JPH1135966A - Water-soluble temper rolling solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble temper rolling soln. which, even after evaporation of water on the surface of a steel strip or the surface of rolls in the step of temper rolling, can inhibit precipitation of a crystal of the amine salt of the carboxylic acid by comprising a salt of a carboxylic acid with an alkanolamine or an alkali metal, and a water-soluble org. solvent. SOLUTION: This water-soluble temper rolling soln. comprises: 100 pts.wt. water-soluble temper rolling soln.; 0.5 to 40 pts.wt. salt of a carboxylic acid with an alkanolamine or an alkali metal; and 0.5 to 10 pts.wt. water-soluble org. solvent. Carboxylic acids usable herein include 3-8 satd. or unsatd. monocarboxylic acids, or 4-12C, satd. or unsatd. dicarboxylic acids, aliph. satd. hydroxy mono- or polycarboxylic acids, arom. mono- or dicarboxylic acids, cyclohexanecarboxylic acid, and (iso)nicotinic acid. Water-soluble org. solvents usable herein include glycols, polyglycols, glycol ethers, polyglycol ethers, and glycidyl ethers.

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 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 is used in a temper rolling process for cold-rolled steel sheets and galvanized steel sheets. As a matter of course, generally, a rust-preventive oil is applied in a post-process, and when the rust-preventive oil is mixed into the temper rolling liquid component in a state where the steel strip is coiled, a viscous substance may be generated. On the other hand, the inorganic temper rolling fluid containing nitrite reacts with alkanolamine to produce nitrosamine, which has a problem that adversely affects the human body. I have.

[0003]

The conventional organic refining rolling fluid is used after the temper rolling process of a cold rolled steel sheet or a galvanized steel sheet.
Sticking substances are formed on the surface of the steel strip by the crystalline precipitate of the carboxylic acid amine salt due to the evaporation of water. As a result, precipitates accumulate on the roll surface in the next step, which induces surface scratches on the steel sheet. In addition, the rust-preventive oil applied after rolling with the temper rolling solution and the amine carboxylate or excess amine, which is a component of the temper rolling solution, cause the steel strip to become viscous due to the heat of the steel strip during rolling and the pressure during coiling. A substance is generated which is mixed into the rust preventive oil. This viscous material is disturbed in dimensional accuracy due to gum-like stains due to adhesion to the roll surface in the next step, or sticky materials in the slitter line, causing a problem in workability.

The present inventor has been working on solving the problem of the temper rolling solution in the past. In this study, an equimolar salt of a carboxylic acid and an alkanolamine was used. A water-soluble temper rolling solution to which a liquid or amorphous carboxylic acid amine salt is added has been developed and has already been filed (Japanese Patent Application Laid-Open No. 8-192902). However, in certain exposure environments, water-soluble organic solvents coexist in the temper rolling solution in consideration of the fact that conventional crystalline salts may have better rust-proofing properties than the above-mentioned amine carboxylate in some cases. By doing so, the alkanolamine salt of the carboxylic acid is not limited to an equimolar salt and is not limited to being liquid or amorphous at room temperature, and may be in the form of a crystal (solid) or an excess of alkanolamine. It has been found in a subsequent study that a temper rolling solution which does not cause the above-mentioned problems can be prepared even if it is present in the steel. Conventionally, an excess alkanolamine has been used in the temper rolling fluid. The reason for this is that most of the conventional carboxylic acid amine salts used in the refining rolling liquid are crystalline (solid), so that the crystalline salt is dissolved and homogenized by coexisting with an excess of alkanolamine. And has been used for more stably maintaining rust prevention. That is, the present inventor can solubilize even a crystalline (solid) carboxylic acid amine salt by using a water-soluble organic solvent in combination, and even if excess alkanolamine coexists, It has been newly found that the reaction with the rust-preventive oil applied in the step can be suppressed, and the above problem can be solved.

[0005]

That is, the present invention provides a steel strip surface in a temper rolling step by coexisting a water-soluble organic solvent in a water-soluble temper rolling liquid containing a carboxylic acid amine salt as a main component. Alternatively, even after the evaporation of water on the surface of each roll, a water-soluble temper rolling liquid capable of suppressing a crystalline precipitate of a carboxylic acid amine salt or an alkali metal salt can be obtained.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a conventional organic water-soluble temper rolling solution, a crystalline carboxylic acid, for example, adipic acid or an aromatic carboxylic acid such as nitrobenzoic acid, may be used in the form of alkanolamine or sodium hydroxide. By adding an alkali metal salt such as potassium hydroxide or the like, a salt is formed in an aqueous solution to be solubilized in water. Further, for the purpose of improving rust resistance, an excess of alkanolamine is usually added to carboxylic acid, which adversely affects the next step or workability. On the other hand, in the present invention, the alkanolamine carboxylate or alkali metal salt, which is a main component of the water-soluble temper rolling liquid, and a water-soluble organic solvent are allowed to coexist, so that the surface of the steel strip after temper rolling is applied. It can homogenize the kimono and prevent the reaction with the rust preventive oil applied in a later step.

[0007] Even if the alkanolamine carboxylate or alkali metal salt used as the main component of the water-soluble temper rolling liquid has a crystalline (solid) property after water evaporation, the salt is dissolved and homogenized. By coexisting a water-soluble organic solvent having a function of forming a hardening solution, it is possible to prepare a water-soluble temper rolling liquid which does not cause precipitation of a hard salt on the surface of a steel strip or the surface of each roll as in the related art. Hereinafter, the carboxylic acid and the water-soluble organic solvent that can be used in the present invention will be described in detail.

(1) Carboxylic acids usable in the present invention (a) Saturated or unsaturated carboxylic acids having 3 to 18 carbon atoms,
Or a saturated or unsaturated dicarboxylic acid having 4 to 12 carbon atoms, specifically, vivalic acid, hexanoic acid, heptanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, decanoic acid, undecanoic acid, 2-butyloctanoic acid, Citraconic acid, itaconic acid, oleic acid and the like.

(B) Aliphatic saturated dicarboxylic acids having 4 to 12 carbon atoms Specific examples include malonic acid, succinic acid, glutaric acid,
Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like.

(C) Aliphatic unsaturated dicarboxylic acid having 4 to 12 carbon atoms The dicarboxylic acid is preferably one having 4 to 7 carbon atoms. Specific examples thereof include fumaric acid, mesaconic acid, and methylene succinic acid. Acid, isopropylidene succinic acid,
Examples thereof include 2,4-hexanedienedioic acid.

(D) Aliphatic saturated hydroxycarboxylic acid or hydroxypolycarboxylic acid The carboxylic acid in this example is preferably one having 2 to 6 carbon atoms, for example, glycolic acid, lactic acid, glyceric acid,
Citric acid can be exemplified.

(E) Aromatic monocarboxylic acid and aromatic dicarboxylic acid Specifically, for example, benzoic acid, salicylic acid, nitrosalicylic acid, o-, m- and p-toluic acid, phthalic acid, isophthalic acid, terephthalic acid -, M- and p-nitrobenzoic acid, n-butylbenzoic acid, t-butylbenzoic acid, p
-Methoxybenzoic acid, phenoxyacetic acid and the like.

(F) cyclohexanedicarboxylic acid For example, cyclohexane-1,2-, 1,3- and 1,
Examples thereof include 4-dicarboxylic acid.

(I) One-nitrogen heterocyclic monocarboxylic acid Examples of the one-nitrogen heterocyclic monocarboxylic acid include nicotinic acid and isonicotinic acid.

Most of the carboxylic acids used in the water-soluble temper rolling fluid as described above are usually crystalline, but can be converted to alkanolamine or alkali metal salts such as sodium hydroxide and potassium hydroxide to obtain water-soluble carboxylic acids. And effectively act on rust prevention or friction characteristics.

(2) Water-soluble organic solvent used in the present invention The water-soluble organic solvent used in the present invention is a carboxylic acid alkanolamine salt or a carboxylic acid sodium or potassium salt, etc. The purpose of this is to homogenize without depositing and solidifying on the surface, and specific examples of the water-soluble organic solvent to be used include the following.

(A) Glycol Ethylene glycol, polyethylene glycol or propylene glycol having an average molecular weight of 700 or less, preferably 200 to 700, and an average molecular weight of 700 or less, preferably 200 to 700
700 polypropylene glycol, polyethylene glycol diacetic acid, 1,3-butylene glycol, tetramethylene glycol, pentamethylene glycol, hexylene glycol, octylene glycol and the like.

(B) Glycol ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyethylene glycol alkyl ether (an alkyl group having 6 or more carbon atoms), diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether And ethylene glycol phenyl ether.

(C) Glycidyl ether Ethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, phenol pentaglycol diglycidyl ether Etc. can be exemplified.

As the alkanolamine in the present invention, those generally used in water-soluble temper rolling fluids are widely used. Specifically, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and the like are targeted. Sodium hydroxide and potassium hydroxide are used as the alkali metal salt. The salt is formed by the reaction of the carboxylic acid with these alkanolamines or alkali metals, and is solubilized in water.

In general, the water-soluble temper rolling liquid is preferably maintained in a pH range of 8 to 10 from the viewpoint of rust resistance and workability, and the amount of alkanolamine or alkali metal added to carboxylic acid. If the amount exceeds the amount required to form a salt, if it becomes too much, a viscous substance is formed and adhered to the roll surface of a roller leveler or a stretcher leveler by the action of rust-preventive oil in the following steps. ,
Alternatively, there arises a problem that dimensional accuracy is disturbed due to deposition of a viscous material on a slitter line such as a shearing line or a blanking line. In the present invention, the problem can be solved by adding a water-soluble organic solvent to the temper rolling liquid, which is effective in preventing the formation of such a viscous material. The carboxylic acid alkanolamine salt or alkali metal salt to be added is 0.5 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the temper rolling solution, and the water-soluble organic solvent is 0.1 to 0.4 parts by weight. It is used in an amount of 5 to 10 parts by weight, preferably 1 to 5 parts by weight.
Furthermore, a surfactant 0.1 as a wettability improver.
A preservative or the like in a range of 5 to 5.0 parts by weight or a predetermined amount can be used.

[0022]

EXAMPLES Examples of the present invention and comparative examples will be described in detail. Examples 1 to 5 and Comparative Examples 1 to 4 Temper rolling solutions were prepared using the components shown in Table 1. That is,
Various temper rolling solutions were prepared by dissolving a predetermined salt of a carboxylic acid and an alkanolamine or a salt of an alkali metal and other predetermined components in a predetermined amount of water. This aqueous solution was further diluted with water to a 10% by weight solution, and subjected to the following tests (1) to (4). On the other hand, the components and properties after the water of the water-soluble temper rolling fluid was heated and evaporated were evaluated in the following (5).
I went for the item.

<Production of test article> Annealing (95% nitrogen gas,
Cold-rolled oil-rolled steel sheet SPCC-SD (width 100 x 0. 0, annealed in a 5% atmosphere of hydrogen gas at a temperature of 700 ° C for 1 hour).
Roll (roll diameter 170 mm, roll surface roughness Ra = 6 mm) using a temper rolling solution shown in Table 1
0.2-0.03μm, 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 (5). On the other hand, rust-preventive oil (DAILLA RX900 manufactured by Daido Chemical Co., Ltd.)
V) and a tension leveler (roll diameter 20 m)
m, lower roll 10 rolls, upper roll 9 rolls / pressure 50kg / c
m ² ). 10 from leveled oiled coil
A test piece was cut out to a size of 0 × 100 mm and subjected to the test of the following item (3).

<Measurement Items> (1) Veneer Indoor Exposure Test (Evaluation Method) Each of the temper-rolled test pieces (100 × 100 mm) was placed on a plastic-grooved pedestal, and exposed to rain in the building. The test piece was exposed to a non-wetting eaves for 10 days, and the state of rust generation on the surface of the test piece was visually observed to evaluate rust prevention. (2) Wetness test (test piece stacking test) A set of five temper-rolled test pieces was fixed by pressure bonding with a clip, left for one week in a wetness test apparatus according to JIS K-2246, and then taken out and stacked. The state of rust generation on the test piece surface was observed to evaluate rust prevention. (3) Rust preventive oil application wetness test (test piece stacking test) Specimens (100 x 100 m
m) One set of 5 sheets is fixed by crimping with a clip.
After standing for 2 weeks in a wet test apparatus according to IS 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 part of the specimen of the cold-rolled steel sheet (SPCC-SD) solvent-degreased was filled with the temper rolling fluid, and the friction coefficient of each temper rolling fluid was measured with the Soda pendulum friction tester. Was measured. (5) Properties after evaporating the temper rolling solution The temper rolling solution is collected in a petri dish and placed in an oven at 70-70.
After heating to 80 ° C., the component properties (liquid / amorphous or crystalline) after water evaporation were observed. Table 2 shows the above characteristics.
Tables 1 and 2 also show test results for commercial products as controls.

[0025]

[Table 1]

The details in Table 1 are as follows. Na: sodium hydroxide MEA: monoethanolamine DEA: diethanolamine MIPA: monoisopropanolamine * 1): A salt composed of carboxylic acid and alkanolamine equivalents or a salt composed of carboxylic acid and sodium hydroxide equivalents is used * 2) : Not a salt but a carboxylic acid and an excess of an amine separately added.

[0027]

[Table 2]

1) Rust generation score: 100 excellent> 50 acceptable 2) ○: No rust generation △: Slight rust generation 3) ○: No oil stain generation △: Slight oil stain generation

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 133: 04) C10N 10:02 30:04 40:24 (72) Inventor Hiroyuki Takahashi 1-2-2 Umeda, Kita-ku, Osaka-shi, Osaka No. 2-1400 Daido Chemical Co., Ltd. (72) Inventor Hideo Shibata 1-2-1400 Umeda, Kita-ku, Osaka City, Osaka Prefecture Daido Chemical Co., Ltd. (72) Inventor Koujiro Fujita Osaka City, Osaka Prefecture 1-2-2, Umeda, Kita-ku Daido Chemical Co., Ltd.

Claims (7)

[Claims] 1. A water-soluble temper rolling liquid containing a salt of a carboxylic acid and an alkanolamine or an alkali metal, and a water-soluble organic solvent. 2. The method according to claim 1, wherein the carboxylic acid is a fatty acid having 3 to 3 carbon atoms.
18 saturated or unsaturated monocarboxylic acid, or 4 carbon atoms
A saturated or unsaturated dicarboxylic acid of from 1 to 12;
Water-soluble temper rolling fluid. 3. The water-soluble temper rolling fluid according to claim 1, wherein the carboxylic acid is a saturated hydroxy mono- or polycarboxylic acid. 4. The water-soluble temper rolling fluid according to claim 1, wherein the carboxylic acid is an aromatic mono- or dicarboxylic acid. 5. The water-soluble refining solution according to claim 1, wherein the carboxylic acid is cyclohexanecarboxylic acid. 6. The water-soluble temper rolling fluid according to claim 1, wherein the carboxylic acid is nicotinic acid and / or isonicotinic acid. 7. The water-soluble temper rolling liquid according to claim 1, wherein the water-soluble organic solvent is at least one of glycol, polyglycol, glycol ether, polyglycol ether and glycidyl ether.