JP5232372B2 - Water-soluble metalworking fluid composition - Google Patents

Description

  The present invention relates to a water-soluble metalworking fluid composition, and more particularly, to a water-soluble metalworking fluid composition excellent in corrosion resistance and hard water resistance regarding aluminum and its alloys.

  Aluminum and its alloys are metals that are susceptible to corrosion by alkali. In general, water-soluble metalworking fluids are often set to be weakly alkaline (pH = about 9 to 10) in the state of the use liquid for the purpose of imparting rust prevention and antiseptic power. Therefore, measures for preventing corrosion are necessary in the processing of aluminum and its alloys using such a water-soluble metalworking fluid.

  The first means is to change the set pH to a neutral range, but there is no effective means for complementing the rust preventive power and antiseptic power that are reduced by the change.

  As a second means, it is possible to remove the water-soluble metalworking fluid by air blow etc. immediately after processing, but it is a burden on the operator, difficult to implement in an unmanned process, in long time processing This is not preferable for reasons such as the occurrence of corrosion during processing.

  As a third means, the addition of a corrosion inhibitor is common. As corrosion inhibitors for aluminum and its alloys, water-soluble sodium metasilicate, potassium metasilicate, phenol, phosphate ester, amide compound, fatty acid and derivatives thereof are already known.

  Sodium metasilicate and potassium metasilicate exhibit a high corrosion prevention effect, but due to their strong alkalinity, the pH of the treatment liquid is raised and the workpiece is corroded, so the corrosion prevention effect cannot be sustained over a long period of time. There is a case. In addition, there is a high possibility of causing component separation by deteriorating the liquid stability of the water-soluble metalworking fluid, and it is currently rarely used.

  Phenol is a flammable substance designated by the Fire Service Act, flammable solids, a deleterious substance designated by the Poisonous and Deleterious Substances Control Law, and a designated drug designated by the Pharmaceutical Affairs Law, so there are problems with its impact on the natural environment and safety for workers. is there.

  Phosphoric acid esters and amide compounds are less effective in preventing corrosion when the pH of the treatment liquid is 9 or higher. In addition, phosphoric acid esters have problems in use, such as phosphoric acid is easily generated by microorganisms in the processing solution, and the antiseptic properties of the processing solution are significantly reduced.

  Fatty acids and derivatives thereof are weaker in corrosion prevention than other corrosion inhibitors, and corrosion is likely to occur in aluminum and its alloys such as A5052, which require a high corrosion prevention effect. In addition, there are problems in terms of foamability by using in combination with an alkali component such as amine, and emulsification of mixed oil such as sliding surface oil. Fatty acids derived from natural fats and oils are also prone to the growth of microorganisms in the treated water, which is also a problem.

On the other hand, a method using an alkylphosphonic acid derivative as a plastic working lubricant for aluminum alloys or non-ferrous metals is known (Patent Document 1). Such alkylphosphonic acid derivatives are less likely to generate phosphoric acid by microorganisms in the processing solution, and are corrosion inhibitors that have less harmful effects, including antiseptic properties, compared to phosphate esters, amides, fatty acids and derivatives thereof. is there. However, there may be a problem in that a salt is formed with a hardness component such as magnesium ion and calcium ion brought from the dilution water when preparing the treatment liquid, and precipitation is likely to occur.
JP-A-5-65493

  The present invention is a water-soluble metalworking oil composition suitable for use in metalworking processing in view of the above-described conventional circumstances in the field, and has anticorrosion and hardwater resistance against aluminum and its alloys. An object is to provide an excellent water-soluble metalworking fluid composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific alkylphosphonic acid derivative achieves the above object, and have completed the present invention.

That is, the present invention relates to the following water-soluble metalworking fluid composition.
Item 1. An alkylphosphonic acid derivative represented by the following general formula (1 ): an octylphosphonic acid and ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether or glycerin ethylene oxide 1 mol adduct A water-soluble metalworking fluid composition comprising one or more phosphoric esterification reaction products .

(In the formula, R ₁ represents an alkyl group having 5 to 60 carbon atoms, R ₂ represents a residue obtained by removing m + 1 OH groups from an n-valent alcohol, m represents an integer of 1 to 7, n Represents an integer of 2 to 8, and the relationship between m and n is m ≦ n−1, when m is 1, R ₃ represents an alkyl group having 1 to 22 carbon atoms, and when m is 2 to 7. , _{R 3} is table H or alkyl group having 1 to 22 carbon atoms, a O is a polyoxyalkylene group represented by the following general formula (2).

A ₁ represents an alkylene group having 3 to 4 carbon atoms, p, q and r each represents 0 or an integer of 1 or more, and the bonding form of the polyoxyalkylene group may be a random or block bond or a mixed form thereof . The m pieces of p, q, and r may be the same or different from each other. )
Item 2. Item 2. The water-soluble metalworking fluid composition according to Item 1, comprising 0.1 to 20% by weight of the alkylphosphonic acid derivative.
Item 3. Item 3. The water-soluble metalworking fluid composition according to Item 1 or 2, wherein the pH during use is 7 to 11.

  By this invention, the water-soluble metalworking fluid which is excellent in the corrosion resistance of aluminum and aluminum alloy, and the hard water resistance of magnesium ion, calcium ion, etc. brought from the water for dilution at the time of preparing a process liquid is obtained.

In the alkylphosphonic acid derivative represented by the general formula (1) or (2), R ₁ is an alkyl group having 5 to 60 carbon atoms, preferably an alkyl group having 6 to 22 carbon atoms, more preferably carbon. It is an alkyl group of several 6-18. When the carbon number is less than 5, the corrosion resistance of aluminum and the aluminum alloy is deteriorated, and when it exceeds 60, the hard water resistance is lowered.

  A C5-C60 alkyl group shows a saturated or unsaturated linear, branched and alicyclic hydrocarbon group, and an aromatic group. Examples of such groups include n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n Examples include, but are not limited to, saturated hydrocarbon groups such as octadecyl group and cyclohexyl group, unsaturated hydrocarbon groups composed of the corresponding carbon skeleton, phenyl group, benzyl group and the like.

R ₂ represents a residue obtained by removing m + 1 OH groups from an n-valent alcohol, m represents an integer of 1 to 7, n represents an integer of 2 to 8, and the relationship between m and n is m ≦ n -1. n is preferably 2 to 3. When n exceeds 8, the viscosity of the resulting alkylphosphonic acid derivative becomes high, causing a problem in handling properties. The n-valent alcohol indicates saturated or unsaturated, linear, branched and alicyclic hydrocarbon alcohols and aromatic alcohols.

  Examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, 1,8 Octanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-dimethyl-1,3-propanediol and 2,5-dimethylhexane Examples include, but are not limited to, 2,5-diol, 2-butene-1,4-diol, 3-methyl-3-butene-1,2-diol, and the like.

  Examples of trivalent alcohols include glycerin, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3, 4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 2,4-dimethyl-2,3,4-pentanetriol , Pentamethylglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, and trimethylolpropane, 2-hexene-1,4,5-triol, 3-hexene-1, Examples include 2,5-triol, but are not limited thereto.

  Examples of 4- to 8-valent alcohols include alkane polyols and intramolecular or intermolecular dehydrates (pentaerythritol, sorbitol, xylitol, mannitol, sorbitan, diglycerin, etc.), sugars and derivatives thereof (glycol, mannose, fructose, Methyl glucoside and the like), but are not limited thereto.

When m is 1, R ₃ represents an alkyl group having 1 to 22 carbon atoms, and when m is 2 to 7, R ₃ represents H or an alkyl group having 1 to 22 carbon atoms. The carbon number of the alkyl group of R ₃ is preferably 1 to 18, more preferably 1-8. When the number of carbon atoms in the alkyl group exceeds 22, the hard water resistance decreases. A C1-C22 alkyl group shows a saturated or unsaturated linear, branched and alicyclic hydrocarbon group, and an aromatic group. Examples thereof include methyl group, ethyl group, n-propyl group, iso-propyl group, n-, iso-, sec-, and tert-butyl group, n-pentyl group, n-hexyl group, 2- Saturated hydrocarbon groups such as ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and cyclohexyl group, and carbon skeletons corresponding thereto An unsaturated hydrocarbon group, and a phenyl group, a benzyl group, and the like, but are not limited thereto.

  AO is a polyoxyalkylene group represented by the following general formula (3).

A ₁ represents an alkylene group having 3 to 4 carbon atoms, p, q and r each represents 0 or an integer of 1 or more, and the bonding form of the polyoxyalkylene group may be a random or block bond or a mixed form thereof . The m pieces of p, q, and r may be the same or different from each other.

  The concentration of the alkylphosphonic acid derivative in the water-soluble metalworking fluid composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, still more preferably 1 to 10% by weight. It is. If the concentration is less than 0.1% by weight, the corrosion resistance of aluminum and aluminum alloy cannot be obtained, and if it exceeds 20% by weight, the raw material cost is increased, which is not preferable in terms of economy.

  The water-soluble metalworking fluid composition of the present invention is in the form of an aqueous solution and is diluted with water at an appropriate dilution ratio (usually 5 to 100 times) depending on its original concentration and performance required during metalworking. Can be used for use. The dilution factor also affects the work material, machining conditions, etc., and may be set so that the machining characteristics are most excellent in the range of 5 to 100 times.

  The pH of the water-soluble metalworking fluid composition of the present invention at the time of use is preferably 7 to 11, more preferably 8 to 10.5. When processing ferrous metals at the same time as aluminum and aluminum alloys, and in order to obtain sufficient rust prevention of equipment made of ferrous materials such as processing machines, the pH is preferably 7 or more, while rough This is because the pH is preferably 11 or less in consideration of the skin irritation that causes the above.

  The water-soluble metalworking fluid composition of the present invention is selected from the group consisting of an antioxidant, an extreme pressure additive, a rust inhibitor, a lubricant, an antiseptic, an antifoaming agent, an aggregating agent, and an emulsion stabilizer as necessary. It can be used by adding more than one kind of additive.

  Examples of the antioxidant include phenolic antioxidants, amine-based antioxidants, zinc dialkyldithiophosphates, zinc diallyldithiophosphates, and organic sulfides.

  Extreme pressure additives include lead soap, sulfurized fatty acid, sulfurized olefin, sulfurized lard, alkylpolysulfide and other sulfur compounds, chlorinated paraffin, chlorinated fatty acid, chlorinated fatty oil and other chlorine compounds, phosphate esters (salts) And phosphorus compounds such as phosphines and phosphines.

  As the rust preventive agent, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylmonoethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, normal butanolamine, isobutanolamine, tert-butanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, ethylenediamine, dimethylaminopropylamine, cyclohexylamine, dicyclohexylamine, n-butylamine, 1, 3-bis (aminomethyl) cyclohexane, N- (2-aminoethyl) piperazine, 1,2-diaminocyclohexane, m-xylylenediamine, etc. Organic amines, caprylic acid, pelargonic acid, isononanoic acid, normal nonanoic acid, capric acid, lauric acid and other aliphatic monocarboxylic acids having 6 to 36 carbon atoms and their amides, adipic acid, suberic acid, sebacic acid, azelaic acid And dicarboxylic acids such as dodecanedioic acid and amides thereof, alkenyl succinic acids having 6 to 36 carbon atoms and amides thereof, benzoic acids, aromatic carboxylic acids such as p-tert-butylbenzoic acid, and benzotriazole.

  Examples of the lubricant include natural fats and oils such as mineral oil and vegetable oil and derivatives thereof, polyoxyalkylene oxide, aliphatic monocarboxylic acids and dicarboxylic acids having 6 or more carbon atoms, and the like.

  Examples of the preservative include triazine compounds, thiazoline compounds, phenol compounds, and the like.

  Examples of the antifoaming agent include polyorganosiloxane having a molecular weight of 100 to 1,000.

  Examples of the emulsion stabilizer include alkyl sulfonic acids, polyoxyalkylene alkyl ethers, and amine salts of aliphatic monocarboxylic acids having 6 to 36 carbon atoms.

Methods for producing the alkyl phosphonic _acid, to alkylphosphonic acids R 1 -PO _{(OH) 2,} an alcohol represented by _{(R 3 -AO -O) m -R} 2 -OH molar ratio 1.0 A method in which an esterification reaction is carried out in a toluene or xylene solvent in the presence of a catalyst such as p-toluenesulfonic acid at 120 to 180 ° C. under normal pressure, or R ₁ —PO (OH ) to ₂ alkylphosphonic acid, inorganic acid chlorides such as thionyl chloride was added under normal pressure at 80 ° C. to 90 ° C., after obtaining the phosphonic acid chloride, to _(R 3 -AO -O) m The alcohol represented by —R ₂ —OH is added in a molar ratio of 1.0 to 1.5 times, and in a toluene or xylene solvent in the presence of a catalyst such as p-toluenesulfonic acid at 120 to 180 ° C. under normal pressure. , Conducted esterification reaction There is that methods such as, but not limited thereto. After completion of the reaction, excess alcohol may be removed by distillation or may be purified by chromatography or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not intended to be limited to these Examples. Table 1 shows alkylphosphonic acids used in Examples and Comparative Examples.

  The test items and evaluation methods of this performance test are as follows. Table 2 shows the composition of the sample solution used for evaluating the corrosion resistance of aluminum, Table 3 shows the composition of the sample stock solution used for evaluating the hard water resistance, and Table 4 shows the results of each evaluation.

1. Anticorrosion of aluminum [Evaluation method]
As an aluminum alloy test piece, ADC12 wet-polished with No. 240 water-resistant abrasive paper was used. The sample solution having the composition shown in Table 2 was adjusted to pH 9.0 using acetic acid or sodium hydroxide. The test piece was half-immersed in the sample solution, and the color change of the test piece after 24 hours at room temperature was visually confirmed. Judgment criteria were as follows: ◎: no discoloration, ○: slight discoloration only at the interface, and x: light discoloration as a whole.

2. Hard water resistance [Evaluation method]
As the sample solution, a sample stock solution in Table 3 diluted to 5% by weight with an ion exchange water aqueous solution of magnesium sulfate or an ion exchange water aqueous solution of calcium chloride was used. The sample solution was allowed to stand at room temperature, and the presence or absence of precipitation of the sample solution after 24 hours was visually confirmed. The ion-exchange water aqueous solution of magnesium sulfate and the ion-exchange water aqueous solution of calcium chloride were prepared so that the magnesium ion and calcium ion concentrations in the sample solution were 100 ppm, respectively.

注）実施例１のアルミニウム防食性は、表２中の実施例１−１を表し、実施例１の耐硬水性は、表３中の実施例１−２を表す。以下、同様に表す。

Note) The aluminum corrosion resistance of Example 1 represents Example 1-1 in Table 2, and the hard water resistance of Example 1 represents Example 1-2 in Table 3. The same applies hereinafter.

  From the results shown in Table 4, it can be seen that the corrosion resistance of each example is superior to that of aluminum and its alloy, and that of Comparative Example 2 is poor. Moreover, regarding the hard water resistance, precipitation does not occur in each example, and the hard water resistance is excellent. In Comparative Example 1, precipitation occurs, and the hard water resistance is poor.

  The present invention relates to a water-soluble metalworking fluid composition, and more particularly, to a water-soluble metalworking fluid composition excellent in corrosion resistance and hard water resistance regarding aluminum and its alloys. The present invention is used for cutting, grinding, plastic working and the like of aluminum and aluminum alloys.

Claims (3)

An alkylphosphonic acid derivative represented by the following general formula (1 ): an octylphosphonic acid and ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether or glycerin ethylene oxide 1 mol adduct A water-soluble metalworking fluid composition comprising one or more phosphoric esterification reaction products .

(In the formula, R ₁ represents an alkyl group having 5 to 60 carbon atoms, R ₂ represents a residue obtained by removing m + 1 OH groups from an n-valent alcohol, m represents an integer of 1 to 7, n Represents an integer of 2 to 8, and the relationship between m and n is m ≦ n−1, when m is 1, R ₃ represents an alkyl group having 1 to 22 carbon atoms, and when m is 2 to 7. , R ₃ represents H or an alkyl group having 1 to 22 carbon atoms , and A 2 O is a polyoxyalkylene group represented by the following general formula (2) .

A ₁ represents an alkylene group having 3 to 4 carbon atoms, p, q and r each represents 0 or an integer of 1 or more, and the bonding form of the polyoxyalkylene group may be a random or block bond or a mixed form thereof . The m pieces of p, q, and r may be the same or different from each other. )
  The water-soluble metalworking fluid composition according to claim 1, comprising 0.1 to 20% by weight of the alkylphosphonic acid derivative.   The water-soluble metalworking fluid composition according to claim 1 or 2, wherein the pH during use is 7 to 11.