KR20100122095A - Rolling oil composition for metalworking - Google Patents

Abstract

(식 중, R¹ 및 R⁴는 각각 독립적으로 탄소수 1 내지 20의 탄화수소기이고, R² 및 R³은 각각 독립적으로 탄소수 0 내지 6의 탄화수소기이고, x는 1 내지 3의 정수를 나타냄)The present invention is formulated with 0.01 to 70% by mass of the sulfur-containing compound represented by the formula (I) in the base oil based on the total amount of the composition, and even if rolling is carried out at a high reduction ratio, surface damage does not occur, and the rolling load can be reduced It provides a rolled oil composition.
<Formula 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 represents an integer of 1 to 3)

Description

Rolling oil composition for metal processing {ROLLING OIL COMPOSITION FOR METALWORKING}

TECHNICAL FIELD The present invention relates to a rolling oil composition for metal processing, and more particularly, to a rolling oil composition which is preferably used when rolling iron-based materials.

When rolling a plate or foil of a metal or its alloy, in general, improvement of productivity, efficiency and improvement of product appearance are required. Techniques related to the improvement of productivity and efficiency include techniques for achieving high reduction ratios and techniques for reducing the reduction force. Techniques related to improvement in product appearance include avoiding roll coating stains and surface damage (heat scratches). Technology for this. In particular, since iron-based materials are hard, and stainless steel or the like often requires excellent surface appearance, various developments have been made for the purpose of improving these processing techniques, and rolling oils used for rolling processing such as stainless are known so far.

For example, Patent Document 1 discloses a lubricating oil for metal processing comprising a diester which is a reaction product of a specific dicarboxylic acid and a specific alcohol. Patent documents 2 and 3 disclose 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 did not necessarily have sufficient performances based on the demanded performance of the recent rolling processing. In particular, it is difficult to attain both good productivity and good product appearance, and there is a problem that surface damage is likely to occur when processing is performed at a high reduction ratio using, for example, conventional rolling oil. Therefore, the improvement of the performance of rolling oil is desired.

Japanese Patent Laid-Open No. 62-201994 Japanese Patent Laid-Open No. 2001-172662 Japanese Patent Laid-Open No. 2001-172663

The present invention has been made under such circumstances, and an object of the present invention is to provide a rolling oil composition having excellent rolling performance, that is, a rolling oil composition that does not cause surface damage even when rolling is performed at a high reduction ratio, and also contributes to a reduction in rolling load. It is to be done.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor discovered that the said subject was solved by using a specific sulfur containing compound as an additive. In addition, sulfur-containing compounds generally have a problem of low solubility in oil, and also have a problem that mist is easily generated during rolling and deterioration of the working environment due to odors, but these problems also characterize sulfur-containing compounds. By discovering what can be solved by this, it came to complete this invention.

That is, this invention provides the following rolling oil compositions.

1. a rolling oil composition for metal processing, comprising 0.01 to 70% by mass of a sulfur-containing compound represented by the formula (I) in a base oil based on the total amount of the composition;

<Formula 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 represents an integer of 1 to 3)

2. The rolling oil composition according to item 1, wherein x of the sulfur-containing compound represented by the formula (I) is 2;

3. The rolling oil composition according to item 1 or 2, wherein the metal working is a work of an iron-based material,

4. The rolling oil composition according to item 1 or 2, wherein the metal working is processing of stainless steel,

According to the present invention, there is provided a rolling oil composition which does not cause surface damage even when rolling is performed at a high rolling reduction rate and contributes to reduction of rolling load. In addition, the rolling oil composition solves the problem of odor while using a sulfur-based additive.

Therefore, according to the rolling oil composition of this invention, since (1) reduction ratio can be improved, productivity can be improved, and (2) rolling load can be reduced, energy consumption can be suppressed and (3) the said excellent The effect that rolling performance can be achieved without accompanying the fall of a working environment is acquired.

The base oil used in the present invention is not particularly limited, and may be appropriately selected from mineral oil, synthetic oil, and fats and oils according to the purpose of use, the conditions of use, and the like. Examples of mineral oils include, for example, residues obtained by atmospheric distillation of paraffinic crude oil, intermediate machinery crude oil or naphthenic crude oil, or distillate obtained by distillation under reduced pressure from atmospheric distillation, or refined oil obtained by refining this according to a conventional method. Examples thereof include solvent refined oil, hydrogenated refined oil, tallow treated oil and clay treated oil. As synthetic oil, For example, C8-14 poly-alpha-olefin, an olefin copolymer (for example, ethylene-propylene copolymer etc.), branched olefins, such as polybutene and polypropylene, these hydrides, Ester compounds, such as polyol ester (fatty acid ester of trimethylol propane, fatty acid ester of pentaerythritol, etc.), alkylbenzene, etc. can be used. As fats and oils, tallow, lard, soybean oil, rapeseed oil, rice bran oil, palm oil, palm oil, palm kernel oil, or these hydrides are mentioned, for example.

In the present invention, as the base oil, one kind of the above mineral oil may be used, two or more kinds thereof may be used, one kind of the synthetic oil may be used, two or more kinds thereof may be used, or one or more kinds of the above-mentioned fats and oils may be used. In addition, it can also use in combination of 2 or more type. Moreover, you may use together 2 or more types chosen from mineral oil, synthetic oil, and fats and oils. It is preferable that the base oil used by this invention exists in the range of 3-30 mm <2> / s of kinematic viscosity in 40 degreeC. If this kinematic viscosity is 3 mm <2> / s or more, a flash point will be high and there is little risk of a fire by a flash. On the other hand, when it is 30 mm <2> / s or less, there exists little possibility that winding shift | offset | difference arises. From the above point, More preferably, it is 5-20 mm <2> / s.

In the rolling oil composition of this invention, the sulfur containing compound represented by General formula (I) is used.

<Formula I>

In formula (I), R <^1> and R <^4> is a C1-C20 hydrocarbon group each independently. If carbon number exceeds 20, it will fall easily in solubility. Moreover, the effect which prevents evaporation of the one with many carbon numbers within the said range is acquired, Preferably it is C2-C18, More preferably, it is 4-18. The hydrocarbon group may be either linear, branched or aromatic cyclic, or may be saturated or unsaturated. R ² and R ³ are each independently a divalent hydrocarbon group having 0 to 6 carbon atoms. When carbon number exceeds 6, solubility will fall easily and the effect of this invention is hard to be acquired. Carbon number becomes like this. Preferably it is 1-4, More preferably, it is 1. The divalent hydrocarbon group may be either linear, branched or aromatic cyclic, or may be saturated or unsaturated. In the case of a hydrocarbon group having 0 carbon atoms, it means that the carbon atom and the 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 for production reasons, the same is preferable. x is any one of 1-3. If x is 4 or more, problems are likely to occur in terms of odor and corrosiveness. Therefore, x may be used alone of any one of the sulfur-containing compounds of 1 to 3, and these mixtures may be used, but as the sulfur-containing compound represented by the formula (I) in view of the above, It is preferable to use. 70 mass% or more is preferable with respect to the sulfur containing compound whole quantity represented by General formula (I), and, as for the quantity of the sulfur containing compound whose x is 2, 90 mass% or more is more preferable, 95 mass% or more is especially preferable.

Although the sulfur containing compound represented by General formula (I) can be manufactured by a conventionally well-known method, it is preferable to manufacture the sulfur containing compound whose x is 2 by the method shown below. That is, oxidative coupling is carried out using sulfur-containing carboxylic acid esters represented by the general formulas (II) and / or (III) as raw materials. According to this production method, a sulfur-containing compound represented by the formula (I) substantially having x of 2 is prepared.

<Formula II>

<Formula III>

(Wherein R ¹ and R ⁴ , R ² and R ³ are the same as above)

Specifically, R ¹ OOC-R ² -SSR ³ -COOR ⁴ , R ¹ OOC-R ² -SSR ² -COOR ¹ , R ⁴ OOC-R ³ -SSR ³ -COOR ⁴ are prepared.

As the oxidizing agent used in the oxidative coupling, an oxidizing agent usually used can be used. For example, oxygen, hydrogen peroxide, halogen (iodine, bromine), hypohalogenic acid (salt), sulfoxide (dimethyl sulfoxide, diiso) Propyl sulfoxide), manganese oxide (IV), and the like. Among these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and the production of the desired sulfur-containing compound is easy.

Specific examples of the sulfur-containing compound represented by the formula (I) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) disulfide, bis (iso Propoxycarbonylmethyl) 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-ethoxycar Carbonylethyl) 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 Feed, 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 butyl thiosalicylic acid, dimer of thiosalicylic acid n-octyl ester, and the like.

In the present invention, one type of sulfur-containing compound represented by the formula (I) may be used alone, or two or more types may be used in combination. The compounding quantity is 0.01-70 mass% on the basis of the whole quantity of rolling oil composition. If it is less than 0.01 mass%, the effect of this invention may not be acquired, and if it exceeds 70 mass%, a suitable effect will not be acquired at it and it will become a problem in terms of odor. 0.1-50 mass% is more preferable from the said viewpoint, and 0.5-30 mass% is especially preferable.

The rolling oil composition of this invention may contain an oily agent other than the said sulfur compound. Examples of the oil agent include monoesters and diesters.

As said monoester, the compound represented by General formula (IV) is mentioned, for example.

<Formula 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.

Preferred total carbon number of the monoester represented by the 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, but among them, butyl stearate is preferable in view of performance and availability.

The content of the monoester in the rolled oil composition is preferably in the range of 0.5 to 40 mass%. If it is the said range, the effect of reducing the glossiness of a rolled sheet and the improvement effect of a heat-resistant scratch performance will be obtained. In view of the above, preferable content of the said monoester is 3-30 mass%, and the range of 5-20 mass% is preferable.

As said diester, the reaction product of C12-C28 aliphatic dicarboxylic acid whose main skeleton contains a saturated or unsaturated branched hydrocarbon chain, and C1-C6 linear aliphatic alcohol is mentioned.

If carbon number of the said aliphatic dicarboxylic acid is the said range, it is preferable at the point of a heat-resistant scratch performance and solubility. Preferable carbon number is 14-24 from said viewpoint, and 16-20.

In addition, the aliphatic dicarboxylic acid has a branched chain as a main skeleton. By having a branched chain, there exists an advantage that the solubility with respect to the base oil of diester improves, and the rolling oil composition which has desired performance is easily obtained.

In this invention, both saturated and unsaturated can be used as said aliphatic dicarboxylic acid, For example, the compound represented by following General formula (V) is mentioned preferably.

(V)

In formula, k is an integer of 0-3, m and n represent the integer of 1-23, respectively, and the sum of k, m, and n is an integer of 8-24.

As a specific example of C12-C28 aliphatic dicarboxylic acid whose main frame | skeleton used for manufacture of diester contains a saturated or unsaturated branched hydrocarbon chain, the compound etc. which are represented by following formula are mentioned.

In addition, as an aliphatic alcohol, a C1-C6 thing is used. Solubility improves that it is this range. Preferable carbon number is 1-4 from the said viewpoint. In addition, the aliphatic alcohol needs to be linear. As having a branched chain, heat scratch resistance is poor. Specific examples of such linear aliphatic alcohols include methanol, ethanol, n-propanol, n-butanol, and the like.

As for content of the said diester in a rolling oil composition, the range of 0.5-30 mass% is preferable. If it is the said range, the improvement effect of heat-resistant scratch performance will be obtained. In view of the above, the preferred content of the diester is in the range of 1 to 20 mass%, particularly preferably in the range of 1 to 15 mass%.

It is preferable that the rolling oil composition of this invention mix | blends a phenolic antioxidant. By mix | blending a phenolic antioxidant, there exists an effect of suppressing the oxidation deterioration of a rolling oil composition.

Examples of the phenolic antioxidants include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4-dimethyl-6-t-butylphenol, and the like. 2,6-di-t-butyl-p-cresol is particularly preferred. The range of 0.01-5 mass% is preferable on the basis of the rolling oil composition whole quantity, and, as for the compounding quantity of a phenolic antioxidant, the range of 0.1-1 mass% is preferable.

Moreover, the rolling oil composition of this invention can mix | blend various additives, such as a rust inhibitor, a corrosion inhibitor, an antifoamer, in the range which does not impair the objective of this invention, if desired.

As a rust inhibitor and a corrosion inhibitor, fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, fatty acid amine, paraffin, alkyl polyoxyethylene ether, etc. are mentioned, for example.

As an antifoamer, dimethyl polysiloxane, polyacrylate, etc. are mentioned, for example.

These additives can be used individually by 1 type or in mixture of 2 or more types, respectively. In addition, the compounding quantity of these additives is the range of 0.1-10 mass% normally on the basis of a composition, respectively, Preferably it is the range of 0.1-5 mass%.

Although there is no restriction | limiting in particular about the viscosity of the rolling oil composition of this invention, It is preferable that dynamic viscosity in 40 degreeC is 3-30 mm <2> / s, and it is more preferable that it is 5-20 mm <2> / s.

When using the rolling oil composition of this invention, this rolling oil composition may be used as it is, and an emulsion may be manufactured and used by adding an emulsifier and water. As an emulsifier, it can select suitably according to the objective, For example, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or these mixture can be used.

The rolling oil composition of this invention can be used suitably as a rolling oil composition for metal processing. In particular, when the rolling oil composition of the present invention is used, it is preferable to use it for rolling processing of various iron-based materials in that it can be efficiently rolled even on a hard material, and for use in rolling processing of stainless steel in terms of obtaining excellent surface appearance. Most preferred.

In general, when excellent surface appearance is required, such as stainless steel rolling, it is preferable to use the rolling oil composition of the present invention as it is, and when the efficiency is prioritized, such as rolling of steel sheet, it is preferable to prepare and use an emulsion. desirable.

<Examples>

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

Examples 1 to 7, Comparative Examples 1 to 6

As shown in the first table, a sulfur-containing compound and other additives were blended with the base oil to obtain a rolled oil composition. The evaluation test which shows these as sample oil was done. The evaluation results are shown in the second table.

In addition, in the 1st table | surface, the compounding quantity of each component when the rolling oil composition whole quantity was 100 mass parts was shown by the mass part.

(1) limit reduction rate

The rolling process was performed at the rolling speed of 100 m / min using the work roll of 40 mm of roll diameters (roll surface roughness Ra 0.10 micrometer). The reduction ratio was increased stepwise from 20% until the occurrence of heat scratching, and the maximum reduction ratio at which no heat scratch occurred was defined as the limit reduction ratio.

In addition, in the evaluation of this evaluation and the following "rolling load in case of 25% of a reduction ratio", the following stainless steel was used as a material.

SUS304: coil size (0.6 mm thickness, 50 mm width)

(2) Rolling load at 25% reduction

The rolling load required for rolling at a reduction ratio of 25% was investigated.

(3) odor test

The sample oil was diluted with the liquid paraffin defined by JIS K2231, and it evaluated on the basis of the following criteria whether or not unpleasant odor was felt. It was evaluated by five panelists and their median is shown in the second table.

1 (slight odor): 1000-fold dilution without sulfur odor.

2 (weak odor): Sulfur odor at 1000-fold dilution, no sulfur odor at 5000-fold dilution.

3 (Strong Odor): Sulfur smell with 5000-fold dilution.

Base oil: Paraffinic mineral oil with a kinematic viscosity of 8 ℃ 2 / s

Sulfur compound 1: In the formula (I), R ¹ and R ⁴ are n-octyl groups, R ² and R ³ are CH ₂ groups, and X is 2

Sulfur compound 2: A sulfur-containing compound of formula (I) wherein R ¹ and R ⁴ are n-butyl groups, R ² and R ³ are CH ₂ groups, and X is 2

Sulfur compound 3: Dimer of thiosalicylic acid n-octyl ester

Sulfur compound 4: A sulfur-containing compound of 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

Sulfur Compound 5: Polysulfide

Sulfur Compound 6: Sulfide Olefin

Sulfur Compound 7: Sulfide Maintenance

Oily agent 1: Butyl stearate

Oily agent 2: Formula below

Diester compound represented by

Antioxidant: DBPC (2,6-di-t-butyl-p-cresol)

According to the rolling oil composition of the present invention, (1) rolling can be performed at a high pressure reduction rate, productivity can be improved, and (2) rolling load is reduced, so that energy consumption can be reduced, and (3) the above-mentioned. The effect of being able to achieve the outstanding rolling performance without accompanying the fall of a work environment is acquired, and this invention is used suitably in a rolling process.

Claims (4)

A rolling oil composition for metal working comprising a compound containing 0.01 to 70 mass% of a sulfur-containing compound represented by the formula (I) in a base oil.
<Formula 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 represents an integer of 1 to 3) The rolled oil composition according to claim 1, wherein x of the sulfur-containing compound represented by the formula (I) is 2. The rolling oil composition according to claim 1 or 2, wherein the metal working is processing of an iron-based material. The rolling oil composition according to claim 1 or 2, wherein the metal working is processing of stainless steel.