KR19980024701A - Water Soluble Ironing Lubricant Composition - Google Patents

Abstract

Drawing lubricant coated on both sides in an amount of 50 to 600 mg / m2 of lubricant having a kinematic viscosity of 5 to 70 mm2 / S at 40 ° C., followed by ironing, redrawing and ironing with ironing lubricant A water-soluble ironing lubricant stock solution used for the production of cans, comprising: (A) esters of C ₆ -C ₁₆ aliphatic carboxylic acids with polyhydric alcohols; or

(B) A water-soluble ironing lubricant stock solution containing a composition comprising an ester of a mixed aliphatic carboxylic acid comprising a C ₁₈ aliphatic carboxylic acid and a C ₆ -C ₁₆ aliphatic carboxylic acid and a polyhydric alcohol. Drawing lubricant coated on both sides in an amount of 50 to 600 mg / m2 of lubricant having a kinematic viscosity of 5 to 70 mm2 / S at 40 ° C., followed by ironing, redrawing and ironing with ironing lubricant A water-soluble ironing lubricant stock solution used in the production of cans comprising: (C) C ₆ -C ₁₆ aliphatic carboxylic acid and C ₂₀ -C ₂₄ aliphatic carboxylic acid and polyhydric alcohol; Or (D) a water-soluble ironing lubricant stock solution comprising a composition comprising an ester of a mixed aliphatic carboxylic acid comprising a C ₁₈ aliphatic carboxylic acid, a C ₆ -C ₁₆ aliphatic carboxylic acid and a C ₂₀ -C ₂₄ aliphatic carboxylic acid and a polyhydric alcohol. . The stock solution is diluted with water when used and when used to iron the ironed or redrawn and drawn cups into DI cans.

Description

Water-soluble ironing lubricant composition.

The present invention relates to water soluble ironing lubricants used therein for the ironing of metal cups, in more detail used in the production of DI cans.

DI (drawing and ironed) cans are widely applied as beverage containers for beer or soft drinks, which draw (cupping) metal sheets, and then draw the cups seamlessly molded body and bottom integrally. By ironing or redrawing and ironing into cans. Drawing is a forming method in which a disk-shaped blank sheet is fixed by a blank holder pad and formed into a bottomed cup using a tool comprising a punch and a die.

The term ironing refers to the process of thinning the side walls of a cup drawn by stretch. In the case of a disc-shaped sheet having a diameter larger than the diameter of the punch, the drawing operation may not be sufficient to form the sheet into the desired cup forming. In such a case, the cup must be redrawn before ironing the drawn cup.

In general, in the production of DI cans, a relatively wide diameter is achieved by drawing a metal sheet using a drawing machine known as a cupping press, followed by redrawing and immediately ironing the cup using a body forming machine (can body forming machine). Form a cup with.

Typically, in the production of DI cans, emulsion-type lubricants have been used in the preprocessing of DI can formation from drawing to ironing or redrawing and ironing.

That is, the emulsion-type lubricant has been used as a lubricant for both drawing of the first process and ironing or redrawing and ironing of the second process in the production of DI cans.

While emulsion-type lubricants have been commonly used in drawing operations, such emulsion-type lubricants present problems in selectively depositing oil fractions on the portion to be lubricated. This property is called the plateout property. Although excellent in lubrication, it is not practical to use emulsion-type lubricants that are poor in plateout properties. A wide range of investments and efforts have been made to solve the above problems, but no conclusion has been reached that leads to a leveled method for improving plateout properties. Importantly, the production of lubricants with improved plate-out properties in practice is the only way to select on the actual production line by trial and error. However, lubricants produced in this manner may fail to adjust to changes in molding conditions, such as changes in the design of the can. It has been considered to compensate for the poor plateout properties of lubricants by adding too much lubricating component. However, in conjunction with changes in molding conditions, changes in the formation of lubricants result in reduced work efficiency.

Alternatively, the use of a water-insoluble drawing lubricant, if poor in lubrication, will result in failure to perform the drawing operation on its own due to damage to the cup-shaped drawn material. Although such breakage can be avoided, the surface of the drawn material will be scratched due to excessive friction between the tool and the drawn material, such as punches and dies. The scratches that may remain even after completion of ironing harm the market price of the final product.

Moreover, the drawing lubricant remaining on the surface of the drawn cup-forming material contributes to the lubrication between the tool (punch and die) and the surface of the drawn material during the ironing process. However, the lubricated lubricant, if lubrication is not sufficient, causes scratches on the surface of the can after ironing, thereby reducing the aesthetics of the final product, leading to a drop in market price.

Drawing lubricants that are too lubricious are susceptible to the following disadvantages. Too much lubricity of the can is because the blank holding pad fails to secure the sheet firmly due to the reduced friction between the holding pad and the sheet, i.e. due to slipping or the formation of earrings due to partial elongation of the sheet. Corrugation is formed in the flange (opening).

The formation of pleats causes the can flange's thickness to be atypical, resulting in an increased ironing ratio in the ironing process. As a result, seizure occurs due to lack of lubrication, resulting in surface staining, so-called bleed-through. Moreover, irregularities in thickness cause breaks in the neck formed in the final molding process. Cups with formed earrings have the problem that the productivity of the cans is steeply impaired about the line that delivers the cups to the ironing machine because of the earrings that are hooked up. Moreover, excessive lubrication in lubrication causes another problem that the sheet slips on the roller device during the transfer of the aluminum or steel sheet to the drawing machine, resulting in a failure of the sheet to be delivered to the drawing machine.

After completion of ironing, the can is de-lubricated and washed with a liquid solution (detergent) containing a surfactant and then finished with surface chemicals for corrosion inhibition. The cans are then painted and printed, and then the opening is sealed and ready for shipping by the process for the neck and flange. Therefore, in the case of using ironing lubricants insufficient for molding, after production of the can-body, it is impossible to reduce the concentration of the surfactant contained in the delubricating agent and the detergent used in the washing process, so that the disposal Failure to improve water disposal performance.

Recently, in terms of environmental protection and resource conservation, lubricants used for the drawing process, in particular for ironing or redrawing during the production of DI cans and for subsequent processing of ironing, can not only be improved in lubrication, but also in cans. There is a strong demand for improvements in the de-lubricant and cleaning performance after this formation, and also in the disposal performance of several hundred tons of waste water per day. In order to produce high quality DI cans, it is important to use a suitable combination of lubricants for drawing and for ironing or for redrawing and ironing. Otherwise, producing the high quality can may fail.

Therefore, the drawing and ironing process or drawing and the lubricant are excellent not only in lubrication but also in delubrication and washing performance, which can reduce the concentration of surfactant contained in the detergent and lead to increased waste performance of the waste water. There has been a strong need for the use of lubricant compositions used in redrawing-ironing processes.

It has been found after extensive investigation that a combination of a drawing lubricant having a certain viscosity coated on a metal sheet to be drawn in a specific amount and a water-soluble ironing lubricant stock solution diluted in water in use can produce a high quality DI can. The composition contains an ester of an aliphatic carboxylic acid having a selected structure and is used in the ironing process or in the redrawing and ironing process and the waste water waste performance is improved.

According to a first aspect of the present invention, a drawing lubricant having a kinematic viscosity of 5 to 70 mm ² / S at 40 ° C. is drawn in a metal sheet having both surfaces coated in an amount of 50 to 600 mg / m ² and then ironing lubricant is drawn. A stock solution of a water soluble ironing lubricant for use in the production process of a DI can, which is ironed or redrawn and ironed using, is provided, the stock containing the following composition:

(A) esters of C ₆ -C ₁₆ aliphatic carboxylic acids and polyhydric alcohols; or

(B) esters of mixed aliphatic carboxylic acids and polyhydric alcohols comprising C ₁₈ aliphatic carboxylic acids and C ₆ -C ₁₆ aliphatic carboxylic acids.

According to a second aspect of the invention, a drawing lubricant having a kinematic viscosity of 5 to 70 mm ² / S at 40 ° C. is drawn in a metal sheet having both surfaces coated in an amount of 50 to 600 mg / m ² and then the ironing lubricant is drawn. A stock solution of a water soluble ironing lubricant for use in the production process of a DI can, which is ironed or redrawn and ironed using, is provided, the stock containing the following composition:

(C) esters of mixed aliphatic carboxylic acids and polyhydric alcohols comprising C ₆ -C ₁₆ aliphatic carboxylic acids and C ₂₀ -C ₂₄ aliphatic carboxylic acids; or

(D) esters of mixed aliphatic carboxylic acids and polyhydric alcohols comprising C ₁₈ aliphatic carboxylic acids, C ₆ -C ₁₆ aliphatic carboxylic acids and C ₂₀ -C ₂₄ aliphatic carboxylic acids.

According to a third aspect of the present invention, there is provided a method of drawing a coated metal sheet in an amount of 50 to 600 mg / m ² of a drawing lubricant having a kinematic viscosity of 5 to 70 mm ² / S at 40 ° C. and the aqueous ironing lubricant solution It provides a process for producing a DI can, consisting of ironing the drawn metal using an ironing lubricant obtained by dilution with water.

The water-soluble ironing lubricant composition of the present invention comprises esters of C ₆ -C ₁₆ aliphatic carboxylic acids and polyhydric alcohols or esters of C ₁₈ aliphatic carboxylic acids, C ₆ -C ₁₆ aliphatic carboxylic acids and polyhydric alcohols.

These esters are referred to below as constituents (A) and (B), respectively.

The C ₆ -C ₁₆ aliphatic carboxylic acid used as component (A) and (B) may be straight or branched, saturated or unsaturated, monobasic or dibasic acid. Aliphatic carboxylic acids of up to six carbon atoms are undesirable due to reduced processing and corrosion of punches and dies.

C ₆ -C ₁₆ monobasic acids are, for example, straight or branched chain nucleic acid, straight or branched heptanoic acid, straight or branched octanoic acid, straight or branched nonanoic acid, straight or branched decanoic acid, straight or branched undecanoic acid, straight or Saturated fatty acids such as branched dodecanoic acid, straight or branched tridecanoic acid, straight or branched tetradecanoic acid, straight or branched pentadecanoic acid, straight or branched hexadecanoic acid; Straight or branched hexenoic acid, straight or branched heptane, straight or branched octenic acid, straight or branched nonenoic acid, straight or branched decenic acid, straight or branched undecenoic acid, straight or branched tridecenoic acid, straight or branched tridecenoic acid, straight chain Or unsaturated fatty acids such as branched tetradecenoic acid, straight or branched pentadecenoic acid, straight or branched hexadecenoic acid, and mixtures thereof. Especially preferred are C ₈ -C ₁₆ saturated aliphatic acids, C ₈ -C ₁₆ unsaturated aliphatic acids and mixtures thereof.

C ₆ -C ₁₆ dibasic acids are, for example, straight or branched chain nucleic acid dibasic acids, straight or branched chain heptane dibasic acids, straight or branched chain octane dibasic acids, straight or branched chain nonane dibasic acids, straight or branched chain decane dibasic acids, straight or branched chains. Saturated dibasic acids such as dodecane dibasic acid, straight or branched tridecane dibasic acid, straight or branched tetradecane dibasic acid, straight or branched heptadecane dibasic acid, straight or branched hexadecane dibasic acid; Straight or branched hexene dibasic acid, straight or branched hepteptic dibasic acid, straight or branched chain octene dibasic acid, straight or branched chain nonene dibasic acid, straight or branched chain decene dibasic acid, straight or branched dodecene dibasic acid, straight or branched tridecene dibasic acid And unsaturated dibasic acids such as straight or branched tetradecene dibasic acids, straight or branched heptadecene dibasic acids, straight or branched hexadecene dibasic acids, and mixtures thereof. Especially preferred are C ₆ -C ₁₂ saturated dibasic acids, C ₆ -C ₁₂ unsaturated dibasic acids and mixtures thereof.

C ₁₈ aliphatic carboxylic acids include oleic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid and hydroxystearic acid, of which oleic acid, linoleic acid, linolenic acid and mixtures thereof are preferred.

The polyhydric alcohols used for the components (A) and (B) may vary from dihydric alcohols to dihydric alcohols, preferably dihydric alcohols to hexavalent alcohols. The dihydric to dihydric alcohols include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (trimers to quinomers of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycols (trimers to quinomers of propylene glycol). ), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1 Dihydric alcohols such as, 2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol and neopentylglycol; Glycerin, polyglycerols (dimers to octahedrons of glycerin such as diglycerin, triglycerine and tetraglycerin), trimethylolalkanes (trimethylolethane, trimethyllopropane and trimethylrobutane) and dimers to octamers thereof, pentaerytes Lithol and its dimers to tetramers, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol Polyhydric alcohols such as sorbitol, sorbitan, sorbitol glycerin condensation products, adonitol, arabitol, xylitol and mannitol; Sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose and sucrose and mixtures thereof. Of these, ethylene glycol, diethylene glycol, polyethylene glycol (trimers to trimers of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (trimers to trimers of propylene glycol), 1,3-propanediol , 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentylglycol, glycerin, diglycerin, triglycerine, trimethylolalkane (trimethylolethane, trimethyllopropane and trimethylrobutane And dimers to tetramers thereof, pentaerythritol and dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2 Preference is given to dihydric to hexavalent alcohols and mixtures thereof, such as, 3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensation products, adonitol, arabitol, xylitol and mannitol. Ethylene glycol, propylene glycol, neopentyl glycol, glycerol More preferred are lean, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan and mixtures thereof.

Component (B) is an ester derived from a mixed carboxylic acid containing C ₁₈ aliphatic carboxylic acid and C ₆ -C ₁₆ aliphatic carboxylic acid in an appropriate ratio, but considering the detergency and degreasing properties of the composition of the present invention, C ₁₈ aliphatic carboxylic acid It should be contained in an amount of 0.5 to 50, preferably 1 to 45, more preferably 2 to 40 mass% based on the total mass of the mixed aliphatic carboxylic acid.

The water-soluble ironing lubricant stock solution of the present invention is excellent in processability, detergency and degreasing properties due to the inclusion of component (A) or (B). In order to further improve the processability of the stock solution of the present invention, it is referred to as a mixed aliphatic acid (hereinafter referred to as component (C) or (D) derived from addition of C ₂₀ -C ₂₄ aliphatic carboxylic acid to the ester acid of component (A) or (B)). Esters containing) may be used. Aliphatic carboxylic acids having at least C ₂₄ have dilution with water, so that their solubility decreases to form solids and sludges, so their addition is undesirable.

Component (C) is an ester of a mixed aliphatic carboxylic acid comprising a C ₆ -C ₁₆ aliphatic carboxylic acid and a C ₂₀ -C ₂₄ aliphatic carboxylic acid and a polyhydric alcohol.

Component (D) is an ester of a mixed aliphatic carboxylic acid comprising a C ₁₈ aliphatic carboxylic acid, a C ₆ -C ₁₆ aliphatic carboxylic acid and a C ₂₀ -C ₂₄ aliphatic carboxylic acid and a polyhydric alcohol.

C ₂₀ -C ₂₄ aliphatic carboxylic acids may be straight or branched, saturated or unsaturated, typically straight or branched eicosane acid, straight or branched hehenic acid, straight or branched docoic acid, straight or branched tricoic acid Saturated aliphatic acids such as acids and straight or branched tetracoic acid; Unsaturated aliphatic acids such as straight or branched eicosane acids, straight or branched heneicosane acids, straight or branched docosene acids, straight or branched tricosene acids and straight or branched tetracosene acids and mixtures thereof.

Component (C) is an ester derived from a mixed carboxylic acid containing C ₆ -C ₁₆ aliphatic carboxylic acid and C ₂₀ -C ₂₄ aliphatic carboxylic acid in an appropriate ratio, but in view of processability, detergency and degreasing, C ₆ -C _{The 16} aliphatic carboxylic acids should be contained in an amount of 50 to 98, preferably 60 to 98, more preferably 70 to 98 mass%, based on the total mass of mixed aliphatic carboxylic acids.

Component (D) is a mixed aliphatic carboxylic acid containing C ₁₈ , C ₆ -C ₁₆ and C ₂₀ -C ₂₄ aliphatic carboxylic acids in an appropriate ratio, but considering the processability, detergency and degreasing properties, the total mass of the mixed aliphatic carboxylic acids On the basis of the C ₁₈ aliphatic carboxylic acid is 30 to 98, preferably 35 to 95, more preferably 40 to 95 mass%, C ₆ -C ₁₆ aliphatic carboxylic acid is 0.5 to 65, preferably 1 to 60, more preferred Preferably 1 to 50 mass%, C ₂₀ -C ₂₄ aliphatic carboxylic acid should be contained in an amount of 0.5 to 50, preferably 0.5 to 40, more preferably 1 to 30 mass%.

The esters of components (A), (B), (C) and (D) are complete esters derived from the complete esterification of all hydroxy groups contained in the polyhydric alcohols, or partially with one or more hydroxy groups which are not esterified. Esters.

Esters of mixed aliphatic carboxylic acids used in the present invention may be those derived from esterification of a mixture of aliphatic carboxylic acids or prepared by mixing esters obtained by esterification of aliphatic carboxylic acids.

The ester content of components (A) to (D) may be optional, but the lower limit is 3, preferably 5, more preferably 10 mass% based on the content of the entire composition in terms of processability, and the upper limit is It is 90, preferably 80, more preferably 70 mass% based on the content of the total composition in terms of stability in the diluent, washability and degreasing.

As long as the stock solution of the present invention contains any of the components (A) to (D), the content of the additional components is arbitrary. However, from the standpoint of stability in the diluent, detergency, degreasing, processability and waste power of the waste water, the surfactant should be contained in an amount of 3 to 80, preferably 5 to 80 mass% based on the total composition. do. The surfactant can be an anionic-based, nonionic-based or cation-based surfactant. Anionic-based surfactants include aliphatic acid salts, petroleum sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate ester salts, alkyl sulfosuccinates, alkyldiphenylether disulfonates, alkyl phosphates, polyoxyalkyls Lenalkyl or alkylallyl sulfate ester salts, formalin naphthalenesulfonate condensates and Turkey red oil.

Nonionic-based surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylallyl ethers, polyoxyalkylene sorbitan aliphatic acid esters, polyoxyalkylene sorbitol aliphatic acid esters, polyoxyalkylene aliphatic acid esters, poly Alkylenealkylamines and alkylalkanolamines.

Cation-based surfactants include alkylamine salts, quaternary ammonium salts, alkylbetaines and amineoxides. Preferred among the surfactants are anionic-based or nonionic-based surfactants and mixtures thereof.

If desired, mineral oil and / or synthetic hydrocarbon oil may be added to the stock solution of the present invention to adjust the viscosity. Suitable mineral oils may be one or more purification processes that can be carried out in combination such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation-dropping, hydrofinishing, sulfuric acid treatment, clay treatment, and the like. It may be paraffin or naphthenic mineral oil prepared by introducing a lubricant fraction derived from atmospheric or vacuum distillation of the crude oil.

Synthetic hydrocarbon oils typically include olefins, polyolefins, hydrides thereof, alkylbenzenes and alkyl naphthalenes.

The olefins referred to herein are those having 8 to 28, preferably 10 to 24, more preferably 12 to 20 carbon atoms, alpha-olefins having double bonds at the ends, and double bonds at portions other than the ends. The branches can be internal olefins or straight or branched olefins. Straight chain olefins are derived from oligomerization products of ethylene and branched chain olefins are derived from oligomerization products of propylene, butene or isobutylene.

Examples of such olefins are straight or branched octenes, straight or branched nonenes, straight or branched decenes, straight or branched undecenes, straight or branched dodecenes, straight or branched tridecenes, straight or branched tetradecenes, straight or branched pentadecenes, Straight or branched hexadecene, straight or branched heptadecene, straight or branched octadecene, straight or branched nonadecene, straight or branched eicosene, straight or branched heneicocene, straight or branched docosene, straight or branched tricocene, straight chain Or branched tetracosenes, straight or branched pentacose, straight or branched hexacosenes, straight or branched heptocenes, straight or branched octacosenes and mixtures thereof. Polyolefins include copolymers of ethylene and propylene, polybutenes, 1-octene oligomers, and 1-decene oligomers.

Preferred hydrides of polyolefins are hydrogenated polyolefins.

The mineral oil and the synthetic hydrocarbon oil may be used alone or in combination.

The water-soluble ironing lubricant stock solution of the present invention may be mixed with suitable additives such as carboxylic acids, lipids and oils, extreme pressure additives, amines, alcohols, rust inhibitors, antifoams, corrosion inhibitors for non-ferrous metals, antioxidants and metal scavengers. Can be.

The carboxylic acid may be an aliphatic carboxylic acid having 8 to 24 carbon atoms, and may be a straight-chain or branched, saturated or unsaturated, 1-base or 2-base acid. Such carboxylic acids include saturated carboxylic acids such as caprylic acid, nonanoic acid, capric acid, lauric acid, palmitic acid, sebacic acid and dodecane 2-basic acid and unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid and ricinoleic acid. do.

Fats and oils include tallow, lard, rapeseed oil, soybean oil, coconut oil, palm oil, rice bran oil and their hydrides. Extreme pressure additives are typically chlorine paraffins, chlorinated aliphatic acids, fatty oil sulfides, polysulfides and alkylphosphates. The alcohol is typically a C ₁₀ -C ₁₈ straight or branched chain alcohol or glycol.

Rust inhibitors are typically aliphatic amides and aromatic carboxylic acids. Defoamers are typically silicone-based compounds. Non-ferrous metal corrosion inhibitors are typically benzotriazole-based compounds. Antioxidants are typically phenol-based antioxidants. Corrosion inhibitors are typically thiazole-based, isothiazole-based, phenol-based or halogen-based additives. Metal scavengers are typically ethylenediaminetetraacetic acid.

The water-soluble ironing lubricant stock solution can be mixed with water such as tap water, iron-exchanged water and distilled water. Although not limited thereto, the water content is 70, preferably less than 60 mass%, based on the total composition.

The water-soluble ironing lubricant stock solution according to the present invention is diluted with water when used as the ironing lubricant, and the amount of water used for the dilution is not limited. However, in order to improve the processability, detergency and degreasing of the stock solution of the present invention, it must be diluted with water such that the amount of the stock solution is 0.5 to 30, preferably 1 to 20 mass% based on the mass of the ironing lubricant. do. Preferred diluents can be tap water, industrial water, iron-exchanged water and distilled water.

The compositions of the present invention diluted with water may perform the desired detergency and degreasing properties, with the ironing lubricant having an average size of 1 μm, preferably 0.7 μm, more preferably less than 0.5 μm particles of the composition dissolved in water. As a result of the better cleaning and degreasing properties and improved stability in the diluent, which are expected when it contains, it contributes to a more stable operation for the production of DI cans. The average size of the dissolved particles can be measured by a measuring device using a laser diffraction method and / or light scattering method such as a particle size distribution measuring device LPA 3000 / LPA 3100 manufactured by Ohtsuka Electronics.

The water-soluble ironing lubricant stock solution of the present invention is drawn after the metal sheet is coated with a drawing lubricant 50 to 600 mg / m ² having a kinematic viscosity of 5 to 70 mm ² , and then ironed or redrawn, and the ironing lubricant It is used in the manufacture of DI cans ironed using.

The upper limit of the kinematic viscosity of the drawing lubricant at 40 ° C. is 70 mm ² / s, preferably 50 mm ² / s, more preferably 40 mm ² / s, and the lower limit is 5 mm ² / s, preferably 7 mm ² / s, more preferably 10 mm ² / s. Kinematic viscosities above the upper limit at 40 ° C. will lead to plate sticking on the cup, plate slip and crease and earring formation on the transfer roller, while kinematic viscosities below 40 ° C. will result in poor processability resulting in can breakage. .

According to the invention, the drawing lubricant is 50 to 600 mg / m ² , preferably 100 to 500 mg / m ² , more preferably on both sides of the metal plate using a gravure roll device or an electrostatic coating machine. It is necessarily coated in an amount of 150 to 450 mg / m ² . Coating amounts in excess of 600 mg / m ² will result in sticking of the cup and slipping of the plates and formation of wrinkles and earrings, and reducing the drawing when less than 50 mg / m ² .

The drawing lubricant is not of a type that is diluted with water when used unlike emulsion type lubricants.

Emulsion type lubricants, which are diluted with water in use, reduce plating properties and processability when changing the forming conditions, so that in order to overcome such defects, a change in the composition of the lubricant is required, which can reduce operating efficiency.

Any suitable drawing lubricant is preferred for use in the present invention as long as their kinematic viscosity is within the above range. Preferred base oils for drawing lubricants can be any oil, from mineral oils, synthetic oils to fats and oils.

Suitable mineral oil base oils are lubricants which are purified by solvent deasphalting, solvent extraction, hydrocracking-cracking, solvent dewaxing, catalytic dewaxing, hydrogenation-purification, sulfuric acid treatment or clay treatment alone or in combination thereof. Paraffin or naphthenic oil available from atmospheric or vacuum distillation fractions.

Suitable fats and oils may be tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil and hydrides thereof.

Suitable synthetic-based oils include polyolefins (ethylene-propylene copolymers, polybutenes, 1-octene oligomers and 1-decene oligomers) and their hydrides and alkynebenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyphenylethers , Dialkyldiphenylethers, phosphoric acid (tricresyl phosphate), fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins) and silicone oils.

Two or more such oils may be used in combination. Among the oils mentioned above, those containing esters in an amount of at least 5%, preferably at least 10%, more preferably at least 20%, based on the total amount of lubricant, are preferred as drawing lubricants.

The alcohol used to produce the ester can be mono or polyhydric alcohol. The acid used to produce the ester may be monobasic or polybasic acid. The monohydric alcohol may be 1 to 24, preferably 1 to 12, more preferably 1 to 8 carbon atoms. Such alcohols may be straight or branched.

Specific examples of C ₁ to C ₂₄ alcohols include methanol, ethanol, straight or branched propanol, straight or branched butanol, straight or branched pentanol, straight or branched hexanol, straight or branched heptanol, straight or branched octanol, straight or Branched nonanol, straight or branched decanol, straight or branched dodecanol, straight or branched tridecanol, straight or branched tetradecanol, straight or branched pentadecanol, straight or branched hexadecanol, straight or branched heptadecanol , Straight or branched octadecanol, straight or branched nonadecanol, straight or branched icosanol, straight or branched henicosanol, straight or branched docosanol, straight or branched tricosanol, straight or branched tetracosanol, and Mixtures are included.

The polyhydric alcohol may be a dihydric alcohol to a dihydric alcohol, preferably a dihydric alcohol to a hexavalent alcohol.

Specific examples of the dihydric to dihydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol (trimers to quinomers of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycols (trimers to trimers of propylene glycol) , 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1, Dihydric alcohols such as 2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, and neopentylglycol; Glycerin, polyglycerols (dimeric to octahedrons of glycerin such as diglycerin, triglycerine and tetraglycerine), trimethylolalkanes (trimethyloletane, trimethylolpropane and trimethylolbutane) and their dimers to octahedrons, penta Erythritol and dimers to dimers thereof, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butane Polyhydric alcohols such as tetrol, sorbitol, sorbitan, sorbitol glycerin condensation products, adonitol, arabitol, xylitol and mannitol; And sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, trehalose and sucrose, and mixtures thereof.

Most preferred of these are ethylene glycol, diethylene glycol, polyethylene glycol (trimers to trimers of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (trimers to trimers of propylene glycol), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentylglycol, glycerin, diglycerin, triglycerine, trimethylolalkane (trimethyloletan, trimethylolpropane and trimethyl Olbutane) and dimers to tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol Dihydric to hexavalent alcohols such as 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensation products, adonitol, arabitol, xylitol and mannitol, and mixtures thereof.

Especially preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and mixtures thereof.

Qualified monobasic acids of the invention are C ₆ -C ₂₄ fatty acids which may be saturated or unsaturated and straight or branched. Examples of such C ₆ -C ₂₄ fatty acids are straight or branched hexanoic acid, straight or branched octanoic acid, straight or branched nonanoic acid, straight or branched decanoic acid, straight or branched bidecanoic acid, straight or branched dodecanoic acid, straight or Branched tridecanoic acid, straight or branched tetradecanoic acid, straight or branched pentadecanoic acid, straight or branched hexadecanoic acid, straight or branched heptadecanoic acid, straight or branched octadecanoic acid, straight or branched hydroxyoctadecanoic acid, straight chain Or saturated fatty acids such as branched nonadecanoic acid, straight or branched eicosanoic acid, straight or branched heneicosanoic acid, straight or branched docosanoic acid, straight or branched tricosanoic acid and straight or branched tetracosanoic acid; Straight or branched hexenoic acid, straight or branched octenoic acid, straight or branched nonenoic acid, straight or branched decenoic acid, straight or branched bidecenoic acid, straight or branched dodecenoic acid, straight or branched tridecenoic acid, straight or branched tetradecese No acid, straight or branched pentadecenoic acid, straight or branched hexadecenoic acid, straight or branched heptadenoic acid, straight or branched octadecenoic acid, straight or branched hydroxyoctadecenoic acid, straight or branched nonadenosane, straight or branched eicosane Unsaturated fatty acids such as senoic acid, straight chain or branched heneicocenoic acid, straight chain or branched docosenoic acid, straight chain or branched trichocenoic acid and straight chain or branched tetrakocenoic acid, and mixtures thereof, and saturated C ₈ -C ₂₀ Fatty acids, C ₈ -C ₂₀ unsaturated fatty acids or mixtures thereof are preferred.

The polybasic acid may be C ₂ -C ₁₆ dibasic acid or trimellitic acid. C ₂ -C ₁₆ dibasic acids may be straight or branched and saturated or unsaturated and specific examples thereof include ethano dibasic acids, propano dibasic acids, straight or branched butano dibasic acids, straight or branched pentano dibasic acids, straight or Branched hexano dibasic acids, straight or branched heptano dibasic acids, straight or branched octanoic dibasic acids, straight or branched nonanodibasic acids, straight or branched decanoic dibasic acids, straight or branched bidecanoic dibasic acids, straight or branched dodecane Saturated dibasic acids such as cano dibasic acids, straight or branched tridecanoic dibasic acids, straight or branched tetradecanoic dibasic acids, straight or branched pentadecanoic dibasic acids, straight or branched hexadecanoic dibasic acids; Buteno dibasic, straight or branched penteno dibasic, straight or branched hexeno dibasic, straight or branched hepteno dibasic, straight or branched octeno dibasic, straight or branched noneno dibasic, straight or branched deseno Dibasic acids, straight or branched bideteno dibasic acids, straight or branched dodeceno dibasic acids, straight or branched trideseno dibasic acids, straight or branched tetradecenodibasic acids, straight or branched pentadeceno dibasic acids, straight or branched hexa Unsaturated dibasic acids such as deceno dibasic acids and mixtures thereof. Suitable combinations of alcohols and acids are readily available and such combinations are as follows:

1) esters of monohydric alcohols with monobasic acids;

2) esters of polyhydric alcohols with monobasic acids;

3) esters of monohydric alcohols with polybasic acids;

4) esters of polyhydric alcohols with polybasic acids;

5) mixed esters of monohydric alcohols, polyhydric alcohols, and polybasic acid mixtures;

6) mixed esters of polyhydric alcohols, monobasic acids and polybasic acid mixtures;

7) Mixed esters of monohydric and polyhydric alcohols and monobasic and polybasic acid mixtures.

When using polyhydric alcohols, the ester may be a full ester derived from full esterification of all hydroxyl groups or a partial ester having one or more hydroxyl groups remaining unesterified. When using a polybasic acid, the ester may be a full ester derived from full esterification of all carboxyl groups or a partial ester with one or more carboxyl groups remaining unesterified.

In addition, in order to improve processability, the base oil of the drawing lubricant preferably contains at least one ester selected from (1), (2), (3) and (4).

Preferred are one or more esters selected from (1), (2) and (4). More preferred are at least one ester selected from (1) and (2). Most preferred are at least one ester of (2).

The base oil can be used with the drawing lubricant and can be added with further suitable additives if desired. Such additives include oils, extreme pressure additives, decay inhibitors, detergent-dispersants, antioxidants and antifoams.

Oil agents can be fatty acids, higher alcohols, amines and amides.

Extreme pressure additives include phosphorus-based compounds such as tricresyl phosphate, sulfur-based compounds such as polysulfide, chlorine-based compounds such as chlorinated paraffin and zinc dialkyldithiophosphates, molybdenum dialkyldithiophosphates, zinc Organometallic compounds such as organometallic compounds such as dialkyldithio carbamate and molybdenum dialkyldithiocarbamate.

Corrosion inhibitors can be benzotriazoles, mercaptobenzothiazoles, sodium salts and tritriazoles thereof.

Detergent-dispersants include alkali or alkaline earth metal sulfonates, alkali or alkaline earth metal salicylates, alkali or alkaline earth metal phenates, fatty acid soaps, alkenylsuccinic acid imidos, alkenylsuccinic acid imidos and non-modified boric acids It may be an ion-based surfactant. Antioxidants can be phenol-based compounds such as 2,6-di-tert-butyl-cresol and aromatic amines such as phenyl-α-naphthylamine.

Defoamers can be silicone-based compounds, higher alcohols, metal soaps, amides and soaps, amides and ethylene-propylene polymers.

These may be added in an amount of 20% or less, preferably 15% or less, based on the total mass of the composition.

The present invention is applicable to aluminum, aluminum alloys (aluminum-manganese alloys), steel sheets, surface-treated steel sheets (galvanized sheet metals and termid sheet metals).

The invention will be further described by the following examples which are provided merely to illustrate the method. The invention is not limited to the examples described below.

According to the formulation of Samples 1-9 of Table 1, there are preferred ironing lubricant stock solutions for Inventive Examples (Samples 1-6) and Comparative Examples (Samples 7-9).

DI having a 350 ml internal volume using the above-described samples of the ironing and drawing lubricants (Samples 10-23) of the formulation identified as Inventive Examples 1-18 and Comparative Examples 1-7 in the methods described below. Create a can.

Drawing lubricant

Sample 10: paraffin-based mineral oil, @ 40 ° C., 2 mm ² / s

Sample 11: paraffin-based mineral oil, @ 40 ° C., 6 mm ² / s

Sample 12: paraffin-based mineral oil, @ 40 ° C., 23 mm ² / s

Sample 13: paraffin-based mineral oil, @ 40 ° C., 76 mm ² / s

Sample 14: neopentylglycoldioleate, @ 40 ° C., 21 mm ² / s

Sample 15: pentaerythritol tetraoleate, @ 40 ° C., 64 mm ² / s

Sample 16: Mixture of samples 10 and 14 (90:10 weight ratio), @ 40 ° C., 2.3 mm ² / s

Sample 17: Mixture of samples 11 and 14 (90:10 weight ratio), @ 40 ° C., 6.7 mm ² / s

Sample 18: Mixture of Samples 12 and 14 (90:10 weight ratio), @ 40 ° C., 22.8 mm ² / s

Sample 19: Mixture of Samples 12 and 15 (45:55 weight ratio), @ 40 ° C., 39.1 mm ² / s

Sample 20: Mixture of Samples 14 and 15 (90:10 weight ratio), @ 40 ° C., 74.7 mm ² / s

Sample 21: Mixture of Samples 14 and 15 (60:40 weight ratio), @ 40 ° C., 32.0 mm ² / s

Sample 22: 45 mass% of sample 12, 45 mass% of sample 15, 7.3 mass% of olefinic acid and 2.7 mass% of diethanolamine, @ 40 ° C., 35 mm ² / s

Sample 23: net composition comprising 67 mass% of mineral oil (@ 40 ° C., 67 mm ² / s), 15 mass% of olefinic acid and 18 weight% of diethanol amine diluted with water, 20 based on total mass mass%

Method of making DI cans.

A 120 mm diameter aluminum alloy sheet (JIS H 4000 3004-H 19) is coated on both surfaces thereof with a 350 mg / m ² amount of drawing lubricant and then formulated into a cup type of 66 mm diameter under the drawing conditions described below.

Drawing conditions

Punch diameter 66.00 mm Die diameter 66.81 mm Blank holding force 1,000 kgf Drawing rate 76 m / min

The drawn cup obtained above is fitted to a punch and ironed to the extent that its content in the lubricant is 3% by mass using the ironing lubricant obtained by diluting the composition with water. Each of the above mentioned combinations of lubricants presented in Table 1 resulted in 10 portions of DI cans.

Ironing Condition

Punch diameter 66.00 mm First ironing die diameter 66.63 mm 2nd ironing die diameter 66.43 mm 3rd ironing die diameter 66.30 mm 4th ironing die diameter 66.22 mm Ironing rate 76 m / min

The resulting DI cans are measured for drawability, ironing and washability with the results presented in Table 2. The measurement is carried out according to the procedure described below.

Drawing

The appearance of each drawing cup is visually observed in an aesthetic sense. Cups without wrinkles are marked with mark O and those with wrinkles are marked with mark X.

Ironing

Visually observe the diameter of the resulting DI can and the occurrence of scratches on the wall and whether or not breakage has occurred in the ironing.

damage

Marking O indicates that there are no breaks in all 10 parts of the DI can and marking X indicates that there is breakage in at least one of the 10 parts of the DI can.

Opening

Cans are measured in 6 grades. Grade cans without black scratches are numbered 5 and fully formed without scratches are numbered 0. Average the grade of each DI can.

Wall panel

Marking O indicates no breakage and marking X indicates the occurrence of scratches.

Detergency

The obtained DI can is spray-washed using a surfactant of varying concentration and then measured with distilled water to visually determine whether lubricant remains on the can surface. In this evaluation, when the lubricant remains on the surface of the can, the sprayed distilled water is water repelled. The detergent used for this evaluation is an aqueous solution of Ridolin NHC 100A (Nihon Paint Co., Ltd., main ingredient: sulfuric acid), and an aqueous solution of Ridolin NHC 100M (Nihon Paint Co., Ltd., main ingredient: surfactant) is described in the formulation described below. It is prepared according to.

Marking O indicates that lubricant remained on the surface of the can and X indicates that lubricant remained.

Detergent 1 100 A: 3.8 mass%

100 M: 0.8 mass%

Rest: water

Detergent 2 100 A: 3.8 mass%

100 M: 0.6 mass%

Rest: water

Detergent 3 100 A: 3.8 mass%

100 M: 0.4 mass%

Rest: water

From the results shown in Table 2, it appears that the stock solution of the present invention consisting of a water-soluble ironing lubricant promotes drawing, ironing and washing. In particular, composition containing stock solutions (inventive examples 5-8 and 11-18) comprising C ₂₀ -C ₂₄ aliphatic carboxylic acids reduce the incidence of black scratches after can forming is complete. Moreover, compositions having an average particle size of 1 μm or less after dilution with water (Examples 1 to 8 and 11 to 18 of the present invention) are more washable than those having an average particle size of greater than 1 μm (Examples 9 and 10 of the present invention). Excellent. The drawing lubricants of Examples 13, 15, 16, 17 and 18 of the present invention containing esters as base oils significantly reduced the occurrence of black scratches. On the other hand, water-soluble ironing lubricant stock solutions (Comparative Example 1) were observed to be poor in ironity when all parts of the esters defined in the present invention were replaced with mineral oil. Ironing lubricant stock solutions (Comparative Example 2) lacking the ester of the present invention were also poor in ironability.

The use of conventional emulsion type lubricants (comparative example 3) for drawing and ironing resulted in poor ironing and washability.

Drawing lubricants (comparative examples 4 and 6) having a viscosity below the range defined by the present invention are inferior in ironing even with the use of the ironing lubricant of the present invention.

Even when used with the ironing lubricant of the present invention, drawing lubricants (comparative examples 5 and 7) exceeding the viscosity beyond the range defined by the present invention are also poor in drawing and ironing properties.

As mentioned above, the present invention can contribute to the improvement in the production of high-quality DI cans and the disposal of wash water.

Sample One 2 3 4 5 6 7 8 9 Composition (mass%) Ester 1 * 1) Ester 2 * 2) Ester 3 * 3) Ester 4 * 4) 12.5 12.5 12.5 12.5 20 7.5 Mineral oil * 5) 5.0 63.8 69.8 Anionic Base Surfactant * 6) 38 38 38 38 33.5 38 13 10 38 Anionic Base Surfactant * 7) 16 16 10 15.5 14 15.5 6 4 16 Nonionic Base Surfactant * 8) 12.5 12.5 12.5 12.5 11 12.5 3 2 12.5 Triethanol amine 9 9 12 9 7 9 4 4 9 Synthetic alcohol * 9) 10 10 10 10 9 10 10 10 10 Benzotriazole 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 water 1.8 1.8 4.8 2.3 5.3 2.3 14.3 * 1): Triesters of trimethyllopropane and C ₁₂ fatty acids * 2): Trimethylopropane and C ₁₂ , C ₁₆ and C ₁₈ fatty acid mixtures (60, 20 and 20 mass% respectively based on the total mass of fatty acids) triesters * 3): ethylene glycol and C ₁₂ and C ₂₀ fatty acid mixture (di-ester of 80 and 20% by mass, respectively, based on the weight of the fatty acid) * 4), propane and C _12, C ₁₈ and C ₂₀ with trimethyl Triesters of fatty acid mixtures (5, 90 and 5% by mass, respectively, based on the total mass of fatty acids): paraffin-based mineral oil, @ 40 ° C, 67 mm2 / s * 6): triethanolamine of oleic acid * 7) : Triethanolamine salt of caprylic acid * 8): Ethylene oxide addition product of nonylphenol (average degree of polymerization: 14) * 9): _C14 synthetic alcohol

Drawing lubricant Ironing lubricant Average particle size (μm) drawing Iron castle Detergency crack Opening Good surface Detergent One 2 3 Invention Example 123456789101112131415161718 111211121112111211121112141718192122 112233445566444444 0.160.160.210.210.320.320.240.241.531.530.240.240.240.240.240.240.240.24 OOOOOOOOOOOOOOOOOO OOOOOOOOOOOOOOOOOO 4.04.14.14.14.34.44.34.44.34.34.04.34.84.64.64.84.64.4 OOOOOOOOOOOOOOOOOO OOOOOOOOOOOOOOOOOO OOOOOOOOOOOOOOOOOO OOOOOOOOXXOOOOOOOO Comparative Example 1234567 18182310131620 7984444 3.160.236.060.240.240.240.24 OOOOXOX XXXXOXO 3.72.73.12.42.72.82.6 XXXXXXX OOOOOOO OOXOOOO XOXOOOO

Claims (3)

A drawing lubricant with a kinematic viscosity of 5 to 70 mm 2 / S at 40 ° C. on both sides, drawing a coated metal sheet in an amount of 50 to 600 mg / m 2, followed by ironing, redrawing and ironing with an ironing lubricant In the water-soluble ironing lubricant stock solution used for the production of cans, (A) esters of C ₆ -C ₁₆ aliphatic carboxylic acids with polyhydric alcohols; or (B) A water-soluble ironing lubricant stock solution containing a composition comprising an ester of a mixed aliphatic carboxylic acid and a polyhydric alcohol comprising a C ₁₈ aliphatic carboxylic acid and a C ₆ -C ₁₆ aliphatic carboxylic acid. Drawing lubricant coated on both sides in an amount of 50 to 600 mg / m2 of lubricant having a kinematic viscosity of 5 to 70 mm2 / S at 40 ° C., followed by ironing, redrawing and ironing with ironing lubricant In the water-soluble ironing lubricant stock solution used for the production of cans, (C) esters of mixed aliphatic carboxylic acids and polyhydric alcohols comprising C ₆ -C ₁₆ aliphatic carboxylic acids and C ₂₀ -C ₂₄ aliphatic carboxylic acids; or (D) A water-soluble ironing lubricant stock solution containing a composition comprising a mixture of a mixed aliphatic carboxylic acid comprising a C ₁₈ aliphatic carboxylic acid, a C ₆ -C ₁₆ aliphatic carboxylic acid and a C ₂₀ -C ₂₄ aliphatic carboxylic acid and a polyhydric alcohol. Drawing lubricant having a kinematic viscosity of 5 to 70 mm 2 / S at 40 ° C. on both sides, drawing a metal sheet coated with an amount of 50 to 600 mg / m 2, and drawing the drawn metal into a stock solution of the water-soluble ironing lubricant according to claim 1. Ironing or redrawing and ironing using an ironing lubricant obtained by diluting.