KR950010600B1 - Cold roll oil of steel foil - Google Patents

Abstract

The cold rolling oil is composed of 20-60 wt% of high viscous hindered monoester combining polyalcohol and fatty acid containing C14-C24 side chain or branched chain, and/or 10-30 wt% of C18-C12 hindered triester with low viscosity and low melting point, and 20-50% refined fats and oils with low melting point such as beef tallow, palm oil, lard, rapeseed oil, and rice bran oil. Futhermore the rolling oil included 1-7% dispersing agent containing amine derivative added with 10-20 moles of ethylene oxide and a polymer having molecular weight of 10,000-30,000, such as styrene-amine block coploymer or oxidized wax.

Description

Thin cold rolled oil with excellent antiseptic and emulsion dispersion

The present invention relates to cold rolled oil that can be used for high speed sheet rolling, and more particularly, to cold rolled oil having excellent lubricity and anti-corrosion resistance and excellent mill cleanness, antiseptic and emulsion dispersibility even when the sheet metal material is rolled at high speed. It is about.

Conventionally, in the cold rolling oil used for high speed, cold rolling mill, the water-soluble cold rolling oil is a base oil (base oil), mainly animal and vegetable oil, mineral oil, etc., and in the case of Mill Clean cold rolling oil, As (base oil), mineral oil and mono ester (mono ester) which are fatty acid esters were mainly used. For these cold rolled oils, oil additives such as fatty acids and alcohols, extreme pressure agents, antirust additives, antioxidants, emulsifiers and the like have been used as additives.

On the other hand, the mass production system was achieved by high speed, large size, and continuous rolling equipment, shortened process (degreasing process), and demand for cold rolled sheet steel such as high value steel with high value added increased. There is an increasing demand for improved lubricity and work safety.

In addition, in consideration of environmental aspects, measures are required to prevent spoilage, odor, and the like of scum caused by aging of rolling oil. It is also getting higher.

However, the conventional rolling oil as described above for the demand for such cold rolling oil has the following problems.

First, the emulsifier used in the conventional rolling emulsion was added mainly for the purpose of improving the emulsion stability. In the case where the main purpose is to improve the emulsifying property, the emulsifying property is improved by adding a lot of kinds and amounts of emulsifier, but the lubricity is lowered, and when improving the lubricity, the emulsifying property is lowered by adding less emulsifier. Therefore, it was difficult to simultaneously improve emulsification and lubricity (Plate Out property).

Second, in the case of a dispersed rolling oil using a cationic emulsifier, it has a large and uniform particle size, and thus has excellent lubricity (Plate Out property), but the emulsion stability is poor, and thus, the operation at the start of rolling is not good. In terms of environment, the contamination of the rolling mill was good, but the rolling oil was sprayed to cause the spoiling of scum powder remaining on the fried part (such as the upper part of the work roll of the rolling mill) or the pipe, and the sludge removed during the rolling ( It was difficult to control the solidification and odor caused by the corruption of Sludge.

Third, in the case of fatty acid mono-esters conventionally used as base oils (base oils), the annealing properties are good but they are not suitable for high-speed sheet rolling in terms of lubricity.

In order to solve the problems of the conventional rolling oil as described above, the present inventors have a base oil consisting of (C ₁₄ -C ₂₄ ) fatty acids of polyhydric alcohol and at least one animal and vegetable oil; Extreme pressure additives selected from acidic esters, organosulfur compounds and mixtures thereof; And a high speed cold rolled oil composed of an emulsifier, an antioxidant, and the like (Korean Patent Application 91-25627).

The rolled oil thus formed showed excellent lubricity and annealing properties at ultra-thin rolling of 1,700mpm or more compared to the conventional rolling oil, and brought great improvement in terms of rolling mill contamination. In terms of oil stain, scum decay and working environment, the results were not satisfactory.

Accordingly, an object of the present invention is to provide an improved cold-rolled oil which is suitable for use in high-speed, high-pressure, low-temperature cold-rolling process that solves the above-mentioned objects and which has both antiseptic and emulsification stability while maintaining high lubricity and milk cleanability. will be.

According to the present invention, 20-60% by weight of a high viscosity hindered mono ester and / or a low viscosity of C ₈ to C ₁₂ which combine a polyhydric alcohol and a linear or branched fatty acid having C ₁₄ -C ₂₄ carbon atoms Thin cold rolled condensed milk comprising 10-30% by weight of hindered tri ester and 20-50% by weight of low melting refined fats and oils such as coke, palm oil, lard, rapeseed oil and rice bran oil is provided.

Hereinafter, the present invention will be described in detail with reference to the respective composition components.

[Base oil]

In recent years, the core technologies in the rolling process include high productivity (high speed), high efficiency (high pressure), error rate improvement, and high quality manufacturing technology. In cold rolled sheet rolling, as the demand for steel sheet increases, ordinary steel sheet is continualized, high speed, high pressure, etc. in order to increase production efficiency. It is. Rolling mill types are also becoming larger and are being developed in the direction (4 → 6 stage mills, etc.) to increase the reduction capacity by designing a small diameter of the working rate.

In conventional rolling of tin or galvanized plate (aka BP: Black Plate), an important property required for cold rolling oil is lubricity and oil and fat of animal and animal plants. However, in the case of rolling oil using animal and vegetable fats and oils due to high frictional heat, processing heat, and pressure generated during rolling, chemical reactions such as hydrolysis occur easily and oxidation of liquid or polymer material is easily generated, resulting in high scum material and high temperature. Due to the large viscosity change, it acts as a deterrent to the stability of high-speed thin-film rolling work, and if the lubrication is insufficient, surface defects called heat scratches are generated.

In the present invention, the base oil does not change easily even at high temperatures, that is, high viscosity hindered mono esters having good annealing properties and low viscosity hinges having good lubricity and low melting point for viscosity adjustment, which is one of important factors in rolling. Hindered tri-ester (C ₈ ~ C ₁₂ ) was used to improve lubricity and annealing.

The high viscosity hindered monoesters and low melting point hindered triesters (C ₈ to C ₁₂ ) used as base oil components in the present invention may be used individually or in combination thereof.

The high viscosity hindered mono ester is a combination of a polyhydric alcohol and a linear or branched fatty acid having C ₁₄ to C ₂₄ and the content thereof is preferably in the range of 20-60% based on the total weight of the cold rolled oil.

If the content of the high viscosity hindered monoester is less than 20%, the lubricity is lowered, whereas if the content of the high viscosity hindered monoester is more than 60%, the lubricity is excellent, but the rolling workability is poor, and operation stability becomes a problem.

On the other hand, the low melting point hindered triester having a carbon atom of C ₈ ~ C ₁₂ is preferably contained 10-30%, when less than 10%, such as high viscosity hindered monoester is less lubricity and 30% or more In this case, lubricity is excellent but rolling workability is poor.

On the other hand, low-melting refined fats and oils, palm oil, pork oil, rapeseed oil, rice bran oil may be used one or two or more kinds, the content is preferably in the range of 20-50% by weight of the rolling oil.

If the amount of these refined fats and oils is less than 20%, there is a problem in that degreasing property is not good, and when the content of the refined fats and oils exceeds 50%, the annealing property is deteriorated.

Extreme pressure

In the cold rolled oil of the present invention, an ordinary extreme pressure agent may be used in an amount of 10% or less based on the weight of the rolled oil.

Extreme pressure agents include phosphate derivatives of triethanol amine, trialkylol phosphate, dioctadecyl-hydrogen phosphate and oleyl azide, which are phosphorus-based and low in oil stain generation. Compounds of phosphate and amine salts can be used, and sulfur-based oils include sulfurized oils, distearyl thio propionate, dioctyl sulfonate, and dibenzyl pentasulfide. Lubrication and baking resistance can be improved by selecting and using one or two sulfur-based extreme pressure agents having a structure of CS, -SS-, or -SSS in an aromatic or alkyl group such as). In addition, an anhydrous benzene derivative compound is used to control carbonization of oil during annealing, organic compounds in annealing gas, precipitation of carbon in steel, and edge carbon remaining on the surface of the plate edge. Oil stain resistance can be improved.

[additive]

In recent years, in the rolling process, not only lubricity and baking resistance but also cleanliness of the rolling mill and the rolled plate surface are required, and the uniformity of the plate surface and the ease of managing the rolled oil are important.

In other words, in order to improve the rolling work environment, the amount of scum generated during rolling is small and the processing is easy, so that the surroundings of the rolling mill can be more clean, and the operation can be stabilized even at high speed rolling by maintaining a uniform particle size, and electrolytic cleaning (ECL) and continuous annealing (CAL) lines, such as properties that can prevent wet stain (Stain) that is likely to occur during congestion is being swear.

These properties cannot be completely solved by the base oil composition or the extreme pressure agent. The emulsifying properties, lubricant additives, antioxidants, and preservatives of the emulsifier required for the water solubilization of the rolled oil are formed in a total combination to exhibit the characteristics.

In the present invention, the amine-based compound of the branched chain hydrocarbon and the nonionic low-HLB polymer styrene amine block copolymer (MW: 10,000-30,000) using the electrical repulsion property of the abrasive generated during rolling among the properties of the emulsifier. Or a combination of those having a polymer dispersing property such as petrolactam oxide and wax oxide, and stable by applying polyoxyethylene, alkyl ester, pentaerythritol and fatty acid alkyl ester, and alkyl phosphate ester as nonionic emulsifiers. Both emulsion and iron dispersibility can be obtained to obtain a large and uniform emulsion particle size, and the performance can be doubled by using a combination of intermediate and higher fatty acids and poly fatty acids used as an oily agent.

Preferably, the emulsifier is 10-20 mol of E0 (ethylene oxide) added to the branched chain hydrocarbon amine derivative, and (MW 10,000-30,000) polymer dispersing agent such as an oxide wax or a styrene amine block copolymer (1). It contains -7%.

In addition, even if a cationic emulsifier or a polymer dispersant is used that has a low melting point, a synthetic effect of base oil, excellent dispersibility of iron abrasion powder, and cleanability of the rolling mill, rolling oil splashes on the upper layer of the rolling mill and splashes on the wall surface. If the pollution is low, and the actual rolling oil used liquid (about 50 ~ 60 ℃) does not reach, the contaminants attached are easily rotted and solidified by anaerobic bacteria, and when the rolling mill vibrates or breaks and cleans, foreign substances fall into the rolling oil. When the rolling oil aging is accelerated and it falls on the rolls and steel sheets, foreign material marks, which are surface defects of the steel sheet, are generated, and scums generated during rolling are removed and collected in the sludge box, which also rots and causes bad odor (H ₂ S GAS). To pollute the working environment.

Therefore, in order to improve the quality of steel plate and defects caused by the drop of scum material, sodium benzoate derivative, a bacterium growth inhibitor, is applied in the range of 0.2 ~ 2% based on the weight of rolling oil. As it softened, it was allowed to flow down and restrain the rolling mill to maintain a clean working environment.

Cold rolled oil of the present invention composed of the above composition is used diluted in water when used and the concentration is 1 ~ 10%.

Hereinafter, the present invention will be described in more detail with reference to Examples.

EXAMPLE

Experiments described below were performed on the inventive oils and comparative oils having various compositions and the results were displayed.

<1> rolling oil composition (value is wt%)

1) the present invention rolling oil

(Sample oil ①)

Synthetic oil-hindered mono-esters; … … … … … … … … … … … … … … … … … 40

Palm oil. … … … … … … … … … … … … … … … … … … … … … … … … … … 45

Oxide wax (WAX). … … … … … … … … … … … … … … … … … … … … … … … … 2

5 moles of E0 added to branched chain hydrocarbon amine derivative. … … … … … … … … 2

15 moles of E0 in the branched chain hydrocarbon amine derivative. … … … … … … … … … … … 2

Alkyl amine phosphate derivatives … … … … … … … … … … … … … … … … … … … … … One

Sulfuric acid maintenance… … … … … … … … … … … … … … … … … … … … … … … … … … … … … 8

Antioxidant (phenolic) … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ②)

Synthetic Oil-Hindered Mono Ester … … … … … … … 60

Uji… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 35

10 moles of E0 to the branched chain hydrocarbon amine derivative and salts of nonamic acid. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 3.5

Alkyl amine phosphate derivatives … … … … … … … … … … … … … … … … … … … … … … One

Zinc Dithio Phosphate... … … … … … … … … … … 0.5

Antioxidant (phenolic) … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ③)

Synthetic Oils Hindered Mono Ester 30

Hindered Tri-ester 20

Palm oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 40

10 moles of EO in the branched chain hydrocarbon amine derivative and the dioctyl acid phosphate ester salt. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 2

Oxide Wax … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 3

Di-benzyl penta sullide… … … … … … … … … … … … … … … … … … … … … … … … 5

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ④)

Synthetic Oils Hindered Mcno Ester 20

Hindered Tri-ester 30

Palm oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 42

10 moles of the E0 moiety and a salt of the dioctyl acid phosphoric acid ester in the branched chain hydrocarbon amine derivative. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 2

Polymer Dispersant (Stylen Amine Block Coplymer). … … … … … … … … … … 1.5

Salicylic anilide halogen compound derivative. … … … … … … 0.5

Didocecyl Tri Sulfide… … … … … … … … … … … … 4

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ⑤)

Synthetic Oils Hindered Mcno Ester 45

Hindered Tree-Ester 10

Palm oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 30.5

10 moles of the E0 moiety and the salt of the dododecyl acidic phosphate ester in the branched chain hydrocarbon amine derivative. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 4

Polymer Dispersant (Stylen Amine Block Coplymer). … … … … … … … … … … … One

Triazine Alkyl Derivatives … … … … … … … … … … … … … … … … … … 0.5

Disteayl thio propionate... … … … … … … 9

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ⑥)

Synthetic Oils Hindered Mono Ester 20

Hindered Tree-Esthe 20

Palm oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 49.5

The addition of 20 moles to the branched chain hydrocarbon amine derivative and the salt of the poly fatty acid amine derivative. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 3

Sorbitol Monoester Nonionic Emulsifier … … … … … … … … … … … … … … … … … 2

Polymer Dispersant (Wax Oxide) … … … … … … … … … … … … … … … … … … … … … … One

Alkyl amine phosphate derivatives … … … … … … … … … … … … … … … … … … … … … … One

Derivatives of Natriate Benzoate Salts … … … … … … … … … … … … … … … … … … … 0.5

Dioctyl sulfornate... … … … … … … … … … … … … … … … 3

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

(Sample oil ⑦)

Synthetic Oils Hindered Mono Ester 20

Hindered Triester 40

Palm oil… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 24.3

15 moles of E0 boron and alkylamine phosphate derivatives in branched chain hydrocarbon amine derivatives. 3

Polymer Dispersant… … … … … … … … … … … … … … … … … … … … … … … … … … … … One

Derivatives of Sodium Benzoate Salts … … … … … … … … … … … … … … … … … … … 1.5

Sulfur-added benzene derivative compound. … … … … … … … … … … … … … … … … … … … … 0.2

Polyalkyl sulfonate… … … … … … … … … … … … … … … … … … … … … … … … 5

Salt of Dioctyl Acid Phosphate and Decanoic Acid … … … … … … … … … … … … … 5

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

2) Comparative Rolled Oil [91, Patent Application No. 25627, "Cold Rolled Oil with Lubricity and Mild Cleanness"]

(Compare ⑧)

Uji… … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 65

Synthetic oil-hindered mono-esters; … … … … … … … … … … … … … … … … … … … 20

Nonyl Phenyl E0 Adduct Ether Emulsifier (E05) … … … … … … … 3

Nonyl Phenyl E0 Adduct Ether Emulsifier (E010) … … … … … … … … … … … … … … 3

Dioctyl acid phosphate ester … … … … … … … … … … … … … … … … … … … … … One

Keep sulfurization… … … … … … … … … … … … … … … … … … … … … … … … … … … … … 8

Antioxidants … … … … … … … … … … … … … … … … … … … … … … … … … … … 0.2

(2) Test Items and Test Methods

1) Lubricant and seizure resistance test

Lubrication was measured by emulsifying 5% wt of rolling oil according to the cold test rolling mill specification of <Table 1> and spraying it between working rolls by circulation method, and keeping the rolling speed and tension constant, then 60-70kgf / mm under extreme pressure ^The rolling was repeated at the minimum thickness while rolling at ^2, and the thinner the exit thickness per pass, the better the lubricity. The friction coefficient was determined by inverting the stone by using the rolling data.

In addition, the baking resistance test was evaluated based on the rolling speed at which baking occurs while increasing the rolling speed and rolling load.

TABLE 1

Specifications of cold test mill

2) Evaluation of lubricity and seizure resistance through four ball tester

3) Iron dispersion performance test, ESI-15 and particle size measurement of oil

After diluting the concentration of each composition with a 3wt% emulsion and stirring for 30 minutes as an M-type Homo Mixer, 1,000 ppm of iron (200 1,000) was added thereto. Measured.

* Stirrer speed: 10,000rpm

* Emulsion amount: 400g

* Emulsion temperature: 50 ℃

* ESI measurement: 30 minutes of the stirred emulsion in a 200ml liquid container and allowed to stand for 15 minutes in a thermostat (50 ℃) and 100ml was taken from the bottom to measure the concentration.

* Emulsion particle size: measured by Culter counter.

* Dispersion performance was visually observed the oil and iron state attached to the beaker and the iron dispersion state of the emulsion during the rotation of the homo mixer.

4) Determination of contaminants, oil emulsification, oil resistance, oil staining

Each composition (1)-(8) was prepared in an emulsion of 3 wt% in a 20-liter steel container, 1,000 ppm of Fe was added while heating and stirring at 50 ° C, and circulated with a pump for 1 day.

* Stirring power: 360ppm

* Pump capacity: 1.5liter / min

At this time, the contamination state of the iron wall surface of the scum material was visually observed, and the oil stain was measured by the overlapping method of two iron specimens, and the emulsification state according to the mixing of oil was measured.

Thereafter, the mixture was cooled to 30 ° C. and cured for 15 days, and then the number of bacteria was measured to determine the degree of decay.

5) Conradson residual carbon measurement The residual carbon amount was measured by a tester.

The results of the above comparative experiments are shown in <Table 2> and <Table 3>.

According to the following <Table 2> and <Table 3>, it turns out that the rolling oil of this invention has the following characteristics compared with the rolling oil (thin cold rolled oil excellent in the milk cleaning property, lubricity, and baking resistance) adopted as the comparative oil.

The particle diameter is larger than that of the comparative oil, and ③-⑦ sample oil shows a more uniform distribution of the particle diameter than that of the comparative oil. In terms of iron dispersibility, contamination, and oil stainability, the particle diameter is superior to the comparative oil. In addition, the residual carbon is smaller than that of non-oil, and is not easily decayed. In addition, the sample oil of the present invention shows similar or superior characteristics in comparison to the comparative oil in terms of baking point, lubricity, and baking rate. Therefore, the rolled oil of the present invention has the same or superior lubricity, baking resistance, and milk cleanness as compared with the comparative oil.

TABLE 2

Comparison of General Characteristics and Performance of Invention Rolled Oils

<Legend>

×: bad 10 ³ : good ○ B: wide distribution

△: Moderate 10 ^(4-5) : Slightly corrupt △ M: Medium

○: Good 10 ⁵ : Severe corruption × ~ △ S: Narrow distribution

◎: Excellent 10 ⁷ : Very corrupt ×

TABLE 3

Comparison of Baking and Lubricity of Invention Rolled Oils

As described above, the rolled oil of the present invention has an advantage of excellent antiseptic and work stability of the rolled oil while maintaining lubrication, baking resistance and milk cleanness when used in sheet rolling rolled at high speed.

Claims (4)

20 to 60% by weight of high viscosity hindered monoesters combining polyhydric alcohols with C ₁₄ to C ₂₄ carbon chains or branched fatty acids and / or low viscosity low melting point hindered triesters of C ₈ to C ₁₂ (Hindered tri ester) 10 ~ 30% by weight, cold lubrication, milk cleanness, antiseptic and emulsification dispersibility, including 20 ~ 50% of low melting point oils such as whey, palm oil, pork, rapeseed oil and rice bran oil Rolling oil. The sheet cold forming apparatus according to claim 1, wherein the branched chain hydrocarbonamine derivative further contains 1 to 75 propellants made of ethylene oxide (E0) 10 to 20 mol parts and propellants made of polymer dispersant (Mw 10000 to 30000). Rolling oil. The method of claim 2, wherein the polymer dispersant is cold rolled cold foil, characterized in that the wax oxide or styreneamine block copolymer. The thin sheet cold rolled milk according to any one of claims 1 to 3, further comprising 0.2 to 2% of a sodium benzoate salt as a corrosion inhibitor.