JP5483310B2 - Raw material composition for chip cleaning and cleaning liquid - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a chip cleaning stock solution composition, and more particularly to a cleaning stock solution composition for cleaning and removing chips generated during metalworking. In particular, the present invention relates to a cleaning stock solution composition and a cleaning liquid that are useful when cleaning metal parts in an ultra-trace oil supply type cutting / grinding process.

  As a novel metal processing method, an ultra-trace amount oil supply type cutting / grinding method has been proposed (Patent Document 1), but this method is 1 / 100,000 to the amount of oil used in normal cutting / grinding. Cutting / grinding is performed while supplying an extremely small amount of oil agent of 1/1000000 to a workpiece together with a compressed fluid (for example, compressed air), and a cooling effect by compressed air is obtained, and an extremely small amount of oil agent is used. In addition, the amount of waste can be reduced, and therefore the environmental impact associated with the large discharge of waste can also be improved. There are several methods for removing generated chips in this ultra-trace oil supply type cutting / grinding method, such as free fall, air blow, suction, liquid removal, etc., but existing equipment can be used. The removal method using a liquid is generally adopted because it has high cleaning efficiency.

However, when a water-soluble cleaning liquid or cutting liquid is used as the chip removal liquid, there is a problem that rust is likely to occur on the workpiece such as iron because it contains water, and the cleaning liquid is likely to rot. . In order to avoid these problems, a method is generally adopted in which a basic compound such as alkanolamine is blended in a stock solution of a water-soluble cleaning liquid or a cutting liquid to keep the pH of the cleaning liquid high (Patent Document 2). However, when aluminum and aluminum alloy chips are removed with such a high pH cleaning solution, the aluminum and aluminum alloy workpieces are discolored and the product value is notably impaired. This makes it impossible to wash away chips efficiently. In addition, the water-soluble cleaning liquid removes even the oil on the sliding part of the machine tool, resulting in poor sliding or poor separability from the processing oil. Many problems were pointed out.
International Publication No. 2002/083823 JP-A-8-157878

  The present invention relates to a method of cutting and grinding a workpiece by an extremely small amount of oil supply system, even when a processing oil is mixed in a water-soluble chip-flowing oil for chip removal (hereinafter abbreviated as a cleaning liquid). Excellent separability from processing oils, prevents spoilage, has excellent wastewater treatment properties, ensures sufficient chip cleaning, and does not cause rust and discoloration of workpieces, adverse effects on the environment, etc. Provide a cleaning solution.

As a result of intensive studies to achieve the above object, the inventors of the present invention have prepared a metal working solution obtained by diluting a water-soluble cleaning stock solution composition containing a specific surfactant with water to a predetermined concentration. It has been found that the above problems can be solved by using it as a chip removing oil, and the present invention has been completed.
That is, the present invention provides the following metal processing chip cleaning stock solution composition and cleaning solution.

[1] Based on the total amount of the composition,
(A) Fatty acid ester of polyalkylene glycol 5-30% by mass,
(B) 1 to 10% by mass of monobasic fatty acid and / or dibasic fatty acid having 8 to 12 carbon atoms,
(C) Castor oil fatty acid condensate 5-20% by mass,
(D) alkanolamine and aliphatic amine 15 to 25% by mass,
And (E) 15-74% by weight of water,
A stock solution composition for metal-working chip cleaning, comprising:

[2] The metal working chip cleaning stock solution composition according to the above [1], wherein the component (A) is a polyalkylene glycol fatty acid ester compound represented by the following general formula (1).
R—CO—O— (AO) _n —H (1)
(In the formula (1), R represents an alkyl group or alkenyl group having 1 to 19 carbon atoms, AO represents an oxyethylene group or oxypropylene group, and n represents an integer having a number average molecular weight of 3600 to 50000.)

[3] The above-mentioned [1] or [3], wherein the blending ratio (mass ratio) of the alkanolamine and the aliphatic amine in the component (D) is in the range of 1: 0.5 to 1: 1.2. [2] A stock solution composition for chip cleaning for metal processing according to [2].

[4] The amount of component (D) is such that the pH of the aqueous solution is 8.2 to 9.5 when the chip cleaning stock solution composition is diluted 30 volumes, and component (C) And (D) component mixing ratio (mass ratio) is in the range of 1: 1 to 1: 2, for metal-working chip cleaning according to any one of [1] to [3] above Stock solution composition.

[5] A cleaning solution obtained by diluting the metal processing chip cleaning stock solution composition according to any one of the above [1] to [4] to 1.5 to 200 times volume with water.

[6] The cleaning liquid as described in [5] above, which is used in a method of cutting and grinding a workpiece by an ultra-trace oil supply method.

  The present invention provides a stock processing composition for metalworking chip cleaning containing a specific surfactant, and the water dilution of the stock composition is used as a cleaning solution for chip removal. Excellent chip removal and removal, without flocculation / fixation of chips, rust and discoloration of workpieces, decay of cleaning fluid, poor lubrication of sliding parts of machine tools, and negative effects on the environment. Chips of the workpiece can be washed and removed by a very small amount of oil supply system.

  Hereinafter, the present invention will be described in detail.

The fatty acid ester of (A) polyalkylene glycol used in the present invention is a compound represented by the following general formula (1).
R—CO—O— (AO) _n —H (1)

  R in Formula (1) represents an alkyl group or alkenyl group having 1 to 19 carbon atoms, may be linear or branched, and may be saturated or unsaturated. Specific examples of the fatty acid constituting the ester include, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid , Linear or branched heptanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched Branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, Linear or branched hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid, linear or branched nonadecanoic acid, linear or branched Saturated fatty acids such as icosanoic acid; acrylic acid, linear Or branched butenoic acid, linear or branched pentenoic acid, linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched Octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, linear or branched undecenoic acid, linear or branched dodecenoic acid, linear Or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or branched hexadecenoic acid, linear or branched heptadecene And unsaturated fatty acids such as acid, linear or branched octadecenoic acid, linear or branched nonadecenoic acid, linear or branched icosenoic acid; and mixtures thereof.

  Among these fatty acids, linear or branched hexanoic acid, linear or branched heptanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, Linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched Saturated fatty acids such as tetradecanoic acid; linear or branched dodecenoic acid, linear or branched tetradecenoic acid, linear or branched hexadecenoic acid, linear or branched Unsaturated fatty acids such as octadecenoic acid and linear or branched icosenoic acid are preferred in terms of chip dispersibility.

  AO in the formula (1) represents an oxyethylene group or an oxypropylene group, and is preferably a random polymerization adduct or a block polymerization adduct of an oxyethylene group (EO) and an oxypropylene group (PO). The molar ratio EO / PO of the oxyethylene group to the oxypropylene group is preferably 5/95 to 95/5, more preferably 10/90 to 50/50, still more preferably 20/80 to 40/60. When the molar ratio of the oxyethylene group is less than 5 mol%, the dispersibility of the chips is poor, and when it exceeds 95 mol%, the separability from the MQL processing oil and the antifoaming property are deteriorated.

  The upper limit of the number average molecular weight of the (A) component polyalkylene glycol fatty acid ester is 50000, preferably 30000, and more preferably 20000. Moreover, a lower limit is 3600, Preferably it is 5000, More preferably, it is 7000. When the number average molecular weight of the component (A) is less than 3600, the dispersibility of the chips is deteriorated, and when it exceeds 50,000, the separability from the MQL processing oil is deteriorated.

  As the component (A), polyethylene-polypropylene glycol monopalmitate, polyethylene-polypropylene glycol monooleate, polyethylene-polypropylene glycol monolinoleate can be used since both stable chip dispersibility and separability from MQL processing oil can be achieved. , And mixtures thereof are preferred examples.

  The upper limit of the content of component (A) is 30% by mass, preferably 25% by mass, more preferably 20% by mass, based on the total amount of the stock solution composition. On the other hand, the lower limit is 5% by mass, preferably 7% by mass, more preferably 10% by mass, based on the total amount of the stock solution composition. When content of (A) component exceeds 30 mass%, it is unpreferable from the point of stability of a stock solution. In addition, when the content of the component (A) is less than 5% by mass, the separability from the MQL processing oil and the dispersibility of chips are not preferable.

  The monobasic fatty acid having 8 to 12 carbon atoms as the component (B) may be linear or branched, and may be saturated or unsaturated. Specific examples of the monobasic fatty acid having 8 to 12 carbon atoms include linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, Linear or branched dodecanoic acid, linear or branched octenoic acid, linear or branched nonenic acid, linear or branched decenoic acid, linear or branched undecenoic acid, linear or branched dodecenoic acid, and these And the like.

  In addition, the dibasic fatty acid having 8 to 12 carbon atoms as the component (B) may be linear or branched, and may be saturated or unsaturated. Specific examples of the dibasic fatty acid having 8 to 12 carbon atoms include, for example, linear or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched Undecanedioic acid, linear or branched dodecanedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid, linear or branched decenedioic acid, linear or branched undecenedioic acid, straight Examples thereof include chain or branched dodecenedioic acid and mixtures thereof.

  As the component (B), a monobasic fatty acid or a dibasic fatty acid may be used alone, or a mixture of the two may be used. From the viewpoint of excellent rust prevention of the workpiece, From the viewpoint of stability, it is desirable to use a monobasic fatty acid.

  The upper limit of the content of component (B) is 10% by mass, preferably 8% by mass, based on the total amount of the stock solution composition. On the other hand, the lower limit is 1% by mass, preferably 2% by mass, based on the total amount of the stock solution composition. When the content of the component (B) exceeds 10% by mass, no further improvement in effect is observed, which is not preferable from the viewpoint of cost. In addition, when the content of the component (B) is less than 1% by mass, the stability of the stock solution becomes poor, the rust prevention property of the work piece is lowered, the emulsion becomes degreased and detergency. It is not preferable because it decreases.

  The condensate of castor oil fatty acid (C) is obtained by dehydrating and condensing fatty acids constituting castor oil. Moreover, what was obtained by carrying out dehydration condensation of the ricinoleic acid which is a main component of a castor oil fatty acid may be used. In general, the degree of condensation of the ricinoleic acid condensate is represented by an acid value, but as the component (C), the acid value is usually 40 to 150 mgKOH / g, preferably 50 to 130 mgKOH / g. .

  The upper limit of the content of the component (C) is 20% by mass, preferably 18% by mass, more preferably 15% by mass, based on the total amount of the stock solution composition. On the other hand, the lower limit is 5% by mass, preferably 7% by mass, based on the total amount of the stock solution composition. When content of (C) component exceeds 20 mass%, the improvement of the effect beyond it is not seen and it is unpreferable from the point of cost. Moreover, when content of (C) component is less than 5 mass%, the discoloration prevention performance of a to-be-processed object, especially aluminum falls, and is unpreferable.

Component (D) is an alkanolamine and an aliphatic amine. The aliphatic amine referred to here includes cycloalkylamine.
Specific examples of the alkanolamine include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monobutanolamine, dibutanol Examples include amines and tributanolamine.
As the aliphatic amine, specifically, alkylamines such as monopentylamine, dipentylamine, tripentylamine, monoheptylamine, diheptylamine, triheptylamine, monooctylamine, dioctylamine, and trioctylamine; Examples thereof include cycloalkylamines such as monocyclohexylamine, dicyclohexylamine, and tricyclohexylamine.

  The blending ratio (mass ratio) of the alkanolamine and the aliphatic amine in the component (D) is preferably in the range of 0.5 to 1.2 when the alkanolamine is 1. Even if the blending ratio of the aliphatic amine is less than or exceeds this range, the stability of the aqueous solution becomes poor.

  The upper limit of the content of component (D) is 25% by mass, preferably 23% by mass, based on the total amount of the composition. On the other hand, the lower limit is 15% by mass, preferably 17% by mass, based on the total amount of the stock solution composition. When the content of the component (D) exceeds 25% by mass, the discoloration prevention performance of aluminum is lowered, which is not preferable. When the content of the component (D) is less than 15% by mass, the rust of the work piece It is not preferable because the stopping property is lowered.

The blending amount of the component (D) is preferably such that the pH of the aqueous solution when the stock solution composition for chip cleaning is diluted 30 times is 8.2 to 9.5, more preferably 8.5. It is the range of -9.5. When the pH of the 30-fold diluted aqueous solution exceeds 9.5, the discoloration prevention performance of aluminum is lowered, and when the pH of the 30-fold diluted aqueous solution is less than 8.2, the rust prevention property of the workpiece is undesirably lowered.
The blending ratio (mass ratio) of the component (C) and the component (D) is preferably in the range of 1 to 2 when the component (C) is 1. When the component (D) is less than 1, the anti-discoloration performance of aluminum is lowered, which is not preferable. When the component (D) is more than 2, the rust preventive property of the workpiece is decreased, which is not preferable.

As the water of component (E), tap water, industrial water, ion exchange water, distilled water, and the like can be used, and the water may be hard water or soft water.
The upper limit of the content of component (E) is 74% by mass, preferably 65% by mass, based on the total amount of the stock solution composition. On the other hand, the lower limit is 15% by mass, preferably 20% by mass, based on the total amount of the stock solution composition. When the content of the component (E) exceeds 74% by mass, the amount of the active ingredient decreases, which is not preferable because the transportation cost is disadvantageous. Moreover, when content of (E) component is less than 15 mass%, it becomes viscous and it becomes difficult to handle and is unpreferable.

  As a cleaning liquid used for metal processing chip cleaning of the present invention, if the stock solution composition having the above-described composition is diluted with water, it is excellent in chip cleaning and removing property, chip aggregation / fixation, It is possible to clean and remove chips of workpieces by supplying a trace amount of oil without causing rust and discoloration of processed parts, decay of cleaning liquid, poor lubrication of sliding parts of machine tools, and adverse effects on the environment. However, if necessary, a known additive can be added to the above-described stock solution composition. Specific examples of such additives include anionic surfactants such as sulfuric acid and sulfonic acid esters; nonionic surfactants such as polyoxyalkylene compounds and derivatives thereof; fatty acids, esters, alcohols, and the like. Rust inhibitors such as sulfonates, phosphates and phosphates, boron compounds; corrosion inhibitors such as nitrogen compounds such as benzotriazole, sulfur and nitrogen compounds; phenols, amines, sulfurs, Phosphorous and chlorine antioxidants; phenolic, formaldehyde donor compounds, salicylanilide compounds and other preservatives; silicone oil and other antifoaming agents; and the like, alone or in combination of two or more Can be added. The content of these additives is usually 15% by mass or less, preferably 13% by mass or less (all based on the total amount of the stock solution composition; total amount).

  The cleaning solution for removing chips for metal processing according to the present invention is a 1.5 to 200 volume times, preferably 1.7 to 150 volume times, more preferably 2.0 to 100 volume times of the above stock solution composition with water. It can be obtained by diluting twice, particularly preferably 10 to 100 times volume. When the amount of dilution water with respect to the stock composition is less than 1.5 volume times, it becomes impossible to wash away chips efficiently, and when it exceeds 200 volume times, discoloration of workpieces such as aluminum occurs, lubrication parts of machine tools May cause the problem of poor lubrication and rot of cleaning liquid. As the dilution water to be used, tap water, industrial water, ion exchange water, distilled water, or the like can be used, regardless of whether it is hard water or soft water.

  Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.

(Examples 1-4, Comparative Examples 1-14)
The following evaluation tests were performed on the stock solution compositions shown in Table 1 using the ingredients shown below.

(Combination agent)
A1: Polyethylene-propylene glycol monooleate (molecular weight 12240, EO / PO ratio = 30 mol% / 70 mol%)
A2: Polyethylene-propylene glycol monooleate (molecular weight 3250, EO / PO ratio = 30 mol% / 70 mol%)
B1: caprylic acid B2: dodecanedioic acid C: polymer of castor oil fatty acid (acid value 90 mgKOH / g)
D1: Diethanolamine D2: Dicyclohexylamine E: Distilled water Others: 2% by mass of polyoxyalkylene alkyl ether (HLB8.1) and 12% by mass of oleic acid based on the total amount of the composition.

[Evaluation test]
(Separability)
The separability from metalworking oil was evaluated as follows.
In a 100 ml graduated cylinder with a stopper, 80 ml of a cleaning solution obtained by diluting the stock solution composition by a factor of 30 and metal working oil (kinematic viscosity at 40 ° C. is 20 mm ² / s, and interfacial tension at 25 ° C. is 5 mN / m or less. 20 ml of a commercially available ultra-trace oil supply type cutting / grinding oil) was taken and shaken vigorously manually for 1 minute, and the state of mixing of the metal working oil into the cleaning liquid after 24 hours was visually observed. The evaluation was determined as follows.
○ Appearance of aqueous solution is not turbid △ Appearance of aqueous solution is slightly turbid × Appearance of aqueous solution is turbid

(Stock solution stability)
The stability of the stock solution composition was evaluated as follows.
100 ml of the stock solution composition was collected in a glass container and allowed to stand at room temperature for 1 week, and then the appearance was visually observed. Evaluation was determined as follows.
○ No turbidity or separation △ Some turbidity or separation × No turbidity or separation

(Aqueous solution stability)
The stability of the cleaning solution (water diluted solution of the stock solution composition) was evaluated as follows.
100 ml of a cleaning solution obtained by diluting the stock composition 30 times in a glass container was collected and allowed to stand at room temperature for 1 week, and then the appearance was visually observed. Evaluation was determined as follows.
○ No turbidity or thickening △ Some turbidity or thickening × Some turbidity or thickening

(Compatibility with aluminum materials)
The compatibility between the cleaning liquid (water dilution of the stock solution composition) and the aluminum material was evaluated as follows.
The lower half of the aluminum test piece (material: A1050, shape: 2.0 × 12 × 75 mm) is immersed in a cleaning solution obtained by diluting the stock solution composition by 30 times, and left at room temperature for 72 hours, and then visually. The appearance was observed. Evaluation was determined as follows.
○ Aluminum material with no discoloration △ Aluminum material with slight discoloration × Aluminum material with discoloration

(Corrosion of work piece)
1 g of cast iron (FC200) chips are evenly distributed in a circle with a diameter of 36 mm on a filter paper (JIS P 3801 for chemical analysis 5 types C) placed in a petri dish, and a stock solution composition is used using a syringe so that the entire cast iron chips are moistened. A washing solution obtained by diluting the product 30 times in volume is added dropwise. Then, after leaving for 24 hours at room temperature without a petri dish lid, the degree of discoloration (transfer of rust) in the circle on the filter paper from which chips were removed was visually observed. Evaluation was determined as follows.
○ No discoloration observed on the filter paper △ Discoloration slightly observed on the filter paper × Discoloration observed on the filter paper

(PH)
A washing solution obtained by diluting the stock solution composition by 30 times volume was measured by the method specified in 7 of JIS Z 8802.

  The stock solution composition for cleaning according to the present invention is useful as a cleaning agent composition for cleaning and removing chips generated during metalworking, and the water dilution liquid is used in cutting / grinding processing by supplying an extremely small amount of oil. In cleaning metal parts, even if processing oil is mixed with water-soluble chip-flowing oil for chip removal, it is excellent in separability from processing oil, is resistant to spoilage, and has excellent drainage treatment performance. It has an excellent effect as a cleaning liquid that has cleanability of chip and does not cause rust and discoloration of the workpiece, adverse effects on the environment, and the like.

Claims (4)

Based on the total amount of the composition,
(A) Polyalkylene glycol fatty acid ester represented by the following general formula (1), which is a compound selected from polyethylene-polypropylene glycol monopalmitate, polyethylene-polypropylene glycol monooleate, and polyethylene-polypropylene glycol monolinoleate 5-30 mass%,
R-CO-O- (AO) n-H (1)
(In the formula (1), R represents an alkyl group or alkenyl group having 1 to 19 carbon atoms, AO represents an oxyethylene group or oxypropylene group, and n represents an integer having a number average molecular weight of 3600 to 50000.)
(B) 1 to 10% by mass of monobasic fatty acid and / or dibasic fatty acid having 8 to 12 carbon atoms,
(C) Castor oil fatty acid condensate 5-20% by mass,
(D) Alkanolamine and aliphatic amine (however, the blending ratio (mass ratio) of alkanolamine and aliphatic amine is in the range of 1: 0.5 to 1: 1.2.) 15 to 25% by mass,
And (E) 15-74% by weight of water,
A stock solution composition for metal-working chip cleaning, comprising: The blending amount of the component (D) is such that the pH of the aqueous solution is 8.2 to 9.5 when the chip cleaning stock solution composition is diluted 30 times by volume, and the component (C) and (D 2) The composition ratio (mass ratio) of the components is in the range of 1: 1 to 1: 2, the stock solution composition for metal-working chip cleaning according to claim 1 . A cleaning solution obtained by diluting the metal-working chip cleaning stock solution composition according to claim 1 or 2 to 1.5 to 200 volume times with water. The cleaning liquid according to claim 3 , wherein the cleaning liquid is used in a method of cutting and grinding a workpiece by an extremely small amount of oil supply method.