阅读说明：本技术 清洗油组合物、其制造方法、以及除水清洗方法 (Cleaning oil composition, method for producing same, and water removal cleaning method ) 是由 田卷匡基 长濑直树 于 2019-08-07 设计创作，主要内容包括：需要分离性和低温稳定性优异的清洗油组合物。清洗油组合物,其包含以下的成分：(A)支链脂肪族单羧酸、(B)直链脂肪族单羧酸、(C)不含氧原子的单胺、(D)烃系溶剂,前述成分(B)相对于前述成分(A)的摩尔比［B/A］为1.4以下。(There is a need for a cleaning oil composition having excellent separability and low-temperature stability. A cleaning oil composition comprising the following ingredients: (A) a branched aliphatic monocarboxylic acid, (B) a straight aliphatic monocarboxylic acid, (C) an oxygen-free monoamine, and (D) a hydrocarbon solvent, wherein the molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.)

1. A cleaning oil composition comprising the following ingredients:

(A) branched aliphatic monocarboxylic acids,

(B) A straight-chain aliphatic monocarboxylic acid,

(C) Monoamines not containing oxygen atom, and

(D) hydrocarbon solvent

The molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

2. The composition according to claim 1, wherein the component (A) is a branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms.

3. The composition according to claim 1 or 2, wherein the component (B) is a linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms.

4. The composition according to any one of claims 1 to 3, wherein the component (C) is an aliphatic monoamine having 6 to 10 carbon atoms.

5. The composition according to any one of claims 1 to 4, wherein the molar ratio [ B/A ] of the component (B) to the component (A) is 0.1 or more and 1.4 or less.

6. The composition according to any one of claims 1 to 5, wherein the molar ratio [ (B + A)/C ] of the total of the component (A) and the component (B) to the component (C) is 0.1 or more and 3 or less.

7. The composition according to any one of claims 1 to 6, wherein the total content of the component (A), the component (B), the component (C) and the component (D) is 80% by mass or more relative to the total mass of the composition.

8. The composition according to any one of claims 1 to 7, wherein the content of the halogen-based solvent is 1% by mass or less with respect to the total mass of the composition.

9. The composition according to any one of claims 1 to 8, wherein the component (D) is a compound obtained by reacting a compound having a structure as defined in JIS K2254: 1998 in a distillation test by a normal pressure method, an isoparaffin solvent having a 100% by volume distillation temperature in the range of 165 to 270 ℃.

10. The composition according to any one of claims 1 to 9, comprising, relative to the total mass of the composition:

0.01 to 10 mass% of the component (A),

0.01 to 10 mass% of the component (B),

0.1 to 10 mass% of the component (C), and

70 to 99 mass% of the component (D).

11. The composition according to any one of claims 1 to 10, which is used for cleaning an object to be cleaned having moisture adhered to a surface thereof, wherein the object to be cleaned is a metal material.

12. A method of making a cleaning oil composition comprising mixing:

(A) branched aliphatic monocarboxylic acids,

(B) A straight-chain aliphatic monocarboxylic acid,

(C) Monoamines not containing oxygen atom, and

(D) hydrocarbon solvent

The molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

13. A method for cleaning an object to be cleaned having moisture adhered to a surface thereof by removing water, which comprises cleaning the object to be cleaned with the composition according to any one of claims 1 to 10.

Technical Field

The invention relates to a cleaning oil composition, a method for producing the same, and a water removal cleaning method.

Background

Processing oils (for example, cutting oil, grinding oil, press oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, processing oil, grease, and wax) are used in metal processing such as cutting, rolling, drawing, pressing, and forging. The processing oil includes an oil system and a water system, and among them, the water system processing oil is widely used mainly for cutting, polishing, and the like which require high cooling performance. After the processing, the aqueous processing oil adheres to the surface of the processing material. Since the aqueous processing oil adhering to the surface causes modification, rusting, discoloration, and the like, the processing material is usually washed after processing to remove the aqueous processing oil adhering to the surface of the material.

In cleaning an object to be cleaned to which an aqueous process oil has adhered, generally, depending on the application, an aqueous cleaning agent, a quasi-aqueous cleaning agent in which a water-soluble solvent is mixed with an aqueous cleaning agent, an alcohol cleaning agent such as isopropyl alcohol, a glycol ether cleaning agent, a halogen cleaning agent, a hydrocarbon cleaning agent in which a surfactant is mixed with a hydrocarbon solvent, and the like are used.

The halogen-based cleaning agent has a strong oil-dissolving ability, is nonflammable, can be recycled, and has excellent cleaning properties. For example, patent document 1 discloses a solvent composition for water removal containing a primary amine salt of a carboxylic acid and a fluorinated propane hydrochloride as a water removal agent that can remove water from the surface of a substrate and separate water and has good operation efficiency. However, the water scavenger using such a halogen-based solvent is concerned about the cost and the influence on the human health. In recent years, environmental issues and safety have been increasingly conscious, and the use of halogen-based solvents and discharge standards have become strict.

Under such circumstances, hydrocarbon-based cleaning agents have attracted attention as cleaning agents that can replace halogen-based solvents because of their excellent cleaning performance and low environmental load, and development and research have been carried out.

For example, patent document 2 discloses a water-removing cleaning agent composition containing an anionic surfactant such as a saturated aliphatic hydrocarbon or a succinate salt, and a nonionic surfactant, and describes a method for removing water and dirt including water adhering to an object to be cleaned by forming a W/O microemulsion or a soluble W/O emulsion in a water-removing cleaning step.

Further, patent document 3 discloses a water scavenger containing a hydrocarbon solvent and an alkanolamine salt of a fatty acid. According to the water scavenger disclosed in this document, water removal can be achieved quickly and with improved operation efficiency.

Further, patent document 4 proposes a method for regenerating a rinse agent of a hydrocarbon-based water scavenger containing a carboxylic acid amine salt as a method for stably reusing the water scavenger which can replace a conventional halogen-based solvent.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 4-334502

Patent document 2: japanese laid-open patent publication (JP 2015-58385A)

Patent document 3: japanese laid-open patent publication No. 9-234303

Patent document 4: the invention disclosed in Japanese patent laid-open No. 2000-167304.

Since the emulsion-forming cleaning agent as disclosed in patent document 2 has poor separability, it is generally necessary to remove the cleaning agent remaining on the surface of the object to be cleaned and the surfactant blended in the cleaning agent in a rinsing step after cleaning, which makes the treatment complicated.

The hydrocarbon-based cleaning agents containing amine carboxylates as disclosed in patent documents 3 and 4 have a problem that precipitates and precipitates are formed in a low-temperature environment and the water replacement property is liable to be lowered.

Further, as in patent document 3, when the content of the oxygen atom-containing monoamine such as alkanolamine is large, the separability may be lowered.

There is a need for a cleaning oil composition having excellent separability and low-temperature stability.

The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by combining a branched aliphatic monocarboxylic acid and a linear aliphatic monocarboxylic acid at a specific ratio and blending them with a monoamine, and have completed the present invention.

The present invention is as follows.

[1] A cleaning oil composition comprising the following ingredients:

(A) branched aliphatic monocarboxylic acids,

(B) A straight-chain aliphatic monocarboxylic acid,

(C) Monoamines not containing oxygen atom, and

(D) hydrocarbon solvent

The molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

[2] A method of making a cleaning oil composition comprising mixing:

(A) branched aliphatic monocarboxylic acids,

(B) A straight-chain aliphatic monocarboxylic acid,

(C) Monoamines not containing oxygen atom, and

(D) hydrocarbon solvent

The molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

[3] The composition according to item [ 1] or the method according to item [ 2], wherein the component (A) is a branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms.

[4] The composition according to [ 1] or [ 3 ], or the method according to [ 2] or [ 3 ], wherein the component (B) is a linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms.

[5] The composition according to any one of [ 1], [ 3 ] and [ 4 ], or the method according to any one of [ 2] to [ 4 ], wherein the component (C) is an aliphatic monoamine having 6 to 10 carbon atoms.

[6] The composition according to any one of [ 1] and [ 3 ] to [ 5 ], or the method according to any one of [ 2] to [ 5 ], wherein a molar ratio [ B/A ] of the component (B) to the component (A) is 0.1 or more and 1.4 or less.

[7] The composition according to any one of [ 1] and [ 3 ] to [ 6 ], or the method according to any one of [ 2] to [ 6 ], wherein a molar ratio [ (B + A)/C ] of the total of the component (A) and the component (B) to the component (C) is 0.1 or more and 3 or less.

[8] The composition according to any one of [ 1] and [ 3 ] to [ 7 ], or the method according to any one of [ 2] to [ 7 ], wherein the total content of the component (A), the component (B), the component (C), and the component (D) is 80% by mass or more relative to the total mass of the composition.

[9] The composition according to any one of [ 1] and [ 3 ] to [ 8 ], or the method according to any one of [ 2] to [ 8 ], wherein the content of the halogen-based solvent is 1% by mass or less with respect to the total mass of the composition.

[10] The composition according to any one of [ 1] and [ 3 ] to [ 9 ], or the method according to any one of [ 2] to [ 9 ], wherein the aforementioned component (D) is a compound obtained by reacting a compound represented by formula (I) in the presence of an acid in the presence of a base in a solvent according to JIS K2254: 1998 in a distillation test by a normal pressure method, an isoparaffin solvent having a 100% by volume distillation temperature in the range of 165 to 270 ℃.

[11] The composition according to any one of [ 1] and [ 3 ] to [ 10 ], or the method according to any one of [ 2] to [ 10 ], wherein the composition comprises, relative to the total mass of the composition:

0.01 to 10 mass% of the above-mentioned component (A),

0.01 to 10 mass% of the above-mentioned component (B),

0.1 to 10 mass% of the component (C), and

70 to 99% by mass of the component (D).

[12] The composition according to any one of [ 1] and [ 3 ] to [ 11 ], or the method according to any one of [ 2] to [ 11 ], wherein the composition is used for cleaning an object to be cleaned having moisture adhering to a surface thereof, and the object to be cleaned is a metal material.

[13] A method for water-removing cleaning an object to be cleaned having water adhered to a surface thereof, which comprises cleaning the object to be cleaned with the composition according to any one of [ 1] and [ 3 ] to [ 12 ], or the composition produced by the method according to any one of [ 2] to [ 11 ].

Provided is a cleaning oil composition having excellent separability and low-temperature stability.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by any modification within the scope of the invention.

The upper limit and the lower limit of the numerical range described in the present specification may be arbitrarily combined. For example, when "a to B" and "C to D" are described, the ranges of "a to D" and "C to B" are also included in the scope of the present invention. The numerical range "lower limit to upper limit" described in the present specification means not lower than the lower limit but not higher than the upper limit.

1. Cleaning oil composition

One embodiment of the present invention relates to a cleaning oil composition. The cleaning oil composition comprises the following components: (A) a branched aliphatic monocarboxylic acid, (B) a straight aliphatic monocarboxylic acid, (C) a monoamine containing no oxygen atom, and (D) a hydrocarbon solvent, wherein the molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

Hydrocarbon-based cleaning oil compositions containing amine carboxylates have been proposed (for example, patent documents 3 to 4), but these compositions contain only amine salts of straight-chain fatty acids as the amine carboxylates, and have a problem that additives such as surfactants contained in the compositions precipitate, and the compositions solidify under a low-temperature environment, and the water replacement property is liable to decrease.

The present inventors have found that a cleaning oil composition having excellent low-temperature stability can be obtained by blending (a) a branched aliphatic monocarboxylic acid, and further found that a cleaning oil composition having excellent separability can be obtained by blending (a) a branched aliphatic monocarboxylic acid and (B) a linear aliphatic monocarboxylic acid in a specific ratio.

The composition of the present embodiment is inhibited from precipitating, clouding and solidifying even in a low-temperature environment (for example, in an extremely cold region which can reach-5 ℃ or-10 ℃), and can be used even in an extremely cold region.

In the present specification, "low-temperature stability" means that no precipitation or cloudiness is observed when the film is left for a certain period of time in a low-temperature environment. Specifically, the cleaning oil composition showed no precipitation or cloudiness when left standing at a low temperature of-5 ℃ for 5 days. In one embodiment, the cleaning oil composition is stable at temperatures above-5 ℃ and below 60 ℃. For example, the cleaning oil composition of the present embodiment does not cause precipitation or cloudiness when left at-5 ℃ for a certain period of time (for example, 5 days or 7 days). In a preferred embodiment, the cleaning oil composition is stable at a temperature of-10 ℃ or higher and 60 ℃ or lower. For example, the cleaning oil composition of the present embodiment does not cause precipitation or cloudiness when left standing at a low temperature (for example, -5 ℃ or-10 ℃) for a certain period (for example, 7 days, 5 days, or 30 days).

In the present specification, "separability" means a property of being able to separate in a short time even if the cleaning oil composition is mixed with water. For example, the term means that the cleaning oil composition can be separated into an aqueous layer and an oil layer within 6 minutes (preferably within 5 minutes, more preferably within 4 minutes) after mixing with water at room temperature and stirring.

The cleaning oil composition of the present embodiment has water-displacing properties and can be used as a water scavenger. As described above, the cleaning oil composition of the present embodiment is excellent in separability. Therefore, the composition of the present embodiment is suitably used for cleaning an object to be cleaned (for example, a metal material) having moisture adhering to the surface thereof. When an object to be cleaned having moisture adhered to the surface thereof is cleaned with the cleaning oil composition of this embodiment, the cleaning oil composition is adsorbed to the surface of the object to be cleaned, thereby removing the moisture from the object to be cleaned (water replacement property). The removed water is separated (separability) from the cleaning oil composition as an oily component, and reattachment to the object to be cleaned is suppressed.

In the present specification, "water-replacement property" means a property capable of removing moisture or a component containing moisture (for example, aqueous processing oil) adhering to the surface of an object to be cleaned.

The cleaning oil composition of the present embodiment may contain other compounds produced by modification, reaction, or the like of at least a part of the components to be blended, and such an embodiment is also included in the cleaning oil composition of the present invention. For example, in the cleaning oil composition of the present embodiment, at least one of (a) a branched aliphatic monocarboxylic acid and (B) a linear aliphatic monocarboxylic acid is reacted with (C) a monoamine containing no oxygen atom to form a carboxylate amine salt. Therefore, the composition of the present embodiment may contain at least one of (a) a monoamine salt of a branched aliphatic monocarboxylic acid produced by reacting (a) a branched aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom, and (B) a monoamine salt of a linear aliphatic monocarboxylic acid produced by reacting (B) a linear aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom. The composition of the present invention also includes an embodiment in which at least a part of (a) a branched aliphatic monocarboxylic acid, (B) a straight aliphatic monocarboxylic acid, and (C) a monoamine containing no oxygen atom is reacted to form a carboxylate amine salt.

Hereinafter, each component will be described in detail.

[ component (A): branched aliphatic monocarboxylic acids

The branched aliphatic monocarboxylic acid is not particularly limited, and a branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms is preferable from the viewpoint of imparting water-substitution properties.

Examples of the branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms include isocaproic acid, 2-ethyl-1-butyric acid, 2-methyl-1-valeric acid, 2-ethylhexanoic acid, 2-n-propyl-1-valeric acid, trimethylhexanoic acid, neodecanoic acid, 2-ethyl-2, 3, 3-trimethylbutanoic acid, 2-isopropyl-2, 3-dimethylbutanoic acid, 2,3, 3-tetramethylpentanoic acid, 2,3, 4-tetramethylpentanoic acid, 2,4, 4-tetramethylpentanoic acid, and isododecanoic acid. Among them, from the viewpoint of water-displacing property and separating property, a branched fatty acid having 7 to 11 carbon atoms (e.g., trimethylhexanoic acid and neodecanoic acid) is preferable, a branched fatty acid having 8 to 10 carbon atoms (e.g., trimethylhexanoic acid and neodecanoic acid) is more preferable, and a branched fatty acid having 9 carbon atoms (particularly, trimethylhexanoic acid) is most preferable.

[ component (B): straight chain aliphatic monocarboxylic acids

The linear aliphatic monocarboxylic acid is not particularly limited, and a linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms is preferable from the viewpoint of low-temperature stability.

Examples of the linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms include n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, and n-decanoic acid. Among them, a linear aliphatic monocarboxylic acid having 7 to 9 carbon atoms (n-heptanoic acid, n-octanoic acid, n-nonanoic acid) is preferable, and a linear aliphatic monocarboxylic acid having 8 carbon atoms (n-octanoic acid) is more preferable. When the number of carbon atoms is 6 or more, the volatility is not excessively high, and the odor is suppressed. On the other hand, when the number of carbon atoms is 10 or less, a composition having excellent low-temperature stability, suppressed crystallization and good workability can be obtained.

[ component (C): monoamines not containing oxygen atom ]

The cleaning oil composition of the present embodiment contains a monoamine containing no oxygen atom. The inclusion of the monoamine containing no oxygen atom is excellent in water-displacing property and separability. In the case of a monoamine containing an oxygen atom such as alkanolamine, separability may be reduced. Therefore, from the viewpoint of separability, the total content of the oxygen atom-containing monoamine in the cleaning oil composition of the present embodiment is preferably 1 mass% or less, and preferably 0 mass% with respect to the total mass of the composition (that is, the oxygen atom-containing monoamine is not included).

As the monoamine containing no oxygen atom, any of an aliphatic monoamine and an aromatic monoamine can be used, but from the viewpoint of water-substitution, an aliphatic monoamine having 6 to 10 carbon atoms is preferable.

Examples of the aliphatic monoamine having 6 to 10 carbon atoms include a linear aliphatic monoamine such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine, a branched aliphatic monoamine such as 2-aminooctane, 2-ethylhexylamine, and 1, 5-dimethylhexylamine, and the like. Among them, a linear aliphatic monoamine having 6 to 10 carbon atoms is preferable, a linear aliphatic monoamine having 7 to 9 carbon atoms is more preferable from the viewpoint of water-substitution property, and a linear aliphatic monoamine having 8 carbon atoms (n-octylamine) is further preferable from the viewpoint of excellent water-substitution property.

[ component (D): hydrocarbon solvent

The hydrocarbon solvent is not particularly limited, and a solvent containing at least 1 kind selected from aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons as a main component can be used. In the present specification, the "main component" specifically means a component which accounts for, for example, 80% by mass or more, preferably 95% by mass or more, and particularly 99% by mass or more, relative to the hydrocarbon-based solvent.

The aliphatic hydrocarbon is preferably a saturated aliphatic hydrocarbon, and examples thereof include n-paraffin hydrocarbons such as n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, and n-pentadecane; isoparaffin hydrocarbons such as isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, and isopentadecane. These may be used alone, or 2 or more of them may be used in combination.

Examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, 4-methyl-1-isopropylcyclohexane (p-menthane), cyclooctane, and decalin. These may be used alone, or 2 or more of them may be used in combination.

Examples of the aromatic hydrocarbon include ethylbenzene, diethylbenzene, isopropylbenzene, and 1-pentylbenzene. These may be used alone, or 2 or more of them may be used in combination.

Among them, an isoparaffinic solvent containing a saturated aliphatic hydrocarbon (preferably an isoparaffinic hydrocarbon) having preferably 5 to 20 carbon atoms, more preferably a saturated aliphatic hydrocarbon (preferably an isoparaffinic hydrocarbon) having 7 to 15 carbon atoms, and still more preferably a saturated aliphatic hydrocarbon (preferably an isoparaffinic hydrocarbon) having 10 to 12 carbon atoms as a main component is preferable.

In addition, from the viewpoint of safety (flash point) in handling and drying properties, the hydrocarbon-based solvent is used in a range of from JIS K2254: the isoparaffin solvent having a 100% by volume distillation temperature in the range of 165 to 270 ℃ in the atmospheric distillation test of 1998 is preferable.

The content of the halogen-based solvent in the composition of the present embodiment is preferably 1% by mass or less, more preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and particularly preferably substantially 0% by mass (i.e., containing no halogen-based solvent) with respect to the total mass of the composition, from the viewpoints of health (safety) for human body and cost. Examples of the halogen-based solvent include chlorine-based solvents such as methylene chloride, trichloroethylene, and tetrachloroethylene, chlorinated fluorinated hydrocarbon-based solvents, fluorine-based solvents such as Hydrofluoroolefin (HFO), and bromine-based solvents such as n-propyl bromide.

[ component (E) other additives ]

The cleaning oil composition may further contain other additives such as an antioxidant, a preservative, and a rust preventive, within a range not impairing the effects of the present invention.

Examples of the antioxidant include 2, 6-di-t-butyl-p-cresol (BHT), thymol, and pyrocatechol. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The content of the antioxidant is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less, based on the total mass of the composition.

Examples of the preservative include benzotriazoles and benzothiazoles. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The content of the preservative is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less, based on the total mass of the composition.

Examples of the rust inhibitor include fatty acid ester-based rust inhibitors such as pentaerythritol monoester and sorbitan monooleate, amine-based rust inhibitors such as amine and amine salt, carboxylic acid-based rust inhibitors such as aromatic carboxylic acid, alkenylsuccinic acid and naphthenate, organic sulfonic acid-based rust inhibitors such as petroleum sulfonate, organic phosphate-based rust inhibitors, and oxidized paraffin-based rust inhibitors. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The content of the rust inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less, based on the total mass of the composition.

[ composition ]

The amount of the component (a) in the composition of the present embodiment is not particularly limited, but is preferably in the range of 0.01 to 2 mass%, more preferably 0.1 to 1.5 mass%, and still more preferably 0.3 to 1.2 mass%, based on the entire mass of the composition.

The amount of the component (B) in the composition of the present embodiment is not particularly limited, but is preferably in the range of 0.01 to 1 mass%, more preferably 0.05 to 0.8 mass%, and still more preferably 0.1 to 0.6 mass%, based on the entire mass of the composition. The greater the amount of component (B) blended, the more the low temperature stability tends to be lowered. If the upper limit or less, the low temperature stability is excellent.

The amount of the component (C) in the composition of the present embodiment is not particularly limited, but is preferably in the range of 0.1 to 2 mass%, more preferably 0.2 to 1.5 mass%, and still more preferably 0.3 to 1.2 mass%, based on the entire mass of the composition. If the amount of the component (C) is too small, the component (a) and the component (B) are less likely to form an amine salt, and the water-replacement property tends to be low. If the lower limit or more, the water-substitution property is excellent.

The amount of the component (D) in the composition of the present embodiment is not particularly limited, and is preferably in the range of 70% by mass or more and 99.9% by mass or less, more preferably 80% by mass or more and 99.5% by mass or less, and further preferably 90% by mass or more and 99% by mass or less, relative to the entire mass of the composition, from the viewpoint of separability.

The total content of the component (a), the component (B), and the component (C) in the composition of the present embodiment is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, and further preferably 0.5% by mass or more and 3% by mass or less, based on the total mass of the composition. When the content is 0.01% by mass or more, the water-substitution property is excellent. On the other hand, when the content is 10% by mass or less, formation of an emulsion can be suppressed in the water removal and washing step, and excellent separability can be exhibited.

In the composition of the present embodiment, the molar ratio [ B/a ] of the (B) straight-chain aliphatic monocarboxylic acid to the (a) branched-chain aliphatic monocarboxylic acid is 1.4 or less. When the molar ratio [ B/A ] of the component (B) to the component (A) exceeds 1.4, sufficient low-temperature stability may not be obtained. From the viewpoint of improving low-temperature stability, the molar ratio [ B/a ] of the component (B) to the component (a) is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.7 or less. From the viewpoint of improving the separability, the molar ratio [ B/a ] of the component (B) to the component (a) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. For example, the molar ratio [ B/a ] of the component (B) to the component (a) is preferably 0.1 or more and 1.4 or less, more preferably 0.1 or more and 1 or less, further preferably 0.2 or more and 0.9 or less, and further preferably 0.3 or more and 0.7 or less.

The combination of (a) a branched aliphatic monocarboxylic acid and (B) a straight aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom is not particularly limited. From the viewpoint of improving the separability, the molar ratio [ (B + a)/C ] of the total of the (a) branched aliphatic monocarboxylic acid and the (B) linear aliphatic monocarboxylic acid to the (C) monoamine that does not contain an oxygen atom is preferably 0.1 or more and 3 or less, more preferably 0.5 or more and 2 or less, and still more preferably 1.2 or more and 1.4 or less.

The total content of the component (a), the component (B), the component (C), and the component (D) in the composition of the present embodiment is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass, based on the total mass of the composition.

For example, the composition of one embodiment has the following composition relative to the total mass of the composition:

(A) 0.01 to 10 mass% of branched aliphatic monocarboxylic acid

(B) 0.01 to 10 mass% of a straight chain aliphatic monocarboxylic acid

(C) 0.1 to 10 mass% of monoamine containing no oxygen atom

(D) 70 to 99 mass% of a hydrocarbon solvent

(E) The other additives are 0 to 10 mass%.

2. Process for producing cleaning oil composition

One embodiment of the present invention provides a method for producing a cleaning oil composition.

The method for producing the cleaning oil composition of the present embodiment comprises mixing the following components: (A) a branched aliphatic monocarboxylic acid, (B) a straight aliphatic monocarboxylic acid, (C) a monoamine containing no oxygen atom, and (D) a hydrocarbon-based solvent; the molar ratio [ B/A ] of the component (B) to the component (A) is 1.4 or less.

The component (E) may be mixed as required in addition to the components (A), (B), (C) and (D).

The specific embodiments of the component (a), the component (B), the component (C), the component (D) and the component (E) are the same as those described in the above "1. cleaning oil composition".

The component (a) and the component (B), and the component (C), the component (D) and, if necessary, the component (E) may be mixed by any method, and the order of mixing and the method thereof are not limited.

As described above, a carboxylate amine salt may be formed in the composition produced by mixing at least one of the component (a) and the component (B) with the component (C). Therefore, the composition produced by the production method of the present embodiment may contain: (i) a monoamine salt of a branched aliphatic monocarboxylic acid produced by reacting (a) a branched aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom, (ii) a monoamine salt of a linear aliphatic monocarboxylic acid produced by reacting (B) a linear aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom, (iii) a branched aliphatic monocarboxylic acid not forming a carboxylate amine salt, (iv) a linear aliphatic monocarboxylic acid not forming a carboxylate amine salt, and/or (v) a monoamine containing no oxygen atom without forming a carboxylate amine salt.

3. Cleaning method one embodiment of the present invention provides a cleaning method using a cleaning oil composition.

The cleaning method of the present embodiment is a method for removing water from an object to be cleaned having water adhered to a surface thereof, and includes cleaning the object to be cleaned using the above-mentioned cleaning oil composition (cleaning step).

The method for cleaning the object to be cleaned using the cleaning oil composition is not particularly limited. For example, the cleaning oil composition of the present embodiment is brought into contact with an object to be cleaned having moisture adhered to the surface thereof, thereby removing the moisture from the object to be cleaned. The contact of the cleaning oil composition may be performed by, for example, immersion, spraying, misting, or the like, and the cleaning effect may be enhanced by, for example, ultrasonic waves, stirring, air bubbling, or shaking of the object to be cleaned, if necessary, at the time of immersion. These may be used alone or in combination of a plurality thereof in consideration of required cleanliness, required time, and the like.

For example, when an object to be cleaned, to which moisture has adhered on the surface thereof, is immersed in the cleaning oil composition, the water enters between the surface of the object to be cleaned and the surface of the object to be cleaned, and the water is adsorbed on the surface of the object to be cleaned, and the water is peeled off and removed from the surface of the object to be cleaned. The removed water is not dissolved in the cleaning oil composition but separated and aggregated to form droplets, and is rapidly collected to the lower part of the cleaning tank by utilizing the difference of specific gravity with the cleaning oil composition to form a water phase. After the object to be cleaned is cleaned, the lower water phase containing water can be easily removed.

The time of the cleaning step is appropriately set depending on the required degree of cleanliness, the type of the object to be cleaned, the moisture content adhering to the surface, and the type of the processing liquid.

From the viewpoint of detergency and prevention of volatilization, the temperature of the cleaning oil composition in the cleaning step is preferably, for example, 0 to 60 ℃ (preferably 15 to 40 ℃, more preferably 20 to 30 ℃).

Since the cleaning oil composition of the present embodiment has water-displacing properties and also has excellent separability, water adhering to the surface of the object to be cleaned is quickly removed and separated from the oil phase such as the cleaning oil composition. Therefore, the cleaning oil composition of the present embodiment can be used for another cleaning process without a regeneration process after the cleaning process, and the operation efficiency of the cleaning process is excellent.

After the washing step, the object to be washed may be dried directly after the liquid is removed. In the cleaning oil composition of the present embodiment, the component (a), the component (B), and the component (C), and the component (a) or a reaction product of the component (B) and the component (C) are excellent in solubility in the component (D), and therefore, are less likely to adhere to the surface of the object to be cleaned after the liquid is removed. Therefore, after the liquid is removed, the object to be cleaned may be dried directly without performing the post-rinsing step to prepare a finished product, or may be subjected to another treatment.

The drying method is not particularly limited, and drying methods used in conventional cleaning methods such as hot air drying, suction drying, spin drying, vacuum drying, and vacuum vapor drying can be used.

After the washing step, a rinsing step of immersing the object to be washed from which the liquid has been removed in a rinsing liquid may be performed. As the rinse liquid, the same hydrocarbon solvent as the hydrocarbon solvent (D) used in the cleaning oil composition may be used, or a hydrocarbon having a lower boiling point than the hydrocarbon solvent (D) may be used. The rinsing step may be performed 1 time or 2 or more times. By performing the rinsing step, the cleaning oil composition remaining on the surface of the object to be cleaned and components contained in the cleaning oil composition can be removed. When the cleaning oil composition contains a surfactant in addition to the components (a) to (C), the rinsing step is preferably performed when a slight amount of surfactant remaining on the surface of the object to be cleaned is a problem. After the rinsing step, the object to be cleaned is usually dried after removing the liquid.

The object to be cleaned is not particularly limited, and examples thereof include metal materials, glass, ceramics, resins, and the like. Among them, a metal material is preferable from the viewpoint of obtaining an excellent cleaning effect. Specific examples of the object to be cleaned made of a metal material include a metal jig; processed products of metals (e.g., quenched steel); iron products such as cold-rolled steel sheets and processed products thereof, hot-rolled steel sheets, galvanized steel sheets and processed products thereof, and forged products thereof; a stainless steel article; aluminum products such as plate-like products and die-cast products mainly made of aluminum; and products made of refractory alloys such as titanium-and molybdenum-containing steels and difficult-to-machine materials.

In the method of the present embodiment, the water to be removed from the surface of the object to be cleaned is not particularly limited as long as it is an aqueous component, and examples thereof include water and water derived from an aqueous processing oil (for example, cutting oil, polishing oil, press oil, rolling oil, rust preventive oil, heat treatment oil, and cleaning oil).

[ examples ]

The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited thereto. In the present specification, "room temperature" generally means about 10 ℃ to about 35 ℃. % represents a mass percentage unless otherwise specified.

Examples 1 to 12 and comparative examples 1 to 4

As shown in table 1 below, the cleaning oil compositions of examples and comparative examples were prepared by adding the components shown in table 1 below to an isoparaffin solvent (component D).

[ evaluation ]

The prepared cleaning oil composition was used as a test oil, and the following evaluations were performed. The results are shown in Table 1.

(1) Water replacement property

The cleaned test piece was immersed in water or a diluted solution of a cutting oil, and taken out. Thereby, a water film is attached to the surface of the test piece. The test piece was placed in a beaker containing test oil, and the time until the water film on the surface of the test piece was broken and aggregated into water droplets was measured as the time required for water replacement.

As the test piece, the following test piece 1 or test piece 2 was used.

Test piece 1: GA material (galvanized steel sheet; 60mm in length X80 mm in width X0.8 mm in thickness)

Test piece 2: SPCC-SD (Cold-pressed steel plate ground with 240 pieces of grinding cloth (Mushou); 60mm in length X80 mm in width X0.8 mm in thickness)

As water, tap water was used. As the cutting oil diluent, the following cutting oil diluent 1 or cutting oil diluent 2 is used.

Cutting oil diluent 1: アルファクール CS (Water-soluble cutting oil, emulsion type, from Shixinghua Co., Ltd.) as a 5% aqueous dilution

Cutting oil diluent 2: アルファクール ML (Water-soluble cutting oil, available from Shixingdao) aqueous dilution with concentration of 5%

(evaluation criteria for respective tests)

Based on the measurement result of the time required for water replacement, evaluation was performed according to the following criteria.

Evaluation A: the time required for water replacement is 5 seconds or less

Evaluation B: the time required for water replacement exceeds 5 seconds

(comprehensive evaluation)

In 6 tests using water, cutting oil diluent 1, and cutting oil diluent 2 in test pieces 1 and 2, overall evaluation was performed as follows based on the above evaluation criteria (evaluation a and evaluation B).

Good (∘): the evaluation of 6 tests was evaluation A

Poor (x): at least one of the evaluations of the 6 tests was evaluation B

(2) Separability

50mL of water or a dilution of a cutting oil was added to a 100mL graduated cylinder, followed by 50mL of test oil added statically. As water, tap water was used. As the cutting oil diluent, the following cutting oil diluent 1 or cutting oil diluent 2 is used.

Cutting oil diluent 1: アルファクール CS (Water-soluble cutting oil, emulsion type, from Shixinghua Co., Ltd.) as a 5% aqueous dilution

Cutting oil diluent 2: アルファクール ML (water-soluble cutting oil prepared by Shikino corporation, solution type) water dilution with concentration of 5%

(evaluation criteria for respective tests)

After stirring vigorously from above and below for 5 seconds, the mixture was left to stand, and the time until the separation of the aqueous layer and the oil layer (oil layer return time) was measured and evaluated according to the following criteria.

Evaluation A: the oil layer return time is 2 minutes or less, and no white turbidity is observed in the oil layer

Evaluation B: the oil layer return time is more than 2 minutes and 6 minutes or less, and no white turbidity is observed in the oil layer

Evaluation C: the return time of the oil layer exceeds 6 minutes, and/or white turbidity is observed in the oil layer

(comprehensive evaluation)

In 3 tests using water, cutting oil diluent 1, and cutting oil diluent 2, comprehensive evaluation was performed as follows based on the evaluation criteria (evaluation a, evaluation B, and evaluation C) of the above tests.

Very good (verycirco): the evaluation of 3 tests was evaluation A

Good (∘): the evaluation of all 3 tests was evaluation A or evaluation B, and at least one was evaluation B

Poor (x): at least one of the evaluations of the 3 tests was evaluation C

(3) Stability at Low temperature

100mL of test oil was added to a 100mL test bottle and left at-5 ℃ for 5 days (condition A) or at-10 ℃ for 7 days (condition B). The appearance was observed to determine the presence or absence of precipitation. The evaluation was made according to the following criteria, with no precipitate judged to be good.

Very good (verycirco): good (no precipitation) in both condition A and condition B

Good (∘): good (no precipitation) in condition A, and visible precipitation in condition B

Poor (x): precipitation was seen in both condition A and condition B

[ tables 1-1]

[ tables 1-2]

。

The ingredients used in table 1 are as follows.

1. Component (A)

Branched C10 fatty acids: neodecanoic acid

Branched C9 fatty acids: trimethylhexanoic acid

2. Ingredient (B)

Linear C8 fatty acids: n-octanoic acid

3. Ingredient (C)

Linear C8 amine: n-octylamine

4. Ingredient (D)

Isoparaffinic solvent: an isoparaffin hydrocarbon (containing isoundecane as a main component; having a 100% by volume distillation temperature of 173 to 178 ℃ in a distillation test by the atmospheric pressure method in accordance with JIS K2254: 1998)

5. Others

Alkanolamine: n-methyldiethanolamine

As shown in table 1, it was confirmed that the cleaning oil compositions of examples in which (a) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid were combined and blended at a specific ratio were excellent in water displacement property and separability, and also exhibited good low-temperature stability in a low-temperature environment of-5 ℃.

It was further confirmed that the cleaning oil compositions of examples 2 to 16 having a molar ratio [ B/A ] of 0.9 or less exhibited good low-temperature stability even in a low-temperature environment of-10 ℃.

In particular, in example 8 in which the molar ratio [ (B + a)/C ] of the total of the branched aliphatic monocarboxylic acid (a) and the linear aliphatic monocarboxylic acid (B) to the monoamine (C) containing no oxygen atom was 1.2 or more and 1.4 or less, it was confirmed that the separability was further improved.

In contrast, comparative example 1 in which (a) a branched aliphatic monocarboxylic acid was not contained and comparative example 2 in which the molar ratio [ B/a ] of (a) a branched aliphatic monocarboxylic acid to (B) a linear aliphatic monocarboxylic acid was more than 1.4 were poor in low-temperature stability.

In addition, in comparative example 3 containing no (B) linear aliphatic monocarboxylic acid, comparative example 4 containing no (C) monoamine containing no oxygen atom, and comparative example 5 containing an alkanolamine instead of the (C) monoamine containing no oxygen atom, sufficient separability was not achieved.

The scope of the present invention is not limited to the above description, and the contents other than the above examples can be appropriately modified and implemented within a range not to impair the gist of the present invention. It should be noted that all documents and publications recited in the present specification are incorporated in their entirety into the present specification by reference, regardless of the purpose thereof. The present specification also includes the disclosure of the claims and the specification of japanese patent application No. 2018-150678 (application 8/9/8/2018), which is the basis for claiming priority of the present application.

Industrial applicability

The cleaning oil composition of the present invention can be suitably used for cleaning an object to be cleaned having water or an aqueous processing oil adhered to the surface thereof.