Patent Application
20250034478
The present invention relates to a water-soluble metalworking oil, and a metalworking fluid obtained by blending the water-soluble metalworking oil with dilution water.
In the art of metalworking such as cutting and grinding, metalworking fluids are used to increase workability for workpieces and to suppress wear of working tools.
Metalworking fluids include oil-based metalworking fluids containing oils such as mineral oils, synthetic oils, and animal and vegetable oils as main components, and water-soluble metalworking fluids provided with water solubility by blending an oil with a surface-active compound. Recently, water-soluble metalworking fluids are increasingly used for safety reasons such as a reduced risk of catching fire.
For example, Patent Literature 1 discloses a water-soluble working oil containing methyldicyclohexylamine.
The water-soluble working oil is diluted with dilution water to provide a metalworking fluid, which is then used in metalworking. Patent Literature 2 also discloses a water-soluble metalworking oil comprising an ether carboxylic acid, and the like.
Meanwhile, machine tools have sliding surfaces to move tools and materials to be cut in any direction, and grease or lubricant compositions have been used to facilitate sliding motion. In recent years, oil skimmers, which separate oil components, have not been installed in the cutting oil tank in much equipment so as to reduce machine tool size and cost, and as a result, in much facility, grease has been used on sliding surfaces.
However, if the grease used for sliding surfaces gets mixed in the cutting oil tank installed in the machine tool, it promotes demulsification of water-soluble metalworking fluid, resulting in deterioration of the water-soluble metalworking fluid. Under such circumstances, a novel water-soluble metalworking oil is desired.
The present invention provides a water-soluble metalworking oil comprising a predetermined amount of a specific ether carboxylic acid, and the like. Specifically, the present invention provides, for example, the following embodiments [1] to:
[1] A water-soluble metalworking oil comprising a base oil (A) and an ether carboxylic acid (B) represented by the following 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 metalworking oil.
When formed into a metalworking fluid, the water-soluble metalworking oil according to a preferred embodiment of the present invention reduces demulsification of the metalworking fluid even when grease for machine tools is mixed in the cutting oil tank.
Concerning the numerical ranges described herein, the upper limits and the lower limits can be suitably combined. For example, when a numerical range is described as being “preferably 30 to 100, and more preferably 40 to 80”, the range of “30 to 80” and the range of “40 to 100” are also included in the numerical range described herein. Moreover, for example, when a numerical range is described as being “preferably 30 or more and more preferably 40 or more, and preferably 100 or less and more preferably 80 or less”, the range of “30 to 80” and the range of “40 to 100” are also included in the numerical range described herein.
In addition, for example, “60 to 100” as a numerical range described herein means the range of “60 or more and 100 or less”.
Herein, two terms “metalworking oil” and “metalworking fluid” used are distinguished according to the water content.
The “metalworking oil” is a stock solution of a metalworking fluid before being diluted with dilution water to provide a metalworking fluid, and is in a form suitable for transportation and storage before being used in metalworking. The “metalworking fluid” is what is obtained by adding dilution water to a stock solution of a metalworking oil to dilute the stock solution, and is in a form suitable when used in metalworking.
The water-soluble metalworking oil of the present invention comprises a base oil (A) and an ether carboxylic acid (B) represented by the following formula (b-1). By including a compound represented by the following formula (b-1) in the water-soluble metalworking oil according to an embodiment of the present invention, the water-soluble metalworking oil can effectively reduce demulsification of metalworking fluid when formed into metalworking fluid, even when an emulsion inhibitor such as grease for machine tools, is mixed.
The water-soluble metalworking oil of the present invention comprises a base oil (A) and an ether carboxylic acid (B) represented by the above formula (b-1), and may also include a component other than those components.
For example, the water-soluble metalworking oil according to an embodiment of the present invention may include one or more selected from a nonionic surfactant (C), an amine compound (D) and a fatty acid (E). The water-soluble metalworking oil according to an embodiment of the present invention may also include water (F). The water-soluble metalworking oil according to an embodiment of the present invention may also include a component other than the components (A) to (F) to the extent that the effect of the present invention is not reduced.
By adjusting the content of water and other components and the content ratio, an emulsion oil classified into Class A1 and a soluble oil classified into Class A2 according to JIS K2241:2017 may be prepared.
In one embodiment of the present invention, the total content of the components (A) and (B) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, yet more preferably 30% by mass or more, particularly preferably 35% by mass or more, and may be 100% by mass or less, 90% by mass or less, 808 by mass or less, 708 by mass or less, 60% by mass or less, 50% by mass or less, or 45% by mass or less based on the total amount (100% by mass) of the water-soluble metalworking oil.
In one embodiment of the present invention, the total content of the components (A) to (C) is preferably 10% by mass or more, more preferably 208 by mass or more, even more preferably 30% by mass or more, yet more preferably 33% by mass or more, particularly preferably 36% by mass or more, and may be 100% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 48% by mass or less, or 458 by mass or less based on the total amount (100% by mass) of the water-soluble metalworking oil.
In one embodiment of the present invention, the total content of the components (A) to (D) is preferably 10% by mass or more, more preferably 208 by mass or more, even more preferably 30% by mass or more, yet more preferably 40% by mass or more, particularly preferably 50% by mass or more, and may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less based on the total amount (100% by mass) of the water-soluble metalworking oil.
In one embodiment of the present invention, the total content of the components (A) to (E) is preferably 50% by mass or more, more preferably 558 by mass or more, even more preferably 60% by mass or more, yet more preferably 65% by mass or more, particularly preferably 70% by mass or more, and may be 100% by mass or less, 97% by mass or less, 95% by mass or less, 93% by mass or less, 90% by mass or less, 87% by mass or less, or 85% by mass or less based on the total amount (100% by mass) of the water-soluble metalworking oil.
In an embodiment of the present invention, the total content of the components (A) to (F) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 658 by mass or more, still more preferably 708 by mass or more and particularly preferably 75% by mass or more, and may be 100% by mass or less, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass or less based on the total amount of the water-soluble metalworking oil (100% by mass).
In an embodiment of the present invention, the mass ratio of the content of the nonionic surfactant (C) to the content of the ether carboxylic acid (B) [(C)/(B)] is preferably 1.0 or more, more preferably 1.10 or more, even more preferably 1.15 or more, still more preferably 1.20 or more, and particularly preferably 1.25 or more, and preferably 25.0 or less, more preferably 20.0 or less, even more preferably 15.0 or less, and particularly preferably 10.0 or less, and may be 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 less or 5.0 or less.
In an embodiment of the present invention, the mass ratio of the content of the amine compound (D) to the content of the ether carboxylic acid (B) [(D)/(B)] is preferably 1 or more, more preferably 1.5 or more, even more preferably 2.0 or more, still more preferably 2.5 or more, yet more preferably 3.0 or more, further preferably 3.5 or more, even further preferably 4.0 or more, still further preferably 4.5 or more, and particularly preferably 5.0 or more, and may be 6.0 or more, 6.5 or more, 7.0 or more, 7.5 or more, or 8.0 or more, and preferably 166 or less, more preferably 120 or less, even more preferably 100 or less, still more preferably 90 or less, yet more preferably 80 or less, further preferably 70 or less, and particularly preferably 60 or less, and may be 56 or less, 50 or less, 45 or less, 40 or less or 35 or less.
In the following, the respective components contained in the water-soluble metalworking oil according to an embodiment of the present invention will be described.
The water-soluble metalworking oil of the present invention comprises a base oil (A). Inclusion of the base oil (A) can provide a water-soluble metalworking oil which can be formed into a metalworking fluid having good workability.
In the water-soluble metalworking oil according to an embodiment of the present invention, one base oil (A) may be used alone, or two or more of them may be used in combination.
From the above viewpoint, in an embodiment of the present invention, the content of the base oil (A) is preferably 9% by mass or more, more preferably 12% by mass or more, even more preferably 14% by mass or more, still more preferably 208 by mass or more, yet more preferably 258 by mass or more, and particularly preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less and particularly preferably 50% by mass or less based on the total amount of the water-soluble metalworking oil (100% by mass).
When an emulsion oil classified into Class A1 according to JIS K2241:2017 is prepared, the content of the base oil (A) may be 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more based on the total amount of the oil (100% by mass).
When a soluble oil classified into Class A2 according to JIS K2241:2017 is prepared, the content of the base oil (A) may be 508 by mass or less, 458 by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less based on the total amount of the oil (100% by mass).
The base oil (A) used in an embodiment of the present invention is at least one selected from a mineral oil and a synthetic oil.
Examples of mineral oils include atmospheric residue obtained by performing atmospheric distillation on crude oil such as paraffinic crude oil, intermediate crude oil, and naphthenic crude oil; distillate obtained by performing vacuum distillation on such atmospheric residue; and refined oil obtained by performing on such distillate one or more refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining.
Examples of synthetic oil include α-olefin and a homopolymer thereof, poly α-olefin such as an α-olefin copolymer (e.g., an α-olefin copolymer having 8 to 14 carbon atoms, such as an ethylene-α-olefin copolymer); isoparaffin; polyalkylene glycol; an ester oil such as polyol ester, dibasic ester and phosphoric acid ester; an ether oil such as polyphenyl ether; alkylbenzene; alkyl naphthalene; and synthetic oil obtained by isomerizing wax (GTL wax (gas to liquid wax)) produced from natural gas by the Fischer-Tropsch process (GTL).
In particular, it is preferable that the base oil (A) used in an embodiment of the present invention includes at least one selected from a mineral oil classified into Group II and Group III of the API (American Petroleum Institute) base oil category, and a synthetic oil.
The base oil (A) according to an embodiment of the present invention may have a kinetic viscosity at 40° C. of 3.0 mm2/s or more, 3.5 mm2/s or more, 4.0 mm2/s or more, 4.5 mm2/s or more, 5.0 mm2/s or more, 5.5 mm2/s or more, 6.0 mm2/s or more, 6.5 mm2/s or more, or 7.0 mm2/s or more. The base oil (A) may have a kinetic viscosity at 40° C. of 100 mm2/s or less, 90 mm2/s or less, 80 mm2/s or less, 70 mm2/s or less, 60 mm2/s or less, 50 mm2/s or less, 45 mm2/s or less, 40 mm2/s or less, 35 mm2/s or less, 30 mm2/s or less, 25 mm2/s or less, or 20 mm2/s or less.
A lubricant base oil according to an embodiment of the present invention may have a viscosity index of 70 or more, 80 or more, 85 or more, 90 or more, 95 or more, or 100 or more.
As used herein, the kinetic viscosity and the viscosity index mean values measured or calculated according to JIS K2283:2000.
The water-soluble metalworking oil of the present invention comprises an ether carboxylic acid (B) represented by the following formula (b-1).
The present inventors have found that when a water-soluble metalworking oil includes an ether carboxylic acid (B) having a carboxyl group in the structure and when the water-soluble metalworking oil is diluted with dilution water to prepare a metalworking fluid, demulsification of the metalworking fluid can be reduced even when grease for machine tools is mixed in the cutting oil tank. The metalworking fluid prepared by using the water-soluble metalworking oil of the present invention is less likely to cause degradation of the quality even when grease on the sliding surface is mixed in the cutting oil tank, and thus the duration of use can be extended.
In the above formula (b-1), A is an alkylene group having 1 to 4 carbon atoms, and when a plurality of A are present, the plurality of A is the same or different from each other. As used herein, the “alkylene group” means a linear, cyclic or branched divalent saturated aliphatic hydrocarbon group having a pre-determined number of carbon atoms.
Examples of alkylene groups described above that can be selected as A include a methylene group, an ethylene group such as 1,1-ethylene group and 1,2-ethylene group, a propylene group such as 1,3-propylene, 1,2-propylene and 2,2-propylene, and a butylene group. The above groups also include structural isomers.
In particular, it is preferable that the alkylene group that can be selected as A is one or more groups selected from an ethylene group and a propylene group.
Furthermore, when a plurality of A are present, the plurality of A may be any of an ethylene group alone, a propylene group alone, or a combination of an ethylene group and a propylene group (i.e., -A-O— may be a group in which an ethylene oxide (EO) group and a propylene oxide (PO) group are bonded at random or in a block); the plurality of A preferably include 1 or more groups selected from an ethylene group and a propylene group, more preferably include at least an ethylene group, and are even more preferably all an ethylene group.
In the above formula (b-1), B is a single bond or an alkylene group having 1 to 4 carbon atoms. Examples of alkylene groups described above that can be selected as B are the same as those for A. In particular, the alkylene group that can be selected as B is preferably a linear alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.
In the formula (b-1), n is 1 or more, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, still more preferably 5 or more, yet more preferably 6 or more, further preferably 7 or more, even further preferably 8 or more, still further preferably 9 or more, and particularly preferably 10 or more in order to obtain a metalworking fluid that effectively reduces demulsification.
In the 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 formula (b-1), R represents a hydrocarbon group. As used herein, the “hydrocarbon group” means a linear, cyclic or branched saturated or unsaturated hydrocarbon group having a pre-determined number of carbon atoms, from which a hydrogen atom is eliminated. Specific examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group.
Examples of alkyl groups include a methyl group, an ethyl group, a propyl group such as a n-propyl group and an isopropyl group, a butyl group such as n-butyl group, isobutyl group, s-butyl group and t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, a docosyl group, a tricosyl group and a tetracosyl group. The above groups also include structural isomers.
Examples of alkenyl groups include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group (an oleyl group), a nonadecenyl group, an icosenyl group, a heneicosenyl group, a docosenyl group, a tricosenyl group and a tetracosenyl group. The above groups also include structural isomers.
Examples of cycloalkyl groups include a cyclopentyl group and a cyclohexyl group. Furthermore, in the cycloalkyl group, at least one hydrogen atom bonded to a ring carbon atom may be substituted by a substituent (e.g., an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a phenyl group). Examples of cycloalkyl groups having such a substituent include a methylcyclohexyl group, an ethylcyclohexyl group and a dimethylcyclohexyl group.
Examples of aryl groups include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
Furthermore, in the aryl group, at least one hydrogen atom bonded to a ring carbon atom may be substituted by a substituent (e.g., an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a cycloalkyl group). Examples of aryl groups having such a substituent include a methylphenyl group, an ethylphenyl group and a dimethylphenyl group.
Of 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, even more preferably a linear alkyl group or a linear alkenyl group, and still more preferably a linear alkenyl group.
To obtain a metalworking fluid that effectively reduces demulsification, R has preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, still more preferably 6 or more, yet more preferably 8 or more, further preferably 9 or more, and particularly preferably 10 or more carbon atoms, and may have 11 or more, 12 or more, 13 or more, 14 or more or 15 or more carbon atoms.
Furthermore, R has preferably 50 or less, more preferably 45 or less, even more preferably 40 or less, still more preferably 35 or less, and particularly preferably 30 or less carbon atoms, and may have 29 or less, 28 or less, 27 or less, 26 or less, or 25 or less carbon atoms.
In an embodiment of the present invention, A in the ether carboxylic acid (B) of the formula (b-1) is one or more groups selected from an ethylene group and a propylene group (preferably including at least an ethylene group, and more preferably all groups being an ethylene group), 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, and even more preferably 10), and 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, and even more preferably an oleyl group).
In an embodiment of the present invention, the ether carboxylic acid (B) has an HLB of 5.0 or more. By using an ether carboxylic acid (B) having an HLB of 5.0 or more, demulsification of metalworking fluid can be reduced. In another embodiment of the present invention, the ether carboxylic acid (B) has an HLB of more than 6.0. By using an ether carboxylic acid (B) having an HLB in that range, demulsification of metalworking fluid can be effectively reduced.
In an embodiment of the present invention, the lower limit 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 and is particularly preferably 12.0 or more in order to prepare a water-soluble metalworking oil that provides a metalworking fluid with more improved emulsion stability and workability. The upper limit of HLB of the ether carboxylic acid (B) is not particularly limited, and the ether carboxylic acid (B) has an HLB of 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.
As used herein, HLB stands for the hydrophile-lipophile balance, which is an indicator of the balance between hydrophilic groups and lipophilic groups in the molecule of surfactant. In the present description, HLB refers to values calculated by Griffin's method.
In an embodiment of the present invention, the content of the ether carboxylic acid (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and particularly preferably 0.5% by mass or more, and may be 0.78 by mass or more, 0.9% by mass or more, 1.08 by mass or more, 1.5% by mass or more, or 2.0% by mass or more based on the total amount of the water-soluble metalworking oil (100% by mass) to obtain a metalworking fluid that effectively reduces demulsification.
The content of the ether carboxylic acid (B) is preferably 12% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, still more preferably 6% by mass or less, and particularly preferably 4% by mass or less, and may be 3.5% by mass or less, 3% by mass or less, or 2.5% by mass or less based on the total amount of the water-soluble metalworking oil (100% by mass) to achieve both stability and workability of the metalworking oil.
It is preferable that the water-soluble metalworking oil according to an embodiment of the present invention further includes a nonionic surfactant (C). Inclusion of the nonionic surfactant (C) can provide a water-soluble metalworking oil which can be formed into a metalworking fluid having more improved emulsion stability and workability.
In an embodiment of the present invention, one nonionic surfactant (C) may be used alone, or two or more of them may be used in combination.
From the above point of view, in an embodiment of the present invention, the content of the nonionic surfactant (C) is preferably 0.1 to 15.0% by mass, more preferably 0.2 to 10.0% by mass, even more preferably 0.3 to 8.0% by mass, still more preferably 0.5 to 6.0% by mass, and particularly preferably 0.7 to 4.0% by mass, and may be 0.9% by mass or more, 1.0% by mass or more, or 1.2% by mass or more, and may be 3.8% by mass or less, 3.5% by mass or less, 3.2% by mass or less, 3.0% by mass or less, 2.8% by mass or less, or 2.5% by mass or less based on the total amount of the water-soluble metalworking oil (100% by mass).
The nonionic surfactant (C) used in an embodiment of the present invention has an HLB of preferably 6.0 or more, more preferably 7.0 or more, even more preferably 8.0 or more, still more preferably 9.0 or more, and particularly preferably 10.0 or more in order to prepare a water-soluble metalworking oil that can provide a metalworking fluid with more improved emulsion stability and workability.
Furthermore, the nonionic surfactant (C) has an HLB of 18.0 or less, preferably 17.0 or less, more preferably 16.0 or less, even more preferably 15.0 or less, and particularly preferably 14.5 or less.
Examples of nonionic surfactants (C) used in an embodiment of the present invention include alkylene glycol, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene aryl ether, an alkylphenol ethylene oxide adduct, a higher alcohol ethylene oxide adduct, polyoxyalkylene fatty acid ester, a fatty acid ester of glycerin and pentaerythritol, a fatty acid ester of sucrose, a fatty acid ester of a polyoxyalkylene adduct of polyhydric alcohol, alkyl polyglycoside and fatty acid alkanol amide.
It is preferable that the nonionic surfactant (C) used in an embodiment of the present invention includes polyoxyalkylene alkyl ether among them in order to prepare a water-soluble metalworking oil that can provide a metalworking fluid with more improved emulsion stability and workability.
The content of polyoxyalkylene alkyl ether is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even 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 of the nonionic surfactant (C) (100% by mass) contained in the water-soluble metalworking oil.
It is preferable that the water-soluble metalworking oil according to an embodiment of the present invention also includes an amine compound (D). When the water-soluble metalworking oil is diluted with dilution water to prepare a metalworking fluid, the water-soluble metalworking oil including the amine compound (D) improves emulsion conditions, and can provide a metalworking fluid with more improved antibacterial properties, antirust properties and workability.
In the water-soluble metalworking oil of one embodiment of the present invention, one amine compound (D) may be used alone, or two or more of them may be used in combination.
From the above viewpoint, the content of the amine compound (D) in one embodiment of the present invention is preferably 2 to 40% by mass, more preferably 4 to 35% by mass, even more preferably 6 to 30% by mass, yet more preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass based on the total amount (100% by mass) of the water-soluble metalworking oil.
Amine compound (D) used in one embodiment of the present invention may be any of monoamine having one amino nitrogen atom within one molecule, diamine having two amino nitrogen atoms within one molecule, and polyamine having 3 or more amino nitrogen atoms within one molecule.
However, from the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having more increased antibacterial properties, antirust properties, workability, and the like, amine compound (D) used in one embodiment of the present invention preferably contains monoamine.
The content of monoamine is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 85 to 100% by mass, yet more preferably 90 to 100% by mass, yet more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass based on the total amount (100% by mass) of amine compound (D) contained in the water-soluble metalworking oil.
Monoamine used as amine compound (D) in one embodiment of the present invention is classified according to the number of substituents R into primary monoamine represented by the following formula (i), secondary monoamine represented by the following formula (ii), and tertiary monoamine represented by the following formula (iii).
From the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having a good emulsion state and more increased antibacterial properties, antirust properties, workability, and the like when combined with dilution water to provide a metalworking fluid, the amine compound (D) used in one embodiment of the present invention preferably contains at least tertiary monoamine, more preferably contains tertiary monoamine and at least one of primary monoamine and secondary monoamine, and even more preferably contains all of the primary monoamine, secondary monoamine, and tertiary monoamine.
In the above formulae, R each independently represents a substituent. A plurality of R may be the same or may be different from each other. Examples of the substituent include an alkyl group, a hydroxyalkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, and a benzyl group.
Examples of the alkyl group that can be selected as a substituent R include a methyl group, an ethyl group, a propyl group (a n-propyl group, an i-propyl group), a butyl group (a n-butyl group, an i-butyl group, a s-butyl group, a t-butyl group), a pentyl group (a n-pentyl group, an i-pentyl group, a neopentyl group), a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
The alkyl group may be a linear alkyl group or may be a branched alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, yet more preferably 1 to 6, and particularly preferably 1 to 4.
Examples of the hydroxyalkyl group that can be selected as a substituent R include groups obtained by replacing at least one hydrogen atom of the above alkyl groups with a hydroxyl group.
The alkyl group that constitutes the hydroxyalkyl group may also be a linear alkyl group or may be a branched alkyl group.
The number of carbon atoms of the hydroxyalkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, yet more preferably 1 to 6, and particularly preferably 2 to 4.
Examples of the alkenyl group that can be selected as a substituent R include an ethenyl group (a vinyl group), a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, and an octadecenyl group.
The alkenyl group may be a linear alkenyl group or may be a branched alkenyl group.
The number of carbon atoms of the alkenyl group is preferably 1 to 30, more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, yet more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
Examples of the cycloalkyl group that can be selected as a substituent R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.
From the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having a good emulsion state and more increased antibacterial properties, antirust properties, workability, and the like, when combined with dilution water, amine compound (D) used in one embodiment of the present invention preferably contains alkanolamine having at least one hydroxyalkyl group.
Examples of alkanolamine include primary alkanolamine in which R in the above formula (i) is a hydroxyalkyl group, secondary alkanolamine in which at least one R in the above formula (ii) is a hydroxyalkyl group, and tertiary alkanolamine in which at least one R in the above formula (iii) is a hydroxyalkyl group.
Examples of primary alkanolamine include ethanolamine, propanolamine, butanolamine, and 2-amino-2-methyl-1-propanol.
Examples of secondary alkanolamine include monoethanolamine such as N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-octylethanolamine, N-stearylethanolamine, N-oleylethanolamine, N-cyclohexylethanolamine, N-phenylethanolamine, and N-benzylethanolamine; monopropanolamine such as N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-octylpropanolamine, N-stearylpropanolamine, N-oleylpropanolamine, N-cyclohexylpropanolamine, N-phenylpropanolamine, and N-benzylpropanolamine; diethanolamine, and dipropanolamine.
Examples of 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, and N-dibenzylpropanolamine; diethanolamine such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, N-oleyldiethanolamine, N-cyclohexyldiethanolamine, N-phenyldiethanolamine, and N-benzyldiethanolamine; dipropanolamine such as N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-octyldipropanolamine, N-stearyldipropanolamine, N-oleyldipropanolamine, N-cyclohexyldipropanolamine, N-phenyldipropanolamine, and N-benzyldipropanolamine; triethanolamine, and tripropanolamine (such as triisopropanolamine).
Among these, from the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having a good emulsion state and more increased antibacterial properties, antirust properties, workability, and the like, when combined with dilution water, amine compound (D) used in one embodiment of the present invention preferably contains at least tertiary alkanolamine, more preferably contains tertiary alkanolamine and at least one of primary alkanolamine and secondary alkanolamine, and even more preferably contains all of the primary alkanolamine, secondary alkanolamine, and tertiary alkanolamine.
The content of alkanolamine may be preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, yet more preferably 308 by mass or more, particularly preferably 35% by mass or more, moreover, 40% by mass or more, 42% by mass or more, 44% by mass or more, 46% by mass or more, 48% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, and may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 68% by mass or less, 66% by mass or less, 64% by mass or less, 62% by mass or less, 60% by mass or less, 58% by mass or less, or 55% by mass or less based on the total amount (100% by mass) of amine compound (D) contained in the water-soluble metalworking oil.
Amine compound (D) used in one embodiment of the present invention preferably contains alicyclic amine.
Examples of alicyclic amine include primary alicyclic amine wherein R in the above formula (i) is a cycloalkyl group, secondary alicyclic amine wherein at least one R in the above formula (ii) is a cycloalkyl group; and tertiary alicyclic amine wherein at least one R in the above formula (iii) is a cycloalkyl group.
Examples of primary alicyclic amine include N-cyclohexylamine.
Examples of secondary alicyclic amine include monocyclohexylamine such as N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, and N-oleylcyclohexylamine; monocyclohexylalkanolamine such as N-cyclohexylethanolamine and N-cyclohexylpropanolamine; and N-dicyclohexylamine.
Examples of tertiary alicyclic amine include dialkylmonocyclohexylamine such as N-dimethylcyclohexylamine, N-diethylcyclohexylamine, N-dipropylcyclohexylamine, N-dioleylcyclohexylamine, and N-dicyclohexylamine; monocyclohexyldialkanolamine such as N-cyclohexyldiethanolamine and N-cyclohexyldipropanolamine; monoalkyldicyclohexylamine such as N-methyldicyclohexylamine, N-ethyldicyclohexylamine, N-propyldicyclohexylamine, and N-oleyldicyclohexylamine; dicyclohexylalkanolamine such as N-dicyclohexylethanolamine and N-dicyclohexylpropanolamine; and tricyclohexylamine.
Among these, from the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having a good emulsion state and more increased antibacterial properties, antirust properties, workability, and the like when combined with dilution water to provide a metalworking fluid, the amine compound (D) used in one embodiment of the present invention preferably contains tertiary alicyclic amine, and more preferably contains tertiary alicyclic amine of formula (iii) wherein two R groups are cycloalkyl groups.
The content of alicyclic amine may be preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, yet more preferably 25% by mass or more, particularly preferably 30% by mass or more, and may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less based on the total amount (100% by mass) of amine compound (D) contained in the water-soluble metalworking oil.
The water-soluble metalworking oil of one embodiment of the present invention may contain another amine (including diamine and polyamine) other than alkanolamine and alicyclic amine as amine compound (D).
The content of another amine may be 0 to 50% by mass, 0 to 40% by mass, 0 to 30% by mass, 0 to 20% by mass, 0 to 10% by mass, 0 to 5.0% by mass, 0 to 2.0% by mass, 0 to 1.0% by mass, 0 to 0.10% by mass, 0 to 0.01% by mass, 0 to 0.001% by mass, 0 to 0.0001% by mass, or 0 to 0.00001% by mass based on the total amount (100% by mass) of amine compound (D) contained in the water-soluble metalworking oil.
Preferably, the water-soluble metalworking oil of one embodiment of the present invention further contains a fatty acid (E).
Containing a fatty acid (E), the water-soluble metalworking oil is capable of becoming a metalworking fluid having more increased emulsion stability, antirust properties, workability, and the like.
In one embodiment of the present invention, one fatty acid (E) may be used alone, or two or more of them may be used in combination.
From the above viewpoint, in one embodiment of the present invention, the content of the fatty acid (E) is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, even more preferably 9 to 40% by mass, yet more preferably 12 to 35% by mass, particularly preferably 14 to 30% by mass, and, moreover, may be 15% by mass or more, or 16% by mass or more, and may be 27% by mass or less, 25% by mass or less, 23% by mass or less, or 21% by mass or less based on the total amount (100% by mass) of the water-soluble metalworking oil.
Examples of fatty acid (E) used in one embodiment of the present invention include fatty acid, hydroxy fatty acid, aliphatic dicarboxylic acid, dimer acid of fatty acid, and polymerized fatty acid of hydroxy unsaturated fatty acid.
Examples of the fatty acid include saturated aliphatic monocarboxylic acid such as octanoic acid, 2-ethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and isostearic acid, and unsaturated aliphatic monocarboxylic acid such as octenoic acid, nonenoic acid, decenoic acid, undecenoic 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.
A mixture of unsaturated fatty acid may be used, such as tall oil fatty acid, soybean oil fatty acid, palm oil fatty acid, linseed oil fatty acid, rice bran oil fatty acid, and cottonseed oil fatty acid.
The number of carbon atoms in 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 hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachic acid, hydroxybehenic acid, and hydroxyoctadecenoic 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 carbon atoms.
Examples of the aliphatic dicarboxylic acid include sebacic acid, dodecanedioic acid, dodecylsuccinic acid, laurylsuccinic acid, stearylsuccinic acid, and isostearylsuccinic acid.
The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 8 to 30, more preferably 10 to 25, and even more preferably 10 to 20 carbon atoms.
Examples of the hydroxy unsaturated fatty acid constituting a polymerized fatty acid of the hydroxy unsaturated fatty acid include ricinoleic acid (12-hydroxyoctadec-9-enoic acid). A fatty acid mixture containing ricinoleic acid, such as castor oil, may be used.
Examples of the polymerized fatty acid of the hydroxy unsaturated fatty acid include condensed fatty acid that is a dehydrative polycondensation product of hydroxy unsaturated fatty acid, and condensed fatty acid obtained by dehydratively condensing an alcoholic hydroxyl group of condensed fatty acid that is a dehydrative polycondensation product of hydroxy unsaturated fatty acid and monocarboxylic acid.
From the viewpoint of providing a water-soluble metalworking oil capable of becoming a metalworking fluid having more increased workability, the acid value of fatty acid (E) is usually 0 mgKOH/g or more, preferably 10 to 100 mgKOH/g, more preferably 20 to 90 mgKOH/g, and even more preferably 30 to 80 mgKOH/g.
The hydroxyl value of fatty acid (E) is preferably 0 to 80 mgKOH/g, more preferably 0 to 60 mgKOH/g, and even more preferably 0 to 40 mgKOH/g.
From the above viewpoint, the ratio of the acid value to the hydroxyl value of fatty acid (E) [acid value/hydroxyl value] is preferably 1.5 to 15, more preferably from 2.0 to 10, and even more preferably from 2.5 to 9.5.
The saponification value of fatty acid (E) is preferably 180 to 220 mgKOH/g, more preferably 190 to 210 mgKOH/g, and even more preferably 195 to 205 mgKOH/g.
Herein, the acid value means a value measured in accordance with JIS K 2501:2003 (indicator photometric titration method), the hydroxyl value means a value measured in accordance with JIS K 0070:1992, and the saponification value means a value measured in accordance with JIS K 2503:1996.
The water-soluble metalworking oil of one embodiment of the present invention may further contain, as necessary, other various additives other than the above components (A) to (F) as long as the effects of the present invention are not impaired.
Examples of such other various additives include anionic surfactants, cationic surfactants, extreme pressure additives, metal deactivators, emulsification aids, antibacterial agents, antifoaming agents, antioxidants, and oily agents.
One of these various additives may be used alone, or two or more of them may be used in combination.
In one embodiment of the present invention, the content of each of these various additives is suitably set according to the type and the function of each component, and is preferably 0.01 to 208 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 metalworking oil.
Examples of the anionic surfactant include polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether phosphoric acids, alkylbenzene sulfonic acids, α-olefinsulfonic acids, and salts thereof.
The acid value of anionic surfactants is preferably 20 to 250 mgKOH/g, more preferably 30 to 200 mgKOH/g, even more preferably 40 to 190 mgKOH/g, and yet more preferably 50 to 180 mgKOH/g.
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.
Examples of extreme pressure additives include chloric extreme pressure additives such as chlorinated paraffin, chlorinated fatty acid, and chlorinated fatty oil; sulfuric extreme pressure additives such as sulfurized olefin, sulfurized lard, alkyl polysulfide, and sulfurized fatty acid; and phosphoric extreme pressure additives such as phosphoric esters, phosphorous esters, thiophosphoric esters, salts thereof, phosphines, and tricresyl phosphate.
Examples of metal deactivators include benzotriazole, imidazoline, a pyrimidine derivative, a benzothiazole derivative and thiadiazole.
Examples of emulsifying aids include unsaturated fatty acid esters such as methyl oleate, ethyl oleate, and propyl oleate.
Examples of antibacterial agents include isothiazoline compounds, triazine compounds, alkylbenzimidazole compounds, and metal pyrithione salts.
Examples of antifoaming agents include silicone antifoaming agents, fluorosilicone antifoaming agents, and polyacrylates.
Examples of antioxidants include amine antioxidants such as alkylated diphenylamine, phenylnaphthylamine, and alkylated phenylnaphthylamine; and phenolic antioxidants such as 2,6-di-t-butylphenol, 4,4′-methylenebis(2,6-di-t-butylphenol), isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, and n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate.
Examples of oily agents include alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and oleyl alcohol.
The method for producing a water-soluble metalworking oil of one embodiment of the present invention is not particularly limited, and is preferably a method comprising the step of blending the above components (A) and (B), and, optionally, the components (C) to (F) and other various additives. The order of blending the respective components can be suitably set.
The metalworking fluid of the present invention is obtained by using the above metalworking oil of one embodiment of the present invention as a stock solution, and adding dilution water to the metalworking oil.
Dilution water may be any of, for example, distilled water, ion exchanged water, tap water, or water for industrial use.
The amount of dilution water added when preparing the metalworking fluid is more than 100 parts by mass based on 100 parts by mass of the total amount of components other than water of the water-soluble metalworking oil and, preferably, is suitably regulated so as to attain a desired dilute concentration.
The dilute concentration of the metalworking fluid of 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.
Herein, the “dilute concentration of the metalworking fluid” means a value calculated from the following equation:
The metalworking fluid according to a preferred embodiment of the present invention may be used in metalworking by a machine tool using an emulsion inhibitor. The metalworking fluid according to a preferred embodiment of the present invention can reduce demulsification of the metalworking fluid even when, for example, an emulsion inhibitor is mixed in the cutting oil tank, preventing deterioration of the metalworking fluid.
Examples of emulsion inhibitors include grease. The type of grease is not particularly limited, and the grease may be soap grease and urea grease. Examples of soap grease include calcium soap grease, lithium soap grease, aluminum complex grease and lithium complex grease.
The workpiece to be processed using the metalworking fluid according to an embodiment of the present invention is not particularly limited. A workpiece made of metal selected from the group consisting of aluminum, aluminum alloy, magnesium alloy, copper, copper alloy, iron, steel, carbon steel, cast iron, titanium, titanium alloy, alloy steel, nickel-based alloy, niobium alloy, tantalum alloy, molybdenum alloy, tungsten alloy, stainless steel and high manganese steel is particularly preferred.
Accordingly, the present invention can also provide [1] and [2] below:
[1] A method of use comprising applying the above metalworking fluid of one embodiment of the present invention to processing of a metal workpiece.
[2] A metalworking method comprising applying the above metalworking fluid of one embodiment of the present invention to process a metal workpiece.
The details of the workpiece set forth in [1] and [2] are as described above.
In [1] and [2], examples of processing of the workpiece include cutting, grinding, punching, polishing, spinning, drawing, and rolling.
In the method of use according to [1] and the metalworking method according to [2], the metalworking fluid is used such that the above water-soluble metalworking oil of one embodiment of the present invention is blended with dilution water and then fed to, and thus brought into contact with, the workpiece. The metalworking fluid provides lubrication between the workpiece and the work tool. Moreover, the metalworking fluid is also used to remove swarf, prevent rust of the workpiece, cool the tool and the work piece, and the like.
Next, the present invention will now be described in more detail by way of Examples, but the present invention is not limited to these Examples in any way.
Various components of the types shown in Tables 1 to 3 were added and mixed in the amounts shown in Tables 1 to 3 to prepare respective water-soluble metalworking oils. Details of each component used in the preparation of the water-soluble metalworking oils are as follows.
Compound in which A is an ethylene group, B is a methylene group, n is 2 and R is an oleyl group in the formula (b-1)
Compound in which A is an ethylene group, B is a methylene group, n is 5 and R is an oleyl group in the formula (b-1)
Compound in which A is an ethylene group, B is a methylene group, n is 8 and R is an oleyl group in the formula (b-1)
Compound in which A is an ethylene group, B is a methylene group, n is 10 and R is an oleyl group in the formula (b-1)
Compound in which A is a combination of an ethylene group and a propylene group, B is a methylene group, n is 3 and R is an isotridecyl group in the formula (b-1)
<Component (b′)>
Compound in which A is an ethylene group, B is a methylene group, n is 10 and R is an oleyl group in the formula (b-1), and which does not have a carboxyl group
Next, emulsion stability of the metalworking fluid was evaluated using the water-soluble metalworking oil prepared. First, the water-soluble metalworking oil was diluted to 20% by volume using water in which the concentration of magnesium was adjusted to 500 ppm to prepare a metalworking fluid. 2.5 g of lithium complex grease (Daphne Eponex SR made by Idemitsu Kosan Co., Ltd.) was added to 50 mL of the metalworking fluid, and the mixture was allowed to stand in a constant temperature bath at 60° C., and days before the metalworking fluid demulsified were counted. Whether the fluid demulsified or not was visually observed, and the time when the fluid was separated into the oil phase and the aqueous phase was judged as the occurrence of demulsification, and the fluids which demulsified after 2 or more days were rated as “Pass.” The results are shown in Tables 1 and 2.
Tables 1 and 2 show that the number of days before demulsification was two or more days for the water-soluble metalworking oils of Examples 1 to 15, proving that the water-soluble metalworking oils had excellent emulsion stability even when mixed with grease. By contrast, Table 3 shows that the number of days before demulsification was 1 day for all the water-soluble metalworking oils of Comparative Examples 1 to 9 which did not contain the ether carboxylic acid of the component (B), proving that the water-soluble metalworking oils of Comparative Examples 1 to 9 had poor emulsion stability than the water-soluble metalworking oils containing the component (B).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-199351 | Dec 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/045143 | 12/7/2022 | WO |
