JP2002212583A - Tempering rolling liquid composition having excellent adhesion suppressing property of zinc abrasive powder to rolling roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble tempering rolling liquid composition having excellent suppressing effects on adhesion of zinc powder produced from a plated surface to a rolling roll in a tempering rolling step of a galvanized steel plate or a one-surface galvanized metal plate. SOLUTION: This water-soluble tempering rolling liquid composition comprises (a) one or more kinds of benzotriazoles, benzothiazolylthioalkylenecarboxylic acids and pyrazoles and (b) an alkanolamine salt of one or more kinds of aliphatic mono- or dicarboxylic acids and aromatic mono- or dicarboxylic acids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble temper rolling solution which is excellent in the effect of suppressing adhesion of zinc powder generated from a galvanized surface to a rolling roll in a temper rolling process of a galvanized steel sheet or a single-sided galvanized steel sheet. Composition.

[0002]

2. Description of the Related Art In the case of galvanized steel sheets or alloy galvanized steel sheets, temper rolling using only water is generally performed. In hot-dip galvanizing, in order to eliminate spangles, temper rolling under light rolling is performed with rolls that have been subjected to dull roll processing to zero spangles, but in this case also, rolls of zinc powder from the galvanized surface accompanying rolling In order to cause the adhesion phenomenon to the surface, a cleaning operation of the roll surface is required.

Further, as a means for improving the coating appearance of the galvanized surface and for enhancing the sharpness or for improving the workability of the galvanized steel sheet, the roughness of the roll is adjusted to be high and the pressure is adjusted under high pressure. When temper rolling is performed, the generation of zinc powder from the galvanized surface or the alloy-plated surface also increases, the wrapping phenomenon of the zinc powder on the rolling roll increases, and the roll and the steel plate surface are flawed, Not only does the product value decrease, but also the rolling workability is significantly impaired.

[0004]

The conventional water-soluble temper rolling solution for galvanized steel sheets is different from the case of temper rolling for cold-rolled steel sheets in general, without using an aqueous solution containing a fatty acid amine salt or the like. Usually, temper rolling with water is simply performed. The reason is that after temper rolling of galvanized steel sheet,
This is because a chemical conversion treatment and a chromate treatment are performed, so that adverse effects due to the refining liquid component are avoided. However, in the case of temper rolling using only water, a large amount of zinc powder is generated from a galvanized steel sheet or an alloy galvanized steel sheet, and the phenomenon of adhesion to the rolling rolls increases. Is generated.

[0005] Therefore, the zinc powder wound around the roll must be removed once using a brush or the like after the rolling operation is interrupted, which significantly reduces the workability and affects the commercial value. . There is a demand for the development of a water-soluble temper rolling fluid that can solve such a problem.

[0006]

In order to prevent the adhesion of zinc powder to rolls caused by temper rolling of hot-dip galvanized or hot-dip galvanized steel sheets, the present inventors have proposed a method of manufacturing a hot-dip galvanized steel sheet. It is believed that this can be solved by inactivating the zinc surface in some way. As one of the methods, by using a substance having high reactivity with zinc as a component of the temper rolling liquid, a reactive film is formed on the zinc surface, chemically deactivated, and adhesion of zinc powder is prevented. It is to suppress.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the temper rolling solution used in the temper rolling process can be used in combination with zinc without affecting workability. The present invention has been completed by finding a substance having high reactivity and capable of forming a passivation film chemically.

In the study of the temper rolling solution of the present invention, as a result of various investigations on substances which react effectively with zinc, a temper capable of chemically inactivating the zinc surface and suppressing adhesion to a rolling roll was obtained. As the rolling material composition, one or more of benzotriazoles, benzothiazolylthioalkylenecarboxylic acids and pyrazoles and one or more of aliphatic mono- and / or dicarboxylic acids and aromatic mono- and / or dicarboxylic acids are used. It has been found that an aqueous solution comprising an alkanolamine salt of a carboxylic acid can solve this problem.

[0009] Among the benzotriazoles used in the present invention, 5-methylbenzotriazole is known as having a rust-preventing effect on copper and copper alloys, as is known. Also, 1-hydroxybenzotriazole is used as a rust-prevention treatment method for steel sheets, or as a water-soluble temper rolling solution for cold-rolled steel sheets, Japanese Patent Nos. 947871 and 1083154,
1247843 and 1376638. As for benzotriazolylthioalkylene carboxylic acid, JP-A-2000-87073 discloses a water-soluble temper rolling composition. Except for 5-methylbenzotriazole, all of which are related to the temper rolling property and the rust prevention property for the cold rolled steel sheet of ordinary steel, and the temper rolling solution of the present invention, at the time of temper rolling of galvanized steel sheet, Preventing the zinc powder generated from zinc from adhering to the rolling rolls has a completely different purpose and a different role. On the other hand, rust prevention of zinc iron plate or partially galvanized or alloyed galvanized steel plate with pyrazoles The processing method is disclosed in Japanese Patent Nos. 1083154 and 938557 and Japanese Patent Publication No. 62-31072. These are rust preventive treatment methods for a galvanized steel sheet or a partially galvanized steel sheet surface, and they do not exert an effect for suppressing the adhesion of zinc to a rolling roll in the present invention. However, it was found that pyrazoles also exhibited an effect of suppressing adhesion to a rolling roll when coexisted with benzotriazoles or benzothiazolylthioalkylenecarboxylic acids.

The temper rolling solution composition of the present invention suppresses the adhesion of zinc powder to rolls generated during temper rolling of a galvanized steel sheet and, at the same time, disperses moisture on the surface of the galvanized steel sheet after the temper rolling. After that, the temper rolling liquid component does not generate any viscous material, and therefore, is fixed to each roll and does not cause surface contamination. It has no effect on chemical conversion treatment such as chromic acid treatment or applied rust preventive oil.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (a) benzotriazoles and benzothiazolylthioalkylenes are used as a temper rolling solution composition which exhibits an effect of suppressing adhesion of zinc powder to a temper roll. This composition contains one or more carboxylic acids and pyrazoles, and (ii) an alkanolamine salt of one or more carboxylic acids of aliphatic mono- and / or dicarboxylic acids and aromatic mono- and / or dicarboxylic acids. By the aqueous solution containing, when performing temper rolling, adhesion of zinc powder to the rolling rolls is suppressed,
In addition, it is possible to manufacture a high-quality galvanized steel sheet that does not cause the surface of the steel sheet to be stained or flawed without the rolling liquid component after moisture diffusion on the steel sheet surface after the temper rolling being fixed to each roll. Further, it has been found that as a temper rolling solution for a galvanized steel sheet, favorable results can be obtained in preventing white rust on zinc, as compared with the case of temper rolling by simple water.

Examples of the benzotriazole used in the present invention include benzotriazole, 5-methylbenzotriazole and 1-hydroxybenzotriazole, and are not limited to these substances. -Hydroxybenzotriazole is preferred, and as a temper rolling solution component, forms a reactive coating on the surface of zinc powder generated at the time of temper rolling of a galvanized steel sheet, and can effectively suppress adhesion to rolls. The amount is used in the range of 0.5 to 10% by weight, preferably 2 to 5% by weight, based on the whole composition.

The pyrazoles include pyrazole, 3,
5-dimethylpyrazole, 4-amino-3, 5-dimethylpyrazole, 3-acetoxy-5-pyrazolone, 5-
Pyrazolone, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole, etc., as a temper rolling solution component of a galvanized steel sheet, for suppressing the adhesion of zinc powder to a rolling roll and for suppressing white rust. 0.5 to 10% by weight, preferably 1
It is used in the range of ５5% by weight.

Examples of the benzothiazolylthiocarboxylic acid include 3- (2-benzothiazolylthio) propionic acid,
2-benzothiazolylthioacetic acid, etc., as a temper rolling solution component, the amount necessary to inactivate the surface of zinc powder generated during temper rolling of galvanized steel sheet and to suppress adhesion to a roll is It is used in an amount of 0.5 to 10% by weight, preferably 2 to 5% by weight.

The benzotriazolylthioalkylene carboxylic acid used in the present invention is used as a rust preventive, as disclosed in Japanese Patent Publication No. 28108/93, with a cooling water system or a heating system with a chemical plant in contact with water. , Rust preventive oil, paint, concrete rust preventive, high water content hydraulic fluid, especially
It has been described that it is effective in antifreeze used in places where there are many combinations of various metals and a heat medium system in a solar system, and a temper rolling fluid capable of suppressing the adhesion of the zinc abrasion powder of the present invention to a roll. It is an area completely different from the role described in the above-mentioned patent gazette because the purpose and use conditions are different from those used as a composition. The alkylene of the benzotriazolylthioalkylenecarboxylic acid generally has about 1 to 5, preferably about 1 to 2 carbon atoms.

The aliphatic carboxylic acid and aromatic carboxylic acid which can be used in the present invention will be described. As the aliphatic mono- and / or dicarboxylic acids, saturated carboxylic acids are usually used, and unsaturated ones are poor in oxidation resistance over time in water-soluble temper rolling, or easily deteriorated during rolling, causing a problem in required performance. This is not preferred because it occurs.
Preferred specific examples of these fatty acid mono- and / or dicarboxylic acids are as follows.

(A) An aliphatic saturated monocarboxylic acid having 3 to 18 carbon atoms, particularly one having 6 to 12 carbon atoms is preferred. At this time, if the number of carbon atoms is less than 3, the rust-proofing property is inferior, and if it exceeds 18, the carboxylic acid amine salt tends to have a high viscosity. Specific examples include hexanoic acid, heptanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, and 2-butyloctanoic acid. (B) An aliphatic saturated dicarboxylic acid having 4 to 12 carbon atoms. If the carbon number is less than 4, the rust-preventing effect is small, and if it is larger than 12, the amine dicarboxylate tends to be crystalline. For example, preferred specific examples are succinic acid, adipic acid, azelaic acid, sebacic acid and the like.

Preferred specific examples of the aromatic mono- and / or dicarboxylic acids are as follows. (C) an aromatic monocarboxylic acid. For example, toluic acid, phenoxyacetic acid, thiophenoxyacetic acid, methoxybenzoic acid, P-tert-butylbenzoic acid, ethoxybenzoic acid, hydroxybenzoic acid, aminobenzoic acid, nitrobenzoic acid, and the like.

(D) Aromatic dicarboxylic acids. For example, phthalic acid, isophthalic acid, terephthalic acid, and the like.

These carboxylic acids are usually used in an amount of 0.5 to 6
%, Preferably in an amount of 2 to 5% by weight.

As the alkanolamine in the present invention, those commonly used in water-soluble temper rolling fluids can be widely used. Specifically, monoethanolamine,
Diethanolamine, triethanolamine, monoisopropanolamine diisopropanolamine, diisopropanolamine, triisopropanolamine and the like can be more preferably used.

A mixed carboxylic acid amine salt is formed with the carboxylic acid and the alkanolamine, and
Alternatively, a predetermined amount of a carboxylic acid and an amine may be added to water to form a salt in an aqueous solution and solubilized.

In the temper rolling liquid of the present invention, known surfactants can be used to improve the wettability of the steel sheet surface, and examples thereof include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. Agent can be used. Preferably, nonionic surfactants such as polyethylene glycol alkyl ether and polyoxyethylene glycol alkyl phenol ether may be added in the range of 0.1 to 3% by weight.

Other additives include chelating agents having a role of sequestering metal ions in an aqueous solution, for example, aminopolycarboxylic acids, for example, ethylenediamine diacetate, ethylenediaminetetraacetic acid, nitriloacetic acid, and alkali metals, such as NaOH or KOH and the like.

The alkanolamine as the temper rolling solution component of the present invention is slightly larger than the amount required to form an alkanolamine salt of a carboxylic acid,
It is preferable to use in the range of 1.2 times. The property required for the water-soluble temper rolling fluid is that the carboxylic acid amine salt, which is a component of the temper rolling fluid adhered to the surface of the galvanized steel sheet after the temper rolling, retains a low viscosity. If the amount of excess free amine is more than necessary, it acts with the rust-preventive oil applied in the post-process of temper rolling to produce a viscous substance, for example, adheres to the roll surface of a roller leveler or a stretcher leveler, Alternatively, dimensional accuracy is disturbed due to the accumulation of viscous substances on a slitter line such as a shirring line or a blanking line, which causes a problem.

In the temper rolling solution of the present invention, known surfactants can be used to improve the wettability of the steel sheet surface. Examples thereof include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. Agent can be used. Preferably, a nonionic surfactant such as polyethylene glycol alkyl ether or polyoxyethylene glycol alkylphenol ether may be added in the range of 0.1 to 3% by weight.

The properties required after the temper rolling of the present invention include the ability to easily control the reduction and the like of the galvanized steel sheet in the temper rolling operation, that is, the properties related to lubricity. It is easy to control the conditions.

Further, in order to improve the appearance of the galvanized steel sheet, regardless of the roll roughness, the effect of suppressing the adhesion of the zinc abrasion powder generated during the temper rolling to the roll is not impaired, or the galvanized steel sheet is not plated. The temper rolling solution component adhering to the steel sheet surface does not adversely affect the chemical conversion treatment.

The temper rolling solution of the present invention can be used in the same manner as in the conventional temper rolling of cold rolled steel sheets. The adjusted temper rolling solution is used after being diluted with a 5 to 10% aqueous solution. ,
The temper rolling liquid is discharged from the spray nozzle to the surface of the rolling roll, and is uniformly adhered to the steel plate surface.

The material to be rolled using the temper rolling solution of the present invention is a galvanized steel sheet, an alloy galvanized steel sheet, a single-sided galvanized steel sheet thereof, or the like.

[0031]

EXAMPLES Next, the features of the temper rolling fluid of the present invention will be described in detail with reference to Examples and Comparative Examples of the present invention.

[0032]

Examples 1 to 10 and Comparative Examples 1 to 6 Temper rolling liquids comprising the components shown in Table 1 (Example) and Table 2 (Comparative Example) were prepared. The properties of these rolling solutions were measured by the following test methods. The results are shown in Table 3 (Example) and Table 4.
(Comparative Example)

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

The evaluations in Tables 3 and 4 are as follows. Evaluation of inhibition of zinc powder adhesion ○: Excellent △: Good ×: Not possible Rust prevention evaluation ○: No rust generation △: Slight rust generation X: Notable rust generation

[0038]

[Temperature rolling test] Oil-free hot-dip galvanized plate (width 100 x
(0.6 mm) was subjected to temper rolling under the following conditions with the temper rolling solution shown in Table 1, and the water adhering to the coil surface was blown off with a nitrogen gas at the roll exit side and wound up. A test piece of 100 × 100 mm size was cut out from the temper-rolled coil and subjected to the test of the following measurement item (2).

[0039]

[Temperature rolling conditions] Small four-roll mill Roll diameter: 170 mm Roll surface roughness: Ra =
2.6-2.8μ Backup roll: 400mm Temper rolling speed: 15m / min Reduction rate: 1%

[0040]

[Measurement items] (1) Evaluation of the ability of zinc powder to prevent adhesion to rolling rolls A hot-dip galvanized coil having a length of 200 m was temper rolled under the above rolling conditions. At every 50 m, the surface of the rolling roll was observed, and the degree of adhesion of zinc powder generated during rolling was examined. (2) Wetness test (test piece stacking test) A set of five temper-rolled test pieces was fixed by crimping with a clip, and after standing for one week in a wetness test device according to JISK-2246. The rusting state of the test pieces taken out and stacked was observed and evaluated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 129/42 C10M 129/42 129/50 129/50 129/52 129/52 133/38 133/38 133 / 44 133/44 135/32 135/32 // C10N 30:00 C10N 30:00 Z 30:12 30:12 40:24 40:24 Z (72) Inventor Mitsuru Tani 1-2-1, Umeda, Kita-ku, Osaka-shi No.2-1400 Daido Chemical Co., Ltd. F term (reference) 4E002 AD06 BC08 BC10 CB09 4H104 AA01C BB16C BB18C BB22C BB23C BE26C BE29C BG17C EA17Z LA06 LA20 PA29 PA34 QA01

Claims (3)

[Claims] (1) one or more of (a) benzotriazoles, benzothiazolylthioalkylenecarboxylic acids and pyrazoles and (b) one or more of aliphatic mono- or dicarboxylic acids and aromatic mono- or dicarboxylic acids; A water-soluble temper rolling liquid composition containing a alkanolamine salt of a carboxylic acid, which is excellent in inhibiting adhesion of zinc powder to a roll during temper rolling of a galvanized steel sheet. 2. The carboxylic acid is an aliphatic carboxylic acid,
2. A saturated monocarboxylic acid having 3 to 18 carbon atoms.
The water-soluble temper rolling liquid composition according to the above. 3. The carboxylic acid is an aliphatic carboxylic acid,
The water-soluble temper rolling fluid according to claim 1, which is a saturated dicarboxylic acid having 3 to 12 carbon atoms.