JPH09221691A - Composition for forming lubricating membrane easily removable by water washing and its formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the objective composition excellent in forming processability, easily removable by a water washing and useful for a lubricating treatment of a metallic material by using a specified acrylic copolymer or a specified polyester, a cellulose ether, a wax emulsion and water therein. SOLUTION: The objective composition comprises (A) a water-soluble copolymer composed of a vinyl monomer having only a carboxyl group as an ionic function group or its salt, vinyl sulfonic acid, a styrene sulfonic acid, a (meth) acrylate containing sulfonic acid or a (meth)acrylamide or these salt and having an average molecular weight (Ma) of 10,000-150,000, or a water-soluble polyester composed of a dihydroxy compound containing an alkylene glycol structure and a polyfunctional carboxylic acid and having the Ma of 10,000-500,000, (B) a water-soluble cellulose ether having the Ma of 10,000-100,000, (C) a wax emulsion having a softening point of 50-160 deg.C and water. The weight ratio of components (A) to (B) is 1/9-9/1 and the amount of the component (C) is 2-90wt. pts. based on 100 pts. of the total of the components (A) and (B). The lubricating membrane is formed by coating and drying the composition on a metallic material, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating film formed on the surface of a metal material having a lubricating performance capable of withstanding a high degree of forming processing, and the lubricating film remaining on the metal surface after forming processing is washed with water. The present invention relates to a lubricating film composition that can be easily removed by a method and a method for forming a lubricating film.

[0002]

2. Description of the Related Art Conventionally, metal materials such as cold-rolled steel, hot-rolled steel, stainless steel, zinc or aluminized steel, titanium, aluminum, aluminum alloy and other metal material plates, pipes and wires are used for home appliances, automobiles. It is widely used by processing and assembling manufacturers of building materials and the like, and it is formed and processed by pressing, forging, drawing, etc., according to each application. These molded materials are used for electrical or molten plating, chemical conversion treatment such as phosphate or chromate treatment, anodization treatment, and painting for the purpose of imparting functionality such as anticorrosion, wear prevention, and decoration. Is often applied.

In the above-mentioned forming process, in order to impart sufficient processability, a metal material having a lubricating film such as a press oil or a wax formed on the surface of the metal material in advance is supplied to the forming process. A method in which a lubricant such as press oil or wax is applied on site immediately before processing is generally performed. However, when the conventional lubricant as described above is used, the molding apparatus and the peripheral portion thereof are contaminated by oil stains and dust scattering, thus forming a very bad environment in terms of pollution prevention and occupational safety and health. Further, in recent years, a cleaning method using an organic solvent such as CFC or trichloroethane for removing a lubricant such as a press oil and a wax remaining after molding has become a serious problem in recent years as a cause of global environmental pollution. Furthermore, these organic solvents have been pointed out as the causative substances that destroy the ozone layer, and their use has been greatly restricted, or the tendency to completely abolish them is increasing.

A molding method using a volatile lubricating oil which does not require cleaning has been studied, but since this lubricating oil is volatile, it has problems such as deteriorating the working environment hygiene.

Many proposals have been made for a method of using waxes as a lubricant. For example, JP-A-62-8
In Japanese Patent No. 1221, montan wax, carnauba wax, oxidized polyethylene wax, and microcrystalline wax are included as main components, and a lubricant containing a surfactant, a metal soap, and a solid lubricant is applied to a metal material and dried. A method of forming a lubricating film and subjecting it to cold plastic working is disclosed. In addition, JP-A-3-134094
The publication discloses an ester of a hindered alcohol having a neo skeleton and a saturated fatty acid having 10 to 14 carbon atoms,
A lubricant containing a synthetic ester wax having an iodine value of 10 or less, an acid value of 5 or less, a hydroxyl value of 10 or less, and a melting point of 50 ° C. or less as a main component is applied to a metal material and dried to form a lubricating film. A method of performing cold plastic working is disclosed.

[0006] In all of these conventional methods, a lubricant containing a wax as a main component is used, and therefore, the ability of the formed lubricating film to be removed by washing with water is poor. Further, since the temperature of the mold in the actual continuous press work reaches 80 ° C. or more due to the frictional heat between the tool and the processing material and the heat generated by the plastic deformation of the processing material, the molten wax will not be melted by the mold or the processing material. There is also a problem that it is unavoidable that it scatters from the tool and contaminates the periphery of the processing equipment and the work environment.

On the other hand, as a measure for reducing the pollution around the processing equipment and the work environment due to the scattering of oil-based and wax-based lubricants, Japanese Patent Laid-Open No. 50-37966 discloses polyethylene glycol and polyvinyl alcohol having specific molecular weights. There is disclosed a method in which and are used as a main component of a lubricating coating and polyethylene oxide is used as a lubricating additive.
In this method, since polyvinyl alcohol has a hard and brittle property as a film, polyethylene glycol is used in combination with it to try to improve the lubricity of the lubricating film. However, since a film formed from a lubricant using polyvinyl alcohol has a low dissolution rate in water, it is necessary to wash with an alkali cleaner to remove the lubricating film after processing. When the alkaline cleaner cleaning is used, a water cleaning step is required to remove the cleaning liquid remaining on the metal material, which complicates the lubricating film removal step. In order to solve such problems, simplify the cleaning process, and reduce the cost, there is a demand for the development of a lubricant capable of forming a film capable of removing the film only by washing with water.

As a method of forming a lubricating film which can be easily removed by washing with water, JP-A-6-100877 discloses that a polyamide is contained as an essential component, and a water-soluble polyester or a water-soluble polysaccharide is contained as a main component. Also disclosed is a lubricant composition containing a wax having a softening point of 50 ° C. to 130 ° C. as a lubricating additive. However, the lubricating film formed from this composition cannot be completely removed without a physical accelerating operation such as spraying in water washing. The above composition cannot be applied to those that cannot be removed.

[0009]

The lubricating coating composition according to the prior art simultaneously satisfies the performance of imparting sufficient moldability and the ability of the lubricating coating to be removed by washing with water so that the film can be removed even under washing with immersion and standing. Things have not been obtained yet. The present invention, the lubricating film formed on the metal material has excellent moldability, the lubricating film after the molding process, stirring,
It can be easily removed by the immersion static water washing method that does not perform a physical accelerating operation such as spraying, and the subsequent post-treatment such as electric or molten plating treatment, chemical conversion treatment such as phosphate or chromate, and anode. An object of the present invention is to provide a composition for a lubricating film of a metal material and a method for forming a lubricating film, which does not adversely affect the treatments such as oxidation treatment and coating.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a lubricating film that simultaneously satisfies the molding processability and the film removal method by washing with water, and as a result, as a resin component on the surface of a metal material, One or more selected from vinyl monomers having only a carboxyl group as an ionic functional group or a salt thereof, vinyl sulfonic acid, styrene sulfonic acid, and (meth) acrylate having an ionic sulfonic acid group in the molecule And a (meth) acrylamide, a polymer with one or more kinds of monomers selected from the following, or a salt thereof, a water-soluble acrylic copolymer having an average molecular weight of 10,000 to 150,000, and a dihydroxy compound having an alkylene glycol structure: Selected from water-soluble polyesters having an average molecular weight of 30,000 to 500,000 selected from esters with polycarboxylic acids One or more, a water-soluble cellulose ether, a wax emulsion, and a composition for a lubricating coating containing water as a main component are removed by rinsing with immersion and water, and a lubricating coating that does not adversely affect the post-treatment is formed. The present invention was newly found and the present invention was completed.

The composition for forming a lubricating film which can be easily removed by washing with water according to the present invention is selected from the following components: (a) (i) a vinyl monomer having only a carboxyl group as an ionic functional group in the molecule and a salt thereof. And one or more of them, vinyl sulfonic acid, styrene sulfonic acid, (meth) acrylate and (meth) acrylamide having a sulfonic acid group as an ionic functional group in the molecule, and a salt of the sulfonic acid group-containing compound. Water-soluble acrylic copolymers having an average molecular weight of 10,000 to 150,000, and (i
i) an ester of a dihydroxy compound having an alkylene glycol structure and a polyvalent carboxylic acid, which is 30,000 to
One or more selected from water-soluble polyesters having an average molecular weight of 500,000, (b) one or more water-soluble cellulose ethers having an average molecular weight of 10,000 to 100,000, (c) 50 to 160 ° C. And (d) water, wherein the weight ratio (a) / (b) of component (a) to component (b) is 1/9 to 9/1. , The weight of the pure wax contained in the component (c) is 2 to 100 parts by weight of the total amount of the components (a) and (b).
It is characterized by being 90 parts by weight. In the lubricating film-forming composition of the present invention, the wax emulsion of the component (c) is preferably selected from polyolefin wax emulsions. The composition for forming a lubricating film of the present invention further comprises the following additional component: (e) a water-soluble compound of a metal having a valence of 2 or more, wherein the content of the additional component (e) is equal to that of the composition for forming a lubricating film. It is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content. The method for forming a lubricating film of the present invention, which can be easily removed by washing with water, is such that the composition for lubricating film of the present invention is applied to the surface of a metal material so that the total solid content is 0.2 to 10.0 g / m ^2. It is characterized in that a lubricating film is formed by applying and then heat-drying it so that the maximum temperature of the surface of the metal material reaches 50 to 200 ° C.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. The lubricating film-forming composition of the present invention contains the component (a) and the component (b) as resin components. The water-soluble acrylic copolymer (i) used as the component (a) is at least one selected from vinyl monomers or salts thereof having only a carboxyl group as an ionic functional group in the molecule, vinyl sulfonic acid, styrene. A copolymer of sulfonic acid, (meth) acrylate having a sulfonic acid group as an ionic functional group in the molecule and (meth) acrylamide, and one or more selected from the salts of the sulfonic acid group-containing compound, It has an average molecular weight of 10,000 to 150,000.

The compounds of the following formulas (A) and (B) are shown as examples of the carboxyl group-containing vinyl monomer and salts thereof.

[Chemical 1][Wherein M is a hydrogen atom, an alkali metal atom or
Represents an ammonium group, R¹Is -H atom or -CH_ThreeBase
Represents, R^TwoIs -CH_TwoCH_Two-Group, -C (CH _Three)_TwoC
H_TwoRepresents a group or a phenylene group]

The compound of the above formula (A) includes acrylic acid, methacrylic acid and salts thereof, and the compound of the formula (B)
Examples of the compound include 2-acrylamidopropionic acid and salts thereof.

The compounds of the following formulas (C) to (G) are shown as examples of the sulfonic acid group-containing monomer and salts thereof.

Embedded image [However, in the above formula, M, R ¹ and R ² are the same as above, and R ³ represents a phenylene group]

Examples of the compound of the above formula (C) include 2-acryloyloxyethanesulfonic acid and salts thereof, and examples of the compound of the formula (D) include 2-acrylamido-2.
-Methyl propane sulfonic acid, 4-acrylamidobenzene sulfonic acid and salts thereof, and the like, the formula (E)
Examples of the compound include 5-acryloyloxy-3-sulfovaleric acid and salts thereof, examples of the compound of formula (F) include vinyl sulfonic acid and salts thereof, and examples of the compound of formula (G) include styrene. Examples include sulfonic acid and salts thereof.

The water-soluble acrylic copolymer (i) used as the component (a) is, for example, at least one selected from the compounds of the examples (A) and (B), and the compounds of the formulas (C) to (C).
At least one selected from the compound (G) is activated by radicals generated from a radical polymerization initiator such as azopisisobutylnitrile, and after a growth process in which polymerization reactions are sequentially performed to generate a polymer, hydroquinone, It can be produced by using a polymerization terminator such as phenothiazine to eliminate radicals from the system. Further, in the formulas (A) to (G), a copolymer is produced from a monomer in which all M are H atoms, and an unneutralized carboxyl group and an unneutralized sulfonic acid group in the obtained copolymer are obtained. May be neutralized with Na or NH ₄ . When the water-soluble acrylic copolymer used as the component (a) has a degree of neutralization of carboxyl groups and sulfonic acid groups of 10 to 80%, the resulting copolymer has a good balance of lubricity and removability with water. It is preferable because it exhibits excellent performance.

In the present invention, the water-soluble acrylic copolymer (a)
-The average molecular weight of (i) is adjusted in the range of 10,000 to 150,000. When the average molecular weight of the water-soluble acrylic copolymers (a)-(i) is less than 10,000, the strength of the lubricating coating obtained from the lubricant composition containing the same is insufficient, and the lubricating performance is reduced. On the other hand, when the average molecular weight exceeds 150,000,
The viscosity of the lubricant composition becomes excessively high, which makes coating difficult.

Vinylsulfonic acid, styrenesulfonic acid, and (meth) acrylate and (meth) acrylamide having an ionic sulfonic acid group in the molecule in the water-soluble acrylic copolymer (i) used as the component (a). The content of one or more kinds of monomers selected from, or a salt thereof is preferably 10 to 60 mol%, more preferably 25 to 50 mol%. This content is 1
When it is less than 0 mol%, the lubricating coating obtained from the obtained lubricant composition has a low dissolution rate in water, resulting in insufficient removability with water. On the other hand, when it exceeds 60 mol%, the hygroscopicity of the obtained lubricating film becomes large, so that the lubricating property is deteriorated. In addition, the above formula (C)
The use of the copolymer containing sulfoethyl (meth) acrylate as a copolymerization component of the above makes it possible for the resulting lubricating coating to exhibit particularly excellent lubricity even in an environment where the humidity is high and moisture is easily absorbed.

As the water-soluble polyesters (ii) of the dihydroxy compound having an alkylene glycol structure and the polyvalent carboxylic acid used as the component (a), for example, 2
A dihydroxy compound having an average molecular weight of 1,000 to 30,000 obtained by addition-polymerizing an alkylene oxide containing ethylene oxide to an organic compound having one active hydrogen group, and a polyvalent carboxylic acid or an anhydride thereof or a lower alkyl ester thereof. It is obtained by reacting.
This water-soluble polyester (ii) has a high average molecular weight of 30,000 to 500,000.

When the average molecular weight of the water-soluble polyester (a)-(ii) is less than 30,000, the solubility in water is sufficient but the hygroscopicity is increased, and the water-soluble polyester is formed from a lubricant composition containing the same. The lubricating film also inevitably increases hygroscopicity, which is not preferable. Further, when the average molecular weight exceeds 500,000, the dissolution rate in water decreases, so that a lubricating film formed from a lubricant composition containing this has insufficient removability by washing with water after molding. It is not preferable because it has a drawback.

Water-soluble polyester (a) as described above
Examples of the organic compound having two active hydrogen groups used in the production of (ii) include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butylamine, polytetramethylene glycol, and aniline. Further, as the ethylene oxide-containing alkylene oxide to be addition-polymerized with the organic compound having two active hydrogen groups, for example, ethylene oxide alone or ethylene oxide,
Other alkylene oxides such as propylene oxide,
Alternatively, a mixture of butylene oxide and the like can be used.

The dihydroxy compound obtained by subjecting the above-mentioned organic compound having two active hydrogens and ethylene oxide-containing alkylene oxide to block addition polymerization by a known method has an average molecular weight of 1,000 to 1,000.
It is necessary to be 30,000. If the average molecular weight is less than 1000, the amount of polyvalent carboxylic acid required for polyester production increases, and the solubility of the resulting polyester in water is insufficient, which is not preferable. Further, if the average molecular weight exceeds 30,000, the ester content decreases and the film forming property deteriorates, which is not preferable.

The polycarboxylic acid or its anhydride or its lower alkyl ester to be reacted with the above-mentioned dihydroxy compound is, for example, oxalic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, sulfophthalic acid, sebacic acid. , Adipic acid or their anhydrides, or their dimethyl or diethyl esters, or the anhydride of pyromellitic acid. The esterification reaction of these polyvalent carboxylic acids or their anhydrides or their lower alkyl esters (hereinafter collectively referred to as polyvalent carboxylic acid compounds) with the above dihydroxy compounds is usually carried out in a closed container.
Further, the mixing ratio of the dihydroxy compound and the polycarboxylic acid compound may be appropriately set so that the average molecular weight of the obtained water-soluble polyester is 30,000 or more. On the other hand, in order to set the average molecular weight to 500,000 or less, the degree of pressure reduction of the closed container used for the reaction may be appropriately adjusted.

Next, the water-soluble cellulose ether (b) used as another one of the resin components will be described. The basic body of the cellulose molecule is C ₆ H ₁₀ O _5, which has three active —OH groups per glucose unit.
The OH group has low reactivity due to the inherent crystallinity of cellulose. However, when this is treated with an aqueous solution of caustic soda to form alkali cellulose and then reacted with an etherifying agent such as methyl chloride, a cellulose ether is obtained. When only methyl chloride is used as the etherifying agent, methyl cellulose having a methoxy group content (weight) of 27 to 32% is obtained. Further, the thermal gelation temperature can be increased by using propylene oxide together with methyl chloride as an etherifying agent and introducing a hydroxypropoxy group in place of a methoxy group. In that case, the content (weight) of the methoxy group of the obtained methylcellulose is 28 to 30%, and the content (weight) of the hydroxypropoxy group is 4 to 12%.
In addition, when polypropylene oxide is used as an etherifying agent, hydroxypropyl cellulose is obtained as a nonionic cellulose derivative.

The average molecular weight of the water-soluble cellulose ether (b) used in the present invention is adjusted to 10,000 to 100,000. If the average molecular weight is less than 10,000, the solubility of the obtained cellulose ether in water is sufficient, but the hygroscopicity becomes excessive, so that the lubricating performance of the film obtained from the composition containing the cellulose ether becomes insufficient. The average molecular weight is 10
If it exceeds 10,000, the obtained cellulose ether will be difficult to hydrate, and the dissolution rate in water will be reduced. Therefore, the film obtained from the composition containing this will be difficult to remove by washing with water, and Since the viscosity of the composition becomes excessively high, coating becomes difficult, which is not preferable.

In the composition of the present invention, the weight ratio (a) / (of the component (a) consisting of the water-soluble acrylic copolymer and / or the water-soluble polyester as the resin component and the water-soluble cellulose ether (b). b) is adjusted to 1/9 to 9/1. If this ratio is less than 1/9, the lubricating performance of the obtained coating film is sufficiently exhibited, but the film removability by washing with water is insufficient, which is not preferable. On the other hand, if this weight ratio exceeds 9/1, the strength of the resulting lubricating coating will be insufficient, which will result in a decrease in lubrication performance and an increase in the hygroscopicity of the coating. More preferable weight ratio (a) /
(B) is 1/4 to 4/1.

However, the resin component having such a structure alone is not yet sufficient to obtain the desired lubricity. In general, wax and inorganic lubricants are known as additives for improving lubricity. In order to impart a higher degree of lubrication performance to the coating film obtained from the water-based lubricant composition of the present invention, it is appropriate to add a wax emulsion, examples of which include hydrocarbon-based, fatty acid amide-based and ester-based coatings. , Alcohol-based and metal soap-based wax emulsions.

The wax component of the wax emulsion (c) used in the composition of the present invention has a softening point of 50.
The thing of -160 degreeC, more preferably 80-140 degreeC is used. When the softening point of the wax is less than 50 ° C., there is a problem that the lubricating film adheres to the mold and the moldability deteriorates in a continuous press in which the mold temperature rises. When the softening point is higher than 160 ° C, the wax is not deformed during processing, resulting in insufficient lubricity.

As the wax emulsion (c),
By selecting and using wax that exists on the surface of the resin film rather than the presence of dispersed wax in the formed resin film, wear due to contact between the surface of the molded product and the mold can be reduced. It is possible to maximize the lubricating effect. A polyolefin wax emulsion is preferably used as a constituent component of the wax that imparts such characteristics. Types of polyolefin wax include petroleum wax and synthetic hydrocarbon wax. Petroleum waxes having paraffin wax having an average molecular weight of 30 to 500 and microcrystalline wax having an average molecular weight of 500 to 700 are synthetic hydrocarbons having a softening point of 50 to 160 ° C. As a wax, the average molecular weight is 100.
Examples include polyethylene wax and polypropylene wax of 0 to 10,000.

The blending amount of the wax emulsion (c) is
The wax content is preferably 2 to 90 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the resin component. When the content of the pure wax component is less than 2 parts by weight with respect to 100 parts by weight of the resin component, sufficient lubricity cannot be obtained due to the obtained composition, and when it exceeds 90 parts by weight, film removability by water washing is obtained. Becomes insufficient.

The composition of the present invention is a water-based composition, and the components (a), (b) and (c) are dissolved or dispersed (emulsified) in the water component (d).

The composition of the present invention may contain known additives for water-based resins. For example, a film-forming aid, a leveling agent, a defoaming agent, a wetting agent, a coating property improving agent such as a thickening agent, and a pigment or a dye for coloring a film can be added. Further, in order to improve the weldability of the metal material coated with the lubricating film, a conductive powder such as metal powder such as carbon black, silver and nickel and metal oxide such as potassium titanate are added to the lubricating composition. You can also do it.

A water-soluble compound of a divalent or higher valent metal may be added as an additional component (e) to the composition of the present invention. It is possible to increase the dissolution rate of the lubricating coating in water and improve the wet resistance by the divalent or higher valent metal ions in the additional portion (e). Examples of metal ions exhibiting those improving effects include ions of chromium, aluminum, magnesium, zinc, cobalt, nickel and the like. Generally, these metal ions are incorporated into the composition as water-soluble compounds such as salts of nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and silicofluoric acid.

The amount of the metal ion added is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total solid content of the composition. If the addition amount is less than 0.01 parts by weight, the effect of the addition component (e) may not be clearly exhibited, and if it exceeds 5 parts by weight, the lubricating performance of the obtained composition may deteriorate.

Next, a method for forming a lubricating film which is easy to wash and remove with water using the lubricating film composition of the present invention will be described. The composition for lubricating film of the present invention is applied to the surface of a metal material so that the total solid content is 0.2 to 10.0 g / m ² , and then the maximum humidity of the surface of the metal material is applied. 50-
A lubricating film is formed by heat drying to reach 200 ° C. The method of applying the lubricating composition includes dipping, spraying,
Examples include roll coaters and electrostatic coating. If this coating amount is less than 0.2 g / m ² , the lubricity of the resulting coating will be insufficient, and if it exceeds 10.0 g / m ² , the removability of the coating due to water washing will be unfavorable. If the maximum temperature reached by the metal material during heating and drying is less than 50 ° C, the lubricity of the resulting film will be insufficient, and if it exceeds 200 ° C, the film removability by water washing will be insufficient. When the composition of the present invention is applied to the surface of a metal material, it is preferable to clean the surface by alkali cleaning or the like, which can prevent cissing during application of the composition.

[0037]

The present invention will be described more specifically with reference to the following examples. Examples 1 to 13 and Comparative Examples 1 to 8 1. Preparation of Test Pieces (1) Test Material The following commercially available aluminum plate and cold-rolled steel sheet were processed in the following steps and used as test materials. A. Aluminum plate material (JIS A 1100F) having a plate thickness of 1 mm and dimensions of 200 × 300 (mm) B. Cold rolled steel sheet with plate thickness = 0.8 mm and dimensions = 200 x 300 (mm) (JIS G3141)

(2) Process: Alkaline degreasing Fine cleaner 4377 (trademark, manufactured by Nippon Parkerizing Co., Ltd.) Concentration: 20 g / liter Liquid temperature: 60 ° C. Spray: 20 seconds: Washing tap water: 20 seconds: Squeeze roll squeezing : Hot air drying: Application of a lubricant composition containing the composition shown in Tables 1 to 4 Group roll coater (wet amount = 10 ml / m ² ).
Was applied. However, the film adhesion amount was adjusted according to the solid content concentration in the lubricant. : Drying It was dried by heating at an ambient temperature of 200 ° C. for 7 seconds (reached plate temperature = 70 ° C.).

2. Performance test (1) Workability (lubricity) A high-speed cylindrical deep-drawing tester was used to perform a cylindrical deep-drawing test under the conditions of wrinkle holding pressure = 1.0 ton and deep drawing speed = 30 m / min. The ratio was calculated and evaluated. For example, in deep drawing with a blank diameter of 80 mmφ and a punch diameter of 40 mmφ, the limit drawing ratio is 2.00. <Evaluation Criteria> Symbol <A. Aluminum plate material><B. Cold-rolled steel sheet> ────────────────────────────── ◎: Limit drawing ratio 2.1 or more 2.4 or more ○: Limit Drawing ratio 2.0 or more 2.3 or more △: Limiting drawing ratio 1.9 or more 2.2 or more ×: Limiting drawing ratio less than 1.9 Less than 2.2

(2) Film removability test A test plate cut to a size of 70 × 150 (mm) was immersed in deionized water at 40 ° C. in a non-stirred state for 5 minutes and allowed to stand to remove the film. After that, the amount of carbon remaining on the surface (mg / m ² ) was measured by a surface carbon adhesion amount measuring device, and the film removability (removal rate) was calculated by the following formula and evaluated.

[0041]

[Equation 1]

(3) Phosphate Treatability A test plate cut to a size of 70 × 150 (mm) was immersed in deionized water at a temperature of 40 ° C. without stirring for 5 minutes and allowed to stand. Phosphate treatment was performed by the process of 1 and the appearance of the film was visually evaluated. (A) Surface preparation: Preparene ZN (trademark, manufactured by Nippon Parkerizing Co., Ltd.) Concentration: 1.0 g / liter Liquid temperature: 20 ° C. Immersion: 20 seconds (b) Chemical conversion treatment: Palbond L3081 (trademark, Nippon Parkerizing Co., Ltd.) Product: Concentration: Free acidity 1.0pt, total acidity 22.0pt, accelerator concentration 2.8pt Liquid temperature: 43 ℃ Immersion: 90 seconds (C) Washing: Tap water pouring, 20 seconds (D) Drying: 100 ℃ Ambient temperature, 120 seconds <Evaluation Criteria> Good: No unevenness at all. Δ: Some unevenness occurs. X: Significant unevenness occurs.

(4) Anodizing Property An aluminum material was cut into a size of 70 × 150 (mm), and a test plate was immersed in deionized water at a temperature of 40 ° C. without stirring for 5 minutes and allowed to stand to form a film. After the removal, hot air drying was performed. Next, the test plate is immersed in a 15 wt% sulfuric acid aqueous solution at a temperature of 20 ° C., and the current density is 1 A / dm while stirring with air.
^An alumite film was formed on the surface under test by applying electricity at ^{2 for} 30 minutes. After this was dried with hot air, the appearance of the alumite film was visually evaluated. <Evaluation Criteria> A: There is no unevenness. Δ: Some unevenness occurs. X: Significant unevenness occurs.

3. Test Results Tables 1 to 4 show the compositions of the compositions of Examples 1 to 13 and Comparative Examples 1 to 8, the coating adhesion amount, and the performance test results. Tables 1 and 2 show the case where the test material is an aluminum plate, and Tables 3 and 4 show the case where the test material is a cold rolled steel sheet. The resin species of the compositions used in Examples and Comparative Examples and the content type of the polyolefin wax are as follows.

(1) Resin Type In Tables 1 to 4, each monomer used in the synthesis of the water-soluble acrylic copolymer is abbreviated as follows. A: acrylic acid monomer B: methacrylic acid monomer C: 2-methacryloyloxyethanesulfonic acid monomer D: 2-acrylamido-2-methylpropanesulfonic acid monomer E: 4-methacrylamidobenzenesulfonic acid monomer F: styrenesulfonic acid monomer

(2) Description of component symbols [Symbol: AC1] Monomer A 70 mol% and monomer C
30 mol% of water-soluble copolymer (average molecular weight: 30,000),
An aqueous solution obtained by subjecting sodium to a neutralization degree of 50%. [Symbol: AC2] Monomer A 50 mol% and Monomer B
An aqueous solution obtained by subjecting a water-soluble copolymer of 10 mol% and a monomer D of 40 mol% (average molecular weight: 50,000) to sodium neutralization with a neutralization degree of 50%. [Symbol: AC3] Monomer A 65 mol% and Monomer B
An aqueous solution obtained by subjecting a water-soluble copolymer of 20 mol% and a monomer E of 15 mol% (average molecular weight: 80,000) to partial sodium neutralization with a neutralization degree of 30%. [Symbol: AC4] 60 mol% of monomer A and monomer D2
An aqueous solution obtained by subjecting a water-soluble copolymer of 0 mol% and 20 mol% of monomer F (average molecular weight: 30,000) to sodium neutralization with a neutralization degree of 50%. [Symbol: AC5] 70 mol% of monomer A and monomer B1
An aqueous solution obtained by subjecting a water-soluble copolymer of 0 mol% and a monomer C of 20 mol% (average molecular weight: 50,000) to sodium neutralization with a neutralization degree of 80%. [Symbol: PE] Water-soluble polyester, polyethylene glycol (average molecular weight 30
00) Addition polymerization of 2000 parts of ethylene oxide with 200 parts of a dihydroxy compound having a weight average molecular weight of 32000 was carried out, and 16 parts of dimethyl isophthalate was added thereto to carry out a demethanol reaction to obtain an average weight molecular weight of 250,000. Water-soluble polymer polyester. [Symbol: HPC] Hydroxypropyl cellulose having an average molecular weight of 40,000. [Symbol: MC] Methylcellulose having an average molecular weight of 20,000. [Symbol: PVA] Completely saponified polyvinyl alcohol having an average molecular weight of 30,000. [Symbol: EAA] Ethylene / acrylic acid = 80/20 weight ratio copolymer neutralized with ammonia, 20% by weight in water
Emulsified by concentration.

(3) Lubricant type [Symbol: WAX1] A polyethylene wax emulsion having a wax softening point of 118 ° C. [Symbol: WAX2] A polyethylene wax emulsion having a wax softening point of 105 ° C. [Code: WAX3] Paraffin wax emulsion having a wax softening point of 55 ° C. [Code: WAX4] Zinc stearate wax emulsion having a wax softening point of 140 ° C. [Code: WAX5] Calcium stearate wax emulsion having a wax softening point of 180 ° C. [Code: O] Commercial press oil, specific gravity = 0.972, viscosity (40 ° C) = 868 cst, pour point = -2.5 ° C, acid value =
0.84

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

Tables 1 and 2 show examples and comparative examples when an aluminum plate material was used as a test material and Tables 3 and 4 used a cold rolled steel sheet as a test material. The types of coating compositions used in Examples 1 to 13 and Comparative Examples 1 to 8 are the same when the test material is an aluminum plate material and when it is a cold rolled steel sheet. In Examples 1 to 13 according to the present invention, the workability, film removability, chemical conversion treatment appearance, and anodizing treatment appearance of the obtained lubricated metal materials were all good. On the other hand, Comparative Examples 2, 3, 4, and 5 are examples in which the coating composition components of the present invention are used, but the coating composition ratio is different from that of the present invention, and the resulting lubricating coatings have workability and coating removability. Both performances were unsatisfactory. Comparative Example 6 is an example in which a wax emulsion different in softening point from the present invention was used, and the workability of the obtained lubricating film was insufficient. Comparative Example 1 was based on the prior art, and the resulting lubricating coating was inferior in the ability to be washed with water, and the appearance of the chemical conversion treatment and the anodization treatment were also poor. Comparative Example 7 is the component (a)
In the example in which PVA different from the component (a) of the present invention was used instead of, the workability of the obtained lubricating film and the water-cleaning removability were poor. Comparative Example 8 is an example in which a self-emulsifying acrylic emulsion (EAA) and a wax (WAX2) as a lubricating component were used instead of the components (a) and (b), and the workability of the obtained lubricating film was good. However, since the removability by washing with water was extremely poor, the chemical conversion treatment layer and the anodizing treatment had poor appearance.

[0053]

By applying the composition for a lubricating coating of the present invention to a metal material by the method of the present invention, the resulting lubricating coating exhibits excellent moldability and the lubricating coating can be easily washed with water. Since it can be removed at any time, it has the characteristic that it does not adversely affect the processing performed thereafter. Therefore, the present invention is useful for a lubrication treatment when a metal material is subjected to molding and then various surface treatments are performed.

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Claims (4)

[Claims] 1. The following components: (a) (i) one or more selected from vinyl monomers having only a carboxyl group as an ionic functional group in the molecule and salts thereof, vinyl sulfonic acid, styrene sulfonic acid, and a molecule. A copolymer with (meth) acrylate and (meth) acrylamide having a sulfonic acid group as an ionic functional group therein and one or more selected from the salts of the sulfonic acid group-containing compound, Water-soluble acrylic copolymers having an average molecular weight of 150,000, and (i
i) an ester of a dihydroxy compound having an alkylene glycol structure and a polyvalent carboxylic acid, which is 30,000 to
One or more selected from water-soluble polyesters having an average molecular weight of 500,000, (b) one or more water-soluble cellulose ethers having an average molecular weight of 10,000 to 100,000, (c) 50 to 160 ° C. And (d) water, wherein the weight ratio (a) / (b) of component (a) to component (b) is 1/9 to 9/1. , The weight of the pure wax contained in the component (c) is 2 to 100 parts by weight of the total amount of the components (a) and (b).
90 parts by weight of a composition for forming a lubricating film, which can be easily removed by washing with water. 2. The lubricating film-forming composition according to claim 1, wherein the wax emulsion of the component (c) is selected from polyolefin wax emulsions. 3. The following additional component: (e) further containing a water-soluble compound of a divalent or higher valent metal, wherein the content of the additional component (e) is 100 parts by weight of the total solid content of the composition for forming a lubricating film. The composition for forming a lubricating film according to claim 1, which is 0.01 to 5 parts by weight with respect to. 4. The surface of the metal material according to claim 1, 2, or 3.
The composition for lubricating film according to 1.
It is applied so as to have a content of 10.0 g / m < ² >, and this is heated and dried so that the maximum temperature of the surface of the metal material reaches 50 to 200 [deg.] C. to form a lubricating film. A method for forming a lubricating film that is easy to use.