JP3168267B2 - Diesel engine oil composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diesel engine oil composition, and more particularly, to a diesel engine oil composition which significantly improves the water separation performance of a diesel engine oil while maintaining high cleanliness.

[0002]

2. Description of the Related Art In recent years, engine oils, especially diesel engine oils, have become less clean due to higher output and improved flammability due to emission regulations. Large amounts of ashless dispersants have been added to oils. The ashless dispersant finely disperses diesel suits generated during combustion and sludge generated by oxidative deterioration of engine oil to prevent the oil from adhering to engine parts and improve the cleanliness of the piston. For this purpose, high-grade diesel engine oils such as API-CE and CF-4 grades contain large amounts of ashless dispersants. However, on the other hand, if water or the like is embraced in the oil, and there is a place where the water easily aggregates and mixes into the engine and its peripheral parts, the additive dissolved in the oil will affect the engine. Receiving oil, it may drop off from the oil, or mayonnaise-like sludge may be generated, preventing the circulation of the oil, preventing the initial performance from being exhibited, and causing a problem. . Therefore, if excellent water separation performance is given to diesel engine oil to which a large amount of ashless dispersant is added,
Such a trouble is eliminated and is extremely useful.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a diesel engine oil composition having good water separation performance while maintaining high cleanliness, in view of the above-mentioned state of the art.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a base oil containing a specific dispersant and calcium salicylate, a specific base number of calcium sulfonate or By blending a specific surfactant in a specific amount, it has been found that good water separation performance can be exhibited while maintaining high cleanliness, and the present invention has been completed based on this finding.

That is, the present invention relates to (A) a base oil of a mineral oil-based lubricating oil, a synthetic lubricating oil, or a mixture thereof.
4 to 15% by weight of alkenyl succinimide or a derivative thereof, (B) 0.5 to 2 % by weight of calcium sulfonate having a base number of 80 mg KOH / g or less, and (C) calcium salicylate having a base number of 100 mg KOH / g or more. At a rate of 2 to 10% by weight (hereinafter referred to as the first invention of the present application). Further, the present invention relates to a method in which a base oil of a mineral oil-based lubricating oil or a synthetic lubricating oil or a mixture of both has a molecular weight of (A) an alkenyl-group polybutene.
1500-2000, triethylenetetramine or te
Tiger ethylene pentamine imidization alkenyl succinic acid mono imide or a derivative thereof 4-15% by weight,
(D) a nonionic surface active agent 0.2-1 wt%, and (C) a base number is characterized by containing in a proportion of 2 to 10% by weight or more calcium salicylate 100 mg KOH / g The present invention provides a diesel engine oil composition (hereinafter, referred to as a second invention).

Hereinafter, the present invention will be described in detail. Application No. 1
The alkenyl succinimide or its derivative as the component (A), which is one of the essential components in the present invention, is not particularly limited, and various ones which can be used as an ashless dispersant for lubricating oils can be used. Specific examples of the alkenyl succinimide or a derivative thereof include, for example, a polyolefin having a molecular weight of about 300 to 5,000 such as polybutene which is reacted with maleic anhydride to obtain monoalkenyl succinic anhydride, and further ethylenediamine, diethylenetriamine, dipropylenetriamine, Triimide tetramine, imidized using a polyamine such as tetraethylene pentamine monoimide, diimide, various alkenyl succinimides such as triimide,
JP-B-42-8013, JP-B-42-8014, JP-A-51-52381, JP-A-51-1
No. 30408, such as boron compound derivatives of alkenyl succinimides, organic phosphonate derivatives, or alkenyl succinimides were reacted with aldehydes, ketones, carboxylic acids, sulfonic acids, alkylene oxides, sulfur and the like. Derivatives of alkenyl succinimide and the like can be mentioned. Preferred among these alkenyl succinimides or derivatives thereof are alkenyl succinic monoimides in which the alkenyl group has a polybutene molecular weight of 1500 to 2000 and is imidized with triethylenetetramine or tetraethylenepentamine. In addition, these alkenyl succinimides or derivatives thereof may be used alone or in combination of two or more. The blending ratio of the alkenyl succinimide or a derivative thereof in the diesel engine oil composition of the first invention of the present application is 4 to 15% by weight, preferably 6 to 10% by weight. If the blending ratio of the alkenyl succinimide or a derivative thereof is too small, the cleaning effect is reduced, and if it is too large, the water separating property is deteriorated.

As the calcium sulfonate having a base number of 80 mg KOH / g or less, which is one of the essential components in the first invention of the present application, for example, alkyl aromatics such as calcium alkyl benzene sulfonate and calcium alkyl naphthalene sulfonate. Calcium salts of group III sulfonic acids are preferred, more preferably calcium salts of alkyl benzene sulfonic acids, and particularly preferably calcium salts of alkyl benzene sulfonic acids having a molecular weight of 400 to 1200. The base number of the calcium sulfonate is preferably 40 mgKOH / g or less, particularly preferably 10 to 40 mgKOH / g. These calcium sulfonates may be used alone or in combination of two or more. Mixing ratio of the calcium sulfonate in a diesel engine oil composition of the first invention is 0.5 to 2 wt%. If the blending ratio of calcium sulfonate is too small, the water separation effect is reduced, and if it is too large, the water separation property is deteriorated.

The calcium salicylate having a base number of 100 mg KOH / g or more, which is one of the essential components in the first invention of the present application, alkylates phenol with an α-olefin having 10 to 18 carbon atoms, and then Kolbe-Schmidt After the introduction of a carboxyl group by a reaction, an alkali earth metal salt obtained by metathesis or the like is used (see, for example, British Patent No. 732,598 and British Patent No. 732,622). Calcium salicylate is preferably overbased for use in diesel engine oil compositions and has a base number of 150 mg KOH /
g or more, preferably 150 to 400 mgKOH / g
Is preferred. These calcium salicylates may be used alone or in combination of two or more. The proportion of the calcium salicylate in the diesel engine oil composition of the first invention of the present application is from 2 to
It is 10% by weight, preferably 3 to 8% by weight. If the proportion of the calcium salicylate is too small, the cleanliness deteriorates. On the other hand, if the proportion is too large, calcium adheres to the upper part of the piston, thereby deteriorating the engine efficiency.

In the first invention of the present application, (A)
The components (B) and (C) are mixed with a base oil of a mineral oil-based lubricating oil or a synthetic lubricating oil or a mixture of both. The viscosity of these base oils may be a normal 0.1~250mm ² / s, preferably is 10 to 150 mm ² / s, particularly preferably 20~120mm ² / s. In the case of a mineral oil-based lubricating oil, a mineral oil-based lubricating oil fraction may be used by purifying it by appropriately combining solvent refining, hydrorefining, and the like. As a synthetic lubricating oil, for example, α having 3 to 12 carbon atoms
Α-olefin oligomer which is a polymer of olefin, dialkyl diesters having 4 to 12 carbon atoms such as sebacate including dioctyl sebacate, azelate, adipate, 1-trimethylolpropane, pentaerythritol and 3 to 12 carbon atoms. Polyol esters including esters obtained from monobasic acids, and alkylbenzenes having an alkyl group having 9 to 40 carbon atoms. The mineral lubricating oil and the synthetic lubricating oil can be used alone or in combination of two or more.

The alkenyl succinimide of the component (A) used in the second invention of the present application or its derivative is
The molecular weight of the polybutene having a kenyl group is 1500 to 2000
With triethylene tetramine or tetraethylene penta
Alkenyl succinic monoimide imidized with min or
Its derivatives. Specific examples of the derivative include the aforementioned
And the like. In addition, these alkenyl
The succinimide or a derivative thereof may be used alone.
Also, two or more kinds may be used in combination. Also book
The base number of the component (C) used in the second invention is 1
The base oil of calcium salicylate of 00 mg KOH / g or more and a mineral lubricating oil or a synthetic lubricating oil or a mixture of both is the same as those of the first invention of the present application. The surfactant of the component (D), which is an essential component of the second invention of the present application, comprises :
It is a nonionic surfactant.

Specific examples of the nonionic surfactant include:
For example, a polyoxyalkylene alkylamine having an alkylamine having an alkyl group having 8 to 22 carbon atoms and having 1 to 10 mol of alkylene oxide added thereto;
Having 0-20 alkyl or alkenyl groups, 1-2
Polyoxyethylene alkyl or alkenyl ether to which 0 mol of ethylene oxide has been added;
Polyoxyethylene alkyl phenyl ether having 1 to 20 moles of ethylene oxide and having 1 to 20 moles of ethylene oxide; polyoxyethylene alkyl phenyl ether having 1 to 20 moles of propylene oxide having an alkyl or alkenyl group having 10 to 20 carbon atoms Oxypropylene alkyl or alkenyl ether; polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having 10 to 20 carbon atoms and having 1 to 20 mol of butylene oxide added thereto; alkyl group or alkenyl having 10 to 20 carbon atoms Having a group,
A nonionic surfactant obtained by adding ethylene oxide and propylene oxide or ethylene oxide and butylene oxide in a total amount of 1 to 30 mol; a higher fatty acid alkanolamide or an alkylene oxide adduct thereof;
A sucrose fatty acid ester composed of a fatty acid having 10 to 20 carbon atoms and sucrose; and a fatty acid glycerin monoester composed of a fatty acid having 10 to 20 carbon atoms and glycerin. Among these nonionic surfactants, polyoxyalkylene nonionic surfactants and the like are preferable, and polyoxyethylene nonionic surfactants are particularly preferable.
As the polyoxyalkylene nonionic surfactant, a polyoxyalkylene nonionic surfactant having an alkyl group having 1 to 30 carbon atoms is particularly preferable.

Specific examples of the polyoxyethylene nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene octyl. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene glycol monooleate and the like, preferably polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl Ether, polyoxyethylene higher alcohol ether,
Polyoxyethylene octyl phenyl ether.

The alkenyl succinimide or its derivative (A) used in the second invention of the present application and the calcium salicylate having a base number of 100 mg KOH / g or more of the component (C) are mixed with those of the first invention of the present invention. The same is true. The mixing ratio of the surfactant of component (D) used in the present second invention is a 0.2 to 1% by weight. If the mixing ratio of the surfactant is too small, the effect of the water separation performance is reduced, and if it is too large, the water separation property is deteriorated.

[0014] In the diesel engine oil composition of the present invention, it is preferable to add a zinc dialkyldithiophosphate. The addition of zinc dialkyldithiophosphate can prevent engine wear as well as oxidation. Although the carbon number of the alkyl group of the zinc dialkyldithiophosphate is not particularly limited, it is usually preferably 6 to 12.
The alkyl group of the zinc dialkyldithiophosphate is preferably linear. The amount of zinc dialkyldithiophosphate added is usually 0.5 to 4% by weight, preferably 1 to 2% by weight.

In the diesel engine oil composition of the present invention, in addition to the above-mentioned additives, various known additives may be used, for example, zinc thiophosphate other than the above-mentioned zinc dialkyldithiophosphate, Phenolic compounds such as -tert-butyl-p-cresol; various antioxidants such as aromatic amine compounds such as N-dimethylaniline; various wear inhibitors such as molybdenum dialkyldithiophosphate; polymethacrylates; Various viscosity index improvers such as polymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers or polyisobutylene, sulfurized fats and oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, iodinated benzyl, fluoro Alkyl polysiloxane, naph Various extreme pressure agents such as lead acid, carboxylic acid including stearic acid, dicarboxylic acid, metal soap, amine salt of carboxylic acid, metal salt of heavy sulfonic acid, carboxylic acid partial ester of polyhydric alcohol, phosphate ester And various kinds of friction modifiers such as higher fatty acids, higher alcohols, amines and esters, and various antifoaming agents such as silicone oil, etc., alone or in combination of two or more. In addition to these, various additives can be appropriately compounded.

The method for preparing the diesel engine oil composition of the present invention may be carried out by appropriately mixing the base oil, the above essential components and various additives as necessary. The mixing order is not particularly limited. The essential components may be sequentially mixed with the oil, or the essential components may be previously mixed and then mixed with the base oil.
Further, various additives may be added to the base oil in advance, or may be added to essential components.

[0017]

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited at all by these examples. In Examples, essential components and various additives were blended with a base oil to prepare a diesel engine oil composition, and water separation properties and cleanability were evaluated. The types of base oil, essential components and additives used in the preparation of the diesel engine oil compositions of the respective examples and comparative examples, and the respective evaluation tests are as follows.

1. Base oil A mineral oil having a viscosity of 40 mm ² / s at 40 ° C. was used. 2. Calcium salicylate (TBN = 170mgKO)
H / g) TBN is the total base number. 3. 3. Alkenyl succinimide alkenyl succinic monoimide having a molecular weight of polybutenyl of 1700 and imidized with triethylenetetramine. Calcium sulfonate (TBN = 25mg KOH
/ G) 5. 5. Polyoxyethylene nonionic surfactant polyoxyethylene nonylphenyl ether 6. Zinc dialkyldithiophosphate Zinc di-n-octyldithiophosphate High base number calcium sulfonate (TBN = 300
mg KOH / g) 8. High base number calcium phenate (TBN = 250m
(gKOH / g) The base number is a value measured according to JIS K25016.

Evaluation Test (1) Water Separation Test 20 ml of diesel engine oil was placed in a 200 ml beaker.
And 5 ml of water, place a beaker in a thermostat (45 ± 2 ° C.), and stir at 750 rpm with a stirring propeller. The stirring propeller used was a special flat piece having a width of 30 mm, a height of 15 mm, and a thickness of 1 mm. 0.
Pour 5 ml of water every 5 hours, pour water until the total amount of water reaches 60 ml, and then stir for 0.5 hour.
After the test is completed, the sample is transferred to a sample tube, and at room temperature, the separated state of oil and water (including the race layer) is observed, and the judgment is made in the manner shown in the following table. If this score is less than 2 points, it may cause trouble depending on the engine. If the score is 1 or less, sludge is generated and the oil line is clogged, causing troubles such as engine seizure. Judgment criteria

[0020]

[Table 1]

(2) Cleanliness Evaluation Test Cleanliness was evaluated by a caterpillar 1G2 engine test. Rotation speed 1,800 rpm Oil temperature 95 ° C Test time 120 hours The test method was performed in accordance with ASTM-STP-509A-P2. The rating of the cleanliness of the comparative example is 1 in the rating of the example.
It was set as 0 point and indicated by relative value.

Embodiment 14  Calcium salicylate, alkenyl
Succinimide, calcium sulfonate and other additives
Ingredients are blended in the proportions (% by weight) shown in the upper row of Table 2 and
An engine oil composition was prepared. The obtained diesel
The water separation property evaluation value of the ginseng oil composition is as shown in the lower part of Table 2.
It is.

[0023]

[Table 2]

The other additives are the sum of antioxidants, antiwear agents and viscosity index improvers. Tables 1, 2,
In 3, 4, 5, and 6, the mixing ratio of the base oil is indicated as balanced because the total amount of the various additives and the base oil is 10%.
It means that it is adjusted to be 0% by weight. Comparative Examples 1 to 9 For Comparative Examples 1 to 7, calcium salicylate, alkenyl succinimide, calcium sulfonate, high base number calcium sulfonate, high base number calcium phenate and other additives were added to the above base oils according to Table 3 and The diesel engine oil composition was prepared by blending at the ratio (% by weight) shown in the upper part of Table 4. Tables 3 and 4 show the results of evaluation tests using the obtained diesel engine oil composition and commercially available diesel engine oil.

[0025]

[Table 3]

[0026]

[Table 4]

Examples 6 to 10 Calcium salicylate, alkenyl succinimide, nonionic surfactant and other additives were blended with the above base oil in the proportions (% by weight) shown in the upper part of Table 5 to obtain a diesel engine oil. A composition was prepared. The water separation property evaluation value of the obtained diesel engine oil composition is as shown in the lower part of Table 5.

[0028]

[Table 5]

COMPARATIVE EXAMPLES 10-16 Calcium salicylate, alkenyl succinimide, nonionic surfactant, high base calcium sulfonate, high base calcium phenate and other additives were added to the above base oils in Tables 6 and 7. 7 were blended in the ratio (% by weight) shown in the upper row to prepare a diesel engine oil composition. Tables 6 and 7 show the lower values of the water separation properties of the obtained diesel engine oil composition and commercially available diesel engine oil.

[0030]

[Table 6]

[0031]

[Table 7]

Evaluation result of cleanliness

[Table 8] Note W. T. D. : Total weighted sediment score (weighted at the part of the piston to express the contamination of the piston) G. FIG. F. : Evaluation of clogging of the top ring group. Under Crown: Evaluation of dirt on the back side of the piston. T. D. , T .; G. FIG. F. And Under
Crown complies with JPI-5S-15-85,
Relative evaluation was made with the example taken as 10.

In an evaluation test using a diesel engine,
The diesel engine oil of Example 1 has the same high level of piston cleanliness as the commercial oil of Comparative Example 8, but has much better water separation. Comparative Example 9 had the same level of water separation performance as that of Example 1, but was inferior in cleanliness. Further, other examples also had the same cleanliness as Example 1.

[0034]

According to the diesel engine oil composition of the present invention, sufficient water separation properties can be obtained without impairing the effect of a large amount of the added ashless dispersant, and cleanliness and water separation can be obtained. Sex can be achieved at a high level. The diesel engine oil composition of the present invention is extremely useful in practical use.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10M 159: 24) C10N 30:04 40:25 (72) Inventor Ken Suzuki 1134-2 Gongendo, Satte City, Saitama Cosmo Sogo Co., Ltd. Inside the Research and Development Center (72) Inventor Hayashi Kimura 1134-2 Gongendo, Satte City, Saitama Prefecture Inside the Research and Development Center, Cosmo Research Institute, Inc. (56) References JP-A-63-15895 (JP, A) JP-A-5-239485 (JP, A) JP-A-5-239483 (JP, A) JP-A-5-93197 (JP, A) JP-A-61-166892 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C10M 135/10 C10M 133/16 C10M 159/20-159/24 C10N 40:25

Claims (2)

(57) [Claims] An alkenyl succinimide or a derivative thereof (A) in an amount of 4 to 15% by weight and a base number of 80 mg KOH / g or less in a base oil of a mineral oil-based lubricating oil or a synthetic lubricating oil or a mixture of both. Of calcium sulfonate
0.5 to 2 % by weight, and (C) a base number of 100 mg KO
2 to 10% by weight of calcium salicylate of H / g or more
A diesel engine oil composition, characterized in that the composition comprises: 2. A method according to claim 1, wherein the base oil of a mineral oil-based lubricating oil or a synthetic lubricating oil or a mixture of the two is added with (A) an alkenyl group polybutene.
Ten molecular weight of 1500-2000
Toramin or tetraethylenepentamine with imidized <br/> alkenyl succinic acid mono imide or a derivative thereof 4-1
5 wt%, by containing in a ratio of (D) a nonionic surface active agent 0.2-1 wt%, and (C) base number or more calcium salicylate 100 mg KOH / g 2 to 10 wt% A diesel engine oil composition comprising: