CN118355096A

CN118355096A - Water-soluble metal processing oil

Info

Publication number: CN118355096A
Application number: CN202280080861.8A
Authority: CN
Inventors: Y·H·谭; 冈野知晃; S·哈迪维贾贾; 见富健志; 地曳洋介
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2021-12-08
Filing date: 2022-12-07
Publication date: 2024-07-16
Also published as: JP2023084942A; WO2023106341A1

Abstract

New water-soluble metal working oils and the like are required. A water-soluble metal working oil comprising a base oil (A) and an ether carboxylic acid (B) represented by the following general formula (B-1), wherein the content of the ether carboxylic acid (B) is 0.1 to 10% by mass based on the total amount of the water-soluble metal working oil,

Description

Water-soluble metal processing oil

Technical Field

The present invention relates to a water-soluble metal working oil and a metal working fluid obtained by mixing dilution water into the water-soluble metal working oil.

Background

In the field of metal working such as cutting and grinding, a metal working fluid is used for the purpose of improving workability of a workpiece and suppressing wear of a working tool.

Examples of the metalworking fluid include an oily metalworking fluid containing an oil component such as a mineral oil, a synthetic oil, or an animal or vegetable oil as a main component, and a water-soluble metalworking fluid in which a compound having a surface activity is mixed with the oil component to impart water solubility. In recent years, water-soluble metal working fluids have been used for safety reasons such as low risk of fire.

For example, patent document 1 discloses a water-soluble processing oil agent obtained by compounding methyl dicyclohexylamine. The water-soluble processing oil is diluted with dilution water to prepare a metal processing liquid, and then used for metal processing. Patent document 2 also discloses a water-soluble metal processing oil containing an ether carboxylic acid.

Prior art literature

Patent literature

Patent document 1: international publication No. 2010/113594

Patent document 2: chinese patent publication No. 106893622

Disclosure of Invention

Problems to be solved by the invention

On the other hand, in a machine tool, a grease or a lubricating oil composition is used to move a tool, a workpiece, or the like in any direction and to smooth sliding movement. In recent years, in order to achieve downsizing and cost reduction of a machine tool, there has been an increase in the number of devices in which a skimmer as another oil separation device is not provided in a cutting oil tank, and in association with this, there has been an increase in the number of devices in which grease is used on a sliding surface.

However, if grease for the sliding surface is mixed into a cutting oil tank provided in a machine tool, emulsion breakdown of the water-soluble metal working fluid is promoted, and there is a problem in that the water-soluble metal working fluid is deteriorated. In this situation, a new water-soluble metal working oil and the like are required.

Means for solving the problems

The present invention provides an aqueous metal working oil or the like containing a predetermined amount of a specific ether carboxylic acid. Specifically, the present invention provides the following modes [1] to [14], for example.

[1] A water-soluble metal working oil comprising a base oil (A) and an ether carboxylic acid (B) represented by the following general formula (B-1),

The content of the ether carboxylic acid (B) is 0.1 to 10% by mass based on the total amount of the water-soluble metal working oil,

[ Chemical formula 1]

[ Wherein A is an alkylene group having 1 to 4 carbon atoms, and when a plurality of A's are present, the plurality of A's may be the same group or may be different groups,

B is a single bond or an alkylene group having 1 to 4 carbon atoms,

N is an integer of 1 to 100,

R is a hydrocarbyl group ].

[2] The water-soluble metal working oil according to [1], wherein B in the general formula (B-1) is methylene.

[3] The water-soluble metal working oil according to [1] or [2], wherein the HLB of the ether carboxylic acid (B) is 5.0 or more.

[4] The water-soluble metal working oil according to [1] or [2], wherein the HLB of the ether carboxylic acid (B) is more than 6.0.

[5] The water-soluble metal working oil according to any one of [1] to [4], wherein A in the general formula (b-1) is ethylene.

[6] The water-soluble metal working oil according to any one of [1] to [4], wherein n in the general formula (b-1) is6 or more.

[7] The water-soluble metal working oil according to any one of [1] to [6], wherein R in the general formula (b-1) is a hydrocarbon group having 10 to 30 carbon atoms.

[8] The water-soluble metal working oil according to any one of [1] to [7], wherein the water-soluble metal working oil further comprises a nonionic surfactant (C).

[9] The water-soluble metal working oil according to [8], wherein the content ratio of the nonionic surfactant (C) to the ether carboxylic acid (B) [ C)/(B) ] is 1 to 25 by mass.

[10] The water-soluble metal working oil according to any one of [1] to [9], wherein the water-soluble metal working oil further comprises an amine compound (D).

[11] The water-soluble metal working oil according to [10], wherein the content ratio of the amine compound (D) to the ether carboxylic acid (B) [ D)/(B) ] is 1 to 166 in terms of mass ratio.

[12] A metal working fluid obtained by diluting the water-soluble metal working oil according to any one of [1] to [11 ].

[13] The metal working fluid according to [12], which is used in metal working by a machine tool using an emulsion suppressing material.

[14] The metal working fluid according to [13], wherein the emulsification suppressing material is grease.

Effects of the invention

In the water-soluble metal working oil according to one preferred embodiment of the present invention, even if grease for machine tools is mixed into a cutting oil tank when a metal working fluid is produced, emulsion breakdown of the metal working fluid is suppressed.

Detailed Description

The numerical ranges described in the present specification may be arbitrarily combined with the upper limit value and the lower limit value. For example, when the numerical range is described as "preferably 30 to 100, more preferably 40 to 80", the numerical range of "30 to 80" and the numerical range of "40 to 100" are also included in the numerical range described in the present specification. For example, when the numerical range is "preferably 30 or more, more preferably 40 or more, still more preferably 100 or less, and still more preferably 80 or less," the range of "30 to 80" and the range of "40 to 100" are included in the numerical range described in the present specification.

The numerical ranges described in the present specification are, for example, ranges of "60 to 100" and "60 to 100 inclusive".

In the present specification, the terms "metal working oil" and "metal working fluid" are used after being distinguished as shown below according to the content of water.

"Metal working oil": the content of water is 0 to 100 parts by mass based on 100 parts by mass of the total amount of components other than water.

"Metal working fluid": the content of water exceeds 100 parts by mass with respect to 100 parts by mass of the total amount of the components other than water.

The "metal working oil" is a stock solution of a metal working fluid before the metal working fluid is prepared by dilution with dilution water, and is in a form suitable for transportation and storage before the metal working. The "metal working fluid" is a metal working oil solution as a stock solution diluted by adding dilution water, and is in a form suitable for use in metal working.

[ Constitution of Water-soluble Metal working oil solution ]

The water-soluble metal working oil of the present invention comprises a base oil (A) and an ether carboxylic acid (B) represented by the following general formula (B-1). In the water-soluble metal working oil according to one embodiment of the present invention, by blending the compound represented by the following general formula (b-1), emulsion breakdown of the metal working fluid can be effectively suppressed even when an emulsion-inhibiting component such as grease for a machine tool is mixed in the metal working fluid.

[ Chemical formula 2]

The water-soluble metal working oil of the present invention contains the base oil (A) and the ether carboxylic acid (B) represented by the above general formula (B-1), but may contain other components than these components.

For example, the water-soluble metal working oil according to one embodiment of the present invention may contain one or more selected from the group consisting of nonionic surfactant (C), amine compound (D) and fatty acid (E). In addition, the water-soluble metal working oil according to one embodiment of the present invention may contain water (F). The water-soluble metal working oil according to one embodiment of the present invention may contain other components than the components (a) to (F) within a range that does not impair the effects of the present invention.

By adjusting the content and the content ratio of water and other components, JIS K2241 can be prepared: 2017, and a soluble type oil agent classified into an A1 type and an A2 type.

In one embodiment of the present invention, the total content of the components (a) to (B) is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, still more preferably 30 mass% or more, particularly preferably 35 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, and may be 100 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, 50 mass% or 45 mass% or less.

In one embodiment of the present invention, the total content of the components (a) to (C) is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, still more preferably 33 mass% or more, and particularly preferably 36 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, and may be 100 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 48 mass% or less, or 45 mass% or less.

In one embodiment of the present invention, the total content of the components (a) to (D) is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 50 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, and may be 100 mass% or less, 95 mass% or less, 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, or 70 mass% or less.

In one embodiment of the present invention, the total content of the components (a) to (E) is preferably 50 mass% or more, more preferably 55 mass% or more, still more preferably 60 mass% or more, still more preferably 65 mass% or more, particularly preferably 70 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, and may be 100 mass% or less, 97 mass% or less, 95 mass% or less, 93 mass% or less, 90 mass% or less, 87 mass% or less, or 85 mass% or less.

In one embodiment of the present invention, the total content of the components (a) to (F) is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 65 mass% or more, still more preferably 70 mass% or more, particularly preferably 75 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, and may be 100 mass% or less, 99 mass% or less, 98 mass% or less, 97 mass% or less, 96 mass% or less, or 95 mass% or less.

In one embodiment of the present invention, the content ratio [ (C)/(B) ] of the nonionic surfactant (C) to the ether carboxylic acid (B) is preferably 1.0 or more, more preferably 1.10 or more, further preferably 1.15 or more, further preferably 1.20 or more, particularly preferably 1.25 or more, further preferably 25.0 or less, further preferably 20.0 or less, further preferably 15.0 or less, particularly preferably 10.0 or less, further preferably 8.5 or less, 8.0 or less, 7.5 or less, 7.0 or less, 6.5 or less, 6.0 or less, 5.5 or 5.0 or less in terms of mass ratio.

In one embodiment of the present invention, the content ratio [ (D)/(B) ] of the amine compound (D) to the ether carboxylic acid (B) is preferably 1 or more, more preferably 1.5 or more, more preferably 2.0 or more, more preferably 2.5 or more, more preferably 3.0 or more, more preferably 3.5 or more, more preferably 4.0 or more, more preferably 4.5 or more, more preferably 5.0 or more, further can be set to 6.0 or more, 6.5 or more, 7.0 or more, 7.5 or more, or 8.0 or more, further preferably 166 or less, more preferably 120 or less, more preferably 100 or less, more preferably 90 or less, more preferably 80 or less, more preferably 70 or less, particularly preferably 60 or less, further can be set to 56 or less, 50 or less, 45 or 40 or 35 or less.

The components contained in the water-soluble metal working oil according to one embodiment of the present invention will be described below.

< Component (a): base oil ]

The water-soluble metal working oil of the present invention contains a base oil (a). By containing the base oil (a), a water-soluble metal working oil solution which can be a metal working fluid having good workability can be produced.

In the water-soluble metal working oil according to one embodiment of the present invention, 1 kind of base oil (a) may be used alone or 2 or more kinds may be used in combination.

From the above point of view, in one embodiment of the present invention, the content of the base oil (a) is preferably 9 mass% or more, more preferably 12 mass% or more, further preferably 14 mass% or more, further preferably 20 mass% or more, further preferably 25 mass% or more, particularly preferably 30 mass% or more, further preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 60 mass% or less, and particularly preferably 50 mass% or less, based on the total amount (100 mass%) of the water-soluble metal working oil.

In addition, JIS K2241 was prepared: in the case of the emulsion-type oil solutions classified into the A1 type as defined in 2017, the content of the base oil (a) may be 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more based on the total amount (100 mass%) of the oil solutions.

In addition, JIS K2241 was prepared: in the case of the soluble type oil agent classified into the A2 type as defined in 2017, the content of the base oil (a) may be 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less based on the total amount (100 mass%) of the oil agent.

The base oil (a) used in one embodiment of the present invention includes at least one selected from mineral oils and synthetic oils.

Examples of the mineral oil include atmospheric residues obtained by atmospheric distillation of crude oils such as paraffinic crude oils, intermediate base crude oils, and naphthenic crude oils; distillate oil obtained by vacuum distillation of these atmospheric residues; refined oil obtained by subjecting the distillate oil to one or more refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrofining.

Examples of the synthetic oil include polyalphaolefins such as α -olefins, homopolymers thereof, and α -olefin copolymers (for example, α -olefin copolymers having 8 to 14 carbon atoms such as ethylene- α -olefin copolymers); isoparaffins; polyalkylene glycols; ester-based oils such as polyol esters, dibasic acid esters, and phosphoric acid esters; ether-based oils such as polyphenylene ether; an alkylbenzene; alkyl naphthalene; synthetic oils (GTL) obtained by isomerizing waxes (GTL waxes (Gas To Liquids WAX)) produced from natural gas by fischer-tropsch processes or the like.

Among them, the base oil (a) used in one embodiment of the present invention preferably contains at least one selected from mineral oils and synthetic oils of group 2 and group 3 classified into API (american petroleum institute) base oil categories.

The base oil (A) of one embodiment of the present invention may have a kinematic viscosity at 40℃of 3.0mm ²/s or more, 3.5mm ²/s or more, 4.0mm ²/s or more, 4.5mm ²/s or more, 5.0mm ²/s or more, 5.5mm ²/s or more, 6.0mm ²/s or more, 6.5mm ²/s or more, Or 7.0mm ²/s or more, and may be 100mm ²/s or less, 90mm ²/s or less, 80mm ²/s or less, 70mm ²/s or less, 60mm ²/s or less, 50mm ²/s or less, 45mm ²/s or less, 40mm ²/s or less, 35mm ²/s or less, 30mm ²/s or less, 25mm ²/s or less, Or 20mm ²/s or less.

The viscosity index of the lubricating base oil according to one embodiment of the present invention may be 70 or more, 80 or more, 85 or more, 90 or more, 95 or more, or 100 or more.

In the present specification, kinematic viscosity and viscosity index refer to those according to JIS K2283:2000 measured or calculated values.

< Component (B): ether carboxylic acid ]

The water-soluble metal working oil of the present invention contains an ether carboxylic acid (B) represented by the following general formula (B-1).

[ Chemical formula 3]

The inventors found that: when a water-soluble metalworking fluid is prepared by diluting the water-soluble metalworking fluid with dilution water, emulsion breakdown of the metalworking fluid can be suppressed even if grease for machine tools is mixed into a cutting oil tank. The metal working fluid using the water-soluble metal working oil of the present invention is less likely to cause deterioration in quality even if the grease used for the sliding surface is mixed into the cutting oil tank, and thus can be used for a prolonged period of time.

In the general formula (b-1), A is an alkylene group having 1 to 4 carbon atoms, and when a plurality of A's are present, the plurality of A's may be the same group or may be different groups from each other. In the present specification, "alkylene" means a straight-chain, cyclic or branched divalent saturated aliphatic hydrocarbon group having a prescribed number of carbon atoms.

Examples of the alkylene group which may be selected as A include ethylene groups such as methylene, 1-ethylene and 1, 2-ethylene, propylene groups such as 1, 3-propylene, 1, 2-propylene and 2, 2-propylene, and butylene groups. The above groups also include structural isomers.

Among them, the alkylene group which can be selected as a is preferably one or more groups selected from ethylene and propylene.

In the case where a plurality of a are present, a plurality of a may be any one of ethylene alone, propylene alone, or a combination of ethylene and propylene (i.e., —a—o—may be a group in which an Ethylene Oxide (EO) group and a Propylene Oxide (PO) group are randomly or block-bonded), but it is preferable that the group contains 1 or more groups selected from ethylene and propylene, more preferably at least ethylene, and still more preferably ethylene in its entirety.

In the general formula (B-1), B is a single bond or an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group which may be used as the substituent for B include the same alkylene groups as those for A. Among them, the alkylene group which can be selected as B is preferably a linear alkylene group having 1 to 3 carbon atoms, more preferably a methylene group.

In the general formula (b-1), n is 1 or more, preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 5 or more, more preferably 6 or more, more preferably 7 or more, more preferably 8 or more, more preferably 9 or more, and particularly preferably 10 or more, from the viewpoint of producing a metal working fluid effective in suppressing emulsion breaking.

In the general formula (b-1), n may be 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 15 or less, or 10 or less.

In the above general formula (b-1), R represents a hydrocarbon group. In the present specification, the term "hydrocarbon group" means a group obtained by removing 1 hydrogen atom from a linear, cyclic or branched saturated or unsaturated hydrocarbon having a predetermined number of carbon atoms. Specifically, alkyl, alkenyl, cycloalkyl, aryl, and the like are exemplified.

Examples of the alkyl group include propyl groups such as methyl, ethyl, n-propyl, and isopropyl groups, butyl groups such as n-butyl, isobutyl, sec-butyl, and tert-butyl groups, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and tetracosyl groups. The above groups also include structural isomers.

Examples of the alkenyl group include vinyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl (oleyl), nonadecenyl, eicosenyl, heneicosenyl, docosyl, tricosyl, tetracosyl and the like. The above groups also include structural isomers.

Examples of cycloalkyl groups include cyclopentyl and cyclohexyl. In addition, in the case of cycloalkyl, a hydrogen atom to which at least one ring-forming carbon is bonded may be substituted with a substituent (an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a phenyl group, or the like). Examples of cycloalkyl groups having such substituents include methylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl and the like.

Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.

The hydrogen atom to which at least one ring-forming carbon of the aryl group is bonded may be substituted with a substituent (an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a cycloalkyl group, or the like). Examples of the aryl group having such a substituent include methylphenyl, ethylphenyl, and dimethylphenyl.

Among them, R is preferably a linear or branched saturated or unsaturated aliphatic hydrocarbon group, more preferably a linear or branched alkyl group or alkenyl group, further preferably a linear alkyl group or a linear alkenyl group, and still further preferably a linear alkenyl group.

The number of carbon atoms of R is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 6 or more, still more preferably 8 or more, still more preferably 9 or more, particularly preferably 10 or more, and may be 11 or more, 12 or more, 13 or more, 14 or more, or 15 or more from the viewpoint of producing a metal working fluid effective in suppressing emulsion breaking.

The number of carbon atoms of R is preferably 50 or less, more preferably 45 or less, still more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less, and may be 29 or less, 28 or less, 27 or less, 26 or less, or 25 or less.

In one embodiment of the present invention, the ether carboxylic acid (B) is represented by the general formula (B-1),

A is a group of 1 or more selected from ethylene and propylene (preferably at least ethylene, more preferably ethylene in its entirety),

B is a linear alkylene group having 1 to 3 carbon atoms (preferably a methylene group),

N is an integer of 6 to 10 (preferably 8 to 10, more preferably 9 to 10, still more preferably 10),

R is a hydrocarbon group having 10 to 30 carbon atoms (preferably a linear or branched alkyl group or alkenyl group having 10 to 30 carbon atoms, more preferably a linear alkenyl group having 10 to 30 carbon atoms, still more preferably an oil group).

In one embodiment of the present invention, the HLB of the ether carboxylic acid (B) is 5.0 or more. By using the ether carboxylic acid (B) having an HLB in this range, emulsion breakdown of the metal working fluid can be suppressed. In another aspect of the invention, the HLB of the ether carboxylic acid (B) is greater than 6.0. By using the ether carboxylic acid (B) having an HLB in this range, emulsion breaking of the metal working fluid can be more effectively suppressed.

In one embodiment of the present invention, the lower limit value of the HLB of the ether carboxylic acid (B) may be 6.5 or more, 7.0 or more, 7.5 or more, 8.0 or more, 8.5 or more, 9.0 or more, 9.5 or more, 10.0 or more, 10.5 or more, or 11.0 or more, particularly preferably 12.0 or more, from the viewpoint of preparing a water-soluble metal working oil agent which can be formed into a metal working fluid which further improves emulsion stability and workability. The upper limit of the HLB of the ether carboxylic acid (B) is not particularly limited, but is 20.0 or less, 19.0 or less, 18.0 or less, 17.0 or less, 16.0 or less, 15.0 or less, or 14.0 or less, and particularly preferably 13.0 or less.

In the present specification, HLB is abbreviated as Hydrophile to lipophile balance (hydrophilic-lipophilic balance), which is an index indicating the balance between hydrophilic groups and lipophilic groups in the molecule of the surfactant. In the present specification, HLB refers to a value calculated by the Griffin method.

In one embodiment of the present invention, the content of the ether carboxylic acid (B) is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, still more preferably 0.3 mass% or more, still more preferably 0.4 mass% or more, particularly preferably 0.5 mass% or more, and may be 0.7 mass% or more, 0.9 mass% or more, 1.0 mass% or more, 1.5 mass% or more, or 2.0 mass% or more, based on the total amount (100 mass%) of the water-soluble metal working oil, from the viewpoint of producing a metal working fluid effective in suppressing emulsion breaking.

The content of the ether carboxylic acid (B) is preferably 12 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass% or less, still more preferably 6 mass% or less, particularly preferably 4 mass% or less, and may be 3.5 mass% or less, 3 mass% or less, or 2.5 mass% or less, based on the total amount (100 mass%) of the water-soluble metal working oil, from the viewpoint of both stability and workability of the metal working oil.

< Component (C): nonionic surfactant-

The water-soluble metal working oil according to one embodiment of the present invention preferably further contains a nonionic surfactant (C). By containing the nonionic surfactant (C), a water-soluble metal working oil solution which can be formed into a metal working fluid having further improved emulsion stability and workability can be produced.

In one embodiment of the present invention, 1 or 2 or more nonionic surfactants (C) may be used alone.

From the above point of view, in one embodiment of the present invention, the content of the nonionic surfactant (C) is preferably 0.1 to 15.0 mass%, more preferably 0.2 to 10.0 mass%, still more preferably 0.3 to 8.0 mass%, still more preferably 0.5 to 6.0 mass%, particularly preferably 0.7 to 4.0 mass%, still more preferably 0.9 mass% or more, 1.0 mass% or more, or 1.2 mass% or more, and may be 3.8 mass% or less, 3.5 mass% or less, 3.0 mass% or less, 2.8 mass% or less, or 2.5 mass% or less, based on the total amount (100 mass%) of the water-soluble metal working oil.

The nonionic surfactant (C) used in one embodiment of the present invention preferably has an HLB of 6.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more, still more preferably 9.0 or more, and particularly preferably 10.0 or more, from the viewpoint of producing a water-soluble metal working oil capable of being formed into a metal working fluid which further improves emulsion stability and workability.

The HLB of the nonionic surfactant (C) is 18.0 or less, preferably 17.0 or less, more preferably 16.0 or less, further preferably 15.0 or less, and particularly preferably 14.5 or less.

Examples of the nonionic surfactant (C) used in one embodiment of the present invention include alkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene aryl ether, alkylphenol ethylene oxide adduct, higher alcohol ethylene oxide adduct, polyoxyalkylene fatty acid ester, fatty acid ester of glycerin and pentaerythritol, fatty acid ester of sucrose, fatty acid ester of polyoxyalkylene adduct of polyhydric alcohol, alkylpolyglycoside, fatty acid alkanolamide and the like.

Among them, the nonionic surfactant (C) used in one embodiment of the present invention preferably contains a polyoxyalkylene alkyl ether from the viewpoint of preparing a water-soluble metal working oil which can be formed into a metal working liquid which further improves emulsion stability and workability.

The content of the polyoxyalkylene alkyl ether is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total amount (100% by mass) of the nonionic surfactant (C) contained in the water-soluble metal working oil.

< Component (D): amine Compound ]

The water-soluble metal working oil according to one embodiment of the present invention preferably further contains an amine compound (D). When the water-soluble metal working oil containing the amine compound (D) is mixed with dilution water to prepare a metal working fluid, the emulsified state is good, and the metal working fluid can be formed to further improve the antibacterial property, rust-preventing property, workability and the like.

In the water-soluble metal working oil according to one embodiment of the present invention, 1 kind of the amine compound (D) may be used alone, or 2 or more kinds may be used in combination.

From the above point of view, in one embodiment of the present invention, the content of the amine compound (D) is preferably 2 to 40 mass%, more preferably 4 to 35 mass%, still more preferably 6 to 30 mass%, still more preferably 8 to 25 mass%, and particularly preferably 10 to 20 mass%, based on the total amount (100 mass%) of the water-soluble metal working oil.

The amine compound (D) used in one embodiment of the present invention may be any one of monoamine having 1 amino nitrogen atom in one molecule, diamine having 2 amino nitrogen atoms in one molecule, and polyamine having 3 or more amino nitrogen atoms in one molecule.

Among them, the amine compound (D) used in one embodiment of the present invention preferably contains monoamine from the viewpoint of preparing a water-soluble metal working oil capable of forming a metal working fluid which is further improved in antibacterial property, rust preventive property, workability, and the like.

The content of the monoamine is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass, based on the total amount (100% by mass) of the amine compound (D) contained in the water-soluble metal working oil.

The monoamines used as the amine compound (D) in one embodiment of the present invention may be classified into monoprimary amines represented by the following formula (i), monoprimary amines represented by the following formula (ii), and monoprimary amines represented by the following formula (iii) according to the number of substituents R.

The amine compound (D) used in one embodiment of the present invention preferably contains at least a mono-tertiary amine, more preferably contains at least one of a mono-primary amine and a mono-secondary amine, and even more preferably contains all of a mono-primary amine, a mono-secondary amine, and a mono-tertiary amine, from the standpoint of producing a water-soluble metalworking fluid that, when diluted with water to produce a metalworking fluid, gives a good emulsification state, and can be formed into a metalworking fluid having further improved antibacterial, rust-preventing, and workability properties.

[ Chemical formula 4]

In the above formula, R each independently represents a substituent. The plurality of R's may be the same or different from each other. Examples of the substituent include an alkyl group, an alkyl group having a hydroxyl group, an alkenyl group, a cycloalkyl group, a phenyl group, and a benzyl group.

Examples of the alkyl group which may be selected as the substituent R include methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (n-pentyl, isopentyl, neopentyl), hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.

The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4.

Examples of the alkyl group having a hydroxyl group which may be selected as the substituent R include those wherein at least one hydrogen atom of the alkyl group is substituted with a hydroxyl group.

The alkyl group constituting the group may be a straight-chain alkyl group or a branched alkyl group.

The number of carbon atoms of the alkyl group having a hydroxyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, still more preferably 1 to 6, particularly preferably 2 to 4

Examples of the alkenyl group which may be selected as the substituent R include vinyl (vinyl group), propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl and the like.

The alkenyl group may be a straight chain alkenyl group or a branched alkenyl group.

The number of carbon atoms of the alkenyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3.

Examples of the cycloalkyl group which may be selected as the substituent R include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl.

From the standpoint of producing a water-soluble metalworking fluid which is excellent in emulsification state when diluted water is compounded to produce a metalworking fluid, the amine compound (D) used in one embodiment of the present invention preferably contains an alkanolamine having at least one alkyl group having a hydroxyl group, and can be formed into a metalworking fluid which is further improved in antibacterial property, rust-preventing property, workability and the like.

Examples of alkanolamines include primary alkanolamines wherein R in formula (i) is an alkyl group having a hydroxyl group, secondary alkanolamines wherein at least one R in formula (ii) is an alkyl group having a hydroxyl group, and tertiary alkanolamines wherein at least one R in formula (iii) is an alkyl group having a hydroxyl group.

Examples of the primary alkanolamine include ethanolamine, propanolamine, butanolamine, and 2-amino-2-methyl-1-propanol.

Examples of the secondary alkanolamine include monoethanolamine such as N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-octylethanolamine, N-stearyl ethanolamine, N-oleylethanolamine, N-cyclohexylethanolamine, N-phenylethanolamine, and N-benzylethanolamine; monopropanolamine such as N-methylpropanol amine, N-ethylpropanolamine, N-propylpropanol amine, N-butylpropanol amine, N-octylpropanol amine, N-stearyl propanol amine, N-oleylpropanolamine, N-cyclohexylpropanol amine, N-phenylpropanolamine, and N-benzylpropanol amine; diethanolamine, dipropanolamine, and the like.

Examples of the tertiary alkanolamine include monoethanolamine such as N-dimethylethanolamine, N-diethylethanolamine, N-dipropylethanolamine, N-dibutylethanolamine, N-dioctylethanolamine, N-distearylethanolamine, N-dioleylethanolamine, N-dicyclohexylethanolamine, N-diphenylethanolamine, and N-dibenzylethanolamine; monopropanolamine such as N-dimethylpropanolamine, N-diethylpropanolamine, N-dipropylpropanolamine, N-dibutylpropanolamine, N-dioctylpropanolamine, N-distearylpropanolamine, N-dioleylpropanolamine, N-dicyclohexylpropanolamine, N-diphenylpropanolamine, N-dibenzylpropanolamine, etc.; diethanolamine such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-octyldiethanolamine, N-stearyl diethanolamine, N-oleyldiethanolamine, N-cyclohexyldiethanolamine, N-phenyldiethanolamine, N-benzyldiethanolamine and the like; dipropanolamine such as N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-octyldipropanolamine, N-stearyl dipropanolamine, N-oleyl dipropanolamine, N-cyclohexyldipropanolamine, N-phenyldipropanolamine, N-benzyldipropanolamine, etc.; triethanolamine, tripropanolamine (triisopropanolamine, etc.), and the like.

Among them, the amine compound (D) used in one embodiment of the present invention preferably contains at least a tertiary alkanolamine, more preferably contains at least one of a primary alkanolamine and a secondary alkanolamine, and further preferably contains all of a primary alkanolamine, a secondary alkanolamine, and a tertiary alkanolamine, from the viewpoint of preparing a water-soluble metalworking fluid that, when diluted with water to prepare a metalworking fluid, gives a good emulsification state, and can be formed into a metalworking fluid that further improves antibacterial properties, rust resistance, processability, and the like.

The content of the alkanolamine is preferably 5 mass% or more, more preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, still more preferably 30 mass% or more, particularly preferably 35 mass% or more, and further may be 40 mass% or more, 42 mass% or more, 44 mass% or more, 46 mass% or more, 48 mass% or more, 50 mass% or more, 55 mass% or more, or 60 mass% or more, and may be 100 mass% or less, 95 mass% or less, 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 68 mass% or less, 66 mass% or less, 64 mass% or less, 62 mass% or less, 60 mass% or less, 58 mass% or 55 mass% or less, based on the total amount (100 mass%) of the amine compound (D) contained in the water-soluble metal working oil.

The amine compound (D) used in one embodiment of the present invention preferably contains a cycloaliphatic amine.

Examples of the alicyclic amine include alicyclic primary amines in which R in the formula (i) is cycloalkyl, alicyclic secondary amines in which at least one R in the formula (ii) is cycloalkyl, and alicyclic tertiary amines in which at least one R in the formula (iii) is cycloalkyl.

Examples of the alicyclic primary amine include N-cyclohexylamine.

Examples of the alicyclic secondary amine include monocyclohexylamines such as N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, N-oleylcyclohexylamine and the like; monocyclohexylalkanolamines such as N-cyclohexylethanolamine and N-cyclohexylpropanolamine; n-dicyclohexylamine, and the like.

Examples of the alicyclic tertiary amine include dialkyl monocyclohexylamines such as N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dipropylcyclohexylamine, N-dioleylcyclohexylamine and N-dicyclohexylamine; monocyclohexyldialkanolamines such as N-cyclohexyldiethanolamine and N-cyclohexyldipropanolamine; mono-alkyl dicyclohexylamines such as N-methyl dicyclohexylamine, N-ethyl dicyclohexylamine, N-propyl dicyclohexylamine, N-oleyl dicyclohexylamine, and the like; dicyclohexylalkanolamines such as N-dicyclohexylamine and N-dicyclohexylamine propanols; tricyclohexylamine, and the like.

Among them, the amine compound (D) used in one embodiment of the present invention preferably contains a cycloaliphatic tertiary amine, more preferably contains a cycloaliphatic tertiary amine in which 2 of R in the above formula (iii) are cycloalkyl groups, from the standpoint of producing a water-soluble metalworking fluid which, when diluted with water, gives a metalworking fluid having a good emulsifying state and can be formed into a metalworking fluid having further improved antibacterial, rust-preventing and workability properties.

The content of the alicyclic amine is preferably 10 mass% or more, more preferably 15 mass% or more, still more preferably 20 mass% or more, still more preferably 25 mass% or more, particularly preferably 30 mass% or more, based on the total amount (100 mass%) of the amine compound (D) contained in the water-soluble metal working oil, and may be 100 mass% or less, 95 mass% or less, 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or 65 mass% or less.

The water-soluble metal working oil according to one embodiment of the present invention may contain an alkanolamine and an amine other than the alicyclic amine (including a diamine and a polyamine) as the amine compound (D).

The content of the other amine may be 0 to 50 mass%, 0 to 40 mass%, 0 to 30 mass%, 0 to 20 mass%, 0 to 10 mass%, 0 to 5.0 mass%, 0 to 2.0 mass%, 0 to 1.0 mass%, 0 to 0.10 mass%, 0 to 0.01 mass%, 0 to 0.001 mass%, 0 to 0.0001 mass%, or 0 to 0.00001 mass% based on the total amount (100 mass%) of the amine compound (D) contained in the water-soluble metal working oil.

< Component (E): fatty acids

The water-soluble metal working oil according to one embodiment of the present invention preferably further contains a fatty acid (E).

By containing the fatty acid (E), a water-soluble metal working oil agent which can be formed into a metal working fluid having further improved emulsion stability, rust resistance, workability, and the like can be produced.

In one embodiment of the present invention, 1 kind of fatty acid (E) may be used alone, or 2 or more kinds may be used in combination.

From the above point of view, in one embodiment of the present invention, the content of the fatty acid (E) is preferably 3 to 60 mass%, more preferably 5 to 50 mass%, still more preferably 9 to 40 mass%, still more preferably 12 to 35 mass%, particularly preferably 14 to 30 mass%, further 15 mass% or 16 mass% or more, and further 27 mass% or less, 25 mass% or less, 23 mass% or less, or 21 mass% or less, based on the total amount (100 mass%) of the water-soluble metal working oil.

Examples of the fatty acid (E) used in one embodiment of the present invention include fatty acids, hydroxy fatty acids, aliphatic dicarboxylic acids, dimer acids of fatty acids, and polymerized fatty acids of hydroxy unsaturated fatty acids.

Examples of the fatty acid include saturated aliphatic monocarboxylic acids such as octanoic acid, 2-ethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, and isostearic acid, and unsaturated aliphatic monocarboxylic acids such as octenoic acid, nonenoic acid, decenoic acid, undecylenic acid, oleic acid, elaidic acid, erucic acid, nervonic acid, linoleic acid, γ -linolenic acid, arachidonic acid, α -linolenic acid, stearidonic acid, eicosapentaenoic acid, and docosahexaenoic acid.

In addition, tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, linseed oil fatty acid, rice bran oil fatty acid, cotton seed oil fatty acid, and the like, which are mixtures of unsaturated fatty acids, may also be used.

The number of carbon atoms of the fatty acid is preferably 8 to 30, more preferably 10 to 25, and even more preferably 10 to 20.

Examples of the hydroxy fatty acid include hydroxy lauric acid, hydroxy myristic acid, hydroxy palmitic acid, hydroxy stearic acid, hydroxy arachidic acid, hydroxy behenic acid, and hydroxy octadecenoic acid.

The number of carbon atoms of the hydroxy fatty acid is preferably 8 to 30, more preferably 10 to 25, and even more preferably 10 to 20.

Examples of the aliphatic dicarboxylic acid include sebacic acid, dodecanedioic acid, dodecylsuccinic acid, lauryl succinic acid, stearyl succinic acid, isostearyl succinic acid, and the like.

The aliphatic dicarboxylic acid has preferably 8 to 30 carbon atoms, more preferably 10 to 25 carbon atoms, and still more preferably 10 to 20 carbon atoms.

Examples of the hydroxy-unsaturated fatty acid constituting the polymerized fatty acid of the hydroxy-unsaturated fatty acid include ricinoleic acid (12-hydroxyoctadec-9-enoic acid) and the like. In addition, a fatty acid mixture containing ricinoleic acid such as ricinoleic acid may be used.

Examples of the polymerized fatty acid of the above-mentioned hydroxy unsaturated fatty acid include a condensed fatty acid which is a dehydrated polycondensate of a hydroxy unsaturated fatty acid, a condensed fatty acid obtained by dehydrating condensation of an alcoholic hydroxy group of a condensed fatty acid which is a dehydrated polycondensate of a hydroxy unsaturated fatty acid with a monocarboxylic acid, and the like.

The acid value of the fatty acid (E) is usually 0mgKOH/g or more, preferably 10 to 100mgKOH/g, more preferably 20 to 90mgKOH/g, and still more preferably 30 to 80mgKOH/g, from the viewpoint of producing a water-soluble metal working oil capable of forming a metal working fluid with further improved workability.

The hydroxyl value of the fatty acid (E) is preferably 0 to 80mgKOH/g, more preferably 0 to 60mgKOH/g, still more preferably 0 to 40mgKOH/g.

The ratio of the acid value to the hydroxyl value of the fatty acid (E) [ acid value/hydroxyl value ] is preferably 1.5 to 15, more preferably 2.0 to 10, still more preferably 2.5 to 9.5 from the above viewpoint.

The saponification value of the fatty acid (E) is preferably 180 to 220mgKOH/g, more preferably 190 to 210mgKOH/g, still more preferably 195 to 205mgKOH/g.

In the present specification, the acid value means that according to JIS K2501:2003 (indicator photometry), the hydroxyl value means a value measured according to JIS K0070:1992, the saponification value refers to a value measured based on JIS K2503: 1996.

< Other additives >

The water-soluble metal working oil according to one embodiment of the present invention may further contain various additives other than the above-mentioned components (a) to (F) as required within a range not to impair the effects of the present invention.

Examples of such other additives include anionic surfactants, cationic surfactants, extreme pressure additives, metal deactivators, emulsification aids, antibacterial agents, antifoaming agents, antioxidants, and oiliness agents.

These various additives may be used alone or in combination of 1 or more than 2.

In one embodiment of the present invention, the content of each of these various additives may be appropriately set according to the type and function of each component, and is preferably 0.01 to 20% by mass, more preferably 0.03 to 15% by mass, and even more preferably 0.01 to 10% by mass, based on the total amount (100% by mass) of the water-soluble metal working oil.

Examples of the anionic surfactant include polyoxyethylene alkyl ether carboxylic acid, polyoxyethylene alkyl ether phosphoric acid, alkylbenzenesulfonic acid, α -olefin sulfonic acid, and salts thereof.

The acid value of the anionic surfactant is preferably 20 to 250mgKOH/g, more preferably 30 to 200mgKOH/g, still more preferably 40 to 190mgKOH/g, and still more preferably 50 to 180mgKOH/g.

Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, and alkyldimethylbenzyl ammonium salt.

Examples of the extreme pressure additive include chlorine-based extreme pressure additives such as chlorinated paraffin, chlorinated fatty acid, and chlorinated fatty oil; sulfur extreme pressure additives such as sulfurized olefins, sulfurized lard, alkyl polysulfides, sulfurized fatty acids, and the like; phosphate esters, phosphite esters, thiophosphate esters, salts thereof, phosphine-based extreme pressure additives such as tricresyl phosphate, and the like.

Examples of the metal deactivator include benzotriazole, imidazoline, pyrimidine derivatives, benzothiazole derivatives, and thiadiazole.

Examples of the emulsifying aid include unsaturated fatty acid esters such as methyl oleate, ethyl oleate, and propyl oleate.

Examples of the antibacterial agent include isothiazoline compounds, triazine compounds, alkyl benzimidazole compounds, and metal pyrithione salts.

Examples of the defoaming agent include silicone-based defoaming agents, fluorinated silicone-based defoaming agents, and polyacrylates.

Examples of the antioxidant include amine antioxidants such as alkylated diphenylamine, phenyl naphthylamine and alkylated phenyl naphthylamine; phenolic antioxidants such as 2, 6-di-t-butylphenol, 4' -methylenebis (2, 6-di-t-butylphenol), isooctyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and n-stearyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate.

Examples of the oily agent include alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol.

< Method for producing Water-soluble Metal working oil >

The method for producing the water-soluble metal working oil according to one embodiment of the present invention is not particularly limited, and is preferably a method having a step of compounding the above components (a) and (B), and if necessary, compounding the components (C) to (F) and other various additives. The order of blending the components can be appropriately set.

[ Morphology of Metal working fluid ]

The metal working fluid of the present invention is a metal working fluid obtained by mixing the metal working fluid of one embodiment of the present invention described above with dilution water as a stock solution.

The dilution water may be, for example, any of distilled water, ion-exchanged water, tap water, industrial water, and the like.

The amount of the dilution water to be mixed in the preparation of the metal working fluid is preferably more than 100 parts by mass relative to 100 parts by mass of the total amount of the components other than water of the water-soluble metal working oil, and is preferably appropriately adjusted to achieve a desired dilution concentration.

The dilution concentration of the metal working fluid according to one embodiment of the present invention is preferably 1 to 50% by volume, more preferably 3 to 40% by volume, and even more preferably 5 to 20% by volume.

In the present specification, the "diluted concentration of the metal working fluid" refers to a value calculated according to the following formula.

"Dilution concentration of metalworking fluid (mass%)" = [ mass of metalworking fluid before dilution ]/[ [ mass of metalworking fluid before dilution ] + [ mass of dilution water ] ] ×100

[ Use of Metal working fluid ]

The metal working fluid according to an embodiment of the present invention can be used for metal working using a machine tool using an emulsification inhibitor. According to the metal working fluid of an embodiment of the present invention, for example, even if an emulsification inhibitor is mixed into the cutting oil tank, the emulsification damage of the metal working fluid can be suppressed, and deterioration of the metal working fluid can be prevented.

Examples of the emulsification inhibitor include grease. The type of grease is not particularly limited, and may be a soap-based grease or a urea-based grease. Examples of the soap-based grease include calcium-based grease, lithium-based grease, complex aluminum-based grease, and complex lithium-based grease.

The material to be processed using the metal working fluid according to one embodiment of the present invention is not particularly limited, but is particularly preferably a material to be processed made of a metal selected from the group consisting of aluminum, aluminum alloy, magnesium alloy, copper alloy, iron, steel, carbon steel, cast iron, titanium alloy, alloy steel, nickel-based alloy, niobium alloy, tantalum alloy, molybdenum alloy, tungsten alloy, stainless steel, and high manganese steel.

Accordingly, the present invention can also provide the following [1] and [2].

[1] The method of use is to apply the metal working fluid according to one embodiment of the present invention described above to the working of a workpiece made of metal.

[2] A metal working method for working a work made of a metal by applying the metal working liquid according to one embodiment of the present invention.

The details of the workpiece described in [1] and [2] above are as described above.

In addition, in the above-mentioned [1] and [2], examples of the work material include cutting, grinding, blanking, polishing, drawing, rolling, and the like.

In the method of using [1] and the method of working metal of [2], the metal working fluid is used by mixing dilution water into the water-soluble metal working oil according to one embodiment of the present invention, and then supplying the diluted water to the workpiece to be contacted with the workpiece. The metalworking fluid lubricates the workpiece and the working tool. Further, the present invention can be used for removing cut chips, preventing rust of a workpiece, cooling a tool, and the like.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 15 and comparative examples 1 to 9

The water-soluble metal working oils were prepared by adding and mixing the various components shown in tables 1 to 3 in the amounts shown in tables 1 to 3. Details of each component used in the preparation of the water-soluble metal working oil are as follows.

< Component (A) >

Paraffin-based mineral oil: paraffin-based mineral oils classified as group II of the API base oil category with a kinematic viscosity at 40 ℃ of 7.117mm ²/s, a viscosity index of 109

< Component (B) >

Polyoxyethylene alkyl ether carboxylic acid (2 EO), hlb=6

In the formula (B-1), A is ethylene, B is methylene, n is 2, R is an oil-based compound.

Polyoxyethylene alkyl ether carboxylic acid (5 EO), hlb=9.6

In the formula (B-1), A is ethylene, B is methylene, n is 5, R is an oil-based compound.

Polyoxyethylene alkyl ether carboxylic acid (8 EO), hlb=11.7

In the formula (B-1), A is ethylene, B is methylene, n is 8, R is an oil-based compound.

Polyoxyethylene alkyl ether carboxylic acid (10 EO), hlb=12.7

In the formula (B-1), A is ethylene, B is methylene, n is 10, R is an oil-based compound.

Polyoxyethylene polyoxypropylene alkyl ether carboxylic acid, hlb=10

In the formula (B-1), A is a combination of ethylene and propylene, B is methylene, n is 3, and R is isotridecyl.

< Component (b') >

Polyoxyethylene oleyl ether (10 EO), hlb=13.0

In the formula (B-1), A is ethylene, B is methylene, n is 10, R is an oil group, but does not have a carboxyl group.

< Component (C) >

Nonionic surfactant (1): polyoxyalkylene alkyl ether, hlb=12.7

Nonionic surfactant (2): polyoxyalkylene alkyl ether, hlb=8.8

< Component (D) >

Amine compound: amine mixtures of monoisopropanolamine, diisopropanolamine, triisopropanolamine, and dicyclohexylamine

< Component (E) >

Fatty acids: mixed fatty acids of dodecanedioic acid, neodecanoic acid, tall oil fatty acid and ricinoleic acid polymerized fatty acid (castor oil polymerized fatty acid), acid value=32.3 mgKOH/g, hydroxyl value=1.1 mgKOH/g

< Component (F) >

Water

< Other ingredients >

Metal passivating agent: benzotriazole and phosphoric acid anticorrosive agent

Emulsification aid: oleic acid methyl ester

Antimicrobial agent: 1, 2-benzisothiazolin-3-one

Defoaming agent: organosilicon defoamer

Next, the emulsion stability of the metal working fluid was evaluated using the prepared water-soluble metal working oil. First, the water-soluble metalworking fluid was diluted to 20 vol% with water having a magnesium concentration adjusted to 500ppm, and a metalworking fluid was prepared. To 50mL of this metal working fluid was added 2.5g of a complex lithium-based grease (DAPHNE EPONEX SR, manufactured by Shimadzu corporation), and the mixture was allowed to stand in a constant temperature bath at 60℃to measure the number of days until emulsion breakdown of the metal working fluid occurred. The emulsion breaking was visually observed, and it was determined that the emulsion breaking occurred at the time of confirming the separation of the oil layer from the water layer, and the number of days until the emulsion breaking was 2 or more was regarded as "acceptable". The results are shown in tables 1 and 2.

TABLE 1

TABLE 2

TABLE 3

As is clear from tables 1 and 2, the water-soluble metal working oils of examples 1 to 15 had a number of days of 2 days or more until emulsion breakdown occurred, and were excellent in emulsion stability even when mixed with grease. On the other hand, as is clear from table 3, the water-soluble metal working oils of comparative examples 1 to 9 containing no component (B) ether carboxylic acid were each 1 day in days until emulsion breaking occurred, and the emulsion stability was inferior to that of the water-soluble metal working oil containing component (B).

Claims

1. A water-soluble metal working oil comprising a base oil (A) and an ether carboxylic acid (B) represented by the following general formula (B-1),

[ Chemical formula 1]

Wherein A is an alkylene group having 1 to 4 carbon atoms, and when a plurality of A's are present, the plurality of A's may be the same group or may be different groups from each other,

B is a single bond or an alkylene group having 1 to 4 carbon atoms,

N is an integer of 1 to 100,

R is a hydrocarbon group.

2. The water-soluble metal working oil according to claim 1, wherein B in the general formula (B-1) is methylene.

3. The water-soluble metal working oil according to claim 1 or 2, wherein the HLB of the ether carboxylic acid (B) is 5.0 or more.

4. The water-soluble metal working oil according to claim 1 or 2, wherein the HLB of the ether carboxylic acid (B) is more than 6.0.

5. The water-soluble metal working oil according to any one of claims 1 to 4, wherein a in the general formula (b-1) is ethylene.

6. The water-soluble metal working oil according to any one of claims 1 to 4, wherein n in the general formula (b-1) is 6 or more.

7. The water-soluble metal working oil according to any one of claims 1 to 6, wherein R in the general formula (b-1) is a hydrocarbon group having 10 to 30 carbon atoms.

8. The water-soluble metal working oil according to any one of claims 1 to 7, further comprising a nonionic surfactant (C).

9. The water-soluble metal working oil according to claim 8, wherein the content ratio of the nonionic surfactant (C) to the ether carboxylic acid (B) [ C)/(B) ] is 1 to 25 in terms of mass ratio.

10. The water-soluble metal working oil according to any one of claims 1 to 9, further comprising an amine compound (D).

11. The water-soluble metal working oil according to claim 10, wherein the content ratio of the amine compound (D) to the ether carboxylic acid (B) [ D)/(B) ] is 1 to 166 in terms of mass ratio.

12. A metal working fluid obtained by diluting the water-soluble metal working oil according to any one of claims 1 to 11.

13. The metal working fluid according to claim 12, which is used in metal working by a machine tool using an emulsion suppressing material.

14. The metal working fluid of claim 13, wherein the emulsion inhibiting substance is a grease.