JPH06179888A - Cold-rolling oil for aluminum and aluminum alloy and method of cold rolling using the same - Google Patents

Abstract

PURPOSE:To provide a water-dispersible cold-rolling oil which has a higher lubricity than a nonaq. rolling oil and causes little oil stain on annealing a sheet after rolling and to provide the method of cold rolling using the same CONSTITUTION:8-93wt.% base oil comprising at least one polymer selected from the group consisting of polypropylene, polyisobutylene, and polybutene having a mol.wt. of 200-330 is compounded with 5-90wt.% alpha-olefin of the formula: CH2=CH(CH2)nCH3 (wherein n is 9-25) and 2-20wt.% at least one oiliness improver selected from the group consisting of a higher alcohol deriv. of the formula: R1O(CmH2mO)nH (wherein R1 is 10-22C alkyl; m is an integer of 2-4; and n is an integer of 1-3), a trimethylolpropane deriv. of, e.g. the formula: CH3CH2C(CH2OCOR2)2CH2OH wherein R2 is 1-9C alkyl), and an alcohol ester of a hydroxymono- or dicarboxylic acid of, e.g. formula: CH3CH(OH)COOR4 (wherein R4 is 1-18C alkyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rolling oil for rolling aluminum and aluminum alloys (hereinafter, simply referred to as "aluminum"), which is superior in lubricity to a non-aqueous rolling oil or a conventional water-soluble rolling oil, and after rolling. The present invention relates to a water-soluble cold rolling oil that does not generate an oil stain when the sheet material is annealed and a cold rolling method for aluminum using the same.

[0002]

2. Description of the Related Art Conventionally, non-aqueous rolling oil has been used for cold rolling of aluminum. This rolling oil is obtained by mixing refined mineral oil having a viscosity of 3 to 4 cst at 40 ° C. as a base oil with lauryl alcohol as an oiliness agent.

This is excellent in that a plate with good gloss can be obtained, but since the cooling capacity is lower than that of the water-based rolling oil, the temperature of the roll or plate is remarkably increased in the rolling under high speed and high pressure, and the plate There are drawbacks that it is difficult to control the shape and there is a danger of fire.

Therefore, in order to solve the above-mentioned drawbacks, a water-soluble rolling oil and its use technology were developed, and 90 to 98 wt.
% Water containing a mineral oil, an alkoxyalkyl ester-containing lubricant (Japanese Patent Laid-Open No. 62-172095), a linear olefin (α-olefin) having a specified carbon number, and water are added to a known emulsifier to form an emulsion. A method of using a lubricant for plastic working (JP-A-2-133495) and a lubricant containing a fatty acid having a C number of 12 to 18 and a sorbitan ester as W / O or W / O / W emulsion for rolling lubrication of aluminum ( JP-A-60-248797), 10
Paraffinic mineral oil having a kinematic viscosity of 2 to 8 at 0 ° F, a fatty acid glycol ester and / or a molecular weight of 350 to 80
0 blended with polyisobutylene, long chain glycol, polyoxyethylene glycol having a molecular weight of 800 to 6000, or polyoxypropylene glycol having a molecular weight of 150 to 1200, polyoxyethylene alkyl ether phosphate ester salt, alkylamine and / or triamine. An aqueous solution lubricant for cold rolling comprising an ethanolamine fatty acid salt, a saturated alcohol having 12 to 16 carbon atoms, α-bromocinnamaldehyde, and the balance water has been proposed.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the invention of 2095, the main component of the lubricant composition is mineral oil,
For cold rolling, light mineral oil of 3 to 5 cst at 40 ° C. is desirable.

Certainly, when aluminum is rolled with a lubricant using a mineral oil having a viscosity of 5 cst or more at 40 ° C. and the rolled material is annealed at a temperature of 330 ° C. or less, the combustion residue of the lubricant remains on the surface of the material, It causes oil stains.

Therefore, it is necessary to use a mineral oil having a viscosity of 5 cst or less at 40 ° C. In that case, the lubricity is remarkably poor as compared with a non-aqueous lubricant using a mineral oil having the same viscosity,
The water-solubilized characteristics are lost. That is, JP-A-6
The lubricant of the invention No. 2-172095 has a drawback that the lubricity is remarkably poor as compared with the non-aqueous lubricant having the same viscosity level. Further, JP-A-2-133495 describes that a linear olefin (α-olefin) is dispersed in water and used as an emulsion. However, if any emulsifier is not used, the emulsification becomes unstable and poor lubrication occurs. The publication also describes that various publicly known emulsifiers are appropriately added, but it is generally impossible to appropriately add emulsifiers because they are difficult to thermally decompose and produce residues when annealing rolled materials.

In short, the invention of JP-A-2-133495 states that the linear olefin can be used as an emulsion, but in that case, it is completely unclear how to use it in combination with an emulsion stabilizer. .

In Japanese Patent Laid-Open No. 60-248797, the C number is 12
When a lubricant containing ~ 18 fatty acid and sorbitan ester is used for rolling lubrication of aluminum as W / O or W / O / W emulsion, C12 ~ 18 fatty acid and sorbitan ester have water-stain prevention effect. However, it cannot prevent the generation of oil stain.

In Japanese Patent Laid-Open No. 50-67304, since substances having a large molecular weight are generally used, there is a concern that oil stain may be generated. In particular, phosphate ester salts are not suitable as aluminum cold rolling oil additives because they promote the generation of oil stain. Polyisobutylene is used as a thickener, but has a molecular weight of 350 to 800.
Because it is large, it causes oil stain.

Therefore, an object of the present invention is to provide a water-dispersible cold rolling oil which is superior in lubricity to a non-aqueous rolling oil and which does not generate oil stain when the rolled sheet material is annealed, and a cold rolling oil using the cold rolling oil. A rolling method is provided.

[0012]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that by combining a specific polyolefin base oil with a specific α-olefin and a specific additive, a cooling agent satisfying the above required characteristics can be obtained. The present invention has been completed by finding that it can be used as a hot rolling oil. That is, the present invention relates to base oils 8 to 9 composed of at least one of polypropylene having a molecular weight of 200 to 330, polyisobutylene and polybutene.
Α-olefin 5 to 90 represented by the following formula (1) in 3 wt%
wt%, and a higher alcohol derivative represented by the following formula (2):
(3), trimethylolpropane derivative represented by the formula (4) and
2 to 20 wt% of one or more oiliness agents selected from the group consisting of alcohol esters of oxymono- or dicarboxylic acids represented by formulas (5), (6), (7), (8) and (9) was added. A cold rolling oil of aluminum and aluminum alloys characterized by the above.

CH ₂ ═CH (CH ₂ ) _n CH ₃ (1) (wherein n represents 9 to 25) R ₁ O (C _m H _2m O) _n H (2) (wherein R ₁ Is an alkyl group having 10 to 22 carbon atoms, and m is 2
To 4 integer, n is an integer of _{1~3) CH 3 CH 2 C (} CH 2 OCOR 2) 2 CH 2 OH (3) ( wherein, R ₂ represents an alkyl group having 1 to 9 carbon atoms _{) CH 3 CH 2 C [CH} 2 O (C m H 2m O) n COR 3] 2 CH 2 OH (4) ( wherein, R ₃ is an alkyl group having 1 to 9 carbon atoms, m is 2-4
And n is an integer of 1 to ₃ ) CH ₃ CH (OH) COOR ₄ (5) (In the formula, R ₄ represents an alkyl group having 1 to 18 carbon atoms)

[0014]

[Chemical 3]

(In the formula, R ₅ represents an alkyl group having 1 to 18 carbon atoms)

[0016]

[Chemical 4]

(In the formula, R ₆ represents an alkyl group having 1 to 18 carbon atoms) R ₇ OOCCH (OH) CH ₂ COOR ₈ (8) (In the formula, R ₇ and R ₈ have 1 to 18 carbon atoms. R ₉ OOCCH (OH) CH (OH) COOR ₁₀ (9) (wherein R ₉ and R ₁₀ represent an alkyl group having 1 to 18 carbon atoms) is the first invention, and 5 to 20 wt% of the rolling oil
% Of water or a cold rolling oil of aluminum or aluminum alloy as a second invention, and further the rolling oil as an aqueous emulsion of 5 to 20 wt% concentration, which is cooled and lubricated during cold rolling of aluminum. A third invention is a cold rolling method used as oil.

Next, each constituent material used in the present invention will be described.

As a base oil for polypropylene, polyisobutylene and polybutene aluminum cold rolling oils, it is desirable that these substances have a molecular weight of 200 to 330. Molecular weight 20
If the substance is less than 0, the viscosity is too low and the lubricity is insufficient. A substance having a molecular weight of more than 330 cannot be used because it causes oil stain. It is desirable that these oligomers are not hydrogenated, but they may be hydrogenated.

Α-Olefin The α-olefin has a double bond at the terminal and has a large chemical adsorption power for aluminum, and therefore has a function of an oily agent. It is considered that the adsorption power of α-olefin is larger than that of polybutene, polypropylene and polyisobutylene, but the amount introduced between the roll and the plate material tends to be smaller than that of polybutene, polypropylene and polyisobutylene.

If the ratio of addition to the above base oil is less than 5%,
If the lubricity is insufficient and exceeds 90 wt%, it becomes difficult to form a uniform emulsion. Also, in the formula (1), n is 9
If it is less than the range, lubricity is insufficient, and if n exceeds 25, the melting point is high and it is difficult to use.

As the α-olefin represented by the formula (1),
1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene, 1-docosene, 1
-Tetracocene, 1-hexacocene, 1-octacocene and the like can be mentioned.

By appropriately combining the above-mentioned base oil and α-olefin, the amount introduced between the roll and the plate can be increased and the chemical adsorption force can be increased, and the lubricity is better than that when used alone. Will also improve.

Higher Alcohol Derivatives Since these compounds represented by the general formula (2) function as an excellent oiliness agent and also have self-emulsifying property, they are suitable as an additive for a water-soluble cold rolling oil.

If the amount added is less than 2 wt%, the lubricity is insufficient, and if it exceeds 20 wt%, oil stain is generated when the rolled sheet is annealed, which is not preferable.

Examples of the compound represented by the general formula (2) include oxyethylene decyl ether, oxyethylene cetyl ether, oxyethylene behenyl ether, dioxyethylene decyl ether, dioxyethylene cetyl ether, dioxyethylene behenyl ether, etc. Can be mentioned.

The hydrocarbon group of these alcohols may be a straight chain hydrocarbon or a hydrocarbon having a side chain.

If the C number of R ₁ is larger than the upper limit, oil stain is generated. Further, if both m and n are larger than the upper limits, oil stain is generated.

Trimethylolpropane Derivative The compounds represented by the general formulas (3) and (4) function as an excellent oiliness agent. In particular, the compound represented by the general formula (4) also has a self-emulsifying property and is therefore suitable as an additive for a water-soluble cold rolling oil.

If the amount added is less than 2 wt%, the lubricity is insufficient, and if it exceeds 20 wt%, oil stain is generated when the rolled sheet is annealed, which is not preferable.

Examples of the ester represented by the general formulas (3) and (4) include trimethylolpropane diacetate, trimethylolpropane dihexanoate, trimethylolpropane didecanoate, trimethylolpropane ethylene oxide 3 mol adduct Acetic acid ester, trimethylolpropane ethylene oxide 3 mol adduct Tricaproic acid ester, trimethylolpropane ethylene oxide 3 mol adduct tricapric acid ester, trimethylolpropane ethylene oxide 6 mol adduct Triacetic acid ester, trimethylolpropane ethylene oxide 6 mol addition Tricaproic acid ester, trimethylolpropane ethylene oxide 6 mol adduct tricapric acid ester, and the like.

The hydrocarbon group of the acid of these esters may be a straight chain hydrocarbon or a hydrocarbon having a side chain.

When the C number of R is larger than the upper limit, oil stain is generated. Further, if both m and n are larger than the upper limits, oil stain is generated.

Esters of oxymono or dicarboxylic acid These compounds represented by the general formulas (5) to (9) function as excellent oiliness agents.

If the added amount is less than 2 wt%, the lubricity is insufficient, and if it exceeds 20 wt%, oil stain is generated when the rolled sheet is annealed, which is not preferable.

Examples of the esters represented by the general formulas (5) to (9) include methyl lactate, ethyl lactate, methyl salicylate, ethyl salicylate, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, dimethyl malate and apple. Examples thereof include ditridecyl acid salt, distearyl malate, dimethyl tartrate, and diethyl tartrate.

The hydrocarbon group of the alcohol of these esters may be a straight chain hydrocarbon or a side chain hydrocarbon.

When the C number of R is larger than the upper limit, oil stain is generated, which is not preferable.

Antioxidant, Antiseptic, Antirust Agent In the rolling oil of the present invention, a small amount of antioxidant, antiseptic agent, antirust agent, etc. may be added, if necessary.

When the rolling oil comes into contact with air, the antioxidant may be oxidized to damage its inherent substance,
Add as necessary to prevent this oxidation. As typical antioxidants, N-salicyloyl-N'-aldehyde hydrazine, α-naphthylamine, 2,6-di-tert-butyl-P-cresol, 2,4-di-methyl-6-tertiary
Butylphenol and the like can be mentioned.

The preservative may proliferate bacteria and mold in the emulsion, and is added as necessary to prevent spoilage of the emulsion. Typical preservatives include triazine compounds, thiazoline compounds, morpholine compounds and phenol compounds.

Next, the formation of the aqueous emulsion used in the second and third inventions will be described.

Formation of Emulsion (Mixing of Water and Oil) Generally, an emulsion is formed by stirring water and oil in a tank, but the rolling oil of the present invention does not use an emulsifier actively. , An emulsion cannot be formed by such a method.

Then, using a mixer as shown in FIG. 1, oil is pressed into water that has been pumped to form an emulsion. The pressure of the water fed under pressure is 2 × 98.1 KPa (2 atm) or more, and the pressure of the oil injected is 2 × 98.
An emulsion can be obtained by increasing the pressure to 1 KPa (2 atm) or more.

When the water-dispersible cold rolling oil for aluminum of the present invention was made into a 3 to 30% emulsion by such a method, the emulsion had an average particle size of 3 to 50 μm and was in an emulsified state suitable for rolling lubrication. When it is desired to form an emulsion having a slightly smaller particle size, it is effective to insert a static mixer after mixing water and oil.

The emulsion thus formed is used as a cooling / lubricating oil for cold rolling of aluminum. Then, the used emulsion is treated in the oil-water separation step and the filtration step described below.

Oil / Water Separation Step In order to remove fine abrasion powder in the filtration step described later,
Filtration using diatomaceous earth and activated clay as a filtration aid is preferable, but it is impossible in an emulsion state. Therefore, in the oil-water separation step, the minute wear powder is separated into oil and water so that most of the minute wear powder is transferred into the separated oil. The separated oil is filtered through the above-mentioned diatomaceous earth. At this time, in order to maintain a high removal rate and a long filtration life for a long time, the water content in the separated oil should be 2000 ppm.
Must be: Further, relatively large abrasion powder exists in water. Although this water also undergoes filtration as described below, a centrifugal separator that reduces the amount of oil to 2000 ppm or less is preferable from the viewpoint of filtration life. By using this centrifuge, continuous processing becomes possible.

The fiber membrane separator has a fiber pore size of 1 to 50.
It is preferable to use a micrometer type.

Filtration Step Since the separated oil contains fine abrasion powder, precision filtration is performed using diatomaceous earth and activated clay as a filtration aid. Since the separated water contains a small amount of oil and a relatively large amount of metal powder, filtration using diatomaceous earth as a filtration aid or filtration with a paper filter may be performed.

[0050]

【Example】

Example 1 As a material to be rolled, plate thickness 1.2 mm, width 70 mm, length 45
Roll 0 mm JIS 5052 aluminum alloy plate material
The rolling load at the time of rolling at a rolling speed of 35 m / min and a reduction rate of 60% was measured with a rolling mill having a roll diameter of 155 mm.

The emulsion used for rolling has a water pressure of 3 × 9.
8.1KPa, hydraulic pressure 8 × 98.1KPa, total flow rate 41 /
The oil concentration was 10%, which was formed under the condition of min.

The emulsion after use was immediately separated into oil and water by a centrifugal separator. The separated oil was filtered through diatomaceous earth, and the separated water was filtered through diatomaceous earth to remove abrasion powder, and then reused. The results are shown in Table 1.

Inventive Example No. The rolling loads of all of Nos. 1 to 43 were 20 Ton-f or less, and no oil stain was observed during annealing.

However, in Comparative Example No. Nos. 44, 46, and 48 have small oligomer molecular weights. No. 50 has a small C number of α-olefin, No. 50 No. 51 has a small addition amount of α-olefin, No. 51 Nos. 52 to 54 have a small addition amount of the oiliness agent, No. No. 57 has a small amount of oligomer, No. 57 No. 58 has a low C number of the alkyl group of alcohol in the oiliness agent. No. 68 has a low oil concentration in the emulsion, and therefore lacks lubricity and has a rolling load of 23 to 26 ton-f.
And became big.

No. 45, 47, 49, 55, 56, 5
9 to 67, 69 have a large oligomer molecular weight, a large amount of the oily agent added, a large C number of the acid or alcohol of the oily agent, a large number of carbon atoms or added moles of the alkylene oxide, or an emulsion. Since the concentration was high, the lubricity was good, but the occurrence of oil sludge was observed.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

Example 2 (Continuous use example) Cold rolling oil N shown in Table 1 of Example 1
o. In 5, rolling oil and water were circulated for rolling. A centrifugal separator was used as the oil-water separator, and the separated oil was filtered using a filter aid consisting of diatomaceous earth and activated clay. For water filtration, diatomaceous earth filtration or paper filter filtration was performed, and rolling oil and water were reused.

No. 2 in Table 2 As shown in 1 to 4, both the water content in oil and the oil-in-water content were 2000 ppm or less in centrifugation (centrifugal force 2000 G) and fiber membrane separation. Further, the separated oil contained about 100 ppm of abrasion powder, but it could be reduced to 5 ppm or less by filtration. As a result of rolling with these regenerated oil and water, no defects were observed on the plate surface, and the rolling load was the same as that of fresh oil and fresh water.

On the other hand, No. 1 of the reference example. In No. 5, since the separated oil was not filtered through diatomaceous earth, the amount of abrasion powder in the oil was as high as 80 ppm, and defects occurred on the rolled plate.

No. In No. 6, the separated water was not filtered, so the amount of abrasion powder in the water was 55 ppm, and minute defects were recognized on the surface of the rolled plate.

No. In No. 7, since the stationary separation tank was used for the oil-water separation, the separation of oil and water was incomplete, clogging occurred in the filtration process, and filtration was impossible.

No. In No. 8, oil and water were mixed by stirring with a stirrer, but no emulsion was formed and the test was stopped.

[0065]

[Table 4]

Example 3 Cold rolling oil No. 1 shown in Table 1 No. 5 is used as a coated rolled material having a plate thickness of 1.2 mm, a width of 70 mm, and a length of 450 mm.
IS5052 aluminum alloy plate material roll diameter 155m
The rolling load when the rolling reduction was changed from 45% to 65% at a rolling speed of 35 m / min with a rolling mill of m was measured and is shown in FIG. In addition, as a comparative example, mineral oil (3.5 cst, 40
(° C) 90 wt% + lauryl alcohol 10 wt% The result when using a non-aqueous rolling oil having a composition is shown by a dotted line. That is, it can be seen that the cold rolling oil of the present invention can be rolled at a rolling reduction of 60% or more in one pass, and the rolling roll and the rolled plate material can be easily cooled, and a rolled plate material having a good shape can be obtained. .

On the other hand, in the case of using the non-aqueous rolling oil, it is found that when the rolling reduction is 50% or more, the rolling load becomes high and rolling irregularities are likely to occur.

[0068]

As described above, the rolling oil of the present invention is superior in lubricity to the non-aqueous rolling oil, and therefore can be rolled at high speed under high pressure, and does not cause oil stain on the material to be rolled. Is. Further, in the cold rolling method in which the rolling oil of the present invention is used as an aqueous emulsion for cooling / lubricating oil during cold rolling of aluminum, the used rolling oil emulsion can be decomposed into oil and water with high efficiency, and fine abrasion powder can be obtained. Since it can be microfiltered, it can be recycled.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a mixer for forming an aqueous emulsion of cold rolling oil according to the present invention.

FIG. 2 is an explanatory view of a rolling method using the cold rolling oil of the present invention.

FIG. 3 is a graph showing the relationship between rolling load and rolling reduction in Example 2 using the rolling oil of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C10M 127: 02 129: 16 129: 76) C10N 20:04 30:00 A 8217-4H 30:06 40:24 A 8217-4H

Claims (3)

[Claims] 1. A base oil of 8 to 93 wt% comprising at least one of polypropylene having a molecular weight of 200 to 330, polyisobutylene and polybutene, and 5 to 90 wt% of an α-olefin represented by the following formula (1), and the following (2): Higher alcohol derivative represented by formula, trimethylol represented by formulas (3) and (4)
2 to 20 wt.% Of a propane derivative and one or more oil-based agents selected from the group consisting of alcohol esters of oxymono- or dicarboxylic acids represented by the formulas (5), (6), (7), (8) and (9)
% Cold-rolling oil of aluminum and aluminum alloys. _{CH 2 = CH (CH 2)} n CH 3 (1) ( wherein, n represents an 9-25) in _{R 1 O (C m H 2m} O) n H (2) ( wherein, R ₁ is the number of carbon atoms 10 to 22 alkyl groups, m is 2
To 4 integer, n is an integer of _{1~3) CH 3 CH 2 C (} CH 2 OCOR 2) 2 CH 2 OH (3) ( wherein, R ₂ represents an alkyl group having 1 to 9 carbon atoms _{) CH 3 CH 2 C [CH} 2 O (C m H 2m O) n COR 3] 2 CH 2 OH (4) ( wherein, R ₃ is an alkyl group having 1 to 9 carbon atoms, m is 2-4
And n is an integer of 1 to ₃ ) CH ₃ CH (OH) COOR ₄ (5) (In the formula, R ₄ represents an alkyl group having 1 to 18 carbon atoms) (In the formula, R ₅ represents an alkyl group having 1 to 18 carbon atoms) (In the formula, R ₆ represents an alkyl group having 1 to 18 carbon atoms) R ₇ OOCCH (OH) CH ₂ COOR ₈ (8) (In the formula, R ₇ and R ₈ represent an alkyl group having 1 to 18 carbon atoms. R ₉ OOCCH (OH) CH (OH) COOR ₁₀ (9) (in the formula, R ₉ and R ₁₀ represent an alkyl group having 1 to 18 carbon atoms) 2. The rolling oil according to claim 1 is contained in an amount of 5 to 20 wt%.
Cold-rolling oil of aluminum and aluminum alloy, which is an aqueous emulsion having a concentration. 3. The rolling oil according to claim 1 is contained in an amount of 5 to 20 wt%.
A cold rolling method characterized by using an aqueous emulsion having a concentration and using this as a cooling / lubricating oil during cold rolling of aluminum and aluminum alloys.