JP2919206B2 - Cold rolling oil for aluminum and aluminum alloy and cold rolling method using the same - Google Patents

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"). The present invention relates to a water-soluble cold-rolling oil which does not generate oil stain when the sheet material is annealed, and a method for cold-rolling 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 a refined mineral oil having a viscosity of 3 to 4 cst at 40 ° C. with base oil and lauryl alcohol as an oil agent.

[0003] This is excellent in that a glossy plate can be obtained. However, since the cooling capacity is lower than that of a water-based rolling oil, the temperature of rolls and plates is significantly increased in high-speed, high-pressure rolling, and There are drawbacks in that shape control is difficult and there is a risk of fire.

[0004] To solve the above-mentioned drawbacks, a water-soluble rolling oil and a technique for using the same have been developed.
% Water, a lubricant containing a mineral oil and an alkoxyalkyl ester (Japanese Patent Application Laid-Open No. Sho 62-172095), a linear olefin (α-olefin) having a defined number of carbon atoms and water and a known emulsifier are added to an emulsion. Using a lubricant for plastic working (JP-A-2-133495) and a lubricant containing a fatty acid having 12 to 18 carbon atoms and a sorbitan ester as a W / O or W / O / W emulsion for rolling lubrication of aluminum ( JP-A-60-248797), 10
A paraffinic mineral oil having a kinematic viscosity at 0 ° F. of 2 to 8, a fatty acid glycol ester and / or a molecular weight of 350 to 80;
0, a mixture containing polyisobutylene of 0, a long-chain glycol, a polyoxyethylene glycol having a molecular weight of 800 to 6000, or a polyoxypropylene glycol having a molecular weight of 150 to 1200, a polyoxyethylene alkyl ether phosphate salt, an alkylamine and / or a triamine. Aqueous lubricants for cold rolling comprising ethanolamine fatty acid salts, saturated alcohols having 12 to 16 carbon atoms, α-bromocinnamaldehyde, and residual water have been proposed.

[0005]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 62-17 / 1987
In the invention of 2095, the main component of the lubricant composition is mineral oil,
It is stated that a light mineral oil of 3 to 5 cst at 40 ° C. is desirable for cold rolling.

Indeed, when aluminum is rolled with a lubricant using 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, combustion residues of the lubricant remain on the material surface, It generates oil stain.

Therefore, a mineral oil having a temperature of 5 cst or less at 40 ° C. must be used. In this case, the lubricating property is remarkably poor as compared with a non-aqueous lubricant using a mineral oil having the same viscosity.
Solubilized features are lost. That is,
The lubricant of the invention of 2-172095 has a disadvantage that lubricity is remarkably poor as compared with a non-aqueous lubricating oil having the same viscosity level. Japanese Patent Application Laid-Open No. 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 too unstable, resulting in poor lubrication. The publication also states that various known emulsifiers are appropriately added. However, in general, emulsifiers are difficult to thermally decompose and generate residues when a rolled material is annealed.

[0008] In short, the invention of JP-A-2-133495 states that a linear olefin can be used as an emulsion, but in that case, it is completely unknown how to use it in combination with an emulsion stabilizer. .

In Japanese Patent Application Laid-Open No. 60-248797, the C number is 12
When a lubricant containing 脂肪酸 18 fatty acids and sorbitan esters is used as a W / O or W / O / W emulsion for rolling lubrication of aluminum, fatty acids and sorbitan esters having 12 to 18 carbon atoms have an effect of preventing water stain. However, the generation of oil stain cannot be prevented.

Japanese Patent Application Laid-Open No. 50-67304 generally uses a large amount of a substance having a high molecular weight. In particular, phosphate ester salts are not suitable as aluminum cold-rolling oil additives because they promote generation of oil stain. Polyisobutylene is used as a thickener, but has a molecular weight of 350 to 800.
It is large and causes oil stain.

Accordingly, 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 is annealed. A rolling method is provided.

[0012]

Means for Solving the Problems As a result of diligent studies, the present inventor has found that a combination of a specific polyolefin base oil with a specific α-olefin and a specific additive provides a refrigeration material satisfying the above-mentioned required characteristics. It has been found that hot rolling oil can be used, and the present invention has been achieved. That is, the present invention provides base oils 8 to 9 comprising at least one of polypropylene, polyisobutylene and polybutene having a molecular weight of 200 to 330.
Α-olefins represented by the following formula (1):
wt%, and a higher alcohol derivative represented by the following formula (2):
(3), trimethylolpropane derivative represented by the formula (4) and
(5), (6), (7), (8), 2 to 20 wt% of at least one oily agent selected from the group consisting of alcohol esters of oxymono or dicarboxylic acids shown in the formulas (9) was added. A cold rolling oil for aluminum and aluminum alloys.

CH ₂ ＣＨCH (CH ₂ ) _n CH ₃ (1) (wherein n represents 9 to 25) R ₁ O (C _m H _{2 m} O) _n H (2) (wherein R ₁ Is an alkyl group having 10 to 22 carbon atoms, and m is 2
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
CH ₃ CH (OH) COOR ₄ (5) (wherein R ₄ represents an alkyl group having 1 to 18 carbon atoms)

[0014]

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(Wherein, R ₅ represents an alkyl group having 1 to 18 carbon atoms)

[0016]

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(Wherein, R ₆ represents an alkyl group having 1 to 18 carbon atoms) R ₇ OOCCH (OH) CH ₂ COOR ₈ (8) (wherein, R ₇ and R ₈ represent 1 to 18 carbon atoms) R ₉ OOCCH (OH) CH (OH) COOR ₁₀ (9) (wherein R ₉ and R ₁₀ each represent an alkyl group having 1 to 18 carbon atoms) as the first invention, 5-20 wt% of the rolling oil
% Of an aqueous emulsion of aluminum or an aluminum alloy in the form of an aqueous emulsion having a concentration of 5% by weight, and the rolling oil is an aqueous emulsion having a concentration of 5 to 20% by weight, which is used for cooling and lubrication during cold rolling of aluminum. The 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 of polypropylene, polyisobutylene and polybutene aluminum cold rolling oil, these substances preferably have a molecular weight of 200 to 330. Molecular weight 20
If the substance is less than 0, the viscosity is too low and lubricity is insufficient. Substances having a molecular weight exceeding 330 cannot be used because oil stain is generated. It is desirable that these oligomers are not hydrogenated, but they may be hydrogenated.

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

When the proportion of the base oil is less than 5%,
If the lubricity is insufficient and exceeds 90% by weight, it is difficult to form a uniform emulsion. In the formula (1), n is 9
If n is less than 3, 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.

By appropriately combining the above base oil and α-olefin, the amount of introduction between the roll and the plate can be increased, and the chemical adsorption power can be increased. Is also improved.

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

If the addition amount is less than 2 wt%, the lubricity becomes insufficient, and if it exceeds 20 wt%, oil stainless steel 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, and the like. No.

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. When both m and n are larger than the upper limits, oil stain is generated.

Trimethylolpropane derivatives The compounds represented by the general formulas (3) and (4) function as excellent oil agents. Particularly, the compound represented by the general formula (4) also has a self-emulsifying property, and thus is suitable as an additive for a water-soluble cold rolling oil.

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

Examples of the esters represented by the general formulas (3) and (4) include, for example, trimethylolpropane diacetate, trimethylolpropanedihexanoate, trimethylolpropanedidecanoate, trimethylolpropaneethylene oxide 3 mol adduct Acetate, trimethylolpropane ethylene oxide 3 mol adduct tricaproate, trimethylolpropane ethylene oxide 3 mol adduct tricaprate, trimethylolpropane ethylene oxide 6 mol adduct triacetate, trimethylolpropane ethylene oxide 6 mol adduct Tricaproic acid ester, trimethylolpropane ethylene oxide 6 mol adduct tricapric acid ester, and the like.

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

If the number of carbon atoms in R is larger than the upper limit, oil stain is generated. When both m and n are larger than the upper limits, oil stain is generated.

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

If the addition amount is less than 2 wt%, the lubricity is insufficient, and if it exceeds 20 wt%, oil stainless steel 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, for example, methyl lactate, ethyl lactate, methyl salicylate, ethyl salicylate, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, dimethyl malate, apple Ditridecyl acid, distearyl malate, dimethyl tartrate, diethyl tartrate and the like.

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

If the number of carbon atoms in R is larger than the upper limit, oil stain is generated, which is not preferable.

Antioxidants, preservatives, rust preventives In the rolling oil of the present invention, small amounts of antioxidants, preservatives, rust preventives and the like can be added as required.

When the rolling oil comes into contact with air, the antioxidant may be oxidized and the specific substance may be damaged.
It is added as needed to prevent this oxidation. Representative antioxidants include N-salicyloyl-N′-aldehyde hydrazine, α-naphthylamine, 2,6-di-tert-butyl-P-cresol, 2,4-di-methyl-6-tert.
Butylphenol and the like.

Preservatives may cause bacteria and fungi to propagate in the emulsion, and are added as necessary to prevent spoilage of the emulsion. Representative 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 positively. However, an emulsion cannot be formed by such a method.

Then, using a mixer as shown in FIG. 1, oil is injected into the water fed under pressure to form an emulsion. The pressure of the pumped water is 2 × 98.1 KPa (2 atm) or more, and the pressure of the injected oil is 2 × 98.
An emulsion can be obtained by increasing the pressure by 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 this method, the emulsion had an average particle diameter 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 an oil-water separation step and a filtration step described below.

Oil / Water Separation Step In order to remove fine wear powder in a filtration step described below,
Filtration using diatomaceous earth and activated clay as filtration aids is preferred, but not possible in the form of an emulsion. Therefore, in the oil / water separation step, the fine wear powder is separated into oil and water such that most of the fine wear powder moves into the separated oil. The separated oil is subjected to the aforementioned diatomaceous earth clay filtration. At this time, in order to maintain a high removal rate and a long filtration life, the water content in the separated oil should be 2000 ppm.
It must be: Also, relatively large wear powder is present in the water. This water is also subjected to filtration as described later, but a centrifugal separator is preferred in which the oil content is 2,000 ppm or less in view of the filtration life. In addition, continuous processing becomes possible by using this centrifugal separator.

The fiber membrane separator has a fiber pore diameter of 1 to 50.
It is preferable to use one of μm.

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

[0050]

【Example】

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

The emulsion subjected to rolling has a water pressure of 3 × 9
8.1 KPa, oil pressure 8 x 98.1 KPa, total flow rate 41 /
The oil concentration was 10% formed under the conditions of min.

The used emulsion 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 reused. The results are shown in Table 1.

No. of the invention example. In all of Nos. 1 to 43, the rolling load was 20 Ton-f or less, and no generation of oil stain was observed upon annealing.

However, in Comparative Example No. Nos. 44, 46 and 48 show that the molecular weight of the oligomer is small; No. 50 is that the C number of the α-olefin is small; No. 51 shows that the addition amount of α-olefin is small, Nos. 52 to 54 show that the amount of the oil agent added was small. No. 57 has a small oligomer content; No. 58 is that the C number of the alkyl group of the alcohol in the oil agent is small. No. 68 has a low oil concentration in the emulsion, so lubricity is insufficient and the rolling load is 23 to 26 ton-f.
And became bigger.

No. 45, 47, 49, 55, 56, 5
Nos. 9 to 67 and 69 are those in which the molecular weight of the oligomer is large, the amount of the oily agent added is large, the C number of the acid or alcohol of the oily agent is large, the number of carbon atoms or the number of moles of the alkylene oxide is large, or the emulsion is Since the concentration was high, although the lubricity was good, the generation of oil slurry was recognized.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

Example 2 (Example of continuous use) Cold rolling oil N shown in Table 1 of Example 1
o. In 5, the rolling was performed by circulating the rolling oil and water. A centrifugal separator was used as the oil-water separator, and the separated oil was filtered using a filtration 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 Figs. 1 to 4, both the water content in oil and the oil content in water were 2000 ppm or less in the centrifugation (centrifugal force 2000 G) and the fiber membrane separation. The oil after the separation contained about 100 ppm of abrasion powder, which could be reduced to 5 ppm or less by filtration. As a result of rolling with these recycled oils and water, no defects were recognized on the sheet surface, and the rolling load was equivalent to that of fresh oil and fresh water.

On the other hand, the reference example No. In No. 5, since the separated oil was not filtered through diatomaceous earth clay, the abrasion powder in the oil was increased to 80 ppm, and defects occurred in the rolled sheet.

No. In No. 6, the separated water was not filtered, so that abrasion powder in the water was 55 ppm, and micro defects were recognized on the rolled sheet surface.

No. In No. 7, since a stationary separation tank was used for oil / water separation, separation of oil and water became incomplete, and clogging occurred in the filtration step, making filtration impossible.

No. In No. 8, the 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 The cold rolling oil No. shown in Table 1 was used. 5 and a coated rolled material having a thickness of 1.2 mm, a width of 70 mm and a length of 450 mm
IS5052 aluminum alloy sheet material with roll diameter of 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. As a comparative example, mineral oil (3.5 cst, 40
C.) The results obtained when a non-aqueous rolling oil having a composition of 90 wt% + lauryl alcohol 10 wt% is used are shown by dotted lines. That is, it can be seen that the cold rolling oil of the present invention enables rolling at a rolling reduction of 60% or more in one pass, facilitates cooling of the rolling roll and the rolled plate, and provides a rolled plate having a good shape. .

On the other hand, when a non-aqueous rolling oil is used, when the rolling reduction is 50% or more, the rolling load increases, and it can be seen that rolling irregularities easily occur.

[0068]

As described above, the rolling oil of the present invention is superior in lubricity to non-aqueous rolling oil, so that high-speed high-pressure rolling is possible, and oil rolling is not generated on the material to be rolled. It is. Further, in the cold rolling method of using the rolling oil of the present invention as a water-based emulsion as a cooling / lubricating oil during cold rolling of aluminum, the used rolling oil emulsion can be hydrolyzed with high efficiency, and fine abrasion powder is also generated. Because it can be microfiltered, it can be recycled.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a mixer for forming an aqueous emulsion of cold-rolled 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 diagram showing a relationship between a rolling load and a rolling reduction in Example 2 using the rolling oil of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 127: 02 129: 16 129: 76) C10N 20:04 30:00 30:06 40:24 (58) Fields surveyed (Int. .Cl. ⁶ , DB name) C10M 169/04 B21B 27/06 C10M 173/00 C10M 105/04 C10M 127/02 C10M 129/16 C10M 129/76 C10N 40:24 WPI / L (QUESTEL)

Claims (3)

(57) [Claims] 1. A base oil comprising at least one of polypropylene, polyisobutylene and polybutene having a molecular weight of 200 to 330, 8 to 93 wt% of an α-olefin represented by the following formula (1): 5 to 90 wt%, and (2) A higher alcohol derivative represented by the formula; and a trimethylo-derivative represented by the formulas (3) and (4).
2 to 20 wt. Of a propane derivative and one or more oily agents selected from the group consisting of alcohol esters of oxymono or dicarboxylic acids represented by formulas (5), (6), (7), (8) and (9).
% Cold rolling oil for aluminum and aluminum alloys. CH ₂ ＣＨCH (CH ₂ ) _n CH ₃ (1) (wherein n represents 9 to 25) R ₁ O (C _m H _{2 m} O) _n H (2) (where R ₁ is the number of carbon atoms 10 to 22 alkyl groups, m is 2
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
CH ₃ CH (OH) COOR ₄ (5) (in the formula, R ₄ represents an alkyl group having 1 to 18 carbon atoms) (Wherein, R ₅ represents an alkyl group having 1 to 18 carbon atoms). (Wherein R ₆ represents an alkyl group having 1 to 18 carbon atoms) R ₇ OOCCH (OH) CH ₂ COOR ₈ (8) (wherein, R ₇ and R ₈ represent an alkyl group having 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) 2. The rolling oil shown in claim 1 is 5 to 20 wt%.
A cold rolling oil for aluminum and aluminum alloys, characterized in that it is an aqueous emulsion having a high concentration. 3. The rolling oil shown in claim 1 is 5 to 20 wt%.
A cold rolling method comprising using an aqueous emulsion having a high concentration and using it as a cooling / lubricating oil during cold rolling of aluminum and aluminum alloys.