KR19980024700A - Water Soluble Ironing Lubricant Composition - Google Patents

Abstract

Drawing metal sheets coated on both sides in an amount of 50 to 600 mg / m ² of a drawing lubricant with a dynamic viscosity of 5 to 70 mm ² / S at 40 ° C., followed by ironing or redrawing and eye drawing with ironing lubricant A water-soluble ironing lubricant stock solution used in the process of annealing to produce DI cans, the stock solution comprising (A) polyoxyalkylenes and / or monoalkyl ethers thereof having an average molecular weight of 300 to 20,000 and (B) C ₆ -C _It contains a composition comprising an ester of ₂₄ aliphatic acids. The stock solution is diluted in water when ironing or redrawing and ironing the drone cup to make a DI can.

Description

Water Soluble Ironing Lubricant Composition

The present invention relates to a water soluble ironing lubricant stock solution used in the production of DI cans, and more particularly, for ironing drone metal cups.

DI (drawing and ironed) cans are widely applied as beverage containers for beer or soft drinks, which draws (cupping) metal sheets, and then allows the drone cups to be integrated without seamless between body and bottom. It is made by ironing or redrawing and ironing with the formed seamless 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 a process of thinning the sidewalls of a drawn cup 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 drone 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 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, use of a water-insoluble drawing lubricant, if poor in lubrication, would result in failure to perform the drawing operation on its own due to damage to the cup-forming drone material. Although such breakage can be avoided, the surface of the drone material will be scratched due to excessive friction between the drone material and tools such as punches and dies. The scratches that may remain after the completion of ironing harm the market price of the final product.

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

Too much lubricated drone lubricants are susceptible to the following fire points. Too much lubrication causes the blank holding pad to fail 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, in lubrication, excessive drone lubricants cause 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 cleaned using 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 the 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 cleaning process, so that it is discarded. 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 improvement 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-grade DI cans, it is important to use a combination of lubricants for drawing and for ironing or for redrawing and ironing as appropriate. Otherwise, producing the high-grade can may fail.

Thus, the lubricant is superior in lubrication as well as degreasability and detergency, which can reduce the concentration of surfactant contained in the detergent, drawing and ironing, leading to increased waste performance of the waste water. There has been a strong need for the use of lubricant compositions used in processes or in drawing and redrawing-ironing processes.

It has been found after extensive investigation that a combination of a drawing lubricant with a specific viscosity and a water-soluble ironing lubricant stock solution coated on a metal sheet to be drawn in a specific amount can produce high grade DI cans, the composition of which Containing esters and used in the ironing process or in the redrawing and ironing process.

According to a first aspect of the invention, a metal sheet coated on both sides in an amount of 50 to 600 mg / m ² of drawing lubricant having a kinematic viscosity of 5 to 70 mm ² / S at 40 ° C. is then drawn, An ironing lubricant is used to provide a water-soluble ironing lubricant stock solution for use in the process of ironing or redrawing and ironing to produce a DI can, wherein the stock solution comprises (A) polyoxyalkylene having an average molecular weight of 300 to 20,000 and And / or a composition comprising a monoalkyl ether thereof and an ester of (B) C ₆ -C ₂₄ aliphatic acid.

According to another aspect of the invention, drawing a coated metal sheet in an amount of 50 to 600 mg / m ² of drawing lubricant having a dynamic viscosity of 5 to 70 mm ² / S at 40 ° C. and the water-soluble ironing lubricant A method of making a DI can, comprising ironing or redrawing and ironing a drone metal using an ironing lubricant obtained by diluting the stock solution with water.

The water-soluble ironing lubricant composition stock solution of the present invention contains a composition comprising (A) a polyoxyalkylene having an average molecular weight of 300 to 20,000 and / or a monoalkyl ether thereof and (B) an ester of a C ₆ -C ₂₄ aliphatic acid do.

Polyoxyalkylenes suitable for the purposes of the present invention may be those obtained from random- or block-polymerization of ethylene oxide, propylene oxide or butylene oxide, of which the use of ethylene oxide or propylene oxide is preferred. Do. The polyoxyalkylene should have an average molecular weight of 300 to 20,000, preferably 500 to 10,000, most preferably 600 to 7,000. An average molecular weight of less than 300 will interfere with the waste performance of the waste water due to the increased water-solubility, whereas an average molecular weight of more than 20,000 will result in a slow operation composition due to the increased viscosity. As used herein, the term mean molecular weight refers to the average number molecular weight calculated from the hydroxyl value.

Given the situation in which the composition is insoluble in water, the propylene oxide unit content in the polyoxyalkylene is at least 10, preferably at least 20, more preferably on a mass basis, as it affects the waste performance of the wastewater in subsequent processes. Preferably at least 30%.

The polyoxyalkylene monoalkyl ethers may be those derived from the polyoxyalkylenes described above.

The alcohol used for the formation of alkyl groups of the polyoxyalkylene monoalkyl ethers may be 1 to 24, preferably 1 to 18, more preferably 4 to 18 carbon atoms. The alcohol may be straight or branched chain.

Specific examples of C ₁ -C ₂₄ alcohols are 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 undecanol, 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 isosanol, straight or branched heneicosanol, straight or branched docosanol, straight or branched tricosanol, straight or branched Tetracosanol and mixtures thereof.

The C ₆ -C ₂₄ aliphatic acid used in the present invention may be straight or branched and saturated or unsaturated. The C ₆ -C ₂₄ aliphatic acid can be, 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 chain 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 hydroxide Saturated aliphatic acids such as oxyoctadecanoic acid, straight or branched nonadecanoic acid, straight or branched isoic acid, straight or branched heneic acid, straight or branched docoic acid, straight or branched trichoic acid and straight or branched tetracoic 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 branched tetradecenoic 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 nonadecenic acid, Unsaturated aliphatic acids such as straight or branched chain isocenoic acid, straight or branched heneicosane acid, straight or branched docosenoic acid, straight or branched tricosenoic acid and straight or branched tetracosenoic acid, and mixtures thereof, among which C ₈ Preferred are -C ₂₀ saturated aliphatic acids, C ₈ -C ₂₀ unsaturated aliphatic acids and mixtures thereof.

Any suitable combination between (A) polyoxyalkylene and / or monoalkyl ethers thereof and (B) C ₆ -C ₂₄ aliphatic acid is available as follows:

1) monoesters of polyoxyalkylenes and aliphatic acids;

2) esters of polyoxyalkylene monoalkyl ethers and aliphatic acids; And

3) diesters of polyoxyalkylenes and aliphatic acids.

Among them, at least one ester selected from the combination of 1) 2) and 3) in terms of increased treatment and stability upon dilution of the water-soluble ironing lubricant stock solution is preferred.

The lower threshold value of the ester content in the composition of the present invention is 3, preferably 5, more preferably 10% based on the total weight of the composition in terms of treatment degree, and the upper limit is stability, delubrication activity and waste water in the diluent. It is 90, preferably 80, more preferably 70% by weight in terms of the waste disposal of.

As long as the composition of the present invention contains the aforementioned components (A) and (B), additional components may optionally be added. The surfactant should be contained in the range of 3 to 80, preferably 5 to 80% by weight of the total composition from the stability, cleanliness and delubrication aspects of the diluent. The surfactant can be an anionic-based, nonionic-based or cation-based surfactant. Anionic-based surfactants include aliphatic acids, petroleum sulfonates, alkylbenzene sulfonates, salts of alkylnaphthalene sulfonates, alkyl sulfuric esters, alkyl sulfosuccinates, alkyldiphenylether disulfonates, salts of alkyl phosphates, polyoxy Salts of alkylenealkyl or alkylallyl sulfuric esters, formalin naphthalenesulfonate condensation products, and sulfonated oils. 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 Oxyalkylenealkylamines and alkylalkanolamines. Cation-based surfactants include alkylamine salts, quaternary ammonium salts, alkylbetaines and amine oxides. Of these, anionic or nonionic based surfactants and mixtures thereof are preferred.

The water-soluble ironing lubricant stock solution of the present invention may contain any suitable additives such as carboxylic acids, fats and oils, extreme pressure additives, amines, alcohols, rust inhibitors, defoamers, corrosion inhibitors, antioxidants and metal captures for non-ferrous metals. Can be blended together.

The carboxylic acid may be an aliphatic carboxylic acid having 8 to 24 carbons which may be straight or branched, saturated or unsaturated, mono or dibasic acid. The carboxylic acids are saturated carboxylic acids such as caprylic acid, nonanoic acid, capric acid, lauric acid, palmitic acid, sebacic acid, dodecane dibasic acid and unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid and ricinoleic acid. Contains acid.

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

Rust inhibitors are, for example, aliphatic amides and aromatic carboxylic acids. Defoamers are, for example, silicone-based compounds. Non-iron metal corrosion inhibitors are, for example, benzotriazole-based compounds. Antioxidants are, for example, phenol-based antioxidants. Corrosion inhibitors are, for example, thiazole-based, isothiazole-based, phenol-based or halogen-based additives. The metal trapping agent is, for example, ethylenediaminetetraacetic acid.

The water-soluble ironing lubricant stock solution may be blended with water such as high quality water, iron-exchanged water, distilled water. Although not limited, the water content is 70 or less, preferably 60% or less, based on the total weight of the composition.

The water-soluble ironing lubricant stock solution according to the present invention is used diluted in water when used as the ironing lubricant, and the content of water used for dilution is not limited. However, in order for the composition of the present invention to be able to perform improved treatment, cleansing and delubrication, the content of the composition is 0.5 to 30, preferably 1 to 20%, based on the weight of the ironing lubricant. Should be diluted in water to the extent possible. Suitable diluents may be high quality water, industrial water, iron-exchanged water or distilled water.

The compositions of the present invention diluted with water have the highest degree of cleanliness and delubrication and dilution that can be expected if the lubricant contains a composition having a particle size dissolved in water of 1 μm, preferably 0.7 μm, more preferably 0.5 μm or less. Desired cleanliness and delubrication can be achieved, resulting from improved stability in time, and contribute to a more stable operation for making DI cans. The average size of the dissolved particles can be measured using a measuring device using laser diffraction and / or light scattering, and the particle size distribution can be measured using an LPA 3000 / LPA 3100 measuring device manufactured by Ohtsuka Electronics. Can be.

The water-soluble ironing lubricant stock solution of the present invention draws a coated metal sheet in an amount of 50 to 600 mg / m ² of drawing lubricant having a dynamic viscosity of 5 to 70 mm ² / S, and then ironed or Used for the production process of DI cans, for redrawing and ironing.

The upper limit of the dynamic viscosity at 40 ° C. of the drawing lubricant mentioned above 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. Dynamic viscosity above the upper limit at 40 ° C. will result in sticking of sheets and cups, slip and crease and formation of earrings on the conveying rollers, while dynamic viscosity below the lower limit at 40 ° C. will also lead to failure of the can causing breakage of the can. Will cause.

According to the invention, the drawing lubricant is a gravure roller applicator or electrostatic coating machine in an amount of 50 to 600 mg / m ² , preferably 100 to 500 mg / m ² , more preferably 150 to 450 mg / m ² . Is essentially coated on both surfaces of the metal sheet. Coating amounts exceeding 600 mg / m ² will result in sticking of the cups, slipping and wrinkling of the sheets and formation of earrings, and if less than 50 mg / m ² , will reduce drawing performance.

The drawing lubricants described above, unlike emulsion-type lubricants, are not lubricants of the type that are diluted in water in use.

Emulsion-type lubricants that are diluted in water during use can reduce plateout properties and throughput as molding conditions change, resulting in a reduction in working efficiency due to the need for changes in lubricant composition to overcome these deficiencies. Can cause.

Any suitable drawing lubricant is suitable for use in the present invention so long as it has a dynamic viscosity within the ranges specified above. Suitable base oils used in the drawing lubricants can be any oil, from mineral oils, synthetic oils to fats and oils.

Suitable mineral oils are atmospheric or vacuum distillation of lubricating oils which are purified by single or combination of solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation purification, sulfuric acid treatment or mud treatment. It may be paraffin or naphthenic mineral oil made for use from fractions.

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

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

Two or more of these oils may be used in combination.

Among the oils mentioned above, preferred as base oils used for the drawing lubricants are those containing esters in a content of at least 5, preferably at least 10 and more preferably at least 20%, based on the total weight of the lubricant.

The alcohol used in the production of the ester may be monohydric to polyhydric alcohol. The acid used for the production of 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 chain.

Specific examples of C ₁ -C ₂₄ alcohols are 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 undecanol, 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 isosanol, straight or branched heneicosanol, straight or branched docosanol, straight or branched tricosanol, straight or branched Tetracosanol and mixtures thereof.

The polyhydric alcohols are generally dihydric alcohols to dihydric alcohols, preferably dihydric to hexavalent alcohols.

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, and polypropylene glycol (trimers to deuteromers 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, trimethylolpropane and trimethylolbutane) and dimers to octets thereof, Pentaerythritol and dimers to tetramers thereof, 1,2,4-butane ethanol, 1,3,5-pentane ethriol, 1,2,6-hexanetriol, 1,2,3 Polyhydric alcohols such as, 4-butane etherol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol and mannitol; And xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose and sucrose and mixtures thereof. It is a saccharide.

Of these, preferred 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, trimethylalkane (trimethylolethane, trimethylolpropane and trimethyl Divalent to hexavalent alcohols such as olbutane) and dimers to tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol , 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitolglycerin condensate, adonitol, arabitol, xylitol and mannitol and mixtures thereof.

Especially preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylethane, trivetillopropane, pentaerythritol, sorbitan and mixtures thereof.

Preferred monobasic acids for the present invention are saturated or unsaturated straight or branched chain C ₆ -C ₂₄ aliphatic acids. Such C ₆ -C ₂₄ aliphatic acids are typically linear or branched hexanoic 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 branched dodecane Kanic 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 hydroxyocta Saturated aliphatic acids such as decanoic acid, straight or branched nonadecanoic acid, straight or branched eicosane, straight or branched heneic acid, straight or branched docoic acid, straight or branched trichoic acid and straight or branched tetracoic acid; And straight or branched hexenoic acid, straight or branched heptenoic acid, straight or branched octenic acid, straight or branched nonenoic acid, straight or branched decenic acid, straight or branched undecenoic acid, straight or branched dodecenoic acid, straight or branched tridecenoic acid, Straight or branched tetradecenoic 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 nonadenoic acid , Unsaturated aliphatic acids such as straight or branched chain eicosenic acid, straight or branched chain heneicosenic acid, straight or branched chain docosenoic acid, straight chain or branched tricosenoic acid and straight chain or branched tetracocenic acid and mixtures thereof, including C Preference is given to _8- C ₂₀ saturated aliphatic acids, C ₈ -C ₂₀ unsaturated aliphatic acids or mixtures thereof.

The polybasic acid may be C ₂ -C ₁₆ 2-basic acid or trimellitic acid. Such C ₂ -C ₁₆ dibasic acids may be straight or branched saturated or unsaturated ones, and certain embodiments thereof are ethane 2-basic acid, propane 2-basic acid, straight or branched butane 2-basic acid, straight chain Or branched pentane 2-basic acids, straight or branched heptane 2-basic acids, straight or branched octane 2-basic acids, straight or branched nonan 2-basic acids, straight or branched decane 2-basic acids, straight or branched undecane 2 -Basic acids, straight or branched dodecane 2-basic acids, straight or branched tridecane 2-basic acids, straight or branched tetradecane 2-basic acids, straight or branched pentadecane 2-basic acids and straight or branched hexadecane 2 Saturated 2-basic acids such as base acids; Butene 2-basic acid, straight or branched pentene 2-basic acid, straight or branched hexene 2-basic acid, straight or branched heptene 2-basic acid, straight or branched octene 2-basic acid, straight or branched nonene 2-basic acid , Straight or branched decene 2-basic acid, straight or branched undecene 2-basic acid, straight or branched dodecene 2-basic acid, straight or branched tridecene 2-basic acid, straight or branched tetradecene 2-basic acid, Unsaturated 2-basic acids, such as straight or branched pentadecene 2-basic acids and straight or branched hexadecene 2-basic acids and mixtures thereof. Any suitable combination of alcohols and acids is available and such combinations are as follows:

1) monohydric alcohols and monobasic acids;

2) polyhydric alcohols and polybasic acids;

3) monohydric alcohols and polybasic acids;

4) polyhydric alcohols and polybasic acids;

5) mixed esters of polybasic acids with mixtures of monohydric and polyhydric alcohols;

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

7) Mixed esters of polyhydric alcohols and mixtures of polyhydric alcohols with mixtures of monobasic and polybasic acids.

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

In order to further improve the processing power, the base oil for the drawing lubricant preferably contains at least one ester selected from (1), (2), (3) and (4).

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

The base oil can be used as drawing lubricant per se, and further suitable additives can be added as necessary. Such additives include non-oil reagents, extreme pressure additives, corrosion inhibitors, detergent-dispersants, antioxidants and defoamers.

Non-oil reagents can be fatty acids, higher alcohols, amines and amides.

Extreme pressure additives include phosphate-based compounds such as tricresyl phosphate, sulfur-based compounds such as sulfidated fats and oils, sulfur-based compounds such as polysulfide, chlorine-based compounds such as chlorinated paraffin and zinc dialkyldithiophosphates, Organometallic compounds such as molybdenum dialkyldithiophosphate, zinc dialkyldithiocarbamate and molybdenum dialkyldithiocarbamate.

Corrosion inhibitors can be benzotriazoles, mercaptobenzothiazoles, their sodium salts and tritritriazoles.

Detergent-injection agents are alkali or alkaline earth metal sulfonates, alkali or alkaline earth metal salicylates, alkali metal or alkaline earth metal phenates, aliphatic acid soaps, alkenylsuccinic acid imido, alkenyl modified by boric acid Citrate imido and nonionic-based surfactants. The oxidation-inhibitor may be a phenol-based compound such as 2,6-di-tert-butyl-cresol and an aromatic amine such as phenyl-α-naphthylamine.

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

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

The present invention can be applied to processed metals such as aluminum, aluminum alloys (aluminum-manganese alloys), steel plates, surface treated steel plates (galvanized sheet metals and termid sheet metals).

The invention will be described in more detail by the following examples, which are provided for illustrative purposes only.

Example

According to the composition of Samples 1-4 of Table 1, ironing lubricant stock solutions for Examples (Samples 1-3) and Comparative Examples (Sample 4) of the present invention were prepared.

350 ml, using the ironing and drawing lubricants formulated as described in Examples 1-12 and Comparative Examples 1-5 of the present invention shown in Table 2 (Samples 5-17), in the following manner: A DI can having a volume inside was prepared.

Drawing lubricant

Sample 5: paraffin-based mineral oil, @ 40 ° C., 2 mm ² / s

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

Sample 7: paraffin-based mineral oil, @ 40 ° C., 23 mm ² / s

Sample 8: paraffin-based mineral oil, @ 40 ° C., 76 mm ² / s

Sample 9: neopentyl glycol dioleate, @ 40 ° C., 21 mm ² / s

Sample 10: pentaerythritol tetraoleate, @ 40 ° C, 64 mm ² / s

Sample 11: Mixture of Samples 5 and 9 (90:10 weight ratio), @ 40 ° C., 2.3 mm ² / s

Sample 12: mixture of samples 6 and 9 (90:10 weight ratio), @ 40 ° C., 6.7 mm ² / s

Sample 13: Mixture of Samples 7 and 9 (90:10 weight ratio), @ 40 ° C., 22.8 mm ² / s

Sample 14: mixture of Samples 7 and 10 (45:55 weight ratio), @ 40 ° C., 39.1 mm ² / s

Sample 15: mixture of samples 8 and 10 (90:10 weight ratio), @ 40 ° C., 74.7 mm ² / s

Sample 16: Mixture of Samples 9 and 10 (60:40 weight ratio), @ 40 ° C., 32.0 mm ² / s

Sample 17: 45 mass% sample 7, 45 mass% sample 10, mixture of 7.3 mass% olefinic acid and 2.7 mass% diethanol amine, @ 40 ° C., 35 mm ² / s

How to make DI cans

An aluminum alloy sheet (JIS H 4000 3004-H 19) with a diameter of 120 mm was coated on both surfaces with a drawing lubricant of 350 mg / m ² , and then formed into a cup shape having a diameter of 66 mm under the following drawing conditions. Let's do it.

Drawing conditions

Punch Diameter: 66.00 mm

Die diameter: 66.81 mm

Blank Holding Force: 1,000 kgf

Drawing rate: 82 m / min

The drawn cup obtained above is fixed to a punch and ironed using an ironing lubricant obtained by diluting the stock solution with 30 times water. Ten pieces of DI cans were produced using lubricants of each of the above-described combinations shown in Table 1.

Ironing Condition

Punch Diameter: 66.00 mm

First ironing die diameter: 66.63 mm

Second ironing die diameter: 66.43 mm

Third ironing die diameter: 66.32 mm

Fourth ironing die diameter: 66.24 mm

Ironing rate: 82 m / min

The resulting DI cans were evaluated in terms of drawing performance, ironing performance and cleaning power, and the results are shown in Table 2. Evaluation is performed according to the following method.

Drawing performance

The appearance of each of the drawn cups is visually observed. Cups without wrinkles are represented by O and those with wrinkles are represented by X.

Ironing performance

Visual observation is also made of scratches on the walls and inlets of the resulting DI cans as well as the breakage due to ironing.

damage

Mark O indicates that not all 10 pieces of the DI can are broken, and mark X indicates that at least one DI can is broken.

Entrance

The cans are rated at six. Cans without bleed-through are rated at 5, and scratches are all rated at 0. Evaluate with an average rating of 10 pieces of DI cans.

Wall surface

Mark O indicates no scratching, and mark X indicates scratching.

Cleaning power

The obtained DI cans are spray-washed with a surfactant of varying concentration and then sprayed with distilled water to visually evaluate whether the lubricant is retained on the surface of the cans. In this evaluation, if the lubricant is maintained on the can surface, the sprayed distilled water is removed. Detergent used in this evaluation is an aqueous solution of Ridolin NHC 100A (main ingredient: surfactant) of Nihon Paint Co., Ltd., and Ridolin NHC 100 M (main ingredient: surfactant) of Nihon Paint Co., Ltd., Prepared according to the composition.

Mark O indicates that the lubricant is not retained on the can surface, and mark X indicates that the lubricant is retained.

Detergent 1 100 A: 3.8 mass%

100 M: 0.8 mass%

Residual: water

Detergent 2 100 A: 3.8 mass%

100 M: 0.6 mass%

Residual: water

Samples 1 to 4 are evaluated in terms of waste performance of waste water, and the results are shown in the right column of Table 2. This evaluation is performed according to the following method.

Wastewater Disposal Performance

A liquid sample is obtained by diluting each sample of the aqueous ironing lubricant stock solution with 500 ppm distilled water by mass.

The resulting liquid sample is introduced into the waste water disposal process. Liquid samples are measured for COD (chemical oxygen demand) values before and after the procedure. The waste performance of waste water is evaluated by the reduction rate calculated from the following formula.

(COD value before course-COD value after course)

COD value before the process

The results are shown in Table 2.

COD values are measured according to the provisions of the chemical oxygen demand (COD _Mn ) by potassium permanganate at 100 ° C in JIS K 0102 of the Test Method for Industrial Wastewater.

How to dispose of waste water

To 1000 ml of liquid sample is added polyaluminum chloride for water operation (corresponding to JIS K 1475) to obtain a mixture with 400 ppm of polyaluminum chloride by mass and stirred at a rate of 120 rpm for 10 minutes. Potassium hydroxide is then added to the mixture so that the pH of the liquid sample is 7 and stirred at a rate of 120 rpm for 15 minutes. A high molecular weight coagulant was added to this mixture so that its content was 2 ppm of mass, and stirred at a rate of 120 rpm for 5 minutes. Filter using 5A filter paper. The resulting filtrate is measured against COD.

As can be seen from the results in Table 2, the water-soluble ironing lubricant stock solution of the embodiment of the present invention is excellent in drawing performance, ironing performance and cleaning power. In particular, this can be seen from Examples 7, 8, 9, 10, 11 and 12 of the present invention in which esters are used in the base oil of the drawing lubricant, in which the occurrence of bleed-through scratching is greatly reduced.

On the other hand, the use of ironing lubricant stock solutions containing polyoxy-alkylene monoethers in place of the esters specified by the present invention (Comparative Example 1) results in poor drawing performance. Moreover, the drawing lubricants of Comparative Examples 2 and 4 having a lower viscosity than those specified by the present invention show unsatisfactory ironing performance even when used with the water-soluble ironing lubricant stock solution of the present invention, while Excessive viscosity than specified is poor in drawing performance and ironing performance (Comparative Examples 3 and 4).

As noted above, the present invention can contribute to the manufacture of high-grade DI cans and to the disposal performance of the wash water.

Ironing lubricant Sample One 2 3 4 Composition (mass%) Ester 1 ^* 1) Ester 2 ^* 2) Ester 3 ^* 3) 20 20 20 Polyoxyalkylene monoethers ^* 4) 20 Anionic-based surfactants ^* 5) 15 15 15 15 Anionic-based surfactants ^* 6) 1.5 1.5 4 Anionic-based surfactants ^* 7) 5 5 5 5 Non-ion-based surfactants ^* 8) 5 5 5 5 Triethanol amine 10.5 10.5 16 10 Benzotriazole 0.3 0.3 0.3 0.3 water 42.7 42.7 34.7 44.7 ^* 1): arbitrary copolymer of ethylene oxide and propylene oxide (average molecular weight: 1000, the ratio of propylene oxide in a copolymer: 50 mass%) and monoester of dodecanoic acid ^* 2): block air of ethylene oxide and propylene oxide Monolauric ether of the copolymer (average molecular weight: 1000, proportion of propylene in the copolymer: 60 mass%) and ester of oleic acid ^* 3): copolymer of propylene oxide (average molecular weight: 1000) and monoester of dodecanoic acid ^* 4): Monolauric ether of ethylene oxide (average molecular weight: 1000) ^* 5): Triethanol amine salt of oleic acid ^* 6): Triethanol amine salt of dodecanoic acid ^* 7): Turkey red oil of castor oil ^* 8): ethylene oxide addition product of nonylphenol (average degree of polymerization: 6)

Drawing lubricant Ironing performance Average particle size (μm) Drawing performance Ironing performance Cleaning power Wastewater Disposal Performance (%) damage hole Wall surface Detergent One 2 3 Example 123456789101112 67676791213141617 112233333333 0.530.530.270.270.080.080.080.080.080.080.080.08 OOOOOOOOOOOO OOOOOOOOOOOO 4.14.24.24.04.24.74.54.54.64.74.5 OOOOOOOOOOOO OOOOOOOOOOOO OOOOOOOOOOOO OOOOOOOOOOOO 646463

Comparative Example 13581115 41111 ≤0.04 ^* 9) 0.530.530.530.53 OOXOX XXXXX 2.22.72.52.62.7 XXXXX OOOOO OOOOO OOOOO 32 * 9): No measurement, transparent.

Claims (2)

Drawing a sheet of metal coated with drawing lubricant 50 to 600 mg / m ² with a dynamic viscosity of 5 to 70 mm ² / S on both sides at 40 ° C., then ironing or redrawing and ironing with ironing lubricant Water-soluble containing a composition comprising (A) a polyoxyalkylene having an average molecular weight of 300 to 20,000 and / or a monoalkyl ether thereof and (B) an ester of a C ₆ -C ₂₄ aliphatic acid used for the production of DI cans Ironing lubricant stock solution. Obtained by drawing a sheet of metal coated on both sides with a drawing lubricant 50 to 600 mg / m ² having a dynamic viscosity of 5 to 70 mm ² / S at 40 ° C. and diluting the water-soluble ironing lubricant stock solution according to claim 1 with water. And ironing or redrawing and ironing the drawn metal using the ironing lubricant.