JPH09316478A - Drawing processing oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a drawing processing oil composition excellent in processability of a drawing processing and capable of being easily removed from a formed material after processing by a heating and evaporating method by blending a specific base oil with a specified fatty acid ester and a phosphoric acid ester-based compound. SOLUTION: This drawing processing oil composition is obtained by blending (A) a base oil of a (hydrogenated) polyolefin having 5-1400mm<2> /s kinematic viscosity at 40 deg.C with, based on the amount of the total composition, (B) 0.5-50wt.% ester of a 4-24C fatty acid with a mono- to deca-functional alcohol [e.g. a 1-18C, especially 1-12C (un)saturated (branched) aliphatic alcohol or a 2-30C, especially 2-24C di- to deca-functional alcohol] and (C) 0.1-10wt.% phosphoric acid ester-based compound such as a compound of formula I (R<1> to R<3> are each H or a 1-24C alkyl group with the proviso that R<1> to R<3> are not simultaneously H) and formula II (R<4> to R<6> are same as R<1> to R<3> ).

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, drawing oil using mineral oil as a base oil is usually used and adheres to the surface of the molded product after drawing. As means for removing the drawn processing oil, degreasing removal by washing with a chlorine-based solvent or fluorine-based solvent and evaporation removal by heating the molded body have been adopted.

[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 removal by a solvent other than a halogenated hydrocarbon solvent or evaporative removal by heating is inferior in removal efficiency as compared with degreasing removal using a halogenated hydrocarbon solvent. There was an inconvenience that it remained on the surface. On the other hand, CFC (chlorofluorocarbon) and HCFC that have been conventionally used as refrigerants for refrigeration systems.
(Hydrochlorofluorocarbon) is also regulated as a causative substance that destroys the ozone layer, and HFC (hydrofluorocarbon) is being used as a refrigerant in place of these substances. However, when the pipe material still having the drawing processing oil remaining on the surface even after the removal treatment, especially the pipe material of copper or copper alloy, is used in the refrigeration system using the new type refrigerant as described above, 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 various problems as described above, and as a result, have been drawn out by adding a specific amount of a specific ester and phosphorus-containing compound to a polyolefin and / or its hydride. It has been found that oil solves the above problems. The object of the present invention is not only excellent in drawing workability, but can be easily removed from the molded body by the heating evaporation method after processing, and even if the molded body is not completely removed in the refrigeration system. The object of the present invention is to provide a drawing oil composition which does not cause a situation in which it is blocked.

[0004]

The drawing oil composition according to the present invention has a kinematic viscosity at 40 ° C. of 5 to 1400 mm ² / s.
Is used as a base oil, and the following component (A) is added in an amount of 0.5 based on the total amount of the composition.
˜50% by mass, and the component (B) is contained by 0.1 to 10% by mass. (A) Ester of fatty acid having 4 to 24 carbon atoms and 1 to 10-valent alcohol (B) Phosphate compound

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The base oil in the drawn oil composition of the present invention is a polyolefin and / or its hydride. The lower limit of the kinematic viscosity of this base oil at 40 ° C 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 1
It is 400 mm ² / s, preferably 1000 mm ² / s, more preferably 600 mm ² / s. The kinematic viscosity of the base oil at 40 ° C is
When it is less than 5 mm ² / s, the lubricity of the composition is insufficient, and conversely,
When it exceeds 1400 mm ² / s, workability in the drawing process is deteriorated, which is not preferable. In the present invention, the polyolefin refers to a homopolymerized or copolymerized olefin having 2 to 16 carbon atoms, preferably 2 to 12 carbon atoms. When this polyolefin is a copolymer of olefins having different structures, there are no particular restrictions on the monomer ratio or the monomer arrangement in the copolymer, and random copolymers, alternating copolymers and block copolymers can be used. Any of these can be used. The olefin monomer forming the polyolefin may be an α-olefin, an internal olefin, a linear olefin, or a branched olefin. Specific examples of olefins that can be used in producing the polyolefin of the present invention include ethylene, propylene, 1-butene, 2-butene, isobutene, linear or branched pentene (α-olefin, Internal olefins), linear or branched hexenes (α-olefins, including internal olefins), linear or branched heptenes (α
-Olefin, including internal olefin), linear or branched octene (including α-olefin and internal olefin), linear or branched nonene (including α-olefin and internal olefin), direct Chain or branched decene (including α-olefins and internal olefins), linear or branched undecene (including α-olefins and internal olefins), linear or branched dodecene (α
-Olefin, including internal olefin), linear or branched tridecene (including α-olefin and internal olefin), linear or branched tetradecene (including α-olefin and internal olefin), direct Examples thereof include linear or branched pentadecene (including α-olefins and internal olefins), linear or branched hexadecene (including α-olefins and internal olefins), and mixtures thereof. Among them, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-
Octene, 1-decene, 1-dodecene and mixtures thereof are preferably used. The polyolefin of the present invention can be produced by any method. For example, it can be produced by a thermal reaction without a catalyst, and an organic peroxide catalyst such as benzoyl peroxide; aluminum chloride, aluminum chloride-polyhydric alcohol system, aluminum chloride-titanium tetrachloride system, aluminum chloride-alkyltin. Friedel-Crafts type catalysts such as halide type and boron fluoride; Ziegler type catalysts such as organic aluminum chloride-titanium tetrachloride type, organic aluminum-titanium tetrachloride type; metallocenes such as aluminoxane-zirconocene type, ionic compound-zirconocene type Type catalyst: It can be produced by homopolymerizing or copolymerizing the above olefins using a known catalyst system such as a Lewis acid complex type catalyst such as aluminum chloride-base system or boron fluoride-base system. As the base oil component of the present invention, the above-mentioned polyolefin can be used. However, since the polymer usually has a double bond, the double bond in the polymer is taken into consideration in view of its thermal / oxidative stability. So-called hydrides of polyolefins with hydrogenated bonds are preferably used as the base oil. In order to obtain a hydride of a polyolefin, an appropriate method can be adopted. For example, hydrogenating a polyolefin with hydrogen in the presence of a known hydrogenation catalyst to saturate the double bond present in the polyolefin. Can be obtained by Further, by selecting the catalyst to be used, the olefin polymerization and the hydrogenation of the double bond existing in the polymer can be completed in one step without going through the two steps of olefin polymerization and polymer hydrogenation. Is also possible. Among the polyolefins or hydrides thereof usable in the present invention, an ethylene-propylene copolymer,
Polybutene (copolymer obtained by polymerization of butane-butene (mixture of 1-butene, 2-butene and isobutene) fraction produced as a by-product during naphtha pyrolysis), 1-octene oligomer, 1-decene oligomer, 1 -Dodecene oligomers and hydrides thereof, and mixtures thereof, etc. are preferable as the base oil of the present invention in that they have excellent heat / oxidation stability, viscosity-temperature characteristics, and low-temperature fluidity, and particularly ethylene. -Propylene copolymer hydride, polybutene hydride, 1-octene oligomer hydride,
1-decene oligomer hydride, 1-dodecene oligomer hydride and mixtures thereof are preferred. Incidentally, ethylene-propylene copolymers currently commercially available as base oils for lubricating oils, synthetic oils such as polybutene and poly-α-olefins are usually those whose double bonds have already been hydrogenated, These commercially available products can also be used as the base oil of the present invention as long as they satisfy the above-mentioned requirements for kinematic viscosity. As the base oil in the composition of the present invention, one or more compounds selected from the group consisting of the above-mentioned polyolefins and hydrides thereof can be used, but a mixture of two or more compounds is used. If you do
The mixing ratio of the individual compounds in the mixture can be arbitrarily selected. The individual compounds constituting the mixture do not need to have a kinematic viscosity at 40 ° C. of 5 to 1400 mm ² / s, and a kinematic viscosity at 40 ° C. of the mixture of 5 to 1400 mm 2.
There is no problem if it is within the range of mm 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,
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, etc. 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 (coconut oil fatty acid, etc.) derived from various fats and oils, etc. , C6-18 fatty acids, or mixtures thereof are preferred. Moreover, as the 1- to 10-valent alcohol referred to as the component (A), the carbon number is 1 to 1
8, preferably an aliphatic monohydric alcohol having 1 to 12 carbon atoms and 2 having 2 to 30 carbon atoms, preferably 2 to 24 carbon atoms
It refers to a 10-valent polyhydric alcohol. 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, ter.
t-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, straight chain or branched tetradecyl alcohol, straight chain or branched pentadecyl alcohol, straight chain Or saturated aliphatic alcohols such as branched hexadecyl alcohol, straight chain or branched heptadecyl alcohol, straight chain or branched octadecyl alcohol; straight chain or branched butenyl alcohol (including all isomers), straight chain or Branched pentenyl alcohol (including all isomers), straight chain Is branched hexenyl alcohol (includes all isomers), straight chain or branched heptenyl alcohol (includes all isomers), straight chain or branched octenyl alcohol (includes all isomers), straight chain Or branched nonenyl alcohol (including all isomers), straight chain or branched decenyl alcohol (including all isomers), straight chain or branched undecenyl alcohol (including all isomers) , Linear or branched dodecenyl alcohol (including all isomers), linear or branched tridecenyl alcohol (including all isomers), linear or branched tetradecenyl alcohol (all ), Linear or branched pentadecenyl alcohol (including all isomers), linear or branched hexadecenyl alcohol (including all isomers), Unsaturated fatty alcohols such as chain or branched heptadecenyl alcohol (including all isomers), straight chain or branched octadecenyl alcohol (including all isomers); and mixtures thereof. Can be mentioned. 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 2 to 10 having 2 to 30 carbon atoms
Specific examples of the polyhydric alcohol include 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, Glycols (dihydric alcohols) such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; trimethylolethane, trimethylolpropane , Trimethylolbutane, di- (trimethylolpropane), tri- (trimethylol) Propane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (2-8 octamer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensation Substances, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol; xylose,
Arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose,
Cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose,
Examples thereof include sugars such as melezitose, 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),
And mixtures thereof 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, 1 of polyhydric alcohol
It may be a so-called partial ester in which one or more hydroxyl groups 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 point that a composition having more excellent lubricity can be obtained. 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 precaution, an amine salt of a phosphoric acid ester represented by the general formula (1) is a monoamine in which any one of R ^{1 to} R ³ is a hydrocarbon group and the remaining two are hydrogen. An ester or a diester in which any two of R ^{1 to} R ³ are hydrocarbon groups and the other one is hydrogen, that is, an amine salt of acid phosphate (acidic phosphoric acid ester), and in the same manner as the general formula The amine salt of a phosphite represented by (2) is a monoester in which any one of R ^{4 to} R ⁶ is a hydrocarbon group and the remaining two are hydrogen, or any one of R ^{4 to} R ⁵ . It means a diester in which two are hydrocarbon groups and the other one is hydrogen, that is, an amine salt of hydrogen phosphite (hydrogen phosphite). In the general formulas (1) and (2), the hydrocarbon group is a straight-chain or branched alkyl group having 1 to 24 carbon atoms, or a straight-chain or branched alkenyl group having 3 to 24 carbon atoms. , A cycloalkyl group having 5 to 13 carbon atoms or an alkylcycloalkyl group, an aryl group having 6 to 18 carbon atoms, a linear or branched alkylaryl group, an arylalkyl group having 7 to 19 carbon atoms, and the like. . And, as the alkyl group, a methyl group, an 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 a branched octyl group, a straight chain or branched nonyl group, a straight chain or branched decyl group, a straight chain or branched undecyl group, a straight chain or branched dodecyl group, a straight chain or branched tridecyl group, a straight chain or branched chain 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 A group, a straight chain or branched henicosyl group, a straight 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 Tetradecenyl group, linear or branched pentadecenyl group, linear or branched hexadecenyl group, linear or branched heptadecenyl group, linear or branched octadecenyl group such as oleyl group, linear or branched nonadecenyl group, linear or Branched icosenyl group, linear or branched henicosenyl group, linear or branched docosenyl group, linear or branched tricoseni Group, straight or branched tetracosenyl group. 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) , A diethylcyclopentyl group (including all substituted isomers), an ethyldimethylcyclopentyl group (including all substituted isomers), a linear or branched propylmethylcyclopentyl group (including all substituted isomers), a straight chain or Branched propyl ethyl cyclopen Group (including all substituted isomers), di-linear or branched propylcyclopentyl group (including all substituted isomers), linear or branched propylethylmethylcyclopentyl group (including all substituted isomers) ), A methylcyclohexyl group (including all substituted isomers), a dimethylcyclohexyl group (including all substituted isomers), an ethylcyclohexyl group (including all substituted isomers), a linear or branched propylcyclohexyl group ( (Including all substituted isomers), ethylmethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (including all substituted isomers), ethyl Dimethylcyclohexyl group (including all substituted isomers), linear or branched propyl Le cyclohexyl group (including all substituted isomers), linear or branched propylethylcyclohexyl group (including all substituted isomers), di-linear or branched propylcyclohexyl group (including all substituted isomers) ), A straight-chain or branched propylethylmethylcyclohexyl group (including all substituted isomers), a methylcycloheptyl group (including all substituted isomers), a dimethylcycloheptyl group (including all substituted isomers), Ethylcycloheptyl group (including all substituted isomers), linear or branched propylcycloheptyl group (including all substituted isomers), ethylmethylcycloheptyl group (including all substituted isomers), trimethylcyclo Heptyl group (including all substituted isomers), diethylcycloheptyl group (including all substituted isomers) , Ethyldimethylcycloheptyl group (including all substituted isomers), straight chain or branched propylmethylcycloheptyl group (including all substituted isomers), straight chain or branched propylethylcycloheptyl group (all substitutions) Alkyl, including isomers), di-linear or branched propylcycloheptyl groups (including all substituted isomers), linear or branched propylethylmethylcycloheptyl groups (including all substituted isomers) Cycloalkyl groups 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) ), Diethylphenyl group (including all substitution isomers), ethyldimethylphenyl group (including all substitution isomers), tetramethylphenyl group ( All substituted isomers), straight-chain or branched pentylphenyl groups (including all substituted isomers), straight-chain or branched hexylphenyl groups (including all substituted isomers), straight-chain or branched A branched heptylphenyl group (including all substituted isomers), a straight chain or branched octylphenyl group (including all substituted isomers), a straight chain or branched nonylphenyl group (including all substituted isomers), Straight-chain or branched decylphenyl group (including all substitution isomers), straight-chain or branched undecylphenyl group (including all substitution isomers), straight-chain or branched dodecylphenyl group (all substitution isomers) (Including the body) and the like are preferable. And as the arylalkyl group, a benzyl group, a methylbenzyl group (including all substituted isomers),
A dimethylbenzyl group (including all substitution isomers), a phenethyl group, a methylphenethyl group (including all substitution isomers), a dimethylphenethyl group (including all substitution isomers) and the like are preferable. R ^{1 to} R ³ or R ^{4 to} R ⁶
Among the above-mentioned hydrocarbon groups that can be taken by, the hydrocarbon group is a linear or branched alkyl group or alkenyl group having 4 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a linear or branched group. Is more preferably a linear alkylaryl group, and particularly, a linear or branched alkyl group having 4 to 18 carbon atoms, an oleyl group, a phenyl group, or a linear or branched chain having 7 to 9 carbon atoms. Most preferably, it is a linear alkylaryl group.

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 Luacid 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, Examples thereof include acid phosphates (acidic phosphates) such as dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate; and mixtures thereof.

Similarly, preferred specific examples of the phosphite represented by the general formula (2) are exemplified by tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite and trioctyl phosphite. Fight, 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 mentioned above, as the component (B) of the present invention, acid phosphate (acidic phosphate ester) 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 10 carbon atoms.
A salt neutralized with an amine compound containing an alkyl group, an alkenyl group or an alkanol group having 24, preferably 1 to 18 carbon atoms in the molecule is included. 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 Examples thereof include a mixture thereof, and among these, an alkylamine having an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms in the molecule is more 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 ester), methylamine, ethylamine,
Propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine,
Particularly preferred are salts with amines such as triethylamine, tripropylamine, tributylamine, 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 the two or more compounds mentioned 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 mass based on the total amount of the composition, preferably 0.2.
The upper limit of the content of the component (B) is
10% by mass, preferably 8.0% by mass, based on the total amount of the composition
It is. The content of the component (B) is 0.1 based on the total amount of the composition.
When it is less than 10% by mass, 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 lubricity corresponding to the content cannot be obtained. ,
Further, since the removability of the composition by heating and evaporation deteriorates,
Each is not preferred.

The basic composition of the drawn oil composition according to the present invention is based on a polyolefin and / or a hydride thereof having a kinematic viscosity of 5 to 1400 mm ² / s at 40 ° C. as a base oil. Component) and component (B) are each mixed in a specific amount. For the purpose of further enhancing various performances of this processing oil composition, a known lubricating oil additive, 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, amine compounds, and organic zinc compounds can be used, and specifically, for example, 2,6- J-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, for example, fatty acid, fatty acid amide, fatty acid metal salt, fatty acid amine salt, fatty alcohol, fatty amine or alkylene oxide adduct thereof 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. When these known additives are contained in the processing oil composition of the present invention, the content can be arbitrarily selected,
Based on the total amount of the drawn oil composition, the content of the antioxidant is usually 0.01 to 5% by mass; the detergent dispersant is usually 0.01 to 5% by mass; the oiliness agent is usually
0.1 to 10% by mass; with a corrosion inhibitor, usually 0.00
1 to 0.5% by mass; with antifoaming agents, usually 0.001 to
0.5% by 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, there are fluoroalkanes (HFC) and / or chlorofluoroalkanes (HC) having 1 to 3 carbon atoms.
FC) is known, and specific examples thereof include difluoromethane (HFC-32) and trifluoromethane (HF).
C-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; Or these two
Examples include a mixture of two or more species. And as said mixed refrigerant, for example, HFC-134a / HFC-32 =
60-80 mass% / 40-20 mass% mixture, HFC
-32 / HFC-125 = 40-70 mass% / 60-3
0% by weight mixture, HFC-125 / HFC-143a
= 40-60 mass% / 60-40 mass% mixture, HF
C-134a / HFC-32 / HFC-125 = 60% by mass / 30% by mass / 10% by mass mixture, HFC-13
4a / HFC-32 / HFC-125 = 40 to 70 mass% / 15 to 35 mass% / 5 to 40 mass% mixture, HF
C-125 / HFC-134a / HFC-143a = 3
A mixture of 5 to 55% by mass / 1 to 15% by mass / 40 to 60% by mass can be mentioned, and more specifically, H
FC-134a / HFC-32 = 70/30 mass% mixture, HFC-32 / HFC-125 = 60/40 mass% mixture, HFC-32 / HFC-125 = 50/5
0 mass% of mixture (R410A; Genetron AZ-20 manufactured by Allied Signal Co., Ltd.), HFC-32 / H
FC-125 = 45/55 mass% mixture (R410
B: DuPont SUVA AC9100), HFC-
125 / HFC-143a = 50/50 mass% mixture (R507C; Allied Signal, Genetro)
n AZ-50), HFC-32 / HFC-125 / H
FC-134a = 30/10/60 mass% mixture, H
FC-32 / HFC-125 / HFC-134a = 23
/ 25/52 mass% mixture (R407C; DuPont SUVA AC9000), HFC-125 / HF
C-134a / HFC-143a = 44/4/52 mass% mixture (R404A; DuPont SUVA H
P-62) and the like.

[0014]

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 11 and Comparative Examples 1 to 5 Extracted processing oil compositions according to the present invention having the compositions shown in Table 1 and processing oil compositions for comparison having the compositions shown in Table 2 were prepared, respectively. The components used for the preparation of each composition are as follows. Base oil A: 1-decene oligomer hydride (kinematic viscosity 420 mm ²
/ s (@ 40 ° C), weight average molecular weight 1800) B: 1-decene oligomer hydride (kinematic viscosity 5.2 mm ²
/ s (@ 40 ° C), weight average molecular weight 280) C: 1-decene oligomer hydride (kinematic viscosity 1350 mm
² / s (@ 40 ° C.), weight average molecular weight 2900) (A) Component D: Methyl oleate E: Neopentyl glycol isononanoic acid diester F: Pentaerythritol isononanoic acid tetraester (B) Component G: Tricresyl phosphate H : Dilauryl hydrogen phosphite I: Dihexylamine salt of dilauryl hydrogen phosphite Other base oil J: Solvent refined mineral oil (kinematic viscosity 200 mm ² / s (@ 40 ° C)) Other additive K: Sulfurized oil and fat ( Sulfur content 11% by mass) L: Chlorinated paraffin (chlorine content 40% by mass) For the processed oil compositions of Examples shown in Table 1 and the processed oil compositions of Comparative Examples shown in Table 2, the following performance evaluations were carried out. The test was conducted. 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, press the copper plate with a round bead die (a die having a convex) and a die having a corresponding concave to press a load of 300 kg.
With f, scissors were used, and the pulling load (kgf) for pulling at a speed of 200 mm / min was determined. The lubricity test is
The evaluations of the above evaporation test and shield tube test were carried out only when the evaluation was ○.

[Table 1]

[Table 2] As is clear from the test results shown in Table 1 and Table 2, the drawn processing oil compositions of Examples 1 to 11 according to the present invention,
It can be seen that it has excellent drawing workability and removability by heating and evaporation, and that it does not cause any problem even when mixed in a refrigeration system using a new refrigerant. 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. Further, the processing oil composition of Comparative Example 3 using a base oil other than those specified by the present invention, or other additives in place of the component (B) is used in Comparative Example 4
Each of the processed oil compositions of Nos. 6 to 6 is inferior in removability by heating and evaporation, and may cause a problem when mixed in a refrigeration system using a new type of refrigerant.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C10M 137: 04) C10N 40:24

Claims (1)

[Claims] 1. The kinematic viscosity at 40 ° C. is 5 to 1400 mm ² / s.
Of the polyolefin and / or its hydride as a base oil, and 0.5% of the following component (A) based on the total amount of the composition.
˜50% by mass, 0.1 to 10% by mass of the following component (B)
A drawn processing oil composition containing the same. (A) Ester of fatty acid having 4 to 24 carbon atoms and 1 to 10-valent alcohol (B) Phosphate compound