JP2000087073A - Water-soluble temper rolling liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a temper rolling liquid compsn. which improves the rust- preventive properties of a steel band, does not stick to the surface of a roll, and does not form a viscous matter comprising the same and a rust-preventive oil by incorporating an alkanolamine salt of a benzothiazolylthioalkylenecarboxylic acid and an alkanolamine salt of an aliph. or arom. monocarboxylic or dicarboxylic acid into the same. SOLUTION: Pref. examples of the benzothiazolylthioalkylenecarboxylic acid (A) are 3-(2-Benzothiazolylthio)propionic and 2-benzothiazolylthioacetic acids, the combination of these two acids being still pref. The content of ingredient A is usually 0.2-10.0 wt.%. The aliph. or arom. monocarboxylic or dicarboxylic acid (B) used is usually a satd. one and is contained in a concn. of 3-20 wt.%. Pref., an alkanolamine is used in an amt. of 1.1-1.2 times the amt. necessary for forming the carboxylates. The liq. compsn. is prepd. by adding ingredients A and B to water and adding the alkanolamine little by little under stirring.

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 composition used in a temper rolling process for cold-rolled steel sheets, galvanized steel sheets and the like.

[0002]

2. Description of the Related Art A water-soluble temper rolling solution has been conventionally used for temper rolling of cold-rolled steel sheets and galvanized steel sheets. Since it is water-soluble, it has excellent rust-preventive properties of a steel strip after temper rolling. However, after the temper rolling, in the coiled state, a viscous substance is often generated by the fatty acid amine salt contained in the temper rolling solution and the rust-preventive oil applied to the steel sheet.

On the other hand, a temper rolling solution containing inorganic nitrite and an amine as main components produces nitrosamine. This nitroneamine has carcinogenicity and has a problem in working environment. Therefore, an organic temper rolling liquid is demanded.

[0004]

In the conventional organic temper rolling solution, after the temper rolling of a cold-rolled steel sheet or a galvanized steel sheet, water contained in the temper rolling liquid evaporates, and the excess amine salt of the fatty acid causes the water to evaporate. Crystals break out. Further, barium sulfonate, which is a rust-preventive component of the rust-preventive oil applied after the temper rolling, acts on the fatty acid amine salt contained in the temper rolling solution to generate a viscous substance. These crystals and viscous substances thus deposited adhere and deposit on the surface of the steel sheet or on the surface of a roll such as a leveler roll, which is a subsequent process, and cause dirt and surface flaws on the surface of the steel sheet. Also,
Crystals and viscous substances fixed to the surface of the steel sheet cause irregularities in the dimensional accuracy of the steel sheet in the slitter line, and significantly reduce commercial value.

As a countermeasure against roll surface contamination by these viscous substances, for example, Japanese Patent Application Laid-Open No. 9-302368 proposes a temper rolling liquid mainly composed of a dibasic acid having a cyclohexane ring and an alkanolamine. It is still inadequate because it has some problems with rust properties and is not fully satisfactory.

Further, the present inventors have developed a water-soluble temper rolling solution containing an equimolar alkanolamine salt of a specific carboxylic acid as a main component, and have already filed an application (Japanese Patent Application No. 8-192902).
No., JP-A-10-17888). However, this temper rolling solution has some problems in rust prevention and cannot be said to be always satisfactory.

[0007]

Means for Solving the Problems In view of the above problems, the present inventors have studied various substances having excellent rust prevention properties. In this study, the research was continued, paying attention to the excellent rust-preventing property of the alkali metal salt of benzothiazolylthioalkylenecarboxylic acid (including alkanolamine salt) proposed in Japanese Patent Publication No. 1-28108. However, the alkali metal salt of benzothiazolylthioalkylenecarboxylic acid has a friction coefficient of 0.1.
5, while the coefficient of friction of the alkanolamine salt of benzothiazolylthioalkylenecarboxylic acid was as low as 0.2, indicating that it could not be used for temper rolling.

In the temper rolling of a cold-rolled steel sheet, removal of the elongation at the yield point, surface roughness adjustment, and shape adjustment are performed by rolling at a rolling reduction of 0.3 to several percent. In the case of the temper rolling, the desirable coefficient of friction of the temper rolling solution is determined to be 0.
3 to 0.4. If it is 0.3 or less, the shape cannot be maintained due to excessive elongation, and if it is 0.5 or more, the rolling load is excessively applied and a problem occurs in increasing power consumption and maintaining the shape, and elongation is reduced.

The present inventors have further studied and found that alkanolamine salts of benzothiazolylthioalkylenecarboxylic acids and one or two or more mixed carboxylic acids of aliphatic mono- or dicarboxylic acids and aromatic mono- or dicarboxylic acids were used. It has been found that a temper rolling solution as a main component can solve this problem.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, benzothiazolylthioalkylenecarboxylic acid, which is a main component of a temper rolling liquid, aliphatic mono- and / or dicarboxylic acid, aromatic mono- and / or dicarboxylic acid, and A temper rolling solution composition containing an alkanolamine salt of a mixed carboxylic acid salt obtained by using an alkanolamine is used, and a steel strip temper-rolled by this composition is used as an uncoated oil material to which a rust-preventive oil is not applied. Improves the rust-preventive properties of the steel strip to be shipped, and at the same time, does not cause the temper rolling components with water diffusion to adhere to the surface of each roll, or to act on the rust-preventive oil applied in the later process. It was found not to produce a viscous material. It has also been found that there is an advantage that the elongation of the steel sheet during rolling can be controlled by the difference in the steel type as the temper rolling liquid.

The rust preventive effect of the benzothiazolylthioalkylene carboxylic acid used in the present invention is described in
No. -28108 and Rust Prevention Control Vol. 35, No. 12
It is used in cooling water systems or heating systems of chemical plants in contact with water, rust preventive oils, paints, concrete rust preventives, highly hydrated hydraulic fluids, especially where there are many combinations of various metals. It is described as being effective in antifreeze for vehicles and heat transfer systems in solar systems.

It should be particularly noted that benzothiazolylthioalkylenecarboxylic acid is used as a sodium salt, a potassium salt or an amine salt, and these are all crystalline or viscous. Even if it is used as a rolling liquid component, it is not possible to suppress surface contamination due to sticking to a roll or formation of a viscous material due to action with a rust preventive oil.

[0013] The role of benzothiazolylthioalkylenecarboxylic acid as a temper rolling solution component used for temper rolling of cold rolled steel sheets and the like and the role of a rust inhibitor in the above-mentioned materials are completely different regions. The purpose and conditions of use are completely different. In temper rolling of cold-rolled steel sheets, the required performance is not limited to rust prevention, but the required performance is long-term rust prevention in a dry state where the steel strip is free of moisture and direct paintability on steel sheets. Or, immediately after temper rolling, after applying a rust-preventive oil and coiling, it is not adversely affected even if the temper-rolling liquid component and the rust-preventive oil adhere to the steel strip surface over time, and Is that the temper rolling component adhering to the steel strip surface does not affect the chemical conversion property.

One of the properties required of the temper rolling solution is that the elongation of the steel sheet in the temper rolling operation can be easily controlled. That is, it relates to lubricity. For example, in the case of general carbon steel, the friction coefficient (μ) measured by a pendulum type friction tester is preferably in a range of 0.30 to 0.40, but benzothiazolylthio. The friction coefficient of the alkylene carboxylate sodium salt or potassium salt is as high as about 0.5, and the friction coefficient of the amine salt is too low as about 0.2, which is problematic in workability. The used aqueous solution has an effect on the temper rolling property.

Surprisingly, however, the coexistence of the aliphatic carboxylic acid and the aromatic carboxylic acid amine salt as in the present invention makes it possible to maintain a friction coefficient suitable for the temper rolling property.

The main component of the temper rolling solution of the present invention, 3-
Temper rolling by complex amine salt of benzothiazolylthioalkylenecarboxylic acid such as (2-benzothiazolylthio) propionic acid or 2-benzothiazolylthioacetic acid, aliphatic fatty acid or aromatic fatty acid and alkanolamine At the time, the contamination of the roll surface, the roll surface such as a leveler roll, or the like on the surface of the steel strip is suppressed. Further, there is no generation of viscous material without being affected by the rust-preventive oil applied in the post-process of temper rolling.

As the benzothiazolylthioalkylene carboxylic acid of the present invention, in particular, 3- (2-benzothiazolylthio) propionic acid or 2-benzothiazolylthioacetic acid is required for the surface treatment of a water-soluble temper rolling fluid. The roll printability on the surface and the uncoated oily steel strip are excellent in long-term rust prevention in a coil state, and the combination of these is particularly preferable. But,
In the present invention, it is needless to say that the present invention is not necessarily limited to these. For example, 4-methyl-2-benzothiazolylthioacetic acid, 6-hydroxy-2-benzothiazolylthioacetic acid, 2-benzothia Zolylthioformic acid, 3
-(4-benzothiazolylthio) propionic acid, 3-
(6-hydroxy-2-benzothiazolylthio) propionic acid, 3- (6-amino-2-benzothiazolylthio) propionic acid, 3- (4,6-dimethyl-2-benzothiazolylthio) propionic acid , 2- (2-benzothiazolylthio) propionic acid, 2- (4-methylbenzothiazolyl) propionic acid and the like are effectively used.

The content of the benzothiazolylthioalkylene carboxylic acid as a component of the temper rolling liquid is 0.2 to 10.
0% by weight, preferably 0.3 to 5.0% by weight. If the content is less than 0.3% by weight, the steel sheet after temper rolling is not sufficiently effective in preventing rust, and 5.0% by weight.
Even if it is added more, it is economically disadvantageous because the effect is not changed.

The aliphatic mono- and dicarboxylic acids and the aromatic mono- and dicarboxylic acids which can be used in the present invention are described below.

As the aliphatic mono- and dicarboxylic acids, saturated carboxylic acids are usually used. Unsaturated carboxylic acids are inferior in oxidative stability of the water-soluble temper rolling fluid over time, or are liable to be deteriorated during use. This is not preferable because it causes problems. Preferred specific examples of these fatty acid mono- and 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. 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. For example, succinic acid, adipic acid, azelaic acid, sebacic acid and the like. Preferred specific examples of the aromatic mono- and dicarboxylic acids are as follows.

(C) Aromatic monocarboxylic acid. Examples thereof include toluic acid, phenoxyacetic acid, thiophenoxyacetic acid, methoxybenzoic acid, P-tert-butylbenzoic acid, ethoxybenzoic acid, and hydroxybenzoic acid.

(D) Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

These carboxylic acids are usually 3 to 20% by weight,
It is preferably used in an amount of 5 to 15% by weight.

As the alkanolamine in the present invention, those commonly used in water-soluble refining rolling fluids are widely used. Specifically, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like are more preferable.

A mixed carboxylic acid amine salt is formed with the carboxylic acid and the alkanolamine, and is solubilized in water. Form carboxylic acid amine salt in advance and solubilize in water,
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.

Known surfactants can be used in the temper rolling solution of the present invention to improve wettability, for example, cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants can be used. . Preferably, a nonionic surfactant such as polyoxyethylene glycol alkyl ether or polyoxyethylene glycol alkylphenol ether may be added in the range of 0.1 to 5.0% by weight.

Other additives include, for example, ethylenediaminetetraacetic acid and nitriloacetic acid as chelating agents, and NaOH or KOH as alkali metals.

The rust-preventive oil applied to the steel sheet is a well-known oil generally used, and barium sulfonate, calcium sulfonate and the like are added to mineral oil.

The alkanolamine as the temper rolling solution component of the present invention is used in an amount larger than necessary to form an alkanolamine salt of a carboxylic acid, and may be used in a range of 1.1 to 1.2 times. preferable. The characteristics required for the water-soluble temper rolling liquid are that the cold-rolled steel sheet after temper rolling is kept rustproof and that the fatty acid amine salt, which is a component of the temper rolling liquid, has low viscosity. If the excess amine salt is unnecessarily large, it acts with the rust-preventive oil applied in the post-pressure adjustment process to form a viscous substance, for example, adheres to a roll surface such as a roller leveler or a stretcher leveler, or a shearing line or The dimensional accuracy is disturbed by the adhesion and deposition of a viscous substance on a slitter line such as a blanking line, causing a problem.

In preparing the temper rolling liquid of the present invention, predetermined amounts of benzothiazolylthioalkylenecarboxylic acid and aliphatic and aromatic carboxylic acids are added to water, and alkanolamine is added little by little with good stirring. It may be prepared by a method of forming a carboxylic acid amine salt and solubilizing it.

When using the temper rolling solution of the present invention, the same method as in the prior art may be used.
Used after being diluted with a 0% aqueous solution, a temper rolling liquid is discharged from a spray nozzle to a roll surface and uniformly adhered to a steel plate surface.

The rolled material as an object using the temper rolling solution of the present invention is the same as the conventional one. For example, in the case of cold-rolled steel sheet, ordinary carbon steel sheet, high carbon steel sheet, high tensile steel sheet, electromagnetic steel sheet, stainless steel sheet or stainless steel sheet is used. It is a galvanized steel sheet or the like.

[0035]

EXAMPLES The features of the present invention will be described in detail with reference to examples of the present invention and comparative examples.

[0036]

EXAMPLES 1 TO 8 AND COMPARATIVE EXAMPLES 1 TO 9 Temper rolling solutions were prepared using the components shown in Table 1. That is, a predetermined amount of a carboxylic acid, an alkanolamine and water were added to prepare various temper rolling solutions. This aqueous solution was further diluted with water to a 10% by weight solution and subjected to the tests of the following items (1) to (4).
On the other hand, the evaluation of the component properties after the water of the water-soluble temper rolling liquid was heated and evaporated was performed for the following item (5).

<Production of test article> Annealed material (nitrogen gas 95
%, Hydrogen gas 5% atmosphere, annealed at 700 ° C for 1 hour) Oil-free cold-rolled steel plate SPCC-SD (width 100 ×
Roll (roll diameter 170 mm, roll surface roughness Ra) using a temper rolling solution shown in Table 1 using a 0.6 mm coil.
= 0.2-0.03 μm, backup roll 400m
m, reduction rate 2%, speed 15 m / min), and the water adhering to the coil surface was blown off with a nitrogen gas on the roll exit side and wound up. 100x100mm from temper rolled coil
A test piece was cut to a size and subjected to the following tests (1), (2) and (3).

On the other hand, a temper-rolled coil was coated with a rust-preventive oil ("DAIRAX RX900V", manufactured by Daido Chemical Co., Ltd.) and a tension leveler (roll diameter 20 mm, lower roll 1) was applied.
0, 9 upper rolls / 50 kg / cm ^{2 of} pressure). 100x100m from oiled coil after leveler treatment
The test piece was cut into an m size and subjected to the test of the following item (3).

<Measurement Items> (1) Veneer Exposure Test Each of the temper-rolled test pieces (100 × 100 mm) was placed on a pedestal in which a groove was cut in a plastic plate, and exposed for 10 days in a hundred-leaf box. The rust occurrence on one surface was visually observed to evaluate the rust prevention. (2) Wetness test (test piece stacking test) Five sets of test pieces (100 x 100 mm) that have been temper-rolled are fixed as a set and fixed by pressing with a clip, according to JIS K-22.
After leaving still for one week in a wet test apparatus according to 46, take out,
The state of rusting of the stacked test pieces was observed to evaluate rust prevention. (3) Rust prevention oil application wetness test (test piece stacking test) Specimens (100 × 100
mm) A set of 5 stacks is fixed by crimping with a clip,
After standing for 2 weeks in a wet test apparatus according to JIS K-2246, the test pieces were taken out, and the surface of the stacked test pieces was observed for oil spots to evaluate rust prevention. (4) Measurement of Coefficient of Friction The sliding surface of a cold-rolled steel plate (SPCC-SD) was degreased with a solvent and filled with a temper rolling liquid, and the friction coefficient was measured with a Soda pendulum friction tester. (5) Properties of Temper Rolling Liquid after Evaporation of Moisture The temper rolling liquid is collected in a petri dish and placed in an oven at 70-70.
The mixture was heated to 80 ° C., and the properties of the components after water evaporation were observed. (6) The temper rolling liquid was heated, and the properties of the components after 1 g of the components after water evaporation and 10 g of rust-preventive oil were sufficiently mixed were observed. Table 2 shows the above characteristics. In addition, Table 1 and Table 2 show the results of similarly treating a commercial product as a control.

[0040]

[Table 1]

The details in Table 1 are as follows.
A commercially available temper rolling solution is "Daiskin P-60K" manufactured by Daido Chemical Co., Ltd. (*): Sanshin Chemical Industry Co., Ltd. product

[0042]

[Table 2]

The evaluation of each physical property in the above Table 2 is as follows. (1) Rust generation score: 100 excellent> 50 possible (2) ○: No rust generation △: Some rust generation (3) ○: No oil stain generation △: Some oil stain or rust generation (4) Normal carbon steel Case (μ) ○: 0.30 to 0.40 ×: 0.29 or less or 0.41 or more (5) ○: Low viscous liquid at 35 ° C ×: Crystalline or solid at 35 ° C (6) ○: No gum-like viscous material ×: Gum-like viscous material generated

[Table 1-1]

[Table 1-2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 105: 28 105: 30 105: 62) C10N 30:00 40:24 (72) Inventor Mitsuru Tani Osaka 1-2-2-1400 Umeda, Kita-ku, Osaka F-term (reference) in Daido Chemical Co., Ltd. 4H104 BB16C BB17C BB18C BB22C BB23C BE04C BG17C LA06 LA20 PA23 PA29 PA34 QA05 QA09

Claims (4)

[Claims] 1. A benzothiazolylthioalkylene carboxylic acid, (b) one or more mixed carboxylic acids of aliphatic mono- or dicarboxylic acids and aromatic mono- or dicarboxylic acids, and respective alkanolamine salts A water-soluble temper rolling solution composition comprising: 2. The method according to claim 1, wherein the benzothiazolylthioalkylene carboxylic acid is 3- (2-benzothiazolylthio) propionic acid,
Or the water-soluble temper rolling solution composition according to claim 1, which is 2-benzothiazolylthioacetic acid. 3. The water-soluble temper rolling composition according to claim 1, wherein the carboxylic acid is an aliphatic fatty acid and is a saturated monocarboxylic acid having 3 to 18 carbon atoms. 4. The carboxylic acid is an aliphatic fatty acid and is a saturated dicarboxylic acid having 4 to 12 carbon atoms.
The water-soluble temper rolling liquid composition according to the above.