JP2005089570A - Water-soluble oil - Google Patents

Abstract

A water-soluble oil agent having excellent antifoaming properties, lubricity and low skin irritation is provided. SOLUTION: Formula N (ROH) ₃ such as monoethanoldiisopropanolamine (where R is an alkylene group having 2 to 4 carbon atoms, except when all three R are alkylene groups having the same carbon number) Water-soluble oil agent characterized by containing 1 or more types of amine (A) shown by these. And the said water-soluble oil agent used for a metalworking fluid agent, a water-system hydraulic fluid, or a water-system wrap liquid use.
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Description

  The present invention relates to a water-soluble oil agent suitable for metal working oil, water-based hydraulic fluid, water-based lapping fluid, and the like used for cutting grinding, plastic working, etc., and in particular, excellent antifoaming properties, lubricity, and low skin irritation. It is related with the water-soluble oil agent which combined.

  Oil agents used in the metal processing field are roughly classified into two types, water-insoluble oil agents mainly composed of mineral oil and water-soluble oil agents mainly composed of water.

  Ingredients that improve anti-corrosion properties are usually added to water-soluble oils. Specifically, water-solubility such as monoethanolamine, diethanolamine, N-alkylalkanolamine, alicyclic amine, and aromatic amine should be added. Is conventionally known.

  For example, a water-soluble metalworking oil (Patent Document 1) is proposed in which an N-alkylalkanolamine, an alicyclic amine, and a tertiary amine are added for the purpose of improving the anti-corrosion and rust prevention properties of the oil. Yes. However, when these water-soluble amines are used as a component of a water-soluble oil agent, the spoilage resistance is improved, but the problem that the skin irritation becomes too strong has been pointed out.

  Therefore, by using a tertiary water-soluble amine with relatively low skin irritation such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, etc. in combination with the above water-soluble amine, the rust-preventing property of the water-soluble oil agent over a long period of time, Attempts have been made to achieve both rot resistance and low skin irritation. However, when triethanolamine, triisopropanolamine, or N-methyldiethanolamine is used as a component of a water-soluble oil agent, all of them have a problem of defoaming property, and also have a problem of poor workability because they are solid at room temperature. there were.

JP 2002-285186 A

  In order to solve the above problems, a water-soluble oil agent having high lubricity, excellent rust prevention and anti-corrosion properties over a long period of time, and low skin irritation and good antifoaming properties. It was sought after.

  The present invention is the following invention.

Contains one or more amines (A) represented by the formula N (ROH) ₃ (wherein R is an alkylene group having 2 to 4 carbon atoms, except when all three R are alkylene groups having the same carbon number) A water-soluble oil agent characterized by

Polyethers, water, and amines represented by the formula N (ROH) ₃ (wherein R is an alkylene group having 2 to 4 carbon atoms, except that all three R are alkylene groups having the same carbon number) One or more types of (A) are contained, The water-soluble oil agent characterized by the above-mentioned.

  Moreover, the water-soluble oil agent of this invention is suitable for using it for a metalworking oil agent, a water-system hydraulic fluid, or a water-system lapping liquid application.

  The water-soluble oil agent of the present invention has high lubricity, is excellent in rust resistance and antiseptic properties over a long period of time, is low in skin irritation, and has good antifoaming properties.

(Amine (A))
In the present invention, an amine (A) represented by the formula N (ROH) ₃ (R is an alkylene group having 2 to 4 carbon atoms, except that all three R are alkylene groups having the same carbon number) is used. use.

  In the above formula, R has 2 to 4 carbon atoms. As R, ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group, 1,1-dimethylethylene group, 2,2-dimethylethylene group, 1,2-dimethylethylene group, 1-ethylethylene group, 2-ethylethylene group, etc. are mentioned. When the number of carbon atoms is 5 or more, the melting point of the amine is increased, which is not preferable.

  The amine (A) is characterized in that all three Rs are not the same carbon number alkylene group. The use of the amine (A) is characterized by a lower melting point than when a conventional water-soluble amine is used. The melting point of the amine (A) is particularly preferably 0 ° C. or lower.

  An organic carboxylic acid is usually blended in the water-soluble oil agent, but the amine (A) is considered to form an amine salt with the organic carboxylic acid. Since the amine salt formed from the amine (A) having a relatively low melting point has relatively high fluidity, even when adsorbed on a bubble film generated at the liquid-surface interface, it easily flows, As a result, it becomes difficult to maintain the foam for a long time, and as a result, the defoaming property is considered to be excellent. This is considered to be related to the crystal structure of amine (A).

  On the other hand, an amine in which all three Rs are alkylene groups having the same carbon number, such as triethanolamine, is considered to form a solid amine salt with an organic carboxylic acid usually blended in a water-soluble oil agent. It is difficult for the foam to disappear once it is adsorbed in the foam film. Therefore, it is thought that antifoaming property will be inferior.

  Specific examples of the amine (A) include monoethanoldiisopropanolamine, diethanolmonoisopropanolamine, monoethanoldiisobutanolamine, diethanolmonoisobutanolamine, monoethanolmonoisopropanolmonoisobutanolamine, monoisopropanoldiisobutanolamine, diisopropanol Monoisobutanolamine.

  Such an amine can be produced by reacting an alkanolamine such as monoethanolamine, diethanolamine or monoisopropanolamine with an alkylene oxide having a carbon number different from that of the alkoxy group of the alkanolamine. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.

  Further, by using the amine (A) in the present invention, the compatibility with other additives usually added to the water-soluble oil agent is improved, and the surfactant added for the purpose of improving the compatibility, Since polyhydric alcohols and the like can be reduced or reduced, it is possible to expect improvement in rust prevention, lubricity, and antifoaming properties of water-soluble oils. In addition, there is an effect of reducing the cost of the water-soluble oil agent.

  The ratio of the amine (A) used in the water-soluble oil agent of the present invention is preferably 1 to 50% by mass and particularly preferably 5 to 30% by mass in the water-soluble oil agent.

  Moreover, since the water-soluble oil agent in this invention can be diluted with water and used according to a use, the preferable usage rate of an amine can change with a use. In the metalworking fluid, the proportion of amine (A) used is preferably 0.1 to 70% by mass, particularly preferably 3 to 50% by mass in the metalworking fluid. If it is less than 0.1%, rust prevention and anti-corrosion properties are not improved, and if it exceeds 70% by mass, lubricity is lowered and skin irritation is enhanced.

  In the aqueous hydraulic fluid, the proportion of amine (A) used is preferably 0.5 to 20% by mass, particularly preferably 1 to 10% by mass. If it is less than 0.5% by mass and more than 20% by mass, the same problems as in metalworking fluids occur. In the aqueous wrapping solution, the proportion of the amine (A) used is preferably 0.1 to 70% by mass, and particularly preferably 3 to 50% by mass. If it is less than 0.1% by mass and more than 70% by mass, problems similar to those of metalworking fluids occur.

(Base oil component)
The water-soluble oil agent of the present invention comprises, as a base oil component, ethylene glycol, propylene glycol, polyethers, mineral oil, fats and oils, fatty acid ester, poly-α-olefin, α-olefin, normal paraffin, isoparaffin, alkylbenzene, polyol ester. Etc. are preferably contained. Examples of the polyethers include polyether polyols such as polyoxypropylene diol, polyoxyethylene diol, and polyoxypropylene oxyethylene diol, and esterified products of these polyether polyols.

  The use ratio of the base oil in the water-soluble oil agent is preferably 1 to 80% by mass. Moreover, since the water-soluble oil agent in this invention can be diluted with water and used according to a use, a preferable base oil and preferable content can change with a use.

  In the metalworking fluid, the use ratio of the base oil is preferably 5 to 80% by mass. In the aqueous hydraulic fluid, the use ratio of the base oil is preferably 10 to 50% by mass. In the aqueous wrapping solution, the base oil is preferably used in an amount of 5 to 80% by mass.

(water)
The water-soluble oil agent of the present invention preferably contains water. In order to maintain the flame retardancy of the oil, it is usually 1 to 70% by mass, preferably 5 to 50% by mass.

  The water-soluble oil agent of the present invention can be further diluted 0.5 to 300 times with water depending on the application. In the metalworking fluid, the proportion of water used in the metalworking fluid is preferably 10 to 70% by mass. In the aqueous working fluid, the proportion of water used in the aqueous working station is preferably 30 to 70% by mass. In the water-based lapping solution, the use ratio of water in the water-based lapping solution is preferably 5 to 80% by mass.

(Organic carboxylic acid)
An organic carboxylic acid may be added to the water-soluble oil agent of the present invention as necessary. It is particularly preferable to use an organic carboxylic acid.

  Organic carboxylic acids include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, caproic acid, enanthic acid, capric acid, pelargonic acid, caprylic acid, undecanoic acid, Undecylenic acid, dodecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, isostearic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid , Ricinoleic acid, erucic acid, lactic acid, glyceric acid, malic acid, citric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, hydroxyarachidic acid, hydroxybehenic acid, hydroxyoctadecenoic acid, oxalic acid Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, dodecyl succinic acid, lauryl succinic acid, stearyl succinic acid, isostearyl succinic acid, dimer acid, trimer acid , Naphthenic acid, 9 (or 10)-(4-hydroxyphenyl) octadecanoic acid, benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, salicylic acid and the like.

  From the viewpoint of improving the rust-preventing property of the water-soluble oil agent, an organic carboxylic acid having 6 to 36 carbon atoms is preferable, and from the viewpoint of further improving the defoaming property, an aliphatic monocarboxylic acid having 6 to 14 carbon atoms or carbon number. 6-18 aliphatic dicarboxylic acids are particularly preferred.

  The use ratio of the organic carboxylic acid is preferably 1 to 50% by mass, and particularly preferably 5 to 30% by mass in the water-soluble oil agent.

  Since the water-soluble oil agent in the present invention can be used by diluting with water according to the application, the preferred use ratio of the organic carboxylic acid can vary depending on the application. In the metalworking fluid, the proportion of the organic carboxylic acid used is preferably 0.1 to 70% by mass, particularly preferably 3 to 50% by mass in the metalworking fluid. In the aqueous working fluid, the proportion of the organic carboxylic acid used is preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass. In the aqueous wrapping solution, the organic carboxylic acid is preferably used in a proportion of 0.1 to 70% by mass, particularly preferably 3 to 50% by mass.

(Other additives)
The water-soluble oil agent of the present invention can further contain other water-soluble amines and / or alkali metal hydroxides (caustic potash, caustic soda, etc.) as necessary.

  Specific examples of other water-soluble amines include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, hexylamine, cyclohexylamine, octylamine, 2-ethylhexylamine, and isononyl. (Cyclo) hydrocarbylamines such as amines; polyalkylenepolyamines such as ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; cyclohexylamine, dicyclohexylamine, 1,3- Cyclic amines such as bisaminomethylcyclohexane, metaxylenediamine, pyridine, piperazine; monoethanol Min, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, 2- (2-aminoethoxy) ethanol, diethylmonoisopropanolamine, N, N -Dibutylaminoethanol, N, N-di-n-butylaminoisopropanol, N, N-di-n-propylaminoisopropanol, N, N-ditertiary butyldiethanolamine, N, N-ethylenediamine (diisopropanol), N, N-ethylenediamine (diethanol), mono-n-butyldiethanolamine, monoethyldiisopropanolamine, N-cyclohexyldiethanolamine, N, N, N ′, N′-tetrakis (hydroxyethyl) ethyl Njiamin, N, N, N ', N'- tetrakis (2-hydroxypropyl) ethylenediamine, and the like.

  Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

  Furthermore, you may use a rust preventive agent as needed. Specific examples include sulfonates such as petroleum sodium sulfonate, carboxylic acid amides, and carboxylic acid sarcosides.

  Furthermore, extreme pressure additives, silicone-based antifoaming agents, alcohol-based antifoaming agents, triazine-based metal anticorrosives, benzothiazole-based metal anticorrosives, alkylbenzimidazole-based antiseptics, alkylbenzimidazole-based metal anticorrosives, carboxylic acid alkanols Nonionic surfactants such as amides, inorganic salts such as phosphates, carbonates, borates and silicates, sequestering agents such as ethylenediaminetetraacetic acid, oxidation wax antioxidants, solid lubricants, water-based resins, etc. It may be added depending on.

Hereinafter, the present invention will be described in more detail with reference to examples. Table 1 shows the structures, melting points and total amine values of amines A1 to A3 and B1 to B4 used in Examples and Comparative Examples. As the amine, a compound represented by the formula N (R ₁ OH) (R ₂ OH) (R ₃ OH) was used, and each carbon number of R ₁ , R ₂ and R ₃ is shown in Table 1. .

  Table 2 shows the results of producing water-soluble oils having the compositions shown in Table 2 and measuring their physical properties. The measurement method of physical properties is shown below. Examples 1 to 5 are examples, and examples 6 to 9 are comparative examples. In addition, about the compounding quantity of the following Table 2, it described in the mass% with respect to the whole quantity. P1 is a polyoxypropylene diol having an average molecular weight of 700.

  (Lubricity) Using a FALEEX tester, the wear amount (mg) of the pin was measured under the conditions of load: 91 kgf, rotation speed: 290 rpm, measurement time: 1 hour and sample concentration: 3% aqueous solution.

  (Defoaming property) 50 mL of a sample obtained by diluting the water-soluble oil agent of Examples 1 to 9 into a 3% aqueous solution was placed in a 100 mL cylinder, shaken for 10 seconds, and then the time until the bubbles disappeared was measured. The criteria for evaluation are as follows: ◯; quickly defoaming, Δ: good time was taken until defoaming, x: it took a long time to defoam.

  (Corrosion-preventing property) It was carried out by a cast iron chip method using a sample obtained by further diluting the water-soluble oil agent of Examples 1 to 9 into a 3% aqueous solution. That is, about 15 g of dry-cut cast iron chips (8-12 mesh sieve) were collected in a glass petri dish (inner diameter: about 60 mm), and about 25 mL of the sample solution diluted in the above 3% aqueous solution was added thereto. After sufficiently shaking, the mixture was allowed to stand for about 4 minutes. Next, the sample solution was removed by the gradient method, and the state of rust generated on the casting chips after 24 hours was evaluated. The evaluation criteria were as follows: ◯: no rust occurred, Δ: several rusts occurred, x: rust occurred on 1/5 or more of the bottom surface.

  (Skin irritation) A sample obtained by further diluting the water-soluble oil agent of Examples 1 to 9 into a 3% aqueous solution was used. One drop was dropped onto a patch test unit (epitest fin chamber) and attached to the upper arm with tape, and the state of the skin after 24 hours was visually determined. Evaluation criteria are 3 points; redness with blisters and papules was observed, 2 points; redness and swelling, 1 point; slightly reddened, 0.5 points; Something was suspicious, 0 points; no response.

  From the results of Table 2, it can be seen that in the examples using amine (A), the lubricity is good, the antifoaming property and the rust-preventing property are excellent, and the skin irritation is also mild. In particular, in Examples 1 and 2 and Example 5, it can be seen that any measurement item shows a result equal to or higher than that of the comparative example.

  On the other hand, Example 6 using monoethanolamine showed lubricity and skin irritation, Example 7 using triethanolamine showed antifoaming properties, and Example 8 using triisopropanolamine showed antifoaming properties and rust prevention properties. In Example 9 using N-methyldiethanolamine, it is recognized that the antifoaming property is inferior to that in Examples using the tertiary water-soluble amine of the present invention.

  In addition, in the case of triethanolamine, triisopropanolamine, and N-methyldiethanolamine having a high melting point, a result that the defoaming property is inferior is recognized.

  The water-soluble oil of the present invention is particularly useful for metalworking fluids, aqueous hydraulic fluids or aqueous wrapping fluids.

Claims (4)

Contains one or more amines (A) represented by the formula N (ROH) ₃ (wherein R is an alkylene group having 2 to 4 carbon atoms, except when all three R are alkylene groups having the same carbon number) A water-soluble oil agent characterized by   Furthermore, the water-soluble oil agent of Claim 1 containing organic carboxylic acid. Polyethers, water, and amines represented by the formula N (ROH) ₃ (wherein R is an alkylene group having 2 to 4 carbon atoms, except that all three R are alkylene groups having the same carbon number) One or more types of (A) are contained, The water-soluble oil agent characterized by the above-mentioned. The water-soluble oil agent according to claims 1 to 3, which is used for metalworking fluids, aqueous hydraulic fluids or aqueous wrapping fluids.