JP2003522282A - Intermediate cold and hot rolling compositions of water-soluble copper, copper alloys and non-ferrous metals - Google Patents

Abstract

The present invention relates to a water-soluble copper, copper alloys and non-ferrous metals intermediate cold and hot rolling composition comprising a base stock oil and, based on the total weight of the composition : from 1 to 80% by weight of a combination of a monoester of a fatty acid with a polyol and a tetraester of a fatty acid with pentaerythritol; the weight monoester : tetraester ratio of said combination ranging from 1:20 to 10:1; and from 0.02 to 2% by weight of an azole derivative. The invention also relates to an oil-in-water emulsion, an intermediate cold rolling process, a hot rolling process and the use of the oil-in-water emulsion in an intermediate cold or hot rolling process. <IMAGE>

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates to an intermediate cold-rolling and hot-rolling composition of water-soluble copper, copper alloys and non-ferrous metals, and a method for intermediate cold-rolling or hot-rolling copper, copper alloys and non-ferrous metals.

[0002]

[Background technology]

In the copper, copper alloy and non-ferrous metal rolling industries, the efficiency of these rolled metal manufacturing processes is
It is required to maximize. Generally speaking, this means that there is a desire to operate at higher rolling speeds and to produce more marketable products per operating shift. In addition, it is also desirable to minimize the number of mill passes required to achieve a given level of reduction. Both of these methods require that performance as well as surface finish is not compromised.

[0003]

DISCLOSURE OF THE INVENTION

Accordingly, the present invention provides an oil composition for a rolling mill that enables the preparation of emulsions, which provides the following customer advantages. -High processing rate: One-pass reduction is often achievable,-Excellent surface finish,-Easy handling,-Long charge life,-Low oil consumption rate,-Long emulsion life , -Long roll life, and-Low sensitivity to dissolved copper salts.

The present invention is effective for any reversible or irreversible rolling in disassembling, intermediate and finishing mills. In particular, the present invention exhibits high reduction and rollability, while providing excellent strip surface finish when rolled at high speeds. The prior art neither teaches nor suggests such an invention. Therefore, the present invention provides a water-soluble copper, a copper alloy and a nonferrous metal rolling oil composition, wherein the composition is 1 to 80 based on the raw material base oil and the total mass of the composition.
%, Preferably 1 to 30% by weight of monoesters of fatty acids and polyols and tetraesters of fatty acids and pentaerythritol, and 0.02 to
2% by mass, preferably 0.05 to 1% by mass of the azole derivative, and the mass ratio of the combination: monoester / tetraester is 1:20 to 10: 1, preferably 1:10 to 5: 1.
It is characterized by being within the range.

As used herein, “intermediate cold” means that the temperature for the copper and copper alloy ingots is ambient temperature. In the present specification, the term "hot rolling" refers to the copper and copper alloy ingot,
It means that the temperature is about 750 ° C. According to one aspect, the oil composition further comprises 0.1-2 based on the total weight of the composition.
It also contains 0% of a mixture of ethoxylated alcohols having 5 to 15 carbon atoms and preferably 12 to 15 carbon atoms. As an example of such a mixture, the trade name Synparonic (Synpe
ronic ^TM) under the A7 and Hyper- (Hypermer ^TM) A60, marketed by the company ICI, available mixture of ethoxylated alcohols, wherein the weight ratio: Shinparonikku A7 / Hyper- A60 is preferably from 1: 10 to It is within the range of 10: 1.

The present invention also provides a method for producing the oil composition. The present invention further provides an emulsion containing the oil composition and a method for producing the emulsion. The invention further provides the use of the oil composition of the invention in the preparation of an emulsion of copper, copper alloys and non-ferrous metals for use in hot or cold rolling processes. The invention also provides a method of hot rolling copper, copper alloys and non-ferrous metal sheets, the method comprising applying an effective amount of the emulsion of the invention. Finally, the invention also relates to the use of said emulsion in hot or intermediate rolling processes.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be explained in more detail in the following description of the specification. The oil composition of the present invention is a neat oil concentrate, generally diluted with water to obtain an oil-in-water emulsion. The feedstock base oil is any oil typically used in the field of intermediate cold or hot rolling. It can be paraffinic or naphthenic.

Paraffinic base oils are produced from crude oils, which have a relatively high alkane content (high paraffin and isoparaffin content). Typical raw materials are Middle East,
It originates from the North Sea and central US continent. The manufacturing process is based on the removal of aromatic compounds (
Usually requires solvent extraction) and dewaxing. Paraffinic base oils are characterized by their good viscosity / temperature properties, ie high viscosity index, good low temperature properties and good stability. These are often solvent neutrals.
The term "solvent" as used herein means that the base oil has been solvent-refined, and the term "neutral substance" means that the oil has a neutral pH. . Another designation is high viscosity index (HVI) base oil. They are available for a whole range of viscosities, ranging from light spindle oils to high viscosity brightstocks.

Naphthenic base oils naturally have a low pour point, are wax-free and can be hydrorefined to reduce the content of polycyclic aromatic components. The preferred base oil is a hydrorefined paraffinic neutral material. The base oil is typically 10 to 150 cSt at 40 ° C, preferably 2 at 40 ° C.
It has a viscosity in the range of 0 to 50 cSt. In the combination of the mono and tetraesters, the fatty acid of the monoester has from 16 to 20 carbon atoms and is preferably oleic acid. The polyol of the monoester is preferably glycerol. The fatty acid of the tetraester has from 16 to 20 carbon atoms and is preferably oleic acid.

The azole derivative is generally selected from the group consisting of aryltriazoles, arylimidazoles and arylthiazoles. Examples of aryltriazoles include benzotriazole, toluoltriazole and toluyltriazole. Examples of aryl imidazoles include benzimidazole and 2- (5-aminopentyl) benzimidazole. Benzothiazole can be used as the arylthiazole. A preferred azole is toluol triazole.

The oil composition of the present invention comprises classical additives such as surfactants, coupling agents or cosurfactants, friction-reducing agents or lubricants, corrosion inhibitors or antioxidants,
Extreme pressure agents and antiwear agents, bactericides and fungicides, defoamers, rust inhibitors may be included. However, an important feature of the present invention is that the oil composition and the emulsion resulting from its use are free of nonyl-phenol type surfactants, which are believed to cause environmental problems. is there. Examples of antifoam agents are those based on silicones, especially polydimethylsiloxane. Examples of corrosion inhibitors are hindered phenols and zinc dialkyldithiophosphates.
(ZDDP).

Examples of extreme pressure agents and antiwear agents are trialkyl phosphates such as dilauryl phosphate, didodecyl phosphite, tri (2-ethylhexyl) phosphate, tricresyl phosphate (TCP), zinc dialkyl (or diaryl), respectively. ) Dithiophosphate (ZDDP), phospho-sulfated fatty acid, zinc dialkyldithiocarbamate, mercaptobenzothiazole, sulfated fatty acid, sulfated terpene, sulfated oleic acid, alkyl and aryl polysulfides, sulfated whale oil, sulfated inorganic oil sulfur chloride -Treated fatty acids, chloronaphthaxanthate, cetyl chloride, chlorinated paraffin petroleum, chlorinated paraffin wax sulfide, chlorinated paraffin wax, and zinc dialkyl (or diaryl) dithiophosphates
(ZDDP), tricresyl phosphate (TCP), trixylyl phosphate (TXP), dilauryl phosphate. Examples of corrosion inhibitors or antioxidants are radical scavengers such as phenolic antioxidants, aminic antioxidants, organic copper salts, hydroperoxide decomposers, butylated hydroxytoluene. An example of a rust inhibitor is an amine derivative of alkenyl succinic anhydride. Additional factors regarding base oils and additives are described in Lubricant Chemistry and Technology (Chemistr
and Technology of Lubricants), RM Mortier & ST Orszulik, VCH Publishers, 1st Edition, 1992.

The following is an example of the composition of the water-soluble oil composition according to the present invention (each percentage is weight% based on the total weight of the composition): 0.1-10% trialkyl ( C _1-4 ) phenol, 0.5-4.0% trialkyl (C _3-10 ) phosphate, 1-4% petroleum sulfonate, 0.1-0.5% aminoalkyl (C _2-3 ) alkanediol (C _{2 -3} ), 1-4
% Trialkanol (C _2-4 ) amine, 2-10% glycerol monofatty acid (C _16-20 ).
Ester, 5-15% pentaerythritol tetrafatty acid (C _16-20 ) ester, 0.5
~ 1.0% 5-carboxy 4-hexyl 2-cyclohexene 1-octanoic acid, 3-6% ethoxylated alcohol (C _5-15 , containing 2-10 CH ₂ O groups), 0.05-0.3% Triazole derivative, 0.05-0.4% siloxane based polymer, balance naphthenic lubricating base oil or naphthenic base oil mixture.

The water-soluble oil composition of the present invention is preferably such that the base oil and the other components are not more than 50 ° C., more preferably not more than 35 ° C. under stirring using any mixing device. As such, it is prepared by mixing while controlling the temperature. The oil-in-water emulsion is prepared by diluting the oil composition of the present invention with water under stirring. One of the interesting features of the present invention is that hard water can be used, containing up to 200 mg calcium carbonate per liter. Deionized water is preferably used, which can be preheated to about 35 ° C. This emulsion generally comprises water and 0.5 to 30% by volume, preferably 1 to 20% by volume, of the oil composition, based on the total volume of the emulsion.

For the purposes of the present invention, the copper alloy is any copper alloy, including bronze and brass alloys. Examples of non-ferrous metals for the purposes of the present invention are nickel, nickel alloys, zinc and zinc alloys. The hot rolling method of the present invention may be a classical method. This is typically done at an ingot temperature of 750 ° C. The cold intermediate rolling method of the present invention may be a classical method. This is typically done at ambient temperature. This rolling method is preferably carried out in a breakdown or finishing mill. The oil-in-water composition of the present invention enables a great reduction in the number of passes. In previously known emulsions, the pass number was typically 3-10. The emulsion according to the invention makes it possible to reduce this number by one pass, which leads to a considerable improvement. When this rolling process is carried out in a cracking mill, the emulsion preferably contains 2-3% by volume of the oil composition, based on its total volume. When this rolling process is carried out in a finishing mill, the emulsion preferably
4-7% by volume of the oil composition, based on its total volume.

[0016]

【Example】

The following examples illustrate the invention without limiting it. Unless otherwise specified, all "parts" and "ratios" in the examples are given on a mass basis. Examples Compositions are prepared by mixing the ingredients set forth in Table 1 below, in the order listed in the table. The temperature is maintained at a maximum of 50 ° C to ensure complete dissolution and homogenization of the components without adversely affecting the properties of the emulsion.

[0017]

[Table 1] Table 1 *: C _12-15 alcohol mixture: marketed by ICI under the trade name Synperonic ^™ A7: 0.6%; trade name Hypermer ^™ A60
Marketed by ICI as: 3.90%.

[0018]   Various properties of the composition shown in Table 1 are shown in Table 2.

[0019]

[Table 2] Table 2 The oil composition of Table 1 is diluted with deionized water preheated to 35 ° C. under stirring to prepare an emulsion. Various properties of the obtained emulsion are given in Table 3.

[0020]

[Table 3] Table 3 1): The stability of this emulsion was measured by the method described below.

Emulsion stability: 470 ml distilled water at room temperature or test temperature, 800 ml
I measured it in my beaker. A 50 ml stirrer with four paddles was attached to the stirrer motor such that the paddle was located approximately 25 mm above the beaker. A 50 ml dropping funnel was placed so that its outlet was 15 mm from the beaker wall. The stirrer was started and its speed was adjusted to 1000 rpm. The sample is then 35 ± 1 ° C
Heated up. 30 ml of test oil was added to the dropping funnel. The drip rate was adjusted to such a value that all of the oil was transferred to the water for 120 ± 20 seconds. Then
The stirring was continued for another 60 seconds while maintaining the temperature of the sample at 35 ± 1 ° C. The obtained emulsion was poured into a 500 ml graduated cylinder and left at room temperature for 20 hours. After 20 hours, the upper layer (yellow cream + oil) was read in% by volume. Experimental Test Method A blank is prepared by diluting a known oil composition. The oil composition has a composition as shown in Table 4.

[0022]

[Table 4] Table 4

Two emulsions are prepared by diluting the oil composition of the present invention and the prior art oil composition, respectively, with deionized water. Both of these emulsions are tested for copper and evaluated for improved surface finish. These tests are performed on copper strips as follows. Any surface imperfections are removed from the test copper strip with silicon carbide paper. Each side is polished by collecting silicon carbide particles with a cotton pad moistened with isooctane. These strips must be handled with stainless steel scissors. After polishing, each strip is washed with isooctane to remove the particles and dipped in fresh isooctane. Next, these isooctanes are taken out of the washing solvent, air-dried, and weighed to the nearest 0.1 mg. Prepare 500 ml of the test metallizing oil emulsion, weigh 200 ± 1 g twice and place a sample of each emulsion in a 250 mf flask.

The dried copper strip is then dipped into flasks containing the emulsion sample and the flasks are stoppered. The flasks are placed in an oven maintained at 50 ° C for the prescribed test period. After the end of this period, the flask is removed from the oven. The strip
Remove from the test emulsion, wash with acetone to remove water and wash with isooctane to remove the oil. The strip is air dried, then 0.1
Weigh up to the mg unit. For a further test cycle, the test strip is re-immersed in the original test sample, the flask is stoppered and placed in an oven kept at the same temperature for the same period as before. The metal loss is then calculated for each strip as follows:

[0025]   Loss in mg = M1 M2 or loss in ppm = (M1-M2) / M1 ・ 10 ^-6 Where M1 is the pre-test strip mass in mg and M2 is in mg.
The mass of the strip after the tested.   Figure 1 shows the loss (or dissolution of copper) in mass (ppm) of copper expressed as a unit of time.
It is the curve obtained when plotted against the strike period.   As will be appreciated, when using the emulsion of the present invention, this copper loss is
Much less than when using emulsions of the prior art. This fact is
Less chemical erosion of the strip means improved surface finish
is doing.   The emulsion according to the invention and the emulsion according to the prior art, then for brass
Test and measure for improvement in rolling force.

FIG. 2 is a graph showing applied rolling force versus number of passes in metric tons (t) / m. When the number of passes increases, the difference between the emulsion of the prior art and the emulsion of the present invention increases, and the rolling force is always smaller for the emulsion of the present invention than for the emulsion of the prior art. Since the smaller the rolling force, the better the emulsion, the emulsion of the present invention is not only better than the emulsion of the known art, but the larger the number of passes is, as compared with the emulsion of the known art, It can be assumed that the emulsion of the present invention is better.

[Brief description of drawings]

1 shows the curves obtained when the loss of copper mass (ppm) is plotted against the elapsed time in hours using the emulsion of the invention and the emulsion of the prior art.

FIG. 2 is a graph showing the applied rolling force, expressed in t / m, against the number of passes, obtained using the emulsion of the invention and the emulsion of the prior art.

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Claims (26)

[Claims] 1. An intermediate cold and hot rolling oil composition of water-soluble copper, a copper alloy and a non-ferrous metal, wherein the raw material base oil and 1 to 80% by mass, based on the total mass of the composition,
A combination of a monoester of a fatty acid and a polyol and a tetraester of a fatty acid and a pentaerythritol and 0.02 to 2% by mass of an azole derivative, and the mass ratio of the combination: monoester / tetraester is 1:20 to 10: 1. The rolling oil composition is characterized in that 2. The method according to claim 1, further comprising a mixture of 0.1 to 20% of ethoxylated alcohols having 5 to 15 carbon atoms and preferably 12 to 15 carbon atoms, based on the total weight of the composition. Water-soluble oil composition. 3. The water-soluble oil composition according to claim 1, which comprises 3 to 30% by mass of the above combination, based on the total mass of the composition. 4. The water-soluble oil composition according to any one of claims 1 to 3, which contains 0.05 to 1% of the azole derivative based on the total weight of the composition. 5. The mass ratio of the combination: monoester / tetraester is 1
The water-soluble oil composition according to any one of claims 1 to 4, which is in the range of 10 to 5: 1. 6. The water-soluble oil composition according to any one of claims 1 to 5, wherein the monoester fatty acid has 16 to 20 carbon atoms and is preferably oleic acid. 7. The water-soluble oil composition according to any one of claims 1 to 6, wherein the monoester polyol is glycerol. 8. The water-soluble oil composition according to any one of claims 1 to 7, wherein the fatty acid of the tetraester has 16 to 20 carbon atoms and is preferably oleic acid. 9. The water-soluble oil composition according to claim 1, wherein the azole derivative is selected from the group consisting of aryltriazole, arylimidazole and arylthiazole. 10. The water-soluble oil composition according to claim 9, wherein the aryltriazole is selected from the group consisting of benzotriazole, toluoltriazole and toluyltriazole. 11. The aryl imidazole is benzimidazole and 2-
The water-soluble oil composition according to claim 9, which is selected from the group consisting of (5-aminopentyl) benzimidazole. 12. The water-soluble oil composition according to claim 9, wherein the aryl thiazole is benzothiazole. 13. The water-soluble oil composition according to claim 10, wherein the aryl triazole is toluol triazole. 14. 0.1% to 10% trialkyl (C _1-4 ) phenol, 0.5% to 4.0% trialkyl (C _3-10 ) phosphoric acid, expressed as% by weight, based on the total weight of the composition. Ester, 1-4% petroleum sulfonate, 0.1-0.5% aminoalkyl (C _2-3 ) alkanediol (C _2-3 ), 1-4% trialkanol (C _2-4 ) amine, 2-10 % Glycerol monofatty acid (C _16-20 ) ester, 5-15% pentaerythritol tetra fatty acid (
C _16-20 ) ester, 0.5-1.0% 5-carboxy 4-hexyl 2-cyclohexene 1-octanoic acid, 3-6% ethoxylated alcohol (C _5-15 , 2-10 CH ₂ O groups. Included), 0
% Of a triazole derivative, 0.05-0.4% of a siloxane-based polymer, the balance being a naphthenic lubricating base oil or a naphthenic base oil mixture.
The water-soluble oil composition according to any one of 1 to 13. 15. The raw base oil is 10 to 150 cSt, preferably 2 at 40 ° C.
The water-soluble oil composition according to any one of claims 1 to 14, which has a viscosity of 0 to 50 cSt. 16. Water and 0.5-30%, preferably 1-15% (v / v),
16. An oil-in-water emulsion, comprising the water-soluble oil composition according to any one of items 1 to 15. 17. A method for producing a water-soluble oil composition according to any one of claims 1 to 15, wherein the raw base oil and other components are stirred or by any mixing device. And the step of mixing. 18. The method for producing an oil-in-water emulsion according to claim 16, comprising the step of diluting the oil composition in water with stirring. 19. An intermediate cold rolling process for rolling copper, copper alloys and non-ferrous metal sheets, comprising the step of applying an effective amount of the emulsion of claim 16. The above method. 20. The water-soluble solution according to claim 1, wherein the rolling step is performed in a cracking mill, and the emulsion is 2 to 3% by volume based on the total volume of the emulsion. 20. The intermediate cold rolling method according to claim 19, comprising a natural oil composition. 21. The method according to claim 1, wherein the rolling step is carried out in a finishing mill, and the emulsion is 4 to 7% by volume based on the total volume of the emulsion.
20. The intermediate cold rolling method according to claim 19, which comprises the water-soluble oil composition described in the above item. 22. A hot rolling process for rolling copper, copper alloys and non-ferrous metal sheets, characterized in that it comprises the step of applying an effective amount of the emulsion of claim 16. Method. 23. The water-soluble solution according to claim 1, wherein the rolling step is carried out in a cracking mill, and the emulsion is 2 to 3% by volume based on the total volume of the emulsion. 23. The hot rolling method according to claim 22, which comprises a strong oil composition. 24. The method of claim 1, wherein the rolling step is performed in a finishing mill and the emulsion is 4-7% by volume based on the total volume of the emulsion.
23. The hot rolling method according to claim 22, which comprises the water-soluble oil composition according to item 22. 25. A water-soluble oil composition according to any one of claims 1 to 15 in the preparation of an emulsion of copper, copper alloys and non-ferrous metals for use in intermediate cold rolling or hot rolling. Use of things. 26. Use of the water-in-oil emulsion according to claim 16 in intermediate cold rolling or hot rolling.