JP4880880B2 - Lubricant composition for processing water-based metal materials - Google Patents

Description

  The present invention relates to a lubricant composition for processing a water-based metal material and a method for producing a warm-pressed metal material using the same. More specifically, the present invention is excellent in workability, degreasing property, work environment and the like, and is suitably used in the plastic working field of various metal materials, particularly magnesium-based and aluminum-based non-ferrous metal materials, particularly in the warm press working field. The present invention relates to a lubricant composition for processing a water-based metal material, and a method for efficiently producing a warm-pressed metal material using the lubricant composition.

In the conventional metal plastic processing, the friction between the metal material and the tool or mold is reduced, the plastic deformation of the metal is performed more smoothly, the tool or mold is cooled and protected, and the metal material from the tool or mold is used. Lubricants are used to facilitate mold release.
By the way, magnesium alloys are the lightest among practical metals and have excellent properties such as electromagnetic wave shielding properties, so that their use is expanding in recent years. Currently, magnesium alloys are mainly processed by die casting and thixomolding, but these processing technologies require surface grinding after processing and are difficult to handle thin products. Has been pointed out.

On the other hand, press working using a magnesium alloy plate as a work material can be applied to thin-walled products and does not require surface grinding after processing. However, since the magnesium alloy has poor workability at room temperature, the temperature during press working is usually 200 to 300 ° C. If the lubrication performance of the press oil is insufficient during the press working, the work material may be broken or adhered to the mold. For this reason, a dedicated lubricant is used.
As described above, the lubricant used for plastic working of the magnesium alloy plate is a lubricating performance that suppresses breakage of the workpiece and adhesion to the mold in the temperature range of 100 to 300 ° C. It is necessary to show the performance which can be removed by a normal degreasing process while showing high processing performance by having.

In warm processing of magnesium alloy sheets, solid coating lubricants have been used so far, but in this case, film removal treatment is necessary after processing, and simple degreasing treatment cannot be performed, so that it is possible to avoid inferior productivity. There wasn't.
On the other hand, with oil-based lubricants, the mold is heated to about 300 ° C. during pressing, so that oil smoke is generated, which causes environmental problems, inferior processability, processing scratches, and cracks. There is. Therefore, there has been a problem that oil-based lubricants are difficult to use.
As a plastic working lubricant for magnesium alloys that has excellent degreasing properties and does not cause deterioration of the working environment, 7 to 20% by mass of an alkali metal salt of a fatty acid having 10 to 18 carbon atoms and an alkaline earth of a fatty acid having 12 to 18 carbon atoms A composition comprising an aqueous solution containing an alkali metal hydroxide in an amount of 2 to 6% by mass of a metal salt and an amount of pH 12 to 14 is disclosed (for example, see Patent Document 1). However, the plastic working lubricant for magnesium alloy does not contain a solid lubricant, and the plastic workability is not always satisfactory.

JP 2003-89797 A

  Under such circumstances, the present invention is excellent in workability, degreasing property, work environment and the like, and in the plastic working field of various metal materials, particularly magnesium-based and aluminum-based non-ferrous metal materials, particularly in the warm press working field. It is an object of the present invention to provide a suitably used lubricant composition for processing a water-based metal material, and a method for producing a warm-pressed metal material using this lubricant composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that an aqueous composition containing a solid lubricant and a specific compound is suitable for the purpose as a lubricant composition for processing an aqueous metal material. And applying the above composition to the surface of the metal material to be processed, heat-treating it to evaporate the moisture, and then pressing the metal material to be processed efficiently, so that the hot-pressed metal material is efficiently obtained. It has been found that it can be manufactured. The present invention has been completed based on such findings.

That is, the present invention
(1) It contains at least one selected from (A) a solid lubricant, (B) (a) an organic carboxylic acid metal salt, and (b) an organic phosphoric acid or boric acid ester metal salt. Lubricant composition for processing water-based metal materials,
(2) Further, (C) the lubricant composition for processing an aqueous metal material according to (1) containing a nitrogen-containing compound (3) The solid lubricant of component (A) is polytetrafluoroethylene, calcium carbonate, zinc oxide The above-mentioned (1) or (2) water-based metal material processing lubricant composition, which is at least one powder selected from molybdenum disulfide and graphite,
(4) The organic carboxylic acid metal salt of component (B) (A) is selected from among alkali metal salts and alkaline earth metal salts of monocarboxylic acids, and alkali metal salts and alkaline earth metal salts of polyvalent carboxylic acids. The lubricant composition for processing a water-based metal material according to any one of the above (1) to (3), which is at least one selected
(5) The organic phosphoric acid or boric acid ester metal salt of component (B) (B) is an alkali metal salt or alkaline earth metal salt of phosphoric acid or phosphite, and an alkali metal salt of orthoboric acid ester. And a lubricant composition for processing an aqueous metal material according to any one of the above (1) to (3), which is at least one selected from alkaline earth metal salts,

(6) The aqueous metal according to any one of (1) to (5) above, wherein the nitrogen-containing compound of component (C) is at least one selected from benzotriazoles, thiadiazoles, amines, amides and imides Lubricant composition for material processing,
(7) The lubricant composition for processing an aqueous metal material according to any one of (1) to (6), further comprising (D) at least one selected from a corrosion inhibitor, an antioxidant, a bactericidal agent and an antifoaming agent. object,
(8) The lubricant composition for processing an aqueous metal material according to any one of the above (1) to (7), wherein the content ratio of the component (A) and the component (B) is 10:90 to 95: 5 by mass ratio. object,
(9) The lubricant composition for processing a water-based metal material according to any one of (1) to (8), wherein the water content is 10 to 50% by mass,
(10) The lubricant composition for processing a water-based metal material according to any one of (1) to (9), wherein the pH is in the range of 3 to 12.

(11) Water-based metal material processing according to any one of (1) to (10), which is for warm pressing, cold pressing, forging, drawing, ironing, bending, rolling, or rolling. Lubricant composition,
(12) The lubricant composition for water-based metal material processing according to (11), which is for warm press processing of a non-ferrous metal material,
(13) The lubricant composition for processing a water-based metal material according to the above (11) or (12), wherein the non-ferrous metal material is a magnesium alloy,
(14) The lubricant composition of the above (1) to (10) is applied to the surface of the metal material to be processed, heat-treated to evaporate water, and then the metal material to be processed is pressed. (15) The above-mentioned (15) the evaporation of moisture in the lubricant composition applied to the surface of the metal material to be processed is carried out on a heated press mold and the press treatment is performed as it is ( 14) a method for producing a warm-pressed metal material,
Is to provide.

According to the present invention, it is excellent in workability, degreasing property, work environment and the like, and is suitably used in various metal materials, particularly in the plastic working field of magnesium-based and aluminum-based non-ferrous metal materials, particularly in the warm press working field. A lubricant composition for processing a metal material can be provided.
Moreover, according to the method of the present invention, by using the lubricant composition, it is possible to efficiently produce a warm-pressed metal material.

The lubricant composition for processing an aqueous metal material of the present invention comprises (A) a solid lubricant, (B) (a) an organic carboxylic acid metal salt, and (b) an organic phosphoric acid or boric acid ester metal salt. And at least one selected from (C) a nitrogen-containing compound and / or (D) a corrosion inhibitor, an antioxidant, a bactericidal agent and an antifoaming agent, and optionally an aqueous medium. It is an aqueous composition.
Examples of the solid lubricant as the component (A) in the lubricant composition of the present invention include powders such as polytetrafluoroethylene, calcium carbonate, zinc oxide, molybdenum disulfide, and graphite. These may be used singly or in combination of two or more, but non-black powders are more workable than black powders such as molybdenum disulfide and graphite. In particular, polytetrafluoroethylene (Teflon) powder is preferable in terms of work environment and lubrication performance. The average particle size of the solid lubricant powder is not particularly limited, but is usually about 0.1 to 20 μm, preferably in the range of 0.2 to 7 μm from the viewpoints of dispersibility and lubricating performance. Examples of the polytetrafluoroethylene (Teflon) powder include “Lublon L-2” (trade name, manufactured by Daikin Industries) as a commercially available product.
Further, the content of the component (A) is preferably 5 to 80% by mass based on the total amount of the composition from the viewpoint of lubricating performance.

On the other hand, the organic carboxylic acid metal salt which is the component (B) (A) has a function of imparting degreasing properties, and an alkali metal salt or an alkaline earth metal salt of a monocarboxylic acid or a polyvalent carboxylic acid may be used. These may be used singly or in combination of two or more.
Examples of the alkali metal salt include sodium salt, potassium salt, and lithium salt. Examples of the alkaline earth metal salt include calcium salt, barium salt, and magnesium salt.
In this organic carboxylic acid metal salt, the hydrocarbon group excluding the carboxylic acid group has a carbon number per carboxylic acid group of preferably 17 or less, more preferably 12 or less from the viewpoint of degreasing properties. Examples thereof include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. Among these, an alkyl group and an alkenyl group are particularly preferable. The alkyl group and alkenyl group may be linear, branched or cyclic. Furthermore, when an alkali metal salt and an alkaline earth metal salt are compared, the alkali metal salt is preferable from the viewpoint of degreasing properties.

  Examples of the organic carboxylic acid metal salt include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, Aliphatic monocarboxylic acids such as myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, crotonic acid, octenoic acid, decenoic acid, oleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline Acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexdecanedioic acid, octadecanedioic acid, 7-ethylhexadecanedicarboxylic acid, sodium salt of aliphatic polycarboxylic acid such as butanetetracarboxylic acid, potassium salt, Alkali metal salts such as lithium salts, calcium salts, barium salts, magnesium salts, etc. It can be exemplified alkaline earth metal salts. Of these, alkali metal salts are preferred.

When using an alkali metal salt, the molar ratio of the organic carboxylic acid to the alkali metal is preferably in the range of 0.5: 1 to 1: 0.5.
In addition, the organic phosphoric acid or boric acid ester metal salt which is the component (B) (b) has a function of imparting degreasing properties, such as an alkali metal salt of phosphoric acid or phosphorous acid (phosphonic acid) ester, Alkaline earth metal salts, alkali metal salts of orthoborates, alkaline earth metal salts, and the like can be used. These may be used individually by 1 type, and may be used in combination of 2 or more types.
Examples of the alkali metal salt include sodium salt, potassium salt, and lithium salt. Examples of the alkaline earth metal salt include calcium salt, barium salt, and magnesium salt.
Further, examples of the hydrocarbon group constituting the ester include an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having a total carbon number of preferably 32 or less, more preferably 24 or less. Of these, alkyl groups and alkenyl groups are particularly preferred. The alkyl group and alkenyl group may be linear, branched or cyclic. Furthermore, when an alkali metal salt and an alkaline earth metal salt are compared, the alkali metal salt is preferable from the viewpoint of degreasing properties.

  Here, as the phosphoric acid ester metal salt, for example, dimethyl phosphoric acid, diethyl phosphoric acid, dipropyl phosphoric acid, dibutyl phosphoric acid, dihexyl phosphoric acid, dioctyl phosphoric acid, didecyl phosphoric acid, dilauryl phosphoric acid, diallyl phosphoric acid, dioctenyl phosphoric acid, didecenyl phosphoric acid, etc. Sodium salt, potassium salt, lithium salt of dialkyl or dialkenyl phosphate ester; monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monobutyl phosphate, monohexyl phosphate, monooctyl phosphate, monodecyl phosphate, monolauryl phosphate Monosodium salt of monoalkyl or monoalkenyl phosphate such as monopalmityl phosphate, monostearyl phosphate, monoallyl phosphate, monooctenyl phosphate, monodecenyl phosphate, monooleyl phosphate, Potassium salt, monolithium salt (monoalkyl or monoalkenyl hydrogen phosphate monoalkali metal salt), etc .; disodium salt, dipotassium salt, dilithium salt (monoalkyl or monoalkenyl phosphate dialkali) of the above monoalkyl or monoalkenyl phosphate ester Metal salt).

  Examples of the phosphite metal salt include dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, dihexyl phosphite, dioctyl phosphite, didecyl phosphite, dilauryl phosphite. Acid, diallyl phosphite, dioctenyl phosphite, didecenyl phosphite, etc. dialkyl or dialkenyl phosphite sodium, potassium, lithium, etc .; monomethyl phosphite, monoethyl phosphite, monopropyl phosphite Acid, monobutyl phosphorous acid, monohexyl phosphorous acid, monooctyl phosphorous acid, monodecyl phosphorous acid, monolauryl phosphorous acid, monopalmityl phosphorous acid, monostearyl phosphorous acid, monoallyl phosphorous acid, monooctenyl phosphorous acid, Monoalkyl such as monodecenyl phosphorous acid and monooleyl phosphorous acid Is a monosodium salt, monopotassium salt, monolithium salt (monoalkyl or monoalkenyl hydrogen phosphite monoalkali metal salt) of monoalkenyl phosphite; disodium salt of the monoalkyl or monoalkenyl phosphite , Dipotassium salts, dilithium salts (monoalkyl or alkenyl phosphite dialkali metal salts) and the like.

Furthermore, examples of orthoboric acid ester metal salts include various alkali metal salts of dialkyl or dialkenyl orthoborates, dialkali metal salts and monoalkali metal salts of monoalkyl or monoalkenyl orthoborates.
In this component (B) (b), when an alkali metal salt is used, the molar ratio of the above phosphate ester, phosphite ester, orthoborate ester (acids) and alkali metal is 0.5: 1 to 1: 0. A range of .5 is preferred.
In the composition of the present invention, as the component (B), the component (a) and the component (b) may be used singly or may be used in appropriate combination. In addition, the content ratio of the component (A) and the component (B) is preferably in the range of 10:90 to 95: 5 in terms of mass ratio from the viewpoint of lubrication performance (workability) and degreasing properties, and further 15:85. A range of ˜95: 5 is preferred.

Furthermore, the nitrogen-containing compound as the component (C) has an action of imparting rust prevention properties, and benzotriazoles, thiadiazoles, amines, amides, and the like can be used. These may be used individually by 1 type, and may be used in combination of 2 or more types.
Examples of benzotriazoles include benzotriazole, N-dialkylaminomethyl-1,2,3, -benzotriazole, and N-methylbenzotriazole. Examples of thiadiazoles include 2, 5-bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3-tetramethylbutyldithio) -1,3,4-thiadiazole, and the like. it can.

Examples of amines include primary, secondary, and tertiary alkylamines, alkenylamines, and cycloalkylamines, such as butylamine, dibutylamine, tributylamine, hexylamine, dihexylamine, trihexylamine, cyclohexylamine, and dicyclohexyl. Amine, tricyclohexylamine, octylamine, dioctylamine, trioctylamine, decylamine, didecylamine, tridecylamine, laurylamine, dilaurylamine, trilaurylamine, palmitylamine, dipalmitylamine, tripalmitylamine, stearyl Examples include amine, distearylamine, tristearylamine, oleylamine, dioleylamine, trioleylamine and the like.
Examples of amides include dioctylamide and N-oleyl sarcosine, and examples of imides include polybutenyl succinimide. Of these, benzotriazoles and amines are preferable, and benzotriazole and dioctylamine are particularly preferable.
In addition, the content of the component (C) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the composition, in terms of rust prevention and efficiency.

In the composition of the present invention, as desired, various additives conventionally used in lubricant compositions for processing aqueous metal materials, such as corrosion inhibitors, antioxidants, bactericides, and antifoaming agents, as component (D) Etc. can be appropriately contained.
In the composition of the present invention, the pH is preferably in the range of 3 to 12, and more preferably in the range of 6 to 10, from the viewpoints of processability and degreasing properties. Moreover, 10-50 mass% is preferable on the basis of the composition whole quantity, and, as for content of water, the range of 15-40 mass% is more preferable. When the water content is in the above range, an appropriate lubricating film is formed on the lubricating surface, and good lubrication performance can be obtained, and handleability is also good.
The lubricant composition of the present invention can be used in the fields of plastic working such as warm pressing, cold pressing, forging, drawing, ironing, bending, rolling, and rolling. In addition, as a workpiece, various metals such as steel, stainless steel, magnesium alloy, aluminum or an alloy thereof, titanium or an alloy thereof, copper, or an alloy thereof can be used.

The lubricant composition of the present invention is particularly suitably used for warm pressing of non-ferrous metal materials such as magnesium alloy, aluminum or its alloy, titanium or its alloy, steel and the like.
In the present invention, the surface of the metal material to be processed is coated with the above-described lubricant composition of the present invention, heat-treated to evaporate the water, and then the metal material to be processed is pressed to warm A method for producing a pressed metal material is provided.
In the above method, it is possible to employ a method in which moisture in the lubricant composition applied to the surface of the metal material to be processed is evaporated on a heated press die and pressed as it is.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The performance of the lubricant composition was evaluated according to the following procedure.
(1) Lubricity (a) Deep drawing test Using a magnesium alloy plate with a thickness of 1 mm, a deep drawing test was conducted under the conditions of a punch speed of 10 mm / s, a punch diameter of 32 mm, a die diameter of 34.4 mm, and a temperature of 250 ° C. The presence or absence of scratches and the presence or absence of cracks were visually observed.
(B) Boundary test Using a magnesium alloy sheet, steel ball: SUJ2 [3/16 inch (4.8 mm)], load: 49 N, speed: 20 mm / s, sliding distance: 50 mm, temperature: 200 ° C. The boundary coefficient test was performed to determine the friction coefficient.
(2) Degreasing property A sample was applied to a magnesium alloy sheet (80 mm × 60 mm), dried at 200 ° C. for 5 minutes, washed with water for 10 minutes, and the area percentage of the degreased portion was determined.
(3) Working environment The case where the handleability of the lubricant composition and the stains around the machine did not become a problem was evaluated as ◯, and the case where the problem occurred was evaluated as x.
(4) Rust prevention test A magnesium alloy sheet was coated with oil, and the presence or absence of corrosion on the sheet surface after one month was evaluated by an eaves exposure test.

Examples 1-11 and Comparative Examples 1-3
Lubricant compositions having the compositions shown in Tables 1 and 2 were prepared and their performance was evaluated. The results are shown in Tables 1 and 2.

(note)
A-1: Teflon powder [manufactured by Daikin Industries, trade name “Lublon L-2”, average particle size of 5 μm or less]
A-2: Calcium carbonate A-3: Zinc oxide A-4: Molybdenum disulfide A-5: Graphite I-1: 7-ethylhexadecanedicarboxylic acid K salt (acid: alkali molar ratio = 1: 0.9)
I-2: Sodium decanoate (acid: alkali molar ratio = 1: 0.9)
I-3: Palmitic acid K salt (acid: alkali molar ratio = 1: 0.9)
B-4: Oleic acid K salt (acid: alkali molar ratio = 1: 0.9)
As can be seen from Table 1, in Examples 7 and 8, molybdenum disulfide and graphite are used as the component (A), respectively, so that the working environment is poor. As can be seen from Table 2, Examples 10 and 11 have poor degreasing properties because fatty acid alkali metal salts having a large number of carbon atoms are used. Further, in Comparative Example 4, white smoke is generated by oil mist and there is a risk of ignition.

Examples 12-21
Lubricant compositions having the compositions shown in Tables 3 and 4 were prepared and their performance was evaluated. The results are shown in Tables 3 and 4.

(note)
A-5: 7-ethylhexadecanedicarboxylic acid K salt (acid: alkali molar ratio = 1: 0.5)
A-6: 7-ethylhexadecanedicarboxylic acid K salt (acid: alkali molar ratio = 1: 0.7)
A-7: 7-ethylhexadecanedicarboxylic acid K salt (acid: alkali molar ratio = 1: 1.3)
A-8: 7-ethylhexadecanedicarboxylic acid K salt (acid: alkali molar ratio = 1: 1.15)
B-1: Mono, dioctyl phosphate K salt (acid: alkali molar ratio = 1: 0.9)
B-2: Monolauryl phosphate K salt (acid: alkali molar ratio = 1: 0.9)
B-3: Monobutyl phosphate K salt (acid: alkali molar ratio = 1: 0.9)
C-1: Benzotriazole C-2: Dioctylamine In addition, A-1 to A-5 and i-1 to i-5 are the same as the footnotes in Tables 1 and 2.

The lubricant composition for processing a water-based metal material of the present invention is excellent in workability, degreasing property, work environment, and the like, and is used for various metal materials, particularly magnesium-based and aluminum-based non-ferrous metal materials, especially in the warm press. It is suitably used in the processing field.

Claims (11)

(A) at least one selected from solid lubricants, (B) (a) alkali metal salts and alkaline earth metal salts of monocarboxylic acids, and alkali metal salts and alkaline earth metal salts of polyvalent carboxylic acids An organic carboxylic acid metal salt, (b) an alkali metal salt or alkaline earth metal salt of phosphoric acid or phosphite, and an alkali metal salt or alkaline earth metal salt of orthoboric acid ester An organic phosphoric acid-based or boric acid-based ester metal salt , and 10-50% by mass of water, and a water-based metal material processing lubricant composition for warm press processing of a non-ferrous metal material .   The lubricant composition for processing a water-based metal material according to claim 1, further comprising (C) a nitrogen-containing compound.   The lubrication for processing an aqueous metal material according to claim 1 or 2, wherein the solid lubricant of component (A) is at least one powder selected from polytetrafluoroethylene, calcium carbonate, zinc oxide, molybdenum disulfide and graphite. Agent composition. The nitrogen-containing compound of component (C) is at least one selected from benzotriazoles, thiadiazoles, amines, amides, and imides. 4. For processing an aqueous metal material according to any one of claims 1 to 3 . Lubricant composition. Furthermore, (D) Lubricant composition for water-system metal material processing in any one of Claims 1-4 containing at least 1 type chosen from a corrosion inhibitor, antioxidant, a disinfectant, and an antifoamer. The content ratio of (A) component and (B) component is 10: 90-95: 5 by mass ratio, The lubricant composition for aqueous metal material processing in any one of Claims 1-5 . (B) The aqueous system according to any one of claims 1 to 6 , wherein the number of carbon atoms per carboxylic acid group of the hydrocarbon group excluding the carboxylic acid group in the organic carboxylic acid metal salt is 17 or less. Lubricant composition for processing metal materials. The lubricant composition for processing a water-based metal material according to any one of claims 1 to 7 , wherein the pH is in the range of 3 to 12. The lubricant composition for processing an aqueous metal material according to any one of claims 1 to 8 , wherein the non-ferrous metal material is a magnesium alloy. A warm, characterized in that the lubricant composition according to any one of claims 1 to 9 is applied to a surface of a metal material to be processed, and after the heat treatment is performed to evaporate water, the metal material to be processed is pressed. A method for producing a pressed metal material. The method for producing a warm-pressed metal material according to claim 10 , wherein the evaporation of water in the lubricant composition applied to the surface of the metal material to be processed is performed on a heated press die and pressed as it is.