JP4993984B2 - Oil composition for warm pressing and method for warm pressing - Google Patents

Description

  The present invention relates to an oil composition for warm pressing and a warm pressing method, and more particularly, an oil composition used in warm pressing of various metal materials, particularly non-ferrous metals such as aluminum and magnesium, and The present invention relates to a warm press working method using an oil composition.

  In the field of plastic working, so-called warm pressing is known in which press forming is performed on a material heated to a predetermined temperature (see, for example, Patent Document 1 below). Warm pressing has an advantage that it is excellent in formability compared to cold pressing when the metal material is an aluminum alloy or the like.

As the oil for warm press processing, a water-insoluble or water-soluble metal processing oil mainly containing a solid lubricant is used (for example, see Patent Document 1 below).
JP 2003-103311 A JP-A-2005-290187

  However, in the case of the conventional metalworking fluid, since it contains a solid lubricant, there is a problem that it is difficult to clean and degrease.

  Mineral oils, synthetic esters, polyalkylene glycols and the like are known as base oils for water-insoluble metalworking fluids used in warm presses such as aluminum alloys, but all base oils do not necessarily have sufficient performance. I can't say that. That is, when mineral oil is used, thermal stability and processability become insufficient. Synthetic esters are excellent in processability (lubricity), but there is room for improvement in terms of adhesion to a mold (annealability) and degreasing properties of the product after processing. Polyalkylene glycol is inferior in lubricity compared to mineral oil or synthetic ester.

  The present invention has been made in view of the above-described problems of the prior art, and is a lubricant composition for warm press working capable of satisfying all of workability, annealing and degreasing properties at a high level in a balanced manner, It is another object of the present invention to provide a warm press working method using the lubricating oil composition.

  As a result of intensive studies to achieve the above object, the present inventors have a specific structure and a specific kinematic viscosity, a polyalkylene glycol and / or a polyalkylene glycol mono- or dialkyl ether, and a specific kinematic viscosity. The present inventors have found that the above-mentioned problems can be solved by a warm press working oil composition containing both a polyhydric alcohol ester and / or a complex ester, and have completed the present invention.

That is, the warm press working oil composition of the present invention is composed of one or more selected from the group consisting of compounds represented by the following general formula (1), and has a kinematic viscosity at 40 ° C. It is composed of 20 to 95% by mass of the first component of 20 to 500 mm ² / s, one or more selected from the group consisting of a polyhydric alcohol ester and a complex ester, and a kinematic viscosity at 40 ° C. And 80 to 5% by mass of a second component that is 10 to 1000 mm ² / s.
R ¹ —O— (R ² —O) _n —R ³ (1)
[In formula (1), R ¹ and R ³ may be the same or different, each represents a hydrogen atom or an alkyl group, R ² represents an alkylene group, and n is a compound represented by the general formula (1) An integer having a weight average molecular weight of 300 to 2000 is shown. ]

  The present invention also provides a warm pressing method characterized by press-molding a workpiece heated to 100 to 350 ° C. using the oil composition for warm pressing according to the present invention.

  According to the oil composition for warm pressing and the warm pressing method of the present invention, it is possible to satisfy all of workability, annealing, and degreasing properties at a high level in a warm balance.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The 1st component concerning this invention consists of 1 type, or 2 or more types chosen from the group which consists of a compound substantially represented by following General formula (1). Here, when both R ¹ and R ³ in the general formula (1) are hydrogen atoms, the compound represented by the general formula (1) is a polyalkylene glycol. When one of R ¹ or R ^{3 in} the general formula (1) is a hydrogen atom, the compound represented by the general formula (1) is a monoalkylated product of polyalkylene glycol. When both R ¹ and R ^{3 in} the general formula (1) are alkyl groups, the compound represented by the general formula (1) is a dietherified product of polyalkylene glycol.
R ¹ —O— (R ² —O) _n —R ³ (1)
[In formula (1), R ¹ and R ³ may be the same or different, each represents a hydrogen atom or an alkyl group, R ² represents an alkylene group, and n is a compound represented by the general formula (1) An integer having a weight average molecular weight of 300 to 2000 is shown. ]

When one or both of R ^{1 and} R ^{3 in} the general formula (1) is an alkyl group, the carbon number of the alkyl group can be arbitrarily selected, but the carbon number of the alkyl group is 1-18. Is preferable, and it is more preferable that it is 1-10. When the carbon number of the alkyl group exceeds 18, there is a possibility that a residue remains after annealing. The alkyl group may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, scc-butyl group, tert-butyl group, linear or branched pentyl group, linear chain Linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched Decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear And a linear or branched pentadecyl group, a linear or branched hexadecyl group, a linear or branched heptadecyl group, and a linear or branched octadecyl group.

In general formula (1) the number of carbon atoms of the alkylene group represented by R ² in is not particularly limited, but preferably is generally from 2 to 10 carbon atoms. Specific examples of the alkylene group having 2 to 10 carbon atoms include ethylene group, propylene group (including 1-methylethylene group and 2-methylethylene group), trimethylene group, butylene group (1-ethylethylene group and 2 -Including ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene Groups (including 1-butylethylene group and 2-butylethylene group), 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group, 1,1,2-trimethylethylene group, 1,2 , 2-trimethylethylene group, hexylene group (including 1-butylethylene group and 2-butylethylene group), 1-methyl-1-propylene Ethylene group, 1-methyl-2-propylethylene group, 2-methyl-2-propylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 2,2-diethylethylene group, 1-ethyl -1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 2-ethyl-1,1-dimethylethylene group, 2-ethyl-1,2-dimethylethylene group, 1,1,2 , 2-tetramethylethylene group, heptylene group (including 1-pentylethylene group and 2-pentylethylene group), octylene group (including 1-hexylethylene group and 2-hexylethylene group), nonylene group (1-heptyl group) Ethylene group and 2-heptylethylene group), decylene group (including 1-octylethylene group and 2-octylethylene group), etc. Rukoto can.

Among the above alkylene groups, R ² is preferably an alkylene group having 3 or more carbon atoms from the viewpoint of low hygroscopicity, excellent lubricity, and hardly hydrolyze, and is an alkylene group having 4 or more carbon atoms. More preferably. The number of carbon atoms of the alkylene group represented by R ² is preferably 8 or less, more preferably 6 or less.

The compound represented by the general formula (1) may be a homopolymer having one R ^{2 in} the same molecule or a copolymer having two or more R ² in the same molecule. Good. Furthermore, when the compound represented by the general formula (1) is a copolymer, the monomer ratio and the monomer arrangement constituting the copolymer are not particularly limited, and a random copolymer or an alternating copolymer is included. And a block copolymer.

In the case where the compound represented by the general formula (1) is a homopolymer, R ² is an alkylene having 4 to 6 carbon atoms from the viewpoint of low hygroscopicity, excellent lubricity, and difficulty in hydrolysis. It is preferably a group, and a butylene group is more preferable from the viewpoint of availability of raw material monomers.

When the compound represented by the general formula (1) is a copolymer, the hygroscopic property is low, the lubricity is excellent, the hydrolysis hardly occurs, the residue during annealing can be further reduced, and the like. In view of this, R ² is preferably an alkylene group having 3 to 6 carbon atoms, and more preferably a propylene group or a butylene group from the standpoint of availability of raw material monomers.

  In the general formula (1), n is an integer such that the compound represented by the general formula (1) has a weight average molecular weight of 300 to 2000, preferably 500 to 1800, more preferably 800 to 1500. . If the weight average molecular weight of the compound represented by the general formula (1) is less than 300, the flash point becomes too low, and there is a risk of ignition and ignition. On the other hand, if the weight average molecular weight of the compound represented by the general formula (1) exceeds 2000, even if the compound represented by the general formula (1) has a structure that is easily decomposed, It may remain.

The 1st component concerning this invention may be comprised by 1 type of the compound represented by the said General formula (1), or may be comprised by 2 or more types. In addition, when the 1st component is a mixture of 2 or more types of compounds, if the kinematic viscosity in 40 degreeC of the said mixture is 20-500 mm < ² > / s, the mixing ratio in particular of each component will not be restrict | limited. Further, the kinematic viscosity at 40 ° C. of the mixture is required to be ²⁰ to 500 mm ² / s, but all the components contained in the mixture do not satisfy the condition of 20 to 500 mm ² / s at 40 ° C. Also good.

The kinematic viscosity at 40 ° C. of the first component according to the present invention is 500 mm ² / s or less, preferably 300 mm ² / s or less, more preferably 150 mm ² / s or less, as described above. When the 40 ° C. kinematic viscosity of the first component exceeds 500 mm ² / s, the annealing and degreasing properties become insufficient. The kinematic viscosity at 40 ° C. of the first component is 20 mm ² / s or more as described above, preferably 30 mm ² / s or more, more preferably 50 mm ² / s or more. When the 40 ° C. kinematic viscosity of the first component is 20 mm ² / s or less, the lubricity becomes insufficient.

  The content of the first component in the oil composition for warm pressing according to the present invention is 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass, as described above, based on the total amount of the composition. It is as follows. When the content exceeds 95% by mass, the lubricity becomes insufficient. Further, the content of the first component is 5% by mass or more as described above, preferably 20% by mass or more, more preferably 30% by mass or more, and most preferably 50% by mass or more, based on the total amount of the composition. is there. When the content is less than 5 masses, the annealing and degreasing properties are insufficient.

  Moreover, the 2nd component in the oil agent composition for warm press processing of this invention consists of 1 type, or 2 or more types substantially chosen from a polyhydric alcohol ester and complex ester.

  As the polyhydric alcohol constituting the polyhydric alcohol ester, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylol alkanes (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and a mixture thereof. It is below.

  Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylol Methylol butane and the like, and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetrio Le, 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols, and mixtures thereof, such as mannitol and the like are preferable. Furthermore, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and a mixture thereof are more preferable. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, pentaerythritol, and a mixture thereof are most preferable because higher thermal / oxidative stability can be obtained.

  Further, the carboxylic acid constituting the polyhydric alcohol ester may be either a monobasic acid or a polybasic acid.

  As the monobasic acid constituting the polyhydric alcohol ester, a fatty acid having 6 to 24 carbon atoms is usually used. Such monobasic acid may be linear or branched, and may be either saturated or unsaturated. Specifically, linear or branched hexanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear Or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear Or branched hexadecanoic acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched eicosanoic acid, linear Saturated fatty acids such as linear or branched heneicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid; Is branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear Or branched decenoic acid, linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear Or branched pentadecenoic acid, linear or branched hexadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecenoic acid, straight Linear or branched eicosenoic acid, linear or branched heneicosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tet Unsaturated fatty acids such as archwire acid, and mixtures of two or more thereof. Among these, a saturated fatty acid having 8 to 20 carbon atoms, an unsaturated fatty acid having 8 to 20 carbon atoms, and a mixture of two or more thereof are preferable.

  Moreover, as a polybasic acid which comprises a polyhydric alcohol ester, a C2-C16 dibasic acid, trimellitic acid, etc. are mentioned. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be either saturated or unsaturated. Specifically, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear or Branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid Linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid; linear or branched Hexenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid, linear or branched decenedioic acid, linear or branched undecenedioic acid, Linear or branched dodecenedioic acid, linear or Are branched tridecenedioic acid, linear or branched tetradecenedioic acid, linear or branched heptadecenedioic acid, linear or branched hexadecenedioic acid, and mixtures of two or more thereof. Can be mentioned.

The combination of the polyhydric alcohol and the carboxylic acid constituting the polyhydric alcohol ester is arbitrary, and examples thereof include the combinations shown below.
(1) Esters of polyhydric alcohols and monobasic acids (2) Esters of polyhydric alcohols and polybasic acids (3) Esters of polyhydric alcohols and monobasic acids and mixed carboxylic acids of polybasic acids.

  The polyhydric alcohol ester may be a complete ester in which all the hydroxyl groups of the polyhydric alcohol are esterified, or a partial ester in which some of the hydroxyl groups are not esterified and remain as hydroxyl groups. May be. In addition, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified. It may be a partial ester remaining.

  Among the combinations shown in the above (1) to (3), (1) an ester of a polyhydric alcohol and a monobasic acid is preferable because it is more excellent in lubricity.

  The number of carbon atoms of the polyhydric alcohol ester is not particularly limited, but is preferably 7 or more, more preferably 9 or more, and even more preferably 11 or more from the viewpoint of excellent lubricity improvement effect. Moreover, since there exists a possibility that a problem may arise in an annealing property when carbon number is too large, 26 or less are preferable, as for carbon number of ester, 24 or less are more preferable, and 22 or less are further more preferable.

  The complex ester is an ester of a fatty acid and a dibasic acid with a monohydric alcohol and a polyhydric alcohol.

  As the monohydric alcohol constituting the complex ester, one having 1 to 24 carbon atoms is usually used, and such alcohol may be either linear or branched. Specific examples of the monohydric alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, direct Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched Hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecane , Linear or branched eicosanol, linear or branched heneicosanol, linear or branched tricosanol, linear or branched tetracosanol and mixtures thereof. .

  As the fatty acid, dibasic acid and polyhydric alcohol constituting the complex ester, those similar to the fatty acid, dibasic acid and polyhydric alcohol exemplified in the description of the polyhydric alcohol ester can be used.

The 2nd component concerning this invention may be comprised by 1 type chosen from the group which consists of a polyhydric alcohol ester and complex ester, or may be comprised by 2 or more types. In addition, when the second component is a mixture of two or more compounds, the mixing ratio of each component is not particularly limited as long as the kinematic viscosity at 40 ° C. of the mixture is 10 to 1000 mm ² / s. Further, the kinematic viscosity at 40 ° C. of the mixture needs to be 10 to 1000 mm ² / s, but all the components contained in the mixture do not satisfy the condition of 10 to 1000 mm ² / s at 40 ° C. Also good.

As described above, the kinematic viscosity at 40 ° C. of the second component according to the present invention is 1000 mm ² / s or less, preferably 500 mm ² / s or less, more preferably 350 mm ² / s or less. When the 40 ° C. kinematic viscosity of the second component exceeds 1000 mm ² / s, the annealing and degreasing properties become insufficient. Further, the kinematic viscosity at 40 ° C. of the second component is 10 mm ² / s or more as described above, preferably 20 mm ² / s or more, more preferably 30 mm ² / s or more. When the 40 ° C. kinematic viscosity is 10 mm ² / s or less, the lubricity becomes insufficient.

  The content of the second component in the warm press working oil composition of the present invention is 95% by mass or less, preferably 80% by mass or less, more preferably 70% by mass, as described above, based on the total amount of the composition. It is as follows. When the said content exceeds 95 mass%, annealing property and degreasing property will become inadequate. Further, the content of the second component is 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, as described above, based on the total amount of the composition. When the content is less than 5 mass, the lubricity becomes insufficient.

  The oil composition for warm pressing according to the present invention may be composed of the first component and the second component, but may further contain other base oils. Specific examples of other base oils include mineral oil and synthetic oil. As mineral oil, lubricating oil fraction obtained by atmospheric pressure distillation and / or vacuum distillation is used to remove solvent, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing Paraffin-based mineral oil, normal paraffin-based base oil, isoparaffin-based base oil or the like purified by combining one or more kinds of refining treatments such as clay processing alone or in combination. Synthetic oils include polyolefins such as propylene oligomers, polybutenes, polyisobutylenes, oligomers of 5 to 20 carbon atoms, co-oligomers of ethylene and 5 to 20 carbon atoms, or hydrides thereof. Alkylbenzenes such as monoalkylbenzene, dialkylbenzene, and polyalkylbenzene; alkylnaphthalenes such as monoalkylnaphthalene, dialkylnaphthalene, and polyalkylnaphthalene; phenyl ethers such as dialkyldiphenyl ether; silicone oils; fluoroethers such as perfluoroether. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, the content of the base oil other than the first component and the second component is preferably 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably, based on the total amount of the composition. Is 10% by mass or less.

  Moreover, it is preferable that the oil agent composition for warm press processing of this invention further contains an extreme pressure agent from the point of the improvement of processing efficiency. Preferred extreme pressure agents include phosphorus compounds and sulfur compounds.

  Specific examples of phosphorus compounds include phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters and phosphorothioates, and the following general formula (2) Or the metal salt of the phosphorus compound represented by (3) is mentioned. These phosphorus compounds are esters of phosphoric acid, phosphorous acid or thiophosphoric acid with alkanols and polyether type alcohols or derivatives thereof.

[In Formula (2), X ¹ , X ² and X ³ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least two of X ¹ , X ² or X ³ are oxygen atoms; , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms]

[In Formula (3), X ⁴ , X ⁵ , X ⁶ and X ⁷ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least 3 of X ⁴ , X ⁵ , X ⁶ or X ⁷ One is an oxygen atom, and R ⁷ , R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

More specifically, the phosphate ester includes 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, xyl Renyl diphenyl phosphate and the like;
Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl 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 , Dihexyl reed Dophosphate, 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, dipentadecyl acid Hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, etc .;
Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, etc .;
Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like;
As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite etc .;
Examples of phosphorothioates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothioate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl. Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate , Triheptadecyl phosphorothioate, trioctadecyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tricresyl phosphorothionate, trixylenyl phosphorothionate, cresyl di Phenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphorothionate, tris (n-butylphenyl) phosphorothionate, tris (Isobutylphenyl) phosphorothionate, tris (s-butylphenyl) phosphorothionate, tris (t-butylphenyl) phosphorothionate and the like can be mentioned.

Moreover, regarding the metal salt of the phosphorus compound represented by the general formula (2) or (3), the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{4 to} R ⁹ in the formula is specifically Includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkaryl group, an aralkyl group, and the like.

  Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the like. Group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups may be linear or branched).

  As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example. Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include an alkylcycloalkyl group having 6 to 11 carbon atoms such as a dimethylcycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).

  Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also optional).

  As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example. Examples of the alkaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl. Group, an alkaryl group having 7 to 18 carbon atoms such as undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is arbitrary). .

  Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group (these alkyl groups may be linear or branched). May be used).

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{4 to} R ⁹ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 3 carbon atoms. It is an 18 alkyl group, more preferably an alkyl group having 4 to 12 carbon atoms.

R ⁴ , R ⁵ and R ⁶ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group, and 1 to 3 of R ⁴ , R ⁵ and R ⁶ are the above hydrocarbon groups. It is preferable that 1 to 2 is the above hydrocarbon group, and more preferably 2 is the above hydrocarbon group.

R ⁷ , R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or the above hydrocarbon group, and 1 to 3 of R ⁷ , R ⁸ and R ⁹ are the above hydrocarbons. It is preferably a group, 1 to 2 are more preferably the hydrocarbon group, and 2 are more preferably the hydrocarbon group.

In the general formula (2) phosphorus compounds represented by, at least two of X ¹ to X ³ is required to be an oxygen atom, that all the X ¹ to X ³ is an oxygen atom preferable.

Further, the phosphorus compound represented by the general formula (3), but at least three of X ⁴ to X ⁷ is required to be an oxygen atom, all of X ⁴ to X ⁷ is an oxygen atom It is preferable.

  Examples of the phosphorus compound represented by the general formula (2) include phosphorous acid and monothiophosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms and monothiophosphorous acid mono Ester; Phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester; Phosphorous acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid Acid triesters; and mixtures thereof. Among these, phosphorous acid monoester and phosphorous acid diester are preferable, and phosphorous acid diester is more preferable.

  Examples of the phosphorus compound represented by the general formula (3) include phosphoric acid and monothiophosphoric acid; phosphoric acid monoester and monothiophosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; And phosphoric acid diesters and monothiophosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; phosphoric acid triesters and monothiophosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. It is done. Among these, phosphoric acid monoester and phosphoric acid diester are preferable, and phosphoric acid diester is more preferable.

  Examples of the metal salt of the phosphorus compound represented by the general formula (2) or (3) include a salt obtained by neutralizing part or all of the acidic hydrogen of the phosphorus compound with a metal base. Examples of such metal bases include metal oxides, metal hydroxides, metal carbonates, metal chlorides and the like. Specific examples of the metal include alkali metals such as lithium, sodium, potassium, cesium, and calcium. And alkaline earth metals such as magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  The metal salt of the phosphorus compound has a different structure depending on the valence of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid diester ( When 2 mol of 1 OH group is reacted, it is considered that a compound having a structure represented by the following formula (4) is obtained as a main component, but it is also considered that polymerized molecules exist.

  Further, for example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (having two OH groups) are reacted, it is considered that a compound having a structure represented by the following formula (5) is obtained as a main component. Polymerized molecules are also thought to exist.

  A mixture of two or more of these can also be used.

  In the present invention, among the above phosphorus compounds, higher processing efficiency can be obtained. Therefore, phosphoric acid ester, acidic phosphoric acid ester, amine salt of phosphoric acid ester and phosphorothionate are preferable, and further higher processing. From the viewpoint that efficiency can be achieved, phosphate ester is more preferable.

  The sulfur compound used in the present invention is not particularly limited as long as it does not impair the properties of the metalworking oil composition, but dihydrocarbyl polysulfide, sulfurized fatty acid, sulfurized olefin, sulfurized ester, sulfide mineral oil, zinc dithiophosphate, dithiocarbamic acid Zinc compounds, molybdenum dithiophosphate compounds, molybdenum dithiocarbamate compounds, thiadiazole compounds, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, and dialkylthiodipropionate compounds are preferably used.

Dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin. Specifically, the following general formula (6):
R ¹⁰ -S _a -R ¹¹ (6)
[In Formula (6), R ¹⁰ and R ¹¹ may be the same or different, and each represents a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms. A 6-20 alkaryl group or a C6-C20 aralkyl group is represented, a represents 2-6, Preferably the integer of 2-5 is represented. ]
The compound represented by these is meant.

Specific examples of R ¹⁰ and R ¹¹ in the general formula (6) include n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched Undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group A linear or branched alkyl group such as a linear or branched octadecyl group, a linear or branched nonadecyl group, a linear or branched icosyl group; an ant such as a phenyl group or a naphthyl group; A tolyl group (including all structural isomers), an ethylphenyl group (including all structural isomers), a linear or branched propylphenyl group (including all structural isomers), a linear or branched group Branched butylphenyl group (including all structural isomers), linear or branched pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), Linear or branched heptylphenyl group (including all structural isomers), linear or branched octylphenyl group (including all structural isomers), linear or branched nonylphenyl group (all structural isomers) Straight chain or branched undecylphenyl group (including all structural isomers), straight chain or branched undecylphenyl group (including all structural isomers), straight chain or branched dodecylphenyl group (including all structural isomers) All structures Isomers), xylyl groups (including all structural isomers), ethylmethylphenyl groups (including all structural isomers), diethylphenyl groups (including all structural isomers), di (linear or linear) Branched) propylphenyl group (including all structural isomers), di (straight or branched) butylphenyl group (including all structural isomers), methylnaphthyl group (including all structural isomers), Ethyl naphthyl group (including all structural isomers), linear or branched propyl naphthyl group (including all structural isomers), linear or branched butyl naphthyl group (including all structural isomers), dimethyl Naphthyl group (including all structural isomers), ethylmethylnaphthyl group (including all structural isomers), diethylnaphthyl group (including all structural isomers), di (straight or branched) propyl naphthyl group Alkaryl groups such as di (straight or branched) butyl naphthyl groups (including all structural isomers); benzyl groups, phenylethyl groups (including all isomers), And aralkyl groups such as phenylpropyl group (including all isomers).

Among these, R ¹⁰ and R ¹¹ in the general formula (6) include an alkyl group having 3 to 18 carbon atoms derived from propylene, 1-butene or isobutylene, an aryl group having 6 to 8 carbon atoms, A reel group or an aralkyl group is preferred. These preferable groups include, for example, isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), branched nonyl group derived from propylene trimer ( Including all branched isomers), branched dodecyl groups derived from propylene tetramers (including all branched isomers), branched pentadecyl groups derived from propylene pentamers (including All branched isomers), branched octadecyl group derived from propylene hexamer (including all branched isomers), sec-butyl group, tert-butyl group, 1-butene 2 A branched octyl group derived from a mer (including all branched isomers), a branched octyl group derived from an isobutylene dimer (including all branched isomers), 1- Branched domain derived from butene trimer Sil group (including all branched isomers), branched dodecyl group derived from isobutylene trimer (including all branched isomers), fraction derived from 1-butene tetramer Alkyl groups such as branched hexadecyl groups (including all branched isomers), branched hexadecyl groups (including all branched isomers) derived from isobutylene tetramer; phenyl groups, tolyl groups (Including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (including all structural isomers), etc .; benzyl group, phenylethyl group (all isomers) An aralkyl group such as a body).

Furthermore, R ¹⁰ and R ¹¹ in the general formula (6) are each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene from the viewpoint of improving the processing efficiency and tool life. It is more preferable that it is a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene.

  Examples of the sulfurized fatty acid include sulfurized oleic acid, and examples of the sulfurized ester include sulfurized methyl oleate, sulfurized rice bran fatty acid octyl, and mixtures thereof.

As a sulfurized olefin, the compound represented by following General formula (7) is mentioned, for example. This compound is obtained by reacting an olefin having 2 to 15 carbon atoms or a dimer to tetramer thereof with a sulfurizing agent such as sulfur or sulfur chloride, and propylene, isobutene, diisobutene and the like are preferable.
R ¹² -S _b -R ¹³ (7)
[Wherein, R ¹² represents an alkenyl group having 2 to 15 carbon atoms, R ¹³ represents an alkyl group or alkenyl group having 2 to 15 carbon atoms, and b represents an integer of 1 to 8. ]

  Specific examples of the sulfurized ester include animal and vegetable fats and oils such as beef tallow, pork tallow, fish fat, rapeseed oil and soybean oil; unsaturated fatty acids (oleic acid, linoleic acid, fatty acids extracted from the above-mentioned animal and vegetable fats and the like, and the like. And an unsaturated fatty acid ester obtained by reacting various alcohols with each other; and a mixture thereof obtained by sulfiding by an arbitrary method.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, although it does not restrict | limit especially as a mineral oil used for the sulfide mineral oil concerning this invention, The mineral oil illustrated in description of the base oil which can be used together with a 1st component and a 2nd component can be used. In addition, as elemental sulfur, any form such as lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled in a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in the sulfur content in the sulfide mineral oil concerning this invention, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0. 5% by mass.

  Preferable examples of the zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate and the molybdenum compound dithiocarbamate include compounds represented by the following general formulas (8) to (11), respectively.

In the formulas (8) to (11), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ⁸ and X ⁹ each represents an oxygen atom or a sulfur atom.

Specific examples of the hydrocarbon group represented by R ^{14 to} R ²⁹ include a methyl group, an ethyl group, a propyl group (including all branched isomers), and a butyl group (including all branched isomers). ), Pentyl group (including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (all branched isomers) ), Nonyl group (including all branched isomers), decyl group (including all branched isomers), undecyl group (including all branched isomers), dodecyl group (all branched isomers) Isomers), tridecyl groups (including all branched isomers), tetradecyl groups (including all branched isomers), pentadecyl groups (including all branched isomers), hexadecyl groups (including all branched isomers) Including branched isomers), heptadecyl group (including all branched isomers), oct Decyl group (including all branched isomers), nonadecyl group (including all branched isomers), icosyl group (including all branched isomers), heicosyl group (including all branched isomers) ), Docosyl groups (including all branched isomers), tricosyl groups (including all branched isomers), tetracosyl groups (including all branched isomers), etc .; cyclopentyl groups, cyclohexyl groups , Cycloalkyl groups such as cycloheptyl group; methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethylcyclopentyl group (including all substituted isomers), propyl Cyclopentyl group (including all branched isomers and substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl (Including all substituted isomers), butylcyclopentyl group (including all branched isomers and substituted isomers), methylpropylcyclopentyl group (including all branched isomers and substituted isomers), diethylcyclopentyl group (Including all substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), Dimethylcyclohexyl group (including all substituted isomers), propylcyclohexyl group (including all branched and substituted isomers), methylethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (all Substituted isomers), butylcyclohexyl groups (including all branched isomers, substituted isomers), methyl Propylcyclohexyl group (including all branched isomers and substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers), methylcycloheptyl group (Including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (all branched isomers, Substituted isomers), methylethylcycloheptyl group (including all substituted isomers), trimethylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (all branched isomers, substituted isomers) ), Methylpropylcycloheptyl group (including all branched isomers and substituted isomers), diethylcycloheptyl group (including all substituted isomers) Alkyl cycloalkyl groups such as dimethylethylcycloheptyl group (including all substituted isomers); aryl groups such as phenyl group and naphthyl group; tolyl group (including all substituted isomers), xylyl Group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (including all branched isomers, substituted isomers), methylethylphenyl group (all substituted isomers) Isomers), trimethylphenyl group (including all substituted isomers), butylphenyl group (including all branched and substituted isomers), methylpropylphenyl group (all branched isomers, substituted) Isomers), diethylphenyl group (including all substituted isomers), dimethylethylphenyl group (including all substituted isomers), pentylphenyl group (all branches) Isomers, including substituted isomers), hexylphenyl groups (including all branched isomers and substituted isomers), heptylphenyl groups (including all branched isomers and substituted isomers), octylphenyl groups (including All branched isomers, including substituted isomers), nonylphenyl group (including all branched isomers, including substituted isomers), decylphenyl group (including all branched isomers, including substituted isomers), Undecylphenyl group (including all branched isomers and substituted isomers), dodecylphenyl group (including all branched isomers and substituted isomers), tridecylphenyl group (all branched isomers and substituted isomers) Isomers), tetradecylphenyl group (including all branched isomers and substituted isomers), pentadecylphenyl group (including all branched isomers and substituted isomers), hexadecylphenyl group (all Branched isomers, substituted isomers of ), Heptadecylphenyl group (including all branched isomers and substituted isomers), octadecylphenyl group (including all branched isomers and substituted isomers), etc .; benzyl group, phenethyl Aralkyl groups such as a group, phenylpropyl group (including all branched isomers), phenylbutyl group (including all branched isomers), and the like.

Examples of the thiadiazole compound include 1,3,4-thiadiazole represented by the following general formula (12), 1,2,4-thiadiazole compound represented by the following general formula (13), and the following general formula (14). The 1,4,5-thiadiazole compound represented by these is mentioned.

In general formulas (12) to (14), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ may be the same or different, and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. C, d, e, f, g and h may be the same or different and each represents an integer of 0 to 8.

  Specific examples of such thiadiazole compounds include 2,5-bis (n-hexyldithio) -1,3,4-thiadiazole, 2,5-bis (n-octyldithio) -1,3,4-thiadiazole. 2,5-bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3-tetramethylbutyldithio) -1,3,4-thiadiazole, 3, 5-bis (n-hexyldithio) -1,2,4-thiadiazole, 3,5-bis (n-octyldithio) -1,2,4-thiadiazole, 3,5-bis (n-nonyldithio) -1 , 2,4-thiadiazole, 3,5-bis (1,1,3,3-tetramethylbutyldithio) -1,2,4-thiadiazole, 4,5-bis (n-hexyldithio) -1,2 , 3-thiadiazole, 4 5-bis (n-octyldithio) -1,2,3-thiadiazole, 4,5-bis (n-nonyldithio) -1,2,3-thiadiazole, 4,5-bis (1,1,3,3) Preferred examples include -tetramethylbutyldithio) -1,2,3-thiadiazole and a mixture thereof.

  Examples of the alkylthiocarbamoyl compound include compounds represented by the following general formula (15).

In general formula (15), R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and q represents an integer of 1 to 8.

  Specific examples of such alkylthiocarbamoyl compounds include bis (dimethylthiocarbamoyl) monosulfide, bis (dibutylthiocarbamoyl) monosulfide, bis (dimethylthiocarbamoyl) disulfide, bis (dibutylthiocarbamoyl) disulfide, and bis (diamil). Preferred examples include thiocarbamoyl) disulfide, bis (dioctylthiocarbamoyl) disulfide, and mixtures thereof.

  As an alkyl thiocarbamate compound, the compound shown by following General formula (16) is mentioned, for example.

In the general formula (16), R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and R ⁴⁴ represents an alkyl group having 1 to 10 carbon atoms. Indicates.

  Preferable examples of such alkylthiocarbamate compounds include methylenebis (dibutyldithiocarbamate), methylenebis [di (2-ethylhexyl) dithiocarbamate] and the like.

  Further, examples of the thioterpene compound include a reaction product of phosphorus pentasulfide and pinene, and examples of the dialkylthiodipropionate compound include dilauryl thiodipropionate, distearyl thiodipropionate, and a mixture thereof. be able to.

  In the present invention, among the above sulfur compounds, it is preferable to use at least one selected from the group consisting of dihydrocarbyl polysulfide, sulfurized ester, sulfurized fat and oil, and thiadiazole compound because the effect of improving the processing efficiency can be obtained at a higher level. Further, it is more preferable to use a sulfurized ester.

  The oil composition for warm pressing according to the present invention may contain only one of a phosphorus compound and a sulfur compound, or may contain both a phosphorus compound and a sulfur compound. From the point that the effect of improving the machining efficiency and the tool life is further enhanced, it is preferable to contain a phosphorus compound alone or both a sulfur compound and a phosphorus compound, and a phosphorus compound alone is more preferred.

  Although the content of the extreme pressure agent is arbitrary, it is preferably 0.005% by mass or more and more preferably 0.01% by mass or more based on the total amount of the composition from the viewpoint of improving the processing efficiency. And more preferably 0.05% by mass or more. From the viewpoint of preventing abnormal wear, the content of the extreme pressure agent is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less, based on the total amount of the composition. More preferably it is.

Moreover, the oil composition for warm press processing of this invention may further contain an oily agent. The oily agent used in the present invention includes those usually used as an oily agent for lubricating oils. However, it is preferable to use one or more oily agents selected from the following (1) to (3) in order to further improve the workability.
(1) Ester oil agent (2) Monohydric alcohol oil agent (3) Carboxylic acid oil agent.

  (1) The alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol. (1) The carboxylic acid constituting the ester oily agent may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol, the monohydric alcohol exemplified in the description of the complex ester according to the second component can be used.

  In addition, as the polyhydric alcohol, the polyhydric alcohol exemplified in the description of the polyhydric alcohol ester according to the second component can be used.

  Among these, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc. ) And their 2-4 tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2 3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols, and mixtures thereof, such as mannitol and the like are more preferable. More preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof.

  (1) As the monobasic acid constituting the ester oily agent, the monobasic acid exemplified in the description of the polyhydric alcohol ester according to the second component can be used.

  Moreover, (1) As a polybasic acid which comprises an ester oily agent, the polybasic acid illustrated in description of the polyhydric alcohol ester concerning the said 2nd component can be used.

(1) As ester oily agent, ester by the combination of arbitrary alcohol and carboxylic acid can be used, and it is not specifically limited. Specific examples of the combination of alcohol and carboxylic acid include the following (1a) to (1g).
(1a) monohydric alcohol and monobasic acid ester (1b) polyhydric alcohol and monobasic acid ester (1c) monohydric alcohol and polybasic acid ester (1d) polyhydric alcohol and polybasic acid ester (1e ) Mixed ester of monohydric alcohol, polyhydric alcohol and polybasic acid (1f) Mixed ester of polyhydric alcohol and monobasic acid, polybasic acid (1 g) Mixture of monohydric alcohol and polyhydric alcohol And mixed esters of monobasic and polybasic acids.

  In addition, when a polyhydric alcohol is used as an alcohol component, the complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified is shown. Further, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, and a part of the carboxyl group is not esterified and remains as a carboxyl group. It may be a partial ester.

  As the ester used in the present invention, any of the above-mentioned esters can be used. Among these, (1a) an ester of a monohydric alcohol and a monobasic acid or (1c) a monohydric alcohol from the viewpoint of superior processability. And (1a) monohydric alcohol and monobasic acid ester, (1a) monohydric alcohol and monobasic ester, and (1c) monohydric alcohol and polybasic ester. It is most preferable to use in combination.

  Although there is no restriction | limiting in particular in the total carbon number of (1a) monohydric alcohol and ester of monobasic acid used as an oil-based agent in this invention, The said total carbon number has preferable 7 or more, 9 or more are more preferable, 11 or more Is particularly preferred. Further, the total carbon number is preferably 26 or less, more preferably 24 or less, and particularly preferably 22 or less. Moreover, especially carbon number of monohydric alcohol is although it does not restrict | limit, 1-10 are preferable, 1-8 are more preferable, 1-6 are still more preferable, 1-4 are especially preferable. Moreover, especially carbon number of a monobasic acid is although it does not restrict | limit, 8-22 are preferable, 10-20 are more preferable, and 12-18 are especially preferable. If the total carbon number, the carbon number of alcohol, and the carbon number of monobasic acid exceed the above upper limits, respectively, there is a tendency to increase the occurrence of stain and corrosion, and the fluidity is lost in winter. There is a tendency that handling becomes difficult, and further, there is a tendency that the solubility in base oil decreases and the possibility of precipitation increases. Further, when the total carbon number, the alcohol carbon number, and the monobasic carbon number are less than the lower limit values, there is a tendency that the lubricity is lowered and the working environment is deteriorated due to odor.

The form of (1c) monohydric alcohol and polybasic acid ester used as an oily agent in the present invention is not particularly limited, but may be a diester represented by the following general formula (17) or an ester of trimellitic acid. preferable.
^{_{R 44 -O-CO (CH 2}} ) m CO-O-R 45 (17)
[In General Formula (17), R ⁴⁴ and R ⁴⁵ may be the same or different and each represents a hydrocarbon group having 3 to 10 carbon atoms, and m represents an integer of 4 to 8. ]

In the general formula (17), R ⁴⁴ and R ⁴⁵ preferably have 3 or more carbon atoms. If the carbon number of R ⁴⁴ and R ⁴⁵ is less than 3, the lubricity improvement effect may not be expected, and the working environment tends to deteriorate due to odor. ^The number of carbon atoms of ^{R 44} and ^{R 45} is preferably 10 or less. If the carbon number of R ⁴⁴ and R ⁴⁵ exceeds 10, there is a risk of increasing the occurrence of stains and corrosion, there is a risk of losing fluidity in winter and handling becomes difficult, and solubility in base oil decreases. The risk of precipitation tends to increase.

Examples of R ⁴⁴ and R ⁴⁵ in the general formula (1) include an alkyl group, an alkenyl group, an alkylcycloalkyl group, an alkylphenyl group, and a phenylalkyl group, and an alkyl group is particularly preferable. The alkyl group includes a linear alkyl group or a branched alkyl group, and a linear alkyl group and a branched alkyl group may be mixed, but a branched alkyl group is preferable. Specific examples of R ⁴⁴ and R ⁴⁵ include linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched A heptyl group, a linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group, etc. can be mentioned.

  Moreover, m in the said General formula (17) shows the integer of 4-8. From the point of increasing the possibility of increasing the occurrence of stains and corrosion, increasing the risk of losing fluidity in winter and becoming difficult to handle, increasing the possibility of precipitation due to lower solubility in base oil, etc. m is preferably 8 or less. Further, m is preferably 4 or more from the viewpoint that the effect of improving the lubrication performance may not be expected, and the working environment is deteriorated by odor. Among these, m is particularly preferably 4 or 6 from the viewpoint of availability of raw materials and price.

  The diester represented by the general formula (17) can be obtained by an arbitrary method. For example, the diester represented by the above formula has a carbon number of 6 to 10 (in order from carbon number 6, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid). Examples thereof include a method of esterifying a chain saturated dicarboxylic acid or a derivative thereof and an alcohol having 3 to 10 carbon atoms. The carbon number of the monohydric alcohol for esterifying trimellitic acid is not particularly limited, but there is a greater risk of increasing the occurrence of stains and corrosion, and there is a greater risk of loss of fluidity and difficulty in handling in winter. From the point that the solubility in oil decreases and the risk of precipitation increases, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and more preferably 1 to 1 carbon atoms. 4 is most preferred. The ester of trimellitic acid may be a partial ester (monoester or diester) or a complete ester (triester).

  (2) As the monohydric alcohol oily agent, specifically, for example, the monohydric alcohols exemplified in the description of the complex ester relating to the second component can be used. (2) The monohydric alcohol oil-based agent is preferably a monohydric alcohol having 6 or more carbon atoms, more preferably an alcohol having 8 or more carbon atoms, and 10 or more carbon atoms from the viewpoint of lubrication performance and deterioration of the working environment due to odor. Are more preferred, and alcohols having 12 or more carbon atoms are most preferred. It also increases the risk of increasing the occurrence of stains and corrosion, increases the risk of loss of fluidity during winter and increases the risk of handling, and increases the risk of precipitation due to decreased solubility in base oil Therefore, an alcohol having 20 or less carbon atoms is preferable, and an alcohol having 18 or less carbon atoms is more preferable.

  (3) The carboxylic acid oily agent may be a monobasic acid or a polybasic acid. Specifically, for example, the monobasic acid or polybasic acid exemplified in the description of the polyhydric alcohol ester according to the second component can be used. Among these, a monovalent carboxylic acid is preferable from the viewpoint of excellent workability. Moreover, from the point which is more excellent in workability, a C6 or more carboxylic acid is preferable, a C8 or more carboxylic acid is more preferable, and a C10 or more carboxylic acid is the most preferable. Moreover, since possibility that the generation | occurrence | production of a stain and corrosion will increase will become large when carbon number is too large, a C20 or less carboxylic acid is preferable, a C18 or less carboxylic acid is more preferable, and a C16 or less carbonic acid is preferable. Carboxylic acid is most preferred.

  In the oil composition for warm press processing of the present invention, only one kind selected from the above various oily agents may be used, or two or more kinds may be used in combination, but from the viewpoint of lubricity. (1) ester oily agents and (2) monohydric alcohol oily agents are preferred, and (1) ester oily agents are more preferred.

  The content of the oily agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more from the viewpoint of workability. From the viewpoint of degreasing properties, the content of the oily agent is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 15% by mass or less, and particularly preferably. Is 12% by mass or less, most preferably 10% by mass or less.

  Moreover, it is preferable that the oil composition for warm press processing of this invention further contains antioxidant. By adding an antioxidant, it is possible to prevent stickiness due to alteration of the constituent components, and to improve thermal and oxidation stability.

  Antioxidants that can be used in the present invention include phenolic antioxidants, amine antioxidants, zinc dithiophosphate antioxidants, and other antioxidants used as food additives.

  As the phenolic antioxidant, any phenolic compound used as an antioxidant for lubricating oils can be used, and is not particularly limited. For example, the following general formula (18) and general formula (19) Preferred examples include one or more alkylphenol compounds selected from the compounds represented by formula (1).

[In the formula (18), R ⁴⁶ represents an alkyl group having 1 to 4 carbon atoms, R ⁴⁷ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group, the following general formula (i) or (ii):
(In the general formula (18-i), R ⁴⁹ represents an alkylene group having 1 to 6 carbon atoms, and R ⁵⁰ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms.)
(In the general formula (18-ii), R ⁵¹ represents an alkylene group having 1 to 6 carbon atoms, R ⁵² represents an alkyl group having 1 to 4 carbon atoms, and R ⁵³ represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group, and p represents 0 or 1.)
The group represented by these is shown. ]

[In General Formula (21), R ⁵⁴ and R ⁵⁶ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms; R ⁵⁵ and R ⁵⁷ may be the same or different; Represents an atom or an alkyl group having 1 to 4 carbon atoms, R ⁵⁸ and R ⁵⁹ may be the same or different, each represents an alkylene group having 1 to 6 carbon atoms, and A represents an alkylene group having 1 to 18 carbon atoms or The following general formula (19-i):
-R ⁶⁰ -S-R ^61- (19-i)
(In the general formula (19-i), R ⁶⁰ and R ⁶¹ may be the same or different and each represents an alkylene group having 1 to 6 carbon atoms)
The group represented by these is shown. ]

  Further, as the amine-based antioxidant used in the present invention, any amine-based compound used as an antioxidant for a lubricating oil can be used, and is not particularly limited. One selected from phenyl-α-naphthylamine or Np-alkylphenyl-α-naphthylamine represented by formula (20) and p, p′-dialkyldiphenylamine represented by the following general formula (21) Or 2 or more types of aromatic amines are mentioned as a preferable thing.

[In formula (20), ^R62 represents a hydrogen atom or an alkyl group. ]

[In Formula (21), R ⁶³ and R ⁶⁴ may be the same or different and each represents an alkyl group. ]

  Specific examples of amine-based antioxidants include 4-butyl-4'-octyldiphenylamine, phenyl-α-naphthylamine, octylphenyl-α-naphthylamine, dodecylphenyl-α-naphthylamine, and mixtures thereof.

  Examples of the zinc dithiophosphate antioxidant used in the present invention include compounds represented by the general formula (8) exemplified in the description of the sulfur compound.

  Moreover, the antioxidant currently used as a food additive can also be used, and although it overlaps with the phenolic antioxidant mentioned above partially, for example, for example, 2,6-di-tert-butyl-p-cresol (DBPC), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-thiobis (6-tert) -Butyl-o-cresol), ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4- Hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trime Rukinorin (ethoxyquin), 2- (1,1-dimethyl) -1,4-benzenediol (TBHQ), can be mentioned 2,4,5-hydroxybutyronitrile phenone (THBP).

  Among these antioxidants, amine-based antioxidants, zinc dithiophosphate antioxidants, and antioxidants used as food additives are preferred, amine-based antioxidants and zinc dithiophosphate-based antioxidants. More preferably, an agent is used in combination. Furthermore, when importance is attached to biodegradability, what is used as the said food additive is more preferable, and among them, ascorbic acid (vitamin C), fatty acid ester of ascorbic acid, tocopherol (vitamin E), 2,6- Di-tert-butyl-p-cresol (DBPC), 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin), 2- (1,1-dimethyl) -1,4-benzenediol (TBHQ), or 2,4,5-tri Hydroxybutyrophenone (THBP) is preferred, ascorbic acid (vitamin C), fatty acid of ascorbic acid Ester, tocopherol (vitamin E), 2,6-di -tert- butyl -p- cresol (DBPC), or 3,5-di -tert- butyl-4-hydroxyanisole are more preferred.

  The content of the antioxidant is not particularly limited, but in order to maintain good thermal and oxidation stability, the content is preferably 0.01% by mass or more based on the total amount of the composition, more preferably 0.05. % By mass or more, most preferably 0.1% by mass or more. On the other hand, since the effect cannot be expected even if it is added more, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less.

  Moreover, the oil composition for warm press processing of this invention can further contain conventionally well-known additives other than the above. Examples of such additives include extreme pressure agents other than the phosphorus compounds and sulfur compounds described above (including chlorine-based extreme pressure agents); amines, alkanolamines, amides, carboxylic acids, carboxylates, sulfonates, phosphoric acids. , Phosphates, partial esters of polyhydric alcohol, etc .; metal deactivators such as benzotriazole and thiadiazole; antifoaming agents such as methylsilicone, fluorosilicone and polyacrylate; alkenyl succinimide, benzylamine And ashless dispersants such as polyalkenylamine aminoamides. The content in the case of using these known additives is not particularly limited, but it is added in such an amount that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the composition. It is common.

Kinematic viscosity at 40 ° C. for warm press working oil composition of the present invention, from the viewpoint of suppressing an increase in the residual rate of annealing after residue is preferably not more than 1000 mm 2 / ^s, more preferably 500 mm ² / s or less, and most preferably 350 mm ² / s or less. On the other hand, since the lubricity may be lowered, the kinematic viscosity at 40 ° C. is preferably 20 mm ² / s or more, more preferably 25 mm ² / s or more, and most preferably 30 mm ² / s or more. is there.

  According to the oil composition for warm press working of the present invention having the above-described configuration, it is possible to satisfy all of workability, annealing and degreasing properties at a high level in a warm balance in warm press working.

  The warm press working method of the present invention is characterized by press-molding a workpiece heated to a temperature of 100 to 350 ° C. using the oil composition for warm press working of the present invention.

  As a preferred embodiment of the warm press working method of the present invention, a step of applying a predetermined amount of the oil composition for warm press working of the present invention to a coiled plate material, a step of cutting the plate material coated with the oil agent, A warm press working method including a step of heating the cut plate material to 100 to 350 ° C. and a step of warm press forming the heated plate material may be mentioned.

  Moreover, as another preferable aspect of the warm press processing method of this invention, the process of cutting the coil-shaped board | plate material of the state in which the oil agent is not apply | coated, The process of heating the cut | disconnected board | plate material to 100-350 degreeC, And a warm press working method comprising a step of applying a predetermined amount of the oil composition for warm press working of the present invention to a heated plate material and a step of warm press forming the plate material after application.

  As described above, the heating temperature of the material in the warm pressing method of the present invention is 100 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher. When the heating temperature is less than 100 ° C., the workability decreases. Further, the heating temperature of the material is 350 ° C. or lower as described above, preferably 300 ° C. or lower, more preferably 250 ° C. or lower. When the heating temperature exceeds 350 ° C., the oil agent is easily decomposed and seized.

Further, in the warm press working method of the present invention, the method of applying the press working oil composition of the present invention to the material is not particularly limited, and spraying, electrostatic coating and dropping, coating with a roll, etc. Can be applied. Although the application quantity to the material of the oil processing composition for press processing of this invention can be selected suitably, 3 g / m < ² > is preferable and 1 g / m < ² > is more preferable.

  The material of the workpiece to which the hot press working oil composition of the present invention is applied is not particularly limited, but is suitable as a non-ferrous metal working oil, and particularly for processing aluminum, magnesium, or alloys thereof. As an oil agent, a very excellent effect can be exhibited.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Examples 1 to 19, Comparative Examples 1 to 12]
In Examples 1 to 19 and Comparative Examples 1 to 12, warm press working oil compositions having the compositions shown in Tables 1 to 5 were prepared using the base oils and additives shown below, respectively.
(Base oil)
Base oil A1: polybutylene glycol (weight average molecular weight: 1000, kinematic viscosity at 40 ° C .: 81 mm ² / s)
Base oil A2: Polypropylene glycol dimethyl ether (weight average molecular weight: 1000, kinematic viscosity at 40 ° C .: 41 mm ² / s)
Base oil A3: Polypropylene glycol monobutyl ether (weight average molecular weight: 1000, kinematic viscosity at 40 ° C .: 57 mm ² / s)
Base oil A4: Polypropylene glycol monobutyl ether (weight average molecular weight: 1400, kinematic viscosity at 40 ° C .: 127 mm ² / s)
Base oil B1: Neopentyl glycol diester (40 ° C. kinematic viscosity: 24 mm ² / s)
Base oil B2: trimethylolpropane trioleate (kinematic viscosity at 40 ° C .: 48 mm ² / s)
Base oil B3: pentaerythritol tetraoleate (kinematic viscosity at 40 ° C .: 64 mm ² / s)
Base oil B4: Dimer acid di-C ₈ · C ₁₀ trimethylolpropane complex ester (40 ° C. kinematic viscosity: 320 mm ² / s)
Base oil C1: Solvent refined mineral oil (40 ° C. kinematic viscosity: 22 mm ² / s)
Base oil C2: Solvent refined mineral oil (40 ° C. kinematic viscosity: 85 mm ² / s)
(Additive)
Additive a: Phenyl-α-naphthylamine additive b: Zinc dialkyldithiophosphate additive c: Phosphate ester additive d: Acidic phosphate ester amine salt additive e: Inactive sulfurized ester additive f: Lauryl alcohol
Additive g: oleic acid.

  The following evaluation tests were conducted on each warm press working oil agent composition of Examples 1 to 19 and Comparative Examples 1 to 12.

(Annealing test)
In an aluminum container having a diameter of 72 mm, 0.5 g of the oil composition for warm pressing was collected and heated at 300 ° C. for 1 hour. The appearance of the fixed state of the residue after heating was judged and the amount of the residual substance was measured to calculate the residual rate (%) with respect to the sampled amount. The obtained results are shown in Tables 1-5.

(Frictional property evaluation test)
Using a Bowden friction tester, a test plate made of aluminum A5000 was heated to 250 ° C., and the coefficient of friction between the test plate and the steel ball was measured in the presence of the oil composition for warm press working.

(Degreasing test)
First, a predetermined amount of an oil composition for warm pressing was applied to a coiled aluminum A5052 plate material, and the coated plate material was cut. The cut plate was heated to 300 ° C. and press-molded.

  About the obtained molded object, a series of degreasing processes were performed and the water wetted area of the surface of the molded object after a process was evaluated visually. The obtained results are shown in Tables 1-5. In the table, A means 100% wetted area, B means less than 100% wetted area, 50% or more, C means less than 50% wetted area, 10% or more, and D means less than 10% wetted area.

Claims (1)

Is composed of the following general formula (1) represented by one or more selected from the group consisting of compounds, and, the first component from 20 to 95 kinematic viscosity at 40 ° C. is 20 to 500 mm ² / s Mass%,
80 to 5% by mass of a second component composed of one or more selected from the group consisting of a polyhydric alcohol ester and a complex ester and having a kinematic viscosity at 40 ° C. of 10 to 1000 mm ² / s;
An oil composition for warm press working, comprising:
R ¹ —O— (R ² —O) _n —R ³ (1)
[In formula (1), R ¹ and R ³ may be the same or different, each represents a hydrogen atom or an alkyl group, R ² represents an alkylene group, and n is a compound represented by the general formula (1) An integer having a weight average molecular weight of 300 to 2000 is shown. ]