JP2009215459A - Rolling oil composition for metal working - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rolling oil composition that causes no surface damages even when exposed to rolling with a high reduction ratio and allows reduction in a rolling load. <P>SOLUTION: The rolling oil composition for metal working comprises a base oil and, incorporated therewith, a sulfur-containing compound represented by general formula (I): R<SP>1</SP>OOC-R<SP>2</SP>-S<SB>x</SB>-R<SP>3</SP>-COOR<SP>4</SP>(I) (wherein R<SP>1</SP>and R<SP>4</SP>are each independently a 1C-20C hydrocarbon group; R<SP>2</SP>and R<SP>3</SP>are each independently a 0C-6C hydrocarbon group; and x is an integer of 1-3) in an amount of 0.01-70 mass% based on the whole composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a rolling oil composition for metal working, and more particularly to a rolling oil composition that is suitably used when rolling iron-based materials.

  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.

  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.

  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 recent rolling process. 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.

JP 62-201994 A JP 2001-172661 A JP 2001-172663 A

  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.

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 1 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). 4. The rolling oil composition as described in any one of 1 to 3 above, wherein the metal processing is processing of stainless steel.

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. Moreover, the said rolling oil composition eliminates the problem regarding an odor, using a sulfur type 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. Examples of mineral oils include, for example, residual oil obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil, or naphthenic crude oil, or distillate oil obtained by vacuum distillation of residual oil of atmospheric distillation, 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.

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.

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.

In the 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, 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. Carbon number becomes like this. Preferably it is 1-4, More preferably, it is 1. The divalent hydrocarbon group may be linear, branched, or aromatic, and may be saturated or unsaturated. 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. Therefore, 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). .

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.

  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-bis 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-) -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.

  In the present invention, one kind of the sulfur-containing compound represented by the general formula (I) may be used alone, or two or more kinds 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 said viewpoint, 0.1-50 mass% is more preferable, and 0.5-30 mass% is especially preferable.

  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.

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 preferable 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 monoester content 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. From the above points, 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.

Examples of the diester include a reaction product of an aliphatic dicarboxylic acid having 12 to 28 carbon atoms and a linear aliphatic alcohol having 1 to 6 carbon atoms, the main skeleton of which is a saturated or unsaturated branched hydrocarbon chain.
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.

  In the formula, k is an integer of 0 to 3, m and n are each an integer of 1 to 23, and the sum of k, m and n is an integer of 8 to 24.

  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 in the production of diesters include compounds represented by the following chemical formulas. Can do.

  On the other hand, as the aliphatic alcohol, those 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. From the above points, 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. 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 preferable. The blending amount of the phenolic antioxidant is preferably in the range of 0.01 to 5 mass%, more preferably in the range of 0.1 to 1 mass%, based on the total amount of the rolling oil composition.

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. Moreover, the compounding quantity of these additives is the range of 0.1-10 mass% normally on a composition basis, respectively, Preferably it is the range of 0.1-5 mass%.

No particular limitation is imposed on the viscosity of the rolling oil composition of the present invention preferably has a kinematic viscosity at 40 ° C. is 3 to 30 mm ² / s, more preferably 5 to 20 mm ² / s.

  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.

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.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

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) 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) Rolling load at a rolling reduction of 25% The rolling load required for rolling at a rolling reduction of 25% was examined.

(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.

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 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). : Dimer sulfur-based compound of thiosalicylic acid n-octyl ester 4: In formula (I), R ¹ and R ⁴ are n-octyl groups, R ² and R ³ are CH ₂ groups, and X is 4 containing sulfur 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

Diester compound antioxidant represented by: DBPC (2,6-di-t-butyl-p-cresol)

  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)

The base oil has 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 1 Indicates an integer of 3.)
The rolling oil composition for metal processing formed by mix | blending 0.01-70 mass% of sulfur containing compounds represented by these on the basis of the composition whole quantity. The rolling oil composition according to claim 1, wherein x of the sulfur-containing compound represented by the general formula (I) is 2. The rolling oil composition according to claim 1, wherein the metal processing is processing of an iron-based material. The rolling oil composition according to any one of claims 1 to 3, wherein the metal processing is stainless steel processing.