Water-soluble metalworking fluid, metalworking liquid, and metalworking method

Abstract

Provided are a water-soluble metalworking oil agent (cutting oil agent or grinding oil agent) and a metalworking liquid, each of which has excellent cutting machining performance or grinding machining performance of aluminum or aluminum alloys, hardly causes rotting deterioration, and has excellent emulsion dispersion stability and stability of undiluted liquid, by containing specified components (A) to (E) as essential components without containing a machinability-improving agent with a high environmental load, such as chlorine, sulfur, and phosphorus. Provided is also a metalworking method using the same.

Claims

1. A water-soluble metalworking oil agent comprising, the following (A) to (E): (A) an -olefin component consisting of one or more C14 to C16 -olefins, in a content of 20 mass % or more and 65 mass % or less, wherein at least 40 mass % of the -olefin component is a C14 -olefin; (B) at least one selected from the group consisting of a dehydration-condensed fatty acid of ricinoleic acid and a dehydration-condensed fatty acid between a ricinoleic acid dehydration-condensed fatty acid and a carboxylic acid, in a content of 5 mass % or more and 30 mass % or less; (C) at least one tall oil fatty acid and at least one C9 to C12 monocarboxylic acid and a dicarboxylic acid, each not containing the component (B), wherein the total amount of (C) is from 10 to 19 mass %; (D) an alkylamine (D1) not containing a hydroxyl group and an alkanolamine (D2), each meeting the following (1) to (3), (1) a content of the component (D1) is 2 mass % or more and 30 mass % or less, (2) a total amount of the component (D) is a neutralization equivalent or more of the components (B) and (C), and (3) a ratio of the component (D1) in the component (D) [(D1)/(D1+D2)] is 15 mol% or more and 60 mol% or less; and (E) at least one nonionic surfactant selected from the group consisting of a monohydric alcohol, a polyhydric alcohol, and derivatives thereof, wherein mass % is based on the total mass of the water-soluble metalworking oil agent.

2. The water-soluble metalworking oil agent according to claim 1, wherein the component (D1) contains at least either dicyclohexylamine or N-methyldicyclohexylamine.

3. The water-soluble metalworking oil agent according to claim 1, further comprising (F) water.

4. A metalworking method comprising: machining a workpiece made of aluminum or an aluminum alloy, with the water-soluble metalworking oil agent according to claim 1.

5. A metalworking method comprising: machining a workpiece made of aluminum or an aluminum alloy, with the metalworking liquid according to claim 2.

6. The metalworking method according to claim 4, wherein the metalworking method is cutting or grinding.

7. The water-soluble metalworking oil agent according to claim 1, wherein the -olefin is present in a total amount of from 25 to 61 mass %.

8. The water-soluble metalworking oil agent according to claim 7, wherein component (B) is present in a total amount of from 9 to 22 mass %.

9. The water-soluble metalworking oil agent according to claim 8, wherein component (C) is present in an amount of from 14 to 21 mass %.

10. The water-soluble metalworking oil agent according to claim 9, wherein total amount of components (D1) and (D2) is from 10 to 20 mass %.

11. The water-soluble metalworking oil agent according to claim 10, wherein total amount of component (D1) is from 5 to 12 mass %.

12. The water-soluble metalworking oil agent according to claim 11, wherein total amount of component (D2) is from 5 to 10 mass %.

13. The water-soluble metalworking oil agent according to claim 1, wherein total amount of component (E) is from 3 to 7 mass %.

14. The water-soluble metalworking oil agent according to claim 1, wherein the compounding ratio [(D1)/(D1+D2)] is from 32 to 46 mol %.

15. The water-soluble metalworking oil agent according to claim 1, wherein the (D) is present in a total amount of from 11 to 26 mass %.

16. A water-soluble metalworking oil agent comprising, the following (A) to (E): (A) an -olefin component consisting of one or more C14 to C16 -olefins, in a content of 20 mass % or more and 65 mass % or less, wherein at least 40 mass % of the -olefin composition is a C14 -olefin; (B) at least one selected from the group consisting of a dehydration-condensed fatty acid of ricinoleic acid and a dehydration-condensed fatty acid between a ricinoleic acid dehydration-condensed fatty acid and a carboxylic acid, in a content of 5 mass % or more and 30 mass % or less; (C) two or more C9 to C12 compounds selected from the group consisting of a monocarboxylic acid and a dicarboxylic acid, each not containing the component (B), wherein the total amount of (C) is from 10 to 19 mass %; (D) an alkylamine (D1) not containing a hydroxyl group and an alkanolamine (D2), each meeting the following (1) to (3), (1) a content of the component (D1) is 2 mass % or more and 30 mass % or less, (2) a total amount of the component (D) is a neutralization equivalent or more of the components (B) and (C), and (3) a ratio of the component (D1) in the component (D) [(D1)/(D1+D2)] is 15 mol % or more and 60 mol % or less; and (E) at least one nonionic surfactant selected from the group consisting of a monohydric alcohol, a polyhydric alcohol, and derivatives thereof, wherein mass % is based on the total mass of the water-soluble metalworking oil agent.

17. The water-soluble metalworking oil agent according to claim 16, wherein the component (C) contains at least one monocarboxylic acid and at least one dicarboxylic acid.

18. A metalworking liquid comprising from 3 to 20 volume % of the water-soluble metalworking oil agent according to claim 1 in water.

19. A metalworking liquid comprising from 3 to 20 volume % of the water-soluble metalworking oil agent according to claim 16 in water.

Description

EXAMPLES

(1) The present invention is hereunder described in more detail by reference to Examples, but it should not be construed that the present invention is limited to the following Examples. Characteristics of the water-soluble metalworking oil agents and the metalworking liquids according to the Examples and Comparative Examples were evaluated by the following evaluation methods.

(2) <Respective Evaluation Methods>

(3) (1) Evaluation of Stability of Undiluted Liquid

(4) 80 ml of each of the undiluted liquids of water-soluble metalworking oil agent (cutting or grinding oil agent) was charged in a 100-mL transparent glass bottle and allowed to stand in a thermostat at 0 C., 25 C., and 50 C., respectively for 24 hours, followed by observing its appearance. Then, the stability of undiluted liquid was evaluated according to the following evaluation criteria.

(5) (Evaluation Criteria of Stability of Undiluted Liquid)

(6) Accepted: Free from separation, sedimentation/precipitation, and solidification Rejected: Found for separation, sedimentation/precipitation, or solidification
(2) Evaluation of Dispersion Stability (Stability of Undiluted Liquid)

(7) Each of the undiluted liquids of water-soluble metalworking oil agent (cutting or grinding oil agent) was diluted with a magnesium-adjusted water (Mg-adjusted water), which was obtained by adjusting with water and magnesium chloride so as to contain 200 ppm of a magnesium ion, to a concentration of 5 volume %, and after 24 hours, its appearance was observed. Then, the dispersion stability was evaluated according to the following evaluation criteria. Accepted: Free from separation and heterogeneity Rejected: Found for separation or heterogeneity
(3) Evaluation of Machining Performance

(8) Each of the undiluted liquids of water-soluble metalworking oil agent (cutting or grinding oil agent) was diluted with water to a concentration of 5 volume %, and drilling for prepared holes was performed under the following conditions, followed by performing form roll tapping. Then, a maximum tap torque during the form roll tapping was measured. An average value of the results was evaluated according to the criteria shown in Table 1.

(9) (Machining Conditions of Drilling for Prepared Holes and Form Roll Tapping)

(10) Machine Used

(11) Tapping center MTV-T350, manufactured by Mectron Inc.

(12) Workpiece

(13) A6061 (JIS standards) and A390 (AA Standards)

(14) Machining for Prepared Holes

(15) Tool used: Igetalloy Supermulti Drill MDS093MG T4120, manufactured by Sumitomo Electric Hardmetal Corporation, drill diameter: 9.3 mm

(16) Speed: 80 m/min

(17) Feed: 0.15 mm/rev

(18) Depth: 30 mm (blind hole)

(19) Tapping

(20) Tool used: New Roll Tap, B-NRT, M10P1.5, manufactured by OSG Corporation

(21) Speed: 20 m/min

(22) Depth: 25 mm

(23) No. of Workpiece (n): 9

(24) The evaluation criteria of machining performance are shown in Table 1.

(25) TABLE-US-00001 TABLE 1 Workpiece Decision A6061 A390 Excellent Less than 8.0 N .Math. m Less than 10.0 N .Math. m Inferior 8.0 N .Math. m or more 10.0 N .Math. m or more
(4) Rotting Resistance

(26) To 100 mL of a sample prepared by diluting each of the undiluted liquids of water-soluble metalworking oil agent (cutting or grinding oil agent) with water to a concentration of 3 volume %, 5 mL of a rotted liquid A and 0.5 mL of a rotted liquid B, each shown below, were added, and the mixture was subjected to shake culturing at 30 C. and 150 rpm for 7 days. On the 7 day, 2.5 mL of the rotted liquid A and 0.25 mL of the rotted liquid B were added, and the resultant was further subjected to shake culturing for 7 days. Then, the number of viable cells was counted. Incidentally, the totting test conditions and the counting method of the number of viable cells are as follows.

(27) (Rotting Test Conditions)

(28) Culturing Conditions:

(29) 3 g of FC200 dry shavings was added, and the mixture was shaken at 30 C. and 150 rpm.

(30) Rotted Liquid A:

(31) To an emulsion-type cutting liquid which had been rotted and deteriorated, an SCD medium Daigo, manufactured by Nihon Pharmaceutical Co., Ltd. was added, and the mixture was activated by means of aeration for 72 hours.

(32) Rotted Liquid B:

(33) To an emulsion-type cutting liquid which had been rotted and deteriorated, a potato dextrose agar medium Daigo, manufactured by Nihon Pharmaceutical Co., Ltd. was added, and the mixture was activated by means of aeration for 72 hours.

(34) (Counting Method of the Number of Viable Cells)

(35) The number of bacterial cells in a sample (1 mL) was counted by a San-Ai Bio-checker TTC, manufactured by San-Ai Oil Co. Ltd. at 6 levels of less than 10.sup.3 cells/mL, 10.sup.3 cells/mL, 10.sup.4 cells/mL, 10.sup.5 cells/mL, 10.sup.6 cells/mL, and 10.sup.7 cells/mL, and the rotting resistance was evaluated according to the following evaluation criteria.

(36) (Evaluation Criteria of Rotting Resistance)

(37) Extremely excellent: 10.sup.3 cells/mL or less Excellent: 10.sup.4 cells/mL or more and 10.sup.5 cells/mL or less Inferior: 10.sup.6 cells/mL or more

Examples 1 to 7

(38) (Preparation of Water-Soluble Metalworking Oil Agent>

(39) The undiluted liquid of a water-soluble metalworking oil agent (cutting or grinding oil agent) used in each of the Examples was prepared by compounding the base materials in a compounding proportion as shown in Table 2.

(40) TABLE-US-00002 TABLE 2 Formulation (mass %) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 1-Tetradecene 10 21 28 10 15 15 20 1-Hexadecene 15 21 28 15 15 15 28 1-Octadecene Mineral oil Polycondensed fatty acid 1 18 18 Polycondensed fatty acid 2 10 8 Polycondensed fatty acid 3 14 14 12 Tall oil fatty acid 5 10 8 5 5 5 5 Neodecanoic acid 3 7 5 3 3 3 3 Pelargonic acid 3 3 2 2 Dodecane diacid 1 1 0.5 1 1 1 1 Sebacic acid 2 1 0.5 2 1 1 1 Dicyclohexylamine 10 10 5 N-Methyldicyclohexylamine 10 12 12 10 Monoisopropanolamine 5 6 5 5 4 5 2-Amino-2-methylpropanol 4 N-Cyclohexyldiethanolamine 6 6 N-Methyldiethanolamine 5 5 Nonionic surfactant 1 3 4 2 3 6 6 4 Nonionic surfactant 2 1 1 2 Nonionic surfactant 3 1 Water 18 8 8 18 15 15 8 Benzotriazole 1 1 1 1 1 1 1 Compounding ratio of -olefin (mass %) 25 42 56 25 30 30 48 Compounding ratio of polycondensate (mass %) 18 10 8 18 14 14 12 Compounding ratio of D1 (mass %) 10 10 5 10 12 12 10 D1/(D1 + D2) (mol %) 34 41 29 32 46 42 43

(41) Details of the compounding base materials shown in the foregoing Table 2 are as follows. Mineral oil (kinetic viscosity at 40 C.: 9.5 mm.sup.2/s, kinetic viscosity at 100 C.: 2.3 mm.sup.2/s) Polycondensed fatty acid 1 (condensate obtained by subjecting ricinolic acid to thermal dehydration condensation at 200 C. under a nitrogen gas stream, acid value: 34 mgKOH/g, hydroxyl value: 28 mgKOH/g, saponification value: 198 mgKOH/g) Polycondensed fatty acid 2 (condensate obtained by subjecting ricinolic acid to thermal dehydration condensation at 200 C. under a nitrogen gas stream, acid value: 53 mgKOH/g, hydroxyl value: 42 mgKOH/g, saponification value: 196 mgKOH/g) Polycondensed fatty acid 3 (condensate obtained by subjecting ricinolic acid to thermal dehydration condensation at 200 C. under a nitrogen gas stream, further adding oleic acid, and subjecting the mixture to thermal dehydration condensation, acid value: 85 mgKOH/g, hydroxyl value: 15 mgKOH/g, saponification value: 195 mgKOH/g) Nonionic surfactant 1 (polyoxyethylene propylene monoalkylene ether, HLB: 13) Nonionic surfactant 2 (diethylene glycol monobutyl ether) Nonionic surfactant 3 (oleyl alcohol)
(Performance Evaluation)

(42) By using each of the above-prepared water-soluble metalworking oil agents and the like, each of the above-described evaluations was performed. The evaluation results are summarizingly shown in Table 3.

(43) TABLE-US-00003 TABLE 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Stability of 0 C. Accepted Accepted Accepted Accepted Accepted Accepted Accepted undiluted 25 C. Accepted Accepted Accepted Accepted Accepted Accepted Accepted liquid 50 C. Accepted Accepted Accepted Accepted Accepted Accepted Accepted Dispersion Tap water Accepted Accepted Accepted Accepted Accepted Accepted Accepted stability Magnesium-adjusted water Accepted Accepted Accepted Accepted Accepted Accepted Accepted Machining Machining torque of A6061 (N .Math. m) 7.7 7.4 7.5 7.6 7.6 7.5 7.4 performance Decision of A6061 Excellent Excellent Excellent Excellent Excellent Excellent Excellent Machining torque of A390 (N .Math. m) 9.5 9.4 9.5 9.5 9.5 9.5 9.4 Decision of A390 Excellent Excellent Excellent Excellent Excellent Excellent Excellent Rotting Number of viable cells (cells/mL) 10.sup.3 or less 10.sup.3 or less 10.sup.4 10.sup.3 or less 10.sup.3 or less 10.sup.3 or less 10.sup.3 or less resistance Decision Extremely Extremely Excellent Extremely Extremely Extremely Extremely excellent excellent excellent excellent excellent excellent

Comparative Examples 1 to 10

(44) Each of undiluted liquids of water-soluble metalworking oil agent (cutting or grinding oil agent) was prepared by compounding the base materials in a compounding proportion as shown in the following Table 4 similarly to the foregoing Examples 1 to 7, and then similarly subjected to various performance evaluations. The results obtained are shown in Table 5.

(45) TABLE-US-00004 TABLE 4 Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- tive tive tive tive tive tive tive tive tive tive Example Formulation (mass %) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 10 1-Tetradecene 8 30 23 10 28 25 1-Hexadecene 8 30 23 15 28 26 1-Octadecene 43 56 Mineral oil 42 48 Polycondensed fatty acid 1 18 Polycondensed fatty acid 2 10 8 10 4 8 8 Polycondensed fatty acid 3 12 16 18 Tall oil fatty acid 5 10 8 10 5 8 4 4 8 8 Neodecanoic acid 3 7 5 7 3 5 4 3 5 5 Pelargonic acid 3 1 1.5 Dodecane diacid 1 1 0.5 1 1 0.5 1 1.5 0.5 0.5 Sebacic acid 2 1 0.5 1 1 0.5 0.5 0.5 Dicyclohexylamine 10 10 5 10 5 4 8 15 N-Methyldicyclohexylamine 10 Monoisopropanolamine 5 6 5 6 5 5 2 4 2 2-Amino-2-methylpropanol N-Cyclohexyldiethanolamine 15 8 N-Methyldiethanolamine 5 5 Nonionic surfactant 1 3 3 2 4 4 2 2 3 2 2 Nonionic surfactant 2 1 2 1 Nonionic surfactant 3 1 1 1 1 Water 27 8 8 8 8 8 8 21 8 8 Benzotriazole 1 1 1 1 1 1 1 1 1 1 Compounding ratio of 16 43 56 0 0 60 46 25 56 51 -olefin (mass %) Compounding ratio of 18 10 8 10 12 4 16 18 8 8 polycondensate (mass %) Compounding ratio of D1 10 10 5 10 10 5 0 4 8 15 (mass %) D1/(D1 + D2) (mol %) 34 41 29 41 43 29 0 14 62 100

(46) TABLE-US-00005 TABLE 5 Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- Compara- tive tive tive tive tive tive tive tive tive tive Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 10 Stability of 0 C. Accepted Rejected Rejected Accepted Accepted Rejected Accepted Accepted Accepted Rejected undiluted (so- lidified) liquid 25 C. Accepted Accepted Rejected Accepted Accepted Rejected Accepted Accepted Accepted Rejected 50 C. Accepted Accepted Rejected Accepted Accepted Rejected Accepted Accepted Accepted Rejected Dispersion Tap water Accepted Accepted Accepted Accepted Accepted Accepted Rejected stability Magnesium- Accepted Rejected Accepted Accepted Accepted Accepted Rejected adjusted water Machining Machining 9.1 7.4 8.6 8.5 8.3 8.9 performance torque of A6061 (N .Math.m) Decision of Inferior Excellent Inferior Inferior Inferior Inferior A6061 Machining 11.2 9.4 10.6 10.6 10.2 10.8 torque of A390 (N .Math.m) Decision of Inferior Excellent Inferior Inferior Inferior Inferior A390 Rotting Number of 10.sup.3 or less 10.sup.3 or less 10.sup.3 or less 10.sup.3 or less 10.sup.6 10.sup.4 resistance viable cells (cells/mL) Decision Extremely Extremely Extremely Extremely Inferior Excellent excellent excellent excellent excellent

INDUSTRIAL APPLICABILITY

(47) According to the water-soluble metalworking oil agent, the metalworking liquid, and the metalworking method using the same of the present invention, more efficient machining of aluminum or an aluminum alloy may be realized; in the view of the fact that rotting deterioration is hardly caused, the working environment may be kept well; and because of excellent emulsion dispersion stability, it is possible to reduce the use amount of the oil agent. Furthermore, because of excellent stability of undiluted liquid, the workability is not impaired in the environments of various production sites.