JP2014159527A - Aqueous metal processing oil agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous metal processing oil agent having excellent rust preventability, a low odor, a low environmental load, and reduced toxicity to the human body.SOLUTION: Provided is an aqueous metal processing oil agent obtained by blending (A) alkanolamine represented by formula (1) and (B) alkanolamine represented by formula (2) as amine components. A molar ratio of an amine component having a molecular weight of 90 or lower to all the amine components (the amine component having a molecular weight of 90 or lower/all the amine components) is 0.67 or lower.

Description

  The present invention relates to an aqueous metalworking fluid used for metalworking such as cutting and grinding.

  Metalworking fluids used in metalworking are classified into oil-based (oil-based) and water-based (water-based), but water-based types that are excellent in cooling and infiltration properties and do not pose a fire hazard are frequently used. The aqueous metalworking fluid is required to have rust prevention properties because it is diluted with water and used. It is generally known to use alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine as such a rust preventive component (see Patent Document 1).

Japanese Patent Laid-Open No. 11-209774

  The rust prevention property of the aqueous metalworking fluid generally becomes better as the blending amount of the rust prevention component increases. On the other hand, mixing amine-based rust preventive ingredients such as alkanolamines may cause amine-derived odors and adversely affect the human body and work environment. There is room for.

  Therefore, an object of the present invention is to provide an aqueous metalworking fluid that is excellent in rust prevention, exhibits low odor, has a low environmental load, and has little harmfulness to the human body.

In order to solve the above-mentioned problems, the present invention provides the following aqueous metalworking fluid.
[1] As an amine component, (A) an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2) are blended, and the molecular weight for all amine components is An aqueous metalworking fluid characterized by having a molar ratio of amine component of 90 or less (amine component having a molecular weight of 90 or less / all amine components) of 0.67 or less.

(In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. N is 1 to 3. Each R ¹ may be the same or different.)

(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms. Z ¹ and Z ² are each independently an alkylene group having 2 to 8 carbon atoms.)
[2] The aqueous metalworking fluid according to [1] above, wherein the alkanolamine of the component (A) is n = 2 or 3 in the formula (1) Oil.
[3] The aqueous metalworking fluid according to [1] or [2] above, wherein the alkanolamine of the component (A) contains 1-amino-2-propanol .
[4] The aqueous metalworking fluid according to the above [1], wherein the alkanolamine of the component (B) is an alkylene group in which Z ¹ or Z ² or both of the formula (2) are 2 carbon atoms An aqueous metalworking fluid characterized by
[5] The aqueous metalworking fluid according to any one of [1] to [4] above, wherein the alkanolamine of the component (B) contains N-methyldiethanolamine and cyclohexyldiethanolamine. A feature of water-based metalworking fluid.
[6] The aqueous metalworking fluid according to any one of [1] to [5] above, wherein an aliphatic carboxylic acid is blended.
[7] An aqueous metalworking fluid obtained by diluting the aqueous metalworking fluid according to any one of [1] to [6] above with water at a mass ratio of 200 times or less.

  According to the water-soluble metalworking fluid of the present invention, an alkanolamine having a specific structure is blended as an amine component, and the molar ratio of the amine component having a molecular weight of 90 or less is set to a specific ratio or less. It is possible to provide an aqueous metalworking fluid that is excellent in properties, exhibits low odor, has a low environmental impact, and is less harmful to the human body.

Hereinafter, embodiments of the present invention will be described.
The aqueous metalworking fluid of the present invention contains, as amine components, (A) an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2), and all amine components The molar ratio of the amine component with a molecular weight of 90 or less (amine component with a molecular weight of 90 or less / all amine components) is 0.67 or less.

First, the component (A) will be described. The component (A) is particularly used as a component that exhibits rust prevention properties. In the above formula (1), R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. n is 1-3. Each R ¹ may be the same or different. Here, when n is 4 or more, the water solubility of the component (A) is lowered, which is not preferable. n is more preferably 2 or 3, and n is most preferably 2. Further, if any ^one of R ¹ has 4 or more carbon atoms, it is not preferable in terms of water solubility and rust prevention against iron.
The component (A) alkanolamine preferably contains an amine compound having a molecular weight of 90 or less from the viewpoint of improving rust prevention.
Specific examples of the component (A) include, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 1-amino-2-butanol, 2-amino-1-propanol, 3- Examples include amino-2-butanol. Among these, 1-amino-2-propanol and 2-amino-2-methyl-1-propanol are preferable from the viewpoint of rust prevention against iron.
In the present invention, the component (A) may be used singly or in combination of two or more.

Next, the alkanolamine as the component (B) will be described. The component (B) contributes to improvement of rust prevention and reduction of odor.
The component (B) is represented by the above formula (2), in which R ² is an alkyl group having 1 to 10 carbon atoms. When R ² is an acyclic structure, it is preferably 1 to 4 carbon atoms, and more preferably 1 carbon atom. When the carbon number of R ² is 11 or more, the water solubility and rust prevention properties of the component (B) are lowered, which is not preferable. Z ¹ and Z ² are each independently an alkylene group having 2 to 8 carbon atoms. Z ¹ or Z ² or both are preferably an alkylene group having 2 carbon atoms. If at least one of Z ¹ and Z ² has 1 carbon, it is decomposed as formaldehyde, which is not preferable in terms of environment. Further, if at least one of Z ¹ and Z ² has 9 or more carbon atoms, the water solubility of the component (B) decreases, which is not preferable.
Specific examples of the component (B) include N-methyldiethanolamine, N-ethyldiethanolamine, cyclohexyldiethanolamine, Nn-propyldiethanolamine, Ni-propyldiethanolamine, Nn-butyldiethanolamine, Ni-butyldiethanolamine. , And Nt-butyldiethanolamine. Among these, it is particularly preferable to use N-methyldiethanolamine and cyclohexyldiethanolamine in combination.
In the present invention, the component (B) may be used singly or in combination of two or more.

As the rust preventive component used in the aqueous metalworking fluid, when the same blending amount of the amine component is used, the smaller the molecular weight, the better the rust preventive property. This means that an amine component having a low molecular weight can obtain the same degree of rust prevention as an amine component having a high molecular weight with a smaller blending amount. However, on the other hand, an amine component having a small molecular weight, particularly an amine component having a molecular weight of 90 or less has high volatility, and the odor becomes stronger as the blending amount in the oil increases. Therefore, conventionally, it has been difficult to achieve both low odor properties and rust prevention properties only by the blending amount of the rust prevention components.
In the aqueous metalworking fluid of the present invention, the molar ratio of the amine component having a molecular weight of 90 or less to all the amine components (amine component having a molecular weight of 90 or less / all amine components) is 0.67 or less, and the preferred molar ratio is It is 0.6 or less and 0.4 or more, and a more preferable molar ratio is 0.55 or less and 0.5 or more. When the molar ratio exceeds 0.67, the odor of the aqueous metalworking fluid is strong, which is not preferable because it adversely affects the human body and working environment.

The water-soluble metalworking fluid of the present invention is preferably prepared as a high-concentration stock solution from the viewpoint of handling properties, and the user appropriately dilutes with water and uses it as a metalworking oil.
As the solvent constituting the stock solution, water is most preferable, but mineral oil or synthetic oil may be used.

The mineral oil or synthetic oil used as the solvent for preparing the stock solution is not particularly limited as long as it is generally used as a base oil for metalworking oil, but the kinematic viscosity at 40 ° C. is 1 to 50 mm ^2. The thing in the range of / s is preferable, and the thing in the range of 2-30 mm < ² > / s is more preferable. When the kinematic viscosity of the base oil is too high, the amount of the oil agent that adheres to the workpiece and is carried away increases, which is not preferable because it may not be economical. On the other hand, if it is too low, workability may be deteriorated due to generation of mist, which is not preferable. The pour point, which is an index of low temperature fluidity of the base oil, is not particularly limited, but is preferably −10 ° C. or lower.
There are various kinds of such mineral oils and synthetic oils, and may be appropriately selected according to the use.

As mineral oil, for example, a distillate obtained by subjecting paraffin-based crude oil, intermediate-based crude oil or naphthenic-based crude oil to atmospheric distillation, or distilling the residual oil of atmospheric distillation under reduced pressure, or using this as a conventional method Therefore, refined oils obtained by refining, for example, solvent refined oil, hydrogenated refined oil, dewaxed oil, and clay-treated oil can be exemplified.
On the other hand, as synthetic oil, for example, poly α-olefin, α-olefin copolymer, polybutene, alkylbenzene, polyol ester, dibasic acid ester, polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol ether, silicone oil And so on. Among the synthetic oils, poly α-olefins and α-olefin copolymers are preferable. These base oils can be used alone or in combination of two or more kinds, and mineral oil and synthetic oil may be used in combination.

A preferable ratio of the component (A) in the stock solution is 1 to 20% by mass based on the total amount of the stock solution, a more preferable ratio is 5 to 14% by mass, and a further preferable ratio is 9 to 13% by mass. When the proportion of the component (A) exceeds 20% by mass, the odor is increased, which is not preferable.
A preferable ratio of the component (B) in the stock solution is 5 to 30% by mass based on the total amount of the stock solution, a more preferable ratio is 10 to 30% by mass, and a further preferable ratio is 22 to 29% by mass. If the ratio of the component (B) is less than 5% by mass, the odor is increased, which is not preferable. Moreover, even if the ratio of (B) component exceeds 30 mass%, the antirust property with respect to iron will not improve any more, it will become high cost and it is unpreferable also from an economical viewpoint.

  When using the aqueous metalworking fluid of the present invention, it is preferable to dilute with 200 times or less of water by mass ratio with respect to the above-mentioned stock solution. A more preferable dilution ratio is 10 to 100 times, and further preferably 20 to 50 times. When the dilution ratio exceeds 200 times, the rust prevention property becomes insufficient, which is not preferable.

  Moreover, various well-known additives can be suitably mix | blended with the aqueous metalworking fluid of this invention in the range which does not inhibit the objective of this invention. For example, bactericides, aliphatic carboxylic acids, metal deactivators (corrosion resistance), extreme pressure agents, oil agents, surfactants, antifoaming agents, and the like.

  As a bactericidal agent, 2-pyridylthio-1-oxide salt is mentioned, for example. Specific examples include sodium 2-pyridylthio-1-oxide, bis (2-pyridyldithio-1-oxide) zinc, and bis (2-sulfidepyridine-1-olato) copper. Among these, 2-pyridylthio-1-oxide sodium is particularly preferable in that it is effective for a wide range of general bacteria and molds at a low concentration. The blending amount of these bactericides is blended in the stock solution so as to be about 0.01 to 5% by mass based on the final diluted oil from the viewpoint of blending effect.

Aliphatic carboxylic acid is added in order to further improve the machinability and grindability of the oil and to further improve the rust prevention. Examples thereof include carboxylic acids having 6 to 60 carbon atoms and / or dicarboxylic acids. Specifically, caproic acid, caprylic acid, nonanoic acid, lauric acid, stearic acid, oleic acid, ricinoleic acid, hydroxy fatty acids (eg, ricinoleic acid, 12-hydroxystearic acid, etc.), arachidic acid, behenic acid, melicic acid , Isononanoic acid (3,5,5-trimethylhexanoic acid), neodecanoic acid, isostearic acid, soybean oil fatty acid extracted from oil and fat, coconut oil fatty acid, rapeseed oil fatty acid, naphthenic acid extracted from petroleum, adipic acid, sebacine Synthetic fatty acids such as acids (decanedioic acid), dodecanedioic acid, mono- or dihydroxyarachidic acid, and dimers and trimers such as oleic acid, ricinoleic acid, ricinoleic acid, and 12-hydroxystearic acid. As a particularly preferred monocarboxylic acid, caproic acid, nonanoic acid, decanoic acid, isononanoic acid and neodecanoic acid having 8 to 10 carbon atoms are used as the dicarboxylic acid from the viewpoint of defoaming properties of the oil and the stability of hard water. Nonanedioic acid, undecanedioic acid, sebacic acid (decanedioic acid), dodecanedioic acid and the like can be mentioned. The blending amount of these carboxylic acids is blended in the stock solution so as to be about 0.1 to 1.5% by mass based on the final diluent oil from the viewpoint of blending effects.
The aliphatic carboxylic acid forms an amine component and an aliphatic carboxylic acid amine salt, and has an effect of improving processability, or acting as an emulsifier to improve emulsion stability and further improve rust prevention.

  Moreover, the preferable ratio of the sum total of the aliphatic carboxylic acid component and the amine component in the stock solution is 40 to 60% by mass or less based on the total amount of the stock solution, more preferably 47 to 55% by mass, and further preferably 50%. It is -53 mass%.

  Examples of the metal deactivator include benzotriazole, benzotriazole derivatives, imidazoline, pyrimidine derivatives, thiadiazole, and thiadiazole. One of these may be used alone, or two or more may be used in combination. The compounding quantity of a metal deactivator is mix | blended with an undiluted | stock solution so that it may become about 0.01-3 mass% on the final dilution oil standard from the point of a mixing effect.

  Examples of the extreme pressure agent include a sulfur-based extreme pressure agent, a phosphorus-based extreme pressure agent, an extreme pressure agent containing sulfur and a metal, and an extreme pressure agent containing phosphorus and a metal. These extreme pressure agents can be used singly or in combination of two or more. Any extreme pressure agent may be used as long as it contains a sulfur atom and / or a phosphorus atom in the molecule and can exhibit load resistance and wear resistance. Examples of extreme pressure agents containing sulfur in the molecule include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiadiazole compounds, alkylthiocarbamoyl compounds, triazine compounds, thioterpene compounds, dialkylthiodipropionate compounds, etc. Can be mentioned. The blending amount of these extreme pressure agents is blended in the stock solution so as to be about 0.05 to 0.5% by mass based on the final diluent oil from the viewpoint of blending effect.

  Examples of the oily agent include fatty alcohols, fatty acid compounds such as fatty acids and fatty acid metal salts, ester compounds such as polyol esters, sorbitan esters, and glycerides, and amine compounds such as aliphatic amines. The blending amount of these oily agents is blended in the stock solution so as to be about 0.2 to 2% by mass based on the final diluted oil from the viewpoint of blending effect.

  Examples of the antifoaming agent include methyl silicone oil, fluorosilicone oil, and polyacrylate. The blending amount of these antifoaming agents is blended in the stock solution so as to be about 0.004 to 0.02% by mass based on the final diluent oil from the viewpoint of blending effect.

There are no particular limitations on the surfactant, and nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and these surfactants can be used in combination. it can. Suitable examples include, for example, nonionic surfactants, anionic surfactants, or mixtures of these surfactants.
Examples of the nonionic surfactant include polyoxyalkylene glycol or a mono-, diether compound thereof, a polyoxyalkylene surfactant such as glycerin or an alkylene oxide adduct thereof, or an ether compound, an ester of a carboxylic acid and an alcohol, Examples include alkylene oxide adducts of alkylamines.
Examples of the anionic surfactant include carboxylic acids (for example, saturated or unsaturated fatty acids having 7 to 22 carbon atoms, hydroxy fatty acids, etc.) or salts of sulfonic acids with amines or metals, and polycondensation of hydroxy fatty acids such as ricinoleic acid. System of partially saponified ester of fatty acid and fatty acid ester or amine or metal salt thereof, phosphate ester salt such as sodium dialkylsulfosuccinate, sulfate copolymer such as styrene, olefin and maleic anhydride copolymer, etc. Examples thereof include polymer surfactants and naphthalenesulfonic acid-formalin condensation type polymer surfactants.

  As described above, the aqueous metalworking fluid of the present invention is appropriately diluted in water so as to have an appropriate concentration according to the purpose of use, and includes various processes such as cutting, grinding, polishing, drawing, drawing, rolling, etc. It can be suitably used in the metal processing field. And since the aqueous | water-based metalworking fluid of this invention has the characteristic which was excellent in the rust prevention effect with respect to a metal product, since it shows low odor property, there is little harmfulness to an environment and a human body.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[Examples 1-4, Comparative Examples 1-3]
An aqueous metalworking fluid (stock solution) was prepared according to the formulation shown in Table 1, diluted with water to a predetermined concentration, and then evaluated for the following characteristics. The evaluation results are shown in Table 1.
(1) Rust prevention (conforms to DIN 51360-02-A)
Rust prevention test using diluted solution diluted with tap water so that the concentration of the stock solution is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 and 2.0% by mass (Room temperature, 2 hours) was carried out, and the minimum concentration at which the degree of rust was 0 was defined as the rust prevention limit concentration (mass%).

(2) Odoriness An aqueous solution was prepared by diluting with ion-exchanged water so that the concentration of the stock solution was 10.0% by mass. 100 mL of this aqueous solution was placed in a 300 mL Erlenmeyer flask, sealed, and heated at 100 ° C. for 3 minutes. About the aqueous solution after a heating, the odor measurement (strength) was performed using the odor sensor (the Calmore company make, e-nose mobile). In addition, a numerical value is an odor index | exponent (relative value), intensity | strength represents the intensity | strength of odor, and the one where a numerical value is large shows that an odor is strong.

1) Other components: (Polyethyleneimine (molecular weight 1000) 30% by weight aqueous solution: 0.3% by weight, benzoisothiazoline 35% by weight aqueous solution: 0.2% by weight, pyrithione sodium: 0.2% by weight, silicone-based Foaming agent: 0.2% by mass)

  As is clear from Table 1, all of the aqueous metalworking fluids of the present invention according to Examples 1 to 4 were excellent in rust prevention and exhibited low odor. On the other hand, since the aqueous metalworking fluid used in Comparative Examples 1 to 3 lacks the essential components in the present invention, the rust resistance is excellent, but the odor strength is high.

  The aqueous metalworking fluid of the present invention can be used in metalworking fields such as cutting and grinding.

Claims (7)

As an amine component, (A) an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2) are blended,
An aqueous metalworking fluid characterized by having a molar ratio of an amine component having a molecular weight of 90 or less to all amine components (amine component having a molecular weight of 90 or less / all amine components) of 0.67 or less.

(In the formula, R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. N is 1 to 3. Each R ¹ may be the same or different.)

(In the formula, R ² is an alkyl group having 1 to 10 carbon atoms. Z ¹ and Z ² are each independently an alkylene group having 2 to 8 carbon atoms.) The aqueous metalworking fluid according to claim 1,
The aqueous metalworking fluid, wherein the alkanolamine of the component (A) is n = 2 or 3 in the formula (1). An aqueous metalworking fluid according to claim 1 or claim 2,
The aqueous metalworking fluid characterized in that the alkanolamine of the component (A) contains 1-amino-2-propanol. The aqueous metalworking fluid according to claim 1,
The aqueous metalworking fluid characterized in that the alkanolamine of the component (B) is an alkylene group in which Z ¹ or Z ² or both of the formula (2) has 2 carbon atoms. The aqueous metalworking fluid according to any one of claims 1 to 4, wherein
The alkanolamine as the component (B) contains N-methyldiethanolamine and cyclohexyldiethanolamine. The aqueous metalworking fluid according to any one of claims 1 to 5, wherein an aliphatic carboxylic acid is blended. An aqueous metalworking fluid prepared by diluting the aqueous metalworking fluid according to any one of claims 1 to 6 with water at a mass ratio of 200 times or less.