WO2020032085A1

WO2020032085A1 - Wash oil composition, method for producing same, and spot-free drying method

Info

Publication number: WO2020032085A1
Application number: PCT/JP2019/031061
Authority: WO
Inventors: 匡基田巻; 直樹長瀬
Original assignee: 出光興産株式会社
Priority date: 2018-08-09
Filing date: 2019-08-07
Publication date: 2020-02-13
Also published as: JP7132023B2; CN112513231B; JP2020026451A; CN112513231A

Abstract

There is a need for a wash oil composition having exceptional separability and low-temperature stability. A wash oil composition containing the following components: (A) a branched aliphatic monocarboxylic acid; (B) a linear aliphatic monocarboxylic acid; (C) an oxygen-atom-free monoamine; and (D) a hydrocarbon solvent, the molar ratio [B/A] of component (B) to component (A) being 1.4 or lower.

Description

Cleaning oil composition, method for producing the same, and method for cleaning draining

(4) The present invention relates to a cleaning oil composition, a method for producing the same, and a method for draining and cleaning.

Processing oil (for example, cutting oil, polishing oil, press oil, extraction oil, heat treatment oil, rust prevention oil, lubrication oil, processing oil, grease, wax) is used for metal processing such as cutting, rolling, drawing, pressing, and forging. Can be Processing oils are classified into oil-based and water-based processing oils. Among them, water-based processing oils are widely used mainly for cutting, polishing, and the like that require high cooling performance. After processing, the water-based processing oil adheres to the surface of the processing material. Aqueous processing oil adhering to the surface causes denaturation, rust, discoloration, and the like. Therefore, usually, after processing, the processing material is washed and the aqueous processing oil adhering to the material surface is removed.

For cleaning of the cleaning object to which the aqueous processing oil is adhered, an aqueous cleaning agent, a semi-aqueous cleaning agent in which a water-soluble solvent is mixed with an aqueous cleaning agent, an alcohol-based cleaning agent such as isopropanol, and a glycol ether, depending on the application, are usually used. Cleaning agents such as a system cleaning agent, a halogen system cleaning agent, and a hydrocarbon cleaning agent obtained by mixing a surfactant with a hydrocarbon solvent are used.
Halogen-based cleaning agents have a high dissolving power for oil, are nonflammable, are recyclable, and have excellent cleaning properties. For example, Patent Document 1 contains a primary amine salt of a carboxylic acid and a hydrogen-containing chlorinated fluorinated propane as a draining agent that can remove water from a substrate surface and simultaneously separate water, and has a high working efficiency. A solvent composition for draining is disclosed. However, there is a concern that such a draining agent using a halogen-based solvent may have an adverse effect on cost and human health. In recent years, awareness of environmental issues and safety has been increasing more and more, and the use regulations and emission standards of halogenated solvents are becoming stricter.

Against this background, hydrocarbon-based cleaning agents have excellent cleaning performance and have a small impact on the environment. ing.
For example, Patent Literature 2 discloses a draining detergent composition containing a saturated aliphatic hydrocarbon, an anionic surfactant such as a succinic acid ester salt, and a nonionic surfactant. , W / O microemulsions or solubilized W / O emulsions to remove water and dirt containing water adhering to objects to be cleaned.

Patent Literature 3 discloses a drainer containing a hydrocarbon solvent and an alkanolamine salt of a fatty acid. According to the draining agent of the document, draining can be performed quickly and with improved work efficiency.
Patent Literature 4 discloses a method of stably repetitively using a method of regenerating a rinse agent of a hydrocarbon-based drainage agent containing a carboxylic acid amine salt as a method capable of replacing the conventional halogen-based solvent drainage agent. A method has been proposed.

JP-A-4-334502 JP 2015-58385 A JP-A-9-234303 JP 2000-167304 A

The cleaning agent that forms an emulsion as described in Patent Literature 2 has poor separability. Therefore, a cleaning agent remaining on the surface of the object to be cleaned and a surfactant incorporated in the cleaning agent are generally removed by a rinsing step after cleaning. It is necessary and the processing is complicated.
The hydrocarbon-based detergent containing a carboxylic acid amine salt as disclosed in Patent Literature 3 and Patent Literature 4 has a problem in that a precipitate or a precipitate is formed in a low-temperature environment, and the water displacement property is likely to be reduced.
Further, when the content of an oxygen atom-containing monoamine such as alkanolamine is large as in Patent Document 3, the separability may decrease.

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

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by combining a branched aliphatic monocarboxylic acid and a linear aliphatic monocarboxylic acid at a specific ratio together with a monoamine, the above-mentioned problems have been solved. The inventors have found that it is possible to solve the problem, and have completed the present invention.

The present invention is as follows.
[1] The following components:
(A) a branched aliphatic monocarboxylic acid,
(B) a linear aliphatic monocarboxylic acid,
(C) an oxygen atom-free monoamine, and (D) a hydrocarbon solvent.
The cleaning oil composition, wherein a molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.
[2] A method for producing a cleaning oil composition,
The following ingredients:
(A) a branched aliphatic monocarboxylic acid,
(B) a linear aliphatic monocarboxylic acid,
(C) mixing an oxygen atom-free monoamine, and (D) a hydrocarbon solvent,
The method, wherein the molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.
[3] The composition according to [1] or the method according to [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 [2] or [3], wherein the component (B) is a straight-chain aliphatic monocarboxylic acid having 6 to 10 carbon atoms. the method of.
[5] The composition according to any of [1], [3] and [4], wherein the component (C) is an aliphatic monoamine having 6 to 10 carbon atoms, or [2] to [4]. 4].
[6] Any of [1] and [3] 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. Or the method according to any one of [2] to [5].
[7] [1] and [3], wherein the total molar ratio of the component (A) and the component (B) to the component (C) [(B + A) / C] is 0.1 or more and 3 or less. The composition according to any one of to [6], or the method according to any one of [2] to [6].
[8] The sum of the content of the component (A), the component (B), the component (C), and the component (D) is 80% by mass or more based on the total mass of the composition. The composition according to any one of [1] and [3] to [7], or the method according to any one of [2] to [7].
[9] The composition according to any one of [1] and [3] to [8], wherein the content of the halogen-based solvent is 1% by mass or less based on the total mass of the composition, or [2]. ] The method according to any one of [8] to [8].
[10] The component (D) is an isoparaffinic solvent having a 100% by volume distillation temperature in the range of 165 to 270 ° C. in an atmospheric distillation test based on JIS K2254: 1998. 9] The method according to any one of [2] to [9].
[11] 0.01% to 10% by mass of the component (A) 0.01% to 10% by mass of the component (B) 0.01% to 10% by mass of the component (C) 0.1 based on the total mass of the composition The composition according to any one of [1] and [3] to [10], which contains at least 10% by mass and not more than 10% by mass, and at least 70% by mass and at most 99% by mass of the component (D), or [2]. The method according to any one of [10] to [10].
[12] The composition according to any one of [1] and [3] to [11], wherein the composition is used for cleaning an object to be cleaned having moisture adhered to the surface, and the object to be cleaned is a metal material. The composition or the method according to any one of [2] to [11].
[13] A method for draining and cleaning an object to be cleaned having moisture adhered to the surface, wherein the composition according to any one of [1] and [3] to [12], or [2] to [11]. A method comprising washing the object to be washed using a composition produced by using the method according to any one of the above.

(4) A cleaning oil composition having excellent separability and low-temperature stability is provided.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist thereof.
The upper and lower limits of the numerical ranges described herein can be arbitrarily combined. For example, when "AB" and "CD" are described, ranges of "AD" and "CB" are also included in the scope of the present invention. Further, the numerical range “lower limit to upper limit” described in this specification means that the range is equal to or more than the lower limit and equal to or less than the upper limit.

1. Cleaning oil composition One aspect 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 linear aliphatic monocarboxylic acid, (C) an oxygen atom-free monoamine, and (D) a hydrocarbon solvent. And the molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.

Conventionally, hydrocarbon-based cleaning oil compositions containing a carboxylic acid amine salt have been proposed (for example, Patent Documents 3 and 4), but in these compositions, only an amine salt using a straight-chain fatty acid as the carboxylic acid amine salt is used. In a low-temperature environment, precipitation and precipitation of additives such as a surfactant compounded in the composition and solidification of the composition occur, and there is a problem that the water displacement property is liable to decrease. .

The present inventors have found that by adding (A) a branched aliphatic monocarboxylic acid, a cleaning oil composition having excellent low-temperature stability can be obtained, and further, (A) a branched aliphatic monocarboxylic acid and (B) ) It has been found that a cleaning oil composition having excellent separability can be obtained by setting the blending ratio with the linear aliphatic monocarboxylic acid to a specific ratio.
The composition of this embodiment suppresses precipitation, turbidity, and solidification even in a low-temperature environment (for example, an extremely cold region where the temperature can be −5 ° C. or −10 ° C.), and can be used in an extremely cold region.

In the present specification, “low-temperature stability” means that no precipitation or cloudiness is observed when left for a certain period of time in a low-temperature environment. Specifically, it means that no precipitation or cloudiness is observed when the cleaning oil composition is left in a low-temperature environment at a temperature of −5 ° C. for 5 days. In one embodiment, the cleaning oil composition is stable at a temperature between -5 ° C and 60 ° C. For example, when the cleaning oil composition of the present embodiment is left at −5 ° C. for a certain period of time (eg, 5 days or 7 days, no precipitation or cloudiness is observed. In a preferred embodiment, the cleaning oil composition has a temperature of −10 ° C.). The cleaning oil composition of the present embodiment is stable at a temperature of not less than 60 ° C. and not more than 60 ° C. For example, the cleaning oil composition of the present embodiment is kept under a low temperature environment (eg, −5 ° C. or −10 ° C.) for a certain period (eg, 7, 5, or 30 days). No precipitation or white turbidity is observed when left for a while.
In the present specification, “separability” means the ability to separate the cleaning oil composition in a short time even when mixed with water. For example, it means that a water layer and an oil layer can be separated within 6 minutes (preferably within 5 minutes, more preferably within 4 minutes) after mixing and stirring the washing oil composition and water at room temperature.

The cleaning oil composition of the present embodiment has water displacement properties and can be used as a drainage agent. Further, as described above, the cleaning oil composition of the present embodiment is excellent in separability. Therefore, the composition of this embodiment is suitably used for cleaning an object to be cleaned (for example, a metal material) having moisture adhered to the surface. When an object to be cleaned having water adhered to the surface is washed with the cleaning oil composition of the present embodiment, the cleaning oil composition is adsorbed on the surface of the object to be cleaned, whereby water is removed from the object to be cleaned (water displacement property). ). The removed water is separated from the cleaning oil composition, which is an oily component (separability), and reattachment to the object to be cleaned is suppressed.
In the present specification, the term “water displacement” means a performance capable of removing water or a component containing water (for example, an aqueous processing oil) attached to the surface of an object to be cleaned.

The cleaning oil composition of the present embodiment may optionally contain another compound produced by at least part of the blended components being denatured or reacted, and such a form is also the cleaning oil of the present invention. It shall be included in the composition. For example, in the cleaning oil composition of this embodiment, at least one of (A) a branched aliphatic monocarboxylic acid and (B) a linear aliphatic monocarboxylic acid reacts with (C) an oxygen atom-free monoamine to form a carboxylic acid. Acid amine salts may be formed. Accordingly, the composition of the present embodiment comprises (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; It may contain at least one of (B) a monoamine salt of a linear aliphatic monocarboxylic acid produced by reacting (B) a linear aliphatic monocarboxylic acid with (C) an oxygen atom-free monoamine. A form in which at least a part of (A) the branched aliphatic monocarboxylic acid, (B) the linear aliphatic monocarboxylic acid, and (C) the oxygen-free monoamine reacts to form a carboxylic acid amine salt is also included. It is intended to be included in the compositions of the present invention.
Hereinafter, each component will be described in detail.

[Component (A): Branched aliphatic monocarboxylic acid]
The branched aliphatic monocarboxylic acid is not particularly limited, but is preferably a branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms from the viewpoint of imparting water substitution.
Examples of the branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms include isohexanoic acid, 2-ethyl-1-butanoic acid, 2-methyl-1-pentanoic acid, 2-ethylhexanoic acid and 2-n-propyl- 1-pentanoic acid, trimethylhexanoic acid, neodecanoic acid, 2-ethyl-2,3,3-trimethylbutanoic acid, 2-isopropyl-2,3-dimethylbutanoic acid, 2,2,3,3-tetramethylpentanoic acid , 2,2,3,4-tetramethylpentanoic acid, and 2,2,4,4-tetramethylpentanoic acid, isododecanoic acid and the like. Among them, branched fatty acids having 7 to 11 carbon atoms (eg, trimethylhexanoic acid, neodecanoic acid) are preferable, and branched fatty acids having 8 to 10 carbon atoms (eg, trimethylhexanoic acid, neodecanoic acid) are more preferable from the viewpoint of water displacement and separability. Preferred and most preferred are branched fatty acids having 9 carbon atoms (particularly trimethylhexanoic acid).

[Component (B): linear aliphatic monocarboxylic acid]
The linear aliphatic monocarboxylic acid is not particularly limited, but is preferably a linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms 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, linear aliphatic monocarboxylic acids having 7 to 9 carbon atoms (n-heptanoic acid, n-octanoic acid, n-nonanoic acid) are preferable, and linear aliphatic monocarboxylic acids having 8 carbon atoms (n-octanoic acid) are preferred. Is more preferred. When the carbon number is 6 or more, the volatility does not become too 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, crystallization is suppressed, and good handleability is obtained.

[Component (C): oxygen atom-free monoamine]
The cleaning oil composition of the present embodiment contains a monoamine containing no oxygen atom. By containing a monoamine containing no oxygen atom, it is excellent in water displacement property and separability. When an oxygen atom-containing monoamine such as an alkanolamine is contained, the separability may decrease. Therefore, from the viewpoint of separability, the cleaning oil composition of the present embodiment has a total content of the oxygen atom-containing monoamine of preferably 1% by mass or less, more preferably 0% by mass, based on the total mass of the composition. (It does not contain an oxygen atom-containing monoamine).

As the oxygen-free monoamine, any of an aliphatic monoamine and an aromatic monoamine can be used, but an aliphatic monoamine having 6 to 10 carbon atoms is preferable from the viewpoint of water substitution.
Examples of the aliphatic monoamine having 6 to 10 carbon atoms include linear aliphatic monoamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; 2-aminooctane; And branched aliphatic monoamines such as -ethylhexylamine and 1,5-dimethylhexylamine. Among them, straight-chain aliphatic monoamines having 6 to 10 carbon atoms are preferable, straight-chain aliphatic monoamines having 7 to 9 carbon atoms are more preferable in terms of water substitution, and straight-chain aliphatic monoamines having 8 carbons are excellent in water substitution. Aliphatic monoamines (n-octylamine) are more preferred.

[Component (D): hydrocarbon solvent]
The hydrocarbon solvent is not particularly limited, and a solvent containing at least one 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 that the solvent occupies, for example, 80% by mass or more, preferably 95% by mass or more, particularly 99% by mass or more with respect to the hydrocarbon solvent.

As the aliphatic hydrocarbon, a saturated aliphatic hydrocarbon is preferable. For example, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n N-paraffinic hydrocarbons such as pentadecane; isoparaffinic hydrocarbons such as isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane and the like can be used. These may be used alone or in combination of two or more.
Examples of the alicyclic hydrocarbon include cyclopentane, cyclohexane, 4-methyl-1-isopropylcyclohexane (p-menthane), cyclooctane, decalin and the like. These may be used alone or in combination of two or more.
Examples of the aromatic hydrocarbon include ethylbenzene, diethylbenzene, isopropylbenzene, 1-pentylbenzene, and the like. These may be used alone or in combination of two or more.
Among these, saturated aliphatic hydrocarbons having 5 to 20 carbon atoms (preferably isoparaffinic hydrocarbons), more preferably saturated aliphatic hydrocarbons having 7 to 15 carbon atoms (preferably isoparaffinic hydrocarbons), Preferably, an isoparaffinic solvent mainly containing a saturated aliphatic hydrocarbon having 10 to 12 carbon atoms (preferably, isoparaffinic hydrocarbon) is used.

Further, as the hydrocarbon solvent, in terms of safety (flash point) during handling and drying property, a 100% by volume distillation temperature in a normal pressure distillation test in accordance with JIS K2254: 1998 is in a range of 165 to 270 ° C. Is preferred.

In the composition of the present embodiment, the content of the halogen-based solvent is preferably 1% by mass or less based on the total mass of the composition, from the viewpoint of health (safety) and cost to the human body, and 0.1% by mass. The content is more preferably not more than 0.01% by mass, more preferably not more than 0.01% by mass, and particularly preferably substantially 0% by mass (that is, containing no halogen-based solvent). 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 brominated n-propyl. And the like.

[Component (E) Other additives]
The cleaning oil composition may further contain other additives such as an antioxidant, a preservative, and a rust preventive as long as the effects of the present invention are not impaired.

Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol (BHT), thymol, pyrocatechin and the like. These may be used alone or in combination of two or more. The content of the antioxidant is preferably 1% by mass or less, more preferably 0.5% by mass or less, and preferably 0.3% by mass or less based on the total mass of the composition. More preferred.
Examples of the preservative include benzotriazoles, benzothiazoles and the like. These may be used alone or in combination of two or more. 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. preferable.
Examples of the rust inhibitor include fatty acid ester rust inhibitors such as pentaerythritol monoester and sorbitan monooleate, amine rust inhibitors such as amines and amine salts, aromatic carboxylic acids, alkenyl succinic acids, naphthenate salts and the like. Carboxylic acid-based rust inhibitors, organic sulfonic acid-based rust inhibitors such as petroleum sulfonates, organic phosphate ester-based rust inhibitors, paraffin oxide-based rust inhibitors, and the like. These may be used alone or in combination of two or more. The content of the rust inhibitor is preferably 1% by mass or less, more preferably 0.5% by mass or less, and preferably 0.3% by mass or less based on the total mass of the composition. More preferred.

[composition]
The amount of the component (A) in the composition of the present embodiment is not particularly limited, but is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.1% by mass or less based on the total mass of the composition. % To 1.5% by mass, more preferably 0.3% to 1.2% by mass.
The amount of the component (B) in the composition of the present embodiment is not particularly limited, but is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.05% by mass, based on the total mass of the composition. % To 0.8% by mass, more preferably 0.1% to 0.6% by mass. As the amount of component (B) increases, the low-temperature stability tends to decrease. Below the upper limit, the low-temperature stability is excellent.
The amount of component (C) in the composition of the present embodiment is not particularly limited, but is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass, based on the total mass of the composition. % To 1.5% by mass, more preferably 0.3% to 1.2% by mass. If the amount of the component (C) is too small, it is difficult to form an amine salt with the component (A) or the component (B), and the water displaceability tends to decrease. If it is not less than the lower limit, the water displacement property is excellent.
The amount of the component (D) in the composition of the present embodiment is not particularly limited, but is preferably 70% by mass or more and 99.9% by mass or less based on the total mass of the composition in terms of separability. It is preferably in the range of 80% by mass to 99.5% by mass, and more preferably in the range of 90% by mass to 99% by mass.
The total content of the components (A), (B), and (C) in the composition of the present embodiment is preferably 0.01% by mass or more and 10% by mass with respect to the total mass of the composition. %, More preferably 0.1 to 7% by mass, and still more preferably 0.5 to 3% by mass. When the content is 0.01% by mass or more, excellent water displacement property is obtained. On the other hand, when the content is 10% by mass or less, the formation of an emulsion is suppressed in the draining and washing step, and excellent separation properties can be exhibited.

において In the composition of the present embodiment, the molar ratio [B / A] of (B) the linear aliphatic monocarboxylic acid to the (A) branched 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. 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 from the viewpoint of improving low-temperature stability. 0.7 or less. Further, 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, from the viewpoint of improving the separability. Is 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, and 0.2 or more and 0.9 or less. The following is more preferable, and more preferably 0.3 or more and 0.7 or less.

配合 The blending of (A) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid with (C) the oxygen-free monoamine is not particularly limited. From the viewpoint of improving the separability, the total molar ratio [(B + A) / C] of (A) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid to (C) the oxygen-free monoamine is determined. , Preferably 0.1 or more and 3 or less, more preferably 0.5 or more and 2 or less, even more preferably 1.2 or more and 1.4 or less.

The total of the contents of the component (A), the component (B), the component (C), and the component (D) in the composition of the present embodiment is preferably 80 mass with respect to the total mass of the composition. %, More preferably 90% by mass or more, and still more preferably 100% by mass.

The composition of one embodiment has, for example, the following composition, based on the total weight of the composition.
(A) 0.01% by mass or less and 10% by mass or less of branched aliphatic monocarboxylic acid (B) 0.01% by mass or more and 10% by mass or less of linear aliphatic monocarboxylic acid (C) Oxygen atom-free monoamine 0.1 (D) Hydrocarbon solvent 70% to 99% by mass (E) Other additives 0% to 10% by mass

2. Method for Producing Cleaning Oil Composition One aspect 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 the following components: (A) a branched aliphatic monocarboxylic acid, (B) a linear aliphatic monocarboxylic acid, (C) an oxygen atom-free monoamine, and (D) A method comprising mixing a hydrocarbon solvent, wherein the molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.
In addition to component (A), component (B), component (C), and component (D), component (E) may be mixed as necessary.
Specific embodiments of the component (A), the component (B), the component (C), the component (C), the component (D), and the component (E) are those described in the above “1. Is the same as
The above components (A), (B), and (C), (D) and, if necessary, component (E) may be mixed by any method, and the order of mixing and the method thereof are limited. Not done.

As described above, at least one of the component (A) and the component (B) and the component (C) can form a carboxylic acid amine salt in a composition produced by mixing. Therefore, the composition produced by the production method of this embodiment includes (i) a branched (a) produced by reacting (A) a branched aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom. A monoamine salt of an aliphatic monocarboxylic acid, (ii) a linear aliphatic monocarboxylic acid (b) produced by reacting (B) a linear aliphatic monocarboxylic acid with (C) a monoamine containing no oxygen atom (Iii) a branched aliphatic monocarboxylic acid that does not form a carboxylic acid amine salt, (iv) a linear aliphatic monocarboxylic acid that does not form a (iv) carboxylic acid amine salt, and And / or (v) an oxygen atom-free monoamine that does not form a carboxylic acid 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 of draining and cleaning an object to be cleaned having moisture adhered to the surface, and includes cleaning the object to be cleaned using the above-described cleaning oil composition (cleaning step).

方法 The method of cleaning the object to be cleaned using the cleaning oil composition is not particularly limited. For example, by bringing the cleaning oil composition of the present embodiment into contact with the object to be cleaned having moisture adhered to the surface, the water is removed from the object to be cleaned. The contact of the cleaning oil composition can be performed, for example, by dipping, showering, spraying, or the like. In the case of dipping, if necessary, ultrasonic waves, stirring, air bubbling, rocking the object to be cleaned, and the like are performed. This can enhance the cleaning effect. These can be used alone or in combination of a plurality of methods in consideration of required cleanliness and required time.

For example, when the object to be cleaned having moisture adhered to the surface is immersed in the cleaning oil composition, it penetrates between the surface of the object to be cleaned and the water and is adsorbed on the surface of the object to be cleaned, and the water is removed from the surface of the object to be cleaned. It is peeled off and removed. The removed water is separated without dissolving in the cleaning oil composition, collects to form droplets, and is quickly collected below the cleaning tank by utilizing the specific gravity difference with the cleaning oil composition, Form an aqueous phase. After washing the object to be washed, the lower aqueous phase containing water can be easily removed.

The time of the cleaning step is appropriately set according to the required degree of cleanliness, the type of the object to be cleaned, the moisture component attached to the surface, and the type of the processing liquid.
The temperature of the cleaning oil composition at the time of performing the cleaning step is, for example, preferably from 0 to 60 ° C. (preferably 15 to 40 ° C., more preferably 20 to 30 ° C.) in terms of detergency and prevention of volatilization.

The cleaning oil composition of the present embodiment has water-replaceability and is excellent in separability, so that 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 a separate cleaning process without performing a regeneration process after the cleaning process, and is excellent in work efficiency of the cleaning process.

After the cleaning step, the object to be cleaned may be dried as it is after draining the liquid. In the cleaning oil composition of the present embodiment, the component (A), the component (B), and the component (C), and the reaction product of the component (A) or the component (B) with the component (C) include the component (C) It has excellent solubility in D), so that it does not easily adhere to the surface of the object to be cleaned after draining. Therefore, the object to be cleaned can be dried as it is without performing a rinsing step after draining to obtain a finished product, or a separate process can be performed.
The drying method is not particularly limited, and a drying method used in a conventional cleaning method such as hot air drying, suction drying, rotary drying, vacuum drying, and vacuum vapor drying can be used.

後 After the cleaning step, a rinsing step of dipping the drained object in a rinsing liquid may be performed. As the rinsing liquid, the same hydrocarbon solvent as the (D) hydrocarbon solvent used in the cleaning oil composition can be used, or a hydrocarbon having a lower boiling point than the (D) hydrocarbon solvent can be used. . The rinsing step may be performed once or may be performed two or more times. By performing the rinsing step, it is possible to remove the cleaning oil composition remaining on the surface of the object to be cleaned and the components blended in the cleaning oil composition. When the cleaning oil composition contains a surfactant in addition to the components (A) to (C), or when a trace amount of the surfactant remaining on the surface of the object to be cleaned poses a problem, a rinsing step is preferably performed. . After the rinsing step, the object to be cleaned is usually drained and dried.

物 The object to be cleaned is not particularly limited, and examples thereof include metal materials, glass, ceramics, and resins. Among them, a metal material is preferable in that an excellent cleaning effect can be obtained. Specific examples of the object to be cleaned of the metal material include metal jigs and tools; metal products (for example, quenched steel); cold-rolled steel plates and their processed products, hot-rolled steel plates, galvanized steel plates, and the like. Iron products such as processed products and forged products; stainless steel products; aluminum products such as plate-like products and die-cast products mainly made of aluminum; heat-resistant alloys such as titanium and molybdenum-containing steel; products using difficult-to-process materials; Can be

The water removed from the surface of the object to be cleaned in the method of the present embodiment is not particularly limited as long as it is an aqueous component. For example, water, water-based processing oil (eg, cutting oil, polishing oil, press oil, rolling oil, rust prevention) Oil, heat-treated oil, washing oil).

Hereinafter, the present invention will be described in detail with reference to examples, but the technical scope of the present invention is not limited thereto. As used herein, "room temperature" usually indicates from about 10 ° C to about 35 ° C. % Indicates mass percent unless otherwise specified.

[Examples 1 to 12, Comparative Examples 1 to 4]
As shown in Table 1 below, the components shown in Table 1 below were blended with an isoparaffin solvent (component D) to prepare cleaning oil compositions of Examples and Comparative Examples.

[Evaluation]
The following evaluation was performed using the prepared cleaning oil composition as a test oil. Table 1 shows the results.
(1) Water displaceability A clean test piece was immersed in water or a diluent of a cutting oil and pulled up. As a result, a water film adheres to the surface of the test piece. The test piece was placed in a beaker containing test oil, and the time required for the water film on the test piece surface to break and aggregate into water droplets was measured as the time required for water replacement.
The following test piece 1 or test piece 2 was used as a test piece.
Test piece 1: GA material (galvanized steel sheet; length 60 mm x width 80 mm x 0.8 mm thickness)
Specimen 2: SPCC-SD (cold rolled steel sheet polished with 240th abrasive cloth; length 60 mm x width 80 mm x 0.8 mm thickness)
City water was used as water. The following cutting oil dilution 1 or cutting oil dilution 2 was used as the cutting oil dilution.
Cutting oil diluent 1: Alpha cool CS (water-soluble cutting oil, emulsion type, manufactured by Idemitsu Kosan Co., Ltd.) at a 5% concentration in water. Cutting oil diluent 2: Alpha cool ML (Idemitsu Kosan, water-soluble) 5% strength water diluent of cutting oil and solvable type (Evaluation criteria for each test)
Based on the measurement results of the time required for water replacement, evaluation was made according to the following criteria.
Evaluation A: Time required for water replacement is 5 seconds or less Evaluation B: Time required for water replacement exceeds 5 seconds (Comprehensive evaluation)
In the six tests using water, cutting fluid diluent 1 and cutting fluid diluent 2 in test pieces 1 and 2, based on the above evaluation criteria (evaluation A and evaluation B), comprehensive evaluation was performed as follows. .
Good (O): All of the six tests are rated A. Poor (X): At least one of the six tests is rated B.

(2) Separability In a 100 mL cylinder, 50 mL of water or a diluent of a cutting oil was put, and then 50 mL of test oil was gently put. City water was used as water. The following cutting oil dilution 1 or cutting oil dilution 2 was used as the cutting oil dilution.
Cutting oil diluent 1: Alpha cool CS (water-soluble cutting oil, emulsion type, manufactured by Idemitsu Kosan Co., Ltd.) at a 5% concentration in water. Cutting oil diluent 2: Alpha cool ML (Idemitsu Kosan, water-soluble) 5% strength water diluent of cutting oil and solvable type (Evaluation criteria for each test)
After vigorously stirring up and down for 5 seconds, the mixture was allowed to stand, and the time until the aqueous layer and the oil layer separated (oil layer return time) was measured and evaluated according to the following criteria.
Evaluation A: Oil layer return time is 2 minutes or less, and no oil turbidity is observed in the oil layer. Evaluation B: Oil layer return time is more than 2 minutes and 6 minutes or less, and no oil turbidity is observed. : Oil return time exceeds 6 minutes and / or cloudiness is observed in the oil layer (Comprehensive evaluation)
In three tests using water, cutting fluid diluent 1, and cutting fluid diluent 2, a comprehensive evaluation was performed as follows based on the evaluation criteria (evaluation A, evaluation B, and evaluation C) of each test described above.
Very good (A): Evaluation of all three tests is evaluation A Good (O): All of evaluations of three tests are evaluation A or evaluation B, and at least one is evaluation B Bad (×) ): At least one of the three test evaluations is evaluation C

(3) Low-temperature stability 100 mL of test oil was placed in a 100-mL test bottle, and left at -5 ° C for 5 days (condition A) or at -10 ° C for 7 days (condition B). The appearance was observed and the presence or absence of the precipitate was determined. Those without precipitation were judged to be good and evaluated according to the following criteria.
Very good (◎): Good (no precipitation) under both conditions A and B Good (○): Good (no precipitation) under condition A and precipitation is seen under condition B Poor (×): Precipitation is seen under both conditions A and B

The components used in Table 1 are as follows.
1. Component (A)
1. Branched C10 fatty acid: neodecanoic acid Branched C9 fatty acid: trimethylhexanoic acid Component (B)
Linear C8 fatty acid: n-octanoic acid3. Component (C)
3. Linear C8 amine: n-octylamine Component (D)
Isoparaffin solvent: Isoparaffinic hydrocarbon (contains isoundecane as a main component; 100% by volume distillation temperature is 173 to 178 ° C. in a normal pressure distillation test based on JIS K2254: 1998)
5. Other alkanolamines: N-methyldiethanolamine

As shown in Table 1, the cleaning oil composition of the example in which (A) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid are combined in a specific ratio has excellent water displacement property. It has been confirmed that the composition exhibits good low-temperature stability in a low-temperature environment of -5 ° C. while having a separation property from the above.
Further, it was 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 ° C.
In particular, the molar ratio [(B + A) / C] of the total of (A) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid to (C) the oxygen-free monoamine is 1.2 or more and 1 or more. In Example 8, which was not more than 0.4, it was confirmed that the separability was further improved.

On the other hand, the molar ratio [B / A] of (A) Comparative Example 1 not containing the branched aliphatic monocarboxylic acid and (A) the branched aliphatic monocarboxylic acid and (B) the linear aliphatic monocarboxylic acid was 1 Comparative Example 2 exceeding 0.4 had poor low-temperature stability.
Further, (B) Comparative Example 3 not containing a linear aliphatic monocarboxylic acid, (C) Comparative Example 4 not containing an oxygen atom-free monoamine, (C) Comparative Example containing an alkanolamine instead of an oxygen atom-free monoamine. In No. 5, sufficient separability was not achieved.

(4) The scope of the present invention is not limited to the above description, and may be appropriately modified and implemented other than the above examples without departing from the spirit of the present invention. All documents and publications described in this specification are incorporated herein by reference in their entirety regardless of the purpose. This specification includes the claims of Japanese Patent Application No. 2018-150678 (filed on Aug. 9, 2018), which is the basis of the priority claim of the present application, and the disclosure content of the specification. I do.

The cleaning oil composition of the present invention is suitably used for cleaning an object to be cleaned having moisture or water-based processing oil adhered to the surface.

Claims

The following ingredients:
(A) a branched aliphatic monocarboxylic acid,
(B) a linear aliphatic monocarboxylic acid,
(C) an oxygen atom-free monoamine, and (D) a hydrocarbon solvent,
Including
A cleaning oil composition, wherein the molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.
組成 The composition according to claim 1, wherein the component (A) is a branched aliphatic monocarboxylic acid having 6 to 12 carbon atoms.
The composition according to claim 1, wherein the component (B) is a linear aliphatic monocarboxylic acid having 6 to 10 carbon atoms.
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.
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 method according to claim 1, wherein a total molar ratio of the component (A) and the component (B) to the component (C) [(B + A) / C] is 0.1 or more and 3 or less. A composition according to claim 1.
The total of the content of the component (A), the component (B), the component (C), and the component (D) is 80% by mass or more based on the total mass of the composition. 7. The composition according to any one of claims 6 to 6.
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 based on the total mass of the composition.
9. The component (D) according to any one of claims 1 to 8, wherein a 100% by volume distillation temperature is an isoparaffinic solvent having a 100% by volume distillation temperature in a range of 165 to 270 ° C. in an atmospheric distillation test according to JIS K2254: 1998. Composition.
Component (A) 0.01% by mass or more and 10% by mass or less Component (B) 0.01% by mass or more and 10% by mass or less with respect to the total mass of the composition Component (C) 0.1% by mass or more The composition according to any one of claims 1 to 9, comprising 10% by mass or less, and 70% to 99% by mass of the component (D).
(11) The composition according to any one of (1) to (10), which is used for cleaning an object to be cleaned having moisture adhered to its surface, wherein the object to be cleaned is a metal material.
A method for producing a cleaning oil composition,
The following ingredients:
(A) a branched aliphatic monocarboxylic acid,
(B) a linear aliphatic monocarboxylic acid,
(C) mixing an oxygen atom-free monoamine, and (D) a hydrocarbon solvent,
The method, wherein the molar ratio [B / A] of the component (B) to the component (A) is 1.4 or less.
A method for draining and cleaning an object to be cleaned having moisture attached to its surface, the method comprising cleaning the object to be cleaned using the composition according to any one of claims 1 to 10.