JPS6395295A - Water dispersion type processing oil composition for drawing-ironing molded can - Google Patents

Abstract

PURPOSE:To provide the titled novel processing oil composition suitable for use in can manufacturing, providing a stable emulsion, containing a specific lubricating oil component and a specific water-soluble high polymer compound as essential components. CONSTITUTION:The aimed processing oil composition containing (A) one or more lubricating oils selected from a group consisting of mineral oils, fatty acid (ester or alcohol) and fats and oils and (B) one or more water-soluble high polymer compounds selected from a group consisting of cationic or ampholytic addition polymers, ring opening polymers, polycondensation polymers, salts of natural high polymer derivatives and quaternary ammonium salts there of, which contain a cationic or basic nitrogen in the molecules, as essential components.

Description

Detailed Description of the Invention [Field of Industrial Application] ■ The present invention relates to a processing oil composition for water-dispersed drawn and ironed cans, and more specifically, it is capable of obtaining a stable emulsion and is easy to manufacture. The present invention relates to a processing oil composition for water-dispersed drawn and ironed cans suitable for use in making cans.

[Conventional technology]

Beverage cans made of steel or aluminum with a capacity of approximately 100d to 31mm, which are used in large quantities for beverages such as juice and cola, can be manufactured using a variety of methods. Currently, one of the main methods is to draw the cup to make it into a cup shape, then use ironing to stretch the side wall of the cup to make it into a cylindrical shape, and then attach a lid to the top to form a can. .

This manufacturing method involves drawing a thin plate (referred to as drawing) and then ironing the sheet (referred to as ironing).
However, cans manufactured by this method are generally referred to as DI cans.

After DI cans are manufactured, they go through processes such as cleaning and printing, and after being filled with contents, they are sold commercially and are made of sialumium, and the thickness of the thin plate for manufacturing DI cans is usually about 0.4 mm. That's about it. (Hereinafter, the method of forming by this drawing or ironing process will be referred to as the DI processing method, and the can manufactured by this DI processing method will be referred to as a DI can.) In the DI processing method, the base material (thin plate) K is This method is similar to press working, in which pressure is applied to give plastic deformation, but due to its use, strict performance is required, such as product accuracy, appearance, and DI can surface characteristics. For this reason, it is impossible to perform DI processing on the material simply by using punches and dies.
Normally, machining oil is used in machining parts to reduce the coefficient of friction between the filler material and the punch or die, reduce machining pressure, clean and smooth the surface, and perform smooth machining.

Furthermore, this processing oil is supplied in the form of a processing oil emulsion using water as a coolant in order to remove the processing heat associated with plastic deformation and improve product precision.

In the DI processing method, a processing oil emulsion is continuously supplied by a pump or the like during both the drawing process, which deforms the material into a cup shape while maintaining its thickness, and the ironing process, which stretches the side wall of the cup.

Here, the processing oil used in this case is generally an emulsion type in which the lubricating oil component of the processing oil is emulsified with a surfactant.

This type of processing oil is mainly composed of hydrocarbons (mineral oil), with the addition of fatty acids or their salts (such as alkanolamines) and fatty acid esters, which act as oiliness improvers in lubrication. In addition, if necessary, some ingredients such as extreme pressure agents and rust preventive agents are added.
The addition of nonionic surfactants or anionic surfactants of sulfonic acid or carboxylic acid salts to form processing oil emulsions in water is generally used.

Further, the concentration of processing oil in the emulsion varies depending on the processing conditions, but is relatively high, approximately 10 to 30%.

On the other hand, the characteristics required for DI cans include no surface defects, high processing accuracy, and processing operation stability. It can be said that the influencing factor of oil is a major factor.

Here, surface defects include scratches or partial discoloration on the can surface,
Alternatively, it indicates the glossiness of the entire can surface. Surface flaws are caused by the seizure phenomenon caused by metal-to-metal contact from the breakage of the lubricating oil film existing between the can surface and the die, or the scratching phenomenon of the can surface by solid objects such as metal powder generated during processing. hand,
Partial discoloration refers to the generation of countless linear lights on the can surface, and local discoloration is thought to be related to the composition of the processing oil, its lubricating performance, DI processing conditions, water, processing heat, etc. "Black streaks" refer to fine brown to black streak-like discolored areas that occur on the surface of cans.

Furthermore, the glossiness of the can surface is considered to be related to surface irregularities, that is, surface phase change and surface dirt status.

These defects are largely due to the processing oil mentioned above, but the DI
Can membrane rupture (in the can inner circumferential direction or can stretching direction), reduction in can dimensional accuracy due to deterioration of lubricity (generation of processing heat), generation of a large amount of metal powder during processing, or large amount of metal powder adhering from emulsion. DI regardless of contamination on the surface of the DI can.
In the processing method, the use of processing oil was essential.

[Problem that the invention seeks to solve]

As mentioned above, emulsified processing oil using a surfactant has been used in the production of DI molded cans.

This type of processed oil is used to remove water and DI as an emulsion.
It is used during processing, but at present, in order to ensure emulsion stability from the initial stage, the amount of emulsifier is increased, for example.

In normal DI processing, machining oil is supplied through a strainer to remove dust and relatively large metal powder from the emulsified machining oil (hereinafter referred to as coolant). In most cases, a circulating system is adopted in which the emulsion is injected into the DI molding can processing section using a conventional pump, and then returned from the processing section to the emulsion storage tank.

In this supply system, when emulsified type processing oil is used, it has the following disadvantages 1 and -, and there are problems with stable operation and the like.

In other words, since the emulsion is made of an emulsifier, the emulsion may become unstable due to the mixing of metal powder, etc. generated during operation, resulting in operational stability, deterioration of the surface quality of the DI molding can, and contamination of equipment, etc. This led to environmental deterioration.

To explain these problems in more detail, the emulsifier used for emulsification must have an optimum H
One with LB is used.

In other words, the stability is maintained by the HLB of the emulsifier, but the characteristics of the processed oil emulsion change greatly over time due to the stability of the oil particles in the emulsion due to the emulsifier and changes in the balance of the emulsifier due to disturbances during operation. 9.It may cause a hindrance to operations.

This involves processing metal powder into emulsions, depending on the operation.
Because different types of oil such as bearing oil are mixed in, the required HLB of the emulsifier changes and the emulsion becomes unstable, or the surface protection of oil particles by the emulsifier in the emulsion is relatively weak. (This is because the oil particle size distribution of the emulsion produced by the emulsifier shows a broad distribution ranging from small ones to large ones produced by the coalescence of these particles, which indicates that the surface protection property of the oil particles is weak. ), these metal powders or foreign oils are caused to be trapped in oil particles, and contamination of the processing oil progresses.

From the above, it can be seen that disturbances caused by operation lead to destabilization and contamination of the emulsion, but the effect on processing of DI molded cans is the unevenness of processing oil (unstable workability) due to emulsion instability. , Changes in can surface properties due to contamination of processing oil [Many scratches on the surface of molded cans due to adhesion of metal powder, damage to dies, etc. Contamination of can surfaces due to adhesion of processing oil (such as gloss, etc.) In history, problems such as environmental pollution due to contaminated processing oil adhering to the surroundings of processing and molding machines) occurred, and many problems occurred over time.

To describe these in more detail, in actual operations, when manufacturing DI cans, an emulsion-type processed oil emulsion is prepared in an emulsion circulation tank (the concentration range is generally 10 to 30 yen). In this case, a stable emulsion is formed using an emulsifier as described above. However,
The distribution of the oil particles in the emulsion at this time ranges over a wide range, from extremely small particles of 1 to 2 µm to coarse particles of several tens of micrometers.

DI cans are continuously manufactured by a circulation method in which this emulsion is supplied to the DI can forming section via a supply pump and a strainer (filter), and then returned to a circulation tank.

Due to emulsion circulation, a large amount of metal powder generated during processing and bearing oil used in processing machines get mixed into the emulsion over time, but these can cause the emulsion to become unstable. Floating of oil containing a lot of metal powder on the emulsion surface in the tank (black color)
The filters of emulsions containing a large amount of metal powder and metal powder (jtK) frequently become clogged, and operations such as draining floating oil and replacing filters are required to clean the emulsion. There were many problems in terms of stability.

In addition, these emulsion deteriorations have a large effect on DI molded cans, and in terms of quality, based on the emulsion instability, lubrication instability due to uneven processing oil adhesion during processing, metal L) Scratch-like flaws on the surface of the molded can caused by powder entrained in the processing oil, or seizure flaws caused by contact between the die and the surface of the molded can due to unstable lubrication (both defects occur in large numbers in a linear manner) Surface damage such as
Due to the adhesion of machining oil, there is surface contamination such as large amounts of metal powder adhering to the can surface, and a decrease in surface gloss due to lubrication instability, etc., and the change in emulsion has a significant impact on quality. I can say it.

In this way, the type of processed oil that uses emulsifiers.

Destabilization of emulsions is a real problem,
It seems that improvements have been made in the past, such as stabilizing operations and improving the unit consumption of processing oil by replacing the processing fluid due to emulsion contamination, but the current situation is that a satisfactory processing oil has not yet been found.

For this reason, there has been a strong desire to develop a so-called "clean" processing oil for DI molded cans, which has a stable emulsion over time and is less contaminated with dirt and the like.

[Means for solving problems]

The inventors of the present invention conducted intensive research to solve the above problems, and found that if a specific water-soluble polymer compound is used without using an emulsifier, the effects of metal powder, machine oil, etc. can be reduced. The present invention has been completed based on the discovery that a processing oil composition can be obtained that does not cause any problems and does not cause any problems in operation.

That is, the present invention provides (&) 1ffl or two or more lubricating oil components selected from the group of mineral oils, fatty acids, fatty acid esters, fatty acid alcohols, and fats and oils, and (b) cationic or basic lubricating oil components in the molecule. Contains nitrogen atoms. One or more water-soluble polymers from the group consisting of cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, salts of natural polymer derivatives, or quaternary ammonium salts thereof. The present invention provides a water-dispersed processing oil composition for drawn and ironed cans, which is characterized by containing a molecular compound as an essential component.

As the lubricating oil component which is component (jL) of the processing oil composition of the present invention, the following can be mentioned.

For example, the viscosity obtained as a petroleum component is 10cat74
Hydrocarbons obtained by polymerization of paraffinic or 7-tene mineral oils and olefins at temperatures above 0°C; fatty acids obtained from beef tallow, palm oil, coconut oil, etc., aliphatic monohydric alcohols having 1 to 22 carbon atoms, and ethylene. Fatty acid esters with glycol, thiopentyl alcohol, pentaerythritol, trimethylolpropane, sorbitol, etc.; linear or branched aliphatic alcohols having 1 to 40 carbon atoms; beef tallow and palm oil having 1 to 22 carbon atoms.

Fatty acids obtained from coconut oil, etc. or polymerized acids of these fatty acids (dimers, trimers, etc.); fatty acid derivatives such as hydroxy fatty acids; or whale oil, beef tallow, lard, rapeseed oil, castor oil, bran oil, palm oil , animal and vegetable oils such as coconut oil, etc., and these can be used alone or in combination of two or more.

Further, as the water-soluble polymer compound of component (b), the following polycondensates can be mentioned.

(2) Homopolymers or copolymers of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas (1) to ([).

CRt is H or 0M5, R2 and R8 are H or carbon number 1
-3 alkyl group] (ml is a number from 1 to 3, nl is a number from 1 to 3, R1-"t
-R3 is the same as formula (1)] (R4 is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R1 is the same as formula (1)) [G and R2 are numbers from 0 to 3, Rs, Rq , Rs.
is the formula (1) [A is one or -1R,, R,, R3,
n' is the same as formulas (1) and (II)]
)] [Turtle is the same as formula CI). The substituent position of pyridine is the 2nd or 4th position] (Rt -R2 is the same as in formula (I). The substituent position of piperidine is the 2nd or 4th position) (Rt -Rt -"s is the same as in the formula (1)) Specific examples of molecules include the following.

3-methacryloxy-2-hydroxypropyldimethylamine, 3-methacryloxy-2-hydroxypropylethylmethylamine, 3-methacryloxy- of the formula (1)
2-hydroxypropyldiethylamine, 3-methacryloxy-2-hydroxypropyldiethylamine, etc.;
(It) of the formula N,N-dimethylaminomethylene capped ethylene glycol methacrylate, N,N-dimethylaminoethylene capped ethylene glycol methacrylate), N,N-dimethylaminopropylene capped ethylene glycol methacrylate Acrylate, N, N
-dimethylaminomethylene-capped diethylene glycol methacrylate, N,N-dimethylaminoethylene-capped diethylene glycol methacrylate, N,N-dimethylaminopropylene-capped diethylene glycol methacrylate, N,N-diethylaminomethylene-capped diethylene glycol methacrylate relay), N, N-dietheraminoethylene capped ethylene glycol methacrylate, N.

N-diethylaminopropylene-capped ethylene glycol methacrylate, N,N-diethylaminomethylene-capped diethylene glycol methacrylate, N,N-diethylaminoethylene-capped diethylene glycol methacrylate, N,N-diethylaminopropylene-capped diethylene glycol methacrylate, etc.; N-2-hydroxymethyl-2-α-methylvinylimidazole of the formula (I), N-2-
Hydroxyethyl-2-α-methylvinylimidazole, N-2-hydroxypropyl-2-α-methylvinylimidazole, etc.;
Renimine methacrylamide, N,N-dimethylethyleneimine methacrylamide, N,N-diethyldimethyleneimine methacrylamide, N,N-dimethyldiethyleneimine methacrylamide, N,N-diethylmethyleneimine methacrylamide, N,N- Examples include diethylethyleneimine methacrylamide, N,N-diethyldimethyleneimine methacrylamide, and N,N-diethyldiethyleneimine methacrylamide. Dimethylamino, ethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminepropylacrylamide, diethylaminopropylacrylamide, dimethylaminepropylmethacrylamide, diethylaminopropylmethacrylamide, etc. of formula (■); Dimethylaminomethylethylene, diethylaminomethylethylene, dimethylaminomethylpropene, diethylaminomethylproben, etc.; (■)
Vinylpyridine, etc. of the formula; vinylpiperidine of the formula (■),
Vinyl-N-methylpiperidine, etc.: (!X) vinylpencylamine, vinyl-N,N-dimethylbenzylamine, and the like.

(1) One or more of the nitrogen-containing monomers or salts thereof represented by the general formulas (1) to ([)0, and α,β-unsaturated carboxylic acid or its derivative, sulfonic acid group A copolymer with one or more vinyl monomers selected from the group consisting of vinyl compounds or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms.

Examples of the vinyl monomer include vinylpyrrolidone, acrylonitrile; acrylic acid, methacrylic acid, maleic acid, or alkali metal salts, ammonium salts, amide compounds, or esters of these acids; vinylsulfonic acid, methallylsulfonic acid, 2-acrylamide-2
Examples include -methylpropanesulfonic acid, p-styrenesulfonic acid, and alkali metal salts or ammonium salts of these acids.

■Salts of ring-opening polymers of ethyleneimine or quaternary ammonium salts or derivatives thereof.

Specifically, the repeating unit is represented by the following general formula (XI)
The average molecular weight is 1,000 to 10,000,000.

[In the formula, n & represents the number of pots from 1 to 5, H4 represents an integer from 0 to 5] @ Salt or quaternary ammonium salt of a condensation product of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine.

Specifically, these repeating units are a condensation product with a polyethylene polyamine represented by the general formula (X[D) and a condensation product with a dipolyoxyethylene alkylamine represented by the general formula ,000~1000
Thousands of things can be mentioned.

-(To QC--〇〇NH-(R/-NH+-1R1-book)-(XII) [In the formula, R1 is a dimer acid residue or an alkylene acid having 1 to 10 carbon atoms, R' is -CH, CH,+,
n' represents an integer of 2 to 7] [In the formula, R1 is the same as in formula (Xll). R6 has 1 or more carbon atoms
B noalkyl group, R1 is H or CHs, n' and n? represents an integer of 1 to 10] Examples of the aliphatic dicarboxylic acids include dimer acid and adipic acid, and examples of polyethylene polyamines include:
Diethylenetriamine, triethylenetetramine, etc. can be used.

■ Dihaloalkane-polyalkylenepolyamine condensation product.

Specifically, a dihaloalkane such as 1,2-dichloroethane, 1゜2-dibromoethane% 113-') chloropropane, and a polyalkylene polyamine having two or more tertiary amino groups in the molecule are used. It is a condensation product that is a quaternary ammonium salt, and its average molecular weight is 1.0
00 to 10 million.

Examples of the polyalkylene polyamines mentioned above include the following.

(Tetramethylpropylenediamine) (Pentamethyldiethylenetriamine) ■ Epihalohylin-amine condensation product Specifically, the repeating unit is represented by the following general formula (XII/), and the average molecular weight is 1,000
There are ~10 million examples.

ll [In the formula, R1°~ass represents CH3 or C2xe represents a halogen ion] (2) Salt of chitosan or cationic modified product of starch or cellulose.

(2) A polyether polyol or polyol polyether derivative having a molecular weight of 600,000 to 600,000 obtained by adding an alkylene oxide to a polyalkylimine having 6 to 200 nitrogen atoms or a derivative thereof.

The polyalkylene polyamine has five or more consecutive skeletons represented by the following formula (XV) in the molecule, and at least one of them is a skeleton represented by the following formula (XVI), and the terminals are OH and / Or polyethyleneimine containing 6 to 100 nitrogen atoms is preferred.

-C-C-C (XV) In addition, the alkylene oxide in the polyether polyol is one or more selected from the group consisting of ethylene oxide, propylene oxide, styrene oxide, and butylene oxide, and the content thereof Preferably the amount is from 3 to 80% by weight of polyether polyol.

The polycondensates of ■~O above have an average molecular weight of 1000~
One million is highly preferable.

In addition, examples of the counteranion forming the salt of the polycondensate include the following (1) to -.

(1) Phosphoric acid, phosphorous acid, or their thio or ester compound (H) 1 on alkyl, alkylaryl or allyl group
Mono- or silicic acid esters having 1 or more hydroxyl groups or thio compounds thereof (III) Mono- or diphosphonic acids having alkyl, alkylaryl or allyl groups of carbon a1 to 8, or thio compounds thereof or derivatives thereof (M Number of carbon atoms 1~
Mono- or di-phosphinic acid having an alkyl, alkylaryl or aryl group or a thio compound thereof or a derivative thereof M Mono- or di- or triphosphonic acid containing a nitrogen atom (vl) Boric acid-lower carboxylic acid or its derivative Specific examples of phosphoric acid compounds include the following.

Examples of (1) include orthophosphoric acid, phosphorous acid, and carbon number 1.
- 8 mono- or silicic acid esters of aliphatic, alicyclic or aromatic alcohols and orthophosphoric acid, or thio compounds thereof, or phosphite esters of the above-mentioned alcohols, or these thio compounds are exemplified. An example of (11) is 2-hydroxypropyl phosphate. (
Examples of II) include phosphonic acids represented by 1 to 8 alkyl groups, alkylaryl groups, or allyl groups, such as methylphosphonic acid and dimethylphosphonic acid having 1 carbon number to n-octylphosphonic acid and dimethylphosphonic acid having 8 carbon atoms. n-octylphosphonic acid, 2-ethylhexylphosphonic acid.

Examples include di-2-ethylhexylphosphonic acid, benzylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxyethane diphosphonic acid, and these thiophosphonic acids. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

phosphinic acid, such as methylphosphinic acid having 1 carbon atom;
Dimethylphosphinic acid to n-octylphosphinic acid having 8 carbon atoms, di-n-octylphosphinic acid, 2-ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid , diphenylphosphinic acid, and these thiophosphinic acids. Examples of (V) include hexamethylphosphoric mono(or di)amide and nitrilotrismethylenephosphonic acid. Nitrilotrismethylenephosphonic acid is a compound represented by the following formula.

Bo-p-.

H The processed oil composition of the present invention is prepared by blending each of the above components, and the blending amount is (a) based on the total composition.
The lubricating oil component of the component is 99.9 to 80% by weight (hereinafter simply referred to as ``chi''), especially 95 to 85% by weight, and the water-soluble polymer compound of component (b) is 0.1 to 20%, especially 0, 1 ~10% is preferred.

In addition to the above-mentioned essential components, the processing oil composition of the present invention may contain various known additives, such as rust inhibitors, extreme pressure agents, antioxidants, and A fungicide or the like may also be added.

As a rust preventive agent, alkenylcono-phosphoric acid and its derivatives,
Esters such as sorbitan monooleate, amines or amine salts of fatty acids, etc.; as extreme pressure agents, phosphorus compounds such as mono- or di- or trialkyl or mono- or di-orthotriphenyl phosphate, zinc dialkyldithiophosphate, etc. The organometallic compound of: 2. as an antioxidant;
Phenyl compounds such as 4-di-1-butyl-p-cresol, aromatic amines such as phenyl α-naphthylamine, and the like; examples of antifungal agents include chlorine and bromine compounds, respectively.

In addition, these various additives may be used in amounts of 0 to 2% by weight of each rust inhibitor based on the total amount of the processing oil composition of the present invention.
They can be added in the following proportions: 1.0 to 5% by weight of the extreme pressure agent, 0 to 5% by weight of the antioxidant, and 0 to 1% by weight of the antifungal agent.

On the other hand, although the processing oil composition of the present invention uses a water-soluble polymer compound, it has a large difference in the emulsion forming mechanism compared to processing oils using conventional emulsifiers. In other words, since conventional processing oils are measured by emulsification (lowering of interfacial tension), processing oils have self-emulsifying properties and can easily form emulsions simply by mixing with water. Since the compound does not have the ability to lower the interfacial tension between the processing oil and water, the oil particles can be stably dispersed by mechanical stirring or the like.

Therefore, in the case where no mechanical force is applied, for example, when preparing a new emulsion of processing oil, for the purpose of quickly homogenizing the initial concentration of the emulsion, the interfacial tension is within a range that does not inhibit the characteristics of the polymer compound in question. It is also possible to add compounds that have the ability to reduce the

Considering the emulsion properties, it is preferable to use such a compound in an amount within twice the weight ratio of the water-soluble polymer compound added.

Compounds that have the ability to lower this interfacial tension include, for example, compounds in which ethylene oxide or both propylene oxide and ethylene oxide are added to aliphatic alcohols, aromatic alcohols, aliphatic amines, fatty acids, norbitol fatty acid esters; Alternatively, alkanolamine salts, salts of compounds having sulfonic acid or sulfuric acid groups, etc. can be mentioned.

To produce the processing oil composition of the present invention, the above-mentioned components are mixed at the time of use, and a strong protective film of a water-soluble polymer compound is formed on the surface of the oil particles in the emulsion by a commonly used method to separate the oil particles individually. It is sufficient if it exists stably in water.

The mechanism of action of the present invention will be described below.

Generally, mineral oil, fatty acids, fatty acid esters, etc.
When present as oil particles in water, the particle surfaces are negatively charged. (At this time, the Ze of the oil particles is electrochemically
(expressed as having a negative ta potential) protects this oil particle,
For stabilization, a strong adsorption film is formed on the surface of the oil particles by using a cationic or amphoteric water-soluble polymer compound containing a cationic or basic nitrogen atom. This polymer compound is thick! The positive charge of the membrane converts the Zeta potential of the oil particles to positive.

The oil particles are extremely stabilized by colloidal or electrical repulsion, allowing them to exist in a stable dispersed state in water. As a result, it becomes possible to obtain a processing oil emulsion that has excellent stability over time.

On the other hand, the various problems associated with conventional emulsification methods using surfactants can also be prevented by the present invention. That is,
According to the composition of the present invention, an extremely stable processing oil emulsion can be obtained, and the water-soluble polymer compound can also be resistant to disturbances, which are one of the factors that cause emulsion instability, that is, the contamination of metal powder and different types of oil. By applying this method, the metal powder can be protected and stabilized in the same way as oil particles, and the metal powder can be precipitated and discharged from the system as a metal powder that has been made hydrophilic by a polymer compound film that has a large compatibility with water.

Regarding different oils, water-soluble polymer compounds are different from surfactants normally used for emulsification and do not themselves have the ability to completely lower the interfacial tension. Oil particles! Once formed, it is possible to hold the foreign oil in a floating state rather than by force.

The thus obtained water-dispersed processing oil composition for drawing, ironing, and forming cans of the present invention is a composition that is effective in processing steel, aluminum, copper, alloys thereof, and the like.

In other words, by applying a water-soluble polymer compound, 1. a composition that is extremely useful in actual use, which eliminates the drawbacks of the conventional emulsion type and retains many of the characteristics of the dispersion type; It is something that provides something.

This is based on the protective stability of the adsorption film on the surface of the oil particles created by a water-soluble polymer compound that does not lower the interfacial tension. It is the basis for creating
This improves lubrication stability (uniform and homogeneous adhesion of large particles)
, emulsion stability over time (ease of removing disturbances such as metal powder and machine oil from the system, stability of oil particles, etc.), and quality stability (supply of a clean emulsion at all times).

Wastewater treatment properties (flocculant function for water-soluble polymer compounds)
The hydrophilic effect of the polymer compound has many excellent effects not seen in conventional emulsified processing oils, such as cleaning pollution and improving the environment.

It is something that can be done.

Furthermore, another excellent feature of the water-soluble polymer compound is the production of uniform and large particle diameter processing oil particles. This is based on the aggregation and stabilization of the oil particles of the polymer compound, and uniform, large oil particles with a hydrophilic surface adhere uniformly to the surface of the processed material (high emulsion wettability). That's a thing. As will be described later, this is considered to be an important factor in the DI molded can lining work.

〔Effect of the invention〕

A new water-dispersed aperture using a water-soluble polymer compound
It is thought that the processing oil composition for iron-formed cans can be manufactured easily by stabilizing the processing oil emulsion, and its quality can also be improved.

In other words, metal powder that gets mixed into the emulsion over time is
It settles as particles at the bottom of the circulation tank, etc., and is also captured as metal powder in the strainer (filter), so there is almost no filter clogging or oil capture, which improves emulsion efficiency. Alternatively, the unit consumption of processing oil can be reduced, and work efficiency can be significantly improved.

Furthermore, since it does not have the ability to mix different types of oil into the emulsion, it is possible to have it exist as an oil layer in the upper part of the circulation tank.

From the above, it can be used as a constantly clean emulsion that removes metal powder or foreign oil from the system, and due to the large particle size of the processing oil and its uniform adhesion, excellent lubricity is maintained and processing By using a low concentration of oil and making emulsion management easier, it is possible to reduce the unit consumption of processing oil.

The emulsified type DI processing oil currently in use.

It is difficult to obtain such characteristics.

Historically, as an excellent effect obtained by applying the processing oil composition of the present invention, the wastewater treatment property (low carbon
Improvements in the work environment (OD load) and the working environment can be measured.

These are based on the action of the water-soluble polymer compound applied, but the wastewater treatment properties range from oil separation (oil separation), which is a common treatment method for used emulsions, to pH adjustment (acidification) of the lower layer. , during pH adjustment in the process leading to neutralization,
Since the polymer compound acts as a coagulation treatment agent, when the treatment property is expressed as a COD value, the value is significantly lower than that of conventional processing oil, and the wastewater treatment property is improved by +1.

In the conventional emulsified type, the oil particle size distribution is wide-ranging, but the extremely small stabilized particles cannot be completely removed by the above-mentioned treatment method, causing problems in wastewater treatment. Ta.

In addition, in terms of the working environment, with the conventional type, contaminated machining oil tends to unstably adhere to the surroundings of the machining part and accumulate dirt, polluting the environment, but with the machining oil of the present invention, Contamination progress is not hindered by constantly supplying a clean emulsion, and already contaminated areas are cleaned by the hydrophilic action of the polymer compound, making this composition useful in terms of the working environment. It can be said that it is a thing.

〔Example〕

Examples will be described below.

Preparation Example The compositions shown in Table 1 below were mixed according to the same method, and the compositions of the present invention and the compositions shown in Table 2 were mixed in the same manner to obtain comparative compositions.

Water-soluble polymer compound: (A) Phosphate of diethylamine methyl methacrylate polymer (MW = 1.3 million) (B)
A copolymer of diethylaminoethyl methacrylate borate/vinyl pyrrolidone/acrylic acid nodah; 5/4/l (shown in molar ratio; the same applies below for wood surface).
MW = 200,000) (C) Copolymer of diethylaminoethyl methacrylate phosphate/sodium methacrylate = 415 (MW = 20,000) (D) 5 for polyethyleneimine (MW = 70,000)
(E) Ethyl phosphonate of dimethylaminoethyl methacrylate/sodium 2-acrylamide-2-methylpropanesulfonate = 4
Copolymer of 71 (MW=100,000) CF) Copolymer of vinylpyridine phosphate group/vinylpyrrolidone/sodium acrylate=6/3/1 (MW=
450,000) CG) Polycondensate of diethylenetriamine thiophosphate and dimer acid (Mw = 13Q) (H) Diethylaminoethylmethacrylamide phosphate/acrylic acid/sodium vinyl sulfonate = 3/1/1 Copolymer (MW=4Q million) (1) Water-soluble polymer compound (D) with ethyleneimine phosphate as borate (J) Quaternary ammonium salt of cationically modified cellulose (MW= 1,000,000) (K) 1. Polycondensate metal of phosphate of 2-diprolethane and hexamethylenetetramine (MW = 50,000) (L)
Ring-opening polymer of phosphite of trimethylamine quaternary ammonium compound of epichlorohydrin (Mw=l Q
(M) Polycondensation metal compound of quaternary ammonium salt of tetramethylfluorobylenediamine with diethylphosphonic acid (
MW = 100,000) (N) Copolymer of phosphorus mW of dimethylaminoethyl methacrylate/Na salt of 2-acrylamido-2-methylpropanesulfonic acid = 2/1 (MW = 30,000) (0) Dimethylaminoethyl methacrylate Phosphate/acrylamide = 3/1 copolymer (MW = 10,000) (P) Hydroxyacetate of ethylphosphonate of dimethylaminoethyl methacrylate of water-soluble polymer compound (E) (Q ) Water-soluble polymer compound (D) with ethyleneimine phosphate as propionate (R) Quaternary ammonium salt of vinylpyridine with dimethyl sulfate/vinylpyrrolidone/sodium acrylate = 6/3/1 (
7) Copolymer (MW = 450,000) (S) 20% addition of ethylene oxyto to polyethyleneimine (MW = 50,000)
, phosphoric acid neutralized (T) Dimethylamine ethyl methacrylate/lauryl methacrylate = 7/1 copolymer sulfate (M
W = 50,000) (U) Diethylaminoethyl methacrylate/stearyl methacrylate; 3/1 copolymer of hydroxyacetic acid/phosphoric acid = 1/2 Hanawa (MW = 30,000) (v) 3-methacroxy-2-hydroxy Phosphate of propyldimethylamine homopolymer (MW = 30,000) (W) N,N-dimethylaminomethylene carboxylated ethylene glycol methacrylate/sodium acrylate (
10/1) copolymer hydroxyacetate (MW=1
00,000) (X) Polymerization of quaternary ammonium salt of N-2-hydroxyethyl-2-α-methylvinylimidazole with 70 pionic acid (MW = 10,000) (Y) N,N-dimethylmethyleneimine methacrylate Hydroxyethane diphosphonate (MW=50,000) of amide/diethylaminoethyl methacrylate (6/4) copolymer (z) Nitrilotrismethylene phosphonate of dimethylaminomethylethylene/lauryl methacrylate (1/1) copolymer Acid acid (AA) 4 (MW=1) of hydroxyacetic acid/phosphoric acid (1/2) of vinyl N-methylpiperidine homopolymer
00,000) (HB) Vinyl N, N-dimethylbenzylamine/
Salt of butyl sesquiphosphate copolymer of stearyl methacrylate (3/1) (MW = 80,000) U, remainder T: Composition used in Table 1 Fatty acid ester A; Trimethylolpropane trioleate B ; Ethylene glycol dioleate ester C; polyoxyethylene (6 mole addition) sorbitan trioleate aliphatic alcohol D; lauryl alcohol E; Guerbet alcohol having 20 carbon atoms antioxidant; 2.4-di-t-butyl p- Cresol extreme pressure agent; triphenyl phosphate additive F: polyoxyethylene (6 mol) nonylphenyl ether G; triethanolamine oleate Example 1 Lucilan stability test Invention product and composition 10 shown as comparative product % concentration emulsion 201f: The emulsion was placed in a circulation tank in the emulsion circulation device shown in Figure IK, and the emulsion was circulated at 30 to 40°C under the condition of the circulation system shown in Figure 1. Here, assuming actual processing, 100 ppm of metal powder (aluminum powder) is added (circulation 43 ppm).
0 minutes later), and the operation was continued for 48 hours.

The evaluation was carried out twice: immediately before the addition of aluminum and once at the end of the operation 48 hours after the addition.
Changes in the amount of aluminum powder present in the emulsion and the amount of floating oil were tracked.

The results are shown in Table-3. Further, typical charts for measuring the diameter of oil particles in the emulsion 48 hours after addition of aluminum are shown in Figures 2 to 5.

Table-3 *1 Oil particle size: Measured in the circulation tank (Coulter counter, aperture Zooμm) *2 After adding At: Data immediately before the end of 48 hours of operation after adding At powder *3 Particle size distribution: ○ Logarithmic plot Shows a sharp pattern in the logarithmic plot x Broad pattern in the logarithmic plot l! NDSXXK2
740 oil film strength test method (Soda four-ball test method). The test sample was prepared using water, containing 10% of the present invention product and Higeki product composition! ! The mixture was stirred using a homomixer at a rotational speed of 10.00 rpm. The test samples were applied using a gear pump with the above stirred solution sprayed at a spray rate of 0.5 #/min (pressure: 0.5 U/cdt) and a sample solution temperature of 50°C, and three pieces fixed with ball holders were used. The coating was applied from below the test steel ball through the space at the center of the three contact points to the rotating steel ball above.

The results are shown in Table-4.

Margin table below - 4 Example 3 Wastewater treatment test Test solution prepared in the same manner as in Example 2 - Diluted to 1/4 to 1 (1 p) and 3% on sulfuric acid bread? After the addition, the solution was stirred for 2 minutes, and further added to KCa (OH%') to adjust the pH to 7.0, followed by stirring for 10 minutes. After standing still for 30 minutes, the subnatant liquid was collected, and COD (KMnO , method) was measured.

The results are shown in Table-5.

The rest below Table-5

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the emulsion circulation device used in Example 1. Figures 2 to 5 are. 3 is a diagram showing the oil particle size distribution in the emulsion 48 hours after aluminum addition in Example 1. FIG. that's all

Claims (3)

[Claims] (1) (a) One or more lubricating oil components selected from the group of mineral oils, fatty acids, fatty acid esters, fatty acid alcohols, or oils and fats, and (b) cationic or basic nitrogen in the molecule. One or two selected from the group consisting of cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, or salts of natural polymer derivatives containing atoms, or quaternary ammonium salts thereof. A processing oil composition for water-dispersed drawn and ironed cans, characterized by containing the above-mentioned water-soluble polymer compound as an essential component. (2) The water-dispersed drawn-iron molded can according to claim 1, wherein the water-soluble polymer compound is cationic or amphoteric and is selected from the group consisting of the following [a] to [h]. Processing oil composition for use. [a] A homopolymer or a copolymer of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas (I) to (IX). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [R_1 is H or CH_3, R_2 and R_3 are H or an alkyl group with 1 to 3 carbon atoms] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [m ^1 is a number from 1 to 3, n^1 is a number from 1 to 3, R_1,
R_2 and R_3 are the same as formula (I)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [R_4 is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R_1 is the same as formula (I)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [m^2 and n^2 are numbers from 0 to 3, R_1, R_2, R
＿3 is the same as formula (I)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [A is -O- or -NH-, R_1, R_2, R_3,
n^1 is the same as formulas (I) and (II)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) [R_1, R_2, R_3, n^1 are the same as formulas (I) and (
Same as II)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) [R_1 is the same as formula (I). The substitution position of pyridine is the 2nd or 4th position] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) [R_1 and R_2 are the same as formula (I). The substituent position of piperidine is the 2nd or 4th position] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IX) [R_1, R_2, R_3 are the same as formula (I)] [b] General formulas (I) to (IX) above One or more nitrogen-containing monomers or salts thereof, α,β-unsaturated carboxylic acids or salts thereof or derivatives thereof, sulfonic acid group-containing vinyl compounds or salts thereof, acrylonitrile,
A copolymer with one or more vinyl monomers selected from the group consisting of vinylpyrrolidone and aliphatic olefins having 2 to 20 carbon atoms. [c] A salt of a ring-opened polymer of ethyleneimine or a quaternary ammonium salt or a derivative thereof. [d] Salt or quaternary ammonium salt of a condensation product of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine. [e] Dihaloalkane-polyalkylenepolyamine condensate. [f] Epihalohydrin-amine condensation product. [g] Chitosan salt, starch or cellulose, or cationically modified products thereof. [h] A polyether polyol or polyol polyether derivative having a molecular weight of 5,000 to 600,000 obtained by adding an alkylene oxide to a polyalkylimine having 6 to 200 nitrogen atoms or a derivative thereof. (3) The amount of water-soluble polymer compound is 0.1 to 2 of the total composition
The processing oil composition for water-dispersed drawn and ironed cans according to claim 1, which has a content of 0% by weight.