JP2003336088A - Cold-rolling oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cold-rolling oil composition which can be desirably used in the cold-rolling of, especially, a high-nickel-content iron/nickel heat- resistant alloy material and is effective to give a rolled material reduced in gloss unevenness and in indentation due to the powder formed by friction during rolling. <P>SOLUTION: The cold-rolling oil composition contains a base oil and (A) 0.01-1.0 mass % sulfur-based extreme-pressure additive and/or (B) 0.01-2.0 mass % phosphorus-based extreme-pressure additive. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold rolling oil composition, and more specifically, it is preferably used for cold rolling treatment of an iron-nickel heat resistant alloy material having a high nickel content, The present invention relates to a cold rolling oil composition that exhibits excellent effects in suppressing uneven gloss and suppressing indentation scratches caused by rolling abrasion powder.

[0002]

2. Description of the Related Art In the rolling of a metal material, a phenomenon called "roll coating" occurs in the work roll in a portion where the rolled material passes while the rolling is normally performed. The roll coating has a great relationship with the rolling property and the surface property of the rolled product, because the work roll is always in direct contact with the rolled material. Since the work roll is thermally expanded by frictional heat and processing heat when a metal material is rolled, the rolling pressure in the plate width direction becomes non-uniform, and unevenness in roll coating is likely to occur.
This coating unevenness causes unevenness on the surface of the rolled plate by transfer to cause uneven glossiness, and particularly in rolling of metal materials such as iron-nickel heat-resistant alloys with high nickel content, which requires high surface quality. However, uneven gloss, which indicates uneven surface quality, is a serious problem.

By the way, in the cold rolling of a hard metal material such as the above-mentioned iron-nickel heat-resistant alloy, a small-diameter roll capable of applying a high load per unit area is used as a work roll by reducing the contact area with the material. Often. However, if the diameter of the roll is small, the rigidity of the roll itself is low, and it is necessary to reinforce with a large-diameter intermediate roll or backup roll. As such a rolling mill, for example, a cluster type rolling mill is known.
In this cluster type rolling mill, the backup roll is divided into five or more rolls in the axial direction, which are called split backup rolls. This split backup roll has a crown adjustment function consisting of a specially designed cylindrical roller bearing, and the extrusion amount of each bearing can be operated independently by the eccentric bushing mechanism, so various crown patterns can be created on the work roll. It is also possible to control the shape of the rolled plate. In a split backup roll type rolling mill, there are portions where the split backup roll comes into contact with the work rolls via the intermediate rolls, and portions where the split backup rolls do not contact each other, which may cause unevenness in the roll coating. Then, this roll coating unevenness is transferred to the rolled plate, which causes uneven gloss on the surface of the rolled plate.

On the other hand, with the recent development of electronics, the demand for electronic equipment parts such as semiconductors and CRTs has increased, and as a material for lead frames and shadow masks used in these parts, nickel content has been increased. The applications of rolled materials such as high-iron-nickel heat-resistant alloys that require highly precise shape control are increasing. But,
The iron-nickel heat-resistant alloy material, due to its material characteristics,
Since uneven glossiness is likely to occur, it has been desired to deal with both shape control and surface quality. Further, the iron-nickel heat-resistant alloy material has a larger amount of rolling wear powder compared to stainless steel, and if the amount of rolling wear powder on the rolling plate is large, it is difficult to remove in the lower step, and also causes surface scratches. And deteriorates the surface quality. Further, the rolling oil may be accumulated in the piping, the tank, and the housing of the rolling mill, and may be pressed into the rolled material to cause scratches.

[0005]

Under such circumstances, the present invention is suitably used for cold rolling of iron-nickel heat-resistant alloy material having a particularly high nickel content, and roll coating of split backup rolls. A cold rolling oil composition that exhibits excellent effects in reducing uneven gloss of a rolled plate due to unevenness, reducing uneven gloss of a rolled plate due to uneven roll coating in the width direction of a work roll, and suppressing indentation scratches due to rolling abrasion powder It is intended to provide.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop a cold rolling oil composition having the above-mentioned excellent function, and as a result, together with a base oil, a sulfur-based extreme pressure agent and / or It has also been found that the object can be achieved by a composition containing a phosphorus-based extreme pressure agent in a specific ratio. The present invention is
It was completed based on this knowledge. That is,
The present invention relates to (A) a sulfur-based extreme pressure agent (0.
01-1.0 mass% and / or (B) phosphorus-based extreme pressure agent.
A cold rolling oil composition, characterized by containing from 01 to 2.0% by mass, (2) at least one oiliness agent selected from esters, alcohols and fatty acids as the component (C) The cold rolling oil composition of the above (1) containing 1 to 60 mass%, the sulfur extreme pressure agent of the component (3) (A),
The above (1) or (2), which is at least one selected from sulfurized fats and oils, polysulfides, and sulfurized olefins.
(4) The cold rolling oil composition of (1) or (2), wherein the phosphorus-based extreme pressure agent of the component (B) is an amine salt of a phosphoric acid ester, and (5) ) A cold rolling oil composition according to the above (1) or (2), which is used for cold rolling an iron-nickel heat resistant alloy material containing 20% by mass or more of nickel.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the cold rolling oil composition of the present invention, a mineral oil and / or a synthetic oil can be used as a base oil. Various types of mineral oil can be used. For example, paraffin-based crude oil, intermediate-based crude oil or naphthene-based crude oil is distilled under atmospheric pressure, or distillate obtained by distilling the residue of atmospheric distillation under reduced pressure, or purified by a conventional method. The refined oil obtained by the above process, for example, a solvent refined oil, a hydrogenated refined oil, a dewaxing treated oil, a clay treated oil and the like can be mentioned. Examples of the synthetic oil include 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 polyols. An ester compound such as an ester (a fatty acid ester of trimethylolpropane, a fatty acid ester of pentaerythritol, etc.), an alkylbenzene or the like can be used.

In the present invention, the mineral oil is used as the base oil.
May be used alone or in combination of two or more
Well, one kind of the synthetic oil may be used, or a combination of two or more kinds.
You may use together. In addition, one or more of the mineral oil and synthetic oil
One or more kinds can be used together. And as the base oil
The kinematic viscosity at a temperature of 40 ° C is 1 to 100 mm. ²
Those in the range of / s are preferable. This kinematic viscosity is 1 mm
²Below / s, the flash point is low, which may
Ruggedness may increase, while 100 mm²Over / s
Then, oil pits are generated on the surface of the rolled plate and the glossiness is low.
Defects such as lowering or winding misalignment during rolling
This will cause a problem. More preferable kinematic viscosity is 4 to 2
0 mm²/ S. In the composition of the present invention,
A sulfur-based extreme pressure agent is used as the component (A). This sulfur
The yellow extreme pressure agent has a sulfur atom in the molecule,
Those that can exhibit extreme pressure effects when dissolved or uniformly dispersed in oil
It is not particularly limited as long as it contains active sulfur.
May be present or may not contain active sulfur
Yes. Whether or not it contains active sulfur depends on the copper plate corrosion test.
(JIS K 2513).

Examples of such sulfur-based extreme pressure agents include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, polysulfides, sulfurized olefins, thiocarbamates, thioterpenes and dialkylthiodipropionates. Of these, sulfurized fats and oils, polysulfides or sulfurized olefins are preferable. The sulfurized fats and oils refer to sulfides of animal and vegetable oils, and include, for example, sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, and sulfurized soybean oil. The sulfurized fats and oils also include disulfide fatty acids such as sulfurized oleic acid and sulfurized esters such as sulfurized methyl oleate. As the sulfurized fats and oils, those containing 5 to 30% by mass of sulfur are preferable.

Examples of the polysulfide include, for example, the general formula (I) R ¹ -Sx-R ² ... (I) (wherein R ¹ and R ² are respectively an alkyl group having 1 to 20 carbon atoms and a carbon atom). Aryl group having 6 to 20 carbon atoms and 7 to 20 carbon atoms
Or an arylalkyl group having 7 to 20 carbon atoms, which may be the same or different from each other. x represents an integer of 2 to 8. The compound represented by these can be mentioned. R ¹ in the above general formula (I)
And specific examples of R ² include methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl Group, cyclohexyl group, cyclooctyl group, phenyl group, naphthyl group, tolyl group, xylyl group, benzyl group, phenethyl group and the like.

Examples of the polysulfide include dibenzyl polysulfide, di-tert-nonyl polysulfide, didodecyl polysulfide and di-te.
Preferable examples include rt-butyl polysulfide, dioctyl polysulfide, diphenyl polysulfide, dicyclohexyl polysulfide and the like. Further, examples of the sulfurized olefin include general formula (II) R ³ —Sy—R ⁴ ... (II) (wherein R ³ is an alkenyl group having 2 to 15 carbon atoms, and R ⁴ is 2 to 15 carbon atoms. Represents an alkyl group or an alkenyl group of
Represents an integer of 1 to 8. The compound represented by these can be mentioned. The compound represented by the general formula (II) is obtained by reacting an olefin having 2 to 15 carbon atoms or a dimer to a tetramer thereof with a sulfurizing agent such as sulfur or sulfur chloride. As the olefin, Propylene, isobutene, diisobutene and the like are preferable.

The sulfur-based extreme pressure agent as the component (A) has a function of particularly reducing the uneven glossiness of the rolled plate. In the present invention, one kind may be used alone, or two or more kinds may be used. You may use it in combination. The content of the sulfur-based extreme pressure agent in the rolling oil composition is selected within the range of 0.01 to 1.0 mass%. If this content is less than 0.01% by mass, the effect of suppressing uneven gloss is not exhibited, while 1.0% by mass
If it exceeds the range, problems occur in terms of odor and the oxidative stability of the rolling oil composition tends to decrease. The preferable content of this sulfur-based extreme pressure agent is in the range of 0.02 to 0.6 mass%. In the composition of the present invention, a phosphorus-based extreme pressure agent is used as the component (B). The phosphorus-based extreme pressure agent is not particularly limited as long as it has a phosphorus atom in the molecule and can exhibit an extreme pressure effect by being dissolved or uniformly dispersed in the base oil, and various compounds can be used. Can be used. Examples of such phosphorus-based extreme pressure agents include phosphoric acid esters, (mono-, di-, tri) thiophosphoric acid esters, amine salts of phosphoric acid esters, amine salts of (mono-, di-, tri) thiophosphoric acid esters, and phosphorus Examples thereof include acid esters and (mono-, di-, tri) thiophosphorous acid esters, and of these, amine salts of phosphoric acid esters are preferable. The amine salt of the phosphoric acid ester has the general formula (III)

[0013]

[Chemical 1]

Examples thereof include compounds represented by:
In the general formula (III), R ⁵ is a hydrocarbon group having 4 to 20 carbon atoms, R ⁶ is a linear, branched or cyclic alkyl group or alkenyl group having 4 to 20 carbon atoms, m and n is 1 or 2 respectively, a plurality of R ⁵ may be the same or different, and a plurality of R ⁶ may be the same or different. Examples of the hydrocarbon group having 4 to 20 carbon atoms represented by R ⁵ include a linear, branched or cyclic alkyl group or alkenyl group having 4 to 20 carbon atoms, and 6 to 20 carbon atoms.
An aryl group of, an alkylaryl group having 7 to 20 carbon atoms,
Examples thereof include an arylalkyl group having 7 to 20 carbon atoms. Specific examples of such compounds include butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, oleyl group, eicosyl group, phenyl group, isopropylphenyl Group, xylyl group, benzyl group, phenethyl group and the like. Examples of R ⁶ include butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, lauryl group,
Examples thereof include a myristyl group, a palmityl group, a stearyl group, an oleyl group, and an eicosyl group. The phosphorus-based extreme pressure agent as the component (B) has an effect of suppressing the occurrence of indentation scratches due to the abrasion powder of the rolled material by making it easier to disperse the rolling abrasion powder in the rolling oil composition. In the present invention, one kind may be used alone, or two or more kinds may be used in combination. Further, the content of the phosphorus-based extreme pressure agent in the rolling oil composition is selected in the range of 0.01 to 2.0% by mass. If this content is less than 0.01% by mass, the rolling abrasion powder dispersion effect will not be exhibited, while if it exceeds 2.0% by mass, the effect will not be improved for that amount, which is rather economically disadvantageous. Becomes In the composition of the present invention,
The combined use of the component (A) and the component (B) is preferable in terms of effects. In the composition of the present invention, if necessary, (C)
An oiliness agent can be contained as a component. The oiliness agent is not particularly limited, and any one can be appropriately selected and used from those conventionally used as oiliness agents in rolling oils. Examples of such oiliness agents include esters, alcohols and fatty acids.

The esters have 6 to 22 carbon atoms.
Examples of the ester include the carboxylic acid and the aliphatic alcohol having 1 to 18 carbon atoms. Here, the carboxylic acid having 6 to 22 carbon atoms may be a monobasic acid,
It may be a polybasic acid of dibasic acid or more, saturated,
It may be unsaturated. Further, it may be linear or branched. Examples of such carboxylic acids are linear or branched, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, hydroxyoctadecanoic acid, icosanoic acid, octenoic acid, decenoic acid. , Dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, hydroxyoctadecenoic acid, icosenoic acid, octanedioic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, icosanedioic acid, octene Examples thereof include diacid, decenedioic acid, dodecenedioic acid, tetradecenedioic acid, hexadecenedioic acid, octadecenedioic acid, and icosendioic acid. Further, the aliphatic alcohol having 1 to 18 carbon atoms may be a monohydric alcohol or a polyhydric alcohol, and may be saturated or unsaturated. Further, it may be linear or branched, but monohydric alcohol is usually used. Examples of such alcohols are methanol, ethanol, allyl alcohol, or linear or branched, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, hexadecanol, Octadecanol, butenol, pentenol, hexenol, octenol, decenol, dodecenol, tetradecenol, hexadecenol, octadecenol and the like can be mentioned.

The ester has 8 to 20 carbon atoms.
The ester consisting of the saturated or unsaturated fatty acid and a monovalent saturated alcohol having 1 to 12 carbon atoms is preferable. In addition, as alcohols, monovalent aliphatic saturated or unsaturated alcohols having 8 to 18 carbon atoms can be preferably mentioned. This alcohol may be linear,
It may be branched, and specific examples thereof include
Examples include linear or branched octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, octenol, decenol, dodecenol, tetradecenol, hexadecenol, octadecenol, and the like. Furthermore, examples of the fatty acids include higher saturated or unsaturated fatty acids such as palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, dimer acid, oleic acid, and icosanoic acid. In the present invention, one type of these oiliness agents may be used alone, or two or more types may be used in combination.

The content of the oiliness agent in the rolling oil composition is usually selected in the range of 1 to 60% by mass. If the content is less than 1% by weight, workability may be insufficient, while if it exceeds 60% by weight, roll slip may occur. The content of the oiliness agent is preferably in the range of 2 to 40% by mass, and particularly preferably in the range of 3 to 20% by mass. In the rolling oil composition of the present invention, various additives as necessary, such as an antiwear agent, an antioxidant, an anticorrosive agent, a corrosion inhibitor, an antifoaming agent, etc., as long as the object of the present invention is not impaired. Can be contained alone or in combination of two or more as appropriate. Here, as the antiwear agent, for example, zinc dithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), sulfurized molybdenum oxydithiocarbamate (MoDTP), molybdenum sulfurized oxydithiocarbamate (MoDTC), and the like, For example, amine-based compounds such as alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated-α-naphthylamine, phenol-based compounds such as 2,6-di-t-butyl-p-cresol, and sulfur-based compounds are used as rust preventives and Examples of the corrosion inhibitor include sorbitan ester, neutral alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal phenate, alkali metal or alkaline earth metal salicylate, thiadiazole, benzotriazole and the like. Examples of the foaming agent include dimethylpolysiloxane and fluoroether.

The total content of these additives used according to need is preferably 10% by mass or less, more preferably 5% by mass or less. In the rolling oil composition of the present invention, the viscosity is not particularly limited, but in order to obtain lubricity and plate surface gloss, the range of 1 to ²⁰ mm ² / s is preferable, and particularly ^{2 to 10} mm ² / s. Ranges are preferred. The cold rolling oil composition of the present invention having such a composition has the following effects. (1) With a rolling mill of the type using divided backup rolls, it is possible to reduce roll coating unevenness and gloss unevenness of a rolled plate while performing shape control with divided backup rolls. That is, the shape and surface quality (uneven gloss) of the rolled product can be improved. (2) When the rolling speed is increased, the calorific value per unit time during rolling is large, the heat accumulated in the roll is large, and the thermal expansion in the plate width direction becomes non-uniform. Although unevenness is likely to occur, by using the rolling oil composition of the present invention, uneven gloss is less likely to occur even if the rolling speed is increased. (3) The in-oil rolling wear powder is easily dispersed, and the occurrence of indentation scratches due to the wear powder being pushed into the rolling surface can be suppressed. (4) From the above items (1) to (3), it is possible to achieve both improved productivity and improved product quality. As a metal material to which the cold rolling oil composition of the present invention is applied, an iron-nickel heat resistant alloy material having a nickel content of 20 mass% or more can be particularly mentioned. By using the rolling oil composition of the present invention for cold rolling of such a nickel-rich iron-nickel heat-resistant alloy material,
The above effect is effectively exhibited.

[0019]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 8 and Comparative Examples 1 and 2 (1) Preparation of Cold Rolling Oil Composition The components shown in Table 1 were added to a paraffin-based mineral oil having a kinematic viscosity at 40 ° C. of 8.0 mm ² / s. A cold rolling oil composition was prepared by blending in the amounts shown in Table 1 based on the total amount of the composition. (2) Rolling Experiment Under the rolling experiment conditions shown in Table 2, a contact roll (φ135 × width 10 mm) was placed at the center of the backup roll 9.
By pressing with a force of 8 kN, the uneven gloss of the contact portion and the non-contact portion of the split roll was evaluated. In addition, the unevenness of gloss was visually evaluated in the following four-stage evaluation. The results are shown in Table 1. 0: No unevenness 1: Slightly unevenness 2: Clear unevenness can be confirmed 3: Uneven strength is recognized (3) Rolling wear powder dispersibility test Rolling oil after the rolling experiment in (2) above is put into a glass container. 1 liter was taken, and the dispersion state of the abrasion powder after 18 hours was evaluated as Δ based on Comparative Example 2 and as ○ when the dispersibility was better than that. The results are shown in Table 1.

[0020]

[Table 1] (Note) Sulfurized oil and fat: Sulfur content 14.5% by mass, saponification value 200 mg
KOH / g Sulfurized olefin: Sulfurized isobutylene polysulfide: Dioctyl polysulfide (sulfur content 40 mass%) Amine salt of phosphoric acid ester: C12 alkylamine salt of oleyl acid phosphate

[0021]

[Table 2]

[0022]

INDUSTRIAL APPLICABILITY According to the present invention, it is particularly suitable for cold rolling of iron-nickel heat-resistant alloy material containing a large amount of nickel, and suppresses uneven gloss of rolled material and indentation damage caused by rolling abrasion powder. It is possible to provide a cold rolling oil composition that exerts an excellent effect on suppression.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10M 129/64 C10M 129/64 129/70 129/70 135/04 135/04 135/06 135/06 135 / 20 135/20 137/08 137/08 // C10N 40:24 C10N 40:24 ZF term (reference) 4H104 BB02C BB03C BB16C BB17C BB19C BB29C BB32C BG02C BG04C BG11C BG12C BG15C BH05C DA02A PA23 PA24 PA28 PA28

Claims (5)

[Claims] 1. A sulfur-based extreme pressure agent (A) 0.01 together with a base oil.
To 1.0 mass% and / or (B) 0.01 phosphorus extreme pressure agent
A cold rolling oil composition, characterized in that the cold rolling oil composition comprises: 2. Further, as the component (C), esters,
The cold rolling oil composition according to claim 1, comprising 1 to 60 mass% of at least one oiliness agent selected from alcohols and fatty acids. 3. A sulfur-based extreme pressure agent of component (A) is a sulfurized oil or fat,
The cold rolling oil composition according to claim 1 or 2, which is at least one selected from polysulfides and sulfurized olefins. 4. The cold rolling oil composition according to claim 1, wherein the phosphorus-based extreme pressure agent as the component (B) is an amine salt of a phosphoric acid ester. 5. The cold rolling oil composition according to claim 1, which is used for cold rolling of an iron-nickel heat resistant alloy material containing nickel in an amount of 20% by mass or more.