JP2000017284A - Rolling mill lubricant composition and cold rolling method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which prevents esp. the oxidative degradation of a rolling mill lubricant used in cold rolling of a direct oil-feeding type by compounding a base oil contg. an oil or fat selected from among animal and vegetable oils and fats with a phenolic antioxidant and an aminic antioxidant. SOLUTION: For example, beef tallow and palm oil can be used as the animal or vegetable oil or fat. Such an oil or fat having been sujected to wintering and having a low m.p. can also be used. The content of an animal or vegetable oil in a base oil is pref. 50 wt.% or higher. The sum of contents of the phenolic and aminic antioxidants is pref. 0.1-5.0 wt.%, and the wt. ratio of the phenolic to the aminic antioxidant is pref. (1:5)-(10:1). Pref., a rust preventive comprising a fatty acid and a 4-18C alkylamine salt is compounded into the compsn. The total content of the phenolic antioxidant, the aminic antioxidant, and the rust preventive is pref. 0.1-10 wt.% of the compsn., and their wt. ratio if pref. (1:5:1)-(10:1:10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rolling oil composition and a cold rolling method, and more particularly to a rolling oil composition and a cold rolling method used in direct oil supply cold rolling of steel.

[0002]

2. Description of the Related Art When rolling a thin plate such as a steel tin plate,
The rolling oil is supplied by a direct lubrication system (direct lubrication) or a circulating lubrication system (recirculation lubrication). Particularly, in a direct oiling type rolling method, a rolling oil composition obtained by forcibly dispersing a natural fat or oil such as beef tallow or palm oil in water is supplied to a material to be rolled or a roll. This rolling oil contains a polymer additive disclosed in Japanese Patent Publication No. Hei 3-13279, and after the rolling oil is supplied, it is devised to make it easily adhere to the material to be rolled. ing. However, the temperature of the material to be rolled in the rolling roll bite increases as the rolling speed increases, and often reaches a high temperature of 150 ° C. or higher. In such a case, the rolling oil remaining on the surface of the material to be rolled is a natural oil or fat having poor thermal stability. An oxide film is formed on the surface of a rolled material (steel plate, etc.), and after plating in the next step, discoloration occurs on the surface of the material to be rolled, especially at the edge portion, causing a significant deterioration in the surface condition and a deterioration in the quality of the material to be rolled. And so on.

[0003] Further, the surface of the steel sheet after rolling is in a state in which a chemical change such as an oxidation reaction on the surface of the material to be rolled is likely to occur due to generation of a new surface. Therefore, a rust inhibitor is generally added to the water-soluble rolling oil, and a measure is taken to suppress a chemical change on the material surface to such an extent that no problem occurs in a subsequent step such as a plating line. However, among commercially available rust preventive agents, barium dinonylnaphthalenesulfonate, sulfonates such as sodium petroleum sulfonate and calcium petroleum sulfonate, and alkanolamine salts of fatty acids and dibasic acids are also used as surfactants. Therefore, when it is added to the base oil, it is easily emulsified in water, so that the emulsified state changes more than necessary, and there is a problem that the amount of rolling oil adhered is reduced.

[0004] Further, phosphate compounds such as dialkyl polyoxyethylene phosphates are also easily emulsified in water due to the large polarity of phosphorus, and the emulsified state is changed more than necessary. In this way, many rust preventives are easily emulsified with water.In order to prevent oxidation of the material to be rolled, especially the surface of the steel sheet, the state of emulsification changes. We need a substance that will not let you down.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a rolling oil composition, and in particular, to prevent oxidative deterioration of a rolling oil used in direct lubricating cold rolling, and preferably to reduce the adsorptive property. It is an object of the present invention to provide a direct lubricating cold rolling oil composition which absorbs a high rust inhibitor to prevent oxidation of the surface of a material to be rolled and does not adversely affect the next step. Another object of the present invention is to provide a direct lubricating cold rolling oil composition capable of suppressing the formation of an oxide film on the surface of a steel sheet without changing the rolling lubrication performance. Still another object of the present invention is to provide a cold rolling method using the above-mentioned rolling oil composition.

[0006]

SUMMARY OF THE INVENTION The present invention provides a rolling oil composition containing the following components. (a) a base oil containing at least one member selected from the group consisting of animal fats and vegetable fats and oils; (b) a phenolic antioxidant; and (c) an amine antioxidant. The present invention also provides a rolling oil composition containing the following components. (a) a base oil containing at least one selected from the group consisting of animal oils and vegetable oils and fats; (b) phenolic antioxidants; (c) amine antioxidants; and (d) fatty acids and 4 carbon atoms. A rust preventive comprising a salt of an alkylamine of No. 18 to No. 18.

The total content of the phenolic antioxidant and the amine antioxidant is preferably 0.1 to 5.0% by weight based on the rolling oil composition. The weight ratio of the phenolic antioxidant to the amine antioxidant is preferably 1: 5-
10: 1. The total content of the phenolic antioxidant, the amine antioxidant, and the rust inhibitor comprising a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms is preferably 0.1 to the rolling oil composition. ~ 10.0% by weight.

The weight ratio of the phenolic antioxidant, the amine antioxidant, and the rust inhibitor comprising a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms is preferably 1:
5: 1 to 10: 1: 10. The rolling oil composition of the present invention is preferably used as a direct lubricating cold rolling oil. The present invention still further provides a cold rolling method characterized by performing cold rolling using the above-mentioned rolling oil composition, in particular, a direct oil supply type cold rolling method.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Animal fats and vegetable fats and oils used as the base oil of the present invention are not particularly limited. For example, commercially available beef tallow or palm oil can be used. Also,
A product having a low melting point wintering treatment may be used. The content of animal fats and vegetable fats in the base oil is preferably 50% by weight or more, more preferably 80% by weight or more, and most preferably 100% by weight.

Specific examples of the phenolic antioxidant used in the present invention include 2,6-di-tert-butyl-
p-cresol (BHT), 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-phenol, 2,4-dimethyl-6-tert-butylphenol, tert-butylhydroxyanisole (BHA) , 4,4'-butylidenebis (3-
Methyl-6-tert-butylphenol), 4,
4'-methylenebis (2,3-di-tert-butylphenol), 4,4'-thiobis (3-methyl-6-
Tertiary butyl phenol) and the like.

Further, specific examples of the amine antioxidant used in the present invention include Nn-butyl-p-aminophenol, 4,4'-tetramethyl-di-aminodiphenylmethane, α-naphthylamine, -Phenyl-α-naphthylamine, phenothiazine and the like. The rolling oil composition of the present invention needs to simultaneously contain a phenolic antioxidant and an amine antioxidant. A phenolic antioxidant or an amine-based antioxidant alone has a low effect and is not economical due to a large amount of added effect.

The total content of the phenolic antioxidant and the amine antioxidant is preferably from 0.1 to 5.0% by weight, more preferably from 0.5 to 3.0% by weight. If the amount is small, the effect is low. If the amount is too large, it is not economical. The weight ratio of the phenolic antioxidant to the amine antioxidant is preferably from 1: 5 to 10: 1, and more preferably from 1: 1 to 5: 1. When the ratio of the amine-based antioxidant exceeds 5 times that of the phenol-based antioxidant, the base oil tends to be easily emulsified in water, resulting in poor adhesion and reduced recovery rate of the recovered oil. If the ratio of the amine antioxidant is less than 10: 1, a sufficient antioxidant effect cannot be expected.

The rolling oil composition of the present invention may contain, in addition to the phenolic antioxidant and the amine antioxidant, a rust preventive comprising a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms. More preferred. Phenolic antioxidants, amine antioxidants, fatty acids and 4-1 carbon atoms
The total content of the rust inhibitor composed of the alkylamine salt of No. 8 is preferably 0.1 to 10.0% by weight, more preferably 0.5 to 5.0% by weight, based on the rolling oil composition. The weight ratio of the phenolic antioxidant, the amine antioxidant, and the rust inhibitor composed of a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms is preferably 1: 5: 1 to 10: 1:
10, more preferably 1: 1: 1 to 5: 1: 5.

The rust inhibitor used in the present invention comprises a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms. The fatty acid is a fatty acid having 6 to 18 carbon atoms, preferably 8 to 12 carbon atoms. May be a monobasic acid or a dibasic or higher polybasic acid. If the number of carbon atoms is less than 4, it tends to be easily dissolved in water, lowering the pH and decreasing the rust-preventive property. If the number of carbon atoms is more than 18, a sufficient rust-preventing effect cannot be obtained.

The monobasic acid may be linear or branched, and may be saturated or unsaturated. Specific examples of the saturated fatty acid include linear hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, and octadecanoic acid, and branched 2-ethylhexanoic acid. Specific examples of unsaturated fatty acids include linear hexenoic acid, octenoic acid, decenoic acid,
Examples thereof include branched 2-ethylhexenoic acid such as dodecenoic acid, hexadecenoic acid, and octadecenoic acid.

The dibasic acid may be linear or branched, and may be saturated or unsaturated. Specific examples of the saturated fatty acid include linear hexanedioic acid, octanedioic acid, decandioic acid, dodecandioic acid,
Examples include branched 2-ethylhexanedioic acid and the like such as hexadecandioic acid and octadecandioic acid. Specific examples of unsaturated fatty acids include linear hexenedioic acid, octenedioic acid, decenedioic acid, dodecenedioic acid, hexadecenedioic acid, octadecenedioic acid, and branched 2-ethylhexenedioic acid and the like. Is mentioned.

As the alkylamine, the alkyl group has 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.
And primary or secondary alkylamines are preferred.
More preferably, it is a primary alkylamine. When the number of carbon atoms is smaller than 4, it is easily dissolved in water, and handling becomes difficult. On the other hand, if the number of carbon atoms is more than 18, the polarity of the nitrogen atoms is weakened, and a sufficient rust prevention effect cannot be obtained. Specific examples of the primary alkylamine include hexylamine, octylamine, decylamine,
Dodecylamine, hexadecylamine, octadecylamine, cyclohexylamine and the like. Specific examples of the secondary alkylamine include dibutylamine, dihexylamine, ethylhexadecylamine, dicyclohexylamine, and the like.

Various additives can be contained in the rolling oil composition of the present invention. For example, a polymer additive that makes the rolling oil easily adhere to the material (for example,
No. 13279, oil-soluble polymers containing N, N-dialkylaminoethyl methacrylate and N, N-dialkylaminoethyl methacrylamide, and other lubricating oil additives such as extreme pressure agents (for example, sulfurized fats and oils, dialkyl Polysulfide, ZnDTP, etc.).

The rolling oil composition of the present invention can be lubricated on the surface of the material to be rolled by any lubricating method, and the present invention is not limited to the lubricating method. For example,
The undiluted solution and water of the rolling oil composition are forcibly dispersed by an agitator or the like, and may be supplied to the material to be rolled on the side of the rolling mill using a nozzle, or the nozzle disclosed in JP-A-5-84508. Oil may be supplied by a refueling method using a header.

Hereinafter, the present invention will be described in more detail with reference to examples. Percentages are by weight unless otherwise specified. Example 1 Tallow 98% 2,6-di-tert-butyl-p-cresol 1.5
% Α-naphthylamine 0.5% (Example 2) 98.8% palm oil 2,6-di-tert-butyl-p-cresol 1.0
% N-phenyl-α-naphthylamine 0.2% (Example 3) 98.8% palm oil 2,6-di-tert-butyl-p-cresol 1.0
% 4,4'-tetramethyl-di-aminodiphenylmethane
0.2%

Example 4 Tallow 98.5% Tertiary butyl hydroxyanisole 1.0% α-Naphthylamine 0.5% (Example 5) Palm oil 98.6% Tertiary butyl hydroxyanisole 1.2% N -Phenyl-α-naphthylamine 0.2% (Example 6) 99.4% beef tallow 0.4% 2,2′-methylenebis (4-methyl-6-tert-butylphenol) 0.4% N-phenyl-α-naphthylamine 2%

Example 7 Palm oil 99.0% 2,6-di-tert-butyl-p-cresol 0.8
% Nn-butyl-p-aminophenol 0.2% (Example 8) Tallow 98.5% 2,2'-methylenebis (4-methyl-6-tert-butylphenol) 0.3% α-naphthylamine 1 0.2% (Example 9) 98.0% palm oil 2,6-di-tert-butyl-p-cresol 0.8
% N-n-butyl-p-aminophenol 1.2%

Example 10 Tallow 97.5% 2,6-di-tert-butyl-p-cresol 1.5
% Α-naphthylamine 0.5% Salt of a fatty acid having 10 carbon atoms and alkylamine having 8 carbon atoms 0.5% (Example 11) Palm oil 97.8% 2,6-di-tert-butyl-p-cresol 1.0
% N-phenyl-α-naphthylamine 0.2% Salt of fatty acid having 8 carbon atoms and alkylamine having 8 carbon atoms 1.0% (Example 12) 98.3% of palm oil 2,6-di-tert-butyl-p -Cresol 1.0
% 4,4'-tetramethyl-diaminodiphenylmethane
0.5% salt of fatty acid with 6 carbon atoms and alkylamine with 18 carbon atoms

(Example 13) Tallow 97.5% Tertiary butyl hydroxyanisole 1.0% α-naphthylamine 0.5% Salt of fatty acid having 8 carbon atoms and alkylamine having 6 carbon atoms 1.0% (Example 14) Palm oil 97.6% Tertiary butyl hydroxyanisole 1.2% N-phenyl-α-naphthylamine 0.2% Salt of a fatty acid having 18 carbon atoms and an alkylamine having 8 carbon atoms 1.0% (Example 15) Tallow 98.4% 2, 2'-methylenebis (4-methyl-6-tert-butylphenol) 0.4% N-phenyl-α-naphthylamine 0.2% Salt of fatty acid having 10 carbon atoms and alkylamine having 6 carbon atoms 1.0%

Example 16 Palm oil 98.0% 2,6-di-tert-butyl-p-cresol 0.8
% Nn-butyl-p-aminophenol 0.2% Salt of fatty acid having 8 carbon atoms and alkylamine having 10 carbon atoms 1.0% (Example 17) Tallow 98.0% 2,2'-methylenebis (4-methyl- 6-tert-butylphenol) 0.3% α-naphthylamine 1.2% Salt of fatty acid having 12 carbon atoms and alkylamine having 4 carbon atoms 0.5% (Example 18) Palm oil 97.5% 2,6-di-tertiary Butyl-p-cresol 0.8
% Nn-butyl-p-aminophenol 1.2% Salt of fatty acid having 6 carbon atoms and alkylamine having 8 carbon atoms 0.5%

Comparative Example 1 Palm oil 98.0% 2,6-di-tert-butyl-p-cresol 2.0
(Comparative Example 2) Palm oil 98.0% Tertiary butyl hydroxyanisole 2.0% (Comparative Example 3) Tallow 99.5% α-naphthylamine 0.5% (Comparative Example 4) Tallow 98.0% Zinonyl Barium naphthalene sulfonate 2.0%

(Comparative Example 5) Palm oil 98.0% Alkenyl succinic acid (C ₁₅ ) 2.0% (Comparative Example 6) Palm oil 96.5% Dodecanedicarboxylic acid 1.0% Triethanolamine 2.5% (Comparative Example 7) ) Tallow 100% (Comparative Example 8) Palm oil 100%

Confirmation test of effect of antioxidant (1) Oxidation stability test To 50 g of a sample oil, 0.1 g (2000 ppm) of 200 micron ultra fine iron powder (manufactured by Vacuum Metallurgy Co., Ltd.) and 20 g of water were added. 12
It was left in a thermostat at 0 ° C. for 72 hours, and the acid value was measured to confirm the change. (2) Test with rolled material Ten test pieces (60 x 80 x 1.0 mm) were coated with a test oil and a rolling mill (roll diameter: 150 mm, roll speed: 30 m)
/ Min) for 3 passes at each pass of 25%, and then rolled test pieces are overlapped and pressed together, and placed in a 120 ° C constant temperature bath.
It was left for 8 hours. The evaluation was performed by extracting the oil attached to the test piece and confirming the change in the acid value.

(3) Emulsification test 12 g of the sample oil was placed in 388 ml of water at 80 ° C., stirred for 1 minute at 8000 rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.), transferred to a separating funnel, and allowed to stand for 30 seconds. After that, ESI (lower layer 100ml
And the concentration of the sample oil solution in 100 ml of the upper layer). (4) Discoloration test on steel plate A test piece (60 x 80 x 1.0 mm) is polished on both sides with a No. 100 polishing cloth, and the test pieces are stacked in a set of three pieces.
The sample prepared in (3) was collected with a dropper, and 5 drops were dropped.
Next, the test piece was pressed and left in a thermostat at 120 ° C. for 24 hours. The discoloration was evaluated by visually observing the degree of discoloration of the surface of the test piece on which the sample was dropped and based on the following criteria. :: no discoloration 〇: almost no discoloration ×: discoloration present The results are shown in Table 1.

[0030]

By rolling using the rolling oil composition to which the antioxidant of the present invention has been added, quality troubles are reduced, and the acid value of the recovered oil is reduced and the recovery rate is improved.

[0031]

[Table 1]

The compositions of Examples 1 to 9 of the present invention which use a phenolic antioxidant and an amine antioxidant in combination have high stability against oxidation, low ESI value, and almost no discoloration of the steel sheet. In addition, fatty acids and 4-18 carbon atoms
Example of adding a rust inhibitor consisting of an alkylamine salt
It can be seen that the compositions of Nos. 10 to 18 have no discoloration of the steel sheet in addition to the above characteristics. Comparative Examples 1 and 2 in which only one of a phenolic antioxidant and an amine antioxidant was added
3. In Comparative Examples 4 to 6 in which only a rust inhibitor was added, and in Comparative Examples 7 and 8 in which neither an antioxidant nor a rust inhibitor was added, stability against oxidation was low.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C10M 135: 30 133: 12 133: 14 135: 36) C10N 30:10 40:24 (72) Inventor Minoru Namiki Kanagawa 1-4-1 Tsujido Shindai, Fujisawa-shi Kyodo Yushi Co., Ltd. Tsujido Factory (72) Inventor Mitsuru Ogawa 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Kawasaki Steel Corporation Chiba Works (72) Inventor Tomohiro Kaneko Chiba Chiba Prefecture 1 Kawasaki-cho, Chuo-ku, Kawasaki Steel Corporation Chiba Works (72) Inventor Shoji Matsumoto 4-17-8 Kokuradai, Wakaba-ku, Chiba-shi, Chiba (72) Inventor Shozo Ogimoto Chuo-ku, Chiba-shi, Chiba No. 1, Kawasaki-cho, Chiba Works, Kawasaki Steel Corporation (72) Inventor, Teruhiro Saito No. 1, Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture, Chiba Works, Kawasaki Steel Corporation

Claims (8)

[Claims] 1. A rolling oil composition comprising the following components: (a) a base oil containing at least one member selected from the group consisting of animal fats and vegetable fats and oils; (b) a phenolic antioxidant; and (c) an amine antioxidant. 2. A rolling oil composition comprising the following components: (a) a base oil containing at least one selected from the group consisting of animal oils and vegetable oils and fats; (b) phenolic antioxidants; (c) amine antioxidants; and (d) fatty acids and 4 carbon atoms. A rust preventive comprising a salt of an alkylamine of No. 18 to No. 18. 3. The total content of the phenolic antioxidant and the amine antioxidant is 0.1 to 0.1 with respect to the rolling oil composition.
3. The rolling oil composition according to claim 1, which is 5.0% by weight. 4. The weight ratio of the phenolic antioxidant to the amine antioxidant is from 1: 5 to 10: 1.
The rolling oil composition according to any one of claims 1 to 3. 5. The total content of a phenolic antioxidant, an amine antioxidant, and a rust preventive comprising a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms, relative to the rolling oil composition The rolling oil composition according to any one of claims 2 to 4, wherein the content is 0.1 to 10.0% by weight. 6. A weight ratio of a phenolic antioxidant, an amine antioxidant, and a rust preventive comprising a salt of a fatty acid and an alkylamine having 4 to 18 carbon atoms in a ratio of 1: 5: 1 to 1: 5: 1.
The rolling oil composition according to any one of claims 2 to 5, wherein the ratio is 10: 1: 10. 7. The rolling oil composition according to claim 1, which is a direct oiling type cold rolling oil composition. 8. A cold rolling method, wherein cold rolling is performed using the rolling oil composition according to any one of claims 1 to 7.