JP2015044928A - Lubricating oil additive, lubricating oil additive composition and lubricating oil composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating oil anti-wear agent which is a liquid and easily handled while having a good anti-wear effect.SOLUTION: A lubricating oil additive composition contains a compound represented by the formula (1), and a specific phosphorus compound with different substituent groups similar to the formula (1), where the content of phenyl groups of all aryl groups but aryl groups constituting X is 3-30 mol%. A lubricating oil additive comprises a compound represented by the general formula (1).

Description

  The present invention relates to a phosphorus-based antiwear agent that can be used in lubricating oils and is easy to handle, and a lubricating oil composition containing the same.

Lubricating oils are widely used in industrial machines and automobiles. Most of them are for reducing frictional wear between metals and for reducing heat generation at the sliding portion. For this purpose, various additives are added to the lubricating oil.
As additives for reducing metal wear, phosphorus compounds such as triphenyl phosphate, tricresyl phosphate and thiophosphate, and sulfur compounds such as sulfurized fats and oils, olefin polysulfide, and dibenzyl sulfide are often used. However, in the lubrication region where the conditions are severe, those having higher effects than these antiwear agents have been desired.

  In view of these demands, polymer-type phosphorus compounds have been developed as an antiwear agent having a higher antiwear effect (see, for example, Patent Documents 1 and 2). These compounds have high wear-preventing effects as additives for lubricating oils, but they have the disadvantage that they are difficult to handle because the product form is solid or highly viscous, and are difficult to dissolve in base oils. It was. Accordingly, the market demanded an antiwear agent that is liquid and easy to handle, has good solubility in base oils, and has a high antiwear effect.

JP 2011-178990 A JP 2012-107108 A

  Accordingly, the problem to be solved by the present invention is to provide an anti-wear agent for lubricating oil that is liquid and easy to handle while having a good anti-wear effect.

  Therefore, the present inventors diligently studied to arrive at the present invention. That is, the present invention provides an additive composition for a lubricating oil containing a compound represented by the following general formula (1) as the component (A) and a compound represented by the general formula (5) as the component (B). And an additive composition for lubricating oil in which the proportion of phenyl groups in all aryl groups excluding the aryl group constituting X is 3 to 30 mol%.

(In the formula, X represents any group represented by the following formulas (2) to (4), n represents a number of 1 to 10, and R ^{1 to} R ⁸ represent a hydrogen atom or 3 to 3 carbon atoms. 5 represents an alkyl group, provided that in the aryl group having two substituents of any of R ^{1 to} R ⁸ , there must be 1 to 3 aryl groups in which both of the two substituents are hydrogen atoms. .)

(In the formula, X represents any group represented by formulas (2) to (4), m represents a number of 1 to 10, and R ^{9 to} R ¹⁶ represent a hydrogen atom or a carbon number of 3 to 5; Represents an alkyl group, provided that in the aryl group having two substituents of any one of R ^{9 to} R ¹⁶ , neither of the two substituents becomes a hydrogen atom.)

  The effect of the present invention is to provide an anti-wear agent for lubricating oil that has a good anti-wear effect, is liquid and easy to handle, and has good solubility in base oil.

  The present invention is an additive composition for lubricating oil containing a compound represented by the following general formula (1) as the component (A) and a compound represented by the general formula (5) as the component (B). In the additive composition for lubricating oil, the ratio of phenyl groups in all aryl groups excluding the aryl group constituting X is 3 to 30 mol%.

  In the present invention, a compound represented by the following general formula (1) is used as the component (A).

(In the formula, X represents any group represented by the following formulas (2) to (4), n represents a number of 1 to 10, and R ^{1 to} R ⁸ represent a hydrogen atom or 3 to 3 carbon atoms. 5 represents an alkyl group, provided that in the aryl group having two substituents of any of R ^{1 to} R ⁸ , there must be 1 to 3 aryl groups in which both of the two substituents are hydrogen atoms. .)

R < ¹ > -R < ⁸ > of General formula (1) represents a hydrogen atom or a C3-C5 alkyl group each independently. Examples of such an alkyl group include a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, and an isopentyl group. Among these, a branched alkyl group is preferable and a tertiary butyl group is more preferable from the balance between the effect of preventing wear and whether the product form is liquid.

Here, the aryl group having two substituents of any of R ^{1 to} R ⁸ must have 1 to 3 aryl groups (phenyl groups) in which both of the two substituents are hydrogen atoms. By mixing an aryl group having an alkyl group having 3 to 5 carbon atoms and a phenyl group in the molecule, it is possible to obtain a liquid product form that is highly wear-resistant and easy to handle.

When all of R ^{1 to} R ⁸ are alkyl groups having 3 to 5 carbon atoms, the product form may be solid or highly viscous, or the wear prevention effect may be reduced.
On the other hand, when R ^{1 to} R ⁸ are all hydrogen atoms, the product is difficult to dissolve in the base oil, and when R ^{1 to} R ⁸ are alkyl groups having 1 or 2 carbon atoms or hydrogen atoms, the ratio of hydrogen atoms Regardless of the product, the product becomes difficult to dissolve in the base oil. On the other hand, in the case of an alkyl group having 6 or more carbon atoms, the effect of preventing wear may be reduced regardless of the amount of hydrogen atoms, or the product form may be solid or highly viscous.

  X in the general formula (1) is represented by any of the following formulas (2) to (4). Among these, the group represented by the formula (2) or the formula (3) is preferable because the raw material circumstances may be preferable in producing the compound of the general formula (1) or the wear prevention effect may be high. . In the case of the group represented by the general formula (2), there are three structures of an ortho form, a meta form and a para form depending on the bonding position, and any structure may be used. does not change.

  In the general formula (1), n represents an average degree of polymerization, and n is a number from 1 to 10. In the present invention, when a plurality of compounds having different n coexist as an antiwear agent, n is expressed as an average degree of polymerization. The average degree of polymerization is calculated from the molar ratio of the active ingredients of the product of the present invention. For example, if the composition of n = 1 is 50 mol% and the compound of n = 2 is 50 mol%, the average degree of polymerization is 1. 5 In addition, the value of n can be calculated from the measurement result of high performance liquid chromatography.

  The component (A) composed of the compound represented by the general formula (1) contains n = 0 (triphenyl phosphate) or a compound having n of 11 or more when the average polymerization degree n is 1 to 10. However, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass, and still more preferably 2 parts by mass or less with respect to 100 parts by mass of the component (A). If the content is 10 parts by mass or more, the effect as an antiwear agent may not be exhibited efficiently.

  In order to obtain a higher effect as an antiwear agent, the average of n in the general formula (1) is preferably 1.0 to 5.0, more preferably 1.0 to 2.0, and 1.0. -1.8 is more preferable, and 1.0-1.5 is most preferable. When the average of n exceeds 5.0, the anti-wear effect may be small or may not dissolve in the base oil.

  In addition, as long as n satisfies the above average degree of polymerization, the composition ratio of n is not particularly limited, but in order to obtain a sufficient effect, n = 1 is 30 to 90% and n = 2 to 2 in molar ratio. 10 is preferably 10 to 70%, n = 1 is preferably 70 to 90%, and n = 2 to 10 is more preferably 10 to 30%. When n = 1 is less than 30 mol% or more than 90 mol%, it may be difficult to dissolve in the base oil or the wear prevention effect may be reduced.

  The additive composition for lubricating oils of this invention contains the compound represented by General formula (5) as (B) component.

(In the formula, X represents any group represented by formulas (2) to (4), m represents a number of 1 to 10, and R ^{9 to} R ¹⁶ represent a hydrogen atom or a carbon number of 3 to 5; Represents an alkyl group, provided that in the aryl group having two substituents of any one of R ^{9 to} R ¹⁶ , neither of the two substituents becomes a hydrogen atom.)

  X in the general formula (5) is the same as X in the general formula (1), and is represented by any one of the formulas (2) to (4). Among these, the group represented by the formula (2) or the formula (3) is preferable because the raw material circumstances may be preferable in producing the compound of the general formula (1) or the wear prevention effect may be high. . In the case of the group represented by the general formula (2), there are three structures of an ortho form, a meta form and a para form depending on the bonding position, and any structure may be used. does not change.

  In the general formula (5), m represents an average degree of polymerization, and m is a number from 1 to 10. In the present invention, when a plurality of compounds having different m coexist as an antiwear agent, m is expressed as an average degree of polymerization. The average degree of polymerization is calculated from the molar ratio of the active ingredients of the product of the present invention. For example, if the composition of m = 1 is 50 mol% and the compound of m = 2 is 50 mol%, the average degree of polymerization is 1. 5 The value of m can be calculated from the measurement result of high performance liquid chromatography.

  (B) component comprised with the compound represented by General formula (5) is m = 0 (trialkylphenyl phosphate) or the compound whose m is 11 or more, if the average degree of polymerization m is 1-10. Although they may be contained, their content is preferably 10 parts by mass or less, more preferably 5 parts by mass, and still more preferably 2 parts by mass or less with respect to 100 parts by mass of the component (B). If the content is 10 parts by mass or more, the effect as an antiwear agent may not be exhibited efficiently.

In order to obtain a higher effect as an antiwear agent, the average of m in the general formula (5) is preferably 1.0 to 5.0, more preferably 1.0 to 2.0, and 1.0. -1.8 is more preferable, and 1.0-1.5 is most preferable. When the average of m exceeds 5.0, the effect of preventing wear may be reduced or may not dissolve in the base oil.
Further, in the relationship between the value of n and the value of m, when n is 1.0 to 2.0, m is preferably 1.0 to 2.0, and when n is 1.2 , M is particularly preferably 1.2.

  In addition, if m satisfies the above average degree of polymerization, the composition ratio of m is not particularly limited, but in order to obtain a sufficient effect, m = 1 is 30 to 90% and m = 2 to 2 in terms of molar ratio. 10 is preferably 10 to 70%, m = 1 is preferably 70 to 90%, and m = 2 to 10 is more preferably 10 to 30%. When m = 1 is less than 30 mol% or more than 90 mol%, it may be difficult to dissolve in the base oil or the wear prevention effect may be reduced.

R ^{9 to} R ^{16 in} the general formula (5) each independently represent a hydrogen atom or an alkyl group having 3 to 5 carbon atoms. Examples of such an alkyl group include a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, and an isopentyl group. Among these, a branched alkyl group is preferable and a tertiary butyl group is more preferable from the balance between the effect of preventing wear and whether the product form is liquid.

The lubricating oil additive composition of the present invention is a mixture of a compound represented by the general formula (1) and a compound represented by the general formula (5), wherein all aryl groups excluding the aryl group constituting X The ratio of the phenyl group in the mixture is a mixture of 3 to 30 mol%, preferably a mixture of 4 to 20 mol%, more preferably a mixture of 4 to 10 mol%. In addition, since the said phenyl group does not exist in the compound represented by General formula (5), the phenyl group in this case is a phenyl group which the compound represented by General formula (1) has.
When the proportion of the phenyl group is less than 3 mol%, the product viscosity increases and the wear prevention effect decreases. If it exceeds 30 mol%, the solubility in the base oil will decrease.

  The additive composition for lubricating oil of the present invention can be produced by a known method. For example, there exists a method of reacting alkylphenol and phenol after reacting benzenediol and phosphorus oxychloride. By this method, a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (5) can be prepared.

For example, in the presence of a catalyst, 2 to 6 moles (preferably 3 to 5 moles) of phosphorus oxychloride is added to 1 mole of benzenediol, and these compounds are reacted. After removing phosphorus chloride, 2.8 to 3.8 mol (preferably 3.0 to 3.8 mol) of mono- or dialkylphenol having an alkyl group having 3 to 5 carbon atoms is added to this reaction product. Can be obtained by reacting 0.1 to 1.2 mol (preferably 0.2 to 1.2).
In addition to benzenediol, bisphenol A (corresponding to general formula (3)) and 4-hydroxy-4-phenylphenol (corresponding to general formula (4)) can also be used.

  When benzenediol and phosphorus oxychloride are reacted, the temperature may be in the range of 80 to 120 ° C. for about 3 to 10 hours. At that time, a catalyst can be used if necessary for the purpose of shortening the reaction time. Catalysts include titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, magnesium chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride and other metal halides; sodium hydroxide, potassium hydroxide, Alkali metal and alkaline earth metal hydroxides, alcoholates, carbonates such as sodium methylate and sodium carbonate; metal oxides such as aluminum oxide, calcium oxide, barium oxide and sodium oxide; tetraisoproprititanate, dibutyltin And organic metal compounds such as dichloride, dibutyltin oxide, and dibutyltin bis (2-ethylhexylthioglycolate). When these catalysts are used, they may be added to the system so as to be 0.01 to 0.5% by mass with respect to the total amount of benzenediol and phosphorus oxychloride.

If unreacted phosphorus oxychloride remains in the system after the reaction of benzenediol and phosphorus oxychloride, it is preferable to remove them. The removal method is not particularly specified, and any of the known methods can be used. However, since the removal method can be easily removed, the removal is preferably performed under reduced pressure. Specifically, it is preferable to reduce the pressure in the system to 5 × 10 ^{2 to} 5 × 10 ³ Pa, further raise the temperature to 90 to 140 ° C., and remove by vacuum distillation.

  After completion of the above reaction, the inside of the system is brought to 80 to 120 ° C., a predetermined amount of mono- or dialkylphenol and phenol are added, and the reaction is performed for 3 to 10 hours to obtain the lubricating oil additive composition of the present invention. it can. When a catalyst is used, it may be removed by a known method such as filtration or adsorption with an adsorbent.

  Further, by synthesizing the compound of general formula (1) and the compound of general formula (5), and mixing so that the ratio of phenyl groups in all aryl groups excluding the aryl group constituting X is within a predetermined range. The additive composition for lubricating oil of the present invention can be obtained.

As a method for producing the compound represented by the general formula (1), any method may be used as long as it is a known method. For example, 1 mol of diphenyl chlorophosphate and 1 mol of 1 mol of benzenediol. And a method of reacting 1 mol of benzene diol with 1 mol of benzene diol and reacting this reaction product with an alkylphenol.
As a method for producing the compound represented by the general formula (5), a method in which 2 mol of dialkylphenyl chlorophosphate is reacted with 1 mol of benzenediol in the same manner as the compound represented by the general formula (1). Is mentioned.

  Furthermore, the present inventors have found that the compound represented by the general formula (1) corresponding to the above component (A) is a liquid and easy to handle wear for lubricating oil while having a good anti-wear effect. It has also been found that it can be used as an inhibitor. That is, this invention also provides the additive for lubricating oil which consists of General formula (1).

(In the formula, X represents any group represented by the following formulas (2) to (4), n represents a number of 1 to 10, and R ^{1 to} R ⁸ represent a hydrogen atom or 3 to 3 carbon atoms. 5 represents an alkyl group, provided that in the aryl group having two substituents of any of R ^{1 to} R ⁸ , there must be 1 to 3 aryl groups in which both of the two substituents are hydrogen atoms. .)

In the additive for lubricating oil composed of the general formula (1) of the present invention, the contents of R ^{1 to} R ⁸ , n, etc. in the general formula (1) apply the description as the component (A). Moreover, the manufacturing method of the compound represented by General formula (1) is also as above-mentioned.

When all of R ^{1 to} R ⁸ are alkyl groups having 3 to 5 carbon atoms, the product form may be solid or highly viscous, or the wear prevention effect may be reduced. For example, when n = 1 in the general formula (1), R ¹ , R ³ , R ⁵ and R ⁷ are hydrogen atoms, and R ² , R ⁴ , R ⁶ and R ⁸ are alkyl groups, The viscosity becomes high. However, when R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms and R ⁵ , R ⁶ , R ⁷ and R ⁸ are alkyl groups, the ratio of the hydrogen atom in the compound to the molecule is Same, but product viscosity is lower.

On the other hand, when R ^{1 to} R ⁸ are all hydrogen atoms, the product is difficult to dissolve in the base oil, and when R ^{1 to} R ⁸ are alkyl groups having 1 or 2 carbon atoms or hydrogen atoms, the ratio of hydrogen atoms Regardless of the product, the product becomes difficult to dissolve in the base oil. On the other hand, in the case of an alkyl group having 6 or more carbon atoms, the effect of preventing wear may be reduced regardless of the amount of hydrogen atoms, or the product form may be solid or highly viscous.

  The additive composition for lubricating oil of the present invention and the additive for lubricating oil of the present invention can be used by adding to various lubricating oils. Any base oil can be used as long as it is a known base oil, but it is preferable to use a commonly used mineral oil, synthetic oil or a mixture thereof as a base oil. Specifically, for example, poly-α-olefin, ethylene-α-olefin copolymer, polybutene, alkylbenzene, alkylnaphthalene, polyalkylene glycol, polyphenyl ether, alkyl-substituted diphenyl ether, polyol ester, aromatic ester, pentaerythritol. Synthetic oils such as hindered esters having a skeleton, dibasic acid esters, carbonic acid esters, and GTLs; paraffinic mineral oils, naphthenic mineral oils, and refined mineral oils obtained by purifying them. These base oils may be used alone or in a mixture.

  The lubricating oil composition of the present invention contains the lubricating oil additive composition of the present invention and the lubricating oil additive of the present invention in an amount of 0.01 to 10% by mass based on the base oil. 0.05-7 mass% is preferable, and 0.1-5 mass% is still more preferable. If the blending amount is too small, the effect as an antiwear agent may not be exhibited. If the blending amount is too large, an insoluble matter may appear or an effect commensurate with the blending amount may not be obtained.

The lubricating oil composition of the present invention does not refuse the addition of known lubricating oil additives, depending on the purpose of use, antiwear agents other than the present invention, friction modifiers, metallic detergents, ashless dispersants, Antioxidants, friction reducers, viscosity index improvers, pour point depressants, rust inhibitors, corrosion inhibitors, load bearing additives, antifoaming agents, metal deactivators, emulsifiers, antiemulsifiers, fungicides, etc. May be added as long as the effects of the present invention are not impaired.
In addition, when using the compound of General formula (1) independently as an additive for lubricants, it is preferable not to contain the compound of General formula (5).

  The lubricating oil composition of the present invention can be used for any application as long as the lubricating oil can be used. These applications include, for example, engine oil, transmission lubricating oil, gear oil, turbine oil, hydraulic oil, flame retardant hydraulic fluid, refrigerator oil, compressor oil, vacuum pump oil, bearing oil, sliding surface oil, Rock drill oil, metal processing oil, plastic processing oil, heat treatment oil, grease, processing oil, etc. are mentioned, but since the lubricating oil composition of the present invention has a high wear prevention effect, engine oil, transmission lubricating oil, It is preferably used for gear oil, turbine oil, bearing oil, sliding surface oil, rock drill oil, processing oil and the like.

  Hereinafter, the present invention will be specifically described by way of examples. The production methods of the compounds and compositions used in the examples are described below. In addition, the kind and compounding quantity of the raw material used for manufacture of each compound and composition were described in Table 1.

(Manufacturing 1)
A condenser connected with a water scrubber was attached to a 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 110 g (1.0 mol) of 1,3-benzenediol, 422 g (2.0 mol) of phenyl dichlorophosphate and 0.5 g of magnesium chloride was charged as a catalyst, and the atmosphere in the reaction apparatus was replaced with nitrogen, and then the temperature was gradually raised to 100 ° C. over 5 hours. After aging at the same temperature for 2 hours, 300 g (2.0 mol) of 4-tert-butylphenol was added to the system, and the reaction was completed after aging for 4 hours. Thereafter, the catalyst was removed by a conventional method and dried under reduced pressure at 140 ° C. to obtain the product 1 of the present invention. In addition, this invention 2 and the comparative products 1-3 were manufactured with the same apparatus and method (all are 1 degree of average polymerization).

(Manufacturing 2)
A condenser connected with a water scrubber was attached to a 1000 ml four-necked flask equipped with a stirrer, thermometer, and nitrogen introduction tube, and 1,3-benzenediol 110 g (1.0 mol), dichlorochlorophosphate (4-tert-butylphenyl) 649 g (2.0 mol) and 0.5 g of magnesium chloride as a catalyst were charged, and the atmosphere in the reactor was replaced with nitrogen, and then the temperature was gradually raised to 100 ° C. over 5 hours. The reaction was completed after aging for 2 hours at the same temperature. Thereafter, the catalyst was removed by a conventional method and dried under reduced pressure at 140 ° C. to obtain a comparative product 4 (both had an average degree of polymerization of 1).

(Manufacturing 3)
A condenser connected with a water scrubber was attached to a 1000 ml four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 110 g (1.0 mol) of 1,3-benzenediol, 608 g (4.0 mol) of phosphorus oxychloride and catalyst As a starting material, 0.5 g of magnesium chloride was charged, and the atmosphere in the reactor was replaced with nitrogen, and then the temperature was gradually raised to 100 ° C. over 5 hours. After aging for 2 hours at the same temperature, the temperature was raised to 130 ° C. under reduced pressure and further aging was performed for 2 hours. To this reaction solution, a mixture of 570 g (3.8 mol) of 4-tert-butylphenol and 19 g (0.2 mol) of phenol was added and aged at 100 ° C. for 5 hours to complete the reaction. Thereafter, the catalyst was removed by a conventional method and dried under reduced pressure at 140 ° C. to obtain the product 3 of the present invention (average polymerization degree 1.2). Inventive products 3 to 5 and comparative products 5 to 8 were produced by the same apparatus and method. In addition, what was manufactured by the method of manufacture 3 on a manufacturing method is a mixture of the compound represented by General formula (1), and the compound represented by General formula (5), and all have an average degree of polymerization. 1.2.

Raw material 1: 1,3-benzenediol raw material 2: Phenyl dichlorophosphate raw material 3: 4-tert-butylphenol raw material 4: 2,6-ditertiary butylphenol raw material 5: Phenol raw material 6: 4-Ethylphenol raw material 7: 4- Hexylphenol raw material 8: Di (4-tert-butylphenyl) chlorophosphate
Raw material 9: Phosphorus oxychloride raw material 10: 4-Butylphenol

(Supplementary explanation)
Invention product 1: In general formula (1), n = 1, R ¹ and R ⁸ are tertiary butyl groups, R ^{2 to} R ⁷ are hydrogen atoms. Invention product 2: in general formula (1), n = 1, R ¹ , R ² , R ⁷ and R ⁸ are tertiary butyl groups, R ^{3 to} R ⁶ are hydrogen atoms

Comparative product 1: In general formula (1), n = 1, R ^{1 to} R ⁸ are hydrogen atoms Comparative product 2: In general formula (1), n = 1, R ¹ and R ⁸ are ethyl groups, R ^{2 to} R ⁷ Is a hydrogen atom comparison product 3: n = 1 in the general formula (1), R ¹ and R ⁸ are hexyl groups, R ^{2 to} R ⁷ are hydrogen atom comparison products 4: n = 1 in the general formula (1), R ¹ , R ³ , R ⁵ and R ⁷ are tertiary butyl groups, R ² , R ⁴ , R ⁶ and R ⁸ are hydrogen atoms

Invention product 3: a mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a tertiary butyl group and hydrogen atom. The proportion of phenyl groups in the mixture is 5 mol%
Invention product 4: a mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a tertiary butyl group and hydrogen atom. The proportion of phenyl groups in the mixture is 25 mol%
Invention product 5: a mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a tertiary butyl group and hydrogen atom. The proportion of phenyl groups in the mixture is 5 mol%
Invention product 6: A mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a butyl group and a hydrogen atom. The proportion of phenyl groups in the mixture is 5 mol%

Comparative product 5: a mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a tertiary butyl group and a hydrogen atom . The proportion of phenyl groups in the mixture is 35 mol%
Comparative product 6: a mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), wherein R ^{1 to} R ¹⁶ are a tertiary butyl group and a hydrogen atom . The proportion of phenyl groups in the mixture is 0 mol%
Comparative product 7: In the mixture of compounds represented by the general formula (1) and the general formula (5) (n = 1.2, m = 1.2), R ^{1 to} R ¹⁶ are hydrogen atoms. The proportion of phenyl groups in the mixture is 100 mol%
Comparative product 8: In the mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), R ^{1 to} R ¹⁶ are an ethyl group and a hydrogen atom. The proportion of phenyl groups in the mixture is 5 mol%
Comparative product 9: In the mixture of compounds represented by general formula (1) and general formula (5) (n = 1.2, m = 1.2), R ^{1 to} R ¹⁶ are a hexyl group and a hydrogen atom. The proportion of phenyl groups in the mixture is 5 mol%

<Fluidity test>
Judgment whether the obtained compound was liquid or solid was made based on the test method of ASTM D4359-90. That is, 20 ml of the compound or composition was placed in a 100 ml screw tube (depth 100 mm) and left in a high temperature bath at 38 ° C. for 24 hours. Thereafter, the screw tube was taken out and placed upside down on a desk, and the compounds in the tube were observed for 3 minutes. If a compound or the like flows within 50 minutes or more within 3 minutes, the compound or the like is a liquid, and if it is less than 50 mm, it is determined as a solid.

<Solubility test>
Kinematic viscosity ^{4.1mm 2 /s(100℃),18.3mm 2 / s (40} ℃), the mineral oil having a viscosity index (VI) = 126, 0.5 wt% of the compound or composition and 1 wt% It added so that it might become. After stirring for 30 minutes, it was left in a high-temperature bath at 25 ° C. for 3 hours, and the state of the liquid after being left was evaluated according to the following criteria.
○: Transparent liquid Δ: Cloudiness is observed in the liquid ×: Undissolved residue can be confirmed

<Lubricity test>
Using the sample dissolved in 1% by mass used in the above-described solubility test, in a shell-type high-speed four-ball tester, the load is 40 kg, the oil temperature is 40 ° C., the rotation speed is 1,500 rpm, and the time is 10 minutes. The wear scar diameter of the ball was measured.

Claims (12)

(A) A component represented by the following general formula (1) as the component and an additive composition for lubricating oil containing the compound represented by the general formula (5) as the component (B), wherein X is The additive composition for lubricating oils, wherein the proportion of phenyl groups in all aryl groups excluding constituting aryl groups is 3 to 30 mol%.

(In the formula, X represents any group represented by the following formulas (2) to (4), n represents a number of 1 to 10, and R ^{1 to} R ⁸ represent a hydrogen atom or 3 to 3 carbon atoms. 5 represents an alkyl group, provided that in the aryl group having two substituents of any of R ^{1 to} R ⁸ , there must be 1 to 3 aryl groups in which both of the two substituents are hydrogen atoms. .)

(In the formula, X represents any group represented by formulas (2) to (4), m represents a number of 1 to 10, and R ^{9 to} R ¹⁶ represent a hydrogen atom or a carbon number of 3 to 5; Represents an alkyl group, provided that in the aryl group having two substituents of any one of R ^{9 to} R ¹⁶ , neither of the two substituents becomes a hydrogen atom.)   The additive composition for lubricating oil according to claim 1, wherein the alkyl group having 3 to 5 carbon atoms is a tertiary butyl group.   The additive for lubricating oil according to claim 1 or 2, wherein n in the general formula (1) represents a number of 1 to 2, and m in the general formula (5) represents a number of 1 to 2. Composition.   4. The additive composition for lubricating oil according to claim 3, wherein n in the general formula (1) represents a number of 1.2 and m in the general formula (5) represents a number of 1.2. .   A lubricating oil composition comprising 0.1 to 10% by mass of the lubricating oil additive composition according to any one of claims 1 to 4 based on a base oil. (I) a step of adding 2 to 6 moles of phosphorus oxychloride to 1 mole of benzenediol, bisphenol A or 4-hydroxy-4-phenylphenol, and reacting these compounds;
(Ii) The reaction product of step (i) is reacted with 2.8 to 3.8 mol of mono- or dialkylphenol having an alkyl group having 3 to 5 carbon atoms and 0.1 to 1.2 mol of phenol. The manufacturing method of the additive composition for lubricating oils including a process.   The manufacturing method of the additive composition for lubricating oils of Claim 6 including removing unreacted phosphorus oxychloride after the said process (i).   The additive composition for lubricating oils obtained by the manufacturing method of Claim 6 or 7. An additive for lubricating oil comprising a compound represented by the following general formula (1).

(In the formula, X represents any group represented by the following formulas (2) to (4), n represents a number of 1 to 10, and R ^{1 to} R ⁸ represent a hydrogen atom or 3 to 3 carbon atoms. 5 represents an alkyl group, provided that in the aryl group having two substituents of any of R ^{1 to} R ⁸ , there must be 1 to 3 aryl groups in which both of the two substituents are hydrogen atoms. .)

  The additive for lubricating oil according to claim 9, wherein the alkyl group having 3 to 5 carbon atoms is a tertiary butyl group.   The additive for lubricating oil according to claim 9 or 10, wherein n in the general formula (1) is 1.   A lubricating oil composition comprising 0.1 to 10% by mass of the additive for lubricating oil according to any one of claims 9 to 11 based on a base oil.