JPH1088178A - Undiluted solution composition of water-soluble lubricant for ironing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an undiluted solution composition of a water-soluble lubricant for ironing capable of not only providing a high quality DI can but also accomplishing improvement of treatment of the waste water. SOLUTION: This undiluted solution composition of a water-soluble lubricant for ironing is used when a metal plate is subjected to cupping by using a water- insoluble lubricant for the cupping having 5-70 mm<2> /s dynamic viscosity at 40 deg.C, and further subjected to ironing, or redrawing and ironing by using the water-soluble lubricant for the ironing to form a DI can. The undiluted solution composition includes (1) an ester of a 6-16C aliphatic carboxylic acid and a polyfunctional alcohol or (2) an ester of mixed aliphatic carboxylic acids comprising a 18C aliphatic carboxylic acid and a 6-16C aliphatic carboxylic acid, with a polyfunctional alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an undiluted composition of a lubricant used in the production of DI cans. More specifically, the present invention relates to drawing a metal plate using a water-insoluble drawing forming lubricant, Ironing or redrawing / ironing and then D
The present invention relates to a stock solution composition of a water-soluble ironing lubricant for use in the production of I-cans.

[0002]

2. Description of the Related Art DI cans are used as containers for beer and soft drinks, and are formed by drawing (cupping) a metal plate.
Next, the drawn product is iron-formed or re-drawn and iron-formed to form a can. The body and bottom of the can have a seamless structure. Draw-forming refers to a processing method in which a plate cut out in a disc shape is fixed with a wrinkle holding device and formed into a cup with a bottom using a tool composed of a punch and a die. Refers to the process of thinning and extending the side wall of If the diameter of the plate cut out in a disk shape is excessively large compared to the diameter of the punch, it may be difficult to obtain a cup of a required shape by one drawing process. In the second step, redrawing is performed so as to have a required shape before ironing, which is a subsequent step. In the manufacture of DI cans, cups having a relatively large diameter are manufactured by a draw forming machine called a cupping press, then redrawing is first performed in a body maker (can forming machine), and then ironing is immediately performed. Is generally performed. In carrying out such draw forming-ironing or draw forming-redrawing / ironing, an emulsion-type lubricant has conventionally been used in each step. That is,
A lubricant used in the first step of the DI can forming process (drawing lubricant) and a lubricant used in the second step of ironing or redrawing / ironing (ironing lubrication) In each case, an emulsion-type lubricant was used.

[0003]

By the way, conventionally, DI
During the can forming process, an emulsion-type lubricant was generally used during drawing, but when lubricating with an emulsion, the oil in the emulsion was selectively and effectively adhered to the lubrication points. There is an issue of whether to do it. Such a property that the oil adheres to the lubricating point is called plate-out property, and even if the emulsion is composed of a component having excellent lubricity, a lubricant having poor plate-out property should be substantially used. Can not. Many studies have been carried out in various fields to solve such problems, but no uniform conclusions have been made to improve the plate-out property. Emulsion type lubricants having a high viscosity are being developed. However, an emulsion-type lubricant obtained by such a method may not be able to cope with a change in molding conditions due to a change in the design of a can or the like. It is also conceivable to supplement the insufficient plate-out property by adding an excessive lubricating component or the like. However, a change in the formulation of the lubricant accompanying a change in the molding conditions reduces the working efficiency.

[0004] Further, even if a water-insoluble lubricant is used as the draw-forming lubricant, if the lubricity is insufficient, the draw-forming itself cannot be performed, and the cup-shaped product may be broken, Even if no break occurs, excessive friction occurs between the tool (punch, die) and the metal material, resulting in partial flaws on the surface of the cup-shaped molding. The scratches thus generated may remain on the surface even after the ironing, which is the second step in the molding process of the DI can, is completed, which significantly impairs the aesthetic appearance of the can and lowers the commercial value.

[0005] In addition, the draw forming lubricant remaining on the surface of the cup-shaped molded product after drawing contributes to the lubrication between tools (punches, dies) and the surface of the cup-shaped molded product at the time of ironing. If the lubricity of the molding lubricant is insufficient, the surface of the can after the ironing is damaged, which significantly impairs the aesthetic appearance of the can and lowers its commercial value. On the other hand, if the lubricity of the drawing lubricant is excessive, the following obstacles occur. If the lubricity of the drawing forming lubricant is excessive, slipping occurs between the plate and the wrinkle holding portion in the plate fixing portion (wrinkle holding portion) at the time of draw forming, and the fixability is reduced. (Opening), wrinkles are generated, or partial elongation of the plate occurs, so-called "ears" are generated. When wrinkles occur, the plate thickness of the can flange becomes uneven, but when the plate thickness becomes uneven, the ironing rate in the thicker part in the ironing process in the subsequent process increases, resulting in insufficient lubrication. Burn-in occurs, and a surface defect called bleed-through occurs. Further, the unevenness of the plate thickness causes necking cracks in necking, which is the final forming step. In addition, cups with “ears” catch the “ears” on the transport line sent to the ironing machine in the post-process, causing a problem that they cannot be smoothly sent to the ironing machine and hinder can productivity. Let it. In addition, when the lubricating property of the drawing forming lubricant is excessive, there is also a problem that the plate cannot be fed by the plate feed roll provided for feeding the aluminum plate or the steel plate to the drawing forming device.

On the other hand, the cans after ironing are degreased and washed with an aqueous solution (washing solution) containing a surfactant, subjected to a surface chemical treatment for corrosion prevention, and then coated and printed, and then subjected to opening ( Draw-forming (necking) and edge bending (flanging) of the mouth are performed before shipment. Therefore, when the composition of the ironing molding lubricant is inappropriate, the surfactant concentration in the ironing molding lubricant cleaning liquid cannot be reduced in the degreasing / cleaning step after the can body is manufactured, and as a result, Improvement in wastewater treatment cannot be achieved.

In recent years, from the viewpoint of global environmental protection and resource saving,
For lubricants used in drawing, ironing, redrawing and ironing, especially lubricants used in the second step of manufacturing, ironing or redrawing and ironing (lubrication for ironing) In addition to lubricity, there has been a strong demand for good degreasing and cleaning properties of cans after molding, and good drainage treatment of cleaning waste liquid that can reach several hundred tons per day. . In addition, in order to manufacture a high-quality DI can, a lubricant (drawing lubricant) used for drawing, which is the first step in the forming process of the DI can,
The combination of the lubricant (ironing lubricant) used in the second step, ironing or redrawing / ironing, is important, and if the combination is inappropriate, high-quality DI cans cannot be obtained. .

[0008] Therefore, not only is excellent lubricity, but also excellent in degreasing and cleaning of the can after molding, and it is possible to reduce the concentration of the surfactant in the cleaning liquid to improve drainage treatment. Combinations of lubricants for forming-ironing or drawing-redrawing / ironing have been strongly desired.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, formed a metal plate by drawing using a water-insoluble drawing forming lubricant and then specified. A high-quality DI is obtained by ironing or re-drawing and ironing a drawn product by diluting with water a water-soluble ironing agent stock solution containing an aliphatic carboxylic acid ester having the structure They have found that cans can be manufactured and that the wastewater treatment properties can be improved, and the present invention has been completed.

That is, the water-soluble ironing stock solution for ironing of the present invention has a kinematic viscosity at 40 ° C. of 5
When a DI can is produced by drawing using a water-insoluble ironing lubricant of up to 70 mm ² / s and then ironing or redrawing and ironing using a water-soluble ironing lubricant. A stock solution composition of a water-soluble ironing lubricant for use, which comprises the following (1) or (2). (1) An ester of an aliphatic carboxylic acid having 6 to 16 carbon atoms and a polyhydric alcohol (2) An aliphatic carboxylic acid having 18 carbon atoms and 6 to 6 carbon atoms
An ester of a mixed aliphatic carboxylic acid comprising 16 aliphatic carboxylic acids and a polyhydric alcohol Further, the water-soluble ironing lubricant stock composition of the present invention has a kinematic viscosity at 40 ° C. of 5 to 70 mm at 40 ° C. ² /
s drawing using a water-insoluble drawing forming lubricant,
Next, an undiluted solution composition of a water-soluble ironing lubricant used in producing a DI can by ironing or re-drawing and ironing using a water-soluble ironing lubricant, the following (3) Or (4) is included. (3) An ester of a mixed aliphatic carboxylic acid composed of an aliphatic carboxylic acid having 6 to 16 carbon atoms and an aliphatic carboxylic acid having 20 to 24 carbon atoms and a polyhydric alcohol (4) An aliphatic carboxylic acid having 18 carbon atoms , Carbon number 6-16
Ester of a mixed aliphatic carboxylic acid comprising an aliphatic carboxylic acid and an aliphatic carboxylic acid having 20 to 24 carbon atoms and a polyhydric alcohol, wherein the average particle diameter of the water-soluble ironing lubricant stock solution composition is diluted with water. It is preferably 1 μm or less.

As described above, the metal plate is formed by drawing using a water-insoluble drawing forming lubricant, and then a water-soluble ironing agent forming stock solution containing an aliphatic carboxylic acid ester having a specific structure is prepared. By diluting with water and ironing or redrawing and ironing the draw-formed product, the drawability and the ironability are excellent, so that a high-quality DI can can be manufactured. Since it has excellent properties and degreasing properties, it is possible to achieve improvement in wastewater treatment properties.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.
The water-soluble ironing stock lubricant composition of the present invention contains the following (1) or (2) as an essential component. (1) An ester of an aliphatic carboxylic acid having 6 to 16 carbon atoms and a polyhydric alcohol (2) An aliphatic carboxylic acid having 18 carbon atoms and 6 to 6 carbon atoms
Ester of a mixed aliphatic carboxylic acid comprising 16 aliphatic carboxylic acids and a polyhydric alcohol having 6 carbon atoms used in the above components (1) and (2)
The aliphatic carboxylic acids (1) to (16) may be monobasic acids or dibasic acids, linear or branched ones, and saturated or unsaturated ones. In addition, when an aliphatic carboxylic acid having less than 6 carbon atoms is used, not only the workability is lowered but also tools such as punches and dies may be corroded, which is not preferable.

Specific examples of the monobasic acid having 6 to 16 carbon atoms include linear or branched hexanoic acid, linear or branched heptanoic acid, and linear or branched octanoic acid. , Linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid Saturated fatty acids such as linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched hexenoic acid, linear or branched Heptenoic acid, linear or branched octenoic acid, linear or branched nonenic acid, linear or branched decenoic acid,
Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid,
Unsaturated fatty acids such as linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or branched hexadecenoic acid, and mixtures thereof. Among them, a saturated fatty acid having 8 to 16 carbon atoms, an unsaturated fatty acid having 8 to 16 carbon atoms, and a mixture thereof are particularly preferable.

As the dibasic acid having 6 to 16 carbon atoms, specifically, for example, linear or branched hexane diacid, linear or branched heptenedioic acid, linear or branched Octane diacid, linear or branched nonanedioic acid, linear or branched decandioic acid, linear or branched dodecandioic acid, linear or branched tridecandioic acid,
Linear or branched tetradecandioic acid, linear or branched heptadecandioic acid, saturated or dibasic acid such as linear or branched hexadecandioic acid, linear or branched hexenedioic acid, Linear or branched heptenedioic acid,
Linear or branched octenedioic acid, linear or branched nonenedioic acid, linear or branched decenedioic acid, linear or branched dodecenedioic acid, linear or branched Unsaturated dibasic acids such as tridecene diacid, linear or branched tetradecene diacid, linear or branched heptadecenedioic acid, linear or branched hexadecene diacid, and mixtures thereof. No. Among these, a saturated dibasic acid having 6 to 12 carbon atoms, or a 6-1 or 2 carbon atom is particularly preferable.
Preferred are two unsaturated dibasic acids, and mixtures thereof. The C18 aliphatic carboxylic acid used in the component (2) includes oleic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, hydroxystearic acid, and the like. Among them, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and a mixture thereof are particularly preferable.

As the polyhydric alcohol used in the above components (1) and (2), those having a valency of usually 2 to 10 and preferably 2 to 6 are used. Specific examples of the di- to polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). ),
1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, Dihydric alcohols such as 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol and neopentyl glycol; glycerin, polyglycerin (glycerin dimer to octamer, For example, diglycerin, triglycerin, tetraglycerin, etc.), trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2
~ 8-mers, pentaerythritol and their 2-4
Monomer, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
Polyhydric alcohols such as 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, Examples include saccharides such as sorbose, cellobiose, maltose, isomaltose, trehalose, and sucrose, and mixtures thereof. Among these, ethylene glycol, diethylene glycol, polyethylene glycol (3-10 mer of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3-10 mer of propylene glycol), 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc. ) And dimers and tetramers thereof, pentaerythritol, dipentaerythritol 1,2,4-butanetriol, 1,3,3
2- to 6-valent compounds such as 5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol and mannitol Polyhydric alcohols and mixtures thereof are more preferred. More preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, and mixtures thereof.

In the present invention, the ratio of the aliphatic carboxylic acid having 18 carbon atoms to the aliphatic carboxylic acid having 6 to 16 carbon atoms in the mixed aliphatic carboxylic acid of the ester (2) is optional, Considering the degreasing property, carbon number 18
Based on the total amount of the aliphatic carboxylic acid having 6 to 16 carbon atoms and the aliphatic carboxylic acid having 6 to 16 carbon atoms, the aliphatic carboxylic acid having 18 carbon atoms is 0.5 to 50% by mass, preferably 1 to 45% by mass,
More preferably, the content is 2 to 40% by mass.

In the present invention, the above (1) or (2)
When the ester of (1) or (2) is contained, an aqueous solution composition of a water-soluble ironing lubricant excellent in workability and also excellent in detergency and degreasing property can be obtained. If an ester using a mixed aliphatic carboxylic acid to which an aliphatic carboxylic acid having 20 to 24 carbon atoms is added, that is, the following (3) or (4) is further contained, the processability can be further improved. it can. Here, when an ester with an aliphatic carboxylic acid having more than 24 carbon atoms is used, the solubility decreases when diluted with water, and solids and sludge are easily generated, which is not preferable. (3) An ester of a mixed aliphatic carboxylic acid composed of an aliphatic carboxylic acid having 6 to 16 carbon atoms and an aliphatic carboxylic acid having 20 to 24 carbon atoms and a polyhydric alcohol (4) An aliphatic carboxylic acid having 18 carbon atoms , Carbon number 6-16
Of mixed aliphatic carboxylic acid consisting of aliphatic carboxylic acid and aliphatic carboxylic acid having 20 to 24 carbon atoms with polyhydric alcohol

The aliphatic carboxylic acid having 20 to 24 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, linear or branched icosanoic acid, linear or branched henicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched A saturated fatty acid such as a branched tetracosanoic acid, a linear or branched icosenoic acid, a linear or branched heicosenoic acid, a linear or branched docosenoic acid, a linear or branched tricosenic acid, Examples thereof include linear or branched unsaturated fatty acids such as tetracosenoic acid, and mixtures thereof. (3) The ratio of the aliphatic carboxylic acid having 6 to 16 carbon atoms to the aliphatic carboxylic acid having 20 to 24 carbon atoms in the mixed aliphatic carboxylic acid of the ester of the component is arbitrary, but the processability, detergency, and degreasing property are all optional. Considering that
Based on the total amount of the aliphatic carboxylic acid having 16 and the aliphatic carboxylic acid having 20 to 24 carbon atoms, the aliphatic carboxylic acid having 6 to 16 carbon atoms is 50 to 98% by mass, preferably 60 to 9% by mass.
It is desirably 8% by mass, more preferably 70 to 98% by mass. In the mixed aliphatic carboxylic acid of the ester of the component (4), an aliphatic carboxylic acid having 18 carbon atoms, an aliphatic carboxylic acid having 6 to 16 carbon atoms, and an aliphatic carboxylic acid having 20 to 2 carbon atoms.
Although the ratio of the aliphatic carboxylic acid of 4 is arbitrary, processability,
In consideration of detergency and degreasing property, the number of carbon atoms is 18 based on the total amount of aliphatic carboxylic acid having 18 carbon atoms, aliphatic carboxylic acid having 6 to 16 carbon atoms and aliphatic carboxylic acid having 20 to 24 carbon atoms. Is 30 to 98% by mass, preferably 35 to 95% by mass, more preferably 4% by mass.
0 to 95% by mass, 0.5 to 65% by mass, preferably 1 to 60% by mass, more preferably 1 to 50% by mass of an aliphatic carboxylic acid having 6 to 16 carbon atoms, and an aliphatic having 20 to 24 carbon atoms. The carboxylic acid is 0.5 to 50% by mass, preferably 0.5% by mass.
It is desirable that the content be from 40 to 40% by mass, more preferably from 1 to 30% by mass.

In the present invention, the above (1),
The ester of (2), (3) and (4) may be a complete ester in which all of the hydroxyl groups in the polyhydric alcohol are esterified, and a part in which part of the hydroxyl groups is not esterified and remains as hydroxyl groups Esters may be used. Further, in the present invention, the ester of the mixed aliphatic carboxylic acid may be one obtained by esterifying with the mixed aliphatic carboxylic acid at the time of producing the ester, or an aliphatic carboxylic acid having a different structure. And then separately esterified, a mixture of these may be used.

The content of the above-mentioned ester (1) to (4) in the water-soluble ironing stock lubricant composition of the present invention is arbitrary, but from the viewpoint of processability, the lower limit is based on the total amount of the stock solution composition. The content is desirably 3% by mass, preferably 5% by mass, more preferably 10% by mass, and the upper limit is 9% based on the total amount of the stock solution composition in terms of dilution stability, detergency, and degreasing property.
0% by weight, preferably 80% by weight, more preferably 70% by weight.
Desirably, it is mass%.

The water-soluble ironing stock lubricant composition of the present invention contains any of the above components (1) to (4) as long as it contains the ester. In view of the properties, degreasing properties, and drainage treatment properties, the surfactant is used in an amount of 3 to 8 based on the total amount of the lubricant stock solution for ironing.
It is desirable to contain 0% by mass, preferably 5 to 80% by mass. Examples of the surfactant used in the present invention include anionic, nonionic, and cationic surfactants. Examples of anionic surfactants include fatty acid salts, petroleum sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxygens Examples thereof include an alkylene alkyl or alkyl allyl sulfate, a naphthalenesulfonic acid formalin condensate, and a sulfated oil (such as a funnel oil). As nonionic surfactants, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether,
Polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene sorbitol fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkylamine, alkyl alkanolamide and the like can be mentioned. Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, an alkyl betaine, and an amine oxide. Among these,
From the viewpoint of excellent dilution stability, an anion, a nonionic surfactant, and a mixture thereof are preferable.

[0022] In the present invention, the water-soluble ironing agent forming composition for ironing is optionally added with various additives, if necessary.
For example, carboxylic acids, fats and oils, extreme pressure additives, various amines, alcohols, rust inhibitors, defoamers, non-ferrous metal corrosion inhibitors, antioxidants, preservatives, metal sequestering agents, and the like can be added. Representative examples of these include aliphatic carboxylic acids having 8 to 24 carbon atoms, such as monobasic acids or dibasic acids, and straight-chain or branched ones. However, it may be saturated or unsaturated. Specific examples of such carboxylic acids include, for example, saturated carboxylic acids such as caprylic acid, nonanoic acid, capric acid, lauric acid, palmitic acid, sebacic acid, and dodecane diacid, and oleic acid, linoleic acid, and linolenic acid. And unsaturated carboxylic acids such as acid and ricinoleic acid. Examples of fats and oils include beef tallow, lard, rapeseed oil, soybean oil, coconut oil, palm oil, nuka oil, and hydrogenated products thereof. Extreme pressure additives include chlorinated paraffins, chlorinated fatty acids, sulfurized fatty oils, polysulfides, alkyl phosphate esters, and the like. Examples of various amines include alkanolamines and alkylamines, and examples of alcohols include linear or branched alcohols having 10 to 18 carbon atoms and various glycols. Examples of the rust preventive include aliphatic amides and aromatic carboxylic acids. Silicone compounds and the like as defoaming agents, benzotriazole compounds and the like as non-ferrous metal anticorrosives, phenolic antioxidants and the like as antioxidants, thiazole and isothiazole as preservatives, Examples of the phenol-based and halogen-based additives include ethylenediaminetetraacetate as the metal-sequestering agent.

The water-soluble ironing stock solution for ironing can be mixed with water. As the water used at this time, any water such as tap water, ion-exchanged water, and distilled water can be used. When water is added, the content is arbitrary, but it is usually 70% by mass or less, preferably 60% by mass or less, based on the total amount of the undiluted lubricant composition for ironing. In the present invention, the water-soluble ironing stock lubricant composition is diluted with water and used as an ironing lubricant, but the dilution ratio is not limited at all. However, in order to exhibit excellent processability, detergency, and degreasing property, the stock solution composition is 0.5 to 30 based on the total amount of the water-soluble ironing lubricant.
It is desirable to dilute with water so as to be 1% by mass, preferably 1 to 20% by mass. Here, as the water used for dilution, any water can be used, and specifically, for example, tap water, industrial water, ion-exchanged water, distilled water and the like can be used.

The above-mentioned water-soluble ironing stock liquid composition for ironing exhibits the necessary detergency and degreasing properties when diluted with water, but the composition has an average particle diameter of 1 μm or less when diluted with water.
Preferably, it is 0.7 μm or less, more preferably 0.5 μm or less.
When it is not more than μm, more excellent detergency and degreasing property are exhibited, and dilution stability is further improved, so that more stable operation can be expected. The average particle diameter at the time of dilution can be determined by a device using a laser diffraction and / or light scattering method, for example, a particle size distribution analyzer LPA3000 / LPA3 manufactured by Otsuka Electronics Co., Ltd.
It can be measured at 100 or the like.

[0025] The water-soluble ironing stock lubricant composition of the present invention has a kinematic viscosity at 40 ° C of 5 to 70 mm.
Draw-forming using a ² / s water-insoluble drawing-forming lubricant, then ironing or re-drawing and ironing
It is a stock solution composition of a water-soluble ironing lubricant for use in manufacturing I cans. The upper limit of the kinematic viscosity at 40 ° C. of the water-insoluble draw forming lubricant is 70 mm ² /
s, preferably 50 mm ² / s, more preferably 40 m ² / s
m ² / s, the lower limit is 5 mm ² / s, preferably 7 mm ² / s
s, more preferably 10 mm ² / s.
If the kinematic viscosity at 40 ° C. exceeds 70 mm ² / s, the sticking of the cup, slip, wrinkles, ears and the like are caused, which is not preferable. On the other hand, if the kinematic viscosity at 40 ° C. is less than 5 mm ² / s, the workability becomes insufficient and the cup may be broken, which is not preferable.
Also, the draw-forming lubricant must be water-insoluble and substantially free of water. Here, the term "substantially free of water" means that it is not diluted with water at the time of use, does not contain water as a constituent component, and has a water content of 1% by mass or less based on the total amount of the lubricant due to moisture absorption or the like. It represents that. In the case of using a water-containing material such as an emulsion-type lubricant, plate-out properties and workability may be reduced when molding conditions are changed,
In order to cope with this, it is necessary to change the formulation of the lubricant, which undesirably lowers working efficiency.

In the present invention, any water-insoluble drawing lubricant may be used as long as it falls within the above viscosity range. As the base oil, any of mineral oil, synthetic oil and fats and oils can be used. As an example of a mineral base oil that can be used as a draw forming lubricant, a lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, Paraffinic or naphthenic mineral oils obtained by appropriately combining one or more kinds of purification means such as solvent dewaxing, contact dewaxing, hydrorefining, sulfuric acid washing, and clay treatment are exemplified. . Examples of the oil-based base oil include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, and hydrogenated products thereof. Examples of the synthetic base oil include polyolefins (ethylene-propylene copolymer, polybutene, 1-octene oligomer, 1-decene oligomer, etc.) and hydrides thereof, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylenes Glycols, polyphenyl ethers, dialkyl diphenyl ethers, phosphates (such as tricresyl phosphate), fluorinated compounds (such as perfluoropolyethers, fluorinated polyolefins), and silicone oils are exemplified. As the base oil of the draw forming lubricant, the above-described base oils may be used alone or in combination of two or more. Among the above-mentioned base oils for the draw forming lubricant, esters are preferably 5% by mass or more, preferably 10% by mass, based on the total amount of the lubricant, because of excellent workability.
It is desirable that the content be at least 20% by mass, more preferably at least 20% by mass.

The alcohol constituting the ester may be a monohydric alcohol or a polyhydric alcohol, and the acid may be a monobasic acid or a polybasic acid. As the monohydric alcohol, it usually has 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms.
12, and more preferably 1 to 8, and such alcohols may be straight-chain or branched. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or branched hexanol, and linear or branched hexanol. Chain 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 icosanol,
Examples include straight or branched henicosanol, straight or branched docosanol, straight or branched tricosanol, straight or branched tetracosanol, and mixtures thereof. As the polyhydric alcohol, usually 2 to
Those having a valence of 10, preferably 2 to 6 are used. Two
Specific examples of the polyhydric alcohol having 10 values include, for example,
Ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 15 mer 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, 1,2-
Pentanediol, 1,3-pentanediol, 1,4
Dihydric alcohols such as pentanediol, 1,5-pentanediol, neopentyl glycol; glycerin;
Polyglycerin (2- to 8-mer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.);
Trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, and the like) and dimer to dimer thereof, pentaerythritol and dimer to tetramer thereof, 1,2,4-butanetriol,
Polyvalents such as 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol Alcohol; saccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof. Among these, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 10 mer of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 10 mer of propylene glycol), 1,3-
Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolpropane) Methylol butane) and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6
Hexanetriol, 1,2,3,4-butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, dihydric polyhydric alcohols such as mannitol, and mixtures thereof. preferable. More preferably, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
Sorbitan, and mixtures thereof.

As the monobasic acid, a fatty acid having 6 to 24 carbon atoms is usually used. Such fatty acids may be straight-chain or branched, and may be saturated or unsaturated. As the fatty acid having 6 to 24 carbon atoms, specifically, for example, linear or branched hexanoic acid, linear or branched heptanoic acid, linear or branched octanoic acid, linear or Branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or Branched tetradecanoic acid, linear or branched pentadecanoic acid,
Linear or branched hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, Saturated fatty acids such as linear or branched henicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid, or linear or branched Branched hexenoic acid, linear or branched heptenoic acid,
Linear or branched octenoic acid, linear or branched nonenic acid, linear or branched decenoic acid, linear or branched undecenoic acid, linear or branched dodecenoic acid, Linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or branched hexadecenoic acid,
Linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched nonadecenoic acid, linear or branched icosenoic acid, linear or branched henicosenoic acid, Unsaturated fatty acids such as linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and mixtures thereof. Among these, a saturated fatty acid having 8 to 20 carbon atoms, an unsaturated fatty acid having 8 to 20 carbon atoms, and a mixture thereof are particularly preferable. Examples of the polybasic acid include dibasic acids having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched heptane diacid, straight or branched octane diacid, straight or branched nonanedioic acid, straight or branched decandioic acid, straight or branched undecane diacid Acid, linear or branched dodecandioic acid, linear or branched tridecandioic acid, linear or branched tetradecandioic acid, linear or branched pentadecandioic acid, linear or Saturated dibasic acids such as branched hexadecane diacid,
Linear or branched butenedioic acid, linear or branched pentenedioic acid, linear or branched hexenedioic acid,
Linear or branched heptenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid,
Linear or branched decenedioic acid, linear or branched undecenedioic acid, linear or branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched Unsaturated dibasic acids such as tetradecenedioic acid, linear or branched pentadecenedioic acid, linear or branched hexadecenedioic acid, and mixtures thereof.

Further, as a combination of an alcohol and an acid, an ester of a monohydric alcohol and a monobasic acid, an ester of a polyhydric alcohol and a monobasic acid, an ester of a monohydric alcohol and a polybasic acid, a polyhydric alcohol and a polybasic Esters with acids Mixed esters of monohydric alcohols, mixtures of polyhydric alcohols and polybasic acids Mixed esters of polyhydric alcohols with monobasic acids, mixtures of polybasic acids With mixtures of monohydric alcohols, polyhydric alcohols Arbitrary combinations such as mixed esters with monobasic acids and polybasic acids are possible. When a polyhydric alcohol is used as the alcohol component, it may be a complete ester in which all of the hydroxyl groups in the polyhydric alcohol are esterified, or a partial ester in which a part of the hydroxyl groups is not esterified and remains as a hydroxyl group. May be. Further, when a polybasic acid is used as the acid component, a complete ester in which all carboxyl groups in the polybasic acid are esterified may be used,
A partial ester in which a part of the carboxyl group is not esterified and remains as a carboxyl group may be used. As the base oil of the drawing lubricant, it is preferable to use one or two or more esters selected from the above and from the viewpoint of further improving the processability. Further, among them, one or two or more esters selected from and among them are more preferable, and one or two or more esters selected from among them are still more preferable. It is most preferable to use the above.

As the draw forming lubricant, a lubricant consisting of only the above-described base oil may be used, or a lubricant containing an appropriate additive in the base oil may be used. Such additives include oily agents, extreme pressure agents, corrosion inhibitors, detergents, dispersants, antioxidants, defoamers, and the like. Examples of the oily agent include fatty acids, higher alcohols, amines and amides. Examples of the extreme pressure agent include phosphorus compounds such as tricresyl phosphate, sulfur compounds such as sulfurized oils and fats, sulfur compounds such as polysulfide, chlorine compounds such as chlorinated paraffin, zinc dialkyldithiophosphate, molybdenum dialkyldithiophosphate, and zinc. Organic metal compounds such as dialkyldithiocarbamate and molybdenumdialkyldithiocarbamate are exemplified. Examples of the corrosion inhibitor include benzotriazole, mercaptobenzothiazole, sodium salt of mercaptobenzothiazole, and tolyltriazole. Examples of the detergent include alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal salicylate, alkali metal or alkaline earth metal phenate, and fatty acid soap. Examples of the dispersant include alkenyl succinimides (including those modified with boric acid) and nonionic surfactants. Examples of the antioxidant include 2,6-di-tert-butyl-
Examples include phenol compounds such as p-cresol (DBPC) and aromatic amines such as phenyl-α-naphthylamine. Examples of the antifoaming agent include silicon compounds, higher alcohols, metal soaps, amides, ethylene-propylene copolymers and the like. It is desirable that the content of each of these additives is 5% by mass or less, preferably 1% by mass or less (all based on the total amount of the lubricant for drawing).

In the present invention, the metal to be processed is aluminum, an aluminum alloy (aluminum alloy).
Manganese alloy, etc.), steel sheet, surface-treated steel sheet (galvanized steel sheet, tin-plated steel sheet) and the like.

[0032]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

First, according to the compounding ratios shown in each column of Samples 1 to 8 in Table 1, the ironing-forming lubricant stock solution (samples 1 to 5) according to the present invention and the ironing-forming lubricant stock solution for comparison were used. Each sample of the composition (samples 6 to 8) was prepared.

[Table 1]

Next, each of the prepared samples and the drawing forming lubricants (samples 9 to 21) shown below were used in Example 1 shown in Table 2.
Using a combination shown in each column of Comparative Examples 1 to 7 and Comparative Examples 1 to 7, a DI can having an inner volume of 350 ml was produced by the method shown below (DI can production method). Draw forming lubricant sample 9: paraffinic mineral oil, @ 40 ° C. 2 mm ² / s Sample 10: paraffinic mineral oil, @ 40 ° C. 6 mm ² / s Sample 11: paraffinic mineral oil, @ 40 ° C. 23 mm ² / s
s Sample 12: paraffinic mineral oil, @ 40 ° C 76 mm ² /
s Sample 13: neopentyl glycoldiolate, $ 40
℃ 21mm ² / s sample 14: pentaerythritol tetra oleate, @ 4
0 ° C. 64 mm ² / s Mixture of samples 15: 9 and 13 (90:10, weight ratio),
＠ 40 ° C. 2.3 mm ² / s Mixture of samples 16:10 and 13 (90:10, weight ratio), ＠ 40 ° C. 6.7 mm ² / s Mixture of samples 17:11 and 13 (90:10, weight ratio) ), ＠ 40 ° C. 22.8 mm ² / s Mixture of samples 18:11 and 14 (45:55, weight ratio), ＠ 40 ° C. 39.1 mm ² / s Mixture of samples 19:12 and 14 (90:10, Weight ratio), ＠ 40 ° C. 74.7 mm ² / s Mixture of samples 20:13 and 14 (60:40, weight ratio), ＠ 40 ° C. 32.0 mm ² / s Sample 21: mineral oil (＠ 40 ° C., 67 mm ² / S) A stock solution composed of 67% by mass, 15% by mass of oleic acid, and 18% by mass of diethanolamine, diluted to 20% by mass with water.

Method for Manufacturing DI Can An aluminum alloy plate having a diameter of 120 mm (JIS H
4000 3004-H19), after applying a draw forming lubricant, a diameter of 6 mm was applied under the following conditions (draw forming conditions).
Draw-forming was performed to obtain a 6 mm cup-shaped material. Draw forming conditions Punch diameter: 66.00 mm Draw die diameter: 66.81 mm Wrinkle pressing force: 1000 kgf The cup-shaped material obtained at the draw forming speed: 76 m / min is fitted into a punch, and the ironing lubricant stock solution composition is poured into water. Ironing was performed under the following conditions (ironing forming conditions) using the lubricant diluted to 3% by mass in the above. Ironing forming conditions Punch diameter: 66.00 mm First ironing die diameter: 66.63 mm Second ironing die diameter: 66.43 mm Third ironing die diameter: 66.30 mm Fourth ironing die diameter: 66.22 mm Ironing speed: 76 m / Min

The DI can thus produced was evaluated for drawability, ironability, and cleaning properties.
Table 2 shows the evaluation results. In addition, each evaluation method is as follows. The appearance of the cup-shaped product obtained by the draw-forming property was visually observed. The evaluation was performed in the following two stages. ○: that there is no occurrence of wrinkles ×: observed whether breakage during Some ironing formability of ironing the occurrence of wrinkles, as well as the appearance of the openings and the wall surface of the resulting DI cans visually. The evaluation was performed by the following method. Of produced whether 10 cans of breaking, what fracture has not occurred ○, rupture was × those caused even one. The evaluation was made on a 6-point scale, with 5 having no black flaws in the opening and 0 being black flaws in the entire opening, and taking the average value of 10 cans produced. The DI cans obtained by the cleaning property were evaluated by spray cleaning using a cleaning solution in which the concentration of the surfactant was variously changed. Distilled water was further sprayed onto the DI can, and the presence or absence of the remaining lubricant was visually determined. In addition, in this evaluation method, when the lubricant remains on the can surface, the distilled water sprayed is repelled. The cleaning solution is Nippon Paint Co., Ltd.
An aqueous solution of Ridolin NHC100A manufactured by Nippon Paint Co., Ltd. (main component: surfactant) and an aqueous solution of Ridolin NHC100M manufactured by Nippon Paint Co., Ltd. (main component: surfactant) were used. Cleaning liquid 1: 100A: 3.8% by mass, 100M: 0.8% by mass, balance: water Cleaning solution 2: 100A: 3.8% by mass, 100M: 0.6% by mass, balance: water Cleaning solution 3: 100A: 3 0.8% by mass, 100M: 0.4% by mass, balance: water

[0037]

[Table 2]

As is evident from the results in Table 2, the water-soluble ironing lubricant stock solution composition according to the present invention was used to obtain D
When I cans were manufactured, all were excellent in draw formability, ironing formability and washability. In particular, carbon number 20 ~
In the case of containing an ester using an aliphatic carboxylic acid of No. 24 (Examples 5 to 8 and Examples 11 to 15), it is found that the occurrence of black scratches after ironing is small. Further, when the average particle diameter when the stock solution composition is diluted with water is 1 μm or less (Examples 1 to 8 and Examples 11 to 15), the average particle diameter exceeds 1 μm (Example 9 and It can be seen that the detergency is better than that of 10).
Further, when esters are used as the base oil of the lubricant for drawing, it can be seen that occurrence of black spots after ironing is particularly small in (Examples 11 to 15). On the contrary,
It can be seen that when an ironing stock lubricant composition containing mineral oil instead of the ester defined in the present invention was used (Comparative Example 1), ironing moldability was poor. In addition, when the ironing lubricant stock solution containing no ester specified in the present invention was used (Comparative Example 2), it was found that ironing moldability was inferior. In addition, when drawing and ironing were performed using a conventional emulsion-type lubricant (Comparative Example 3), it was found that ironing formability and detergency were poor. Further, when a draw forming lubricant having a viscosity lower than that specified in the present invention was used (Comparative Examples 4 and 6), it was assumed that the ironing-forming lubricant stock solution composition according to the present invention was used during ironing. Also, it can be seen that ironing formability is inferior. Further, when a draw forming lubricant having a higher viscosity than specified in the present invention was used (Comparative Examples 5 and 7), it was assumed that the ironing-forming lubricant stock solution composition according to the present invention was used during ironing. Also, it is found that draw formability and ironing formability are inferior.

[0039]

As described above, according to the present invention, it is possible to manufacture a high-quality DI can and to achieve an improvement in wastewater treatment.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10N 40:24 80:00 (72) Inventor Hideo Yokota 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Oil & Oil Co., Ltd. (72 ) Inventor Kazuhiko Endo 8 Chidoricho, Naka-ku, Naka-ku, Yokohama-shi, Kanagawa Prefecture, Japan Nippon Oil & Oil Co., Ltd. (72) Inventor Kazuka Dai 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Prefecture, Japan Nippon Oil & Oil Co., Ltd. (72) Inventor Ryo Kanai 1-3-12 Nishi-Shimbashi, Minato-ku, Tokyo Inside Nippon Oil & Oil Co., Ltd.

Claims (3)

[Claims] A kinematic viscosity at 40 ° C. of 5 to 7 for a metal plate.
Used to produce DI cans by drawing using a water-insoluble ironing lubricant of 0 mm ² / s and then ironing or redrawing and ironing using a water-soluble ironing lubricant. A stock solution composition of a water-soluble ironing lubricant, which comprises the following (1) or (2): (1) An ester of an aliphatic carboxylic acid having 6 to 16 carbon atoms and a polyhydric alcohol (2) An aliphatic carboxylic acid having 18 carbon atoms and 6 to 6 carbon atoms
Ester of mixed aliphatic carboxylic acid comprising 16 aliphatic carboxylic acids and polyhydric alcohol 2. A metal plate having a kinematic viscosity at 40 ° C. of 5-7.
Used to produce DI cans by drawing using a water-insoluble ironing lubricant of 0 mm ² / s and then ironing or redrawing and ironing using a water-soluble ironing lubricant. A stock solution composition of a water-soluble ironing lubricant, which comprises the following (3) or (4): (3) An ester of a mixed aliphatic carboxylic acid composed of an aliphatic carboxylic acid having 6 to 16 carbon atoms and an aliphatic carboxylic acid having 20 to 24 carbon atoms and a polyhydric alcohol (4) An aliphatic carboxylic acid having 18 carbon atoms , Carbon number 6-16
Of mixed aliphatic carboxylic acid consisting of aliphatic carboxylic acid and aliphatic carboxylic acid having 20 to 24 carbon atoms with polyhydric alcohol 3. The stock solution according to claim 1, wherein the water-soluble ironing stock lubricant composition has an average particle diameter of 1 μm or less when diluted with water.