CN1332001C - Cold-rolled lubricating oil for steel plate - Google Patents

Abstract

Provided is a lubricating oil capable of giving such a cold rolling oil as to improve productivity by making a cold rolling speed still higher, when a steel sheet is subjected to cold rolling at a high speed, to make resistance to deposition of the oil around a mill and treatment of waste water excellent, and to solve problems of cleaning deficiencies, etc., in a cleaning process. This lubricating oil for the cold rolling oil for the steel sheet contains (a) oils which contain 12-14C fatty acids in an amount of >=50 wt% in fatty acids composing oils and (b) compound esters.

Description

Steel cold rolling oil

technical field

The present invention relates to cold rolling oil for steel plate and lubricating oil used therein.

Background technique

As the rolling oil supply system for steel plate cold rolling, there are two types of circulating rolling oil supply system and direct rolling oil supply system. The so-called circulating rolling oil supply system is to supply a large amount of oil to the steel plate and roll. The rolling oil emulsion is used to recycle the used rolling oil emulsion to remove the wear iron powder and use it for a long time. The so-called direct rolling oil supply system is to supply a small amount of rolling oil emulsion to the rolled steel plate. At the same time, a large amount of water is supplied to the rolls, and the used rolling oil emulsion is not recycled but treated as waste water.

In the past, when direct supply cold rolling (hereinafter referred to as direct cold rolling), palm oil or tallow or rolling oil added with oiliness improver and extreme pressure additives were used, mixed with water to form 6-20 wt. % of the emulsion used. However, since the high-concentration emulsion is prepared simply by mechanical stirring, the particle size of the emulsion is unstable, and the amount of oil attached to the roll and rolled steel plate changes, resulting in unstable lubricity and other problems. In addition, the oil-water separation effect is not good, and the oil recovery rate during wastewater treatment is not high.

In recent years, in order to rationalize production, multi-variety rolling is carried out, high-speed rolling is carried out at a speed exceeding 1800 m/min, and high tension is generated in order to reduce the wall thickness of the steel plate, so direct cold rolling oil is required to have good lubrication stability and lubrication stability and low cost.

In the past, direct cold-rolling oil with palm oil or tallow as the main component was relatively low in cost, but due to its high melting point, it accumulated in large quantities around the rolling mill (Japanese: ミル迴り), which not only deteriorated the operating environment, but also caused Fire accidents, thus requiring rolling oil to have a lower melting point.

In addition, thin steel sheets such as tin-plated steel sheets have to go through processes such as lye cleaning and continuous annealing after rolling, and then tin-plated, but poor cleaning still occurs in these processes, and they are caused by roll accumulation in the annealing furnace. Steel plate surface defects, poor plating and other problems. This is considered to be due to the fact that the temperature of the steel plate after rolling is high, and the rolling oil adhering to the steel plate is thermally deteriorated, resulting in a decrease in washability. By adding an anti-deterioration agent such as an antioxidant, thermal deterioration can be suppressed to a certain extent, and the above-mentioned problems can also be avoided by changing washing conditions, but this reduces productivity and increases production costs.

As measures to solve these problems, various rolling oils have been proposed. For example, there is a rolling oil described in JP-A7-150184 as a rolling oil using an oil-soluble polymer compound, but this rolling oil is affected by the water quality of the water used, so the lubrication stability is insufficient and cannot be used. Solve problems such as low melting point and washability during high-speed rolling. In addition, as a rolling oil using a polyester compound and an amine salt of an organic acid phosphate, there is a rolling oil described in JP-A9-53089. Although this rolling oil can solve the lubricity problem, the lubrication stability It is not ideal, and the problems of waste water treatment, low melting point, and washability during high-speed rolling have not been solved.

On the other hand, when using the conventional circulating rolling oil supply system for cold rolling (hereinafter referred to as cold rolling for circulating supply), as rolling oil, tallow and palm oil are used as base oils and oiliness improvers are used. , extreme pressure additives, rust inhibitors and antioxidants, etc., using emulsifiers and water to form an O/W emulsion, generally 1-10% by weight of lower concentration rolling oil. However, conventional cold-rolling oils mainly composed of natural fats and oils are low in cost, but due to their high melting points, a lot of scum accumulates around the rolling mill, which not only deteriorates the operating environment, but also causes accidents such as fires. In addition, there are problems such as insufficient long-term cycle stability.

In addition, when high-speed rolling is performed at a speed exceeding 1800 m/min, problems such as insufficient lubricity and poor cleaning occur similarly to direct cold rolling oil.

As a countermeasure against these problems, various rolling oils have been proposed. For example, rolling oils using fats and oils and complex esters are disclosed in JP-A10-231494. Although this kind of rolling oil can solve the problems of lubricity and long-term cycle stability during high-speed rolling, as well as washability when the temperature of the steel plate after rolling is low (equivalent to low-speed), it is not suitable for high-speed rolling on actual machines. In the case of rolling, it is difficult to obtain sufficient washability when the temperature of the rolled steel sheet is high.

Contents of the invention

The task of the present invention is to provide a kind of cold-rolling oil and lubricating oil used therein. In the occasion of carrying out high-speed cold-rolling of steel plate, there is no problem such as the cost of rolling oil increases and the stability of lubrication is low, so that the previous rolling It becomes possible to increase productivity through high-speed rolling, which cannot be achieved with oil, and at the same time, it can prevent oil and scum from accumulating around the rolling mill, and the waste water treatment and lubricity are excellent, and it can solve the problems of poor washing in the washing process, etc. .

The present invention relates to a steel plate cold rolling oil that is excellent in lubricity, lubrication stability, rolling mill pollution resistance, and waste water treatment, and is also very washable in the washing process, and a lubricating oil used in the cold rolling of steel plates .

For the problems existing in the above-mentioned actual production, the inventors found that if the cold rolling oil containing specific greases and specific complex esters is used, the accumulation of rolling oil around the rolling mill can be reduced, the danger of fire and the operability can be avoided. Deterioration and other problems, showing good lubricity, high-speed rolling can be carried out at a speed of 1800 m/min or more, and at the same time, when the temperature of the rolled steel plate is high due to high-speed rolling, the washability will not be reduced. Compared with the previous cold rolling oil, its performance is very superior. In addition, the present inventors also found that the use of a specific water-soluble polymer compound in a specific quantitative ratio can further improve lubricity, while improving lubrication stability and waste water treatment, thereby solving the above-mentioned tasks.

That is, the present invention relates to a lubricating oil for steel cold rolling oil and a steel cold rolling oil comprising the lubricating oil and water, wherein the lubricating oil contains (a) fatty acids having 12 to 14 carbon atoms Oils and fats [hereinafter referred to as (a) component] and (b) complex esters [hereinafter referred to as (b) component] in which fatty acids account for 50% by weight or more.

The lubricating oil for steel plate cold rolling oil of the present invention preferably further contains (c) one or more water-soluble polymer compounds [hereinafter referred to as (c) component], and the water-soluble polymer compound is a polymer selected from the following: (c1) Homopolymers of monomers represented by general formula (1) or salts thereof, (c2) copolymers of two or more such monomers, and (c3) one or more such monomers with (meth)acrylic acid or salts thereof , a copolymer of one or more of its alkyl esters or its alkyl amides; its weight-average molecular weight is in the range of 10,000-1,000,000.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ represent an alkyl group with 1-3 carbon atoms, A represents -O- or -NH-, and m represents an integer of 1-3.

The present invention provides a method of cold rolling a steel plate using the steel plate cold rolling oil comprising the above lubricating oil and water, and uses the above lubricating oil as a lubricating oil for steel plate cold rolling oil.

Detailed ways

The component (a) in the lubricating oil for cold-rolling oil of the present invention is a fatty acid having 12 to 14 carbon atoms accounting for more than 50% by weight of the fatty acids constituting the oil, preferably 40% by weight of fatty acid having 12 carbon atoms. The oils and fats above % can be natural oils or synthetic oils. The above-mentioned fats and oils include, for example, coconut oil, palm kernel oil, babassu kernel oil, aleurone kernel oil and the like. For example, animal and vegetable oils such as tallow and palm oil used in conventional direct cold-rolled oils mainly contain glycerides of aliphatic fatty acids with 16 or 18 carbon atoms. Glycerides of aliphatic saturated fatty acids with 12 to 14 carbon atoms are used as the main component. Compared with tallow and palm oil, etc., the glyceride has a lower melting point and has the effect of reducing the accumulation of rolling oil around the rolling mill. Compared with palm oil, its iodine value is lower, and the rolling oil adhering to the steel plate is less likely to be thermally degraded, so it has the effect of suppressing the detergency of the detergency during high-speed rolling. Fractionated oils such as tallow oil and palm olein have a low melting point and have the effect of reducing the accumulation of rolling oil around the rolling mill. Decreased detergency. Adding a large amount of anti-deterioration agents such as antioxidants can suppress the deterioration of the detergency to a certain extent, but it is not preferable because the oil price increases. From the perspective of rolling oil accumulation and washability during high-speed rolling, the melting point is preferably below 30°C, and the iodine value is more preferably below 25 (I ₂ g/100g). In addition, if the kinematic viscosity at 40°C (according to JISK2283) is below 30 mm ² /s, the kinematic viscosity of the lubricating oil using this grease is relatively low, and when used as rolling oil, the surface smoothness of the rolled steel plate is good , You can get a rolled steel plate with good luster. In addition, the above-mentioned (a) component preferably has less glyceride content of aliphatic saturated fatty acid having 8 carbon atoms, and especially the proportion of fatty acid having 8 or less carbon atoms in the constituent fatty acids is 5% by weight or less. Fats and oils, more specifically, palm kernel oil are particularly preferably selected because of their low odor and the fact that they generate less smoke at the rolling operation site and are good in the operating environment.

The fats and oils of these (a) components may be used alone or in combination of two or more. Its addition amount is preferably used in an amount of 50% by weight or more in the lubricating oil component for direct cold rolling oil. From the viewpoint of improving the washability during high-speed rolling, it is preferably 75-95% by weight, most preferably 80-95% by weight.

In addition, it may be added to classified oils and fats such as palm oil and palm olein as cold rolling oil for circulating supply. Its addition amount is preferably 20% by weight or more in the lubricating oil components. It is preferably 40-95% by weight, more preferably 50-90% by weight, from the viewpoint of improving the washability during high-speed rolling.

The complex esters of component (b) of the present invention are ester compounds obtained from polybasic acids, polyhydric alcohols, monohydric alcohols, and/or monobasic fatty acids. Considering the effect of improving lubricity, the kinematic viscosity at 40°C is 400 mm ² /s or more Preferably, it is preferably a complex ester of 750 mm ² /s or more, more preferably a part obtained from at least one of dimer acid and polymer acid of a higher aliphatic unsaturated acid with 16 to 20 carbon atoms and a polyhydric alcohol An ester compound with a weight average molecular weight of 750-20000, in which the residual carboxyl or hydroxyl group of the ester is esterified by a monohydric alcohol or a monohydric fatty acid with 12-22 carbon atoms. When its molecular weight is above 750, its lubricity is better than that of grease. When its molecular weight is below 20,000, it has good solubility for lubricating components, and its viscosity is suitable for operation. Its molecular weight is more preferably 1,000-10,000, most preferably 1,500-4,000. In addition, the weight average molecular weight of (b) component is measured by gel permeation chromatography (GPC) under the following conditions.

condition

・Column: G2000H×L+G1000H×L (manufactured by Tosoh Corporation)

·Column temperature: 40℃

Eluent: THF (tetrahydrofuran)

Detector: RI (refractive index G)

・Injection volume: 3% by weight THF solution, 20 μl

·Liquid flow rate: 1.0ml/min

Molecular weight standard: polystyrene

The dimer acid and polymer acid used to manufacture the (b) component are dimer acids and polymer acids of higher aliphatic monoenoic acid or dienoic acid with 16-20 carbon atoms, for example, squalic acid, Dimer acid and polymer acid of oleic acid, linoleic acid, tall oil fatty acid. Examples of polyhydric alcohols include propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, butylene glycol, pentylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, and pentaerythritol. , Glycerin, etc. Examples of the monohydric alcohol having 12 to 22 carbon atoms include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol and the like. In addition, examples of monobasic fatty acids having 12 to 22 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, tallow fatty acid, palm oil fatty acid, coconut fatty acid etc.

The complex esters of component (b) have a large number of ester groups and a high kinematic viscosity compared with fats and oils such as tallow used as lubricating components in the past, so they have a significant effect of improving lubricity.

These complex esters of component (b) may be used alone or in combination of two or more. Its addition amount is more than 1% by weight in the lubricating oil components. From the comprehensive consideration of lubricity and oil price, it is preferably 1-25% by weight for direct cold rolling oil, preferably 5-20% by weight. For cold rolling oil for circulating supply, it is considered from the same point of view , the added amount is preferably 5-40% by weight in the lubricating oil component, preferably 10-30% by weight.

In addition, the weight ratio of (a) component to (b) component in the lubricating oil for cold rolling oil of the present invention is from the viewpoint of improving the washability and lubricity during high-speed rolling. , (a)/(b)=75/25-99/1 is more suitable, especially preferably 80/20-95/5, for cold rolling oil for circulating supply, (a)/(b)=50 ^- /50-95/5 is more suitable, especially preferably 63/37-90/10.

The polymer compound of component (c) used in the lubricating oil for cold rolling oil of the present invention is one or more selected from the following:

(1) It is a homopolymer of a monomer or its salt represented by the above (c) general formula (1), and a water-soluble polymer compound with a weight average molecular weight in the range of 10,000-1,000,000;

(2) It is a copolymer of two or more monomers represented by the general formula (1) in the above (c) or a salt thereof, and a water-soluble polymer compound with a weight average molecular weight in the range of 10,000-1,000,000;

(3) One or more monomers represented by the above (c) general formula (1) and their salts, and one or more of acrylic acid, methacrylic acid, their salts, their alkyl esters, and their alkylamides The above copolymer is a water-soluble polymer compound with a weight average molecular weight in the range of 10,000-1,000,000.

Specific examples of the monomer represented by the general formula (1) include dimethylaminomethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl acrylate, Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylmethacrylamide, diethylaminomethacrylamide, diethylaminomethylmethacrylamide, and the like.

In addition, examples of acids that form salts with the above-mentioned monomers include acetic acid, butyric acid, caproic acid, caprylic acid, glycolic acid, succinic acid, tartaric acid, phosphoric acid, butyl acid phosphate, octyl acid phosphate, boric acid wait.

In addition, in acrylic acid and methacrylic acid copolymerized with the above-mentioned monomers, examples of salts thereof include alkali metals, ammonium, alkylamines, polyoxyethylene alkylamines, alkanolamines, and the like; examples of alkyl esters thereof include Examples thereof include butyl acrylate, lauryl acrylate, butyl methacrylate, and lauryl methacrylate; and examples of their amidated products include acrylamide, dimethylacrylamide, and methacrylamide.

The polymer compound of the component (c) preferably has a weight-average molecular weight of 10,000-1,000,000, more preferably 30,000-500,000. When it is more than 10,000, it forms an emulsion and has good stability during emulsification and dispersion. In addition, it is less than 1,000,000. When used, the stability of the polymer compound itself is good, a suitable viscosity is formed, and the workability is also good. In addition, the weight-average molecular weight of the component (c) is the molecular weight analyzed by the GPC method under the following conditions after the polymer compound is hydrolyzed, and the original molecular weight is converted from the analysis result.

condition

・Column: G2000SW (silica gel system: manufactured by Tosoh Corporation) x 2

·Column temperature: 40℃

·Eluent: 0.1N sodium chloride solution/acetonitrile=70/30

Detector: RI (refractive index G)

・Injection volume: 1% by weight eluent solution, 20 μl

·Liquid flow rate: 0.4ml/min

Molecular weight standard: sodium polystyrene sulfonate

(c) The polymer compound of a component can be used 1 type or in mixture of 2 or more types. The surface potential of the rolling oil particles is negative. With the addition of component (c), the surface potential of the rolling oil particles becomes approximately 0, and the rolling oil particles aggregate to form a coarse particle size, so the adhesion is very good. Shows very excellent lubricity. When the component (c) is further added, the surface potential of the rolling oil particles becomes positive, and at the same time, due to the protective colloid, the rolling oil particles form a large particle size and the emulsification dispersion is also good, so the adhesion is good, showing good Lubricity, long-term cycle stability is also very good. When the component (c) is further added, although the emulsification and dispersibility is good, the particle size of the rolling oil becomes medium, so the adhesion is not so good, and the lubricity tends to decrease. Therefore, for the direct cold rolling oil, from the viewpoint of the agglomeration effect of the rolling oil particles, the amount added to the lubricating oil component is preferably 0.01-0.5% by weight, most preferably 0.01-0.1% by weight. When the amount added is within this range, the coagulation effect is good, no self-emulsification or emulsification dispersion occurs, and the particle size of the rolling oil is appropriate. In addition, for the cold-rolling oil for circulating supply, from the perspective of rolling oil particle size and long-term cycle stability, the addition amount to the lubricating oil component is preferably 0.1-3 wt%, most preferably 0.5-2 wt%. When the added amount is within this range, the particle size of the rolling oil is larger, and the long-term cycle stability is also very good.

In the lubricant for cold rolling oil of the present invention, various well-known additives such as oiliness improvers, extreme pressure resistance additives, rust and corrosion inhibitors, antioxidants, and emulsifiers may be added as needed in addition to the above-mentioned ingredients. wait.

As the oiliness improver, for example, fatty acids such as oleic acid, tallow fatty acid, palm oil fatty acid, polymeric acid of tall oil fatty acid can be used, and up to 10% by weight can be added to the lubricating oil component.

Examples of phosphorus-based extreme pressure additives include trioctyl phosphate, tricresyl phosphate, trioleyl phosphate, dioctyl acid phosphate, dilauric acid phosphate, tributyl phosphate, phosphoric acid Trioleyl ester, ditridecyl acid phosphate, dioleyl acid phosphate, aromatic amine salt of mono-2-ethylhexyl acid phosphate, etc. In addition, examples of sulfur-based extreme pressure additives include sulfurized lard, sulfurized tallow, and sulfurized vegetable oil esters, sulfurized olefins, various active and inactive types of sulfurized mineral oils, dibenzyl disulfide, di tert-butyl disulfide, zinc dialkyl dithiophosphate, etc. These extreme pressure additives may be used alone or in combination. Its addition amount is used within the range of 0.5-5.0% by weight in the lubricating oil components. The greater the amount added, the greater the improvement in lubricity, but if it exceeds 5.0% by weight, the price of the oil will increase, and the improvement in bake resistance will decrease with the increase in the amount added, so it is not practical. The range of 1.0 to 3.0% by weight is practically preferable in view of the price of oil and the effect of improving lubricity.

Examples of rust and corrosion inhibitors include alkenylsuccinic acid and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate, benzotriazole and its derivatives, and other amines. They can be added in amounts of up to 2% by weight relative to the lubricating oil components.

In addition, as an antioxidant, for example, 2,4-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, etc. can be used Aromatic amines such as phenolic compounds, phenyl α-naphthylamine, phenothiazine, etc. They can be added in amounts of up to 5% by weight relative to the lubricating oil components.

In addition, as an emulsifier, for example, anionic surfactants such as oleic acid triethanolamine salt and petroleum sulfonic acid sodium salt, and nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene sorbitan trioleate can be used. . Up to 2% by weight can be added to lubricating oil components.

Lubricating oil for cold-rolling oil of the present invention, from the viewpoint of alkali degreasing (or claiming alkali degreasing) and economical efficiency, its iodine value is advisable at 5-50, preferably 10-40, most preferably 10- 35. In addition, from the perspective of reducing the accumulation of rolling oil on the rotating mechanism of the rolling mill, the melting point of the lubricating oil is preferably 10-40°C, preferably 15-35°C, most preferably 20-30°C.

The cold rolling oil of the present invention can be obtained by dispersing the above lubricating oil of the present invention in water by a known method. Moreover, (c) component may be added separately with (a), (b) component, and other components. The dilution ratio at this time is not particularly limited. As direct cold-rolling oil, the concentration of lubricating oil is usually 1-20% by weight, preferably 6-20% by weight. In addition, as cold-rolling oil for circulating supply, usually lubricating oil The concentration is 1-10% by weight, and the emulsion is sprayed to supply the surface of rolls and steel plates. When the concentration is low, the amount of adhesion on the surface of the steel plate decreases, and a sufficient lubricating effect cannot be obtained. In addition, the above-mentioned various additives may also be blended in the rolling oil.

When the steel plate is cold-rolled, an emulsion of palm oil and tallow is sprayed and supplied to the surface of the roll and the steel plate, thereby generating accumulation of rolling oil and dross around the rolling mill. In addition, during high-speed rolling, the surface temperature of the steel plate rises, and the rolling oil adhering to the steel plate deteriorates thermally, resulting in high viscosity, and thus the washability is significantly reduced. In the present invention, since the complex esters of the (b) component are contained in the oils and fats composed of the (a) component, that is, a specific fatty acid composition, the melting point of the rolling oil is reduced, and the rolling oil and scum around the rolling mill are reduced. accumulation. In addition, since the iodine value of the rolling oil is reduced, the thermal deterioration resistance is greatly improved, so even if the surface temperature of the steel plate rises during high-speed rolling, the viscosity of the rolling oil attached to the steel plate does not increase significantly, and the The detergency is reduced, and the lubricity is significantly improved. In addition, by adding an appropriate amount of a specific water-soluble polymer compound (c) component, as direct cold rolling oil, the surface potential of the rolling oil particles is neutralized, and large particles are formed due to agglomeration. Increased adhesion increases lubricity. Due to the protective colloid effect of these water-soluble polymer compounds, large rolling oil particles are formed, which can remain stable for a long time, thus improving the stability of lubrication. In addition, since these water-soluble polymer compounds uniformly disperse the rolling oil particles, they also have the effect of preventing clogging of nozzles and the like by foreign matter. Moreover, the water-soluble polymer compound has a chelating effect on Ca ions and Fe ions, so the particle size of the rolling oil is determined by its addition amount, which is not affected by water quality and has good stability. In addition, as a cold rolling oil for circulating supply, the emulsification and dispersibility is good, and the durability against the leakage of rolling wear powder and engine oil is improved, so the particle size of rolling oil can be stably maintained for a long time, and the initial good rolling can be maintained for a long time. Lubricity.

The cold-rolling oil using the lubricating oil of the present invention has better lubricity and washability than conventional rolling oils, and thus can improve productivity during high-speed rolling. Moreover, due to the low melting point, the accumulation of rolling oil and dross around the rolling mill is reduced, and problems such as the risk of fire, poor product appearance, and deterioration of the operating environment are improved. In addition, since the washability during high-speed rolling is not lowered, it is possible to avoid an increase in production cost due to the use of conventional cold rolling oil. In addition, since the nature of the rolling oil emulsion is not affected by water quality, it is very stable and has good long-term cycle stability. Compared with the previous rolling oil, the operation stability is improved, and it can be used at a lower cost and with higher efficiency. Production of steel plates.

Example 1

Using various lubricating oils for rolling oil (products 1-6 of the present invention and comparative products 1-6) shown in Table 1 and Table 2, the rolling oil (emulsion) with a concentration of 15% by weight was prepared by a conventional method. In the test examples described above, lubricity, lye degreasing property, waste water treatability (ESI (%)) and particle size stability were evaluated. The evaluation results are summarized in Table 1 and Table 2.

<Test Example 1 (Rolling Test)>

For the various rolling oils prepared, use a two-roll mill (φ200mm×200mm wide, SUJ-2, Hs=90) to carry out the rectangular single-pass rolling test under the following conditions. Lubricity was evaluated by the control load (tonf/m). If the rolling load is lower than 95% of the value of the conventional palm oil (comparative product 1), it means that the lubricity is good. In addition, the degreasing property (also referred to as alkali degreasing property) was evaluated by the water-wet area ratio (%) after degreasing the rolled steel plate under the following conditions. The water-wet area ratio mentioned here is estimated by immersing the degreased rolled steel sheet in water at room temperature, then lifting it up, and visually observing the area ratio (%) wetted by water on the surface of the steel sheet. If the water-wetted area ratio is 80% or more, it means that the degreasing property is good.

rolling condition

Rolling material: low carbon steel (SPCC-B, 30mm wide x 700mm long x 2mm thick, Ra = 0.02μm)

Roll roughness: use sandpaper to grind along the rolling direction, adjust to Ra=0.3-0.4μm (Rz=2.8-3.2μm)

Steel plate temperature: 100°C

Rolling speed: 400 m/min

Reduction rate: 40%

Rolling oil concentration: 15% by weight

Liquid condition: 80℃, 30L

Stirring conditions: M-type homogeneous mixer, 12000 rpm

Spraying volume: 0.5 liters/min x 1 each up and down, 200kPa

Degreasing conditions

Pre-heat treatment: 150°C x 12 hours (in the atmosphere) (This pre-heat treatment is carried out assuming the high-speed rolling of the real machine, and this condition is equivalent to the case of real rolling at a speed of 1800 m/min or more)

Degreasing solution: caustic soda 2% + polyoxyethylene nonylphenyl ether (HLB=12.4) 0.1% + sodium gluconate 0.1% solution

Degreasing method: dipping → electrolysis → rinsing

Immersion conditions: 80°C, 1 second

Electrolysis conditions: 80°C, 5A/dm ² , 1 second

Rinsing conditions: Spray with warm water at 70°C (1 liter/min x 1 second on each side).

<Test Example 2 (Cyclic Emulsion Stability Test)>

For the various rolling oils prepared, a cyclic emulsification stability test was carried out using a cyclic test device under the following conditions, and the average particle diameter of the emulsion before and after the addition of Fe ions was measured using a Coulter counter (manufactured by Malchisaiza one, manufactured by BECKMAN COULTER). The emulsion stability index (ESI) and adhesion amount were measured. The particle size stability was evaluated in terms of the absolute value (µm) of the amount of change in the average particle size (volume distribution). The absolute value of the variation is at a usable level of 10 μm or less, and the particle size stability is particularly good when it is 5 μm or less. ESI is an indicator of wastewater treatability, and the lower the ESI, the better the wastewater treatability. In addition, the amount of adhesion is an index of lubricity and lubrication stability, and the greater the amount of adhesion and the smaller the change, the better the lubricity and stability of lubrication. The amount of change in the amount of adhesion has a positive correlation with the above-mentioned particle size stability, and those with a large amount of adhesion and a small absolute value of change in the average particle size (those with good particle size stability) indicate that the emulsification stability is good.

loop condition

Circulation pump: Centrifugal pump (250L/min), pipe with diameter 50mm

Circulation volume; 100L/min

Cycle time: 30 minutes

Rolling oil concentration: 15% by weight

Liquid conditions: 80°C, 30 liters

Fe ion: 5mg/kg

ESI measurement conditions

Collect 400mL of rolling oil emulsion and put it into a separatory funnel, measure the rolling oil concentration of the upper and lower layers of the specified capacity after standing for 5 minutes (use the oil content flask to read the volume %, or use the oil content meter to read the weight % ). ESI was then calculated using the following formula.

ESI(%)＝B/A×100

A: The rolling oil concentration of the upper layer 100mL after standing still

B: Rolling oil concentration of the lower layer 100mL after standing

Determination method of adhesion amount

Spray the rolling oil emulsion on the pre-degreased and weighed test piece according to the following conditions, make it adhere to the rolling oil, and then wash it with running water. The weight was measured after drying, and the adhesion amount (g/m ² ) was calculated from the weight difference of the test pieces.

Attachment conditions

Test piece: low carbon steel (SPCC-D, 100mm×100mm×0.5mm)

Steel plate temperature: room temperature

Spray volume: 0.5L/min on each side, 200kPa

Spray distance: 150mm

Spraying method: vertical spraying on both sides

Spraying time: 1 second

Washing flow: 3L/min

Washing time: 1 second

Table 1

 Products of the present invention 1 2 3 4 5 6 lubricating oil Composition wt% (a) Grease A 90.98 Grease B 87.00 90.92 85.96 80.96 75.96   Fat C Fat D (b) Complex Ester A 5.00 20.00 Complex Ester B 10.00 10.00 Complex Ester C 15.00 5.00 (c) Polymer compound A 0.04 0.02 Polymer compound B 0.04 0.04 Polymer compound C 0.08 Polymer compound D other Additive A 3.0 4.0 4.0 4.0 4.0 4.0 Additive B 1.0 Additive C 1.0 Dynamic viscosity (mm ² /s, 40℃) 40 36 40 45 55 26 Iodine value (I ₂ g/100g) twenty two 20 twenty two twenty four 26 14 Melting point (℃) (rising method) 26 27 26 25 twenty four 25 Rolling Oil Properties Test example 1 Lubricity (tonf/m) 600 560 550 540 530 570 Alkaline degreasing (%) 95 100 95 95 90 95 Test example 2 Average particle size (μm) 29 60 49 51 53 66 Particle size stability (μm) 8 1 0 0 0 1 Adhesion amount(g/m ² ) 1.5 4.5 4.8 4.8 4.9 4.0 ESI(%) twenty two 1 0.5 0.5 0.5 3

Table 2

Compare products 1 2 3 4 5 6 lubricating oil Composition wt% (a) Grease A Grease B 95.97   Fat C 100 99.93 96.0 87.0 Fat D 96.9 (b) complex ester A complex ester B 10.0 complex ester C complex ester D 2.0 (c) Polymer compound A 0.1 Polymer compound B 0.03 Polymer compound C polymer compound D 0.07 other Additive A 2.0 4.0 3.0 Additive B 1.0 Additive D 1.0 Additive E 1.0 Dynamic viscosity (mm ² /s, 40℃) 40 43 40 42 28 55 Iodine value (I ₂ g/100g) 52 50 52 51 18 50 Melting point (℃) (rising method) 38 40 38 38 28 37 Rolling Oil Properties Test example 1 Lubricity (tonf/m) 660 620 620 630 640 590 Alkaline degreasing (%) 30 40 30 30 100 20 Test example 2 Average particle size (μm) 26 35 62 19 56 28 Particle size stability (μm) 8 0 twenty two 10 1 8 Adhesion amount(g/m ² ) 1.2 3.0 4.5 1.0 5.0 1.5 ESI(%) 27 52 1 35 0.5 25

In the above table, the meanings of the greases, complex esters, polymer compounds and other additives are as follows.

・Fat A...coconut oil (iodine value 13, melting point 26°C, dynamic viscosity at 40°C 25 mm ² /s, fatty acid ratio of 12 to 14 carbon atoms in the constituent fatty acids is 72% by weight and fatty acid with 8 or less carbon atoms ratio is 8% by weight)

Fat B...palm kernel oil (with an iodine value of 19, a melting point of 28°C, a kinematic viscosity of 28 mm ² /s at 40°C, a ratio of 61% by weight of fatty acids with 12 to 14 carbon atoms in the constituent fatty acids, and 8 or less carbon atoms Fatty acid ratio is 3% by weight)

Fat C ... palm oil (iodine value 52, melting point 38°C, kinematic viscosity at 40°C 41 mm ² /s, proportion of fatty acids with 12 to 14 carbon atoms in constituent fatty acids is 1% by weight)

・Fat and fat D... tallow (iodine value 49, melting point 40°C, kinematic viscosity at 40°C 43 mm ² /s, ratio of fatty acids having 12 to 14 carbon atoms in constituent fatty acids is 4% by weight)

Complex ester A...is composed of polymer acid of oleic acid (dimer acid: polymer acid above trimer acid = 60: 40 (weight ratio)) / diethylene glycol / lauryl alcohol = 2/1/2 ( molar ratio) obtained ester (acid value 8, hydroxyl value 6, average molecular weight 1800, kinematic viscosity at 40°C 820mm ² /s)

Complex ester B...is composed of tall oil fatty acid polymer acid (dimer acid: polymer acid above trimer acid = 75: 25 (weight ratio)) / pentaerythritol / lauric acid = 1/2/6 ( molar ratio) obtained ester (acid value 4, hydroxyl value 8, average molecular weight 3000, dynamic viscosity at 40°C ^1000mm2 /s)

・Complex ester C...composed of polymer acid of tall oil fatty acid (dimer acid: polymer acid above trimer acid=90:10 (weight ratio))/trimethylolpropane/lauric acid=1/ 2/4 (molar ratio) obtained ester (acid value 3, hydroxyl value 6, average molecular weight 1900, dynamic viscosity at 40°C 450 mm ² /s)

・Complex ester D...Ester obtained from adipic acid/pentaerythritol/oleic acid/octanol=0.9/1/1.8/0.2 (molar ratio) (acid value 3, hydroxyl value 35, average molecular weight 50000)

・Polymer compound A...copolymer of phosphoric acid neutralized product of diethylaminoethyl methacrylate/sodium methacrylate=4/5 (weight average molecular weight=20,000)

・Polymer compound B...a copolymer of phosphoric acid neutralized product of dimethylaminoethyl methacrylate/sodium acrylate=6/1 (weight average molecular weight=600,000)

・Polymer compound C...Dimethylaminopropyl methacrylamide glycolic acid neutralized product/sodium acrylate = 3/1 copolymer (weight average molecular weight = 100,000)

・Polymer compound D... octanoic acid neutralized product of a homopolymer of diethylaminoethyl methacrylate (weight average molecular weight = 80,000)

・Additive A…Oiliness improver (palm oil fatty acid)

・Additive B...antioxidant (2,4-di-tert-butyl-p-cresol)

・Additive C… Trioleyl Phosphate

Additive D... 4-octyldiphenylamine salt of butyl acid phosphate

・Additive E... polymer acid of tall oil fatty acid (dimer acid: polymer acid higher than trimer acid = 7:3 (weight ratio))

The iodine value of lubricating oil is measured by the method of JISK0070, and the melting point (rising melting point) is measured according to the method of "Standard oil analysis test method" (Chapter 2, Section 2, 4.2, edited by Japan Oil Chemical Society, published in 1996) .

In Table 1 and Table 2. The kinematic viscosity as well as the iodine value and melting point of various lubricating oils for direct cold rolling are summarized and recorded. The melting point is an index for evaluating the accumulation of rolling oil around the rolling mill, and the lower the melting point, the better the resistance to accumulation of rolling oil. It can be seen from the results shown in the table that compared with the comparative product, the direct cold rolling oil of the product of the present invention has good degreasing property and rolling oil accumulation resistance. Especially compared to the prior art palm oil of comparative product 1, all properties are very superior.

Example 2

Water was added to various lubricating oils for cold rolling oil for circulating supply shown in Table 3 and Table 4 (invention products 7-12 and comparative products 7-12) to prepare rolling oils with a concentration of 3% by weight. (Emulsion), lubricity, washability, resistance to scum accumulation, and long-term cycle stability were evaluated by the test examples described below, and the evaluation results are summarized in Table 3 and Table 4. In Table 3 and Table 4, each component (-part) is the same as Example 1.

<Test Example 3 (Rolling Test)>

For the various rolling oils prepared, use a two-roll mill (φ200mm×200mm wide, SUJ-2, Hs=90) to carry out the rectangular single-pass rolling test under the following conditions. Lubricity was evaluated by the control load (tonf/m). If the rolling load is lower than 95% of the value of the conventional tallow-based cold rolling oil (comparative product 7), it means that the lubricity is good. In addition, the degreasing property (alkali degreasing property) was evaluated by the water-wet area ratio (%) after degreasing the rolled steel plate under the following conditions. If a water-wet area ratio of 80% or more is shown, it means that the degreasing property is good.

rolling condition

Rolling material: low carbon steel (SPCC-B, 30mm wide x 700mm long x 2mm thick, Ra = 0.02μm)

Roller roughness: grind along the rolling direction with sandpaper, adjust to Ra=0.3-0.4μm (R z=2.8-3.2μm)

Steel plate temperature: 100°C

Rolling speed: 400 m/min

Reduction rate: 40%

Rolling oil concentration: 3% by weight

Liquid condition: 60℃, 10L

Mixer: M-type homogeneous mixer (manufactured by Special Kikka Kogyo Co., Ltd.)

Speed: 9000 rpm

Spraying volume: 2 liters/min x 1 each up and down, 100kPa

Degreasing conditions

Pre-heat treatment: 150°C x 12 hours (in the atmosphere) (This pre-heat treatment is carried out assuming the high-speed rolling of the real machine, and this condition is equivalent to the case of real rolling at a speed of 1800 m/min or more)

Degreasing solution: caustic soda 2% + polyoxyethylene nonylphenyl ether (HLB=12.4) 0.1% + sodium gluconate 0.1% solution

Degreasing method: dipping → electrolysis → rinsing

Immersion conditions: 80°C, 1 second

Electrolysis conditions: 80°C, 5A/dm ² , 1 second

Rinsing conditions: Spray with warm water at 60°C (1 liter/min x 1 second on each side).

<Test Example 4 (Continuous Rolling Test)>

For each of the prepared rolling oils, a three-pass rolling test of coil tension was carried out using the above-mentioned two-roll mill under the following conditions, and the resistance to scum accumulation was evaluated based on the scum accumulation amount (g). If the scum accumulation amount is less than 50% of the value of the conventional tallow-based cold-rolled oil (comparative product 7), it means that the scum accumulation resistance is good. In addition, the particle size of the emulsion before and after the test was measured with a Coulter counter (Mulchisaiza-, manufactured by BECKMAN COULTER), and the long-term cycle stability was evaluated from the absolute value (μm) of the change in the average particle size (volume distribution). If the absolute value of the change is below 2 μm, it means that the particle size stability (long-term cycle stability) is good.

rolling condition

Rolling material: low carbon steel (SPCC-D, 50mm wide x 100m long x 1mm thick, Ra = 0.5μm)

Roll roughness: adjusted to Ra=1.5μm

Steel plate temperature: room temperature

Rolling speed: 10 m/min

Rolling tension: 68.6MPa

Reduction rate: 25% per pass (total reduction rate 58%)

Rolling oil concentration: 3% by weight

Liquid condition: 60℃, 10L

Stirring conditions: M-type homogeneous mixer 9000 rpm

Spraying volume: 1 liter/min x 1 each up and down, 100kPa

Atmosphere temperature: 20°C

table 3

Products of the present invention 7 8 9 10 11 12 lubricating oil Composition wt% (a) Grease A 60 Grease B 68 75 79 70 50 Fat D Fat E 20 (b) complex ester A 20 15 complex ester B 10 20 complex ester C 20 30 (c) Polymer compound A Polymer compound B 1 1 1 Polymer compound C 2 2 other Ester A Ester B Ester C Additive A 5 5 5 5 5 5 Additive B 1 1 1 1 1 1 Additive C 2 2 2 2 1 Additive D Additive E Additive F Additive G 1 1 1 1 1 1 Additive H 3 1 1 Dynamic viscosity (mm ² /s, 40℃) 45 45 40 57 54 65 Iodine value (I ₂ g/100g) 26 twenty four twenty two 26 36 30 Melting point (℃) (rising method) twenty four 25 26 twenty four 20 twenty three Rolling Oil Properties Test example 1 Lubricity (tonf/m) 560 555 560 550 550 540 Alkaline degreasing (%) 100 100 100 100 90 95 Test example 2 Resistance to scum accumulation (g) 26 14 18 14 12 13 Particle size stability (μm) 2 1 0 1 0 1

Table 4

Compare products 7 8 9 10 11 12 lubricating oil Composition wt% (a) Grease A Grease B 90 70 Fat D 98 Fat E 70 30 (b) complex ester A complex ester B 20 38 complex ester C (c) Polymer compound A Polymer compound B 1 1 Polymer compound C 2 2 other Cool A 19 Ester B 20 74 Ester C 15 Additive A 5 5 5 3 6 Additive B 1 1 1 2 Additive C 2 2 Additive D 2 Additive E 2 Additive F 1 Additive G 1 1 1 1 Additive H 2 1 1 3 1 Dynamic viscosity (mm ² /s, 40℃) 43 28 34 72 70 75 Iodine value (I ₂ g/100g) 49 18 30 59 56 65 Melting point (℃) (rising method) 40 28 twenty two 12 0 12 Rolling Oil Properties Test example 1 Lubricity (tonf/m) 600 660 660 550 600 545 Alkaline degreasing (%) 60 100 95 30 40 20 Test example 2 Resistance to scum accumulation (g) 56 20 14 11 28 11 Particle size stability (μm) 5 o 1 1 2 1

Fat E ... palm oil (iodine value 65, melting point 8°C, kinematic viscosity at 40°C 41 mm ² /s, ratio of fatty acids having 12 to 14 carbon atoms in constituent fatty acids is 1% by weight)

・Ester A…2-Ethylhexyl Stearate

・Ester B...Ester obtained from trimethylolpropane/oleic acid/stearic acid=14.4/60.0/25.6 (weight ratio) (acid value 5)

・Ester C...Ester obtained from pentaerythritol/oleic acid/stearic acid=14.4/60.0/25.6 (weight ratio) (acid value 5)

・Additive F…antioxidant (phenyl-α-naphthylamine)

・Additive G…rust inhibitor (hexadecenyl succinic acid)

・Additive H…Emulsifier (polyoxyethylene nonylphenyl ether, HLB=12.4)

From the results shown in Table 3 and Table 4, it can be seen that compared with the comparative product, the cold rolling oil for circulating supply of the present invention has very good lubricity and degreasing properties, especially compared with the prior art of comparative product 7 Compared with tallow cold-rolled oil, all properties are very superior.

Claims (10)

1. cold-rolled lubricating oil for steel plate lubricating oil is characterized in that, this lubricating oil contains: (a) lipid, wherein the lipid acid of carbonatoms 12-14 accounts for more than the 50 weight % in constituting greasy lipid acid, and (b) complex ester class, and the iodine number of this lubricating oil is 5-40.

2. the described cold-rolled lubricating oil for steel plate lubricating oil of claim 1 is characterized in that, in the greasy lipid acid that constitutes (a), the ratio of the lipid acid of carbonatoms below 8 is below the 5 weight %.

3. claim 1 or 2 described cold-rolled lubricating oil for steel plate lubricating oil is characterized in that, described (b) composition is the ester that is obtained by polyprotonic acid, polyvalent alcohol and monohydroxy-alcohol and/or unary fatty acid.

4. claim 1 or 2 described cold-rolled lubricating oil for steel plate lubricating oil, it is characterized in that, described (b) composition is, by the carboxyl of the remnants of the dipolymer acid of the senior aliphatics unsaturated acid that is selected from carbonatoms 16-20 and the part ester that obtains with polyalcohols more than a kind in the polymeric acid or hydroxyl by the ester of the monohydroxy-alcohol of carbonatoms 12-22 or unary fatty acid esterification, weight-average molecular weight 750-20000.

5. claim 1 or 2 described cold-rolled lubricating oil for steel plate lubricating oil, it is characterized in that, also contain in (c) following water-soluble high-molecular compound more than a kind, this water-soluble high-molecular compound is to be selected from following polymkeric substance: (c1) by the monomer of general formula (1) expression or the homopolymer of its salt, (c2) this monomeric multipolymer more than 2 kinds, (c3) this monomeric more than a kind with (methyl) vinylformic acid, its salt, the multipolymer more than a kind in its alkyl ester or its alkylamide, its weight-average molecular weight is in the scope of 10000-1000000

In the formula, R ¹Expression hydrogen atom or methyl, R ²And R ³The alkyl of expression carbonatoms 1-3, A represent-O-or-N H-, m represents the integer of 1-3.

6. cold-rolled lubricating oil for steel plate is characterized in that, contains claim 1 or 5 described lubricating oil and water.

7. the described cold-rolled lubricating oil for steel plate of claim 6 is characterized in that, is the cold-rolled lubricating oil that direct type is supplied with usefulness.

8. the described cold-rolled lubricating oil for steel plate of claim 6 is characterized in that, is the cold-rolled lubricating oil of circulating supply usefulness.

9. the cold rolling process of steel plate is characterized in that, uses to contain the cold-rolled lubricating oil for steel plate that claim 1 or 5 described lubricating oil and water form.

10. claim 1 or 5 described lubricating oil are used as cold-rolled lubricating oil for steel plate and are coated with the usefulness of lubricating oil.