JPH1112588A - Production of lubricant oil composition and over based and sulfurated alkaline earth metal phenate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of manifesting high cleanness by including a specific over based sulfurized alkaline earth metal phenate and an aromatic component in a specific proportion. SOLUTION: This composition comprises (A) an over based sulfurized alkaline earth metal phenate having 550-700 mgKOH/g base number and (B) a lubricant base oil containing 1-10 wt.% aromatic component. Further, the composition preferably contains 8-32C fatty acids or a salt thereof. The base number of this composition is preferably 10-200 mgKOH/g, and cleanliness evaluation by the hot tube test is over 5.5 points. The component A can be obtained by reacting an alkaline earth metal reagent with phenols, sulfur, a dihydric alcohol, and distilling off the excess dihydric alcohol and water from the obtained product, and further distilling off the phenols from the bottom product of the distillation column.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an overbased sulfurized alkaline earth metal phenate having a high base number, a high heat resistance and a high oxidation stability, which is useful as a lubricant or a fuel oil detergent or an alkali detergent. It relates to a lubricating oil composition.

[0002]

2. Description of the Related Art Alkaline earth metal phenates are main additives used in addition to lubricating oils for internal combustion engines, and mainly neutralize acidic substances generated by the combustion of fuel in internal combustion engines to neutralize metal. It is used for the purpose of suppressing corrosion and deterioration of lubricating oil, and at the same time, promoting the dispersal of sludge and its precursors in oil to suppress sticking and wear of engine parts. For this purpose, cleanliness and oil solubility at high temperatures are important, and sulfurization of alkylphenols is a known technique for improving them. The base number is an index of the acid neutralizing ability, and the larger the value, the higher the acid neutralizing ability of the additive. Are referred to as "overbased" alkaline earth metal phenates. Improvement of the base number is an important research and development issue from the viewpoint of improving the economics of additives, and many attempts have been reported so far. For example, Japanese Patent Application Laid-Open No. 1-501399,
In Japanese Patent Application Laid-Open No. 1-501400, it is 2 to 40 with respect to the total weight.
By carrying out metal addition reaction several times by including a carboxylic acid by weight in the phenate, a base number of 300 mg KO is obtained.
It has succeeded in obtaining an overbased alkaline earth metal phenate having a viscosity exceeding 100 H / g and 1000 cSt at 100 ° C. However, there has been a demand for providing an overbased sulfurized alkaline earth metal phenate having a higher base number and higher detergency and an effective method of using the same.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an overbased alkaline earth metal sulfide having a high base number and excellent detergency at high temperatures, which is useful as a lubricant or fuel oil detergent or alkali detergent. The present invention relates to a lubricating oil composition containing phenate and a method for producing an overbased sulfurized alkaline earth metal phenate. What has been conventionally introduced as an overbased alkaline earth metal phenate is an overbased alkaline earth metal phenate concentrate referred to in the present application (conventionally, an overbased alkaline earth metal sulfide). Some were introduced as metal phenate concentrates). That is, it is an overbased sulfurized alkaline earth metal phenate which still contains some of the diluent used in the synthesis. Since the exact structure of the overbased sulfurized alkaline earth metal phenate cannot be analyzed, it has been defined by its physical properties in conventional patents and the like, but this method has various problems. For example, even if defined by base number, it is not the base number of the overbased sulfurized alkaline earth metal phenate, but the base number as the overbased sulfurized alkaline earth metal phenate concentrate. Therefore, even if the overbased sulfurized alkaline earth metal phenate has the same base number (there is no way to confirm it), it can be treated as having a different base number by adjusting the amount of the diluent. It is possible. Conversely, even when the overbased sulfurized alkaline earth metal phenate concentrate (or lubricating oil composition) has the same base number, the cleanliness is different. Similarly to the base number, the viscosity often used as the physical property of the overbased sulfurized alkaline earth metal phenate can be similarly adjusted by the amount of the diluent used. As described above, conventionally, the overbased sulfurized alkaline earth metal phenate was defined by the physical properties of the overbased sulfurized alkaline earth metal phenate concentrate, not the overbased sulfurized alkaline earth metal phenate itself. No, it is actually judged that they are different even though they are the same overbased sulfurized alkaline earth metal phenate, or conversely, they are judged to be the same even if they are different overbased sulfurized alkaline earth metal phenates It is possible. Therefore, there is a problem that accurate judgment cannot be made even when considering to obtain a more excellent overbased alkaline earth metal phenate.

[0004]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present inventors have found that it is not possible to expect a rational solution to the problems based on the conventional studies based on the physical properties of the overbased sulfurized alkaline earth metal phenate concentrate. As a result of judging and diligently examining, even if a lubricating oil is prepared so as to have the same base number, the base component obtained by extracting and removing diluents and neutral substances such as mineral oil has a high base number That the lubricating oil prepared using the neutralized sulfurized alkaline earth metal phenate concentrate shows higher cleanliness at high temperatures, and that the lubricating base oil contains 1 to 10% by mass of an aromatic component. Thus, the present inventors have found that they exhibit higher cleanliness, and have completed the present invention based on the findings. Here, the overbased alkaline earth metal phenate concentrate refers not to a pure overbased alkaline earth metal phenate but to a substance diluted with a diluent such as mineral oil. In addition, the basic component is a substance obtained by removing a diluent such as mineral oil and a neutral substance from an overbased sulfurized alkaline earth metal phenate, which is close to a pure product of the overbased sulfurized alkaline earth metal phenate. .

According to the present invention, the base number is 550 to 700 mgK.
It is intended to provide a lubricating oil composition comprising an overbased sulfurized alkaline earth metal phenate of OH / g and a lubricating base oil of 1 to 10% by mass of an aromatic component. Further, the present invention relates to an alkaline earth metal oxide, an alkaline earth metal hydroxide or a mixture thereof (hereinafter, referred to as an alkaline earth metal reagent), an alkaline earth metal reagent 1
It is obtained by reacting 1 to 100 equivalents of phenols, sulfur, and dihydric alcohol per mole, or reacting them in the presence of water, and then distilling off excess dihydric alcohol and at least excess water. The bottom of the distillation column is treated with carbon dioxide in the presence of 0.3 to 0.8 moles of water per mole of alkaline earth metal reagent, and the alkaline earth metal reagent 1
0.001 to 0.3 moles of fatty acids per mole are present at the latest before the carbon dioxide treatment, and the excess amount of phenols in the carbon dioxide treatment product is distilled off. A method for producing an overbased sulfurized alkaline earth metal phenate, comprising: allowing a diluent to be present before distilling off phenols; and subsequently extracting the extract with a diluent and an extraction solvent capable of extracting a neutral substance. To provide. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an overbased sulfurized alkaline earth metal phenate having a base number of 550 to 700 mg KOH / g for use in the lubricating oil composition of the present invention is not particularly limited, but is preferred. As a manufacturing method, for example,
Alkaline earth metal oxide, alkaline earth metal hydroxide or a mixture thereof (hereinafter referred to as alkaline earth metal reagent), 1 to 100 per mole of alkaline earth metal reagent
Equivalent phenols, sulfur and dihydric alcohol,
Alternatively, these are reacted in the presence of water, and then an excess amount of dihydric alcohol and at least an excess amount of water are distilled off. Carbon dioxide treatment in the presence of 0.8 mol of water and 0.001 per mol of alkaline earth metal reagent
~ 0.3 moles of fatty acids are present at the latest before carbon dioxide treatment, and excess phenols in the carbon dioxide treated product are distilled off, and excess phenols in the carbon dioxide treated product are distilled off. By the time the diluent is present,
Subsequently, a method for producing a high base number overbased sulfurized alkaline earth metal phenate having a high base number by extracting with a diluent and an extraction solvent capable of extracting a neutral substance can be mentioned.

As the alkaline earth metal reagent, an oxide or hydroxide of an alkaline earth metal or a mixture thereof is usually used. As the alkaline earth metal, calcium, barium, strontium, magnesium and the like can be used alone or as a mixture, but calcium is preferred. Phenols are hydrocarbon side chains having 4 to 36 carbon atoms, preferably 8 to 32 carbon atoms, such as alkyl groups,
Phenols having an alkenyl group, an aralkyl group and the like can be mentioned. Specifically, it is derived from hydrocarbon groups such as butyl, amyl, octyl, nonyl, dodecyl, cetyl, ethylhexyl, and triacontyl, or liquid hydrocarbons such as liquid paraffin, wax, and olefin polymers (polyethylene, polypropylene, polybutene, etc.). The phenols having a group are used alone or in a mixture thereof. Usually, those which can become liquid at about 130 ° C., preferably about 120 ° C. or less are desirable. The amount of the phenol to be used is 1 to 100 equivalents, preferably 1.6 to 10 equivalents, particularly preferably 2 to 3 equivalents, per 1 mol of the alkaline earth metal reagent. If the amount of the phenol relative to the alkaline earth metal reagent is too small, the intermediate will gel and the reaction will not proceed further, and the desired good product cannot be obtained. On the other hand, if the amount of the phenol relative to the alkaline earth metal reagent is too large, not only the yield of the product relative to the raw material decreases, but also the utility and time spent for recovering the phenol increase, which is economically disadvantageous.

As the dihydric alcohol, those having a relatively low boiling point, low viscosity and high reactivity are used. The dihydric alcohol preferably has 2 to 6 carbon atoms, particularly preferably ethylene glycol and propylene glycol. Dihydric alcohols help the conversion of phenols to an oil-soluble substance by the reaction of the alkaline earth metal reagent with the phenols and stabilize it, and some are incorporated into the overbased sulfurized alkaline earth metal phenate to convert the multi-equivalent phenate. Make up. The metal addition reaction may be performed with or without the addition of water having a reaction promoting effect. In the case where the addition is performed, the amount of the dihydric alcohol to be used is about 1 mol per 1 mol of the alkaline earth metal reagent. 0.15 to 3.0 mol, especially about 0.3 to
1.5 mole is preferred. When the reaction is carried out without adding water, the amount of the dihydric alcohol used is the alkaline earth metal reagent 1
About 1.0 to 3.0 moles, particularly about 1.2 to 3.0 moles per mole
2.0 moles is preferred. If the amount of the dihydric alcohol used is too small, the conversion of the reaction raw materials, particularly the product of the alkaline earth metal reagent, decreases.If the amount is too large, the metal addition reaction to the phenols proceeds smoothly, but the excess The time and utility for distilling off the dihydric alcohol is excessive.

[0009] The amount of sulfur used is the alkaline earth metal reagent 1
0.001 to 3.0 mol per mol, preferably 0.0
The amount is preferably 1 to 0.5 mol, more preferably 0.05 to 0.4 mol, and particularly preferably 0.1 to 0.2 mol. When water is added to the reaction system to promote the reaction in the metal addition reaction of the alkaline earth metal reagent to phenols, not only distilled water but also canned water, industrial water, water generated by the metal addition reaction, etc. There are no particular restrictions on the quality, and any state of water, such as cold water, hot water, or steam, can be used. The water used for promoting the metal addition reaction may be added to the reactor alone with water, or part or all of the water may be added as a mixture with other raw materials such as phenols and dihydric alcohols. The timing of adding water to the reactor is not particularly limited, and may be before or after all of the reaction materials other than water are mixed, but it is preferable to add the water within about one hour after mixing all of the reaction materials.

The amount of water used to promote the metal addition reaction in the reaction system is about 0.01 to 10 mol, preferably 0.1 to 10 mol, per mol of the alkaline earth metal reagent used.
2.0 moles. When the metal addition reaction is carried out by adding water from the outside to the reaction system, the reaction proceeds smoothly compared with the case where the reaction is carried out under the same conditions except that water is not added, and the reaction raw material, particularly the alkaline earth metal reagent Product conversion rate increases.
Therefore, if the amount of water added to the reaction system is too small, the product conversion of the alkaline earth metal reagent will decrease. Conversely, if the amount is too large, the advantage that the distillation step after the reaction is simplified is lost.

In the carbon dioxide treatment step, after completion of the metal addition reaction, excess dihydric alcohols and at least excess water in the system are distilled off, and if fatty acids are not added first or fatty acids added first If the amount is small,
After adding fatty acids to a predetermined amount and allowing a predetermined amount of water to exist in the system, the reaction temperature is about 50 to 230 ° C.
Preferably, it is reacted with carbon dioxide under a temperature condition of 80 to 200 ° C. This reaction may be performed under reduced pressure, normal pressure, or increased pressure. Usually, a range of 0.01 to 51 atm.A, preferably 0.1 to 31 atm.A is employed. The reaction is generally carried out until the absorption of carbon dioxide is substantially stopped, and is for 20 minutes to 10 hours, usually 20 minutes to 3 hours.
The product obtained here may be further subjected to 0 to 20 atm. G, preferably 0 to 10 atm.
It is maintained at a pressure of G at about 100 to 230 ° C. for several minutes to several tens of hours.

The addition of water coexisting during the carbon dioxide treatment involves reacting a raw material mixture comprising phenols, dihydric alcohols, alkaline earth metal reagents and sulfur, or water to this. After completion of the metal sulfide addition reaction, distillation is generally carried out after distilling off water and excess dihydric alcohol. There is no limitation on the quality and state of the water coexisting during the carbon dioxide treatment, similarly to the water used for promoting the metal addition. The amount of water in the reaction system is from 0.3 to 0.8 mol, preferably from 0.3 to 0.8 mol per mol of the alkaline earth metal reagent.
Adjust to 0.6 mole. If there is an excess of dihydric alcohol in the system, any water in the system such as water added at the time of distillation and water generated by the reaction is distilled off as a forerunner. After distilling off the excess, it is necessary to add a predetermined amount of water. On the other hand, if there is no excess dihydric alcohol in the system,
After the completion of the reaction, only the excess amount may be distilled off, leaving only a predetermined amount of water from the water present in the system, such as water added for promoting the reaction before the metal sulfide addition reaction or water generated during the reaction. However, when the remaining amount is unclear, it is preferable to add a predetermined amount of water after once distilling off the entire amount of water. The amount of water coexisting during carbon dioxide treatment increases the base number of the product as it increases, but if the amount is too large, the product is too hydrolyzed, causing a decrease in the base number and oil solubility, and if the amount is too small, The effect of improving the base number of the product cannot be sufficiently obtained.

The fatty acids to be present before the carbon dioxide treatment include fatty acids having 8 to 32 carbon atoms, preferably 10 to 30 carbon atoms, particularly preferably 16 to 24 carbon atoms, or salts thereof.
In the case of a salt, it is preferably an alkaline earth metal salt. Examples of the alkaline earth metal include calcium, barium, magnesium, strontium and the like. Further, it is more preferable that the alkyl group has a straight chain. Specific examples include decanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melicic acid.
Preferably, stearic acid is used. The fatty acids may be a mixture having a molecular weight distribution, and commercially available stearic acid having a stearic acid purity of about 60 to 70% can be used.
The amount of the fatty acids is 0.001 to 0.3 mol, preferably 0.01 to 0.3 mol per mol of the alkaline earth metal reagent.
Moles, more preferably 0.02 to 0.3 mole, and most preferably 0.05 to 0.2 mole. If the amount of the fatty acid to be added is small, the base number of the phenate is not further improved, and the hue and the oil solubility are reduced.
If it is too large, the base number will decrease.

As the diluent, a petroleum fraction having a suitable viscosity such as a paraffinic, naphthenic, aromatic or mixed base oil, for example, a boiling point of about 220 to 550 ° C. and a viscosity of about 2 at 100 ° C. Lubricating oil fractions of ４０40 cSt. Other organic solvents also exhibit hydrophobicity and lipophilicity, and can be used as a diluent if they are harmless at the time of reaction or in the application of the product. For example, carbon number 8-24
Higher alcohols can also be used. In the above method for producing an overbased sulfurized alkaline earth metal phenate, it is preferable that an alkaline earth metal reagent, phenols and sulfur, or these and water are first charged into a reactor to form a charged mixture. Further, fatty acids may be charged together with these. The order of charging these reactants and reactants is not particularly limited and may be appropriately selected.

The above mixture is mixed with a dihydric alcohol at a pressure in the reactor of 0 to 200 kPa-G, preferably 0 to 200 kPa-G.
It is preferable to add in a state of １００100 kPa-G. By adding the dihydric alcohol to the above mixture in this pressure range, an overbased sulfurized alkaline earth metal phenate having a high base value and excellent hydrolysis stability can be produced. The addition of the dihydric alcohol is performed within the above-mentioned range of the pressure in the reactor, and it is preferable that at least 60% by mass or more, preferably 80% by mass or more of the total amount of the dihydric alcohol be performed within the above-mentioned range.

The temperature of the charged mixture at the time of adding the dihydric alcohol is preferably 60 ° C. or higher, particularly preferably 120 ° C. or higher. The upper limit temperature of the charged mixture at the time of adding the dihydric alcohol is usually not higher than the boiling point of the charged mixture, but is preferably not higher than 200 ° C. It is preferable that the dihydric alcohol to be added is also heated to this temperature range in advance. The addition time of the dihydric alcohol is usually 20 to
90 minutes, preferably 30 to 60 minutes. After completion of the addition of the dihydric alcohol, the reaction is carried out at a temperature of about 60 to 200 ° C, preferably about 90 to 190 ° C. The pressure is not particularly limited, and is selected in the range of 0.01 to 21 atm · A, preferably 0.1 to 11 atm · A. This reaction is almost completed within a period of usually 1 to 9 hours.

Extraction and removal of the diluent and neutral substances from the reaction product may be carried out so as to produce an overbased sulfurized alkaline earth metal phenate having a base number of 550 to 700 mg KOH / g. Examples of the extraction solvent from which the diluent and the neutral substance can be extracted include hydrocarbons having 5 to 10 carbon atoms, preferably aliphatic hydrocarbons having 5 to 10 carbon atoms, and particularly preferably hexane and heptane. The amount of the extraction solvent used is not particularly limited, but is usually 2 to 10 of the overbased sulfurized alkaline earth metal phenate to be extracted.
The mass is 0 times, preferably 5 to 50 times, particularly preferably 10 to 40 times. The extraction time is not particularly limited, but may be usually set in the range of 10 to 30 hours, preferably 12 to 20 hours.

A preferred specific example of the extraction performed with an extractant capable of extracting a diluent and a neutral substance is a rubber membrane extraction method. The rubber membrane extraction method is a general method as a method for separating and analyzing lubricating oil additives. For example, the method is disclosed by Fujita in Lubrication Journal Vol. 12, No. 1, page 8 in 1967. Specifically, using a commercially available glass Soxhlet extractor, the overbased alkaline sulfide metal phenate concentrate to be extracted is put into a latex cylinder (rubber membrane), which is held in a cylindrical filter paper and hexane When a continuous extraction is performed using as an extraction solvent, a diluent (eg, mineral oil) and neutral substances are extracted, and only the dissolved basic components remain in the rubber membrane. The basic component as an extraction residue is an overbased sulfurized alkaline earth metal phenate.
Examples of neutral substances to be extracted include unreacted alkylphenol, alkylphenol sulfide dimer, saturated aliphatic hydrocarbon, aromatic hydrocarbon, and ethylene glycol (alkylphenyl) ether. The method for producing an overbased sulfurized alkaline earth metal phenate of the present invention is not a method of increasing the component concentration of the basic component in the overbased sulfurized alkaline earth metal phenate concentrate, but increasing the base number of the basic component. Is the way. The overbased sulfurized alkaline earth metal phenate obtained by the above production method can be used as a detergent for lubricating oil or fuel oil or an alkali detergent.

The base oil component used in the lubricating oil composition of the present invention is a lubricating base oil containing 1 to 10% by mass of an aromatic component. The preferred content of the aromatic component in the lubricating base oil is
The content is 1 to 7% by mass, particularly preferably 2 to 5% by mass. As a specific example of the lubricating base oil in which the aromatic component is 1 to 10% by mass, a lubricating base oil refined by solvent dewaxing and a lubricating base oil refined by cryogenic dewaxing are preferable. In the hydrodewaxed and refined base oil, those having less than 1% by mass of an aromatic component are not preferred. The base oil may be used singly or as a mixture of two or more.
A chemically synthesized base oil may be mixed in a range containing 0% by mass of an aromatic component.

The lubricating oil composition of the present invention has a base number of 5
The content ratio of the overbased sulfurized alkaline earth metal phenate of 50 to 700 mgKOH / g and the lubricating base oil of 1 to 10% by mass of the aromatic component is such that the base number of the usually obtained lubricating oil composition is 10 to 10. What is necessary is just to make it in the range of 200 mgKOH / g. Further, the lubricating oil composition of the present invention preferably has a cleanliness rating of 5.5 or more, particularly preferably 6.0 or more, as determined by a hot tube test. The lubricating oil composition of the present invention can be used for various lubricating parts requiring lubrication.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these are merely examples and do not limit the present invention. The rubber film extraction method, hot tube test, and measurement method of the aromatic component of the lubricating base oil performed in the examples are shown below. (1) Rubber Film Extraction Method As shown in FIG. 1, rubber film extraction was performed using a glass Soxhlet extractor (21300-01 manufactured by Ogura Glass Industry Co., Ltd.).
Set a cylindrical filter paper with a diameter of 60 mm and a length of 200 mm (Model 21500-05 manufactured by Ogura Glass Industry Co., Ltd.) in the mold and use a rubber membrane bag (skinless skin crown thin almighty manufactured by Okamoto Co., Ltd.) with hexane before use. )), 20 g of a sample was put therein, tied to a glass ball with a thread, and set in a cylindrical filter paper. 700 ml of hexane in the flask
, And the mixture was heated under reflux in a water bath at 85 ° C. for 15 hours to perform extraction.

(2) Hot tube test The hot tube test method is a general cleanliness test method for those skilled in the art. A glass tube (inner diameter 2 mm, length 300 mm) through which air was flowed at a rate of 10 ml / min using an HT-201 type manufactured by Komatsu Equipment Co., Ltd.
Was heated to 300 ° C., the sample was passed at 0.31 ml / h, and coloring after 16 hours was evaluated on a scale of 10 out of 10 by comparison with a standard sample. Note that the hot tube tests of the examples and comparative examples were all performed at the same time in order to suppress test errors.
It is the average value of the number of times.

(3) Method for Measuring Aromatic Components of Lubricating Base Oil The aromatic components of a lubricating base oil can be obtained by the following method. Method and a four-fold scale, as a sorbent No. It analyzed using 7734 (70-230 mesh). That is, using a glass chromatographic tube filled with 40 g of silica gel dried and activated at 160 ° C. for 8 hours, 2 g of lubricating base oil was precisely weighed, diluted with 40 ml of petroleum ether, poured into the chromatographic tube, and added with petroleum ether. Elution was carried out until the oil was no longer eluted, and a saturated portion was collected. Next, the aromatic components were eluted with diethyl ether, and the components were desolvated at 30 ° C. under a reduced pressure of about 30 mmHg using a rotary evaporator, and the mass was measured.

Example 1 A 1-liter autoclave equipped with a stirrer, a gas inlet tube and a thermometer was charged with a purity of 9%.
531.2 g (1.9 mol) of 7.9% dodecylphenol, 40.91 g of calcium oxide having a purity of 96.0%
(0.7 mol) and 3.37 g (0.105 mol) of sulfur (0.15 mol per mol of calcium oxide), 25.2 g (0.091 mol) of stearic acid (0.13 mol per mol of calcium oxide) ) Was sealed and stirred.
To the obtained suspension, 65.21 g (1.05 mol) of ethylene glycol having a purity of 94.5% was added at 125 ° C. and 60 kP.
a-G, and this is added at 130 ° C. to about 500 kPa-G
After stirring for about 3.0 hours under pressurized and sealed conditions, the generated water, some unreacted ethylene glycol and a small amount of dodecylphenol are distilled off while gradually reducing the pressure in the reaction system. As a result, 791.9 g of a liquid distillation residue was obtained. The final distillation temperature at this time is 141 ° C. (5 mmH
g). Next, 5.67 g (0.32 mol) of water (0.45 mol per mol of calcium oxide) was added to 791.9 g of the distillation residue, and carbon dioxide was absorbed at a temperature of 150 ° C. from a reduced pressure for 30 minutes. I let it. At this time, the supply rate of carbon dioxide to the autoclave was 0.315
Liter / min. Then, the temperature was raised to 178 ° C,
The pressure was again increased with carbon dioxide until the gauge pressure reached 5.0 atm, and the pressure was maintained for 2.0 hours to obtain 829.1 g of a reaction product. To the reaction product was added 58.92 g of 150 neutral oil as a diluent. 820.78 g of the diluted reaction product was transferred to a 1-liter three-necked pear-shaped flask and distilled under reduced pressure to remove a small amount of ethylene glycol and most of the unreacted dodecylphenol.
8 g were obtained. The final distillation temperature at that time is 225 ° C. (3 mm
Hg). Thereafter, the distillation residue was diluted with a large amount of hexane, and after removing 2.15 g of insoluble matter by centrifugation, 167.09 g of a concentrated product was obtained by removing the hexane added in a large amount by distillation. This concentrated product has a base number of 426 mg KOH / g and a viscosity at 100 ° C. of 43.
8 cSt. The base value of a light brown solid, which is an extraction residue obtained by treating the concentrated product by a rubber membrane extraction method for 15 hours, was 576 mgKOH / g. The extraction residue is diluted with a solvent dewaxed refined base oil (3.2% by mass of aromatics) to a base number of 30 and cleaned at 300 ° C. using a hot tube tester (HT-201, manufactured by Komatsu Equipment Co., Ltd.). As a result of performing the sex evaluation, the score was 6.0 points.

Example 2 The same procedure as in Example 1 was carried out except that the amount of water added was 0.5 mol per mol of calcium oxide. The yield of the concentrated product was 164.39 g.
The base value of the concentrated product is 444 mg KOH / g, 100 ° C.
Was 390 cSt. The base value of a light brown solid, which is an extraction residue obtained by treating the concentrated product by a rubber membrane extraction method for 15 hours, was 617 mgKOH / g.
The extraction residue was diluted with a lubricating base oil to a base number of 30, and a hot tube tester (HT-201 manufactured by Komatsu Equipment Co., Ltd.)
As a result of performing cleanliness evaluation at 300 ° C. using the mold, the score was 6.0 points.

Comparative Example 1 Example 1 was repeated except that a highly hydrorefined base oil (aromatic 0.6 mass%) was used as a diluent oil.
Was performed in the same manner as described above. The cleanliness rating of the hot tube tester was 4.5.

Example 3 As a diluent oil, a highly hydrogenated refined base oil (aromatic 0.6% by mass) and a solvent dewaxed refined base oil (aromatic 3.2% by mass) were mixed and used in equal amounts. The procedure was performed in the same manner as in Example 1 except for the above. The cleanliness score by the hot tube tester was 6.5.

Example 4 As a diluent oil, a chemically synthesized base oil containing no aromatics and a purified base oil dewaxed by solvent (aromatic 3.2
% By mass) was used in the same manner as in Example 1 except that an equal amount was used. The cleanliness score by the hot tube tester was 6.0.

[Comparative Example 2] Base number: 370 mgKOH / g
The commercially available overbased calcium sulfide phenate type additive was treated by the rubber membrane extraction method in the same manner as the concentrated product of Example 1 to obtain a light brown solid having a base number of 559 mg.
KOH / g. When this extraction residue was subjected to a hot tube test in the same manner as in Example 1, the score was 3.0.

Comparative Example 3 The same operation as in Example 1 was carried out except that a chemically synthesized base oil containing no aromatic was used as the diluent oil. The cleanliness score of the hot tube tester is 5.0
Was a point.

[0031]

The lubricating oil composition of the present invention has excellent cleanliness at high temperatures. The overbased sulfurized alkaline earth metal phenate obtained by the production method of the present invention can be used as a detergent for lubricating oil or fuel oil or an alkali detergent.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an example of a rubber film extraction device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Water bath 2 Beaker 3 Thermometer 4 Sample oil 5 Rubber film 6 Cylindrical filter paper 7 Fixing by thread 8 Glass ball 9 Cooling tube 10 Water

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 101: 02 129: 40) C10N 20:00 30:00 30:04 70:00 (72) Inventor Jun Imai Satte-shi, Saitama 1134-2 Gongendo Research and Development Center, Kosmo Research Institute Co., Ltd. (72) Inventor Yukio Takagi 1134-2 Gongendo, Satte City, Saitama Prefecture Research and Development Center Cosmo Research Institute Co., Ltd. (72) Inventor Haruhiko Takeya 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center

Claims (5)

[Claims] 1. A lubricating oil composition comprising an overbased sulfurized alkaline earth metal phenate having a base number of 550 to 700 mg KOH / g and a lubricating base oil having an aromatic component of 1 to 10% by mass. Stuff. 2. The lubricating oil composition according to claim 1, which comprises a fatty acid having 8 to 32 carbon atoms or a salt thereof as a constituent component. 3. The lubricating oil composition according to claim 1, which has a cleanliness rating of 5.5 or more as determined by a hot tube test. 4. The lubricating oil composition according to claim 1, which has a base number of 10 to 200 mg KOH / g. 5. An alkaline earth metal oxide, an alkaline earth metal hydroxide or a mixture thereof (hereinafter referred to as an alkaline earth metal reagent), 1 to 100 equivalents of phenols per mole of the alkaline earth metal reagent, Reacting sulfur and a dihydric alcohol, or these in the presence of water,
Subsequently, the distillation column bottom obtained by distilling off the excess amount of the dihydric alcohol and at least the excess amount of water is subjected to carbon dioxide in the presence of 0.3 to 0.8 moles of water per mole of the alkaline earth metal reagent. Treated, and 0.001 to 0.3 moles of fatty acids per mole of alkaline earth metal reagent are present at the latest until carbon dioxide treatment, and further, excess phenols in the carbon dioxide treated product are distilled off, An overbased method characterized by allowing a diluent to be present before distilling off an excess amount of phenols in the carbon dioxide-treated product, and then extracting with a diluent and an extraction solvent capable of extracting neutral substances. A method for producing a sulfurized alkaline earth metal phenate.