JP3527936B2 - Metalworking oil composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal working oil composition, and more particularly to a metal working oil particularly useful for plastic working such as rolling, drawing, ironing and drawing of metals. Composition. 2. Description of the Related Art In metal working such as cold rolling, drawing, ironing, drawing, pressing, cutting, and grinding, generation of abrasion powder, generation of organic metal salts, and the like cause severe foaming and difficult work. Bring. In order to suppress this frothing, an organic silicon compound or the like has been mainly used as an antifoaming agent. [0003] However, when the above-mentioned antifoaming agent is used, the persistence of the defoaming effect is short, and oil is repelled due to adhesion to the surface of a work material, which may cause unevenness of coating. And causes problems such as blockage of the filter. SUMMARY OF THE INVENTION An object of the present invention is to provide a metal working oil having less wrinkles than conventional metal working oils. Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding a specific compound to a metal working oil, the appearance of the metal working oil has been reduced. The inventors have found that the performance of the oil itself is not reduced, and have completed the present invention. That is, the present invention uses at least one selected from mineral oils, synthetic oils and fats and oils as a base oil, and (A) at least one oxygen-containing compound selected from % (A1) an alkylene oxide adduct of a polyhydric alcohol having 3 to 6 hydroxyl groups having a number average molecular weight of 200 to less than 1000 (A2) having 3 to 6 hydroxyl groups having a number average molecular weight of 200 to less than 1000 0.1 to 10% by mass of a hydrocarbyl ether of an alkylene oxide adduct of a polyhydric alcohol and (B) an oxygen-containing compound selected from the following: (B1) a number average molecular weight of 150 to less than 1000 Polyalkylene glycol (B2) Hydrocarbyl polyalkylene glycol having a number average molecular weight of 150 or more and less than 1000 Ether (B3) is to provide a metal working oil composition characterized by containing a dihydric alcohol having 2 to 8 carbon atoms. DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below.
The metalworking oil composition of the present invention comprises at least one base oil selected from mineral oils, fats and oils, and synthetic oils. As an example of a mineral base oil usable in the present invention, a lubricating oil fraction obtained by distilling crude oil under normal pressure and reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Examples include paraffinic or naphthenic mineral oils obtained by appropriately combining one or more purification means such as solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. The fats and oils include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, and hydrogenated products thereof. As the synthetic oil, for example, poly-α-
Olefins (ethylene-propylene copolymer, polybutene, 1-octene oligomer, 1-decene oligomer,
And hydrides thereof), alkylbenzene, alkylnaphthalene, monoester (butyl stearate, octyl laurate), diester (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-
2-ethylhexyl sepacate, etc.), polyester (such as trimellitic acid ester), polyol ester (trimethylolpropane caprylate, trimethylolpropaneperargonate, pentaerythritol-2)
-Ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, polyphenyl ether, dialkyl diphenyl ether,
Phosphate esters (such as tricresyl phosphate),
Examples include fluorinated compounds (such as perfluoropolyethers and fluorinated polyolefins) and silicone oils. As the base oil of the metalworking oil composition of the present invention, the above base oils may be used alone or in combination of two or more. The viscosity of the base oil used in the present invention is not particularly limited, but generally, the kinematic viscosity at 40 ° C. is preferably in the range of 1 to ²⁰ mm ² / s. The component (A) of the present invention is at least one oxygen-containing compound selected from the following. (A1) Alkylene oxide adduct of a polyhydric alcohol having 3 to 6 hydroxyl groups having a number average molecular weight of 200 to less than 1000 (A2) having 3 to 6 hydroxyl groups having a number average molecular weight of 200 to less than 1000 Hydrocarbyl ether of alkylene oxide adduct of polyhydric alcohol As the polyhydric alcohol constituting component (A1), a polyhydric alcohol having 3 to 6 hydroxyl groups is used. Specifically, for example, glycerin, polyglycerin (2 to tetramer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.), trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) ) And their 2-4 tetramers,
Pentaerythritol, dipentaerythritol, 1,
2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,2
Polyhydric alcohols such as 3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, iditol, talitol, dulcitol, and allitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, Galactose,
Mannose, sorbose, cellobiose, maltose,
Saccharides such as isomaltose, trehalose, and sucrose can be mentioned. Among them, glycerin, trimethylolalkane, sorbitol and the like are preferable because of excellent defoaming properties. As the alkylene oxide constituting the component (A1), one having 2 to 6, preferably 2 to 4 carbon atoms is used. As the alkylene oxide having 2 to 6 carbon atoms, specifically, for example, ethylene oxide,
Propylene oxide, 1,2-epoxybutane (α-
Butylene oxide), 2,3-epoxybutane (β-
Butylene oxide), 1,2-epoxy-1-methylpropane, 1,2-epoxyheptane, 1,2-epoxyhexane and the like. Among them, ethylene oxide, propylene oxide and the like are preferable because of their excellent defoaming properties. preferable. When two or more alkylene oxides are used, there is no particular limitation on the type of polymerization of the oxyalkylene groups, and they may be random copolymerized or block copolymerized. In addition, when an alkylene oxide is added to a polyhydric alcohol having 3 to 6 hydroxyl groups, the alkylene oxide may be added to all the hydroxyl groups or may be added only to a part of the hydroxyl groups. Therefore, those added to all hydroxyl groups are preferable. Further, the component (A1) of the present invention has a number average molecular weight of 200 or more and less than 1000, preferably 2 or less.
It is necessary to be 50 or more and less than 750. When the number average molecular weight is less than 200, the solubility in oil decreases, which is not preferable. Further, when the number average molecular weight is 1000 or more, when the metal working oil composition of the present invention is used as a rolling oil, the metal working oil composition may remain on the sheet surface at the time of annealing after rolling to cause stain, which is not preferable. The component (A1) of the present invention has a number average molecular weight of 200 to 10 when the alkylene oxide is added to a polyhydric alcohol having 3 to 6 hydroxyl groups.
The reaction may be performed so as to be less than 00, or a mixture of an alkylene oxide adduct of a polyhydric alcohol having 3 to 6 hydroxyl groups obtained by an arbitrary method or a commercially available hydroxyl group of 3 to 6 A mixture of polyalkylene oxide adducts of polyhydric alcohols having a number average molecular weight of 200 or more and less than 1000 may be used by distillation or chromatography. The component (A2) of the present invention has a number average molecular weight of 200 to less than 1,000, preferably 250 to 750.
It is obtained by hydrocarbyl etherifying an alkylene oxide adduct of a polyhydric alcohol having 3 to 6 hydroxyl groups, which is less than the above. As the component (A2), (A
The component (1) in which some or all of the terminal hydroxyl groups of the alkylene oxide adduct of the component are hydrocarbyl etherified can be used. Here, the hydrocarbyl group refers to a hydrocarbon group having 1 to 24 carbon atoms. Carbon number 1-2
Specific examples of the hydrocarbon group of No. 4 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Butyl, tert-butyl, straight or branched pentyl, straight or branched hexyl, straight or branched heptyl, straight or branched octyl, straight or branched Nonyl group, straight or branched decyl group, straight or branched undecyl group, straight or branched dodecyl group, straight or branched tridecyl group, straight or branched tetradecyl group, straight chain Or branched pentadecyl, straight or branched hexadecyl, straight or branched heptadecyl, straight or branched octadecyl, straight or branched nonadecyl, straight or branched icosyl An alkyl group having 1 to 24 carbon atoms such as a group, a linear or branched henicosyl group, a linear or branched docosyl group, a linear or branched tricosyl group, a linear or branched tetracosyl group; ] A linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched Branched octenyl group, straight or branched nonenyl group, straight or branched decenyl group, straight or branched undecenyl group, straight or branched dodecenyl group, straight or branched tridecenyl group Linear or branched tetradecenyl group, linear or branched pentadecenyl group, linear or branched hexadecenyl group, linear or branched heptadecenyl group, linear or branched octadecenyl group, linear or branched A branched nonadecenyl group, a straight or branched icosenyl group, a straight or branched henicocenyl group, a straight or branched docosenyl group,
An alkenyl group having 2 to 24 carbon atoms such as a linear or branched tricosenyl group, a linear or branched tetracosenyl group; a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; A methylcyclopentyl group, a dimethylcyclopentyl group (including all structural isomers), a methylethylcyclopentyl group (including all structural isomers), a diethylcyclopentyl group (including all structural isomers), a methylcyclohexyl group, Dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (including all structural isomers), methylcycloheptyl group, dimethylcycloheptyl group (including Including all structural isomers), methyl ethyl cyclohepti Alkylcycloalkyl groups having 6 to 11 carbon atoms, such as phenyl group (including all structural isomers) and diethylcycloheptyl group (including all structural isomers); and 6 to 10 carbon atoms, such as phenyl group and naphthyl group. Aryl groups of the following formulas: tolyl group (including all structural isomers), xylyl group (including all structural isomers), ethylphenyl group (including all structural isomers), linear or branched Propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl group (including all structural isomers) Linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (including all structural isomers), linear or branched octylphenyl group (all Structure of Isomers), linear or branched nonylphenyl groups (including all structural isomers), linear or branched decylphenyl groups (including all structural isomers), linear or branched An alkylaryl group having 7 to 18 carbon atoms such as an undecylphenyl group (including all structural isomers), a linear or branched dodecylphenyl group (including all structural isomers); Phenylethyl group, phenylpropyl group (including isomer of propyl group), phenylbutyl group (including isomer of butyl group), phenylpentyl group (including isomer of pentyl group), phenylhexyl group (including isomer of hexyl group) An arylalkyl group having 7 to 12 carbon atoms, including isomers). Among these, a linear or branched alkyl group having 3 to 12 carbon atoms is preferable from the viewpoint of excellent defoaming properties. In the present invention, as the component (A), one type of oxygen-containing compound selected from the above (A1) and (A2) may be used alone, or a compound having a different structure may be used.
A mixture of two or more oxygen-containing compounds may be used. In the present invention, the upper limit of the content of the component (A) based on the total amount of the composition is 10% by mass, preferably 5% by mass, and the lower limit is 0.1% by mass, preferably 0.2% by mass.
It is. When the content of the component (A) is more than 10% by mass, the solubility may be lowered or the performance as a metal working oil may be adversely affected, which is not preferable. Also, (A)
When the content of the component is less than 0.1% by mass, the effect of suppressing foaming is small, which is not preferable. The component (B) of the present invention is at least one oxygen-containing compound selected from the following. (B1) a polyalkylene glycol having a number average molecular weight of 150 or more and less than 1000 (B2) a hydrocarbyl ether of a polyalkylene glycol having a number average molecular weight of 150 or more and less than 1000 (B3) a dihydric alcohol having 2 to 8 carbon atoms The component B1) is a polyalkylene glycol having a number average molecular weight of 150 or more and less than 1000. As the polyalkylene glycol, one obtained by homopolymerizing or copolymerizing an alkylene oxide having 2 to 6, preferably 2 to 4 carbon atoms is used. Specific examples of the alkylene oxide having 2 to 6 carbon atoms include (A1)
Examples of the alkylene oxide constituting the component include those enumerated above. Among them, from the point of excellent defoaming property,
Preferred are ethylene oxide and propylene oxide. When two or more kinds of alkylene oxides are used in the polyalkylene glycol, the polymerization form of the oxyalkylene group is not particularly limited, and may be random copolymerization or block copolymerization. Further, the component (B1) has a number average molecular weight of 150 to less than 1,000, preferably 150 to 5
It must be less than 00. Number average molecular weight is 15
If the value is less than 0, the solubility in oil decreases, which is not preferable. When the number average molecular weight is 1000 or more,
When using the metalworking oil composition of the present invention as a rolling oil,
It is not preferable because it may remain on the plate surface during annealing after rolling and cause stain. As the component (B1), those which are reacted so that the number average molecular weight becomes 150 or more and less than 1000 when polymerizing the alkylene oxide may be used, or the polyalkylene obtained by any method may be used. A glycol mixture or a commercially available polyalkylene glycol mixture is distilled or chromatographed to have a number average molecular weight of 150.
It is also possible to use one separated so as to be less than 1,000. The component (B2) is obtained by hydrocarbyl etherifying a polyalkylene glycol having a number average molecular weight of 150 to less than 1,000, preferably 150 to less than 500. As the component (B2), (B1)
A component obtained by partially or entirely hydrocarbyl etherifying terminal hydroxyl groups of a polyalkylene glycol as a component can be used. Here, the hydrocarbyl group means a hydrocarbon group having 1 to 24 carbon atoms, and specifically, for example, (A
Each group listed in 2) can be mentioned. Among them, a linear or branched alkyl group having 3 to 12 carbon atoms is preferable from the viewpoint of excellent defoaming properties. The component (B3) is a dihydric alcohol having 2 to 8 carbon atoms, preferably 5 or 6 carbon atoms. The term "dihydric alcohol" as used herein means a compound having no ether bond in the molecule. . As such a dihydric alcohol having 2 to 8 carbon atoms, specifically, for example, ethylene glycol,
1,3-propanediol, propylene glycol,
1,4-butanediol, 1,2-butanediol, 2
-Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-
Examples thereof include 2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 1,8-octanediol. Among these, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-
Methyl-1,3-propanediol and the like are preferred. In the present invention, the component (B) is selected from (B1), (B2) and (B3).
One kind of oxygenates may be used alone, or a mixture of two or more kinds of oxygenates having different structures may be used. In the present invention, the upper limit of the content of the component (B) based on the total amount of the composition is 10% by mass, preferably 5% by mass, and the lower limit is 0.1% by mass, preferably 0.2% by mass.
It is. If the content of the component (B) exceeds 10% by mass, the solubility may be lowered or the performance as a metal working oil may be adversely affected, which is not preferable. (B)
If the content of the component is less than 0.1% by mass, the effect of suppressing foaming becomes small, which is not preferable. The metalworking oil composition of the present invention is characterized in that the base oil contains the component (A) and the component (B) in predetermined amounts.
Although it has excellent defoaming effects and various properties as a metalworking oil, known additives can be used as needed to further enhance the excellent performance. Specific examples of the additive include oil agents such as higher alcohols, fatty acids, fatty acid esters, and sulfurized fats and oils; extreme pressure agents such as phosphate esters, acid phosphate esters, phosphite esters, and zinc dithiophosphate; Rust inhibitors such as petroleum sulfonate, dinonylnaphthalene sulfonate, sorbitan ester; metal deactivators such as benzotriazole; diphenylamine, phenyl-α-naphthylamine, 2,
Antioxidants such as 6-di-tert-butyl-p-cresol; antifoaming agents such as organosilicon compounds;
These can be added alone or in combination of two or more. The content of these additives is usually 15% by mass.
Or less, preferably 10% by mass or less (all based on the total amount of the composition; total amount). The metalworking oil composition of the present invention comprises iron, stainless steel, special steel, aluminum, aluminum alloy,
The present invention can be preferably used for plastic working such as cold rolling, drawing, ironing, drawing, and pressing of various metals such as copper and copper alloys or alloys of these metals, cutting, and grinding. EXAMPLES The contents 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. (Example 1) As shown in Table 1, the following base 1 was used as a base oil.
(Paraffinic mineral oil, @ 40 ° C. 1.7 mm ² / s) at 99.0% by mass, and the following component A1 [propylene oxide adduct of glycerin (number average molecular weight: 6)
00)] as 0.5% by mass and the following B1 as component (B):
[Tripropylene glycol (number average molecular weight: 19
2)] was used to prepare a metalworking oil composition of the present invention. This composition was subjected to a foam stability test, a solubility test and a stain test by the following methods. The results are shown in Table 1. Examples 2 to 9 According to the compositions shown in Table 1,
A metalworking oil composition of the present invention was prepared. The components used are as follows. For these compositions, a foam stability test, a solubility test, and a stain test were performed in the same manner as in Example 1, and the results are also shown in Table 1. Comparative Examples 1 to 8 According to the compositions shown in Table 2,
A composition for comparison was prepared. The components used are as follows. Example 1 for these compositions
A foam stability test, a solubility test, and a stain test were performed in the same manner as described above, and the results are also shown in Table 2. Base oil base 1: paraffinic mineral oil, @ 40 ° C. 1.7 mm ² / s Base 2: polybutene, @ 40 ° C. 2.5 mm ² / s (A) Component A1: propylene oxide adduct of glycerin (Number average molecular weight: 600) A2: Propylene oxide adduct of trimethylolpropane (Number average molecular weight: 600) A3: Propylene oxide adduct of sorbitol (Number average molecular weight: 750) A4: Triisopropyl ether compound of A1 (B) Component B1: Tripropylene glycol (number average molecular weight: 19
2) B2: polyethylene glycol (number average molecular weight: 60)
0) Monolauryl ether B3: hexylene glycol Other components C1: propylene oxide adduct of glycerin (number average molecular weight: 1500) C2: polypropylene glycol (number average molecular weight: 13)
00) C3: dimethylpolysiloxane (@ 40 ° C., 500 mm
² / s) [0043] (the presence of foam stability test) the rolled material each composition was rolled under the following conditions, the composition 200mL
JIS K 2518 "Petroleum products-Lubricating oil-
The foam stability at 24 ° C. was measured in accordance with “Foaming test method”. The smaller the value of the foam stability, the higher the effect of suppressing foaming. Rolling conditions: Rolled material: A-1100 H18 (0.4 mm thickness) Reduction rate: 40% Rolling speed: 300 m / min Using a line filter (1 μm) (Solubility test) 100 mL of each composition was put into a mixer. After stirring at about 10,000 rpm for 1 minute, the state of the composition was visually observed. The evaluation was as follows: 完全 when completely dissolved, △ when some were hardly soluble, and x when insoluble. (Stain test) Inst. Met
als, 88 (1959) 481 (RD GUMIN)
KI) in accordance with the Can test method.
That is, 0.1 m of each composition was placed in an aluminum cup.
L was dropped, and the mixture was heated from room temperature to 350 ° C. over 150 minutes, and the heating was stopped after 60 minutes. The case where no stain was generated in the cup was evaluated as ○, the case where slight generation of stain was recognized was evaluated as Δ, and the case where stain was generated on the entire bottom surface of the cup was evaluated as x. [Table 1] [Table 2] As is clear from the results of Tables 1 and 2,
The compositions of Examples 1 to 9 are highly effective in suppressing foaming, have excellent solubility, and do not generate stain. On the other hand, when an alkylene oxide adduct (C1) of a polyhydric alcohol having a number average molecular weight exceeding 1000 was used (Comparative Example 1)
In the case, generation of stain was recognized, and the number average molecular weight was 100.
When a polyalkylene glycol (C2) exceeding 0 was used (Comparative Example 2), foaming was large and generation of stain was observed. Further, when the content of the component (A) is small (Comparative Example 3), the effect of suppressing foaming is small and the solubility is poor, and when the content of the component (A) is large (Comparative Example 4).
As for, generation of stain was recognized and solubility was deteriorated. In addition, when the content of the component (B) is small (Comparative Example 5), the effect of suppressing foaming is small, and when the content of the component (B) is large (Comparative Example 6), the solubility is poor and the stain is not improved. Occurrence was observed. When 200 ppm of the organosilicon compound (C3) was used as a defoaming agent (Comparative Example 7), foaming increased. When the amount of the organic silicon compound (C3) was increased (Comparative Example 8), the solubility was poor, and the generation of stain was observed. The metalworking oil composition of the present invention is a metalworking oil composition particularly useful for plastic working such as rolling, drawing, ironing, and drawing of metal. It does not drop, has little foaming, has excellent solubility, and does not generate stain.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification code FI C10M 129: 08 C10M 129: 16 129: 16) 145: 26 (C10M 161/00 C10N 20:04 129: 08 30:00 A 129 : 16 30:12 145: 26) 30:18 C10N 20:04 40:20 Z 30:00 30:12 30:18 40:20 (72) Inventor Hiroshi Kinoshita 8 Chidoricho, Naka-ku, Yokohama-shi, Yokohama, Japan (56) References JP-A-58-187494 (JP, A) JP-A-62-34696 (JP, A) JP-A-6-128583 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C10M 129/02 C10M 129/08 C10M 129/16 C10M 145/26-145/38 C10M 161/00 C10N 20:04 C10N 30:00 C10N 30:12 C10N 30: 18 C10N 40:20-40:24

Claims (1)

(57) [Claim 1] At least one selected from mineral oil, synthetic oil and fats and oils is used as a base oil, and (A) at least one oxygen-containing compound selected from the following is used as a base oil. 0.1 to 10% by mass (A1) The number average molecular weight is 200 or more and less than 1000, and the alkylene oxide adduct (A2) of a polyhydric alcohol having 3 to 6 hydroxyl groups has a number average molecular weight of 200 or more and less than 1000. 0.1 to 10% by mass of hydrocarbyl ether of an alkylene oxide adduct of a polyhydric alcohol having 3 to 6 hydroxyl groups and (B) at least one oxygen-containing compound selected from the following: (B1) Number average molecular weight Of polyalkylene glycol (B2) having a number average molecular weight of 150 or more and less than 1000 Ether (B3) metalworking oil composition characterized by containing a dihydric alcohol having 2 to 8 carbon atoms.