in Tables 8 to 12. The results are summarized below.

(1) The dispersion performance of calcium sulfate was tested within the range of 0.05 to 5% by weight of the amino alcohol of the present invention. As a result, the added amount is 0.05% by weight.
Then the dispersion performance is poor. However, when the addition amount is 0.1% by weight or more, the dispersion effect is exhibited, and when the addition amount is 0.25% or more, the dispersion effect is very good.

(2) The effect of the amino alcohol of the present invention was tested on a lubricating oil composition containing no ashless dispersant and extreme pressure lubricant. As a result, sufficient dispersion performance is exhibited by adding only the amino alcohol of the present invention. Further, the effect was equivalent to the effect that can be confirmed in the composition to which the ashless dispersant and the extreme pressure lubricant were added.

(3) Almost no ashless dispersant used in a diesel engine lubricating oil has the effect of dispersing calcium sulfate (hydrated salt). And coarse particles are precipitated on the bottom of the container (Comparative Examples 1 and 2).

[0141]

[Table 8]

[0142]

[Table 9]

[0143]

[Table 10]

[0144]

[Table 11]

[0145]

[Table 12]

[0146]

EFFECT OF THE INVENTION The lubricating oil additive for diesel engines of the present invention dramatically improves the cleanability of the lubricating oil, and the addition amount of the metallic detergent can be reduced thereby, and The life can be extended.

[Brief description of drawings]

FIG. 1 is a diagram showing an outline of a hot tube tester used for evaluation of cleanliness of a lubricating oil composition in Example 1.

FIG. 2 is a diagram showing a portion where the cleanliness of a piston is evaluated in Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C10M 129: 18) (C10M 159/12 133: 12 129: 18) C10N 30:04 30:06 30 : 08 40:25

Claims (15)

[Claims] 1. An amino having an amino group and a hydroxyl group in the molecule, the hydroxyl group being present on the carbon atom at the β-position from the nitrogen atom, and having the function of dispersing calcium sulfate containing water in oil. Lubricating oil additive for diesel engines consisting of one or more alcohols. 2. The diesel engine according to claim 1, wherein the amino alcohol is obtained by an epoxy ring-opening reaction of an amine compound having one or more primary and / or secondary amino groups with a compound having an epoxy group. Lubricating oil additive. 3. The lubricating oil additive for diesel engines according to claim 2, wherein the compound having an epoxy group has one epoxy group in the molecule. 4. The lubricating oil additive for diesel engines according to claim 2, wherein the compound having an epoxy group has 2 to 4 epoxy groups in the molecule. 5. The diesel engine lubricating oil additive according to any one of claims 2 to 4, wherein the compound having an epoxy group has a 1,2-epoxy group. 6. The lubricating oil additive for diesel engines according to claim 4, wherein the compound having 2 to 4 epoxy groups in the molecule has 4 to 30 carbon atoms. 7. The compound having an epoxy group is a compound having a hydroxyl group in the molecule.
The lubricating oil additive for diesel engines according to any one of claims 1. 8. The lubrication for a diesel engine according to claim 2, wherein the amine compound having one or more primary and / or secondary amino groups has a molecular weight of 29 to 2,500. Oil additive. 9. An amine compound having at least one primary and / or secondary amino group is a primary amine represented by the general formula (I), a secondary amine represented by the general formula (II), or a general formula.
The lubricating oil additive for diesel engines according to any one of claims 2 to 8, which is a polyalkylene polyamine represented by (III). [Chemical 1] (In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group.) (In the formula, R ₂ and R ₃ may be the same or different and each may have a hydroxyl group, and is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group. Alternatively, it represents an aralkyl group.) (In the formula, R ₄ , R ₅ , R ₇ , R ₈ and R ₉ may be the same or different and each is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, Or an aryl group or an aralkyl group, R ₆ represents an alkylene group having 2 to 4 carbon atoms, and n represents 0 to 20). 10. A compound obtained by an epoxy ring-opening reaction of an amine compound having at least one primary and / or secondary amino group with a compound having an epoxy group is represented by the general formula (I):
An amine compound represented by (II) or (III), 1,2-
Reaction with an epoxy compound selected from the group consisting of epoxy propanol, glycerin monoglycidyl ether, trimethylolpropane monoglycidyl ether, pentaerythritol monoglycidyl ether, ethylene glycol monoglycidyl ether, bisphenol A monoglycidyl ether, and propylene glycol monoglycidyl ether. The lubricating oil additive for diesel engine according to claim 9, which is obtained by 11. A compound obtained by an epoxy ring-opening reaction of an amine compound having one or more primary and / or secondary amino groups with a compound having an epoxy group is represented by the general formula (IV) or the general formula (V). , General formula (VI), general formula (VII), general formula (VIII),
General formula (IX), general formula (X), general formula (XI), general formula (XII)
The lubricating oil additive for diesel engines according to claim 2, which is one or more selected from the group consisting of compounds represented by the general formula (XIII), the general formula (XIV), and the general formula (XV). [Chemical 4] (In the formula, A ₁ and A ₂ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₁₀ represents A linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group is shown, provided that the number of carbon atoms of A ₁ + A ₂ + R ₁₀ is 6 ˜62.) (In the formula, A ₃ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₁₁ has 1 carbon atom which may have a hydroxyl group. To 22 are a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group, provided that A ₃ + R ₁₁ has 6 to 42 carbon atoms. (In the formula, A ₄ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. R ₁₂ and R ₁₃ may be the same or different, Each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or an aralkyl group, provided that A ₄ + R ₁₂ + R
_The number of carbon atoms of ₁₃ is 6 to 64. ) [Chemical 7] (In the formula, A ₅ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₁₄ , R ₁₆ , R ₁₇ and R ₁₈ are the same or different. A _5-
CH (OH) CH ₂ — group, hydrogen atom, carbon atom number 1 to 2
2 represents a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group. R
₁₅ represents an alkylene group having 2 to 4 carbon atoms. Also, n
Indicates 0 to 20. However, A ₅ + R ₁₄ + R ₁₆ + R ₁₇ + R
_The number of carbon atoms of ₁₈ is 6 to 86 + 22n. ) [Chemical 8] (In the formula, A ₆ and A ₇ may be the same or different and each represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. R ₁₉ is hydroxyl. Represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or an aryl group or aralkyl group which may have a group, provided that R ₁₉ + A ₆ + A ₇
Has 6 to 66 carbon atoms. ) [Chemical 9] (In the formula, A ₈ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, an aryl group or an aralkyl group. R ₂₀ represents the number of carbon atoms which may have a hydroxyl group. 1 to 22 is a linear or branched alkyl group or alkenyl group, or an aryl group or an aralkyl group, provided that R ₂₀ + A ₈ has 6 to 44 carbon atoms. (In the formula, A ₉ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group. R ₂₁ and R ₂₂ may be the same or different and each is a hydroxyl group. Represents an alkyl group or an alkenyl group having 1 to 22 carbon atoms, or an aryl group or an aralkyl group which may have a group, provided that the number of carbon atoms of A ₉ + R ₂₁ + R ₂₂ is 6 to 6
It is 6. ) [Chemical 11] (In the formula, A ₁₀ represents a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group or an aralkyl group. R ₂₃ , R ₂₅ , R ₂₆ and R ₂₇ are the same or different. A _10-
O—CH (OH) CH ₂ — group, hydrogen atom, carbon atom 1
~ 22 are linear or branched alkyl or alkenyl groups, or aryl or aralkyl groups. However, the number of carbon atoms of A ₁₀ + R ₂₃ + R ₂₅ + R ₂₆ + R ₂₇ is 6 to 88 + 22n. R ₂₄ represents an alkylene group having 2 to 4 carbon atoms, and n represents 0 to 20. ) [Chemical 12] (In the formula, A ₁₁ and A ₁₂ may be the same or different and each may have a hydroxyl group, and is a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group. R ₂₈ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may have a hydroxyl group, or an aryl group or aralkyl group, provided that A ₁₁ + A _The number of carbon atoms of ₁₂ + R ₂₈ is 6 to
66. ) [Chemical 13] (In the formula, A ₁₃ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₂₉ represents a hydroxyl group. A linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, or an aryl group or aralkyl group which may be carried out, provided that the number of carbon atoms of A ₁₃ + R ₂₉ is 6 to 44.
Is. ) [Chemical 14] (In the formula, A ₁₄ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₃₀ and R ₃₁ are And a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, which may be the same or different and each may have a hydroxyl group, or an aryl group or an aralkyl group, provided that A ₁₄ + R ₃₀ + R ₃₁ has 6 carbon atoms
~ 66. ) [Chemical 15] (In the formula, A ₁₅ represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms which may have a hydroxyl group, or an aryl group or an aralkyl group. R ₃₂ , R ₃₄ , R ₃₅ and R ₃₆ may be the same or different and each is A ₁₅ —C (O) OCH ₂ —CH.
(OH) CH ₂ — group, hydrogen atom, linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms,
Alternatively, it represents an aryl group or an aralkyl group. However,
The number of carbon atoms of A ₁₅ + R ₃₂ + R ₃₄ + R ₃₅ + R ₃₆ is 6 to 88.
It is + 22n. R ₃₃ represents an alkylene group having 2 to 4 carbon atoms, and n represents 0 to 20. ) 12. A secondary amine represented by the general formula (II) and glycerin triglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol. Triglycidyl ether,
Pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, propylene glycol diglycidyl ether, tartaric acid diglycidyl ester, succinic acid diglycidyl ester, malic acid diglycidyl ester,
The lubricating oil additive for diesel engines according to claim 9, which is obtained by reaction with an epoxy compound selected from the group consisting of maleic acid diglycidyl ester, citric acid triglycidyl ester, and trimellitic acid triglycidyl ester. 13. The lubricating oil additive for diesel engines according to claim 1, which is 0.1 to 10 parts.
A lubricating oil composition for a diesel engine, which is added in a weight percentage. 14. The lubricating oil composition for diesel engines according to claim 13, which further contains a metallic detergent. 15. A base oil containing 0.1 to 10% by weight of one or more of the lubricating oil additives for diesel engines according to claim 1, and 0.5 to 0.5 parts of a metallic detergent.
-50% by weight, an ashless dispersant of 0.1-10% by weight, and an extreme pressure lubricant of 0.01-5% by weight are blended, and a lubricating oil composition for a diesel engine.