JPH05194983A - Organic lubricating film-forming agent composition and metal sheet lubricated therewith - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can give a lubricated metal sheet improved in moldability in pressing and can easily be removed by washing from the sheet after pressing by using an ester prepared by esterifying a maleic acid/styrene copolymer with a specified hydroxylic compound. CONSTITUTION:The objective composition comprises an ester prepared by esterifying a copolymer of a monomer mixture mainly consisting of a maleic acid and a styrene in a maleic acid to styrene molar ratio of 1:99 to 75:25 with a hydroxylic compound mixture comprising at least 10wt.%, based on the total weight, hydroxylic compound containing 4-9 C alkyl or alkenyl to a degree of esterification of at least 5wt.% based on the carboxyl groups of the copolymer or a salt of the ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic lubricating film agent composition for plastic working of a thin metal plate and a metal thin plate coated with the same, and more specifically, to improve the formability in the plastic working of the thin metal plate, The present invention relates to an organic lubricating film agent composition for plastic working, which has improved adhesiveness with an adhesive and cleaning and removal properties of a film agent from a thin plate, and a metal thin plate coated with the composition.

[0002]

2. Description of the Related Art A technique for reducing the working load and preventing seizure by using a lubricant when plastically working a thin metal plate such as a steel plate to improve the lubricity between the die and the thin metal plate. Has been conventionally used as a conventional means. However, in recent years, due to environmental problems when using lubricants, customers do not apply lubricants during plastic working, and lubricated metal thin plates in which a solid lubricant film is pre-formed on the surface of metal thin plates are widely used. It has come to be used. This lubricated metal thin plate is produced by applying an organic lubricant film composition containing various lubricants at the stage of producing the metal sheet or at an appropriate stage up to the consumer.

The organic lubricant film composition is a known film forming component such as an acrylic resin, an epoxy resin, a melamine resin or a phenol resin, and a fatty acid, a fatty acid salt or a fatty acid metal soap as a lubricating component, A mixture of fatty acid ester, fatty acid amide, higher alcohol, polyethylene resin powder, graphite, molybdenum disulfide, and fluorine resin powder has been proposed. For example, JP-A-62-84193 discloses an aqueous dispersion of acrylic resin and metal soap, JP-B-52-22948 discloses a mixture of wax and water-soluble resin, and JP-A-54-40259. Japanese Patent Laid-Open Publication No. Sho-06-29187 discloses a mixture of polymethacrylic acid ester and mineral oil.
63-8489 discloses a mixture of a thermosetting acrylic resin, a surfactant and a wax, respectively.

The following characteristics are mainly required for such an organic lubricating coating agent for plastic working. (1) Good lubricity is exhibited even when the film thickness is thin. (2) After applying the coating agent, the thin metal plates do not stick together. (3) The film can be easily washed and removed. However, when the present inventors tried, none of the known organic lubricating coating agents sufficiently satisfied all the required properties.

Waxes containing wax as the main component, which are generally said to have good lubricity, need to be diluted with an organic solvent before application, which poses a serious problem in handling at the time of film formation and environmental protection. It is difficult to remove by washing. In order to improve this drawback, some waxes are made into a water emulsion or water dispersion using a surfactant. This does not require an organic solvent, but due to the strong hydrophobicity of wax, it is difficult to clean and remove the lubricating film after plastic working with an aqueous cleaning solution, and a vigorous cleaning operation such as solvent cleaning or alkaline boiling cleaning is required. However, there is still a problem in cleaning and removability. Further, a resin containing a water-soluble resin or a water-dispersible resin as a main component can be easily removed by washing because the resin itself is hydrophilic, but the resin does not have an alkyl group or an alkenyl group that contributes to lubricity. However, in order to exert the necessary lubricity, it is necessary to apply it thickly, and in some cases a lubricating film with a thickness of several tens of μm is required, which is a problem in economic efficiency.

The present inventors have conducted extensive research aiming at the development of a novel organic lubricating coating agent satisfying all of the above-mentioned required properties, and as a result, have found that maleic anhydride and styrene are the main monomer constituents. An organic lubricating coating agent composition containing an esterified product obtained by esterifying a polymer with a hydroxyl group-containing compound having an alkyl group or an alkenyl group having 10 to 30 carbon atoms or a salt thereof as an essential component has been previously proposed (JP-A-3-2039).
No. 96).

[0007]

Generally, the metal thin plate after plastic working is subjected to degreasing process to wash and remove the lubricant, and then surface painting or assembly with other parts is performed. Conventionally, metal welding, riveting, bolting, etc. have been used as the assembling method. However, in recent years, as the weight of structural members has become lighter, the types of metal materials have diversified, and the use of thin-walled steel sheets has increased, so that the conventional assembly method often causes adverse effects such as deformation of welded parts and tightened parts. Therefore, expectations for adhesive bonding using an adhesive are increasing. Also, in the work process, it is more efficient to wash and remove the press oil, rust preventive oil, cleaning oil, etc. collectively after assembling the metal members, and it is common to perform the assembly before the cleaning process. It is becoming more common.

As an adhesive for assembling metal members,
There are epoxy-based, vinyl chloride-based, urethane-based, vinyl acetate-based, and synthetic rubber-based adhesives, but the epoxy-based adhesives that are widely used are rust preventive oils and cleaning oils on the surface of thin metal plates. It is an adhesive that adheres firmly even if oil such as press oil is present.

However, since this type of adhesive was developed for a metal member having a residual oil content such as general press oil, rust preventive oil, cleaning oil, etc., the present inventors first It has been found that when a thin metal plate coated with the above-mentioned developed organic lubricating coating composition is bonded with this adhesive, sufficient adhesiveness may not be obtained, which causes a practically important problem.

The object of the present invention is to prevent the adhesiveness from being hindered and to be excellent in workability and degreasing property when it is adhered using an adhesive of the type conventionally used for assembling metal members. Another object of the present invention is to develop an organic lubricant film composition for plastic working and a thin metal plate coated with the composition. Another object of the present invention is to provide an organic lubricating coating agent composition and a coated thin sheet which can be easily discriminated from the appearance whether or not it is a metal thin sheet coated with the lubricating coating agent composition.

[0011]

The present inventors have found that the following objects can be achieved by the following organic lubricating coating agent composition. Here, the present invention provides a copolymer containing maleic acid and styrene having a molar ratio of maleic acid: styrene of 1:99 to 75:25 as a main monomer, and at least one hydroxyl group-containing compound. An organic lubricating coating agent composition comprising, as an essential component, an esterified product or a salt thereof esterified at an esterification rate of 5 equivalent% or more based on the carboxyl group in the copolymer,
The gist of an organic lubricating coating agent composition is characterized in that weight% or more is a hydroxyl group-containing compound having an alkyl group or an alkenyl group having 4 to 9 carbon atoms.

The composition may further contain pigments and / or dyes, whereby the presence or absence of coating can be easily discriminated. In another aspect, the present invention is a metal thin plate coated with such an organic lubricating coating composition on at least one side.

[0013]

The structure of the present invention will be described in detail below together with its operation. The composition of the present invention can be applied not only to steel plates and stainless steel plates, but also to various thin metal plates made of various materials such as various non-ferrous metals such as aluminum, nickel and zirconium, and alloys thereof. Here, the metal thin plate refers to hot rolled and pickled metal thin plate, cold rolled metal thin plate, surface-treated metal thin plate.
(Eg, surface-treated products such as plating, thermal spraying, vapor deposition, etc.), and also all metal thin plates to which plastic working is applied, such as multi-layer thin plates such as clad materials.

As used herein, the term "maleic acids" means
At least one selected from maleic acid and its derivatives
Means a class of compounds. Examples of the maleic acid derivative include maleic anhydride, maleic acid ester, maleic acid salt, maleic acid amide, and maleic acid imide.
Similarly, "styrenes" means at least one compound selected from styrene and its derivatives, and examples of the styrene derivative include substituted styrene compounds such as α-methylstyrene.

The copolymer containing maleic acid and styrene as the main monomers (hereinafter referred to as maleic acid-styrene copolymer) is the above-mentioned at least one maleic acid and at least one styrene. Is a copolymer obtained by using 50 mol% or more in total as an essential monomer.

The most preferred example of the maleic acid-styrene type copolymer is a copolymer essentially containing maleic acid and styrene as monomers, but this copolymer is other than maleic acids and styrenes. The other monomer may be contained as a constituent element. Such other monomers include other ethylenically unsaturated monomers such as olefins and their derivatives, ethylenically unsaturated carboxylic acids and their derivatives, vinyl alcohol and its derivatives. It is necessary that the total number of moles of such other monomers is smaller than the total number of moles of maleic acids and styrenes.

The ratio of maleic acid to styrene in the maleic acid-styrene copolymer is 1:99 to 75:25, preferably 10:90 to 50:50, from the viewpoint of lubricity and lubricating film strength. Limited to When the ratio of maleic acids is less than 1 mol% based on the total amount of both, the amount of the hydroxyl group-containing compound introduced by esterification of the copolymer is small, and sufficient lubricity cannot be obtained. Also, the ratio of maleic acids is
If the content exceeds 75 mol%, the styrene content will be small and the lubricating film will be weak and plastic workability will be poor.

From the viewpoint of the strength of the lubricating coating and the viscosity of the lubricating coating composition, the maleic acid-styrene copolymer has a number average molecular weight of 200 to 100,000, particularly 500 to 10,000.
The range of is preferable. Moreover, this copolymer can use 1 type (s) or 2 or more types.

The polymerization method for obtaining the maleic acid-styrene copolymer is not particularly limited, and industrially practicable polymerization methods such as gas phase polymerization, bulk polymerization, solution polymerization and emulsion polymerization can be adopted. For example, in gas phase polymerization, there is a method in which necessary monomers are introduced in a gas state into a high pressure resistant reaction vessel heated to 100 to 300 ° C, and polymerization is caused in the presence or absence of a polymerization catalyst. .. 60 for bulk or solution polymerization
There is a method in which necessary monomers are melted or dissolved in a chemically inert solvent and introduced into a pressure resistant reaction vessel heated to ˜200 ° C., and polymerization is caused in the presence of a polymerization catalyst. The former is a method suitable for obtaining a relatively low molecular weight copolymer having a molecular weight of 200 to 10,000, and the latter is a molecular weight of 5,000 to 100,000.
It is suitable for obtaining a relatively high molecular weight copolymer of
The maleic acid-styrene copolymer is esterified by the reaction with the hydroxyl group-containing compound. The hydroxyl group-containing compound used for this esterification is composed of one or more compounds containing at least one alcoholic hydroxyl group. 10% by weight or more of this hydroxyl group-containing compound,
A hydroxyl group-containing compound having an alkyl or alkenyl group having 4 to 9 carbon atoms (hereinafter referred to as a C _{4 to} C ₉ hydroxyl group-containing compound).

Examples of the above C _{4 to} C ₉ hydroxyl group-containing compound include saturated or unsaturated straight-chain or branched-chain containing alcohols obtained by reduction of natural fatty acids and synthetic alcohols obtained from olefins and polyolefins. An aliphatic alcohol having a C _{4 to} C ₉ alkyl group or an alkenyl group; an aliphatic alcohol epoxide adduct obtained by adding an epoxide compound such as ethylene oxide, propylene oxide, butylene oxide, glycidol or styrene oxide to these aliphatic alcohols; ethylene oxide, propylene oxide, a polyalkylene glycol is a polymer of alkylene oxides such as butylene oxide, having a C ₄ -C ₉ alkyl or alkenyl group derived from such natural fatty acids or olefins or polyolefins case And the like monoester esterified with fatty acids.

In the hydroxyl group-containing compound used for esterification
If the proportion of the C _{4 to} C ₉ hydroxyl group-containing compound is less than 10% by weight, or if all the alkyl groups of this hydroxyl group-containing compound have 3 or less carbon atoms, sufficient lubricity cannot be obtained. On the other hand, when 10% by weight or more of the hydroxyl group-containing compound is composed of a compound having an alkyl group or an alkenyl group having 10 or more carbon atoms, the releasing property of the hydrocarbon chain causes the adhesiveness by an epoxy adhesive or the like. Is damaged.
Further, depending on the processing conditions, the lubricity is too high, and surface strains and wrinkles occur during plastic working.

The esterification rate of this esterified product is 5 equivalent% or more with respect to the carboxyl group (including the free carboxyl group and the carboxyl derivative group) in the molecule of the maleic acid-styrene copolymer. The esterification rate is preferably 10 to 90 equivalent%, particularly preferably 20 to 70.
Equivalent%. When the esterification rate is less than 5 equivalent%, the amount of C _{4 to} C ₉ hydroxyl group-containing compound introduced into the copolymer is small,
Sufficient lubricity cannot be obtained. On the other hand, if the esterification rate exceeds 90 equivalent%, the hydrophilicity tends to be poor. In this case, a hydroxyl group-containing compound having a highly hydrophilic oxyethylene chain or amine salt moiety in the molecule is introduced,
It is preferable to take appropriate hydrophilicity imparting means such as esterification of a polyol ethylene oxide adduct or the like with an excess amount of hydroxyl groups to leave hydroxyl groups so that the cleaning and removability is not deteriorated. In this way, a completely esterified product having an esterification rate of 100% can be used for the purpose of the present invention.

The esterification method for obtaining the esterified product of the present invention is not particularly limited, and various industrially practicable esterification methods can be adopted. For example, as a usual esterification method, a copolymer and a hydroxyl group-containing compound are mixed in a nitrogen atmosphere in the presence or absence of a suitable solvent, and if necessary, sulfuric acid, p-toluenesulfonic acid, or the like. There is a method of adding an esterification catalyst and heating at 80 to 250 ° C. for esterification, or a method of dropping a hydroxyl group-containing compound into a heated copolymer to perform esterification in the same manner. In addition, the esterification rate of the maleic anhydride copolymer is 50 mol%.
When the esterification is carried out at less than 1, the esterification can be carried out at a lower temperature by utilizing the ring-opening reaction of the carboxylic acid anhydride moiety in the copolymer. Furthermore, in the case of a maleic acid ester copolymer such as a methyl ester, it can be easily esterified by utilizing a transesterification reaction.

The organic lubricating coating composition of the present invention contains the above esterified product or salt thereof as an essential component.
Usually, an aqueous composition comprising a composition in which this essential component is dissolved, emulsified or dispersed in a suitable liquid medium and water is used as the medium is desirable.

The salt of the esterified product used in the present invention is a maleic acid in the copolymer molecule, such as a salt obtained by neutralizing the remaining unreacted unreacted carboxyl group or carboxylic acid anhydride group with a basic compound. Is a compound having a chemical structure in which the carboxyl group derived from is neutralized with a basic compound. This has the advantage that the hydrophilicity can be further increased as compared with the unneutralized esterified product, and the production of the water-based lubricating coating agent composition and the cleaning and removal of the lubricating coating after plastic working are easier. Further, by using an amine salt using an organic amine as the basic compound, it is possible to increase the adhesion of the lubricating coating to the metal thin plate.

The basic compound used for producing the esterified salt may be either an organic compound or an inorganic compound. For example, there are nitrogen-containing compounds such as ammonia, amines and polyamines, and metal compounds such as alkali metals and alkaline earth metals. As the nitrogen-containing compound,
Ammonia; Aliphatic amines such as methylamine, dimethylamine, trimethylamine; monoethanolamine,
Alkanolamines such as triethanolamine; aromatic amines such as aniline and morpholine; polyamines such as ethylenediamine and polyethyleneimine; and adducts of these nitrogen-containing compounds with the epoxide compounds. As the metal-based compound, potassium, sodium,
Lithium, calcium, magnesium, aluminum,
Inorganic compounds of metals forming carboxylates such as zinc, iron, nickel, cobalt, tin, lead and copper are preferable, and these metals, metal oxides, metal hydroxides, metal chlorides,
Metal carbonates, hydrates and the like can be used.

The neutralization method for obtaining the salt of the esterified product of the present invention is not particularly limited, and various industrially practicable neutralization methods can be adopted. For example, in the case of a carboxyl derivative group such as a carboxylic acid anhydride, which contains an esterified product and a basic compound in water and heated at 50 to 80 ° C. for neutralization,
A salt of an esterified product can be obtained by, for example, heating at 90 ° C. to obtain a neutralized product. Further, an aqueous composition in which the salt of the esterified product is dissolved, emulsified or dispersed in water can be obtained by these neutralization methods.

The organic lubricating coating composition of the present invention is preferably an aqueous composition as described above, but toluene,
Hydrocarbons such as xylene and kerosene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as methyl butyl ether and diethylene glycol monomethyl ether; esters such as ethyl acetate; organic solvents such as alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol Alternatively, a solvent-based composition using a mixed solvent of an organic solvent and water as a medium can be used. As a result, advantages such as shortening of work time for forming a film and reduction of heating and drying temperature can be obtained. Further, although the workability is great, the above esterified product or its salt can be directly melted and applied.

The concentration of the esterified product or salt thereof in the composition of the present invention is not particularly limited as long as a coatable composition is obtained, but in the case of an aqueous composition, it is usually 1 to 50% by weight, The solvent-based composition can have a higher concentration than this.

In addition to the above-mentioned esterified products or salts thereof, pigments and / or dyes as colorants can be added to the organic lubricating coating composition of the present invention. When the colorant is not contained, the obtained lubricating film is a transparent thin film, and therefore it cannot be easily judged from the appearance whether or not it has been applied. By including a colorant, the lubricating film exhibits a unique color, and the presence or absence of coating can be easily discriminated from the appearance. Even in the case of single-sided coating, the coated surface can be easily identified. Also, if the color is changed for each product type, it is useful for identifying the product type.

Suitable coloring pigments for this purpose are iron oxide pigments, titanium oxide pigments, carbon, etc., and dyes are azo, anthraquinone, indigo, phthalocyanine, carbonyl, quinoneimine, methine, quinoline. Examples thereof include dyes such as system dyes and nitro dyes, but the dyes are not limited to these. The amount of these colorants added is
The amount based on the dry weight (solid content weight) of the organic lubricating coating agent composition is 1 to 30% by weight in the case of a pigment, preferably 3 to
10% by weight is 0.1 to 3% by weight in the case of a dye, preferably 0.3 to 1% by weight. When the addition amount of the pigment and / or the dye is small, the color development is dull, and it becomes difficult to identify the color. On the other hand, if the amount is too large, the lubricity and the cleaning / removal solution for the film may deteriorate, which is not preferable.

In addition to the above, the organic lubricating coating composition of the present invention may further contain additives such as oiliness agents, extreme pressure agents and rust preventives which are added to usual lubricants.

The lubricated metal sheet coated with the organic lubricating coating composition of the present invention can be easily produced by a usual coating method which is industrially used. For example,
Application is performed by applying the above coating agent composition to a thin metal plate by dipping, roll coating, curtain coating, spraying, electrostatic coating, electrodeposition coating, etc., and drying the coating by heating or irradiation with active energy rays. can do. The coating is usually applied to both sides of the thin metal plate, but may be applied to only one side depending on the application.

From the viewpoint of lubricity and cleaning removability, the organic lubricating coating agent composition of the present invention is preferably applied so that the dry coating amount per one surface is 0.1 to 10 g / m ² . In particular, a deposit amount of 0.2 to 3 g / m ² is preferable.

A rust preventive oil may be further applied on the organic lubricating film. The application of rust preventive oil is useful for improving the rust preventive property and maintaining the lubricity during storage of the thin metal plate. The metal thin plate coated with the lubricant film agent composition of the present invention has blocking resistance, and the films on the surface or the film and the metal thin plate do not stick to each other during storage. Therefore, the composition of the present invention is
It is suitable for use in the production of a lubricated metal thin plate which is previously applied to a metal thin plate at an appropriate stage up to the consumer. Next, the present invention will be described in more detail with reference to Examples.

[0036]

Example 1 Table 1 shows the composition and molecular weight of the maleic acid-styrene copolymer, and the hydroxyl group-containing compound used for esterification, for the inventive and comparative organic lubricating coating compositions used in this example. The type, the ratio of use, the esterification rate, the basic compound used for salt formation, and the neutralization rate are shown.

The esterified product of the maleic acid-styrene copolymer shown in Table 1 or a salt thereof is added to water to give a solid content of 10%.
An organic lubricating coating agent composition was prepared by dissolving it to a weight percentage of 0.7%, and a 0.7 mm thick sheet of alloyed molten zinc was used to obtain a dry coating film of 1 g / m ² using a bar coater. It was applied to both sides of a plated steel sheet and dried with hot air to produce a lubricated steel sheet. Commercially available rust preventive oil was further applied to the lubricated steel sheet, and the lubricity, alkali cleaning removability and adhesiveness were evaluated.

Lubricity : Using the high surface pressure U forming die shown in FIG. 1, the plate-pressing pressure was changed to form the lubricated steel plate, and the measured forming load P (kgf) and the plate-pressing pressure were measured. H (k
The friction coefficient was calculated from the relationship with gf / cm ² ). The value of the friction coefficient is preferably within the range of 0.150 to 0.250, and if it exceeds 0.250, the lubricity is insufficient and the steel sheet surface is likely to be scratched or cracked by press working. On the other hand, when the coefficient of friction is less than 0.150, the pressing of the plate is not effective depending on the press machine, and surface strain and wrinkles are likely to occur. Prior to each molding test, the surface of the mold was polished using Emery Polishing Paper # 600.

Alkali cleaning / removability : A lubricated steel sheet was immersed in a 2% by weight aqueous solution of an alkaline degreasing agent (Nippon Paint, Surf Cleaner SD 550) used in automobile coating lines at 40 ° C. for 1 minute and then with running water. It was washed with water, and the wettability of the steel sheet surface at that time was evaluated according to the following three grades.

○: Good wettability (wet area 100%) △: Small water repellency (wet area 80% or more) ×: Large water repellency (wet area less than 80%) Adhesiveness with adhesive : Used in automobile coating lines The commercially available epoxy adhesive is used to bond the lubricated surfaces of two lubricated steel plate specimens together, and the adhesive is applied at 170 ° C.
After heat-curing for 30 minutes, the adhesive strength was obtained and evaluated by a T-shaped peel test according to JIS K 6829. The required adhesive strength is 6 kgf or more.

Table 2 shows the above test results. As can be seen from the results shown in Table 2, the steel sheet coated with the organic lubricating coating agent composition of the present invention has appropriate lubricity and excellent alkali detergency and adhesiveness. On the other hand, among the comparative examples,
In Comparative Example 2, the lubricity is too high, surface distortion and wrinkles occur, and the adhesive strength is low. Comparative Example 5 has insufficient lubricity and poor alkali cleaning removal property, and other Comparative Examples have insufficient lubricity.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

Example 2 5% by weight of red iron oxide (red iron oxide pigment) was added to the organic lubricating coating agent composition of composition No. 1 in Table 1 used in Example 1 for coloring, When the obtained colored composition was applied to both sides of an alloyed hot-dip galvanized steel sheet in the same manner as in Example 1 and dried with hot air, the formed lubricating film exhibited a red color, and the presence or absence of application was easy only by the appearance color. I was able to identify.

Similarly, when a colored organic lubricating coating agent composition containing 5% by weight of a yellow iron oxide pigment instead of red iron oxide is applied to an alloyed hot-dip galvanized steel sheet, the lubricating coating exhibits a yellow color. The presence or absence of coating was easily recognizable only by the appearance.

Further, 0.2% by weight of Congo red (red dye) based on the dry weight of the organic lubricating coating composition of composition No. 2 in Table 1 was added to the composition for coloring, and the obtained coloring composition was obtained. When applied to an electrogalvanized steel sheet to give a film thickness of 0.5 g / m ² as in Example 1, the formed lubricating film has a red color, and the presence or absence of the application can be easily identified by the appearance color alone. It was

With respect to the plated steel sheet having the red and yellow colored lubricating coatings obtained above, the appearance color could be distinguished between red and yellow. Therefore, forming different lubrication coatings on different base steel sheets helps to identify the type.
The plated steel sheet having the colored lubricating coating obtained above was tested for lubricity, washability and adhesion in the same manner as in Example 1, but
There was no significant change compared to Example 1.

When the coating was not colored as described above, it was substantially difficult to distinguish the coated surface and the uncoated surface by their appearance.

[0049]

When the organic lubricating coating agent composition of the present invention is applied to a thin metal plate, a lubricating coating having strong adhesion is formed on the thin metal plate. The lubricity of this film is due to the alkyl group or alkenyl group introduced into the maleic acid-styrene copolymer, and the strong adhesion to the surface of the metal sheet is due to the presence of the carboxyl group or its salt on the surface of the metal sheet. It seems to be strongly adsorbed chemically. This lubricating film is
Since it has high lubricity as well as high hydrophilicity, it is possible to clean and remove the lubricating film with an aqueous cleaning liquid after plastic working. In particular, when the hydroxyl group-containing compound used has a long ethylene oxide chain, the cleaning / removing property is further improved.
Further, by limiting the number of carbon atoms of the alkyl group or alkenyl group of the hydroxyl group-containing compound to 4 to 9, the releasability due to the alkyl group or alkenyl group introduced into the maleic acid-styrene copolymer is suppressed, and the adhesive agent It is possible to secure the adhesiveness. This lubricating film also has good blocking resistance, and a metal thin plate having this film can be stored without any trouble.

When a pigment and / or a dye is added to the organic lubricant film agent composition of the present invention for coloring, the presence or absence of coating can be easily identified. In addition, if each type is colored with a different color, the product type can be easily identified.
Therefore, there is no mistake in the material, and the press work can be performed smoothly.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a high surface pressure U-forming test die used for measuring a friction coefficient in Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C10N 20:00 Z 8217-4H 30:00 Z 8217-4H 30:06 30:20 40:24 A 8217-4H Z 8217-4H 50:02 60:00 (72) Inventor Masamitsu Matsumoto 4-53-3 Kitahama, Chuo-ku, Osaka City Sumitomo Metal Industries, Ltd. (72) Inventor Naomichi Matsuda 4 Ohjo Nishimachi, Amagasaki City −12-1 (72) Inventor Ishi ▲ Saki ▼ Koji 2-8-19, Ojo Nishimachi, Amagasaki City (72) Inventor Shinji Nakamura 14-30, Uedanaka Town, Nishinomiya City

Claims (3)

[Claims] 1. A copolymer of maleic acids and styrenes having a molar ratio of maleic acids: styrenes of 1:99 to 75:25 and styrenes as a main monomer is treated with at least one hydroxyl group-containing compound. An organic lubricating coating agent composition comprising an esterified product or a salt thereof esterified at an esterification rate of 5 equivalent% or more based on a carboxyl group in a copolymer as an essential component, and 10% by weight of the hydroxyl group-containing compound. The above is a hydroxyl group-containing compound having an alkyl group or an alkenyl group having 4 to 9 carbon atoms, which is an organic lubricating coating agent composition. 2. The organic lubricating film agent composition according to claim 1, further comprising a pigment and / or a dye. 3. A lubrication-treated thin metal plate coated with the organic lubricating coating agent composition according to claim 1 or 2 on at least one surface thereof.