JP2017155219A - Lubricating oil additive and lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating oil additive that has an effect of reducing wear in lubricating oil and an effect of preventing seizure, and a lubricating oil composition containing a lubricating oil additive and base oil.SOLUTION: There is provided a lubricating oil additive containing a calcium-containing polyether compound (A) represented by following general formula (1). R[-(OA)-B(Ca)](1). [Ris a residue obtained by removing f hydroxyl groups from a hydroxyl group-containing compound. (OA) is an oxyalkylene group having 2 to 4 carbon atoms. m is an integer of 2 to 100. 2 or more Amay be the same or different. f is an integer of 1 to 6. When f is 1, B is X(Ca), Xis an anionic group having a valency of a, and Cais calcium ion. When f is 2 or more, B is X(Ca)or hydroxyl group, and at least one is X(Ca).].SELECTED DRAWING: None

Description

  The present invention relates to a lubricating oil composition comprising a lubricating oil additive and a lubricating oil additive and a base oil.

Conventionally, sulfur-based and / or chlorine-based extreme pressure agents have been used in lubricating oils based on petroleum-based base oils. In addition, overbased calcium sulfonate is used as a chlorine-free extreme pressure agent and / or antiwear agent from the viewpoint of toxicity and carcinogenicity (see Patent Documents 1 and 2).
On the other hand, in recent years, lubricating oils based on compounds containing hydroxyl groups such as ethylene glycol, propylene glycol and polyether have been used from the viewpoint that there is no problem of water solubility, biodegradability, and hydrolysis. (See Patent Document 3).
However, in lubricating oils based on a compound containing a hydroxyl group, conventional extreme pressure agents such as sulfur-based and / or chlorine-based extreme pressure agents and overbased calcium sulfonate have poor compatibility and are unstable. The effect of reducing wear and the effect of preventing seizure cannot be expected.

JP-A-5-320679 Special table 2010-507718 JP 2006-083378 A

  An object of the present invention is to provide a lubricating oil additive having an effect of reducing wear in a lubricating oil and an effect of preventing seizure, and a lubricating oil composition comprising the lubricating oil additive and a base oil. And

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a lubricating oil additive containing a calcium-containing polyether compound (A) represented by the following general formula (1).
R ¹ [-(OA ¹ ) _m -B] _f (1)
[R ¹ is a residue obtained by removing f hydroxyl groups from a hydroxyl group-containing compound. (OA ¹ ) is an oxyalkylene group having 2 to 4 carbon atoms. m is an integer of 2-100. Two or more (OA ¹ ) may be the same or different. f is an integer of 1-6. When f is 1, B is X ^a− (Ca ²⁺ ) _{a / 2} , X ^a− is an anionic group having a valence of a, and Ca ²⁺ is a calcium ion. When f is 2 or more, B is X ^a- (Ca ²⁺ ) _{a / 2} or a hydroxyl group, and at least one is X ^a- (Ca ²⁺ ) _{a / 2} . ]

The lubricating oil additive of the present invention has the following effects.
(1) Improve the lubricity of the lubricating oil.
(2) Improve the wear resistance of the lubricating oil.
(3) It is stable in a lubricating oil having a hydroxyl group-containing compound as a base oil.

  The lubricating oil additive of the present invention contains a calcium-containing polyether compound (A).

The calcium-containing polyether compound (A) of the present invention is represented by the following general formula (1).
R ¹ [-(OA ¹ ) _m -B] _f (1)
[R ¹ is a residue obtained by removing f hydroxyl groups from a hydroxyl group-containing compound. (OA ¹ ) is an oxyalkylene group having 2 to 4 carbon atoms. m is an integer of 2-100. Two or more (OA ¹ ) may be the same or different. f is an integer of 1-6. When f is 1, B is X ^a− (Ca ²⁺ ) _{a / 2} , X ^a− is an anionic group having a valence of a, and Ca ²⁺ is a calcium ion. When f is 2 or more, B is X ^a- (Ca ²⁺ ) _{a / 2} or a hydroxyl group, and at least one is X ^a- (Ca ²⁺ ) _{a / 2} . ]

In general formula (1), R ¹ is a residue obtained by removing f hydroxyl groups from a hydroxyl group-containing compound. However, R ¹ includes a residue obtained by removing a hydroxyl group from ethylene glycol, propylene glycol, butanediol, and methylpropanediol, but other than that, a hydroxyl group is obtained from a hydroxyl group-containing compound having an oxyalkylene group having 2 to 4 carbon atoms. Excluded residues are not included.

Examples of the hydroxyl group-containing compound include aliphatic or alicyclic monohydric alcohols, aliphatic or alicyclic polyhydric alcohols, diols, aromatic alcohols, and hydroxy acids.
Specific examples of the aliphatic or alicyclic monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, Examples include pentadecanol, hexadecanol, heptadecanol and octadecanol, cetyl alcohol, oleyl alcohol, isododecanol, isotridecanol, isotetradecanol, and cyclohexanol.
Specific examples of the aliphatic or alicyclic polyhydric alcohol include glycerin, diglycerin, triglycerin, trimethylolpropane, hexanetriol, pentaerythritol and sorbitol.
Diols include ethylene glycol, propylene glycol, butanediol, methylpropanediol, pentanediol, methylpentanediol, hexanediol, neopentylglycol, 2-butyl-2-ethyl-1,3-propanediol, 2,2 ′ -Diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanediol, 1,4-cyclohexanedimethanol and tricyclode Examples include candimethanol.
Aromatic alcohols include benzyl alcohol, octylphenol, and nonylphenol.
Examples of the hydroxy acid include hydroxypivalic acid-neopentyl glycol ester, dimethylolpropionic acid and dimethylolbutanoic acid.
Among these hydroxyl group-containing compounds, aliphatic or alicyclic monohydric alcohols, aliphatic or alicyclic polyhydric alcohols, diols and aromatic alcohols from the viewpoint of raw material costs and ease of synthesis. From the viewpoint of environmental regulations, aliphatic or alicyclic monohydric alcohols, aliphatic or alicyclic polyhydric alcohols and diols are preferred.
Specifically, butanol, lauryl alcohol, cetyl alcohol, oleyl alcohol, isododecanol, isotridecanol, isotetradecanol, cyclohexanol, glycerin, propylene glycol, pentaerythritol, sorbitol, ethylene glycol, propylene glycol, butane Diol, hexanediol, octylphenol and nonylphenol are preferred, butanol, lauryl alcohol, glycerin, propylene glycol, pentaerythritol and sorbitol are more preferred.

  m is an integer of 2-100. From the viewpoints of stability, lubricity and wear resistance, it is preferably an integer of 3 to 95.

(OA ¹ ) is an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, and an oxybutylene group. When m is 2 or more, (OA ¹ ) may be the same or different.
Of these, from the viewpoints of stability, lubricity and wear resistance, oxyethylene groups, oxypropylene groups, oxybutylene groups, and combinations thereof are preferred, and oxyethylene groups, oxyethylene groups and oxypropylenes are more preferred. Group combination, oxyethylene group and oxybutylene group, oxyethylene group, oxypropylene and oxybutylene group.

f is an integer of 1-6. When f is 1, B is X ^a− (Ca ²⁺ ) _{a / 2} . X ^a− is an anionic group having a valence of a, and Ca ²⁺ is a calcium ion. When f is 2 or more, B is X ^a- (Ca ²⁺ ) _{a / 2} or a hydroxyl group, and at least one is X ^a- (Ca ²⁺ ) _{a / 2} . From the viewpoint of stability, lubricity and wear resistance, f is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and particularly preferably 1.
An anionic group is an anionic hydrophilic group, and includes a carboxylic acid anionic group (—COO ⁻ , —CH ₂ COO ⁻ ), a sulfonic acid anionic group (—S (═O) ₂ O ⁻ ), and phosphoric acid. Anionic groups (—OP (═O) (OH) O ⁻ and —OP (═O) (O ⁻ ) ₂ ), sulfate anionic groups (—OS (═O) ₂ O ⁻ ), phosphonic acid (—P (= O) (OH) O - and ^{-P (= O) (O -} ) 2) and phosphinic acid ^{(-PH (= O) O -} ) , and the like.

Examples of (A) include a calcium salt of a terminal anionic group-modified product of an alkylene oxide adduct having 2 to 4 carbon atoms of the hydroxyl group-containing compound.
Examples of the hydroxyl group-containing compound include aliphatic or alicyclic monohydric alcohols, aliphatic or alicyclic polyhydric alcohols, diols, aromatic alcohols, and hydroxy acids. Specific examples of the hydroxyl group-containing compound include those obtained by adding a hydroxyl group to R ¹ in the general formula (1).

Examples of the alkylene oxide (hereinafter abbreviated as AO) to be added to the hydroxyl group-containing compound include AO having 2 to 4 carbon atoms, specifically ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene. Oxide (hereinafter abbreviated as PO), 1,2-butylene oxide (hereinafter abbreviated as BO), tetrahydrofuran (hereinafter abbreviated as THF)) and the like. EO, PO, BO, THF, and the like may be used alone or in combination, and the addition format when used in combination may be random addition or block addition.
Among these, from the viewpoint of stability, lubricity, abrasion resistance and reactivity, EO addition, EO / PO random addition, EO / BO random addition, EO / THF random addition, EO / PO block addition, PO / EO block addition, EO / BO block addition, BO / EO block addition, EO / PO / BO random addition, EO / PO / THF random addition, and EO / BO / THF random addition, more preferably EO addition, EO / PO random addition, EO / BO random addition, EO / THF random addition, EO / PO block addition, PO / EO block addition, EO / BO block addition, and BO / EO block addition.

  The number average molecular weight of the alkylene oxide adduct having 2 to 4 carbon atoms of the hydroxyl group-containing compound is 150 to 43200, preferably 410 to 27000, from the viewpoints of stability, lubricity, and wear resistance.

  Examples of the terminal anionic group include a carboxylic acid anionic group, a sulfonic acid anionic group, a phosphoric acid anionic group, a sulfuric acid anionic group, phosphonic acid, and phosphinic acid. When two or more terminal anionic groups are contained, they may be the same or different. Among these, a carboxylic acid anionic group, a sulfonic acid anionic group, and a phosphate anionic group are more preferable from the viewpoint of ease of synthesis.

Specific examples of (A) include a calcium salt of terminal acetyl oxide of an EO / PO random adduct of butanol, a calcium salt of terminal sulfonate of an EO / BO random adduct of butanol, and an EO / PO random adduct of butanol. Calcium salt of terminal phosphate, EO adduct of lauryl alcohol, calcium salt of terminal acetylate, PO / EO block adduct of propylene glycol, terminal acetylate calcium salt, terminal phosphate of glycerin EO adduct Examples thereof include calcium salts, calcium salts of terminal sulfonated products of PO adducts of pentaerythritol, calcium salts of terminal acetic oxides of EO / PO random adducts of sorbitol, and the like.
Said (A) may be used independently or may be used in combination of 2 or more type.

The lubricating oil composition of the present invention is a lubricating oil composition comprising a lubricating oil additive containing a calcium-containing polyether compound (A) and a base oil (B).
Base oil (B) is a compound represented by ethylene glycol, propylene glycol and the following general formula (2) from the viewpoint of stability.
R ² [— (A ² O) _n —H] _g (2)
[R ² is a residue obtained by removing part or all of g active hydrogens from an active hydrogen-containing compound, and (A ² O) is an alkyleneoxy group having 2 to 4 carbon atoms. n is a number from 1 to 350. When n is 2 or more, (A ² O) may be the same or different. g is an integer of 1-8. ]

In the general formula (2), R ² is a residue obtained by removing part or all of g active hydrogens from the active hydrogen-containing compound.
The residue obtained by removing part or all of g active hydrogens from the active hydrogen-containing compound is a group obtained by removing active hydrogen that can react with an alkylene oxide described later from a compound containing a hydroxyl group and an amino group.
Examples of the active hydrogen-containing compound include alcohols, amines and carboxylic acids.

Examples of alcohols include 1 to 6 valent alcohols.
Examples of monohydric alcohols include linear or branched aliphatic monohydric alcohols having 1 to 24 carbon atoms, alicyclic monohydric alcohols having 4 to 24 carbon atoms, and aromatic monohydric alcohols having 6 to 24 carbon atoms. It is done.
Specific examples of the linear or branched aliphatic monohydric alcohol having 1 to 24 carbon atoms include methanol, ethanol, propanol, butanol, pentyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol and stearyl. Alcohol etc. are mentioned.
Specific examples of the alicyclic monohydric alcohol having 4 to 24 carbon atoms include cyclobutane alcohol, cyclopentyl alcohol, cyclohexyl alcohol, and the like.
Specific examples of the aromatic ring-containing monohydric alcohol having 6 to 24 carbon atoms include phenol and benzyl alcohol.
Examples of the dihydric alcohol include a linear or branched aliphatic dihydric alcohol having 2 to 18 carbon atoms, an alicyclic dihydric alcohol having 6 to 24 carbon atoms, and an aromatic ring-containing dihydric alcohol having 6 to 24 carbon atoms. It is done.
Specific examples of the linear or branched aliphatic dihydric alcohol having 2 to 18 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol (hereinafter abbreviated as PG), neopentyl glycol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol (hereinafter abbreviated as BG), 1,6-hexanediol, 1,2-dodecanediol, and the like.
Specific examples of the alicyclic dihydric alcohol having 6 to 24 carbon atoms include cyclohexanediol.
Specific examples of the aromatic ring-containing dihydric alcohol having 6 to 24 carbon atoms include hydroquinone and the like.
Examples of the trihydric alcohol include glycerin (hereinafter abbreviated as GR) and trimethylolpropane.
Examples of the tetrahydric alcohol include glycerin pentaerythritol (hereinafter abbreviated as PE) and sorbitan.
Examples of pentahydric alcohols include glucose and fructose.
Examples of the hexahydric alcohol include sorbitol, xylitol, mannitol, dipentaerythritol, tetraglycerin and the like.

  Examples of the amines include alkylamines having 2 to 18 carbon atoms, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

  Examples of the carboxylic acids include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

(A ² O) is an alkyleneoxy group having 2 to 4 carbon atoms, and specific examples include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. When n is 2 or more, (A ² O) may be the same or different. Among the alkyleneoxy groups of 2 to 4, preferably from the viewpoint of lubricity and wear resistance, ethyleneoxy group, combined use of ethyleneoxy group and propyleneoxy group, combined use of ethyleneoxy group and butyleneoxy group, and ethyleneoxy group And a propyleneoxy group butyleneoxy group, more preferably an ethyleneoxy group.

  n is an integer of 1 to 350. n is preferably an integer of 1 to 100, more preferably an integer of 1 to 10, from the viewpoints of stability, lubricity and wear resistance.

  g is an integer of 1-8. g is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2, from the viewpoints of stability, lubricity and wear resistance.

The compound represented by formula (2) in the - (A ² O) _n - can be represented by the following general formula (3).
_{^{- (A 3 O) h -}} (A 4 O) i - (A 5 O) j - (3)
[In Formula (3), (A ³ O) represents an ethyleneoxy group, (A ⁴ O) represents a propyleneoxy group, and (A ⁵ O) represents a butyleneoxy group. These alkyleneoxy groups may be in any order. When h, i, and j are each 2 or more, the addition format may be random addition or block addition. h + i + j is an integer of 1 to 350, h is an integer of 1 to 350, i and j are each an integer of 0 to 100, and h / (h + i + j) is 0.5 to 1.0. When n is 2 or more, (A ² O) may be the same or different. ]

h + i + j is an integer of 1 to 350, and more preferably 1 to 349.
h is an integer of 1 to 350, and h is preferably 1 to 266, more preferably 1 to 100, and most preferably 1 to 10 from the viewpoints of stability, lubricity, and wear resistance.
In the case of containing a propyleneoxy group, i is preferably an integer of 0 to 100, more preferably an integer of 1 to 50, and most preferably an integer of 1 to 5 from the viewpoints of stability and ease of synthesis.
In the case of containing a butyleneoxy group, j is preferably an integer of 0 to 100, more preferably an integer of 1 to 50, and most preferably an integer of 1 to 5 from the viewpoints of stability and ease of synthesis.
In the case of containing a propyleneoxy group and a butyleneoxy group, h / (h + i + j) is preferably 0.5 to 1.0, more preferably 0.5 to 0.99, and most preferably 0.8 from the viewpoint of water solubility. 6-0.99.
When h, i, and j are each 2 or more, the addition format may be random addition or block addition, but is preferably random addition. Note that h + i + j = n.

  Examples of the base oil (B) include ethylene glycol, propylene glycol, polyethylene glycol, EO / PO random adduct of butanol, EO adduct of glycerin, EO / PO random adduct of sorbitol, EO / BO of pentaethylenehexamine. Block adduct, EO / BO random adduct of laurylamine, EO / BO block adduct of diethylenetriamine, EO / PO / BO block adduct of 1,2-dodecanediol, EO / BO random adduct of ethylenediamine, 1, An EO / PO random adduct of 6-hexanediol is exemplified.

  The number average molecular weight of (B) is preferably 150,000 or less, more preferably 100,000 or less, and most preferably 62-88,000 from the viewpoint of stability and ease of synthesis.

  The content of the calcium-containing polyether compound (A) is preferably 0.2 to 99.8% by weight based on the total weight of (A) and (B) from the viewpoint of lubricity and wear resistance. More preferably, it is 1 to 40 weight%, Most preferably, it is 5 to 30 weight%.

The content of the calcium-containing polyether compound (A) is preferably 0.2 to 99.8% by weight based on the amount of the lubricating oil additive, and more preferably 1 from the viewpoint of lubricity and wear resistance. -40% by weight, particularly preferably 5-30% by weight.
When the base oil (B) is used as the lubricating oil additive, the content of the base oil (B) is 0.2 based on the total weight of (A) and (B) from the viewpoints of lubricity and wear resistance. It is ˜99.8% by weight, preferably 60 to 99% by weight, more preferably 70 to 95% by weight.
A lubricating oil composition comprising the lubricating oil additive according to claim 1 or 2 and a base oil (B), wherein the base oil (B) is ethylene glycol, propylene glycol and the following general formula (2): A lubricating oil composition comprising at least one selected from the group consisting of the compounds represented and containing 0.2 to 99.8% by weight of (A) based on the total weight of (A) and (B).

  In the lubricating oil composition of the present invention, water may be used as an additive, and any of pure water, ion exchange water, tap water, industrial water and the like may be used.

In the present invention, the number average molecular weight (hereinafter abbreviated as Mn) is measured by gel permeation chromatography at 40 ° C. using polyethylene oxide as a reference substance.
Device body: HLC-8120 (manufactured by Tosoh Corporation)
Column: TSKgel α6000, G3000 PWXL manufactured by Tosoh Corporation
Detector: Differential refractometer detector built in the device body Eluent: 0.5% sodium acetate / water / methanol (volume ratio 70/30)
Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C
Sample: 0.25% eluent solution Injection volume: 200 μl
Reference material: TSK TANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation
Data processing software: GPC-8020 model II (manufactured by Tosoh Corporation)

  The lubricating oil composition of the present invention may contain an oily agent, a rust preventive agent and the like as an additive in addition to the calcium-containing polyether compound (A).

  Examples of the oily agent include monocarboxylic acids such as caprylic acid and oleic acid, and dicarboxylic acids such as azelaic acid and dimer acid.

  Examples of the rust inhibitor include amine compounds such as diethanolamine, triethanolamine, and cyclohexylamine EO adducts (eg, 2 mol adducts, etc.) excluding (B).

  The lubricating oil additive of the present invention can be used in applications such as metalworking oil, hydraulic oil, bearing oil and the like from the viewpoints of lubricity and stability.

The following examples further illustrate the invention, but the invention is not limited thereto. Below, a part represents a weight part.
<Examples 1-13, Comparative Examples 1-3>
Stirring and mixing the ingredients in the number of parts listed in Table 1 at the compounding temperature described in Table 1, the lubricating oils (S1) to (S13) of the present invention and the comparative lubricating oils (H1) to (H3) 100 parts each were obtained.

The abbreviations in Table 1 represent the following compositions.
(A1) butyl acetate EO / PO random adduct (number average molecular weight 540, molar ratio EO / PO = 50/50) acetic acid calcium salt (A2) butanol EO / BO random adduct (number average molecular weight 3, 900, Calcium salt of sulfonated product in molar ratio EO / PO = 50/50) (A3) Phosphorylation of EO / PO random adduct of butanol (number average molecular weight 2,000, molar ratio EO / PO = 50/50) (A4) lauric alcohol EO adduct (number average molecular weight 410) acetic acid calcium salt (A5) propylene glycol PO / EO block adduct (number average molecular weight 2,400, molar ratio PO / EO) = 70/30) calcium salt of vinegar oxide (number of B: 2)
(A6) Calcium salt of phosphate of glycerin EO adduct (number average molecular weight 500) (number of B: 2)
(A7) sulfonated calcium salt of erythritol EO / PO random adduct (number average molecular weight 1,000, molar ratio EO / PO = 60/40) (number of B: 1)
(A8) Calcium salt of terminal acetate of EO / PO random adduct of sorbitol (number average molecular weight 27,000, molar ratio EO / PO = 70/30) (number of B: 3)
(B1) Ethylene glycol (B2) Propylene glycol (B3) Polyethylene glycol (number average molecular weight 300)
(B4) Butanol EO / PO random adduct (number average molecular weight 540, molar ratio EO / PO = 57/43)
(B5) EO adduct of glycerin (number average molecular weight 600)
(B6) EO / PO random adduct of sorbitol (number average molecular weight 88,000, molar ratio EO / PO = 84/16)
(B7) EO / BO block adduct of pentaethylenehexamine (number average molecular weight 3,000, molar ratio EO / PO = 52/48)
(B8) EO / BO random adduct of laurylamine (number average molecular weight 16,100, molar ratio EO / BO = 67/33)
(B9) EO / BO block adduct of diethylenetriamine (number average molecular weight 22,800, molar ratio EO / BO = 95/5)
(B10) 1,2-dodecanediol EO / PO / BO block adduct (number average molecular weight 1,650, molar ratio EO / PO / BO = 66/27/7)
(B11) EO / BO random adduct of ethylenediamine (number average molecular weight 72,800, molar ratio EO / BO = 71/29)
(B12) 1,6-hexanediol EO / PO random adduct (number average molecular weight 33,260, molar ratio EO / PO = 71/29)
(C1) Chlorinated paraffin (C14-17)
(C2) Overbased calcium sulfonate (base number 350 mgKOH / g)

(A1), (A4), (A5), and (A8) use potassium hydroxide as a catalyst and use a pressurized reactor at a suitable temperature of 100 to 150 ° C. for 4 to 20 hours. The alkylene oxide addition reaction of raw material alcohol was performed over suitable time. And chloroacetic acid was prepared, it acetic-acidated over the suitable time among 5 to 15 hours at suitable temperature among 40-60 degreeC, and the acetic acid oxide was produced. And neutralized with Ca hydroxide.
(A2) and (A7) are prepared by using potassium hydroxide as a catalyst and using a pressurized reactor at a suitable temperature of 130 to 150 ° C. over a suitable time of 4 to 8 hours. An alkylene oxide addition reaction was performed. Then, chlorosulfonic acid was charged and sulfonated at a suitable temperature of 0 to 70 ° C. over 2 hours to prepare a sulfonated product. And neutralized with Ca hydroxide.
In (A3) and (A6), potassium hydroxide was used as a catalyst, and an alkylene oxide addition reaction of raw material alcohol was performed at 150 ° C. over 4 hours using a pressure reactor. And phosphoric acid was prepared, and it phosphorylated over suitable time among 4 to 12 hours at suitable temperature among 60-90 degreeC, and produced phosphorous oxide. And neutralized with Ca hydroxide.
(A1) to (A8) were dehydrated at 70 ° C. for 3 hours under reduced pressure using an evaporator as necessary.

  (B4) to (B10) are prepared by adding alkylene oxide over a suitable time of 4 to 20 hours at a suitable temperature of 100 to 150 ° C. using potassium hydroxide as a catalyst and using a pressure reactor. Reaction was carried out to produce. (B11) and (B12) were produced by performing an alkylene oxide addition reaction at 110 ° C. for 20 hours using cesium hydroxide as a catalyst and using a pressure reactor. In addition, the other compound used the commercial item.

<Evaluation example>
The resulting lubricating oil composition was tested for stability, lubricity and wear resistance.
The test method is as follows. The results are shown in Table 1.
(1) Stability 50 ml of the lubricating oil of the present invention was put in a 100 ml glass beaker and allowed to stand at 25 ° C. for 10 minutes, and then the stability was evaluated from the appearance.
[Stability]
○: Uniform and transparent ×: Cloudiness or separation

(2) Lubricity and Abrasion Resistance Using a vibration friction wear tester (SRV tester manufactured by Optimol Co., Ltd.), the coefficient of friction in a point contact (load 300 N) between a steel ball and a flat steel disk was evaluated. Test conditions are shown below.
Amplitude: 2 mm, Frequency: 50 Hz, Temperature: 40 ° C
Time: 10 minutes [Lubricity]
○: Average friction coefficient for 10 minutes <0.10
X: Average friction coefficient for time 10 minutes ≧ 0.10
[Abrasion resistance]
A: Wear mark of steel ball after 10 minutes wear <0.4 mm
○: Wear mark of steel ball after 10 minutes wear 0.4 to 0.5 mm
×: Wear mark of steel ball after 10 minutes wear> 0.5 mm

  As can be seen from Table 1, the lubricating oil compositions of the examples are excellent in all of stability, lubricity, and wear resistance. On the other hand, the lubricating oil composition of the comparative example is inferior to the lubricating oil composition of the example in any one or more of stability, lubricity, and wear resistance.

  The lubricating oil additive of the present invention is stable, excellent in lubricity and wear resistance, and contains the lubricating oil additive and the lubricating oil additive and the base oil obtained as described above. And can be suitably used for working oil, bearing oil, gear oil, etc. for metalworking oil, construction machinery, ships and metalworking machinery.

Claims (4)

A lubricating oil additive comprising a calcium-containing polyether compound (A) represented by the following general formula (1).
R ¹ [-(OA ¹ ) _m -B] _f (1)
[R ¹ is a residue obtained by removing f hydroxyl groups from a hydroxyl group-containing compound. (OA ¹ ) is an oxyalkylene group having 2 to 4 carbon atoms. m is an integer of 2-100. When m is 2 or more, (OA ¹ ) may be the same or different. f is an integer of 1-6. When f is 1, B is X ^a− (Ca ²⁺ ) _{a / 2} , X ^a− is an anionic group having a valence of a, and Ca ²⁺ is a calcium ion. When f is 2 or more, B is X ^a- (Ca ²⁺ ) _{a / 2} or a hydroxyl group, and at least one is X ^a- (Ca ²⁺ ) _{a / 2} . ]   The lubricating oil additive according to claim 1, wherein in the general formula (1), the anionic group is at least one selected from the group consisting of a carboxylic acid anionic group, a sulfonic acid anionic group, and a phosphoric acid anionic group. A lubricating oil composition comprising the lubricating oil additive according to claim 1 or 2 and a base oil (B), wherein the base oil (B) is ethylene glycol, propylene glycol and the following general formula (2): A lubricating oil composition comprising at least one selected from the group consisting of the compounds represented and containing 0.2 to 99.8% by weight of (A) based on the total weight of (A) and (B).
R ² [— (A ² O) _n —H] _g (2)
[R ² is a residue obtained by removing part or all of g active hydrogens from an active hydrogen-containing compound, and (A ² O) is an alkyleneoxy group having 2 to 4 carbon atoms. n is an integer of 1 to 350. When n is 2 or more, (A ² O) may be the same or different. g is an integer of 1-8. ] The base oil (B) is ethylene glycol, propylene glycol, the polyether in which A ² O in the general formula (2) is an ethyleneoxy group, and — (A ² O) _n — in the general formula (2) The lubricating oil composition according to claim 3, wherein the lubricating oil composition is one or more selected from the group consisting of polyethers represented by the following general formula (3).
_{^{- (A 3 O) h -}} (A 4 O) i - (A 5 O) j - (3)
[In Formula (3), (A ³ O) represents an ethyleneoxy group, (A ⁴ O) represents a propyleneoxy group, and (A ⁵ O) represents a butyleneoxy group. These alkyleneoxy groups may be in any order. When h, i, and j are each 2 or more, the addition format may be random addition or block addition. h + i + j is an integer of 1 to 350, h is an integer of 1 to 350, i and j are each an integer of 0 to 100, and h / (h + i + j) is 0.5 to 1.0. When n is 2 or more, (A ² O) may be the same or different. ]