JPH09272889A - Drawing-processing oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a drawing-processing oil, excellent in drawing workability, capable of readily evaporating from moldings under heating after molding and having no anxiety forming precipitates by bringing it into contact with a new type of refrigerant in a case that the processing oil remains more or less on the moldings after its excluding step. SOLUTION: This drawing-processing oil comprises by blending a polyalkylene glycol and/or its alkyl ether with a kinematic viscosity of 5-3000mm<2> /s at 40 deg.C with 0.5-50 mass% of an ester from a fatty acid bearing 4-24 carbon atoms and a mono-or polyhydric alcohol and 0.1-10 mass% of a phosphoric ester-based compound on the basis of the composition total amount.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a drawing oil composition, and more particularly to a drawing oil composition exhibiting good performance as a drawing oil for metals, particularly copper or copper alloys.

[0002]

2. Description of the Related Art In the production of metal, particularly copper or copper alloy rods or pipes, a drawing oil containing mineral oil as a base oil is usually used. Degreasing removal using a chlorine-based solvent or a fluorine-based solvent, or evaporation removal by heating and evaporating a molded body has been adopted as means for removing the attached drawing oil.

[0003]

In recent years, the destruction of the ozone layer has been regarded as a problem, but with this, the use of chlorine-based solvents and fluorine-based solvents for degreasing drawn products is restricted. Currently, solvents other than these halogenated hydrocarbon solvents are used. However, degreasing and evaporative removal with solvents other than halogenated hydrocarbon solvents are less efficient in removing the processing oil than cleaning methods that use halogenated hydrocarbon solvents. There was the inconvenience that it remained on the body surface.
On the other hand, C which has been conventionally used as a refrigerant for refrigeration systems
FC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon) are also regulated as causative substances that destroy the ozone layer. Instead of these, H
FC (hydrofluorocarbon) is being used as a refrigerant. However, pipes that still have drawing oil remaining on the surface after degreasing and evaporation removal, especially copper and copper alloy pipes, were used in a refrigeration system that uses a new type of refrigerant as described above. In this case, it has been pointed out that the drawing processing oil remaining on the surface of the pipe material adversely affects the refrigerant used in the refrigeration system and causes the refrigeration system to be blocked. The present inventors have conducted intensive studies aiming at solving the above-mentioned various problems, and as a result, have made polyalkylene glycol and / or its alkyl ether contain a specific ester and a phosphorus-containing compound in specific amounts. It has been found that the above-mentioned problems can be solved by using drawing oil. The object of the present invention is not only excellent in drawing workability, but also
After processing, it can be easily removed from the molded body by the heating evaporation method, and even if the molded body is not always completely removed of the processing oil, it will be blocked in the refrigeration system. An object of the present invention is to provide a drawn processing oil composition that does not lead to the above.

[0004]

The drawing oil composition according to the present invention has a kinematic viscosity at 40 ° C. of 5 to 3000 mm ² / s.
The polyalkylene glycol and / or its alkyl ether as a base oil is used as a base oil, and the total amount of the composition is 0.5 to 50 mass% of the following component (A) and 0.1% of the component (B).
-10 mass% is contained. (A) an ester of a fatty acid having 4 to 24 carbon atoms and a monovalent to 10-valent alcohol, (B) a phosphoric acid ester-based compound,

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The base oil in the drawn oil composition of the present invention is polyalkylene glycol and / or its alkyl ether. The lower limit of the kinematic viscosity at 40 ° C. of this base oil is 5 mm ² / s, preferably 30 mm ² / s,
More preferably 50 mm ² / s, while the upper limit of kinematic viscosity at 40 ° C. is 3000 mm ² / s, preferably 2000
mm ² / s, more preferably 1000 mm ² / s. If the kinematic viscosity of the base oil at 40 ° C. is less than 5 mm ² / s, the lubricity of the composition will be insufficient, and conversely, if it exceeds 3000 mm ² / s, the workability in drawing will be reduced, which is not preferable. . In the present invention, the polyalkylene glycol is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide,
Homopolymerized or copolymerized. When this polyalkylene glycol is a copolymer of alkylene oxides having different structures, there are no particular restrictions on the monomer ratio or the arrangement of the monomers in the copolymer, and random copolymers, alternating copolymers and Any of the block copolymers can be used. Among the polyalkylene glycols that can be used in the present invention, a homopolymer of propylene oxide (polypropylene glycol) and a copolymer of ethylene oxide and propylene oxide (polyoxyethyleneoxypropylene glycol) are preferable, and polyoxyethyleneoxypropylene. As for the monomer constitution ratio in glycol, it is more preferable that oxypropylene / oxyethylene (molar ratio) is 0.5 or more.

In the present invention, the alkyl ether of polyalkylene glycol refers to the above-mentioned polyalkylene glycol in which the hydrogen atom of the hydroxyl group is substituted with an alkyl group, which includes a monoalkyl ether compound and a dialkyl ether compound. Both are included. The number of carbon atoms of the alkyl group to be ether-bonded is arbitrary, but the number of carbon atoms of the alkyl group is usually 1 to 18, preferably 1 to 10
In the range. This alkyl group may be linear or branched, and specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
sec-butyl group, tert-butyl group, straight chain or branched pentyl group, straight chain or branched hexyl group, straight chain or branched heptyl group, straight chain or branched octyl group, straight chain or branched nonyl group, Straight-chain or branched decyl group, straight-chain or branched undecyl group, straight-chain or branched dodecyl group, straight-chain or branched tridecyl group, straight-chain or branched tetradecyl group, straight-chain or branched pentadecyl group, straight-chain Alternatively, a branched hexadecyl group, a straight chain or branched heptadecyl group, a straight chain or branched octadecyl group and the like can be exemplified. In the case of a dialkyl ether compound, the alkyl groups bonded to both ends of the polyalkylene glycol may be the same or different. Among the alkyl ethers of polyalkylene glycol that can be used in the present invention, the monoalkyl ether of polyalkylene glycol is preferable from the viewpoint of excellent removability by heating and evaporation, and the monoalkyl ether of polypropylene glycol and polyoxyethyleneoxypropylene glycol. Is more preferable, and polypropylene glycol monoalkyl ether having an alkyl group having 1 to 10 carbon atoms and polyoxyethyleneoxypropylene glycol monoalkyl ether having an alkyl group having 1 to 10 carbon atoms are even more preferable. In the base oil in the composition of the present invention,
One or two selected from the group consisting of the above polyalkylene glycol and its alkyl ether compound
Two or more compounds can be used, but when a mixture of two or more compounds is used, the mixing ratio of the individual compounds in the mixture can be arbitrarily selected. In addition, the individual compounds constituting the mixture have a kinematic viscosity of 5 at 40 ° C.
~3000mm ² / s need not be in the range of kinematic viscosity at 40 ° C. as a mixture is not a problem as long as it is within the range of 5~3000mm ² / s.

The component (A) in the drawn oil composition of the present invention is an ester of a fatty acid having 4 to 24 carbon atoms and a 1 to 10-valent alcohol. The above fatty acid may be a linear fatty acid or a branched fatty acid, and may be a saturated fatty acid or an unsaturated fatty acid, but the lower limit of the number of carbon atoms is 4, preferably 6, while the upper limit of the number of carbon atoms is 24, It is preferably 18. When the fatty acid has less than 4 carbon atoms, the drawability of the resulting composition is insufficient, and when the fatty acid has more than 24 carbon atoms, the solubility in the base oil may cause a problem. Each is not preferable. 4 to 4 carbon atoms
Specific examples of the 24 fatty acids include straight chain or branched butanoic acid, straight chain or branched pentanoic acid, straight chain or branched hexanoic acid, straight chain or branched heptanoic acid, straight chain or branched chain. 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, Straight-chain or branched tetradecanoic acid, straight-chain or branched pentadecanoic acid, straight-chain or branched hexadecanoic acid, straight-chain or branched heptadecanoic acid, straight-chain or branched octadecanoic acid, straight-chain or branched Nonadecanoic acid, straight chain or branched icosanoic acid, straight chain or branched henicosanoic acid, straight chain or branched docosanoic acid, straight chain or branched tricosanoic acid, straight chain or branched tetracosanoic acid, etc. Saturated fatty acids Straight-chain or branched butenoic acid, straight-chain or branched pentenoic acid, straight-chain or branched hexenoic acid, straight-chain or branched heptenoic acid, straight-chain or branched octenoic acid, straight-chain or branched Nonenoic acid, linear or branched decenoic acid, linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid,
Straight-chain or branched tetradecenoic acid, straight-chain or branched pentadecenoic acid, straight-chain or branched hexadecenoic acid, straight-chain or branched heptadecenoic acid, straight-chain or branched octadecenoic acid, straight-chain or branched Nonadecenoic acid, linear or branched icosenoic acid, linear or branched henicosenoic acid,
Mention may be made of unsaturated fatty acids such as linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid; and mixtures thereof.
Among these fatty acids, as a fatty acid as the component (A), caproic acid (n-hexanoic acid), isohexanoic acid,
n-heptanoic acid, isoheptanoic acid, caprylic acid (n-octanoic acid), isooctanoic acid, 2-ethylhexanoic acid,
Pelargonic acid (n-nonanoic acid), isononanoic acid, capric acid (n-decanoic acid), isodecanic acid, lauric acid (n
-Dodecanoic acid), myristic acid (n-tetradecanoic acid), palmitic acid (n-hexadecanoic acid), stearic acid (n-octadecanoic acid), oleic acid (n-octadecenoic acid), straight-chain fatty acids derived from various fats and oils C6-C18 fatty acids, such as (coconut oil fatty acids, etc.), or mixtures thereof are preferred.

The 1-10-hydric alcohol referred to as the component (A) has 1-18 carbon atoms, preferably 1 carbon atoms.
~ 12 aliphatic monohydric alcohol and 2-30 carbon atoms,
Preferably, it means a polyhydric alcohol having 2 to 10 carbon atoms and having 2 to 10 carbon atoms. The aliphatic monohydric alcohol may be a straight chain alcohol or a branched alcohol, and may be a saturated alcohol or an unsaturated alcohol. Specific examples of the aliphatic monohydric alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec.
-Butyl alcohol, tert-butyl alcohol, straight-chain or branched pentyl alcohol, straight-chain or branched hexyl alcohol, straight-chain or branched heptyl alcohol,
Straight-chain or branched octyl alcohol, straight-chain or branched nonyl alcohol, straight-chain or branched decyl alcohol, straight-chain or branched undecyl alcohol, straight-chain or branched dodecyl alcohol, straight-chain or branched tridecyl alcohol Saturated aliphatic alcohols such as, straight-chain or branched tetradecyl alcohol, straight-chain or branched pentadecyl alcohol, straight-chain or branched hexadecyl alcohol, straight-chain or branched heptadecyl alcohol, straight-chain or branched octadecyl alcohol A linear or branched butenyl alcohol (including all isomers), a linear or branched pentenyl alcohol (including all isomers), a linear or branched hexenyl alcohol (including all isomers), Straight chain or branched heptenyl alcohol (including all isomers), straight chain or Branched octenyl alcohol (includes all isomers), straight chain or branched nonenyl alcohol (includes all isomers), straight chain or branched decenyl alcohol (includes all isomers), straight chain Or branched undecenyl alcohol (including all isomers), straight chain or branched dodecenyl alcohol (including all isomers), straight chain or branched tridecenyl alcohol (all isomers) Including), straight-chain or branched tetradecenyl alcohol (including all isomers), straight-chain or branched pentadecenyl alcohol (including all isomers), straight-chain or branched hexadecenyl Alcohols (including all isomers), linear or branched heptadecenyl alcohols (including all isomers), linear or branched octadecenyl alcohols (including all isomers) It can be mentioned, and mixtures thereof; unsaturated aliphatic alcohols such as. Among these aliphatic monohydric alcohols, one or two or more monohydric alcohols of saturated aliphatic monohydric alcohols having 1 to 12 carbon atoms are more preferable from the viewpoint of obtaining a composition having excellent drawability. . And if the specific example of a C2-30 dihydric-alcohol is shown, ethylene glycol, propylene glycol, trimethylene glycol (1,3-propanediol), butylene glycol (1,2-butanediol), 1 , 1-dimethylethylene glycol (2-methyl-1,3-propanediol), 1,2-dimethylethylene glycol (2,3-butanediol), 1-methyltrimethylene glycol (1,3-butanediol), 2-Methyltrimethylene glycol (2-methyl-1,3-propanediol), tetramethylene glycol (1,4-butanediol), pentylene glycol (1,2-pentanediol), 2,2-dimethyltrimethylene Glycol (2,2-dimethyl-1,3-propanediol),
1,5-pentanediol, neopentyl glycol,
Hexylene glycol (1,2-hexanediol),
1,6-hexanediol, 2-ethyl-2-methyl-
1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
1,8-octanediol, 1,9-nonanediol,
Glycols (dihydric alcohols) such as 1,10-decanediol, 1,11-undecanediol and 1,12-dodecanediol; trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri -(Trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (2-8 octamer of glycerin), 1,
Polyhydric alcohols such as 3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose. , Isomaltose, trehalose, sucrose, raffinose, gentianose, melezitose, and the like, partial etherified products thereof, methyl glucoside (glycoside); and mixtures thereof.
Among these polyhydric alcohols, from the viewpoint of obtaining a composition having excellent drawability, neopentyl glycol, trimethylolethane, trimethylolpropane,
Trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri-
(Pentaerythritol), a mixture thereof, and the like are more preferable. When an ester of a polyhydric alcohol and a fatty acid is used as the component (A) of the present invention, the component (A) may be a so-called complete ester (full ester) in which all the hydroxyl groups of the polyhydric alcohol are esterified. Further, it may be a so-called partial ester in which one or more hydroxyl groups of the polyhydric alcohol remain without being esterified.

As the component (A) in the present invention, caproic acid (n-hexanoic acid), isohexanoic acid, n-heptanoic acid, isoheptanoic acid, caprylic acid (from the viewpoint of obtaining a composition having more excellent lubricity) n-octanoic acid),
Isooctanoic acid, 2-ethylhexanoic acid, pelargonic acid (n-nonanoic acid), isononanoic acid, capric acid (n-decanoic acid), isodecanic acid, lauric acid (n-dodecanoic acid), myristic acid (n-tetradecanoic acid) , Palmitic acid (n-hexadecanoic acid), stearic acid (n-octadecanoic acid), oleic acid (n-octadecenoic acid), straight-chain fatty acids derived from various fats and oils (coconut fatty acid, etc.)
And one or more kinds of fatty acids having 6 to 18 carbon atoms exemplified by, for example, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylol) (Propane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol) and the like, more preferably a complete ester (full ester) or partial ester with one or more hindered polyhydric alcohols. . The lower limit of the content of the component (A) in the drawn oil composition of the present invention is
The total amount of the composition is 0.5% by mass, preferably 1.0% by mass, while the upper limit of the content of the component (A) is 50% by mass, preferably 30% by mass, based on the total amount of the composition. is there. When the content of the component (A) is less than 0.5% by mass based on the total amount of the composition, the lubricity of the composition is insufficient, and when the content of the component (A) exceeds 50% by mass based on the total amount of the composition. Is
The effect of improving the lubricity corresponding to the content cannot be obtained, and the removability of the composition by heating and evaporation is deteriorated, which is not preferable.

The component (B) in the drawn oil composition of the present invention is a phosphate compound. The phosphoric acid ester-based compound referred to here has the following general formula (1)
The phosphoric acid ester represented by and its amine salt, and the phosphorous acid ester represented by the following general formula (2) and its amine salt are included.

Embedded image In the general formula (1), R ¹ , R ² and R ^{3 each} independently represent hydrogen or a hydrocarbon group having 1 to 24 carbon atoms,
Except when R ¹ , R ² and R ³ are simultaneously hydrogen.

Embedded image In the general formula (2), R ⁴ , R ⁵ and R ⁶ individually represent hydrogen or a hydrocarbon group having 1 to 24 carbon atoms,
Except when R ⁴ , R ⁵ and R ⁶ are simultaneously hydrogen.

In addition, as a reminder, in the amine salt of a phosphoric acid ester represented by the general formula (1), any one of R ^{1 to} R ³ is a hydrocarbon group and the remaining two are hydrogen. A monoester or a diester in which any two of R ^{1 to} R ³ are hydrocarbon groups and the remaining one is hydrogen, that is, an amine salt of acid phosphate (acidic phosphate ester), and in the same manner, the amine salts of the phosphorous acid ester represented by the general formula (2), any one of R ⁴ to R ⁶ is a hydrocarbon group, monoesters or R ⁴ to R ⁶ are the remaining two are hydrogen A diester in which any two of the above are hydrocarbon groups and the other one is hydrogen,
Hydrogen phosphite (hydrogen phosphite)
Means an amine salt of.

In the general formulas (1) and (2), the hydrocarbon group is a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkyl group having 3 to 24 carbon atoms. -Like alkenyl group, cycloalkyl group or alkylcycloalkyl group having 5 to 13 carbon atoms, aryl group having 6 to 18 carbon atoms or linear or branched alkylaryl group, arylalkyl group having 7 to 19 carbon atoms Are included. And, as the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, straight-chain or branched pentyl group, straight-chain or branched hexyl group, straight-chain or branched heptyl group, straight-chain or branched octyl group, straight-chain or branched Nonyl group, straight-chain or branched decyl group, straight-chain or branched undecyl group, straight-chain or branched dodecyl group, straight-chain or branched tridecyl group, straight-chain or branched tetradecyl group, straight-chain or branched pentadecyl group , Straight-chain or branched hexadecyl group, straight-chain or branched heptadecyl group, straight-chain or branched octadecyl group, straight-chain or branched nonadecyl group, straight-chain or branched icosyl group, straight-chain or branched henicosyl group, direct A chain or branched docosyl group, a straight chain or branched tricosyl group, a straight chain or branched tetracosyl group and the like are preferable. As the alkenyl group, a propenyl group, an isopropenyl group, a linear or branched butenyl group, a butadienyl group, a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or Branched octenyl group, straight chain or branched nonenyl group, straight chain or branched decenyl group, straight chain or branched undecenyl group, straight chain or branched dodecenyl group, straight chain or branched tridecenyl group, straight chain or branched A tetradecenyl group,
Straight-chain or branched pentadecenyl group, straight-chain or branched hexadecenyl group, straight-chain or branched heptadecenyl group, straight-chain or branched octadecenyl group such as oleyl group, straight-chain or branched nonadecenyl group, straight-chain or branched icosenyl group A group, a straight-chain or branched henicosenyl group, a straight-chain or branched docosenyl group, a straight-chain or branched tricosenyl group, a straight-chain or branched tetracosenyl group and the like are preferable. The cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc., and the alkylcycloalkyl group is a methylcyclopentyl group, a dimethylcyclopentyl group (including all substituted isomers), an ethylcyclopentyl group (all substituted groups). (Including isomers),
Linear or branched propylcyclopentyl group (including all substituted isomers), ethylmethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers), diethylcyclopentyl group (all , Including the substituted isomers), ethyldimethylcyclopentyl group (including all substituted isomers), straight-chain or branched propylmethylcyclopentyl group (including all substituted isomers), straight-chain or branched propylethylcyclopentyl group (Including all substituted isomers), di-linear or branched propylcyclopentyl group (including all substituted isomers), linear or branched propylethylmethylcyclopentyl group (including all substituted isomers), Methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl Group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), linear or branched propylcyclohexyl group (including all substituted isomers), ethylmethylcyclohexyl group (all Substituted isomers), trimethylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (including all substituted isomers), ethyldimethylcyclohexyl group (including all substituted isomers), straight chain or Branched propylmethylcyclohexyl group (including all substituted isomers), linear or branched propylethylcyclohexyl group (including all substituted isomers), di-linear or branched propylcyclohexyl group (all substituted isomers) ), Straight-chain or branched propylethylmethylcyclohexyl groups (all units (Including isomers), methylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), straight chain Or a branched propylcycloheptyl group (including all substitution isomers), ethylmethylcycloheptyl group (including all substitution isomers), trimethylcycloheptyl group (including all substitution isomers),
Diethylcycloheptyl group (including all substituted isomers), ethyldimethylcycloheptyl group (including all substituted isomers), straight-chain or branched propylmethylcycloheptyl group (including all substituted isomers), direct Chain or branched propylethylcycloheptyl group (including all substituted isomers), di-linear or branched propylcycloheptyl group (including all substituted isomers), linear or branched propylethylmethylcycloheptyl group Alkylcycloalkyl groups such as groups (including all substituted isomers) are preferred. Further, the aryl group of the general formulas (1) and (2) is preferably a phenyl group, a naphthyl group and the like, and the alkylaryl group is also a tolyl group (including all substituted isomers), a xylyl group (all Substituted isomers), ethylphenyl groups (including all substituted isomers), linear or branched propylphenyl groups (including all substituted isomers), ethylmethylphenyl groups (including all substituted isomers) ), A trimethylphenyl group (including all substituted isomers), a linear or branched butylphenyl group (including all substituted isomers), a linear or branched propylmethylphenyl group (including all substituted isomers) ), A diethylphenyl group (including all substitution isomers), an ethyldimethylphenyl group (including all substitution isomers),
Tetramethylphenyl group (including all substituted isomers), straight chain or branched pentylphenyl group (including all substituted isomers), straight chain or branched hexylphenyl group (including all substituted isomers), Linear or branched heptylphenyl group (including all substituted isomers), linear or branched octylphenyl group (including all substituted isomers), linear or branched nonylphenyl group (all substituted isomers) , A straight-chain or branched decylphenyl group (including all substituted isomers), a straight-chain or branched undecylphenyl group (including all substituted isomers), a straight-chain or branched dodecylphenyl group (including (Including all substitution isomers)
Are preferred. And as the arylalkyl group, a benzyl group, a methylbenzyl group (including all substitution isomers), a dimethylbenzyl group (including all substitution isomers), a phenethyl group, a methylphenethyl group (all substitution isomers are included). Preferred), dimethylphenethyl group (including all substituted isomers), and the like. Among the above-mentioned hydrocarbon groups that R ^{1 to} R ³ or R ^{4 to} R ⁶ can take, the hydrocarbon group has a linear or branched carbon number of 4 to 18
Is more preferably an alkyl group or alkenyl group, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkylaryl group, and particularly 4 to 4 carbon atoms.
Most preferably, it is a linear or branched alkyl group having 18 carbon atoms, an oleyl group, a phenyl group, or a linear or branched alkylaryl group having 7 to 9 carbon atoms.

Preferred examples of the phosphoric acid ester represented by the general formula (1) include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate. , Triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate , Trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, etc. Sulfate (phosphoric acid triester); monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, mono Dodecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate Phosphate, Diheki Ruacid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, Acid phosphates (acidic phosphates) such as dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate;
And a mixture thereof; and the like.

Similarly, preferred specific examples of the phosphite represented by the general formula (2) will be exemplified. Tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, tributyl phosphite Octyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, tritridecyl phosphite,
Tritetradecyl phosphite, tripentadecyl phosphite, trihexadecyl phosphite, triheptadecyl phosphite, trioctadecyl phosphite,
Triphosphites such as trioleyl phosphite, triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, cresyl diphenyl phosphite, xylenyl diphenyl phosphite (phosphorous acid triester); monobutyl hydrogen Phosphite, monopentyl hydrogen phosphite, monohexyl hydrogen phosphite, monoheptyl hydrogen phosphite, monooctyl hydrogen phosphite, monononyl hydrogen phosphite, monodecyl hydrogen phosphite, monoundecyl hydrogen phosphite Phosphite, monododecyl hydrogen phosphite, monotridecyl hydrogen phosphite, monotetradecyl hydrogen phosphite, monopec Data decyl hydrogen phosphite, mono hexadecyl hydrogen phosphite,
Monoheptadecyl hydrogen phosphite, monooctadecyl hydrogen phosphite, monooleyl hydrogen phosphite, dibutyl hydrogen phosphite, dipentyl hydrogen phosphite, dihexyl hydrogen phosphite, diheptyl hydrogen phosphite, dioctyl hydrogen phosphite Phosphite, dinonyl hydrogen phosphite, didecyl hydrogen phosphite, diundecyl hydrogen phosphite, didodecyl hydrogen phosphite, ditridecyl hydrogen phosphite, ditetradecyl hydrogen phosphite,
Hydrogen phosphite (hydrogen phosphite) such as dipentadecyl hydrogen phosphite, dihexadecyl hydrogen phosphite, diheptadecyl hydrogen phosphite, dioctadecyl hydrogen phosphite, dioleyl hydrogen phosphite And a mixture thereof; and the like.

As described above, as the component (B) of the present invention, acid phosphate (acid phosphate) is used.
An amine salt of hydrogen phosphite (hydrogen phosphite) can also be used. This amine salt contains
A part or all of the acidic hydrogen remaining in the acid phosphate or hydrogen phosphite has 1 to 2 carbon atoms.
4, preferably a salt neutralized with an amine compound containing an alkyl group, an alkenyl group or an alkanol group having 1 to 18 carbon atoms in the molecule. Specific preferred examples of the amine compound include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine,
Monoheptylamine, monooctylamine, monononylamine, monodecylamine, monoundecylamine, monododecylamine, monotridecylamine, monotetradecylamine, monopentadecylamine, monohexadecylamine, monoheptadecylamine, Monooctadecylamine, monononadecylamine, monoicosylamine, monohenicosylamine, monohenicosylamine, monotricosylamine, monotetracosylamine,
Dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diun Decylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine,
Alkylamines such as dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, diicosylamine, dihenicosylamine, dihenicosylamine, ditricosylamine, ditetracosylamine May be chain-like or branched);
Monobutenylamine, monopentenylamine, monohexenylamine, monoheptenylamine, monooctenylamine, monononenylamine, monodecenylamine, monoundecenylamine, monododecenylamine, monotridecenylamine, monotetra Decenylamine, monopentadecenylamine, monohexadecenylamine, monoheptadecenylamine, monooctadecenylamine, monononadecenylamine, monoicosenylamine, monohenicosenylamine, monohenicosenylamine, Monotricocenylamine, monotetracocenylamine, dibutenylamine, dipentenylamine, dihexenylamine, diheptenylamine, dioctenylamine, dinonenylamine, didecenylamine, diundecenylamine, didodecenylamine Amine, ditridecenylamine, ditetradecenylamine, dipentadecenylamine, dihexadecenylamine, diheptadecenylamine, dioctadecenylamine, dinonadecenylamine, diicocenylamine, dihenico Alkenylamines such as cenylamine, dihenicosenylamine, ditricocenylamine, ditetracocenylamine (alkenyl groups may be linear or branched); monomethanolamine, monoethanolamine, monopropanolamine, mono Butanolamine, monopentanolamine, monohexanolamine, monoheptanolamine, monooctanolamine, monononanolamine, monodecanolamine, monoundecanolamine, monododecanolamine, monotridecanolamine, monotetrade Nolamine, Monopentadecanolamine, Monohexadecanolamine, Monoheptadecanolamine, Monooctadecanolamine, Monononadecanolamine, Monoicosanolamine, Monohenicosanolamine, Monohenicosanolamine, Mono Tricosanol amine, monotetracosanol amine, dimethanol amine, methanol ethanol amine, diethanol amine, methanol propanol amine, ethanol propanol amine, dipropanol amine, methanol butanol amine, ethanol butanol amine, propanol butanol amine, dibutanol amine, dipen Tanolamine, dihexanolamine, diheptanolamine, dioctanolamine, dinonanolamine, didecananolamine Amine, diundecanol amine, didodecanol amine, ditridecanol amine, ditetradecanol amine, dipentadecanol amine, dihexadecanol amine, diheptadecanol amine, dioctadecanol amine, dinonadeca Alkanolamines (alkanol groups may be linear or branched), such as anolamines, diicosanolamines, dihenicosanolamines, dihenicosanolamines, ditricosanolamines, ditetracosanolamines; and A mixture of these;
And the like, but among these, the number of carbon atoms is 1-2.
Alkylamines containing 4, preferably 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms in the molecule are desirable.

When an amine salt is used as the component (B) of the present invention, the amine salt is acid phosphate (acidic phosphate ester) or hydrogen phosphite (hydrogen phosphite), and methylamine, ethylamine, propyl. Amine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, triethylamine Particularly preferred are salts with amines such as butylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine. The component (B) of the present invention is selected from the group consisting of the above-mentioned phosphoric acid ester, phosphorous acid ester and amine salt of acid phosphate (acidic phosphoric acid ester) and hydrogen phosphite (hydrogen phosphorous acid ester). It is also possible to use mixtures of two or more compounds in any proportion.

The lower limit of the content of the component (B) in the drawn oil composition of the present invention is 0.
1% by weight, preferably 0.2% by weight, while
The upper limit of the content of the component (B) is 10 based on the total amount of the composition.
It is mass%, preferably 8.0 mass%. When the content of the component (B) is less than 10% by mass based on the total amount of the composition, the lubricity of the composition is insufficient, and when the content of the component (B) exceeds 10% by mass based on the total amount of the composition, The effect of improving the lubricity corresponding to the content cannot be obtained, and the removability of the composition by heating and evaporation is deteriorated, which is not preferable.

The basic composition of the drawn oil composition according to the present invention is based on polyalkylene glycol and / or its alkyl ether having a kinematic viscosity of 5 to 3000 mm ² / s at 40 ° C. A) component and (B)
Each of the components is blended in a specific amount, and for the purpose of further enhancing various performances of the processing oil composition, a known lubricating oil additive is added to the processing oil composition, for example, an antioxidant, a detergent dispersant, an oiliness agent. , A corrosion inhibitor, an antifoaming agent and the like can be blended alone or in a combination of several kinds. As the antioxidant, any of those generally used in lubricating oils such as phenol compounds and amine compounds can be used, and specifically, for example, 2,6-di-t.
Alkylphenols such as ert-butyl-4-methylphenol, methylene-4,4-bis (2,6-di-)
tert-butyl-4-methylphenol) and other bisphenols, phenyl-α-naphthylamine and other naphthylamines, dialkyldiphenylamines, di-
It is possible to use zinc dialkyldithiophosphates such as zinc 2-ethylhexyldithiophosphate. Examples of the detergent dispersant include metal detergents such as neutral, basic or overbased alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates, alkenyl succinimide, and benzylamine. An ashless dispersant such as a polyamine or a modified product thereof with a boron compound, an organic acid or a sulfur compound can be used. As the oiliness agent, fatty acid, fatty acid amide, fatty acid metal salt,
A fatty acid amine salt, an aliphatic alcohol, an aliphatic amine or an alkylene oxide adduct thereof, an organic (sub) phosphoric acid ester, an organic (sub) phosphoric acid ester amine salt and the like can be used. As the corrosion inhibitor, for example, benzotriazole-based, thiadiazole-based, imidazole-based compounds and the like can be used. As the defoaming agent, silicones such as dimethyl silicone and fluorosilicone can be used. The content when these known additives are contained in the processing oil composition of the present invention can be arbitrarily selected, but the content thereof is based on the total amount of the drawn processing oil composition,
For antioxidants, usually 0.01-5% by mass; for detergent dispersants, usually 0.01-5% by mass; for oiliness agents, usually 0.1-10% by mass; for corrosion inhibitors, usually , 0.
001 to 0.5% by mass; usually 0.001 for antifoaming agents
It is desirable to set it in the range of 0.5 mass%.

The drawing oil composition of the present invention comprises a metal,
In particular, it exhibits excellent workability and evaporation removal property in the drawing process of copper and copper alloys. Not only that, when the pipe material of copper or copper alloy drawn using the processing oil composition of the present invention is used in a refrigeration system using a new type of refrigerant developed as an ozone layer depletion prevention measure. Even if the drawn oil composition of the present invention remains on the surface of the pipe material, it exhibits excellent performance of not causing problems such as clogging of the refrigeration system.
For reference, to add to the above-mentioned new type refrigerant, as the new refrigerant, a fluoroalkane (HFC) having 1 to 3 carbon atoms and / or a chlorofluoroalkane (HFC) can be used.
CFC) is known, and specific examples thereof include difluoromethane (HFC-32) and trifluoromethane (H
FC-23), pentafluoroethane (HFC-12
5), 1,1,2,2-tetrafluoroethane (HFC
-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a) and other HFCs; Monochlorodifluoromethane (HCFC-22), 1-chloro-1,1-
HCF such as difluoroethane (HCFC-142b), dichlorotrifluoroethane (HCFC-123), monochlorotetrafluoroethane (HCFC-124)
C, trichloromonofluoromethane (CFC-11),
CF such as dichlorodifluoromethane (CFC-12), monochlorotrifluoromethane (CFC-13) and monochloropentafluoroethane (CFC-115)
C; or a mixture of two or more of these; and the like. The mixed refrigerant is, for example, HFC-
134a / HFC-32 = 60-80 mass% / 40-2
0 wt% mixture, HFC-32 / HFC-125 = 4
Mixture of 0 to 70% by mass / 60 to 30% by mass, HFC-
125 / HFC-143a = 40-60 mass% / 60-
40 wt% mixture, HFC-134a / HFC-32
/ HFC-125 = 60% by mass / 30% by mass / 10% by mass mixture, HFC-134a / HFC-32 / HFC
-125 = 40 to 70% by mass / 15 to 35% by mass / 5
40% by weight mixture, HFC-125 / HFC-134
a / HFC-143a = 35 to 55% by mass / 1 to 15% by mass / 40 to 60% by mass, and more specifically, HFC-134a / HFC-3.
2 = 70/30 wt% mixture, HFC-32 / HFC
-125 = 60/40 wt% mixture, HFC-32 /
HFC-125 = 50/50 mass% mixture (R410
A: Genetron AZ- manufactured by Allied Signal
20), a mixture of HFC-32 / HFC-125 = 45/55 mass% (R410B; DuPont SUVA
AC9100), HFC-125 / HFC-143a =
50/50 mass% mixture (R507C; Genetron AZ-50 manufactured by Allied Signal Co.), HFC-
32 / HFC-125 / HFC-134a = 30/10
/ 60% by weight mixture, HFC-32 / HFC-125
/ HFC-134a = 23/25/52 mass% mixture (R407C; DuPont SUVA AC900)
0), HFC-125 / HFC-134a / HFC-1
43a = 44/4/52 mass% mixture (R404A;
Examples include SUVA HP-62) manufactured by DuPont.

[0020]

EXAMPLES The contents of the present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Examples 1 to 12 and Comparative Examples 1 to 6 Extraction processing oil compositions according to the present invention having the compositions shown in Table 1 and processing oil compositions having the compositions shown in Table 2 for comparison were prepared, respectively. The components used to prepare each composition are as follows. Base oil A: polyoxyethylene oxypropylene glycol mono n-butyl ether (kinematic viscosity 420 mm ² / s (@ 40
℃), weight average molecular weight 4300, oxyethylene / oxypropylene (molar ratio) = 1: 1) B: polyoxypropylene glycol mono n-butyl ether (kinematic viscosity 8.2 mm ² / s (@ 40 ° C.), weight average molecular weight 340) C: polyoxyethylene oxypropylene glycol monomethyl ether (kinematic viscosity 960 mm ² / s (@ 40 ° C.),
Weight average molecular weight 5000, oxyethylene / oxypropylene (molar ratio) = 1: 1) D: Polyoxyethylene oxypropylene glycol monomethyl ether (kinematic viscosity 1980 mm ² / s (@ 40 ° C))
, Weight average molecular weight 5200, oxyethylene / oxypropylene (molar ratio) = 1: 1) ( A) Component E: methyl oleate F: neopentyl glycol isononanoic acid diester G: pentaerythritol isononanoic acid tetraester ( B) component H : Tricresyl phosphate I: dilauryl hydrogen phosphite J: dihexyl amine salt of dilauryl hydrogen phosphite Other base oil K: solvent refined mineral oil (kinematic viscosity 200 mm ² / s (@ 40 ° C)) L: ethylene Glycol mono-n-butyl ether Other additives M: Sulfurized fats and oils (sulfur content 11% by mass) N: Chlorinated paraffin (chlorine content 40% by mass) Processing oil compositions of Examples shown in Table 1 and Table 2 and The following performance evaluation tests were performed for each of the processed oil compositions of Comparative Examples. The results are shown in Tables 1 and 2. [Evaporation test] 0.2 mg of sample oil was sampled in an aluminum petri dish having a diameter of 75 mm and a depth of 14 mm, heated to 450 ° C in a nitrogen atmosphere, and the dried state of the sample was observed. In the table, ◯ means "no residue" and x means "colorless residue". [Shield tube test] Refrigerating machine oil (using 2-ethylhexanoic acid tetraester of pentaerythritol as a base oil) was added with 1% by mass of sample oil as a test oil, and 13 ml of this test oil and a refrigerant ( HFC-
134a) 2 ml and catalyst (Fe, Cu, Al)
Was sealed in a glass tube and kept at 175 ° C. for 168 hours, and then the state change of the liquid layer was observed. In the table, ◯ means “no change”, and x means “white turbidity or precipitate”. [Lubricity test] Thickness 0.5 mm, width 30 mm, length 35
After applying the sample oil to both sides of a 0 mm copper plate, the copper plate was sandwiched with a pressing load of 200 kgf at a speed of 100 mm / min with a round bead die (a die having a protrusion) and a die having a corresponding recess. The pulling load (kgf) at the time of pulling out was determined. The lubricity test was carried out only when the above-mentioned evaporation test and shield tube test were evaluated as ◯.

[Table 1]

[Table 2] As is clear from the test results shown in Table 1 and Table 2, the drawn oil compositions of Examples 1 to 12 according to the present invention are excellent in drawability and removability by heating and evaporation, and are frozen using a new refrigerant. You can see that it does not cause any problems even if it is mixed in the system. On the other hand, the processing oils of Comparative Examples 1 and 2 composed only of the base oil of the present invention have extremely poor lubricity. In addition, the processed oil compositions of Comparative Examples 3 to 4 using a base oil other than those specified by the present invention, and the processed oil compositions of Comparative Examples 5 to 6 using other additives instead of the component (B). Not only are all inferior in removability by heating and evaporation, but they may cause problems when mixed in a refrigeration system using a new type of refrigerant.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C10N 30:00 40:20

Claims (1)

[Claims] 1. A kinematic viscosity at 40 ° C. of 5 to 3000 mm ² / s.
Is used as a base oil, and the total amount of the composition is 0.5 to 50 mass% of the following component (A) and 0.1 to 10 weight% of the following component (B). A drawn processing oil composition containing mass%. (A) an ester of a fatty acid having 4 to 24 carbon atoms and a monovalent to 10-valent alcohol, (B) a phosphoric acid ester-based compound,