WO1997021792A1

WO1997021792A1 - Lubricating oil

Info

Publication number: WO1997021792A1
Application number: PCT/JP1996/003634
Authority: WO
Inventors: Yasuyuki Kawahara; Mikio Saito; Ichiro Fushimi; Yasuhisa Mitsuya; Yasuhisa Yoshida; Michihide Tokashiki
Original assignee: New Japan Chemical Co., Ltd.
Priority date: 1995-12-12
Filing date: 1996-12-12
Publication date: 1997-06-19
Also published as: JP3826404B2

Abstract

A lubricating oil containing an ester of an alicyclic polycarboxylic acid represented by general formula (I), wherein A represents a cyclohexane or cyclohexene ring, R1 represents hydrogen or a methyl group, X represents hydrogen or COOR4, Y represents hydrogen or COOR?5, and R2, R3, R4, and R5¿ represent each a branched alkyl group having 3 to 18 carbon atoms. This lubricating oil has a good hydrolysis stability and is suitable for use as a lubricating oil for metal working, a lubricating oil for a refrigerator, and the like.

Description

Specification

Technical field of invention

The present invention relates to a lubricating oil, and more particularly, to a lubricating oil containing an organic acid ester having excellent hydrolysis stability, such as an industrial lubricating oil, an automotive lubricating oil and a marine lubricating oil. In addition to metal working lubricating oils used as oils for metal cutting, rolling, grinding, pressing, ebony, extrusion, drawing, etc., and industrial lubricating oils such as refrigerator oils and hydraulic oils Things.

Further, the present invention relates to a lubricating oil for metal working used as a water-soluble oil agent, particularly a lubricating oil for cold rolling used as an emulsion with water and a car cooler using a chlorofluorocarbon as a refrigerant, a refrigerator and the like. It is intended to provide a hydrolysis-resistant lubricating base oil suitable for lubricating oil for refrigerators and the like. Background art

For lubricating oils, hydrolytic stability is one of the basic quality requirements for maintaining lubricating performance in the presence of moisture and other contaminants, especially for cutting fluids, steel or aluminum. Lubricating oils used for metal working such as rolling oils, press working lubricants, drawing oils, hydraulic fluids, textile oils and other emulsions, and lubricating oils used under water-mixed conditions. For lubricating oils for refrigerators and the like, hydrolysis stability is required as an indispensable performance.

Conventionally, oils for metalworking such as cutting, rolling, grinding, pressing, forging, extrusion, drawing, etc. have been used as non-aqueous oils using mineral oils and oils and fats. Water-soluble oils dissolved or emulsified in water have been used. In recent years, processing to improve productivity As the speed increases, the cooling of the machined surface becomes more important, and flame retardancy is required to avoid ignition of oil. Water-soluble oils are superior to nonaqueous oils in terms of economy, cooling, and safety, and the specific gravity of water-soluble oils is increasing.

However, water-soluble oils have the disadvantage that they have poor lubricity, especially under low-speed processing conditions, compared to non-aqueous oils. In order to solve this drawback, water-soluble oils, which mainly used naphthenic mineral oils until now, have been used. Natural oils and synthetic esters have also been used as base oils or as additives to base oils as oils with improved lubricating properties.

As the water-soluble oil agent, generally, a mixture of the above-mentioned fats and oils and / or synthetic esters with a surfactant and other necessary additives is used by diluting it 10- to 100-fold with water. This water-soluble oil has better lubricity than that using mineral oil. However, since it is an ester, it has the disadvantage of being hydrolyzed. Therefore, when used or stored for a long time as an aqueous processing oil, the ester is decomposed into acid and alcohol by hydrolysis, and the performance of the oil agent changes. As a result, the metal may be corroded, or the separation of the oil agent may be uneven and the processing performance may be degraded. Further, even in non-aqueous oils, esters are used as the oil agent component, and performance degradation of the oil due to hydrolysis may become a problem.

Also, in the case of lubricating oils for metal rolling, cold rolling oils for sheet rolling use natural oils and fats with excellent lubricity, especially tallow, which is relatively resistant to deterioration, in the form of emulsion with water. However, in recent years, the rise in temperature of rolling oil accompanying the increase in rolling speed has caused hydrolysis of tallow and various problems resulting therefrom.

In other words, when rolling oil is used in an emulsified state under high temperature conditions, free fatty acids are generated from beef tallow by hydrolysis, which reacts with metals such as iron to produce stones, and the performance of the oil is reduced. Deteriorate. Stone mixes with oil, water and iron powder to form scum that is difficult to remove and clean. In addition, the deposits are flammable and can cause serious accidents. Also, a lot of stone If the scum contained in the emulsion is contaminated, the conforming effect, that is, the effect of reducing the surface roughness becomes excessive, and the roll surface may be worn away at an early stage.

On the other hand, various synthetic esters that replace tallow, for example, esters of neopentyl polyol such as trimethylolpropane and pentaerythritol with oleic acid, and branched forms such as 2-ethylhexanol and isobutanol. The use of esters of alcohols and linear fatty acids is also being studied. These are more expensive than beef tallow, but have good heat stability. However, it is not sufficiently stable against hydrolysis, like tallow.

In addition, refrigerants containing chlorine atoms in the molecule, such as CFC-11 (trichloromonofluoromethane) and CFC-12 (dichlorodifluoro), have been used as refrigerants in refrigerators conventionally used. Volatile substances such as Lometan) and HCFC-22 (monochlorodifluromethane) can destroy the ozone layer, cause global warming, and gradually affect the human body and the global environment in various ways. As it turned out, the production of CFCs has already been banned, and HCFCs have decided to reduce the quantity in stages in an international agreement. Therefore, in recent years, it has been switched to an alternative flow represented by HFC-134a, which does not contain chlorine atoms and does not destroy the ozone layer. Conventional chlorine-containing CFCs have good compatibility with mineral oil-based lubricating oils, so mineral oil-based lubricating oils have been used as lubricating oils for refrigerators. Since it has a higher molecular polarity than CFC-containing, it has poor compatibility with mineral lubricating oils.

Accordingly, polyglycols (polyalkylene glycol, polyether) or esters having good compatibility have been used as lubricating oils for CFC substitutes. However, polyglycols have a problem in electrical insulation. Yes, it can be used for power-conditioning compressors, but cannot be used for motor-integrated hermetic refrigeration compressors. Esters, on the other hand, have high electrical insulation properties and can be used for any purpose, especially neopentylpolyol. Esters of monovalent carboxylic acids are in practical use.

However, even in the case of these polyol esters, esters of linear carboxylic acids have difficulty in hydrolytic stability, so that mixed acids of branched carboxylic acids and linear carboxylic acids or esters of only branched carboxylic acids are used. Used. Nevertheless, hydrolytic stability is not sufficient, and complicated operations are required, such as the need to control air and moisture when assembling or repairing refrigerators.

Under these circumstances, lubricating oils with good hydrolysis resistance have become indispensable in various fields, and there has been an eager demand for their development.

Disclosure of the invention

A first object of the present invention is to provide a novel lubricating oil having excellent hydrolytic stability in view of the development situation of the lubricating oil for metal working, the lubricating oil for a refrigerator, and the like.

A second object of the present invention is to provide a synthetic ester-based lubricating base oil having good hydrolysis resistance.

Further, a third object of the present invention is to provide a synthetic ester-based lubricating base oil having excellent hydrolytic stability, and various lubricating lubricating oils containing the lubricating base oil, particularly metal rolling. The purpose of the present invention is to provide lubricating oils that can be used in various fields in addition to lubricating oils for refrigerators and refrigerators.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific alicyclic polycarboxylic acid ester has excellent hydrolysis stability. It has been found that a predetermined object can be achieved by using an acid ester as a lubricating base oil, and the present invention has been completed based on such findings.

That is, the present invention provides a compound represented by the general formula [I]:

X

R ¹ [I]

Y (In the above general formula [I], A represents a cyclohexane ring or a cyclohexene ring, R ¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or C 0 R ⁴ , Y represents a hydrogen atom or COOR ⁵ , R ² , RR ⁴ , and R ⁵ may be the same or different from each other; a branched alkyl group having 3 to 18 carbon atoms; a cycloalkyl having 3 to 10 carbon atoms Represents a linear alkyl group having 1 to 18 carbon atoms or a linear alkylene group having 2 to 18 carbon atoms.)

A lubricating oil comprising one or more alicyclic polycarboxylic acid esters represented by the following formula (hereinafter referred to as “the present ester” as necessary).

Further, the present invention provides a lubricating oil for metal working, particularly a metal rolling oil, a cutting oil, and a press working, containing one or more kinds of the alicyclic polycarboxylic acid ester represented by the above general formula [I]. And lubricating oil for refrigerators.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the alicyclic polycarboxylic acid ester used as a component of the lubricating oil of the present invention will be described.

Alicyclic polycarboxylate

The alicyclic polycarboxylic acid ester is represented by the following general formula [I].

X

Y In the above general formula [I], A represents a cyclohexane ring or a cyclohexene ring, R ¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or C 0 R ⁴ , Y represents a hydrogen atom or C 0 R ⁵ , and R ² , R ³ , and RR ⁵ may be the same or different from each other; a branched alkyl group having 3 to 18 carbon atoms; and 3 to 10 carbon atoms. Cycloalkyl group, charcoal Represents a linear alkyl group having a prime number of 1 to 18 or a linear alkylene group having a carbon number of 2 to 18;

This ester is obtained by esterifying a predetermined acid component and an alcohol component in a conventional manner, preferably under an inert gas atmosphere such as nitrogen, with heating and stirring in the presence or absence of an esterification catalyst. This is a compound prepared by

Examples of the acid component constituting the ester include cycloalkane polycarboxylic acid or cycloalkene polycarboxylic acid and anhydrides thereof, and one or more compounds thereof can be used in combination. The substitution position of each hydroxyl group may be either a cyclohexane ring or a cyclohexene ring, and is not particularly limited.

Specifically, 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,1,2-dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,1,2-cyclohexanedicarboxylic acid, 3-methyl-4-cyclohexene-1,1, 2-dicarboxylic acid, 4-methyl-14-cyclohexene: I, 2-dicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2 , 4,5-cyclohexanetetracarboxylic acid and anhydrides thereof are exemplified. Of these, 1,2-cyclohexanedicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, -Methyl-1,2 Chlohexane dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid, 4-methyl-1-cyclohexene-1,2— Dicarboxylic acids and their anhydrides are preferred.

As the acid component, the above-mentioned acids can be used alone, and esterification can be performed using two or more kinds of acids.

The alcohol component that constitutes the present ester is composed of 3 to 18 carbon atoms. Examples include a branched alcohol, a cyclic alcohol having 3 to 10 carbon atoms, or a linear alcohol having 1 to 18 carbon atoms.

Specific branched alcohols include isopropanol, isobutanol, sec-butanol, isopenenol, isohexanol, 2-methylhexanol, 1-methylheptanol, 2- Methylheptanol, Isoheptanol, 2-Ethylhexanol, 2—Chetanol, Isooctanol, 3,5,5—Trimethylhexanol, Isodecanol, Isondanol, I Sododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isooctadecanol, 2,6-dimethyl-4-heptanol, isononanol, etc. Is done.

Examples of the cycloalcohol include cyclohexanol, methylcyclohexanol, and dimethylcyclohexanol.

Furthermore, linear alcohols include methanol, ethanol, and n-brono. Knol, n—butanol, n—pentanol, n—hexanol, n—hepanol, n—butanol, n—nonanol, n—decanol, n— Independence force, n — Dodecane force, n — Tridecane force, n — Tetradecane force, n — Pentadecanol, n — Hexadeforce force, n — Octadecanol, 9-octadecenol and the like.

In particular, isobutanol, cyclohexanol, isoheptanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 2,6-dimethyl-4-heptanol, Isodecanol, Isondanol, Isolidanol, Isooctanol, n-hepnool, n-octanol, n-decanol, n-force, n-dodecanol, n-tetradecanol , N-hexadenicol and n-octanedecanol are preferred.

As the alcohol component, the above alcohol alone is used in the esterification reaction. It is also possible to use a mixture of two or more alcohols.

In carrying out the esterification reaction, the alcohol component is used, for example, in an amount of 1 to 1.5 equivalents, preferably 1.05 to 1.2 equivalents, per equivalent of the acid component.

Furthermore, instead of the acid component or the alcohol component, a lower alcohol ester of the acid component and Z or an ester acetate, propionate ester or the like of the alcohol component are used, and the alicyclic polyolefin resin is subjected to a transesterification reaction. It is also possible to obtain acid esters.

Examples of the esterification catalyst include Lewis acids, alkali metals, sulfonic acids and the like. Specifically, examples of Lewis acid include aluminum derivatives, tin derivatives, and titanium derivatives. Examples of alkali metals include sodium alkoxide, potassium alkoxide, and the like. Examples of the acids include p-toluenesulfonic acid, methanesulfonic acid, and sulfuric acid. Among them, organic titanium compounds having 3 to 8 carbon atoms, sodium alkoxides having 1 to 4 carbon atoms, and p-toluenesulfonic acid are preferred. The amount used is, for example, about 0.1% by weight to i% by weight based on the total weight of the acid component and the alcohol component, which are the raw materials for ester synthesis. The esterification temperature is, for example, 150 ° C. to 230 ° C., and the reaction is usually completed in 3 hours to 30 hours.

After completion of the esterification reaction, the excess raw material is distilled off under reduced pressure or normal pressure. Subsequently, the resulting ester can be purified by a conventional purification method, for example, liquid-liquid extraction, vacuum distillation, adsorption purification such as activated carbon treatment, or the like.

The alicyclic polycarboxylic acid ester according to the present invention can also be produced by subjecting the corresponding aromatic polycarboxylic acid ester to nuclear hydrogenation.

Among the alicyclic polycarboxylic acid branched alkyl esters and cycloalkyl esters thus obtained, in particular, diisobutyl 1,2-cyclohexanedicarboxylate and dicyclobutyl 1,2-cyclohexanedicarboxylate Oral hexyl, 1,2-cyclohexanedicarboxylate diisoheptyl, 1,2-cyclohexanedicarboxylate di (2-ethylhexyl), 1,2—cyclohexanedicarboxylate di (3, 5,5—trimethylhexyl), 1,2—cyclohexanedicarboxylic acid di (2,6—dimethyl-4-heptyl), 1,2—cyclohexanedicarboxylic acid diisodecyl, 1,2— Diisodecyl cyclohexanedicarboxylate, 1,2-cyclodiisotridecyl 1,2-cyclohexanedicarboxylate, diisooctadecyl 1,2-cyclohexanedicarboxylate 4-cyclohexene-1,2, -dicyclohexyl dicarboxylate, 4-cyclohexene-1,2,2-diisoheptyl dicarboxylate, 4-cyclohexene-1,2 —Dicarboxylic acid di (2-ethylhexyl), 4-cyclohexene-1,2, -dicarboxylic acid di (3,5,5—trimethylhexyl), 4-cyclohexene1-1,2— Dicarboxylic acid di

(2,6-Dimethyl-4-heptyl), 4-cyclohexene-1,2, -diisodecyl dicarboxylate, 4-cyclohexene-1,2,2-diisodecyl dicarboxylate, 4-cyclohexene-1,2 —Diisotridecyl dicarboxylate, 4-cyclohexene-1,2,2-dicarboxylic acid didecyl ester, 3-methyl-1,2,2-dioxobutyl dicyclohexanedicarboxylate, 3-methyl-1,2—cyclohexyl Dicyclohexyl xandicarboxylate, 3-Methyl-1,2-diisoheptyl cyclohexanedicarboxylate, 3-Methyl-1,2—Dihexylcyclohexanedicarboxylate (2-Ethylhexyl), 3 —Methyl-1,2—Dicyclohexanedicarboxylate

(3,5,5-trimethylhexyl), 3-methyl-1,2-cyclohexanedicarboxylic acid di (2,6-dimethyl-4-heptyl), 3-methyl-1,2, cyclo Hexanedicarboxylate diisodecyl, 3-methyl-1,2-cyclohexanedicarboxylate diisodecyl, 3-methyl-1,2, cyclohexanedicarboxylate diisotridecyl, 3-methyl-1,2, cyclohexyl Diisoxandicarboxylate kutadecyl, 4-methyl-1-, 2-diisobutylcyclohexanedicarboxylate, 4-methyl 1,2-Dicyclohexyl cyclohexanedicarboxylate, 4-Methyl-1,2-dioctylcyclohexanedicarboxylate, 4-methyl-1,2,2-Dicyclohexyldicarboxylate (2-ethylhexyl) ), 4-Methyl-1,2-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl), 4-methyl-1,2, cyclohexanedicarboxylic acid di (2,6-dimethyl) 4 1-Heptyl), 4-Methyl-1-, 2-cyclohexanediisodecyl dicarboxylate, 4-Methyl-1.2-Cyclohexanedicarboxylic acid diisodecyl, 4-Methyl-11,2-cyclohexadiene Diisotridecyl dicarboxylate, diisooctadecyl 4-methyl-1,2-cyclohexanedicarboxylate, 1,2,2-diisobutyl dicarboxylate, 3-Methyl-4-cyclohexene-1,2-dicarboxylic acid dicyclohexyl, 3-methyl-14-cyclohexene-1,2-dicarboxylic acid diisoheptyl, 3-methyl-4-cyclohexene 1,2-dicarboxylic acid di (2-ethylhexyl), 3-methyl-14-cyclohexene-1,2-dicarboxylic acid di (3,5,5-trimethylhexyl), 3-methyl-4 —Cyclohexene-1,2-dicarboxylate di (2,6-dimethyl-4-heptyl), 3-methyl-4-cyclohexene-1,2-dicarboxylate diisodecyl, 3-methyl-4- Cyclohexene-1,2-dicarboxylic acid diisonddecyl, 3-methyl-4-cyclohexene-1,2,2-dicarboxylic acid diisotridecyl, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid 1,2-dicarboxylic acid Sill, four Methyl-4-cyclohexene diisobutyl 1,2-dicarboxylate, 4-methyl-4-cyclohexene 1,2-dicyclohexyl dicarboxylate, 4-methyl-4-cyclohexene-1,2-dicarboxylic acid Diisoheptyl, 4-methyl-4-cyclohexene-1,2-dicarbonate di (2-ethylhexyl), 4-methyl-4-cyclohexene-1,2, -dicarboxylic acid di (3,5,5- Trimethylhexyl), 4-methyl-4-cyclohexene-1,2, -dicarboxylic acid di (2,6-dimethyl-4-heptyl), 4-methyl-4-cyclohexene-1,1,2-dica Diisodecyl rubonate, 4-methyl-4-cyclohexene-1,2, -dicarboxylate diisodecenyl, 4-methyl-4-cyclohexene-1,1,2-dicarboxylate diisotridecyl, 4-methyl-4-cyclohexene- One or more esters selected from the group consisting of diisooctadecyl 1,2-dicarboxylate are recommended.

The alicyclic polycarboxylic acid linear alkyl ester is usually preferably used in combination with one or more of the above-mentioned alicyclic polycarboxylic acid branched alkyl ester and / or cycloalkyl ester. Sile

Specific examples of the alicyclic polycarboxylic acid linear alkyl ester include diheptyl 1,2-cyclohexanedicarboxylate, dioctyl 1,2-cyclohexanedicarboxylate, 1,2-cyclohexane Didecyl dicarboxylate, 1,2-cyclohexanedicarboxylate didodecyl, 1,2-cyclohexanedicarboxylate didodecyl, 1,2-cyclohexanedicarboxylate ditetradecyl, 1,2—Cyclohexanedicarboxylate Hexadecyl, dioctadecyl 1,2-cyclohexanedicarboxylate, 4-cyclohexene-1,2-dicarboxylate diphenyl, 4-cyclohexene-1,2-dioctyl dicarboxylate, 4-cyclohexene 1,1,2-didecyl dicarboxylate, 4-cyclohexene-1,2,2-dicarboxylate didecyl, 4-cyclohexene-1,2, Didodecyl carboxylate, 1,2-dihexadecyl 1,2-dicarboxylate, 4-cyclohexa-1,2-dihexadecyl dicarboxylate, 4-cyclohexene-1,2-dioctadecyl dicarboxylate, 3-Methyl-1,2-cyclohexyldiheptyldicarboxylate, 3-Methyl-1,2-cyclohexyldicarboxylate, 3-Methyl-1,2,2-cyclohexanedicarboxylate, 3-methyl- 1,2-cyclohexanedicarboxylate didedecyl, 1,2-cyclohexanedicarboxylate didodecyl, 3-methyl-1,2-cyclohexanedicarboxylate ditetradecyl, 3-methyl-1,2— Cyclohexanedicarboxylic acid dihexade Sil, 3-methyl-1,2, -dioctadecyl cyclohexanedicarboxylate, 4-methyl-1,2,2-dihexylcyclohexanedicarboxylate, 4-methyl-1,1,2-dioctyl cyclohexanedicarboxylate, 4-methyl Ro 1,2-cyclohexanedicarboxylic acid didecyl, 4-methyl-1,2-cyclohexanedicarboxylic acid didecyl, 4-methyl-1,1, λ '— cyclohexanedicarboxylic acid dododecyl, 4-methyl-1,2-cyclohexanedicarboxylic acid Ditetradecyl acid, 4-methyl-1-, 2-cyclohexanedicarboxylate dihexadecyl, 4-methyl-1,2-cyclohexyldicarboxylate dioctyldecyl, 3-methyl-4-cyclohexene-1 1 , 2-Diheptyl dicarboxylate, 3-Methyl-4-cyclohexene-1,2, -Dioctyl dicarboxylate, 3-Me 4-cyclohexene-1,2-dicarboxylic acid didecyl, 3-methinole-1-cyclohexene-1,2-dicarboxylic acid dindecyl, 3-methyl-4-cyclohexene-1,1,2-dicarboxylic acid dododecyl , 3—Methyl-4-cyclohexene 1-1,2—ditetradecyl dicarboxylate, 3—Methyl-4-cyclohexene1-1,2-hexadecyl dicarboxylate, 3-methyl-1-cyclohexene-1,1, 2 —Dioctadecyl dicarboxylate, 4-methyl-1,4-cyclohexene-1,2, diheptyl dicarboxylate, 4-methyl-1,4-cyclohexene 1,1,2-dioctyl dicarboxylate, 4-methyl-1,4- Cyclohexene-1,2-dicarboxylate didecyl, 4-methyl-4-cyclo mouthhexene-1,2,2-dicarboxylate didecyl, 4-methyl-4-cyclohexene-1,2 Didodecyl dicarboxylate, 4-Methyl-4-cyclohexene-1,2-dicarboxylate ditetradecyl, 4-Methyl-4-cyclohexene-1,2,2-Dihexadecyl dicarboxylate, 4-Methyl-4-cyclohexane Examples thereof include one or more esters selected from the group consisting of xen-1,2-dioctadecyl dicarboxylate.

Further, as the alcohol component, one or more of a branched alcohol and / or a cyclic alcohol and one or two of a linear alcohol are used. It is also possible to synthesize an alicyclic polycarboxylic acid mixed group ester by using a mixture of two or more species.

It is recommended that the total content of the linear alcohol having 1 to 18 carbon atoms in the alcohol component in the alicyclic polycarboxylic acid ester composition thus obtained be 50 mol% or less. In particular, when the total content of the linear alcohol having 12 to 18 carbon atoms exceeds 50 mol%, the ester has a high melting point and tends to have poor fluidity.

Generally, when the ester is exposed to high temperatures in the presence of water, it decomposes to the given carboxylic acid and alcohol. Here, a small increase in the acid value of the hydrolysis product of the ester indicates that hydrolysis is suppressed, and the stability is considered to be large. When compared by this method, for example, tallow, 2-ethylhexyl palmitate, isobutyl stearate, and oleic acid ester of trimethylolpropane, which have been conventionally used as base oils for metalworking lubricating oils, However, the acid value rises greatly, the weight of iron pieces immersed in oil changes greatly, and the surface of iron, copper, aluminum and other metal pieces changes state due to corrosion. In addition, aliphatic polycarboxylic acid esters and aromatic polycarboxylic acid esters also have a large increase in acid value.

On the other hand, cycloalkane polycarboxylate or cycloalkene polycarboxylate has a small increase in acid value, a small change in the weight of iron pieces, and a high degree of change in which there is almost no apparent change in the metal surface. Has hydrolysis resistance.

It is recommended that the content of this ester in lubricating oil be 10% by weight or more. If the amount is less than 10% by weight, there may be a problem in hydrolysis stability.

Next, a lubricating oil for metal working and a lubricating oil for refrigerator using the hydrolysis-resistant lubricating base oil containing the alicyclic polycarboxylic acid ester of the present invention will be described.

Lubricating oil for metal processing

This ester is suitable as a base oil for lubricating oils for metalworking. Is selected from the group consisting of the present ester alone or other base oils such as mineral oil, synthetic hydrocarbon oil, animal and vegetable oils, and esters other than the present ester (hereinafter referred to as “combined ester”). It is also possible to use species or a mixture of two or more.

Examples of the mineral oil include lubricating oil fractions obtained by distillation under normal pressure and reduced pressure, such as paraffin-based crude oil, intermediate-based crude oil, and naphthene-based crude oil.

Synthetic hydrocarbon oils include low-molecular-weight polybutene, low-molecular-weight propylene, and α-olefins having 8 to 14 carbon atoms and hydrogenated compounds thereof, alkylbenzene, alkylnaphthalene, etc. Is shown as an example.

Animal and vegetable oils include tallow, lard, palm oil, coconut oil, rapeseed oil and the like.

Examples of the concomitant ester include fatty acid monoester, adipic acid ester, azelaic acid ester, sebacic acid ester, phthalic acid ester, trimellitic acid ester and polyol ester.

It is recommended that the content of mineral oil, synthetic hydrocarbon oil, animal and vegetable oil and / or concomitant ester in the lubricating oil for metal working be 10% by weight to 90% by weight based on the total weight of the composition.

The lubricating oil for metalworking according to the present invention contains a surfactant, an extreme pressure additive, a gas-proofing agent, a gas-phase gas-proofing agent, a metal-corrosion-proofing agent, and a cutting oil in order to improve the performance of the base oil. It is also possible to appropriately mix one or more of an additive, a pour point depressant, a thickener, an antiseptic, a defoamer, a dye, a fragrance and other additives. The amounts of these additives are the same as those of conventional lubricating oils for metalworking. The additive is not particularly limited as long as it has a predetermined effect as an additive of a lubricating oil for metal working. Specific examples thereof are shown below.

Examples of the surfactant include fatty acid soap, sulfate ester type, sulfonic acid type anion type, polyoxyethylene type, polyvalent alcohol type, and alkylolamide type nonionic type. Extreme pressure additives include chlorinated paraffins, chlorinated fatty acids, chlorinated fatty acid esters and other chlorine-based materials, sulfurized mineral oils, sulfurized oils and other sulfur-based materials, and phosphates such as ester phosphates and phosphites. The main components are oil-based, but sometimes they contain organometallic compounds and solid lubricants.

Examples of the inhibitor include amines such as carboxylate, sulfonate and triethanolamine; amides such as diethanolamide oleate and cyclohexyl adipate; esters such as sorbitan oleate; There are dibasic acids such as sebacic acid, and inorganic ones such as nitrite, phosphate and borate.

Gas phase inhibitors include lower amine nitrite, morpholine, and cyclohexylamine.

Metal anticorrosives include benzotriazole, imidazoline, mercaptobenzothiazole, thiadiazole, polysulfide, and the like. The force Bburi ring agent, Petit diglycol, there ^¾ Puchiruse port cellosolve such force.

Pour point depressants include ethylene glycol and propylene glycol.

Examples of the thickener include polyalkylene glycols, cellulose derivatives, and sodium polyacrylate.

Examples of preservative disinfectants include phenolic compounds such as o-phenylphenol and p-chloro-m-xylenol, and formaldehyde such as hexahydritotriazine, 2-hydroxymethyl-2-nitro-1,3-propanediol. There is a donor.

Antifoaming agents include silicones, higher alcohols, polyalkylene glycols, and fluorinated polyethers.

When the metal working lubricating oil prepared by the above method is used as a water-soluble oil, it can be used after diluting it 10 to 100 times with water.

In addition, this ester is one of the lubricating oils for metal processing, It is also suitable as a base oil. Mineral oil, synthetic hydrocarbon oil, animal and vegetable oils, and concomitant esters can also be used as a base oil for lubricating oils for metal rolling, but 50% by weight so as not to impair hydrolytic stability. % Is more preferable. In addition, to improve the performance of the base oil so as to be suitable for metal rolling lubricants, oil agents, extreme pressure agents, viscosity index improvers, antioxidants, antioxidants, emulsifiers, metal deactivators, metal corrosion One or more known additives such as an inhibitor and an antifoaming agent can be appropriately compounded, and are not particularly limited as long as they exhibit a predetermined effect. The following are the columns.

Examples of the oiliness agent include higher fatty acids and higher alcohols, and it is usually preferable to add 0.1 to 2% by weight to the base oil.

Examples of extreme pressure agents include alkyl phosphates, dialkyl phosphates, alkyl polyethylene oxyphosphates and the like. Usually, it is preferable to add 0.1 to 5% by weight based on the base oil.

Examples of the viscosity index improver include polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer and the like. Usually, it is preferable to add 1% by weight to 20% by weight to the base oil.

Antioxidants include those based on phenols, amines, and sulfur. For example, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methylenebis (2,6 —Di-tert-butylphenol, 2,2′-thiobis (4-methyl-6-tert-butylphenol), phenol-ct-naphthylamine, octylphenol α-naphthylamine, Ρ, ρ′—dioctyldiph Unilamine, dibenzyl disulfide and the like can be used. These antioxidants are usually added to the base oil

0.1 Q 1% by weight to 5% by weight, preferably 0.1% by weight to 2% by weight.

Examples of the emulsifier include fatty acid soap, sulfonate, ester nonion, and ether nonion.

% To 10% by weight. Benzotriazole, alkylbenzotriazole, mercaptobenzothiazole, thiadiazol derivatives and the like can be used as the metal deactivator and corrosion inhibitor. These metal deactivators and corrosion inhibitors are preferably added in an amount of 0.01 to 1% by weight based on the base oil.

Lubricating oil for refrigerator

Further, the present ester can be used for lubricating oil for refrigerators, and as a base oil, one or more compounds of the present ester or another ester (hereinafter referred to as “ester in combination”) in addition to the present ester. By mixing, a lubricating base oil for a refrigerator can be prepared.

Particularly preferred alicyclic polycarboxylic esters for refrigerator lubricating oils are diisobutyl 1,2-cyclohexanedicarboxylate, dicyclohexyl 1,2-cyclohexanedicarboxylate and 1,2-cyclohexane. Diisoheptyl xandicarboxylate, 1,2-cyclohexanedicarboxylate di (2-ethylhexyl), 1,2-cyclohexanedicarboxylate di (3,5,5-trimethylhexyl), 1 1,2-cyclohexanedicarboxylic acid di (2,6-dimethyl-4-heptyl), 1,2-cyclohexanedicarboxylic acid diisodecyl, 1,2-cyclohexanedicarboxylic acid diisopentadecyl, 4-cyclohexeneone 1,2-Dicyclohexyl dicarboxylate, 4-Cyclohexene 1,2,2-Diisoheptyl dicanolevonate, 4-Cyclohexene 1,1,2-Dicarbo Di (2-ethylhexyl) acid, 4-cyclohexene-1,2-dicarboxylic acid di (3,5,5, -trimethylhexyl), 3-methyl-1,2-cyclohexanedicarbonate Acid di (3,5,5—trimethylhexyl), 4-monomethyl-1,2-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl), 3-methyl-1-cyclohexyl Xen-1,2-dicarboxylic acid di (3,5,5-trimethylhexyl), 4-methyl-4-cyclohexene-1,1,2-dicarboxylic acid di (3,5,5-trimethylhexyl) , 1,2,4,5-cyclohexanetetracarboxylic acid tetra (3,5,5-trimethylhexyl) and the like. These may be used in combination of two or more. Can also be.

Examples of the concomitant ester include adipic acid ester, azelaic acid ester, sebacic acid ester, phthalic acid ester, trimellitic acid ester, and polyol ester. Considering the balance of physical properties as a lubricating oil for refrigerators, such as compatibility with the viscosity and viscosity, a polyol ester of neopentyl polyol and a monovalent carboxylic acid is particularly preferred. Polyol esters include polyhydric alcohol components such as neopentyl glycol, trimethylolpropane, trimethylolpropane, tritrimethylolpropane, penduris erythritol, dipentaerythritol, and the like. Sobutyric acid, 2-ethylbutyric acid, isovaleric acid, bivalic acid, cyclohexanecarboxylic acid, 2-methylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 3, An ester composed of 5,5-trimethylhexanoic acid is recommended.

The content of the combined ester in the lubricating oil for refrigerators is recommended to be 10% by weight to 90% by weight.

The lubricating oil for refrigerators according to the present invention contains one of additives such as an antioxidant, a metal deactivator, an antiwear agent, an antifoaming agent, and a hydrolysis inhibitor in order to improve the performance of the base oil. It is also possible to appropriately mix two or more species. There is no particular limitation as long as the predetermined effects are achieved, but specific examples are shown below.

As the antioxidant, the same amount as the phenol-based, amine-based, sulfur-based, etc. used in the above-described lubricating oil for metal rolling can be used.

As the metal deactivator, the same benzotriazole or the like used in the lubricating oil for metal rolling can be used in the same amount.

Anti-wear agents include phosphates such as tricresyl phosphate, cresyl diphenyl phosphate, alkyl phenyl phosphates, tributyl phosphate, dibutyl phosphate, etc., tributyl phosphite, dibutyl phosphite , Triisopropyl phosphite, etc. Phosphite esters are common. These antiwear agents are incorporated in an amount of 0.01 to 5% by weight, preferably 0.01 to 2% by weight, based on the base oil.

Liquid silicone is suitable as the defoaming agent, and is preferably added in an amount of 0.0005% by weight to 0.01% by weight based on the base oil.

Examples of the hydrolysis inhibitor include epoxy compounds, for example, alkyl glycidyl ethers, alkylene glycol glycidyl ethers, alicyclic epoxy compounds, phenyl glycidyl ether and derivatives thereof. 0.05 to 2% by weight of the oil is appropriate.

Example

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. The properties of the lubricating oil in each example were evaluated by the following methods. Hydrolysis stability test

Put a 4 cm long iron, copper and aluminum wire into a glass test tube 6.6 mm in height and 30 cm in height, weigh 2.0 g of the sample ester and 0.2 g of distilled water. . Seal the test tube while degassing with an aspirator, place in an oven and heat at 160 ° C for 16 hours. After that, remove the sample ester, measure the acid value and visually observe the surface condition of the iron wire, and evaluate it in three steps as follows.

〇: No change

Δ: Some discoloration is seen

: Change to black

When evaluating as lubricating oil for refrigerators, heat in an oven at 175 ° C for 20 hours.

Kinematic viscosity

Use an Ubbelohde viscometer to measure according to JIS-K-2283.

Pour point

Measure according to JIS-K-226. Volume resistivity

Measure at 25 ° C in accordance with JIS-C-2101.

CFC compatibility test

Add a sample oil and a hydrofluoric carbon refrigerant HFC-134a so that the sample oil becomes 10% by weight in a glass tube, seal the tube, and measure the two-phase separation temperature at 160 to 100 at I do.

Production Example 1

In a 4-neck flask equipped with a stirrer, thermometer, and water distilling unit equipped with a cooling tube, 4-six-hexene-1,2-dicarboxylic anhydride (this product is usually used for maleic anhydride and 1,3-butadiene. 152.1 (1 mol) and 286.5 g (2.2 mol) of 2-ethylhexanol were charged, and the mixture was added to tetraisopropyl titanate. The temperature was raised to 200 ° C. under reduced pressure in the presence of a catalyst. The esterification reaction was performed for about 9 hours while taking the generated water into a water fractionator. After the reaction, excess 2-ethylhexanol was removed by distillation, neutralized with sodium hydroxide, and then washed with water until neutral. Then, the mixture was treated with activated carbon and filtered. Thus, 343.2 g of di (2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate was obtained. Table 1 shows the acid value and the kinematic viscosity.

Production Examples 2 to 13

In the same manner as in Production Example 1, each ester shown in Table 1 was prepared. The same table shows the acid value and Δ viscosity of each ester.

Production example 1 4

The same reactor and reaction vessel as in Production Example 1 were charged with 92.0 g (1.0 mol) of trimellitic anhydride and 522.1 g (3.3 mol) of isodecanol. Esterification was carried out in the same manner as in Production Example 1 to obtain 598 g of triisodecyl trimellitate. Next, 80 g (0.15 mol) of trimeric triisotridecyl acid (0.15 mol) was taken in an autoclave and subjected to a hydrogen pressure of 50 kg at 130 ° C. in the presence of a nuclear hydrogenation catalyst. Hydrogenation was performed for 1 hour under the condition of / cm ² G to obtain 77 g of tri (1,2,4-cyclohexanetricarboxylic acid) (isodecyl). Table 1 shows the acid value and the kinematic viscosity. Table 1 Ester properties, ester name [abbreviation] Acid value 勖 viscosity [Production example [mgKOII / g] 40 ° C

14-Cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) [DOTP] 0.01 17.8 33.4

24 4-cyclohexene di (isodecyl) 1,2-dicarboxylate [DIDT] 0.022.9.4.8

34-Cyclohexene-1,2-dicarboxylic acid di (n-tetradecyl) 0.02 30.16.0.0

4 Mixed ester 10 .03 28 .4 5.2

5 Mixed ester 20.03 28.45.0

6 4-Methyl-4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) 0.01 18.8.3.6

7 1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.0118.0.3.4

8 1,2-cyclohexanedicarboxylic acid di (isodecyl) 0.0129.8.4.8

9 1,2-cyclohexanedicarboxylic acid di (n-tetradecyl) 0.02 30-46.2

1 0 Mixed ester 3 0 .02 30 .1 5 • 2

1 1 4-Mono-methyl 1,2-cyclohexane carboxylate (2-ethylhexyl) 0.02 19 .0 3.7

1 2 1, 3-Dicyclohexanedicarboxylic acid di (2-ethylhexyl) 0.01 15.13.4

1 3 1,4-Disodecyl cyclohexanedicarboxylate 0.02 29.75 6

14 1,2,4-cyclohexanetricarboxylic acid tris (isodecyl) 0 • 03 89.10 100 Composition of mixed ester: acid component / alcohol component

Mixed ester 1: 4-cyclohexene-1,2 dicarboxylic acid η-Tetradecanol 50 mol% and isodecanol 50 mol% Mixed ester 2: 4-cyclohexene-1,2 dicarboxylic acid Ζη-tetradecanol 30 Mixture of mol% and isodecanol 70 mol% Mixed ester 3: 1,2 cyclohexanedicarboxylic acid Ζη-Tetradecanol 50 mol% and isodecanol 50 mol%

〇 Production Comparative Examples 1-4

By the same method as in Production Example 1, each ester shown in Table 2 was obtained. Table 2 shows the acid value and kinematic viscosity of each ester. Table 2 Properties of esters

Example 1 1 4

The hydrolysis stability of the esters obtained in Production Examples 1 to 14 was evaluated. Table 3 shows the obtained results.

Example 15

The ester of Production Example 2 and the ester of Production Example 3 were mixed at a weight ratio of 1: 1 to obtain the compound of Example 15, and the hydrolysis stability of the compound was evaluated. Table 3 shows the obtained results. Table 3 Hydrolytic stability

Ester name [abbreviation] Acid value (mgKOHZg) Iron wire condition Example Test ¾ After test Weight change (mg) Surface :)

1 4 * ~ t -square--19 -di; J し 'δ tl & x （(, 一 τ τ J J; * ·; 1 1 * η η T 10 .0 10. 1 5-0.3

2 4 ~ *-, ^ D D hex-14 J--±}; 'TjR' ¾χ (Sote), 1 f D T D Ρ Ρ 1 j 0.0.02 0.09-0.5

4 1 Know Γ 3, no 19 、, ^ A /) r Jf S HS II nII-k 千 1000 し 0.02 0. 1 2 — 0.6

4 tgirfc-¾- τ or ÷ _ // 10 .0 3 0 .1 4 0

Lef 0.03 0.14 . Four

4 4-, each 1-"i-h bano r JH ',, (9-10 1 0 1 0. 1 5-0.2

7 1 9 n To UJ 70's J ', [J¾ ヮ 41 一门门 J 0. 0 1 0. 1 1 1 0.6 リ ο1 ヮ 1 ゥ Γ3 ^ San, mosquito) τΚ' BS 1) 0. 0 1 0. 1 2 — 0.2

1 to ¹ \: _ ^ Λ 卄, no ^ 7) then τΗ ', no R Hfe¾ V n' — child, J, 0.0 2 0. 1 4 1 0.4

(tc σf ^ ^) then "¾ 0-0 2 0.1 3-0.2

1 1 4-Methyl-1-, 2-cyclohexanedicarboxylate di (2-ethylhexyl) 0.0 2 0.10 10.5 〇

1 2 1, 3-Dicyclohexanedicarboxylate di (2-ethylhexyl) 0 • 0 1 0.28-0.6 〇

1 3 1, 4-cyclohexanedicarboxylic acid di (isodecyl) 0.0 2 0.35 10.5 〇

1 41,2,4-Tricyclohexanetricarboxylic acid tris (isodecyl) 0-03 0.27-0.3〇5 Mixed ester 40.0.20 0.10 -0.5〇 Mixed ester Composition of acid / alcohol components

Mixed ester 14-cyclohexene-12-dicarboxylic acid Zn-tetradecanol 50% by mole and isodecanol 50% by mole Mixed ester 24 4-cyclohexene-1,1,2-dicarboxylic acid Zn-tetradecanol Mixture of 30 mol% and 70 mol% of isodecanol Mixed ester 3 12-Cyclohexanedicarboxylic acid Mixture of 50 mol% of Zn-tetradecanol and 50 mol% of isodecanol Mixed ester 4: Compound of Production Example 2 50% by weight and 50% by weight of the compound of Production Example 3

Example 16

The ester of Production Example 1 and mineral oil (500 neutral) were mixed at a weight ratio of 1: 1 and the 勖 viscosity, pour point and hydrolysis stability of the resulting mixed oil were measured. Table 4 shows the results.

Example 17

The ester of Production Example 2 and beef tallow were mixed at a weight ratio of 1: 1 and the kinematic viscosity, pour point and hydrolysis stability of the resulting mixed oil were measured. Table 4 shows the results.

Example 18

The ester of Production Example 4 and beef tallow were mixed at a weight ratio of 1: 1 and the kinematic viscosity, pour point and hydrolysis stability of the resulting mixed oil were measured. Table 4 shows the results.

Example 19

The ester of Production Example 4 was mixed with the trimellitic acid tri (2-ethylhexyl) at a weight ratio of 1: 1 and the kinematic viscosity, pour point and hydrolysis stability of the resulting mixed oil were measured. did. Table 4 shows the results.

Example 20

The ester of Production Example 4 and trimethylolpropane thiol were mixed at a weight ratio of 1: 1 and the kinematic viscosity, pour point and hydrolysis stability of the obtained mixed oil were measured. Table 4 shows the results.

Example 2 1

The ester of Production Example 10 and beef tallow were mixed at a weight ratio of 1: 1 and the kinematic viscosity, pour point and hydrolysis stability of the resulting mixed oil were measured. The result is

It is shown in Table 4.

Comparative Examples 1-4

The hydrolysis stability of the esters obtained in Production Comparative Examples 1 to 4 was evaluated. Table 4 shows the obtained results.

Comparative Example 5

Commercially available tallow was directly used as a sample oil, and the hydrolysis stability was evaluated. Get The results are shown in Table 4.

Comparative Example 6

Paraffin-based neutral oil (500 neutral) was used as it was as the sample oil of Comparative Example 5, and the viscosity and pour point were evaluated. Table 4 shows the obtained results.

Comparative Example 7

Were evaluated C ₁₂ -C ₁₈ fraction of hydrolytic stability of the methyl ester of coconut oil fatty acids. Table 4 shows the evaluation results.

Table 4 Various physical property tests

Base oil components Pour point Kinematic viscosity [Paint ² / s] Hydrolysis stability, iron wire state

Acid value [mgKOH / g]

(Te) 40. C 100 ° c Before test After test Weight change (mg) Surface condition Example Q

16 DO TP 50% by weight — 1. b c

t> V υ. one π 〇〇 f Pl fi D one "? one, si") Π ¾B ¾

1 7 DI DTP 50% by weight 4 6. 7 1 1 1-2-0 3 Δ10 fl> U-ri /.

1 8 Mixed ester 1 50% by weight 0 34.5. 9. 1. 38 8.5-0 3 Δ Tallow 50 Coulomb%

1 9 Mixed ester 1 50% by weight-32.5 62. 9 7.10. 01 0.2 1 0 4 〇 TOTM 50% by weight

U {¾ί3- ^ Λ ノ丄 t> υ ¾¾ ¾¾ι -30. 0 43.7 8.20.02 2.6 one 0 2

ΤΜΡ Trioleate 50% by weight

2 1 Mixed ester 3 50% by weight 1.2.5 31.1 6.7 1.35 8.2 1.20 0 △ Tallow 50% by weight

I Trimethylolpropane trioleate-37.5 58.9 1 1.20 .02 19.9 1 0 2 X

[ΤΜ ΡTrioleet]

2 2-Ethylhexyl palmitate 1.2.5 8. 1.2.7 0 .02 0.44 1 0 3 X

3 尸リリ..........

4 Tri trimellitate (2-ethylhexyl) -43. 0 97. 3 8.90. 01 0. 40-1.3 〇 [TOTM]

5 Tallow 1 2.5 41.3 8.7 2.66 100 1 3 3 X

6 Mineral oil (500 neutral)-1 2. 5 97. 4 1 1.10 0.02 0.02 + 0.1 Δ

7 Methyl coconut oil fatty acid 0 3.2 1.3 0. 10 5.8 1 1 · 3 X Composition of mixed ester: acid component Ζ alcohol component

Mixed ester 1: 4-cyclohexene-1,2-dicarboxylic acid / mixture of 50 mol% of η-tetradecanol and 50 mol% of isodecanol Mixed ester 3: 1,2-cyclohexanedicarboxylic acid Ζη-tetradecano A mixture of 50 mol% of ole and 50 mol% of isodecanol

Production example 1 5

Four-necked flask equipped with a stirrer, thermometer, and water separator equipped with a cooling tube 1,2-cyclohexanedicarboxylic anhydride (This product is based on 4-cyclohexene-1,1,2-dicarboxylic anhydride. 243.2 g (1.6 mol) and 408.3 g (3.5 mol) of isohepanol were charged in the presence of a tetraisopropyl isopropyl titanate catalyst. The temperature was raised to 200 ° C. under reduced pressure. The esterification reaction was performed for about 9 hours while taking the generated water into a water fractionator. After the reaction, excess isoheptanol was removed by distillation, neutralized with caustic soda, and then washed with water until neutral. After that, it was treated with activated carbon, and after filtration, 1,8-cyclohexanedicarboxylic acid diisoheptyl 483.O g was obtained. Table 5 shows the acid value and pour point.

Production example 16 to 25

By the same method as in Production Example 13, each ester shown in Table 5 was obtained. The table shows the acid value and kinematic viscosity of each ester.

Table 5 Properties of Ester

£ ij one two one

31 (¾ 工人丁ノレ acid value Kinematic viscosity [Oki ² / S]

[fngKOH / gl 40 "C 10 o.c

1 5 1,2-Disoheptyl cyclohexanedicarboxylate 0.01 12.4.29

16 1, 2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.01 1 18. 0 3.4

1 7 1,2-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl) 0.02 28.4 4 .7

181,2-cyclohexanedicarboxylic acid di (2,6-dimethyl-41-heptyl) 0.02 25.6.4.6

1 9 Mixed ester 5 0.01 1 23 .2 4.1

20 Mixed ester 60.01 1 ύ5.7.9 Δ

2 1 Mixed ester 7 0.01 27 .0 4.6

22 Mixed ester 80.01 2 1 .0 4.1

23 Disodecyl 1,2-cyclohexanedicarboxylate 0.01 19.8.4.8

24 Dicyclohexyl 1,1-cyclohexanedicarboxylate 0.02 243.2 2 13.6

25 3-Methyl-1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.03 18.2 3.5 Note) Composition of mixed ester: acid component / alcohol component

Mixed ester 5: Equimolar mixture of 1,2-cyclohexanedicarboxylic acid / 3,5,5-trimethylhexanol and 2-ethylhexanol Mixed ester 6: 1 1,2-Cyclohexanedicarboxylic acid / 3 Equimolar mixture of 1,5,5-trimethylhexanol and cyclohexanol Mixed ester 7: 1 1,2-cyclohexanedicarboxylic acid _ 3,5,5-trimethylhexanol and 2,6-dimethyl-4-heptanol Equimolar mixture with

Mixed ester 8: 1 Equimolar mixture of 1,2-cyclohexanedicarboxylic acid / π-nonanol and 2,6-dimethyl-4-heptanol

Production Example 2 6 to 32

By the same method as in Production Example 15, each ester shown in Table 6 was obtained. The table shows the acid value and kinematic viscosity of each ester.

Production Example 33

Esterification using pyromellitic anhydride and 3,5.5-trimethylhexanol as raw materials, and hydrogenation of the resulting tetra (3,5,5-trimethylhexyl) pyromellitic acid as a nucleus. Thus, 1,2,4,5-cyclohexanetetracarboxylic acid tetra (3,5,5-trimethylhexyl) was prepared. Table 6 shows the acid value and the kinematic viscosity.

Table 6 Properties of esters

,

Production Releasing Ester name Acid value Kinematic viscosity [tnm ² / _S ]

[mgKOH / g] 40 ° C 100 ° C

2 6 4-Meter-1, 2-cyclohexane carboxylate (2-ethylhexyl) 0.02 18 .8 3.6

2 7 4 -Cyclohexene di (1,2-dicarboxylic acid) di (2-ethylhexyl) 0.0 1 17.8 .33.4

284-Cyclohexene-1,2-dicarboxylic acid di (3,5,5-trimethylhexyl) 0.03 29.4 4.7

2 94 4-Cyclohexene-1,2-disoheptyl dicarboxylate 0.03 12.7 .22.9

30 4-Cyclohexene di 1,2-dicarboxylic acid di (cyclohexyl) 0.02 244.13.13.5

3 1 3 —Methyl-4-cyclohexene di 1,2-dicarboxylate (2-ethylhexyl)

3 2 4 -Methyl-4-cyclohexene di (2-ethylhexyl) 1,2-dicarboxylate 0.0 1 11.8 .8 3.6

3 3 1 2, 4,5-Cyclohexanetetracarboxylic acid tetra (3,5,5-trimethylhexyl) 0.04 449 .3 24 2

Production Comparative Examples 8 to 11

By the same method as in Production Example 15, each ester shown in Table 7 was obtained. Table 7 shows the acid value and kinematic viscosity of each ester.

Production Comparative Example 1 2

Using pyromellitic anhydride and 3,5,5-trimethylhexanol as raw materials, esterification was carried out in the same manner as in Production Example 13 to give tetramer pyromellitic acid (3,5, 5-trimethylhexyl) was obtained. Table 7 shows the acid value and pour point.

Production Comparative Examples 13 to 18

An aliphatic dibasic acid ester and an aromatic ester used for a commercially available plasticizer were prepared.

Table 7 Properties of esters

Production Ester name Acid value Kinematic viscosity [mm Vs] Comparative example [mg OH / g] 40. C100. C

8 Trimethylolpropane tri (3,5,5-trimethylhexanoetriol) 0.02 50 .4 7.0

9 Pentaerythritol tetra (3,5,5-trimethylhexanoate) 0.06 1 12 .9 1 1.4

1 0 Mixed ester 9 0.03 80 .39.0

1 1 Mixed ester 1 0 0.01 73 .8 8.7

1 2 Tetra pyromellitic acid (3,5,5-trimethylhexyl) 0.02 353. 9 23.0

1 3 Disodecyl adipate 0.02 14 .0 3.6

14 Di (2-ethylhexyl) adipate 0.02 7.8 2.3

1 5 Disobutyl fluorate 0.01 1 10 .6 2.3

1 6 Di (2-ethylhexyl) phthalate 0.0] 27.2.4.2

1 7 Disodecyl phthalate 0.02 42 .9 5.2

1 8 Tri trimellitate (2-ethylhexyl) 0.01 01 97-38.9 Note) Composition of mixed ester: acid component Z alcohol component

Mixed ester 9: Equimolar mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid / pentaerythritol mixed ester] 0: Caprylic acid and 3,5,5-trimethylhexanoic acid Equimolar mixture of nopentaerythritol

Example 2 2 to 3 2

The hydrolysis stability of the esters obtained in Production Examples 15 to 25 was evaluated. Table 8 shows the obtained results.

Example 3 3-4 0

The hydrolysis stability of the esters obtained in Production Examples 26 to 33 was evaluated. Table 9 shows the results.

Comparative Examples 8 to 12

Hydrolysis stability of the esters obtained in Production Comparative Examples 8 to 12 was evaluated. Table 10 shows the obtained results.

Comparative Examples 13 to; 18

Aliphatic dibasic acid esters and aromatic esters used as commercially available plasticizers were used as the esters of Comparative Examples 13 to 18, and their hydrolytic stability was evaluated. Table 10 shows the obtained results.

Table 8 Hydrolysis stability

Example Ester name gKOH / g] After test After test Steel Copper Aluminum Oil condition

2 21, 2-cyclohexanedicarboxylic acid diisoheptyl 0.0 1 0.48 〇 Δ 白色 white

231,2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.010.5 0.20 Δo white

2 4 1 2—Cyclohexanedicanolone bond (3,5,5-trimethylhexyl) 0.02 0.58 58 Δ Δo White

25 1, 2-Dicyclohexanedicarboxylic acid di (2,6-dimethyl-14-heptyl) 〇 0.20 o 20 o Δo White α j 又 / レ ν 0.0 1 0.5 6 o Δ o white

2 7-^ τ sukore fi 0. 0 1 0. 3 2 o o

2 8 Mixed ester 7 0.0 1 0.29 o Δo White

2 9 Mixed ester 80 .0 1 0.18 〇 Δ 〇 White

3 0 1, 2-cyclohexanedicarboxylic acid disodecyl 0.01 0.18 8 Δ 白色 white

3 1 1, 2-Dicyclohexylcyclohexanedicarboxylate 0.02 0.18 白色〇白色 White

3 2 3-Methyl-1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.0 30.57 Δ Δ 〇 white Note) Composition of mixed ester: acid component alcohol component

Mixed ester 5: 1,2-cyclohexanedicarboxylic acid Z 3.5.5 Equimolar mixture of 5-methylhexanol and 2-ethylhexanol Mixed ester 6: 1,2-cyclohexanedicarboxylic acid / 3, Equimolar mixture of 5,5-trimethylhexanol and cyclohexanol

Mixed ester 7: 1,2-cyclohexanedicarboxylic acid / 3,5,5-trimethylhexanol and 2,6-dimethyl-4-heptanol

Equimolar mixture with

Mixed ester 8: 1 Equimolar mixture of 1,2-cyclohexanedicarboxylic acid / n-nonanol and 2,6-dimethyi13-ru-l-heptanol

Bacteria 1

G

Table 9 Hydrolysis stability

Example Ester name Acid value [mgKOH / g] After test Before test After test Class Copper Aluminum State of oil

33 4-Methyl-1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl) 0.02 0.52 52 Δ Δ 白色 White

34 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) 0.0 1 0.51 Δ Δ Δ pale yellow

35 4-Cyclohexene-1,2-dicarboxylic acid di (3,5,5-trimethylhexyl) 0.03 0.55 Δ Δ 〇 pale yellow

36 4-cyclohexene di-isoheptyl 1,2-dicarboxylate 0.03 0.52 〇 Δ 白色 white

37 4-cyclohexene-1,2-dicarboxylic acid di (cyclohexyl) 0.02 0.19 Δ △ 淡 pale yellow

38 3-Methyl-4-cyclohexene-1, 2-dicarboxylic acid di (2-ethylhexyl) 0.05 0.05.70 Δ Δ 〇 pale yellow

39 4-Methyl-4-cyclohexene-1,2,2-dicarboxylic acid di (2-ethylhexyl) 0.01 0.01.68 Δ Δ 〇 pale yellow

40 1.2,4,5-tetracyclohexanetetracarboxylic acid tetra (3,5,5-trimethy 0.04 0.35 white hexyl)

Table I 0 Hydrolysis stability

Ester name Acid value [mgKOH / g] Comparative example after test After test Steel Copper Aluminum State of oil

8 Trimethylolpropanetri (3,5,5-trimethylhexanoet) 0 6.07 X 〇白色 White

9 Pen erythritol tetra (35,5-trimethylhexanoe) 0. U ο ο ο. Υ υ X Δ 〇

10 Mixed ester 9 0 .03 4.05 〇 Δ 〇 Light yellow

1 1 τ_ dried 1 0 0 Π 1 36.00 ο 〇 ο

1 2 Tetra pyromellitic acid (355-trimethylhexyl) 0. U Δ 57.39 X 〇 Δ Brown

1 3 Disodecyl adipate 0 Δ 47.99 X 〇 Δ Dark brown

1 4 Di (2-ethylhexyl) adipate 0 74.30 X 〇茶色 Brown

1 5 Disobutyl phthalate 0.0 1 2.75 Δ〇白色 White

1 6 Di (2-ethylhexyl) phthalate 0 • 0 1 2.26 X Δ 〇 White

1 7 Disodecyl phthalate 0 • 02 1.28 Δ Δ 〇 White

1 8 Trimellitic acid tri (2-ethylhexyl) 0.0 1 1 0.02 Δ Δ 〇 white Note) Composition of mixed ester: acid component / alcohol component

Mixed ester 9: equimolar mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid

Mixed ester 10: equimolar mixture of caprylic acid and 3,5,5-trimethylhexanoic acid / pentaerythritol

Table 11 Various physical property tests

Example Kinematic viscosity [mraVs] Volume specific resistance Freon compatibility Hydrolysis stability (acid value [mgKOH / gj)

40 ° C 100 ° C [Ω · cm] low temperature side (° C) high temperature side rc) after pre-test Test Example 41 52. 8 7. 04 2 X 1 0 13 - 19> 100 0. 03 3. 98 implementation Example 42 52. 1 7.05 2 X 10 ¹³ -25> 100 0.03 2.83 Comparative example 19 7 X 10 ¹³ -40> 100

Comparative example 20 2 X 10 ¹³ -27> 100

Example 4 1

A mixture of 1,2-cyclohexanedicarboxylic acid di (3,5,5—trimethylhexyl) and pentaerythritol tetra (3,5,5-trimethylhexanoe unit) at a weight ratio of 1: 1 The resulting mixed ester was measured for viscosity, volume resistivity, CFC compatibility, and hydrolysis stability. Table 11 shows the results.

Example 4 2

1,2—cyclohexanedicarboxylic acid di (3,5,5—trimethylhexyl), pentaerythritol toltra (3,5,5—trimethylhexanoate), trimethylolprono, . Triethyl (3,5,5—trimethylhexanoet) is mixed at a weight ratio of 1: 1: 1, and the resulting mixed ester has a kinematic viscosity, a volume resistivity, a foam compatibility and a hydrolytic stability. Properties were measured. Table 11 shows the results.

Comparative Example 19 to 20

The esters of Production Comparative Examples 8 to 9 were used as the esters of Comparative Examples 19 to 20, and the volume resistivity and CFC compatibility were measured in the same manner as in Example 41. Table 11 shows the results. As is clear from Examples 1 to 15, the alicyclic polycarboxylic acid ester has good hydrolysis stability, a small increase in the acid value, and almost no change in the metal surface is observed. On the other hand, as shown in Comparative Examples 1 to 7, trimethyl monopropaneoleate, fatty acid monoester, and tallow have a large increase in acid value and large metal corrosion. In addition, as shown in Examples 16 to 21, when the alicyclic polycarboxylic acid ester was used in combination with the mineral oil of the comparative example or another ester, the case where the sample oil of the comparative example was used alone. Hydrolysis stability is improved.

Furthermore, as shown in Examples 22 to 40, the alicyclic polycarboxylic acid ester according to the present invention has excellent hydrolysis stability and is used as a refrigerating machine oil as shown in Examples 41 and 42. Required refrigerant compatibility, specific resistance Therefore, it is possible to provide high-quality refrigerating machine oil for a hydrofluorocarbon-based refrigerant. Industrial applicability

The lubricating oil containing the alicyclic polycarboxylic acid ester of the present invention is excellent in hydrolytic stability, has a low acid value increase under severe conditions, has a small surface change of metal, and is required in each application. Since it also has properties, it can be used as a cutting oil, a rolling oil, a grinding oil, a drawing oil, a metal oil such as a pressing oil, a hydraulic oil, a textile oil, a grease, or as an emulsion, or under water mixing conditions It can be used as a base oil for lubricating oils used in various applications. It also has excellent compatibility with chlorofluorocarbons at low temperatures and has no fluorine atom in the molecule. Fluorocarbons with high molecular weight, such as HFC-134a, HFC-134, HFC-125, HFC- 32. It can be used as a base oil for lubricating oil for refrigerators using HFC-143a and a mixture thereof as a refrigerant, and its industrial utility value is extremely large.

Claims

1. The following general formula [I]

X

R C00R ²

[I]

C00R ³

Y Al 3D-blue

Request

(In the above general formula [I], A represents a cyclohexene ring hexane ring or cycloheteroalkyl, R ¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a C 00 R ^4, Y is a hydrogen atom Or C 00 R ⁵ , R ² , R ³ , and RR ⁵ may be the same or different from each other, and may be a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl having 3 to 10 carbon atoms Represents a linear alkyl group having 1 to 18 carbon atoms or a linear alkylene group having 2 to 18 carbon atoms.)

A lubricating oil comprising one or more alicyclic polycarboxylic acid esters represented by the formula:

2. The alicyclic polycarboxylic acid ester is 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-tyl-11,2-cyclohexanedicarboxylic acid, 4-methyl- Consists of 1,2-cyclohexanedicarboxylic acid, 3-methyl-1-cyclohexene-1,2-dicarboxylic acid, 4-methyl-1,4-cyclohexene-1,2-dicarboxylic acid and their anhydrides The lubricating oil according to claim 1, wherein the lubricating oil is an ester containing one or more compounds selected from the group as an acid component.

3. The alicyclic polycarboxylic acid esters are isobutanol, cyclohexanol, isobutanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, 2,6-dimethyl- —Heptane, n-decanol, isodenicol, isotridecanol, isotridecanol, n-heptanol, n-octanol, n-decanol, An ester containing at least one compound selected from the group consisting of n-decanocanole, n-dodecanole, n-tetradecanole, n-hexadecanol and n-octadecanol as an alcohol component Claim The lubricating oil according to item 1 of the range.

4. The lubricating oil according to any one of claims 1 to 3, wherein the lubricating oil is a lubricating oil for metal working.

5. In the alicyclic polycarboxylic acid ester represented by the general formula [1], a linear alkyl group having 1 to 18 carbon atoms in R ² , R ³ , R ⁴ and R ^5. 5. The lubricating oil for metal working according to claim 4, wherein the content of the metal is 50 mol% or less.

6. The lubricating oil for metal working according to claim 4, wherein the content of the alicyclic polycarboxylic acid ester is 10% by weight or more.

7. The lubricating oil according to any one of claims 1 to 3, wherein the lubricating oil is a refrigerator oil.

8. The alicyclic polycarboxylic acid ester is one or two selected from the group consisting of 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid and anhydrides thereof. 8. The lubricating oil for a refrigerator according to claim 7, wherein the lubricating oil is an ester containing at least one compound as an acid component.

9. The alicyclic polycarboxylic acid ester is one or more selected from the group consisting of cyclohexanol, isohepanol, 2-ethylhexanol and 3,5,5-trimethylhexanol. 8. The lubricating oil for a refrigerator according to claim 7, wherein the lubricating oil is an ester containing the compound of the formula (1) as an alcohol component.

10. The alicyclic polycarboxylic acid ester is converted to diisobutyl 1,2-cyclohexanedicarboxylate, dicyclohexyl 1,2-cyclohexanedicarboxylate, diisobutyl 1,2-cyclohexanedicarboxylate. Butyl, 1,2-cyclohexanedicarboxylic acid di (2-ethylhexyl), 1,2-cyclohexanedicarboxylic acid di (3,5,5-trimethylhexyl), 1,2-cyclohexyl Xandicarboxylic acid di (2,6-dimethyl-4 1-heptyl), diisodecyl 1,2-cyclohexanedicarboxylate,

I, 2-Dicyclohexanedicarboxylate diisopendecyl, 4-cyclohexene-1,2-dicanolebonate dicyclohexyl, 4-cyclohexene-1,2,2-dicarboxylate diisoheptyl, 4-cyclohexene1-1,2 Di (2-ethylhexyl) dicarboxylate, 4-cyclohexene-1,2,2-dicarboxylic acid di (3,5,5, -trimethylhexyl), 3-methyl-1,2-cyclohexanedicarboxylic acid Di (3,5,5-trimethylhexyl), 4-methinolate 1,2-cyclohexanedicarboxylic acid

(3,5,5-trimethylhexyl), 3-methyl-14-cyclohexene-1,2-dicarboxylic acid di (3.5,5-trimethylhexyl), 4-methyl-14-cyclo Hexene di 1,2, -dicarboxylate (3,5,5 trimethylhexyl), 1,2,4,5, cyclohexane tratracarbonate tetra (3,5,5 trimethyl) 8. The lubricating oil for a refrigerator according to claim 7, which is one or more esters selected from the group consisting of hexyl).

II. The content of the linear alkyl group having 3 to 18 carbon atoms in R ² , R ³ , R ⁴ and R ⁵ represented by the general formula [1] is 50 mol% or less. Item 8. The lubricating oil for refrigerators according to Item 7.

12. The lubricating oil for a refrigerator according to claim 7, wherein the content of the alicyclic polycarboxylic acid ester is 10% by weight or more.