TW201437360A - Water-based metal working oil agent - Google Patents

Abstract

A water-based metal working oil agent which comprises an amine component comprising (A) an alkanolamine represented by formula (1) and (B) an alkanolamine represented by formula (2), said water-based metal working oil agent being characterized in that the molar ratio of an amine component having a molecular weight of 90 or less to the all of the amine components (i.e., (an amine component having a molecular weight of 90 or less)/(all of the amine components)) is 0.67 or less. (In formula (1), R1's independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents 1 to 3, wherein R1's may be the same as or different from each other.) (In formula (2), R2 represents an alkyl group having 1 to 10 carbon atoms, and Z1 and Z2 independently represent an alkylene group having 2 to 8 carbon atoms).

Description

Aqueous metal processing oil Field of invention

The present invention relates to an aqueous metalworking oil agent used in metal processing such as cutting, grinding, and the like.

Background of the invention

The metal working oil used for metal working is oil-based (oily) and water-based (aqueous), and is often an aqueous type which is excellent in cooling property and wettability and has no risk of fire. The aqueous metalworking oil agent is used because it is diluted with water, and thus rust resistance is required. Such an anti-rust component is generally known to use an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine (refer to Japanese Laid-Open Patent Publication No. Hei 11-209774).

The rust preventive property of the aqueous metal working oil agent is generally better as the blending amount of the rust preventive component is larger. On the other hand, when an amine-based rust-preventing component such as an alkanolamine is added, there is a generation of malodor derived from an amine, which may adversely affect the human body or the working environment, and the type and blending amount of the relevant rust-preventing component remain to be determined. There is room for review.

Summary of invention

It is an object of the present invention to provide an aqueous metal working oil agent which is excellent in rust resistance and which has low odor, low environmental load, and little harmfulness to human body.

In order to solve the above problems, the present invention provides an aqueous metal working oil agent as described below.

[1] An aqueous metalworking oil agent characterized in that an amine component is blended with (A) an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2); The molar ratio (amine component/all amine component having a molecular weight of 90 or less) of an amine component having a molecular weight of 90 or less is 0.67 or less with respect to all the amine components.

(wherein R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. n is 1 to 3. Each of R ^{1 's} 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 and are an alkylene group having 2 to 8 carbon atoms.)

[2] An aqueous metal working oil agent according to the above-mentioned aqueous metal working oil agent, wherein n=2 or 3 in the alkanolamine formula (1) of the component (A).

[3] An aqueous metal working oil agent, wherein the alkanolamine of the component (A) contains 1-amino-2-propanol.

[4] An aqueous metalworking oil agent according to the above-mentioned aqueous metalworking oil agent, wherein the alkanolamine compound (B) of the component (B) has Z ¹ or Z ² or both of carbon atoms 2 Alkyl.

[5] An aqueous metalworking oil agent for the above aqueous metalworking oil In the agent, the alkanolamine of the component (B) contains N-methyldiethanolamine and cyclohexyldiethanolamine.

[6] An aqueous metal working oil agent in which an aliphatic carboxylic acid is blended in the above aqueous metal working oil.

[7] An aqueous metal working oil agent obtained by diluting an aqueous metal working oil agent according to any one of [1] to [6] with a mass ratio of 200 times or less.

According to the water-soluble metal working oil agent of the present invention, the amine component is obtained by blending an alkanolamine having a specific structure, and the molar ratio of the amine component having a molecular weight of 90 or less is set to a specific ratio or less, thereby providing excellent rust resistance. It is a water-based metalworking oil agent with low odor, low environmental load and low harmfulness to the human body.

Embodiment of the invention

Hereinafter, embodiments of the present invention will be described.

The aqueous metal working oil agent of the present invention is characterized in that the amine component contains (A) an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2), and is relative to all The amine component and the molar ratio of the amine component having a molecular weight of 90 or less (amine component/all amine component having a molecular weight of 90 or less) are 0.67 or less.

First, the component (A) will be described. The component (A) is particularly used as a component that exhibits rust preventive properties. In the above formula (1), R ¹ is hydrogen or an alkyl group having 1 to 3 carbon atoms. n series 1~3. Each R ¹ may be each 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 better for 2 or 3, and n is better for 2. Further, when R ¹ is a carbon number of 4 or more, it is not preferable from the viewpoint of water solubility and rust resistance to iron.

The alkanolamine of the component (A) preferably contains an amine compound having a molecular weight of 90 or less from the viewpoint of improving the rust preventive property.

Specific examples of the component (A) include, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 1-amino-2-butanol, and 2-amine. Keto-1-propanol, 3-amino-2-butanol, and the like. Among these, from the viewpoint of rust prevention of iron, 1-amino-2-propanol or 2-amino-2-methyl-1-propanol is preferred.

In the present invention, the component (A) may be used singly or in combination of two or more.

Next, the alkanolamine of the component (B) will be described. The component (B) contributes to the improvement of rust resistance and the reduction of odor.

The component (B) is represented by the above formula (2), and R ² in the formula is an alkyl group having 1 to 10 carbon atoms. When R ^{2 is an} acyclic structure, it is preferred that the carbon number is from 1 to 4, and more preferably, the carbon number is 1. When the carbon number of R ² is 11 or more, the water solubility or the rust preventive property of the component (B) is lowered, which is not preferable. And, Z ^1, Z ² are each independently an alkylene group having a carbon number of 2 to 8. Z ¹ or Z ² or both are preferably a C 2 alkylene group. When at least one of Z ¹ and Z ² has a carbon number of 1, formaldehyde is formed and decomposed, which is not desirable in the environment. Further, when at least one of Z ¹ and Z ² has a carbon number of 9 or more, the water solubility of the component (B) is lowered, which is not preferable.

Specific examples of the component (B) include N-methyldiethanolamine, N-ethyldiethanolamine, cyclohexyldiethanolamine, N-n-propyldiethanolamine, N-isopropyldiethanolamine, and N-positive Butyldiethanolamine, N-isobutyldiethanolamine, and N-t-butyldiethanolamine. Among these, N-methyldiethanolamine and cyclohexyldiethanolamine are used in combination.

In the present invention, the component (B) may be used singly or in combination of two or more.

When the same blending amount of the amine component is used as the rust preventive component used for the aqueous metalworking oil agent, the rust resistance of the amine component having a smaller molecular weight is better. The reason is that the amine component having a small molecular weight can obtain the same rust preventive property as the amine component having a large molecular weight in a small 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 a high volatility, and an increase in the amount of the blend in the oil agent causes an odor to become strong. Therefore, it is conventionally difficult to achieve both low odor and rust resistance by using only the blending amount of the rust preventive component.

In the aqueous metalworking oil of the present invention, the molar ratio of the amine component having a molecular weight of 90 or less (the amine component of the molecular weight of 90 or less / the total amine component) is 0.67 or less, preferably the molar ratio is 0.6 or less, relative to the total amine component. 0.4 or more, more preferably a molar ratio of 0.55 or less and 0.5 or more. When the molar ratio exceeds 0.67, the odor of the aqueous metal working oil agent becomes strong, which adversely affects the human body and the working environment, and is not preferable.

The water-soluble metal working oil agent of the present invention is preferably prepared into a high-concentration stock solution from the viewpoint of workability, and is further diluted by a user into a metal working oil by water.

The solvent constituting the stock solution is preferably water, but may be mineral oil or synthetic oil.

As for the mineral oil and the synthetic oil used as the solvent in the preparation of the raw liquid, it is only required to be used as a base oil which is generally used as a metal working oil, and the rest is not particularly limited, but the dynamic viscosity at 40 ° C is preferably Those in the range of 1~50mm ² /s, and better in the range of 2~30mm ² /s. If the dynamic viscosity of the base oil is too high, the oil will adhere to the workpiece and the amount of entrainment removal will increase, which may be uneconomical, so it is not ideal. On the other hand, if it is too low, it may cause haze and it may cause deterioration of workability, which is not ideal. Further, the flow point of the low-temperature fluidity index of the base oil is not particularly limited, but is preferably -10 ° C or lower.

Such mineral oils and synthetic oils have various substances, and may be appropriately selected as long as they are used together.

The mineral oil may, for example, be a distillation oil obtained by subjecting a paraffinic base crude oil, an intermediate base crude oil or a naphthenic crude oil to atmospheric distillation, or a vacuum distillation of atmospheric residue; or A refined oil obtained by performing purification according to a usual method, for example, a solvent refined oil, a hydrogenated refined oil, a dewaxed oil, a clay treated oil, or the like.

On the other hand, the synthetic oil may, for example, be a poly-α-olefin, an α-olefin copolymer, a polybutene, an alkylbenzene, a polyol ester, a dibasic acid ester, a polyoxyalkylene glycol, a polyoxidation. Alkyl glycol esters, polyoxyalkylene glycol ethers, polyoxygenated oils, and the like. The synthetic oil is preferably a poly-α-olefin or an α-olefin copolymer. These base oils may be used alone or in combination of two or more kinds, and mineral oil and synthetic oil may be used in combination.

The preferred ratio of the component (A) in the stock solution is 1 to 20% by mass based on the total amount of the stock solution, preferably 5 to 14% by mass, and more preferably 9 to 13% by mass. When the proportion of the component (A) exceeds 20% by mass, the odor property is improved, which is not preferable.

The preferred ratio of the component (B) in the stock solution is 5 to 30% by mass based on the total amount of the stock solution, preferably 10 to 30% by mass, and more preferably 22 to 29% by mass. When the ratio of the component (B) is less than 5% by mass, the odor property is improved, which is not preferable. Further, even if the proportion of the component (B) exceeds 30% by mass, the rust resistance of iron does not greatly increase, which in turn leads to high cost, and is not ideal from the viewpoint of economy.

When the aqueous metal working oil agent of the present invention is used, it is suitably diluted with water in an amount of 200 times or less by mass with respect to the above-mentioned stock solution. The preferred dilution ratio is 10 to 100 times, more preferably 20 to 50 times. If the dilution ratio exceeds 200 times, the rust prevention property is insufficient, which is not ideal.

Further, in the aqueous metal working oil agent of the present invention, various known additives may be appropriately blended insofar as the object of the present invention is not impaired. For example: bactericides, aliphatic carboxylic acids, metal passivators (corrosion inhibitors), extreme pressure agents, oily agents, surfactants, defoamers, and the like.

The fungicide may, for example, be 2-pyridylsulfur-1-oxide. Specific examples thereof include 2-pyridylthio-1-oxide, bis(2-pyridinedithio-1-oxide) zinc, and bis(2-thioether pyridin-1-ol) copper. Among them, from the viewpoint of having a low concentration and having an effect on a wide range of general bacteria and molds, sodium 2-pyridylthio-1-oxide is particularly preferred. From the viewpoint of the blending effect, the blending amount of the sterilizing agent is blended in the stock solution to the extent of 0.01 to 5% by mass based on the final dilution oil.

The aliphatic carboxylic acid is added to further improve the machinability and grindability of the oil agent, and to further improve the rust preventive property. For example, a carboxylic acid having a carbon number of 6 to 60 and/or a dicarboxylic acid. Specifically, for example, hexanoic acid, octanoic acid, citric acid, lauric acid, and stearic acid are mentioned. Acid, oleic acid, ricinoleic acid, hydroxy fatty acid (such as ricinoleic acid, 12-hydroxystearic acid, etc.), arachidic acid, eucalyptus acid, melamine, isonic acid (3,5,5-trimethyl) Benzoic acid), neodecanoic acid, isostearic acid, soybean oil fatty acid extracted from oil, coconut oil fatty acid, rapeseed oil fatty acid, naphthenic acid extracted from petroleum, adipic acid, decanedioic acid And dodecanedioic acid, mono- or dihydroxyarachiic acid, and the like; and dimers, trimers, and the like of oleic acid, ricinoleic acid, ricinoleic acid, 12-hydroxystearic acid, and the like, synthetic fatty acids. From the viewpoint of the defoaming property of the oil agent and the viewpoint of hard water stability, a more preferred monocarboxylic acid is a hexanoic acid having a carbon number of 8 to 10, a citric acid, a citric acid, an isonic acid, a neodecanoic acid, and a dicarboxylic acid. The acid may, for example, be azelaic acid, undecanedioic acid, decanedioic acid or dodecanedioic acid. From the viewpoint of the blending effect, the blending amount of the carboxylic acid is blended in the stock solution to the extent of 0.1 to 1.5% by mass based on the final dilution oil.

The aliphatic carboxylic acid and the amine component form an aliphatic carboxylic acid amine salt, and have an effect of improving workability, improving emulsification stability by an emulsifier action, and further improving rust resistance.

In addition, the appropriate ratio of the total of the aliphatic carboxylic acid component and the amine component in the stock solution is 40 to 60% by mass or less, preferably 47 to 55% by mass, and more preferably 50 to 53%, based on the total amount of the original liquid. quality%.

The metal deactivator may, for example, be a benzotriazole, a benzotriazole derivative, an imidazoline, a pyrimidine derivative, a thiadiazole, or a thiadiazole. One type of these may be used alone or two or more types may be used in combination. From the viewpoint of the blending effect, the blending amount of the metal deactivator is blended in the stock solution to the extent of 0.01 to 3% by mass based on the final dilution oil.

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 may be used alone or in combination of two or more. The extreme pressure agent may be one which contains a sulfur atom and/or a phosphorus atom in the molecule and which can exhibit load resistance and abrasion resistance. The extreme pressure agent containing sulfur in the molecule may, for example, be a sulfurized fat, a sulfurized fatty acid, a sulfurized ester, a sulfurized olefin, a dihydrocarbyl polysulfide, a thiadiazole compound, an alkylthioamine formamidine compound, or the like. A compound, a thioterpene compound, a dialkyl thiodipropionate compound or the like. From the viewpoint of the blending effect, the blending amount of the extreme pressure agents is blended in the stock solution to a degree of 0.05 to 0.5% by mass based on the final dilution oil.

The oily agent may, for example, be a fatty acid compound such as an aliphatic alcohol, a fatty acid or a fatty acid metal salt; an ester compound such as a polyol ester, a sorbitan ester or a glyceride; an amine compound such as an aliphatic amine or the like. From the viewpoint of the blending effect, the blending amount of the oily agents is blended in the stock solution to a degree of 0.2 to 2% by mass based on the final dilution oil.

Examples of the antifoaming agent include methyl polyoxyphthalic acid oil, fluorinated polyoxygenated oil, and polyacrylate. From the viewpoint of the blending effect, the blending amount of the antifoaming agent is blended in the stock solution to the extent of 0.004 to 0.02% by mass based on the final dilution oil.

The surfactant is not particularly limited, and a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant can be used, and these surfactants can also be used in combination. As a suitable example, a nonionic surfactant, an anionic surfactant, or a mixture of such surfactants may be mentioned.

The nonionic surfactant may, for example, be a polyoxyalkylene glycol or a mono- or diether compound thereof; or a polyoxyalkylene-based surfactant such as glycerin or an alkylene oxide adduct or an ether compound thereof; An ester of a carboxylic acid and an alcohol, an alkylene oxide adduct of an alkylamine, and the like.

The aforementioned anionic surfactant may, for example, be a carboxylic acid such as carbon. a saturated or unsaturated fatty acid, a hydroxy fatty acid, etc., or a sulfonic acid, a salt with an amine or a metal; a polycondensate of a hydroxy fatty acid such as ricinoleic acid; a salt with a fatty acid or an amine or a metal thereof; a phosphate salt such as a sulfate salt such as sodium sulfosuccinate; a polymerized polymer surfactant partially saponified by an olefin such as styrene and a maleic anhydride copolymer, or naphthalenesulfonic acid-formaldehyde A condensation type polymer surfactant or the like.

The water-based metal processing oil agent of the present invention is suitable for various metal processing such as cutting, grinding, and grinding, drawing, drawing, rolling, etc., as described above, and appropriately diluted in water to have an appropriate concentration for use. field. Then, the aqueous metal working oil agent of the present invention has an excellent property against rust prevention of metal products, and is low in odor, so that it is less harmful to the environment and the human body.

Example

Next, the present invention will be further described in more detail by way of examples, but the invention is not limited by the examples.

[Examples 1 to 4, Comparative Examples 1 to 3]

The aqueous metalworking oil agent (stock solution) was prepared by the blending prescription shown in Table 1, and after dilution with water to a predetermined concentration, the following characteristics were evaluated. The evaluation results are shown in Table 1.

(1) Rust prevention (according to DIN 51360-02-A)

A dilution liquid having a stock solution concentration of 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, and 2.0% by mass was diluted with tap water to carry out a rust prevention test (room temperature, 2 hours), and the lowest concentration at which the degree of rust was 0 was set. Anti-rust limit concentration (% by mass).

(2) odor

Diluted to 10.0% by mass of the stock solution by ion-exchanged water to prepare water-soluble liquid. 100 mL of this aqueous solution was placed in a 300 mL Erlenmeyer flask, sealed, and heated at 100 ° C for 3 minutes. The odor measurement (strength) was performed using the odor sensor (manufactured by Karumoa Co., Ltd., e-nose mobile) for the heated aqueous solution. In addition, the numerical value is an odor index (relative value), and the intensity is an odor intensity, and the larger the coefficient value in terms of strength, the stronger the odor is.

[Table 1] 1) Other components: (30% by mass aqueous solution of polyethylenimine (molecular weight 1000): 0.3% by mass, 35 mass% aqueous solution of benzisothiazoline: 0.2% by mass, sodium pyrithione: 0.2 Mass%, polyfluorene defoamer: 0.2% by mass)

As is apparent from Table 1, the aqueous metal working oil agents of the present invention of Examples 1 to 4 were excellent in rust resistance and low in odor. On the other hand, in the aqueous metal working oil used in Comparative Examples 1 to 3, since the essential components of the present invention are lacking, the rust resistance is excellent, but the odor intensity is high.

Claims (7)

An aqueous metalworking oil agent characterized in that an amine component (A) is blended with an alkanolamine represented by the following formula (1) and (B) an alkanolamine represented by the following formula (2), and is relatively The molar ratio (amine component/all amine component having a molecular weight of 90 or less) of the amine component having a molecular weight of 90 or less to the total amine component is 0.67 or less; (wherein 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) (wherein R ² is an alkyl group having 1 to 10 carbon atoms; and Z ¹ and Z ² are each independently a C 2 to 8 alkyl group). The aqueous metalworking oil according to claim 1, wherein the alkanolamine of the above component (A) is n = 2 or 3 in the formula (1). The aqueous metalworking oil according to claim 1, wherein the alkanolamine of the aforementioned component (A) contains 1-amino-2-propanol. The requested item 1 of aqueous metalworking fluid, wherein the alkanol amine of formula (B) component (2) Z ¹ or Z ^2, or both, is an alkylene group having a carbon number of 2. The aqueous metalworking oil according to claim 1, wherein the alkanolamine of the component (B) contains N-methyldiethanolamine and cyclohexyldiethanolamine. An aqueous metalworking oil agent according to claim 1 which is blended with an aliphatic carboxylic acid. An aqueous metalworking oil agent obtained by diluting an aqueous metal working oil agent according to any one of claims 1 to 6 with a mass ratio of 200 times or less.