WO2009113473A1 - Rolling oil composition for metalworking - Google Patents

Rolling oil composition for metalworking Download PDF

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Publication number
WO2009113473A1
WO2009113473A1 PCT/JP2009/054385 JP2009054385W WO2009113473A1 WO 2009113473 A1 WO2009113473 A1 WO 2009113473A1 JP 2009054385 W JP2009054385 W JP 2009054385W WO 2009113473 A1 WO2009113473 A1 WO 2009113473A1
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Prior art keywords
rolling
oil composition
sulfur
rolling oil
oil
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PCT/JP2009/054385
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French (fr)
Japanese (ja)
Inventor
秀夫 杉井
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出光興産株式会社
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Priority to CN200980108838XA priority Critical patent/CN101970623A/en
Publication of WO2009113473A1 publication Critical patent/WO2009113473A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

  • the present invention relates to a rolling oil composition for metal working, and in particular, relates to a rolling oil composition that is suitably used when rolling iron-based materials.
  • Patent Document 1 discloses a lubricating oil for metal working formed by blending a diester that is a reaction product of a specific dicarboxylic acid and a specific alcohol.
  • Patent Documents 2 and 3 disclose a cold rolling oil for stainless steel containing a specific diester and a specific alcohol.
  • the present invention has been made under such circumstances, a rolling oil composition having excellent rolling performance, that is, no surface damage occurs even when rolling is performed at a high rolling reduction, and the rolling load is reduced.
  • An object of the present invention is to provide a rolling oil composition that contributes to the above.
  • the present inventor has found that the above problem can be solved by using a specific sulfur-containing compound as an additive. Furthermore, in general, sulfur-containing compounds have a problem of low solubility in oil, and mist is likely to be generated during rolling, and the working environment is deteriorated due to a bad odor. The inventors have found that the problem can be solved by specifying a compound, and have completed the present invention. That is, the present invention provides the following rolling oil composition. 1.
  • R 1 OOC—R 2 —S x —R 3 —COOR 4 (I) Wherein R 1 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrocarbon group having 0 to 6 carbon atoms, and x is 1 to Indicates an integer of 3.)
  • a rolling oil composition for metal working comprising 0.01 to 70% by mass of a sulfur-containing compound represented by the following formula: 2.
  • the rolling oil composition according to 1 above, wherein x of the sulfur-containing compound represented by the general formula (I) is 2; 3.
  • a rolling oil composition that does not cause surface damage even when rolling is performed at a high rolling reduction and contributes to a reduction in rolling load.
  • the rolling oil composition solves the problems related to odor while using a sulfur-based additive. Therefore, according to the rolling oil composition of the present invention, (1) the rolling reduction can be increased and productivity can be improved, (2) the rolling load can be reduced, and energy consumption can be suppressed, (3 ) The above-mentioned excellent rolling performance can be achieved without lowering the working environment.
  • the base oil used in the present invention is not particularly limited, and can be appropriately selected from mineral oil, synthetic oil and fat according to the purpose of use and use conditions.
  • Mineral oils include, for example, residual oil obtained by atmospheric distillation of paraffin-based crude oil, intermediate-based crude oil, or naphthenic-based crude oil, or distillate oil obtained by vacuum distillation of residual oil of atmospheric distillation or Examples include refined oils obtained by refining according to the method, such as solvent refined oil, hydrogenated refined oil, dewaxed oil, and clay-treated oil.
  • Synthetic oils include, for example, poly- ⁇ -olefins having 8 to 14 carbon atoms, olefin copolymers (for example, ethylene-propylene copolymers), branched olefins such as polybutene and polypropylene, hydrides thereof, and polyol esters ( Trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, and the like), alkylbenzene, and the like can be used.
  • Examples of fats and oils include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, and hydrides thereof.
  • the base oil one kind of the mineral oil may be used, two or more kinds may be used in combination, one kind of the synthetic oil may be used, or two or more kinds may be used in combination,
  • the fats and oils may be used singly or in combination of two or more.
  • 2 or more types chosen from mineral oil, synthetic oil, and fats and oils can also be used together.
  • the base oil used in the present invention preferably has a kinematic viscosity at 40 ° C. in the range of 3 to 30 mm 2 / s. When this kinematic viscosity is 3 mm 2 / s or more, the flash point becomes high and the risk of fire due to ignition is small. On the other hand, when it is 30 mm 2 / s or less, there is little possibility of winding deviation. From the above points, it is more preferably 5 to 20 mm 2 / s.
  • R 1 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms. If the carbon number exceeds 20, the solubility tends to be poor. Further, the larger the number of carbons within the above range, the effect of preventing evaporation is obtained, and the number of carbons is preferably 2-18, more preferably 4-18.
  • the hydrocarbon group may be linear, branched or aromatic, and may be saturated or unsaturated.
  • R 2 and R 3 are each independently a divalent hydrocarbon group having 0 to 6 carbon atoms. If the number of carbon atoms exceeds 6, the solubility tends to be poor, and the effects of the present invention are difficult to obtain.
  • the number of carbon atoms is preferably 1 to 4, more preferably 1.
  • the divalent hydrocarbon group may be linear, branched, or aromatic, and may be saturated or unsaturated. In the case of a hydrocarbon group having 0 carbon atoms, it means a state in which the carbon atom and sulfur atom of the ester group are directly bonded.
  • R 1 and R 4 or R 2 and R 3 may be the same or different, but are preferably the same for reasons of production.
  • x is any one of 1 to 3. When x is 4 or more, problems are likely to occur in terms of odor and corrosivity. Accordingly, any of the sulfur-containing compounds having x of 1 to 3 may be used alone, or a mixture thereof may be used.
  • the sulfur-containing compound represented by the general formula (I) It is preferable to use a sulfur-containing compound where x is 2 as the compound.
  • the amount of the sulfur-containing compound in which x is 2 is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more based on the total amount of the sulfur-containing compound represented by the general formula (I). .
  • the sulfur-containing compound represented by the general formula (I) can be produced by a conventionally known method, but the sulfur-containing compound wherein x is 2 is preferably produced by the method shown below. That is, as a raw material, general formula (II) and / or general formula (III) R 1 OOC-R 2 -SH (II) R 4 OOC—R 3 —SH (III) (In the formula, R 1 and R 4 , R 2 and R 3 are the same as described above.) Oxidative coupling is performed using a sulfur-containing carboxylic acid ester represented by: According to such a production method, the sulfur-containing compound represented by the general formula (I) where x is substantially 2 is produced.
  • R 1 OOC—R 2 —S—S—R 3 —COOR 4 R 1 OOC—R 2 —S—S—R 2 —COOR 1 , R 4 OOC—R 3 —S—S— R 3 —COOR 4 is produced.
  • a commonly used oxidizing agent can be used.
  • oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and easy to produce the target sulfur-containing compound.
  • sulfur-containing compound represented by the general formula (I) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, and bis (isopropoxycarbonyl).
  • Methyl) disulfide bis (n-butoxycarbonylmethyl) disulfide, bis (n-octoxycarbonylmethyl) disulfide, bis (n-dodecyloxycarbonylmethyl) disulfide, bis (cyclopropoxycarbonylmethyl) disulfide, 1,1-bis (1-methoxycarbonylethyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-propyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-butyl) disulfide, 1,1-bisulfide (1-methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-octyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-dodecyl) disulfide, 2,2- Bis (2-methoxycarbonyl-n-propyl) disulfide, 1,
  • one of the sulfur-containing compounds represented by the general formula (I) may be used alone, or two or more may be used in combination.
  • the blending amount is 0.01 to 70% by mass based on the total amount of the rolling oil composition. If the amount is less than 0.01% by mass, the effect of the present invention may not be obtained. If the amount exceeds 70% by mass, an effect commensurate with it cannot be obtained, and an odor is likely to be a problem. From the above viewpoint, 0.1 to 50% by mass is more preferable, and 0.5 to 30% by mass is particularly preferable.
  • the rolling oil composition of the present invention may contain an oily agent in addition to the sulfur compound.
  • oily agent include monoesters and diesters.
  • RCOOR '(IV) In the formula, R represents an alkyl group having 11 to 22 carbon atoms, R ′ represents an alkyl group having 1 to 25 carbon atoms, and the total carbon number of R and R ′ is 12 to 47.
  • the preferred total carbon number of the monoester represented by the general formula (IV) is in the range of 13 to 36.
  • Specific examples of the monoester include methyl stearate, butyl stearate, octyl stearate, octyl palmitate and the like. Among these, butyl stearate is preferred from the viewpoint of performance and availability. Is preferred.
  • the content of the monoester in the rolling oil composition is preferably in the range of 0.5 to 40% by mass. If it is the said range, the reduction effect of the gloss nonuniformity of a rolled sheet and the improvement effect of heat-scratch-proof performance will be acquired.
  • the preferable content of the monoester is in the range of 3 to 30% by mass, and more preferably in the range of 5 to 20% by mass.
  • the diester examples include a reaction product of an aliphatic dicarboxylic acid having 12 to 28 carbon atoms composed of a saturated or unsaturated branched hydrocarbon chain in the main skeleton and a linear aliphatic alcohol having 1 to 6 carbon atoms. It is preferable that the carbon number of the aliphatic dicarboxylic acid is in the above range from the viewpoint of heat scratch resistance and solubility. From the above viewpoint, the preferred carbon number is 14 to 24, and further 16 to 20.
  • the aliphatic dicarboxylic acid has a branched chain as the main skeleton. By having the branched chain, there is an advantage that the solubility of the diester in the base oil is improved and a rolling oil composition having desired performance can be easily obtained.
  • the aliphatic dicarboxylic acid either saturated or unsaturated can be used.
  • a compound represented by the following general formula (V) can be preferably exemplified.
  • k is an integer of 0 to 3
  • m and n are integers of 1 to 23, respectively, and the sum of k, m, and n is an integer of 8 to 24.
  • aliphatic dicarboxylic acid having 12 to 28 carbon atoms the main skeleton of which is a saturated or unsaturated branched hydrocarbon chain
  • diesters include compounds represented by the following chemical formulas. Can do.
  • aliphatic alcohols having 1 to 6 carbon atoms are used. Within this range, solubility is improved. From the above viewpoint, the preferred carbon number is 1 to 4. Further, the aliphatic alcohol needs to be linear. Those having a branched chain are inferior in heat scratch resistance. Specific examples of such a linear aliphatic alcohol include methanol, ethanol, n-propanol, and n-butanol.
  • the content of the diester in the rolling oil composition is preferably in the range of 0.5 to 30% by mass. If it is the said range, the improvement effect of heat-scratch-proof performance will be acquired.
  • the preferable content of the diester is in the range of 1 to 20% by mass, and particularly preferably in the range of 1 to 15% by mass.
  • the rolling oil composition of the present invention preferably contains a phenolic antioxidant.
  • a phenolic antioxidant By blending a phenolic antioxidant, there is an effect of suppressing oxidative deterioration of the rolling oil composition.
  • phenolic antioxidants include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol, and the like. Of these, 2,6-di-t-butyl-p-cresol is particularly preferred.
  • the blending amount of the phenol-based antioxidant is preferably in the range of 0.01 to 5% by mass, more preferably in the range of 0.1 to 1% by mass, based on the total amount of the rolling oil composition.
  • the rolling oil composition of this invention can mix
  • the rust inhibitor and corrosion inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, oxidized paraffin, alkyl polyoxyethylene ether, and the like.
  • the antifoaming agent include dimethylpolysiloxane and polyacrylate. These additives can be used singly or in combination of two or more. The amount of these additives is usually in the range of 0.1 to 10% by mass, preferably in the range of 0.1 to 5% by mass, based on the composition.
  • the viscosity of the rolling oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to 30 mm 2 / s, and more preferably 5 to 20 mm 2 / s.
  • the rolling oil composition may be used as it is, or an emulsion may be prepared by adding an emulsifier and water.
  • the emulsifier may be appropriately selected according to the purpose. For example, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or a mixture thereof can be used.
  • the rolling oil composition of the present invention can be preferably used as a rolling oil composition for metal working.
  • it is preferable to use it for rolling of various iron-based materials because it can be efficiently rolled even for hard materials, and an excellent surface appearance can be obtained.
  • it is used for rolling stainless steel.
  • it is preferable to use the rolling oil composition of the present invention as it is, and priority is given to efficiency as in the rolling of steel sheets. In such a case, it is preferable to prepare and use an emulsion.
  • Examples 1-7, Comparative Examples 1-6 As shown in Table 1, a sulfur-containing compound and other additives were blended with the base oil to obtain a rolling oil composition. The following evaluation tests were conducted using these as sample oils. The evaluation results are shown in Table 2. In Table 1, the compounding amount of each component when the total amount of the rolling oil composition is 100 parts by mass is expressed in parts by mass.
  • kinematic viscosity paraffinic mineral oils chalcogenides 8mm 2 / s 1 In the general formula (I), R 1 and R 4 is n- octyl group, R 2 and R 3 are CH 2 group, X Is a sulfur-containing compound in which R 2 is a sulfur-containing compound 2: a sulfur-containing compound in which R 1 and R 4 are n-butyl groups, R 2 and R 3 are CH 2 groups, and X is 2 in the general formula (I) 3 : Dimer sulfur-based compound of thiosalicylic acid n-octyl ester 4: Contains sulfur in general formula (I), wherein R 1 and R 4 are n-octyl groups, R 2 and R 3 are CH 2 groups, and X is 4 Compound sulfur-based compound 5: Polysulfide sulfur-based compound 6: Sulfurized olefin sulfur-based compound 7: Sulfurized oil and fat oil agent 1: Buty
  • Diester compound antioxidant represented by: DBPC (2,6-di-t-butyl-p-cresol)
  • the rolling oil composition of the present invention (1) rolling at a high pressure reduction rate is possible and productivity can be improved. (2) Since rolling load is reduced, energy consumption can be reduced. 3) The above-described excellent rolling performance can be achieved without lowering the working environment, and the present invention is suitably used in rolling.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Disclosed is a rolling oil composition obtained by blending a sulfur-containing compound represented by general formula (I) R1OOC-R2-SX-R3-COOR4 ⋅⋅⋅ (I) (wherein R1 and R4 independently represent a hydrocarbon group having 1-20 carbon atoms, R2 and R3 independently represent a hydrocarbon group having 0-6 carbon atoms, and x represents an integer of 1-3) into the base oil in an amount of 0.01-70% by mass based on the total amount of the composition. By using the rolling oil composition, no surface damage occurs even when rolling is performed at a high draft, and rolling load can be reduced.

Description

金属加工用圧延油組成物Rolling oil composition for metal working
　本発明は、金属加工用の圧延油組成物に関し、詳しくは、鉄系材料を圧延する際に好適に用いられる圧延油組成物に関する。 The present invention relates to a rolling oil composition for metal working, and in particular, relates to a rolling oil composition that is suitably used when rolling iron-based materials.
　金属又はその合金の板あるいは箔を圧延加工する際は、一般に、生産性や効率の向上および製品外観の向上が求められる。生産性や効率の向上に関連する技術としては、高い圧下率を達成する技術や、圧下力を低減化させる技術が挙げられ、製品外観の向上に関連する技術としては、ロールコーティングむらや表面損傷（ヒートスクラッチ）を回避するための技術が挙げられる。特に鉄系材料は硬く、またステンレス等においては優れた表面外観が求められることが多いため、これらの加工技術の向上を目的として様々な開発が行われており、これまでにステンレス等の圧延加工に用いられる圧延油が知られている。 When rolling a metal or its alloy plate or foil, generally, improvement in productivity and efficiency and improvement in product appearance are required. Technologies related to improving productivity and efficiency include technologies that achieve high rolling reduction and technologies that reduce rolling force. Technologies related to improving product appearance include roll coating unevenness and surface damage. A technique for avoiding (heat scratch) is mentioned. In particular, iron-based materials are hard, and stainless steel is often required to have an excellent surface appearance. Therefore, various developments have been made with the aim of improving these processing techniques. The rolling oil used for is known.
　例えば、特許文献１は、特定のジカルボン酸と特定のアルコールとの反応生成物であるジエステルを配合してなる金属加工用潤滑油を開示する。特許文献２および３は、特定のジエステルと特定のアルコールを含むステンレス用冷間圧延油を開示する。 For example, Patent Document 1 discloses a lubricating oil for metal working formed by blending a diester that is a reaction product of a specific dicarboxylic acid and a specific alcohol. Patent Documents 2 and 3 disclose a cold rolling oil for stainless steel containing a specific diester and a specific alcohol.
　上記のようにこれまでに様々な圧延油が知られているが、これらは近年の圧延加工に関する要求性能を基準にすると必ずしも十分な性能を有するものではなかった。特に、優れた生産性と優れた製品外観を両立させることは困難であり、例えば、従来の圧延油を用いて高い圧下率で加工を行うと表面損傷が発生しやすいという問題があった。したがって、圧延油の性能向上が望まれている。 As described above, various rolling oils have been known so far, but these have not always had sufficient performance on the basis of the required performance related to the rolling process in recent years. In particular, it is difficult to achieve both excellent productivity and excellent product appearance. For example, when processing is performed at a high reduction rate using conventional rolling oil, there is a problem that surface damage is likely to occur. Therefore, the performance improvement of rolling oil is desired.
特開昭６２－２０１９９４号公報JP-A-62-201994 特開２００１－１７２６６２号公報JP 2001-172661 A 特開２００１－１７２６６３号公報JP 2001-172663 A
　本発明はこのような状況下でなされたものであり、優れた圧延性能を有する圧延油組成物、すなわち高い圧下率で圧延加工を行っても表面損傷が発生せず、また圧延荷重の低減化に寄与する圧延油組成物を提供することを目的とするものである。 The present invention has been made under such circumstances, a rolling oil composition having excellent rolling performance, that is, no surface damage occurs even when rolling is performed at a high rolling reduction, and the rolling load is reduced. An object of the present invention is to provide a rolling oil composition that contributes to the above.
　本発明者は、鋭意研究を重ねた結果、特定の硫黄含有化合物を添加剤として使用することで上記の課題が解決されることを見出した。さらに、一般に硫黄含有化合物は油に対する溶解性が低いという問題があり、また圧延加工の際にはミストが発生しやすく、悪臭により作業環境が悪化するという問題があるが、これらの問題も硫黄含有化合物を特定化することで解決できることを見出し、本発明を完成するに至った。
　すなわち、本発明は以下の圧延油組成物を提供するものである。
１．　基油に、一般式（Ｉ）
Ｒ1ＯＯＣ－Ｒ2－Ｓx－Ｒ3－ＣＯＯＲ4　・・・（Ｉ）
（式中、Ｒ1及びＲ4はそれぞれ独立に炭素数１～２０の炭化水素基であり、Ｒ2及びＲ3はそれぞれ独立に炭素数０～６の炭化水素基であり、ｘは１～３の整数を示す。）
で表される硫黄含有化合物を組成物全量基準で０．０１～７０質量％配合してなる金属加工用の圧延油組成物、
２．　一般式（Ｉ）で表される硫黄含有化合物のｘが２であることを特徴とする、上記１に記載の圧延油組成物、
３．　金属加工が鉄系材料の加工であることを特徴とする、上記１または２に記載の圧延油組成物、
４．　金属加工がステンレスの加工であることを特徴とする、上記１または２に記載の圧延油組成物。 As a result of intensive studies, the present inventor has found that the above problem can be solved by using a specific sulfur-containing compound as an additive. Furthermore, in general, sulfur-containing compounds have a problem of low solubility in oil, and mist is likely to be generated during rolling, and the working environment is deteriorated due to a bad odor. The inventors have found that the problem can be solved by specifying a compound, and have completed the present invention.
That is, the present invention provides the following rolling oil composition.
1. In the base oil, the general formula (I)
R 1 OOC—R 2 —S x —R 3 —COOR 4 (I)
Wherein R 1 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrocarbon group having 0 to 6 carbon atoms, and x is 1 to Indicates an integer of 3.)
A rolling oil composition for metal working, comprising 0.01 to 70% by mass of a sulfur-containing compound represented by the following formula:
2. The rolling oil composition according to 1 above, wherein x of the sulfur-containing compound represented by the general formula (I) is 2;
3. The rolling oil composition according to 1 or 2 above, wherein the metal processing is processing of an iron-based material,
4). 3. The rolling oil composition as described in 1 or 2 above, wherein the metal processing is processing of stainless steel.
　本発明によれば、高い圧下率で圧延加工を行っても表面損傷が発生せず、また圧延荷重の低減化に寄与する圧延油組成物が提供される。また当該圧延油組成物は硫黄系添加剤を使用しながらも、臭気に関する問題を解消したものである。
　したがって本発明の圧延油組成物によれば、（１）圧下率を高めることができ、生産性が向上する、（２）圧延荷重を低減化できるため、エネルギー消費を抑えることができる、（３）上記の優れた圧延性能を作業環境の低下を伴わずに達成することができる等の効果が得られる。 According to the present invention, there is provided a rolling oil composition that does not cause surface damage even when rolling is performed at a high rolling reduction and contributes to a reduction in rolling load. In addition, the rolling oil composition solves the problems related to odor while using a sulfur-based additive.
Therefore, according to the rolling oil composition of the present invention, (1) the rolling reduction can be increased and productivity can be improved, (2) the rolling load can be reduced, and energy consumption can be suppressed, (3 ) The above-mentioned excellent rolling performance can be achieved without lowering the working environment.
　本発明で用いる基油としては特に限定されず、使用目的や使用条件などに応じて鉱油、合成油および油脂の中から適宜選ぶことができる。鉱油としては、例えば、パラフィン基系原油、中間基系原油あるいはナフテン基系原油を常圧蒸留した残渣油、あるいは常圧蒸留の残渣油を減圧蒸留して得られる留出油、またはこれを常法にしたがって精製することによって得られる精製油、例えば、溶剤精製油、水添精製油、脱ロウ処理油、白土処理油等を挙げることができる。合成油としては、例えば、炭素数８～１４のポリ－α－オレフィン、オレフィンコポリマー（例えば、エチレン－プロピレンコポリマーなど）、あるいはポリブテン、ポリプロピレン等の分岐オレフィンやこれらの水素化物、さらにはポリオールエステル（トリメチロールプロパンの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステルなど）等のエステル系化合物、アルキルベンゼン等を用いることができる。油脂としては、例えば、牛脂、豚脂、大豆油、菜種油、米ぬか油、ヤシ油、パーム油、パーム核油、あるいはこれらの水素化物が挙げられる。 The base oil used in the present invention is not particularly limited, and can be appropriately selected from mineral oil, synthetic oil and fat according to the purpose of use and use conditions. Mineral oils include, for example, residual oil obtained by atmospheric distillation of paraffin-based crude oil, intermediate-based crude oil, or naphthenic-based crude oil, or distillate oil obtained by vacuum distillation of residual oil of atmospheric distillation or Examples include refined oils obtained by refining according to the method, such as solvent refined oil, hydrogenated refined oil, dewaxed oil, and clay-treated oil. Synthetic oils include, for example, poly-α-olefins having 8 to 14 carbon atoms, olefin copolymers (for example, ethylene-propylene copolymers), branched olefins such as polybutene and polypropylene, hydrides thereof, and polyol esters ( Trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, and the like), alkylbenzene, and the like can be used. Examples of fats and oils include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, and hydrides thereof.
　本発明においては、基油として、前記鉱油を一種用いてもよいし、二種以上組み合わせて用いてもよく、前記合成油を一種用いてもよいし、二種以上組み合わせて用いてもよく、前記油脂を一種用いてもよいし、二種以上組み合わせて用いてもよい。また、鉱油、合成油および油脂から選ばれる二種以上を併用することもできる。本発明で用いる基油は、４０℃における動粘度が３～３０ｍｍ2／ｓの範囲にあるものが好ましい。この動粘度が３ｍｍ2／ｓ以上であると引火点は高いものとなり、引火による火災の危険性は少ない。一方、３０ｍｍ2／ｓ以下であると、巻きズレが発生する恐れが少ない。以上の点から、より好ましくは、５～２０ｍｍ2／ｓである。 In the present invention, as the base oil, one kind of the mineral oil may be used, two or more kinds may be used in combination, one kind of the synthetic oil may be used, or two or more kinds may be used in combination, The fats and oils may be used singly or in combination of two or more. Moreover, 2 or more types chosen from mineral oil, synthetic oil, and fats and oils can also be used together. The base oil used in the present invention preferably has a kinematic viscosity at 40 ° C. in the range of 3 to 30 mm 2 / s. When this kinematic viscosity is 3 mm 2 / s or more, the flash point becomes high and the risk of fire due to ignition is small. On the other hand, when it is 30 mm 2 / s or less, there is little possibility of winding deviation. From the above points, it is more preferably 5 to 20 mm 2 / s.
　本発明の圧延油組成物においては、一般式（Ｉ）
Ｒ1ＯＯＣ－Ｒ2－Ｓx－Ｒ3－ＣＯＯＲ4　・・・　（Ｉ）
で表される硫黄含有化合物が使用される。 In the rolling oil composition of the present invention, the general formula (I)
R 1 OOC—R 2 —S x —R 3 —COOR 4 (I)
A sulfur-containing compound represented by is used.
　一般式（Ｉ）中、Ｒ1及びＲ4はそれぞれ独立に炭素数１～２０の炭化水素基である。炭素数が２０を上回ると溶解性が劣りやすい。また上記範囲内で炭素数が多いほうが蒸発を防止する効果が得られ、好ましくは炭素数２～１８、より好ましくは４～１８である。当該炭化水素基は直鎖状、分岐状、芳香族環状のいずれであってもよく、また飽和であっても不飽和であってもよい。Ｒ2及びＲ3はそれぞれ独立に炭素数０～６の２価の炭化水素基である。炭素数が６を上回ると溶解性が劣りやすく、また本発明の効果が得られにくい。炭素数は、好ましくは１～４、より好ましくは１である。当該２価の炭化水素基は直鎖状、分岐状、芳香族環状のいずれであってもよく、また飽和であっても不飽和であってもよい。なお、炭素数が０の炭化水素基の場合は、エステル基の炭素原子と硫黄原子が直接結合する状態のことをいう。Ｒ1とＲ4やＲ2とＲ3は同一であっても異なっていてもよいが、製造上の理由から同一であることが好ましい。ｘは１～３のいずれかである。ｘが４以上のときは臭気や腐食性の点で問題が生じ易い。したがって、ｘが１～３の硫黄含有化合物のいずれかを単独で使用してもよく、またこれらの混合物を使用してもよいが、上記観点から、一般式（Ｉ）で表される硫黄含有化合物として、ｘが２の硫黄含有化合物を使用することが好ましい。ｘが２の硫黄含有化合物の量は、一般式（Ｉ）で表される硫黄含有化合物全量に対して、７０質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が特に好ましい。 In general formula (I), R 1 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms. If the carbon number exceeds 20, the solubility tends to be poor. Further, the larger the number of carbons within the above range, the effect of preventing evaporation is obtained, and the number of carbons is preferably 2-18, more preferably 4-18. The hydrocarbon group may be linear, branched or aromatic, and may be saturated or unsaturated. R 2 and R 3 are each independently a divalent hydrocarbon group having 0 to 6 carbon atoms. If the number of carbon atoms exceeds 6, the solubility tends to be poor, and the effects of the present invention are difficult to obtain. The number of carbon atoms is preferably 1 to 4, more preferably 1. The divalent hydrocarbon group may be linear, branched, or aromatic, and may be saturated or unsaturated. In the case of a hydrocarbon group having 0 carbon atoms, it means a state in which the carbon atom and sulfur atom of the ester group are directly bonded. R 1 and R 4 or R 2 and R 3 may be the same or different, but are preferably the same for reasons of production. x is any one of 1 to 3. When x is 4 or more, problems are likely to occur in terms of odor and corrosivity. Accordingly, any of the sulfur-containing compounds having x of 1 to 3 may be used alone, or a mixture thereof may be used. From the above viewpoint, the sulfur-containing compound represented by the general formula (I) It is preferable to use a sulfur-containing compound where x is 2 as the compound. The amount of the sulfur-containing compound in which x is 2 is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more based on the total amount of the sulfur-containing compound represented by the general formula (I). .
　一般式（Ｉ）で表される硫黄含有化合物は従来公知の方法で製造することができるが、ｘが２の硫黄含有化合物は以下に示す方法で製造することが好ましい。すなわち、原料として、一般式（ＩＩ）及び／又は一般式（ＩＩＩ）
　Ｒ1ＯＯＣ－Ｒ2－ＳＨ　　・・・（ＩＩ）
　Ｒ4ＯＯＣ－Ｒ3－ＳＨ　　・・・（ＩＩＩ）
（式中、Ｒ1及びＲ4、Ｒ2及びＲ3は前記と同じである。）
で表される硫黄含有カルボン酸エステルを用い、酸化カップリングする。このような製造方法によれば、実質的にｘが２の一般式（Ｉ）で表される硫黄含有化合物が製造される。
　具体的には、Ｒ1ＯＯＣ－Ｒ2－Ｓ－Ｓ－Ｒ3－ＣＯＯＲ4、Ｒ1ＯＯＣ－Ｒ2－Ｓ－Ｓ－Ｒ2－ＣＯＯＲ1、Ｒ4ＯＯＣ－Ｒ3－Ｓ－Ｓ－Ｒ3－ＣＯＯＲ4が製造される。
　上記酸化カップリングにおいて使用する酸化剤としては、通常使用される酸化剤が使用でき、例えば、酸素、過酸化水素、ハロゲン（ヨウ素、臭素）、次亜ハロゲン酸（塩）、スルホキシド（ジメチルスルホキシド、ジイソプロピルスルホキシド）、酸化マンガン（ＩＶ）等が挙げられる。これらの酸化剤の中で酸素、過酸化水素、ジメチルスルホキシドが安価であり、目的の硫黄含有化合物の製造が容易であることから好ましい。 The sulfur-containing compound represented by the general formula (I) can be produced by a conventionally known method, but the sulfur-containing compound wherein x is 2 is preferably produced by the method shown below. That is, as a raw material, general formula (II) and / or general formula (III)
R 1 OOC-R 2 -SH (II)
R 4 OOC—R 3 —SH (III)
(In the formula, R 1 and R 4 , R 2 and R 3 are the same as described above.)
Oxidative coupling is performed using a sulfur-containing carboxylic acid ester represented by: According to such a production method, the sulfur-containing compound represented by the general formula (I) where x is substantially 2 is produced.
Specifically, R 1 OOC—R 2 —S—S—R 3 —COOR 4 , R 1 OOC—R 2 —S—S—R 2 —COOR 1 , R 4 OOC—R 3 —S—S— R 3 —COOR 4 is produced.
As the oxidizing agent used in the oxidative coupling, a commonly used oxidizing agent can be used. For example, oxygen, hydrogen peroxide, halogen (iodine, bromine), hypohalous acid (salt), sulfoxide (dimethyl sulfoxide, Diisopropyl sulfoxide), manganese oxide (IV) and the like. Among these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and easy to produce the target sulfur-containing compound.
　前記一般式（Ｉ）で表される硫黄含有化合物の具体例としては、ビス（メトキシカルボニルメチル）ジスルフィド、ビス（エトキシカルボニルメチル）ジスルフィド、ビス（ｎ－プロポキシカルボニルメチル）ジスルフィド、ビス（イソプロポキシカルボニルメチル）ジスルフィド、ビス（ｎ－ブトキシカルボニルメチル）ジスルフィド、ビス（ｎ－オクトキシカルボニルメチル）ジスルフィド、ビス（ｎ－ドデシルオキシカルボニルメチル）ジスルフィド、ビス（シクロプロポキシカルボニルメチル）ジスルフィド、１，１－ビス（１－メトキシカルボニルエチル）ジスルフィド、１，１－ビス（１－メトキシカルボニル－ｎ－プロピル）ジスルフィド、１，１－ビス（１－メトキシカルボニル－ｎ－ブチル）ジスルフィド、１，１－ビス（１－メトキシカルボニル－ｎ－ヘキシル）ジスルフィド、１，１－ビス（１－メトキシカルボニル－ｎ－オクチル）ジスルフィド、１，１－ビス（１－メトキシカルボニル－ｎ－ドデシル）ジスルフィド、２，２－ビス（２－メトキシカルボニル－ｎ－プロピル）ジスルフィド、１，１－ビス（２－メトキシカルボニルエチル）ジスルフィド、１，１－ビス（２－エトキシカルボニルエチル）ジスルフィド、１，１－ビス（２－ｎ－プロポキシカルボニルエチル）ジスルフィド、１，１－ビス（２－イソプロポキシカルボニルエチル）ジスルフィド、１，１－ビス（２－シクロプロポキシカルボニルエチル）ジスルフィド、１，１－ビス（２－メトキシカルボニル－ｎ－プロピル）ジスルフィド、１，１－ビス（２－メトキシカルボニル－ｎ－ブチル）ジスルフィド、１，１－ビス（２－メトキシカルボニル－ｎ－ヘキシル）ジスルフィド、１，１－ビス（２－メトキシカルボニル－ｎ－プロピル）ジスルフィド、２，２－ビス（３－メトキシカルボニル－ｎ－ペンチル）ジスルフィド、チオサリチル酸ブチルエステルの二量体、チオサリチル酸ｎ－オクチルエステルの二量体などを挙げることができる。 Specific examples of the sulfur-containing compound represented by the general formula (I) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, and bis (isopropoxycarbonyl). Methyl) disulfide, bis (n-butoxycarbonylmethyl) disulfide, bis (n-octoxycarbonylmethyl) disulfide, bis (n-dodecyloxycarbonylmethyl) disulfide, bis (cyclopropoxycarbonylmethyl) disulfide, 1,1-bis (1-methoxycarbonylethyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-propyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-butyl) disulfide, 1,1-bisulfide (1-methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-octyl) disulfide, 1,1-bis (1-methoxycarbonyl-n-dodecyl) disulfide, 2,2- Bis (2-methoxycarbonyl-n-propyl) disulfide, 1,1-bis (2-methoxycarbonylethyl) disulfide, 1,1-bis (2-ethoxycarbonylethyl) disulfide, 1,1-bis (2-n -Propoxycarbonylethyl) disulfide, 1,1-bis (2-isopropoxycarbonylethyl) disulfide, 1,1-bis (2-cyclopropoxycarbonylethyl) disulfide, 1,1-bis (2-methoxycarbonyl-n- Propyl) disulfide, 1,1-bis (2-methoxycarbonyl) n-butyl) disulfide, 1,1-bis (2-methoxycarbonyl-n-hexyl) disulfide, 1,1-bis (2-methoxycarbonyl-n-propyl) disulfide, 2,2-bis (3-methoxycarbonyl) -N-pentyl) disulfide, dimer of thiosalicylic acid butyl ester, dimer of thiosalicylic acid n-octyl ester, and the like.
　本発明においては、一般式（Ｉ）で表される硫黄含有化合物の一種を単独で用いてもよく、二種以上を併用してもよい。その配合量は圧延油組成物全量基準で０．０１～７０質量％である。０．０１質量％を下回ると本発明の効果が得られないことがあり、７０質量％を上回るとそれに見合った効果が得られず、また臭気の点で問題になり易い。上記観点から０．１～５０質量％がより好ましく、０．５～３０質量％が特に好ましい。 In the present invention, one of the sulfur-containing compounds represented by the general formula (I) may be used alone, or two or more may be used in combination. The blending amount is 0.01 to 70% by mass based on the total amount of the rolling oil composition. If the amount is less than 0.01% by mass, the effect of the present invention may not be obtained. If the amount exceeds 70% by mass, an effect commensurate with it cannot be obtained, and an odor is likely to be a problem. From the above viewpoint, 0.1 to 50% by mass is more preferable, and 0.5 to 30% by mass is particularly preferable.
　本発明の圧延油組成物は、上記硫黄化合物の他に油性剤を含有してもよい。油性剤としては、モノエステルやジエステルが挙げられる。 The rolling oil composition of the present invention may contain an oily agent in addition to the sulfur compound. Examples of the oily agent include monoesters and diesters.
　上記モノエステルとしては、例えば一般式（ＩＶ）で表される化合物を挙げることができる。
ＲＣＯＯＲ’　　　　　　　　　　　　　　・・・（ＩＶ）
式中、Ｒは炭素数１１～２２のアルキル基、Ｒ’は炭素数１～２５のアルキル基を示し、ＲとＲ’の合計炭素数は１２～４７である。
　前記一般式（ＩＶ）で表されるモノエステルの好ましい全炭素数は１３～３６の範囲である。該モノエステルの具体例としては、ステアリン酸メチル、ステアリン酸ブチル、ステアリン酸オクチル、パルミチン酸オクチルなどが好ましく挙げられるが、これらの中で、性能及び入手の容易さなどの点から、ステアリン酸ブチルが好ましい。 As said monoester, the compound represented, for example by general formula (IV) can be mentioned.
RCOOR '(IV)
In the formula, R represents an alkyl group having 11 to 22 carbon atoms, R ′ represents an alkyl group having 1 to 25 carbon atoms, and the total carbon number of R and R ′ is 12 to 47.
The preferred total carbon number of the monoester represented by the general formula (IV) is in the range of 13 to 36. Specific examples of the monoester include methyl stearate, butyl stearate, octyl stearate, octyl palmitate and the like. Among these, butyl stearate is preferred from the viewpoint of performance and availability. Is preferred.
　圧延油組成物における該モノエステルの含有量は、０．５～４０質量％の範囲が好ましい。上記範囲であれば圧延板の光沢むらの低減効果及び耐ヒートスクラッチ性能の向上効果が得られる。以上の点から、該モノエステルの好ましい含有量は３～３０質量％の範囲であり、さらに５～２０質量％の範囲が好ましい。 The content of the monoester in the rolling oil composition is preferably in the range of 0.5 to 40% by mass. If it is the said range, the reduction effect of the gloss nonuniformity of a rolled sheet and the improvement effect of heat-scratch-proof performance will be acquired. In view of the above, the preferable content of the monoester is in the range of 3 to 30% by mass, and more preferably in the range of 5 to 20% by mass.
　上記ジエステルとしては、主骨格が飽和又は不飽和の分岐炭化水素鎖からなる炭素数１２～２８の脂肪族ジカルボン酸と炭素数１～６の直鎖脂肪族アルコールとの反応生成物が挙げられる。
　該脂肪族ジカルボン酸の炭素数が上記範囲であると、耐ヒートスクラッチ性能や溶解性の点で好ましい。上記観点から好ましい炭素数は１４～２４であり、さらには１６～２０である。
　また、該脂肪族ジカルボン酸は主骨格として分岐鎖を有する。分岐鎖を有することにより、ジエステルの基油に対する溶解性が良くなり、所望の性能を有する圧延油組成物が容易に得られるという利点がある。
　本発明においては、前記脂肪族ジカルボン酸として、飽和及び不飽和のいずれも用いることができ、例えば下記一般式（Ｖ）で表される化合物を好ましく挙げることができる。 Examples of the diester include a reaction product of an aliphatic dicarboxylic acid having 12 to 28 carbon atoms composed of a saturated or unsaturated branched hydrocarbon chain in the main skeleton and a linear aliphatic alcohol having 1 to 6 carbon atoms.
It is preferable that the carbon number of the aliphatic dicarboxylic acid is in the above range from the viewpoint of heat scratch resistance and solubility. From the above viewpoint, the preferred carbon number is 14 to 24, and further 16 to 20.
The aliphatic dicarboxylic acid has a branched chain as the main skeleton. By having the branched chain, there is an advantage that the solubility of the diester in the base oil is improved and a rolling oil composition having desired performance can be easily obtained.
In the present invention, as the aliphatic dicarboxylic acid, either saturated or unsaturated can be used. For example, a compound represented by the following general formula (V) can be preferably exemplified.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式中、ｋは０～３の整数、ｍ及びｎは、それぞれ１～２３の整数を示し、ｋ、ｍ及びｎの合計は８～２４の整数である。 In the formula, k is an integer of 0 to 3, m and n are integers of 1 to 23, respectively, and the sum of k, m, and n is an integer of 8 to 24.
　ジエステルの製造に用いられる、主骨格が飽和又は不飽和の分岐状炭化水素鎖からなる炭素数１２～２８の脂肪族ジカルボン酸の具体例としては、下記の化学式で表される化合物などを挙げることができる。 Specific examples of the aliphatic dicarboxylic acid having 12 to 28 carbon atoms, the main skeleton of which is a saturated or unsaturated branched hydrocarbon chain, used for the production of diesters include compounds represented by the following chemical formulas. Can do.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一方、脂肪族アルコールとしては、炭素数１～６のものが用いられる。この範囲であると溶解性が向上する。上記観点から好ましい炭素数は１～４である。また、該脂肪族アルコールは直鎖状であることが必要である。分岐鎖を有するものでは、耐ヒートスクラッチ性能が劣る。このような直鎖状脂肪族アルコールの具体例としては、メタノール、エタノール、ｎ－プロパノール、ｎ－ブタノールなどを挙げることができる。 On the other hand, aliphatic alcohols having 1 to 6 carbon atoms are used. Within this range, solubility is improved. From the above viewpoint, the preferred carbon number is 1 to 4. Further, the aliphatic alcohol needs to be linear. Those having a branched chain are inferior in heat scratch resistance. Specific examples of such a linear aliphatic alcohol include methanol, ethanol, n-propanol, and n-butanol.
　圧延油組成物における該ジエステルの含有量は、０．５～３０質量％の範囲が好ましい。上記範囲であれば耐ヒートスクラッチ性能の向上効果が得られる。以上の点から、該ジエステルの好ましい含有量は１～２０質量％の範囲であり、特に１～１５質量％の範囲が好ましい。 The content of the diester in the rolling oil composition is preferably in the range of 0.5 to 30% by mass. If it is the said range, the improvement effect of heat-scratch-proof performance will be acquired. In view of the above, the preferable content of the diester is in the range of 1 to 20% by mass, and particularly preferably in the range of 1 to 15% by mass.
　本発明の圧延油組成物は、フェノール系酸化防止剤を配合することが好ましい。フェノール系酸化防止剤を配合することにより、圧延油組成物の酸化劣化の抑制の効果がある。
　フェノール系酸化防止剤としては、２，６－ジ－ｔ－ブチルフェノール、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、２，４－ジメチル－６－ｔ－ブチルフェノール、などが挙げられ、これらのうち、２，６－ジ－ｔ－ブチル－ｐ－クレゾールが特に好ましい。フェノール系酸化防止剤の配合量は、圧延油組成物全量基準で０．０１～５質量％の範囲が好ましく、さらには０．１～１質量％の範囲が好ましい。 The rolling oil composition of the present invention preferably contains a phenolic antioxidant. By blending a phenolic antioxidant, there is an effect of suppressing oxidative deterioration of the rolling oil composition.
Examples of phenolic antioxidants include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol, and the like. Of these, 2,6-di-t-butyl-p-cresol is particularly preferred. The blending amount of the phenol-based antioxidant is preferably in the range of 0.01 to 5% by mass, more preferably in the range of 0.1 to 1% by mass, based on the total amount of the rolling oil composition.
　さらに、本発明の圧延油組成物は、所望に応じ、本発明の目的を損なわない範囲で、防錆剤、腐食防止剤、消泡剤等の各種添加剤を配合することができる。
　防錆剤及び腐食防止剤としては、例えば、脂肪酸、アルケニルコハク酸ハーフエステル、脂肪酸セッケン、アルキルスルホン酸塩、脂肪酸アミン、酸化パラフィン、アルキルポリオキシエチレンエーテル等が挙げられる。
　消泡剤としては、例えばジメチルポリシロキサン，ポリアクリレート等が挙げられる。
　これらの添加剤は、それぞれ一種単独で、又は二種以上を混合して使用することができる。また、これらの添加剤の配合量は、通常、それぞれ組成物基準で０．１～１０質量％の範囲であり、好ましくは０．１～５質量％の範囲である。 Furthermore, the rolling oil composition of this invention can mix | blend various additives, such as a rust inhibitor, a corrosion inhibitor, and an antifoamer, in the range which does not impair the objective of this invention as desired.
Examples of the rust inhibitor and corrosion inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, oxidized paraffin, alkyl polyoxyethylene ether, and the like.
Examples of the antifoaming agent include dimethylpolysiloxane and polyacrylate.
These additives can be used singly or in combination of two or more. The amount of these additives is usually in the range of 0.1 to 10% by mass, preferably in the range of 0.1 to 5% by mass, based on the composition.
　本発明の圧延油組成物の粘度については特に制限はないが、４０℃での動粘度が３～３０ｍｍ2／ｓであることが好ましく、５～２０ｍｍ2／ｓであることがより好ましい。 The viscosity of the rolling oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to 30 mm 2 / s, and more preferably 5 to 20 mm 2 / s.
　本発明の圧延油組成物を使用する際は、当該圧延油組成物をそのままの状態で用いてもよいし、乳化剤および水を加えてエマルジョンを調製して用いてもよい。乳化剤としては、目的に合わせて適宜選択すればよく、例えば、アニオン系乳化剤、カチオン系乳化剤、ノニオン系乳化剤、またはこれらの混合物を使用することができる。 When using the rolling oil composition of the present invention, the rolling oil composition may be used as it is, or an emulsion may be prepared by adding an emulsifier and water. The emulsifier may be appropriately selected according to the purpose. For example, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or a mixture thereof can be used.
　本発明の圧延油組成物は、金属加工用の圧延油組成物として好ましく使用できる。特に、本発明の圧延油組成物を使用すると硬い材料に対しても効率よく圧延加工をすることができることから各種鉄系材料の圧延加工に用いることが好ましく、優れた表面外観が得られることからステンレスの圧延加工に用いることが最も好ましい。
　一般にステンレスの圧延加工のように優れた表面外観が必要な場合は、本発明の圧延油組成物をそのままの状態で使用することが好ましく、また、鋼板の圧延加工のように効率が優先される場合は、エマルジョンを調製して用いることが好ましい。 The rolling oil composition of the present invention can be preferably used as a rolling oil composition for metal working. In particular, when the rolling oil composition of the present invention is used, it is preferable to use it for rolling of various iron-based materials because it can be efficiently rolled even for hard materials, and an excellent surface appearance can be obtained. Most preferably, it is used for rolling stainless steel.
In general, when excellent surface appearance is required as in stainless steel rolling, it is preferable to use the rolling oil composition of the present invention as it is, and priority is given to efficiency as in the rolling of steel sheets. In such a case, it is preferable to prepare and use an emulsion.
　次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１～７、比較例１～６
　第１表に示すように、基油に硫黄含有化合物およびその他添加剤を配合し、圧延油組成物を得た。これらを試料油として以下に示す評価試験を行った。評価結果を第２表に示す。
　なお、第１表においては圧延油組成物全量を１００質量部としたときの各成分の配合量を質量部で表した。 Examples 1-7, Comparative Examples 1-6
As shown in Table 1, a sulfur-containing compound and other additives were blended with the base oil to obtain a rolling oil composition. The following evaluation tests were conducted using these as sample oils. The evaluation results are shown in Table 2.
In Table 1, the compounding amount of each component when the total amount of the rolling oil composition is 100 parts by mass is expressed in parts by mass.
（１）限界圧下率
　ロール径４０ｍｍ（ロール表面粗さＲａ０．１０μｍ）のワークロールを用い、圧延速度１００ｍ／ｍｉｎで圧延加工を行った。圧下率を２０％から段階的に上昇させ、ヒートスクラッチが発生し始めるまで実施し、ヒートスクラッチが発生しない最大の圧下率を限界圧下率とした。
　なお、本評価および下記の「圧下率２５％の時の圧延荷重」の評価において、材料には以下のステンレスを用いた。
ＳＵＳ３０４：コイルサイズ（０．６ｍｍ厚、５０ｍｍ幅） (1) Limit rolling reduction Using a work roll having a roll diameter of 40 mm (roll surface roughness Ra 0.10 μm), rolling was performed at a rolling speed of 100 m / min. The rolling reduction was increased stepwise from 20% until the start of heat scratching, and the maximum rolling reduction at which no heat scratching occurred was defined as the critical rolling reduction.
In this evaluation and the following evaluation of “rolling load at a rolling reduction of 25%”, the following stainless steel was used as a material.
SUS304: Coil size (0.6mm thickness, 50mm width)
（２）圧下率２５％の時の圧延荷重
　圧下率２５％で圧延するために要する圧延荷重を調べた。 (2) Rolling load at a rolling reduction of 25% The rolling load required for rolling at a rolling reduction of 25% was examined.
（３）臭気試験
　ＪＩＳ　Ｋ２２３１に定める流動パラフィンで試料油を希釈し、不快な臭気を感じるか否かを下記基準に基づき評価した。パネラー５人で評価しその中央値を第２表に示す。
１（僅かな臭気）：１０００倍希釈で硫黄臭がない。
２（弱い臭気）：１０００倍希釈で硫黄臭があり、５０００倍希釈で硫黄臭がない。
３（強い臭気）：５０００倍希釈で硫黄臭がある。 (3) Odor test The sample oil was diluted with liquid paraffin defined in JIS K2231, and whether or not an unpleasant odor was felt was evaluated based on the following criteria. Table 2 shows the median values evaluated by five panelists.
1 (slight odor): No sulfur odor at 1000-fold dilution.
2 (weak odor): Sulfur smell at 1000 times dilution, no sulfur odor at 5000 times dilution.
3 (strong odor): There is a sulfur odor at a dilution of 5000 times.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
基油：４０℃動粘度が８ｍｍ2／ｓのパラフィン系鉱油
硫黄系化合物１：一般式（Ｉ）中、Ｒ1およびＲ4がn－オクチル基、Ｒ2およびＲ3がＣＨ2基、Ｘが２の硫黄含有化合物
硫黄系化合物２：一般式（Ｉ）中、Ｒ1およびＲ4がn－ブチル基、Ｒ2およびＲ3がＣＨ2基、Ｘが２の硫黄含有化合物
硫黄系化合物３：チオサリチル酸ｎ－オクチルエステルの２量体
硫黄系化合物４：一般式（Ｉ）中、Ｒ1およびＲ4がn－オクチル基、Ｒ2およびＲ3がＣＨ2基、Ｘが４の硫黄含有化合物
硫黄系化合物５：ポリサルファイド
硫黄系化合物６：硫化オレフィン
硫黄系化合物７：硫化油脂
油性剤１：ステアリン酸ブチル
油性剤２：以下の式 Base Oil: 40 ° C. kinematic viscosity paraffinic mineral oils chalcogenides 8mm 2 / s 1: In the general formula (I), R 1 and R 4 is n- octyl group, R 2 and R 3 are CH 2 group, X Is a sulfur-containing compound in which R 2 is a sulfur-containing compound 2: a sulfur-containing compound in which R 1 and R 4 are n-butyl groups, R 2 and R 3 are CH 2 groups, and X is 2 in the general formula (I) 3 : Dimer sulfur-based compound of thiosalicylic acid n-octyl ester 4: Contains sulfur in general formula (I), wherein R 1 and R 4 are n-octyl groups, R 2 and R 3 are CH 2 groups, and X is 4 Compound sulfur-based compound 5: Polysulfide sulfur-based compound 6: Sulfurized olefin sulfur-based compound 7: Sulfurized oil and fat oil agent 1: Butyl stearate oil agent 2: The following formula
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
で表されるジエステル化合物
酸化防止剤：ＤＢＰＣ（２，６－ジ－ｔ－ブチル－ｐ－クレゾール） Diester compound antioxidant represented by: DBPC (2,6-di-t-butyl-p-cresol)
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　本発明の圧延油組成物によれば、（１）高圧下率での圧延加工が可能になり生産性が向上できる、（２）圧延荷重が低下するため、エネルギー消費の低減化ができる、（３）上記の優れた圧延性能を作業環境の低下を伴わずに達成することができる等の効果が得られるものであり、本発明は圧延加工において好適に用いられる。 According to the rolling oil composition of the present invention, (1) rolling at a high pressure reduction rate is possible and productivity can be improved. (2) Since rolling load is reduced, energy consumption can be reduced. 3) The above-described excellent rolling performance can be achieved without lowering the working environment, and the present invention is suitably used in rolling.

Claims (4)

  1. 基油に、一般式（Ｉ）
    Ｒ1ＯＯＣ－Ｒ2－Ｓx－Ｒ3－ＣＯＯＲ4　・・・（Ｉ）
    （式中、Ｒ1及びＲ4はそれぞれ独立に炭素数１～２０の炭化水素基であり、Ｒ2及びＲ3はそれぞれ独立に炭素数０～６の炭化水素基であり、ｘは１～３の整数を示す。）
    で表される硫黄含有化合物を組成物全量基準で０．０１～７０質量％配合してなる金属加工用の圧延油組成物。     In the base oil, the general formula (I)
    R 1 OOC—R 2 —S x —R 3 —COOR 4 (I)
    Wherein R 1 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrocarbon group having 0 to 6 carbon atoms, and x is 1 to Indicates an integer of 3.)
    A rolling oil composition for metal working, comprising 0.01 to 70% by mass of a sulfur-containing compound represented by the formula, based on the total amount of the composition.
  2. 一般式（Ｉ）で表される硫黄含有化合物のｘが２であることを特徴とする、請求項１に記載の圧延油組成物。 The rolling oil composition according to claim 1, wherein x of the sulfur-containing compound represented by the general formula (I) is 2.
  3. 金属加工が鉄系材料の加工であることを特徴とする、請求項１または２に記載の圧延油組成物。 The rolling oil composition according to claim 1, wherein the metal processing is processing of an iron-based material.
  4. 金属加工がステンレスの加工であることを特徴とする、請求項１または２に記載の圧延油組成物。 The rolling oil composition according to claim 1, wherein the metal processing is stainless steel processing.
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