JP7123045B2 - W/O emulsion detergent composition, cleaning method using W/O emulsion detergent composition, and method for producing W/O emulsion detergent composition - Google Patents

Description

The present invention relates to a W/O emulsion detergent composition, particularly parts used in various industrial fields such as automobiles, machinery, precision equipment, electricity, electronics, and optics, and pipes used in various factories such as oil refining plants and chemical plants. W/O type emulsion detergent composition used for cleaning various articles used in daily life, such as dismantled parts of automobiles, industrial machines, etc., metal products, resin products, and textiles, W/ The present invention relates to a cleaning method using an O-type emulsion cleaning composition and a method for producing a W/O-type emulsion cleaning composition.

Conventionally, when processing parts handled in various industrial fields such as automobiles, machinery, precision equipment, electricity, electronics, optics, (i) water-insoluble processing oil mainly composed of mineral oil etc., (ii) mineral oil etc. A water-soluble processing oil emulsified in water by adding a surfactant to (iii) an abrasive, etc. are used, and various stains adhere to the object to be cleaned. When cleaning items with such soiling components, depending on the soiling component, hydrocarbon-based cleaning agents, water-based cleaning agents, quasi-aqueous cleaning agents mixed with water-based cleaning agents and water-soluble solvents, isopropanol, etc. Alcohol-based cleaning agents, glycol ether-based cleaning agents, etc. are used. However, in any case, there are parts where various kinds of dirt, from low-polarity dirt such as mineral oil to high-polarity dirt such as water-soluble processing oil, are attached in combination, and parts that are denatured by heat during processing and need to be cleaned. It satisfies well-balanced requirements such as detergency, dryness, safety, economic efficiency, and toxicity against dirt adhered to the surface of objects, chemically bonded dirt, and fine particles stuck in the surface due to mechanical force during processing. I haven't been able to.

A detergent composition containing a hydrocarbon solvent, a fatty acid alkanolamide, and an N-alkylpropylenediamine fatty acid salt (for example, patent References 1 to 3), a draining composition containing an aliphatic hydrocarbon-based solvent, an amine having a predetermined carbon number, and a saturated fatty acid having a predetermined carbon number (see, for example, Patent Document 4), a hydrocarbon, and an aliphatic A draining solvent composition containing a salt of a monocarboxylic acid and an aliphatic monoamine, a nonionic surfactant, and a saturated aliphatic alcohol is disclosed (see, for example, Patent Document 5).

JP-A-10-121098 JP-A-11-293286 Japanese Patent Application Laid-Open No. 2002-188098 JP-A-10-15302 JP-A-11-293280

However, even in the detergent compositions of Patent Documents 1 to 5, since they do not contain water and do not form an emulsion, the detergency against highly polar stains may not be sufficient, and they may be denatured by heat during processing. Therefore, it is difficult to wash away stains adhered to the surface, chemically bonded stains, or fine particles stuck in the surface due to mechanical force during processing.

The present invention has been made in view of the above, and is capable of cleaning and removing a combination of low-polarity dirt and high-polarity dirt adhering to parts, and denaturing by heat during processing. a W/O type emulsion detergent composition capable of cleaning and removing stains or chemically bonded stains adhered to the surface of an object to be cleaned, or fine particles stuck in the surface of an object to be cleaned by mechanical force during processing; An object of the present invention is to provide a cleaning method using a W/O emulsion detergent composition and a method for producing a W/O emulsion detergent composition.

In order to solve the above problems, the present inventors have conducted extensive research and found that at least By using a W/O type emulsion detergent composition containing one kind of compound and/or mixture and water, it is possible to clean the complex stains of low-polarity stains and high-polarity stains adhering to parts. Not only can it be removed, but also by giving it a high dispersing power, dirt that is denatured by heat during processing and adheres to the surface of the object to be cleaned or chemically bonded dirt, or the surface of the object to be cleaned by mechanical force during processing. The inventors have found that fine particles sticking to the surface can also be removed by washing, leading to the completion of the present invention.

That is, the W/O type emulsion detergent composition of the present invention comprises a hydrocarbon solvent (A), a fatty acid alkanolamide (B), and an N-alkylpropylenediamine fatty acid salt represented by the following general formula (1). (C-1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
And at least one compound and / or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, and water (D) , 30.0 to 98.7% by mass of the hydrocarbon solvent (A), 0.2 to 12.0% by mass of the fatty acid alkanolamide (B), and 0.6 to 0.6% by mass of the compound or mixture (C) 32.0% by mass, containing the water (D) at a ratio of 0.5 to 45.0% by mass, the hydrocarbon solvent (A), the fatty acid alkanolamide (B) and the compound and / or mixture The total content of (C) is greater than the content of the water (D), and the ratio of the content of the hydrocarbon solvent (A) to the content of the water (D) ((A) / (D) ) is 0.9 or more.

Further, in the W/O type emulsion detergent composition of the present invention, in the above invention, the hydrocarbon solvent (A) is a normal paraffin solvent having 5 to 17 carbon atoms or isoparaffin having 5 to 20 carbon atoms. It is preferably a system solvent.

In addition, the cleaning method using the W/O type emulsion detergent composition of the present invention can be applied to a combination of stains with low polarity and stains with high polarity, stains that are denatured by heat during processing and adhered to the surface, and chemical stains that adhere to the surface. A method for cleaning an object to be washed to which bound dirt or fine particles stuck to the surface due to mechanical force during processing are attached, wherein the W/O type emulsion detergent composition according to any one of the above is applied to the object to be washed. It is characterized by comprising a cleaning step of immersing and cleaning the object to be cleaned, and a rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A) after the cleaning step.

In addition, the cleaning method using the W/O type emulsion detergent composition of the present invention can be applied to a combination of stains with low polarity and stains with high polarity, stains that are denatured by heat during processing and adhered to the surface, and chemical stains that adhere to the surface. A method for cleaning an object to be washed to which bound dirt or fine particles stuck to the surface due to mechanical force during processing are attached, wherein the W/O type emulsion detergent composition according to any one of the above is applied to the object to be washed. A washing step of immersing and washing the washed object, after the washing step, a hydrocarbon solvent (A), a fatty acid alkanolamide (B), and an N-alkylpropylenediamine fatty acid salt represented by the following general formula (1) (C-1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, and the hydrocarbon 55.0 to 99.2% by mass of the system solvent (A), 0.2 to 12.0% by mass of the fatty acid alkanolamide (B), and 0.6 to 32.0% by mass of the compound or mixture (C) %, and the content of water (D) is 1.0% by mass or less, immersing the object to be cleaned in a cleaning composition (E) to replace the W/O emulsion cleaning agent. and a rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A).

Further, the method for producing the W/O type emulsion detergent composition of the present invention comprises 30.0 to 98.7% by mass of the hydrocarbon solvent (A) and 0.2 to 12% of the fatty acid alkanolamide (B). .0% by mass, and an N-alkylpropylenediamine fatty acid salt (C-1) represented by the following general formula (1);
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, in an amount of 0.6 to 32.0 % by mass, and after mixing, the total content of the hydrocarbon solvent (A), the fatty acid alkanolamide (B), and the compound and/or mixture (C) is higher than the content of water (D). Often, the water (D) is added to 0 so that the ratio of the content of the hydrocarbon solvent (A) to the content of the water (D) ((A)/(D)) is 0.9 or more. .5 to 45.0% by mass.

According to the present invention, in addition to low-polarity dirt and high-polarity dirt adhering to the object to be cleaned, dirt that is denatured by heat during processing and adheres to the surface of the object to be cleaned, chemically bonded dirt, and processed Fine particles stuck in the surface of the object to be cleaned by the mechanical force of time can be removed by cleaning.

Embodiments of the present invention are described in detail below.

The W/O type emulsion detergent composition of the present invention comprises a hydrocarbon solvent (A), a fatty acid alkanolamide (B), and an N-alkylpropylenediamine fatty acid salt (C -1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, and water (D), 30.0 to 98.7 mass % of the hydrocarbon solvent (A), 0.2 to 12.0 mass % of the fatty acid alkanolamide (B), and 0.6 to 32 mass % of the compound or mixture (C). 0% by mass, containing 0.5 to 45.0% by mass of the water (D), the hydrocarbon solvent (A), the fatty acid alkanolamide (B) and the compound and / or mixture (C ) is greater than the content of the water (D), and the ratio of the content of the hydrocarbon solvent (A) to the content of the water (D) ((A)/(D)) is 0.9 or more, and if necessary, other components are included.

The hydrocarbon-based solvent (A) used in the present invention may be any commercially available hydrocarbon-based solvent, and is not particularly limited, but it is desirable to select one that is less polluting to the environment. As such a solvent, a solvent mainly composed of one having 5 to 20 carbon atoms, preferably 7 to 16 carbon atoms, particularly preferably 9 to 15 carbon atoms can be used. Those having less than 5 carbon atoms have a low flash point and are difficult to handle during work. On the other hand, if the number of carbon atoms exceeds 20, the drying property is deteriorated and the viscosity of the W/O type emulsion detergent composition is increased. . Furthermore, when good drying property is required, it is desirable to use a hydrocarbon having the same number of carbon atoms or a mixture of two kinds of hydrocarbons having one different number of carbon atoms. Examples of such hydrocarbon solvents include normal paraffin solvents having 5 to 17 carbon atoms, isoparaffin solvents having 6 to 20 carbon atoms obtained by polymerizing olefins having 3 or 4 carbon atoms, and isoparaffin solvents having 5 to 20 carbon atoms. mixed naphthenic solvents, aromatic solvents with 6 to 20 carbon atoms, and kerosene.

Normal paraffinic solvents having 5 to 17 carbon atoms, preferably 7 to 14 carbon atoms, and particularly preferably 9 to 13 carbon atoms can be used. When the number of carbon atoms exceeds 17, the drying property is deteriorated and the viscosity of the W/O type emulsion detergent composition is increased, which is not preferable because the ability to remove stains adhering to the object to be washed is lowered. Furthermore, since the melting point is high, some of them cannot be dissolved without heating, and the boiling point is too high to be recovered by distillation when used in the rinsing process.

The isoparaffin-based solvent may have 5 to 20 carbon atoms, preferably 8 to 16 carbon atoms, and more preferably 8 to 12 carbon atoms. , 9, 12 and 16. In this case, in order to obtain good drying properties, when mixing solvents having a carbon number different by one, a combination of isoparaffinic solvents having carbon numbers of 8 and 9 is used, or an isoparaffinic solvent and the isoparaffinic solvent are used. It is used in combination with a normal paraffinic solvent having a boiling point equivalent to that of the boiling point.

The content of the hydrocarbon-based solvent (A) is not particularly limited as long as it is 30.0% by mass to 98.7% by mass with respect to the W/O type emulsion detergent composition, depending on the purpose. Although it can be selected as appropriate, from the viewpoint of obtaining well-balanced detergency, it is preferably 50.0% by mass to 98.0% by mass, more preferably 55.0% by mass to 92.0% by mass, and 60.0% by mass. % to 90.0% by weight is particularly preferred. If the content of the hydrocarbon-based solvent (A) is less than 30.0% by mass with respect to the W/O emulsion detergent composition, the detergency against stains with low polarity will be particularly insufficient. There is fear.

The fatty acid alkanolamide (B) used in the present invention has 7 to 22 carbon atoms, preferably 8 to 20 carbon atoms. Specific examples include saturated fatty acids such as octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid, unsaturated fatty acids such as oleic acid, mixtures thereof, and naturally occurring fatty acids. . Among these, unsaturated fatty acids such as oleic acid can be preferably used because they have a lower melting point. Amines may also include diethanolamine, monoethanolamine, monoiso-propanolamine, or mixtures thereof. Dodecanoic acid (lauric acid) monoethanolamide, dodecanoic acid diethanolamide, octadecanoic acid diethanolamide, octadecanoic acid monoethanolamide, oleic acid diethanolamide, oleic acid monoethanolamide, coconut oil derived from the above fatty acids and amines Fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, tetradecanoic acid (myristic acid) diethanolamide, tetradecanoic acid monoethanolamide, dodecanoic acid tetradecanoic acid diethanolamide, hexadecanoic acid (palmitic acid) diethanolamide, hexadecanoic acid monoethanolamide, dodecanoic acid Isopropanolamide, iso-octadecanoic acid diethanolamide, iso-octadecanoic acid monoethanolamide, palm kernel oil fatty acid diethanolamide, palm kernel oil fatty acid monoethanolamide and the like can be mentioned, among these, dodecanoic acid monoethanolamide, dodecane Acid diethanolamide, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, palm kernel oil fatty acid diethanolamide, and palm kernel oil fatty acid monoethanolamide are preferred in terms of availability.

As a method for producing fatty acid alkanolamide, a method such as adding a double molar amount of diethanolamine, monoethanolamine, or monoiso-propanolamine to a predetermined amount of fatty acid, heating under a nitrogen stream, and dehydration condensation is used. can be done. As in the case of the N-alkylpropylenediamine fatty acid salt, the fatty acid to be used does not have to be a single component, and there is no problem in using a mixture of two or more types or naturally derived fatty acids.

The content of the fatty acid alkanolamide (B) is not particularly limited as long as it is 0.2% by mass to 12.0% by mass with respect to the W/O emulsion detergent composition, and may be appropriately selected depending on the purpose. Although it can be selected, from the viewpoint of obtaining well-balanced detergency, it is preferably 0.2% by mass to 10.0% by mass, more preferably 0.3% by mass to 7.0% by mass, and 0.3% by mass. ~5.0% by weight is particularly preferred. If the content of the fatty acid alkanolamide (B) is less than 0.2% by mass with respect to the W/O emulsion detergent composition, the W/O emulsion formation, stability and dispersibility are insufficient. is likely to be sufficient. On the other hand, if it exceeds 12.0% by mass, the viscosity of the cleaning agent will be significantly increased, which may conversely reduce the dispersing power.

The N-alkylpropylenediamine fatty acid salt (C-1) used in the present invention is represented by the following general formula (1).
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms.

As the amine of the N-alkylpropylenediamine fatty acid salt (C-1), the alkyl group (R ¹ ) has 7 to 22 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 14 to 18 carbon atoms. Among them, octadecylpropylenediamine, hexadecylpropylenediamine, and tetradecylpropylenediamine are particularly preferred due to their easy availability.

As the fatty acid of the N-alkylpropylenediamine fatty acid salt (C-1), those having 7 to 22, preferably 8 to 20 carbon atoms in the alkyl group (R ² ) can be used. Specifically, saturated fatty acids such as octanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), and unsaturated fatty acids such as oleic acid. Mention may be made of fatty acids. Among these, unsaturated fatty acids such as oleic acid can be preferably used because of their low melting points.

N-alkylpropylenediamine fatty acid salt (C-1) can be synthesized by various methods. For example, a method in which a corresponding N-alkyl primary amine and acrylonitrile are reacted at 100 to 200° C. using a catalyst under a nitrogen atmosphere, hydrogenated, and a fatty acid is added to the resulting N-alkylpropylenediamine under a nitrogen atmosphere. can be adopted. The N-alkylpropylenediamine and fatty acid need not be of a single type, and there is no problem in using a mixture of two or more types or naturally occurring ones. In particular, when beef tallow or vegetable oil is used as a raw material, the raw material is inexpensive, so it is preferable for producing products at low cost.

The mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms is an actual mixture of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, in addition to , and mixtures of fatty acids having 7 to 22 carbon atoms and amines having 7 to 22 carbon atoms.

Fatty acids having 7 to 22 carbon atoms, preferably 8 to 20 carbon atoms can be used. Specifically, saturated fatty acids such as octanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), and unsaturated fatty acids such as oleic acid. Mention may be made of fatty acids.

As the amine, those having 7 to 22 carbon atoms, preferably 8 to 20 carbon atoms can be used. Specific examples include octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 2-ethylhexylamine, di(2-ethylhexyl)amine, and oleoylamine. The amines and fatty acids do not have to be single ones, and there is no problem in using a mixture of two or more kinds or naturally derived ones.

and/ Alternatively, the content of the mixture (C) is not particularly limited as long as it is 0.6% by mass to 32.0% by mass with respect to the W/O type emulsion detergent composition, and is appropriately selected according to the purpose. 0.8% by mass to 31.0% by mass is preferable, and 1.0% by mass to 30.0% by mass is particularly preferable. If the content of the compound or mixture (C) is less than 0.6% by mass with respect to the W/O emulsion detergent composition, the W/O emulsion will not have sufficient power to form and disperse. There is fear. On the other hand, if it exceeds 32.0% by mass, the viscosity of the cleaning agent will be significantly increased, which may conversely reduce the dispersing power.

In addition, fatty acid alkanolamide (B), compound and / or N-alkyl propylene diamine fatty acid salt (C-1), which is one of the options for the mixture (C), when dissolved alone in a hydrocarbon solvent, fatty acid Only about 1% by mass of alkanolamide and about 2% by mass of propylenediamine fatty acid salt are dissolved. However, when these two are mixed, the solubility is dramatically improved to about 20 times. Although the reason for this is not clear, it is considered to be one of the factors that enables the adjustment of the emulsion forming power, stability and dispersing power of detergents over a wider range.

The content ratio of the fatty acid alkanolamide (B) and the N-alkylpropylenediamine fatty acid salt (C-1) is such that the fatty acid alkanolamide (B) content is the N-alkylpropylenediamine fatty acid salt (C-1) content, Desirably, the range is 0.01 to 2.0 times, preferably 0.1 to 1.5 times, more preferably 0.2 to 1.0 times. Within this range, it is possible to greatly improve the surfactant concentration in the hydrocarbon. If this is less than 0.01 times or exceeds 2.0 times, it becomes difficult to increase the surfactant concentration.

Distilled water, ion-exchanged water, tap water, etc. can be used as the water (D) used in the present invention, and there is no particular limitation.

The content of water (D) is not particularly limited as long as it is 0.5% by mass to 45.0% by mass with respect to the W/O type emulsion detergent composition, and is appropriately selected according to the purpose. 1.0% by mass to 30.0% by mass is preferable, and 5.0% by mass to 25.0% by mass is particularly preferable.
If the content of water (D) is 45.0% by mass or more with respect to the W/O type emulsion detergent composition, there is a possibility that the detergency against dirt with low polarity may be insufficient, and at the same time particles, etc. There is a risk that the dispersing power will be insufficient, and if it is less than 0.5% by mass, there is a risk that the detergency against highly polar stains will be insufficient, and at the same time, there will be a risk that the dispersing power of particles, etc. will be insufficient. be.

Further, the content of water (D) is 0.5% by mass to 45.0% by mass, preferably 1.0% by mass to 30.0% by mass, relative to the W/O type emulsion detergent composition, Particularly preferably, 5.0% by mass to 25.0% by mass of oils containing metal salts such as calcium, magnesium, lithium and molybdenum such as water-insoluble cutting oils, water-insoluble press oils and greases. It is possible to improve the detergency against dirt.

The relationship between the content of the hydrocarbon solvent (A), fatty acid alkanolamide (B), compound and/or mixture (C), and water (D) used in the present invention is the hydrocarbon solvent (A) and fatty acid At least selected from the group consisting of alkanolamides (B), N-alkylpropylenediamine fatty acid salts (C-1), and mixtures of fatty acids having 7 to 22 carbon atoms and amines having 7 to 22 carbon atoms (C-2) The total content of one compound and/or mixture (C) is greater than the content of water (D), and the ratio of the content of hydrocarbon solvent (A) to the content of water (D) ((A )/(D)) is not particularly limited as long as it is 0.9 or more and can be appropriately selected depending on the purpose, but it is preferably 1.4 or more, particularly 1.8 or more. preferable. When the total content of hydrocarbon solvent (A), fatty acid alkanolamide (B) and compound and/or mixture (C) is equal to or less than the content of water (D), or hydrocarbon solvent (A)/water If (D) is less than 0.9, it may not be possible to produce a W/O emulsion having both detergency and dispersibility.

The W/O type emulsion detergent composition of the present invention contains ingredients such as esters, alcohols, ketones, etc., and other surfactants, in a range that does not impair the object of the present invention, preferably 10% by mass or less. Conventional additives such as additives, antioxidants, UV absorbers, rust inhibitors and the like can be included.

Other surfactants are preferably nonionic surfactants such as higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid esters of sorbitol and sorbitan. , sucrose fatty acid ester, silicon-based, fluorine-based, and the like can be used.

Further, as the ultraviolet absorber and antioxidant, known ones can be used as long as they are soluble in the W/O type emulsion detergent composition of the present invention. It is useful for improving stability in such as. Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, and hindered amine-based ultraviolet absorbers.
Furthermore, the antioxidants include, for example, phenolic, amine, sulfur, and phosphorus antioxidants, and it is particularly preferable to add 100 to 1000 ppm of phenolic antioxidants.

The W/O type emulsion detergent composition of the present invention is prepared by weighing predetermined amounts of the above hydrocarbon solvent (A), fatty acid alkanolamide (B), compound and/or mixture (C), mixing them, and adding water. It can be produced by adding (D). There are no restrictions on the mixing order or mixing method of the components other than water (D). can be manufactured. A W/O emulsion can be produced by adding only water (D) after mixing other components. It should be noted that the components other than water (D) are preferably mixed substantially uniformly, and such homogenization is performed by, for example, stirring. In addition, in order to produce a W/O emulsion more appropriately, it is preferable to apply a physical force such as stirring or ultrasonic irradiation after adding water (D).

Further, as one aspect of the cleaning method using the W/O type emulsion detergent composition of the present invention, an object to be cleaned is immersed in the W/O type emulsion detergent composition of the present invention for cleaning, and then the object is washed. It can be carried out by immersing the object to be cleaned in the hydrocarbon solvent (A) to rinse off the W/O type emulsion detergent composition adhering to the object to be cleaned. By immersing the object to be cleaned in the W/O type emulsion detergent composition according to the present invention, stains of low polarity and high polarity adhering to the object to be cleaned, and denatured by heat during processing. It is possible to clean the dirt adhered to the surface of the object to be cleaned, the dirt chemically bonded to the surface of the object to be cleaned, or fine particles stuck in the surface of the object to be cleaned by the mechanical force during processing. This is because the W/O type emulsion detergent composition according to the present invention dissolves dirt with low polarity in the hydrocarbon solvent (A) and dirt with high polarity in water (D). , and particles etc. are removed by the dispersing power of fatty acid alkanolamide (B), compound and / or mixture (C), and water (D) functioning as a surfactant, so that dirt is washed. It is considered to be

When the object to be cleaned is immersed in the W/O type emulsion detergent composition of the present invention, it is preferable to combine stirring, shaking, ultrasonic irradiation, jet flow or air bubbling, etc., in order to enhance the cleaning effect. . In the case of ultrasonic waves, the irradiation conditions are preferably, for example, an oscillation frequency of 20 to 100 kHz and an oscillation output of 0.1 to 200 W/L. Ultrasonic irradiation improves the dissolution rate of dirt from the surface of the object to be cleaned and the dispersing power of fine particles, and separates dirt that is insoluble in the W/O type emulsion detergent composition and raises it together with air bubbles to remove it. can.

The washing time is preferably 15 seconds to 30 minutes, particularly preferably 30 seconds to 15 minutes. If the amount is less than the above range, the cleaning is insufficient and the attached dirt cannot be sufficiently removed. The washing temperature is preferably 20-90°C. If the washing temperature is less than the above range, the washing tends to be insufficient, so the washing effect can be significantly increased by treating at a higher temperature. It is preferable to wash with

For the purpose of removing components other than the hydrocarbon solvent (A) contained in the W/O emulsion detergent composition after washing the object to be washed with the W/O emulsion detergent composition of the present invention. , The rinsing step is performed with the hydrocarbon solvent (A). The hydrocarbon solvent (A) used in the rinsing step is the hydrocarbon solvent (A ) or those with a lower boiling point are preferred. Also, the rinsing step may be performed once or twice or more.

In the rinsing step of the cleaning method according to the present invention, it is preferable to combine stirring, shaking, ultrasonic wave irradiation, jet flow, air bubbling, or the like, in order to enhance the rinsing effect. In the case of ultrasonic waves, the irradiation conditions are preferably, for example, an oscillation frequency of 20 to 100 kHz and an oscillation output of 0.1 to 200 W/L. Ultrasonic irradiation improves the dissolving and dispersing power of each component in the W/O emulsion detergent composition and the dirt component carried out from the surface of the object to be cleaned, and also has a shape such as a blind hole that is difficult to clean by immersion alone. Each component of the W/O type emulsion detergent composition and the dirt components carried out can also be dissolved and dispersed from the portion with the handle, and lifted up together with the air bubbles to be removed.

Further, as another aspect of the cleaning method using the W/O type emulsion detergent composition of the present invention, an object to be cleaned is immersed in the W/O type emulsion detergent composition of the present invention for washing, The object to be cleaned is immersed in a cleaning composition (E) containing the same components as the W/O emulsion cleaning composition according to the present invention and having a water content of 1.0% by mass or less. The W/O type emulsion detergent composition (E) adhering to the object to be cleaned can be rinsed by replacing the emulsion detergent, immersing the object to be cleaned in the hydrocarbon solvent (A), and rinsing the W/O emulsion detergent composition (E) adhering to the object to be cleaned. can. When the water content in the W/O type emulsion detergent composition according to the present invention is high (for example, the content of water (D) is 35% by mass or more), the emulsion detergent composition can only be immersed in a hydrocarbon solvent. Although there is a risk that the water particles inside may not be sufficiently removed by washing, the object to be washed can be immersed in a W/O type emulsion detergent composition (E) that has a low water content and retains the ability to form an emulsion. , water particles adhering to the object to be cleaned are sufficiently removed, and contained in the W/O type emulsion detergent composition (E) adhering to the object to be cleaned by immersion in the hydrocarbon solvent (A). components other than the hydrocarbon-based solvent can be sufficiently removed by washing.

The cleaning composition (E) used in the substitution step comprises a hydrocarbon solvent (A), a fatty acid alkanolamide (B), and an N-alkylpropylenediamine fatty acid salt (C -1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, and a hydrocarbon-based 55.0 to 99.2% by mass of solvent (A), 0.2 to 12.0% by mass of fatty acid alkanolamide (B), and 0.6 to 32.0% by mass of compound or mixture (C), The content of water (D) is 1% by mass or less. The detergent composition (E) has the same composition ratio of components other than water (D) as the W/O emulsion detergent composition used for washing the object to be washed, and the content of water (D) is is 1% by mass or less, and the composition ratio of components other than water (D) may be different as long as the content of water (D) is 1% by mass or less.

In the replacement step of the cleaning method according to the present invention, when the object to be cleaned is immersed in the cleaning composition (E), stirring, shaking, ultrasonic irradiation, jet flow, air bubbling, or the like is performed in order to enhance the cleaning effect. are preferably combined. In the case of ultrasonic waves, the irradiation conditions are preferably, for example, an oscillation frequency of 20 to 100 kHz and an oscillation output of 0.1 to 200 W/L. Ultrasonic irradiation improves the dispersing power of water particles in the W/O emulsion detergent composition from the surface of the object to be cleaned, and also cleans from areas such as blind holes that are difficult to clean by immersion alone. It is also possible to disperse water particles in the agent composition (E) and raise them together with air bubbles to remove them.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Tables 1 and 2 show the compositions of the detergent compositions prepared as Examples 1 to 15 and Comparative Examples 1 to 3.

<Detergency evaluation 1>
In washability evaluation 1, aluminum alloy workpieces (objects to be washed) processed with a water-soluble working oil (A1 type No. 2) were washed in Examples 1 to 15 and Comparative Examples 1 to 3 shown in Tables 1 and 2. It was immersed in the detergent composition and washed at room temperature at 28 kHz for 10 minutes using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)). After washing, the object to be cleaned was immersed in n-decane and rinsed at room temperature at 28 kHz for 10 minutes using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)). After that, it was dried at 80° C. for 30 minutes. After drying the object to be washed, the surface of the object to be washed was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Detergency evaluation 2>
In washability evaluation 2, aluminum alloy workpieces (objects to be washed) processed with a water-soluble working oil (A1 type No. 2) were subjected to the cleaning of Examples 1 to 15 and Comparative Examples 1 to 3 shown in Tables 1 and 2. It was immersed in the detergent composition and washed at room temperature at 28 kHz for 10 minutes using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)). After cleaning, the object to be cleaned is immersed in the cleaning composition of Example 1, and is subjected to 10 minutes at room temperature at 28 kHz using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)). Displacement wash for 1 minute. After washing, the object to be cleaned was immersed in n-decane and rinsed for 1 minute at room temperature at 28 kHz using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Electronics Co., Ltd.)). After that, it was dried at 80° C. for 30 minutes. After drying the object to be washed, the surface of the object to be washed was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Washability evaluation 3>
In Detergency Evaluation 3, the cleaning composition used for the second cleaning in Detergency Evaluation 2 (the cleaning composition of Example 1) was added to the cleaning composition of Comparative Example 1 (the cleaning composition (E)). equivalent), and the cleaning test was conducted in the same manner as in the cleaning property evaluation 2, and the surface of the object to be cleaned was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Detergency Evaluation 4>
In washability evaluation 4, the bearing was immersed in a 5% by mass aqueous solution of water-soluble working oil (A1 type No. 1) or a 2.5% by mass aqueous solution of water-soluble working oil (A3 type No. 1) to make a simulated work. Otherwise, a cleaning test was conducted in the same manner as in Detergency Evaluation 1, and the surface of the object to be cleaned was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Washability evaluation 5>
In washability evaluation 5, the bearing was immersed in a 5% by mass aqueous solution of water-soluble working oil (A1 type No. 1) or a 2.5% by mass aqueous solution of water-soluble working oil (A3 type No. 1) to make a simulated work. Otherwise, a cleaning test was conducted in the same manner as in Detergency Evaluation 3, and the surface of the object to be cleaned was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Detergency evaluation 6>
In washability evaluation 6, the bearing was immersed in a water-insoluble working oil to make a simulated work, but the washing test was performed in the same manner as in washability evaluation 1, and the surface of the object to be cleaned was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

<Detergency evaluation 7>
In washability evaluation 7, the bearing was immersed in water-insoluble working oil to make a simulated work, but the washing test was conducted in the same manner as in washability evaluation 3, and the surface of the object to be cleaned was visually observed. The results are shown in Tables 1 and 2 for the evaluation of washability.

As shown in Tables 1 and 2, the W/O type emulsion detergent compositions of Examples 1 to 15 were found to have low polarity stains and high polarity stains or stains that were denatured by heat during processing and adhered to the surface. It has been confirmed that dirt that is chemically bonded, or fine particles stuck in the surface due to mechanical force during processing can be cleaned and removed.

Next, an evaluation of the detergency of parts to which water-insoluble cutting oil containing calcium and magnesium, water-insoluble press oil containing calcium, or grease containing lithium and molybdenum is adhered will be described. In the past, chlorine-based extreme pressure agents were included in water-insoluble cutting oils and water-insoluble press oils used in various industrial fields. Switching to extreme pressure agents is progressing. Water-insoluble cutting oil and water-insoluble press oil using a sulfur-based extreme pressure agent contain calcium and the like in order to enhance the performance of the sulfur-based extreme pressure agent. Greases used in various industrial fields contain lithium as a thickening agent and molybdenum as a solid lubricant. When cleaning parts to which water-insoluble cutting oil containing calcium and magnesium, water-insoluble press oil containing calcium, or grease containing lithium and molybdenum are adhered, calcium, etc. may be removed from the surface of the parts after washing. If the metal salt of remains, problems may occur in the post-process such as heat treatment.

The present inventors used the detergent compositions prepared as Examples 16 and 17 and Comparative Examples 4 to 7 as shown in Table 3, and used a water-insoluble cutting oil containing calcium and magnesium. A cleaning test was carried out on parts to which water-insoluble press oil or grease containing lithium and molybdenum was attached, and cleaning performance was evaluated.

The detergent compositions of Examples 16 and 17 and Comparative Examples 4 and 5 have the same composition as the detergent compositions of Examples 3 and 11 and Comparative Examples 1 and 3 shown in Tables 1 and 2. Further, 3-methoxy-3-methylbutyl acetate contained in the cleaning composition of Comparative Example 7 was the above-mentioned hydrocarbon solvent (A), fatty acid alkanolamide (B), compound and/or or mixture (C).

<Detergency evaluation 8>
In washability evaluation 8, the aluminum parts (objects to be washed) processed with a water-insoluble cutting oil containing calcium and magnesium were washed with the detergent compositions of Example 16 and Comparative Examples 4 and 5 shown in Table 3. and washed with an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.) at 28 kHz and room temperature for 1 minute. The washed object was dried at 80° C. for 60 minutes. After drying the object to be washed, the surface of the object to be washed was visually observed. Table 3 shows the results of the evaluation of washability.

<Washability evaluation 9>
In detergency evaluation 9, a stainless steel flat plate (object to be washed) to which calcium-containing water-insoluble press oil adhered was placed in the detergent composition of Example 17 and Comparative Examples 5 and 7 shown in Table 3. It was immersed and washed for 1 minute at 28 kHz and room temperature using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)). The washed object was dried at 80° C. for 60 minutes. After drying the object to be cleaned, the surface of the object to be cleaned was analyzed. Table 3 shows the results of the evaluation of detergency.

<Detergency evaluation 10>
In washability evaluation 10, an aluminum flat plate (object to be washed) to which grease containing lithium and molybdenum was adhered was immersed in the detergent compositions of Example 17 and Comparative Examples 5 and 7 shown in Table 3. Using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.)), cleaning was performed at 28 kHz and room temperature for 30 seconds. The washed object was dried at 80° C. for 60 minutes. After drying the object to be washed, the surface of the object to be washed was visually observed. Table 3 shows the results of cleaning property evaluation, with ◯ indicating no residual metal salt and x indicating presence of residual metal salt.

<Detergency evaluation 11>
In washability evaluation 11, the chromium-molybdenum steel material (to-be-washed) having water-insoluble press oil containing calcium adhered to the blind holes was washed in the detergent compositions of Example 17 and Comparative Examples 6 and 7 shown in Table 3. and washed with an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Denshi Co., Ltd.) at 28 kHz and room temperature for 1 minute. The washed object was dried at 80° C. for 60 minutes. After drying the object to be washed, the surface of the pocket hole of the object to be washed was analyzed. Table 3 shows the results of the evaluation of detergency.

As shown in Table 3, the W/O emulsion detergent compositions of Examples 16 and 17 contained water-insoluble cutting oil containing calcium and magnesium, water-insoluble press oil containing calcium, lithium and molybdenum. It was confirmed that the dirt contained in the grease can be removed by washing, and that the metal salt can be suppressed from remaining on the surface of the object to be washed.

The W/O type emulsion detergent composition of the present invention can be suitably used for cleaning parts used in various industrial fields such as automobiles, machinery, precision instruments, electricity, electronics and optics.

Claims (5)

a hydrocarbon-based solvent (A);
fatty acid alkanolamide (B);
N-alkylpropylenediamine fatty acid salt (C-1) represented by the following general formula (1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms;
water (D),
30.0 to 98.7% by mass of the hydrocarbon solvent (A), 0.2 to 12.0% by mass of the fatty acid alkanolamide (B), and 0.6 to 32% of the compound or mixture (C) .0% by mass, containing the water (D) at a ratio of 0.5 to 45.0% by mass,
the total content of the hydrocarbon-based solvent (A), the fatty acid alkanolamide (B), and the compound and/or mixture (C) is greater than the content of the water (D);
W/O type emulsion cleaning, characterized in that the ratio of the content of the hydrocarbon solvent (A) to the content of the water (D) ((A)/(D)) is 0.9 or more. agent composition. 2. The W/O emulsion according to claim 1, wherein the hydrocarbon solvent (A) is a normal paraffin solvent having 5 to 17 carbon atoms or an isoparaffin solvent having 5 to 20 carbon atoms. cleaning composition. a cleaning step of immersing and cleaning an object to be cleaned in the W/O type emulsion cleaning composition according to claim 1 or 2;
and a rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A) after the cleaning step. a cleaning step of immersing and cleaning an object to be cleaned in the W/O type emulsion cleaning composition according to claim 1 or 2;
After the washing step,
a hydrocarbon-based solvent (A), a fatty acid alkanolamide (B), and an N-alkylpropylenediamine fatty acid salt (C-1) represented by the following general formula (1);
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of mixtures (C-2) of fatty acids having 7 to 22 carbon atoms and amines having 7 to 22 carbon atoms,
55.0 to 99.2% by mass of the hydrocarbon solvent (A), 0.2 to 12.0% by mass of the fatty acid alkanolamide (B), and 0.6 to 32% by mass of the compound or mixture (C). 0% by mass, and the content of water (D) is 1.0% by mass or less. replacing;
and a rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A). A cleaning method using a W/O emulsion cleaning composition. 30.0 to 98.7% by mass of the hydrocarbon solvent (A),
0.2 to 12.0% by mass of fatty acid alkanolamide (B),
N-alkylpropylenediamine fatty acid salt (C-1) represented by the following general formula (1),
R ¹ —NH(CH ₂ ) ₃ NH ^{2.2R 2} _—COOH (1)
(In formula (1), R ¹ and R ² are alkyl groups having 7 to 22 carbon atoms)
and at least one compound and/or mixture (C) selected from the group consisting of a mixture (C-2) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms, in an amount of 0.6 to 32.0 % by mass;
After mixing
the total content of the hydrocarbon-based solvent (A), the fatty acid alkanolamide (B), and the compound and/or mixture (C) is greater than the content of water (D);
so that the ratio ((A)/(D)) between the content of the hydrocarbon solvent (A) and the content of the water (D) is 0.9 or more,
A method for producing a W/O type emulsion detergent composition, characterized by adding 0.5 to 45.0% by mass of water (D).