JP2002363591A - Solid lubricant for hydroforming and metal tube having solid lubricant layer - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] For a hydroform comprising a water-soluble or water-dispersible film-forming component having excellent performance in a well-balanced manner in terms of lubricity, degreasing property, emulsion resistance and other properties. Provide a solid lubricant and a metal tube using the same. SOLUTION: The organic polymer type rust inhibitor is 0.5 to 3.5%, higher fatty acid having a hydroxy group and / or its salt is 2 to 9%, and higher fatty acid amide lubricant is 0% by mass in terms of solid content. 0.5 to 2.5%, 22 to 87% of a ternary copolymer salt of α-olefin-maleic acid monoester / maleic acid monoester salt, which is a high molecular weight synthetic wax having a number average molecular weight of 6000 or more, a carboxyl group A solid lubricant for hydroforms, comprising a water-soluble or water-dispersible film-forming component comprising 10 to 75% of an organic polymer compound having the following formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid lubricant for plastic working of a metal tube and a metal tube having a solid lubricating layer, and more particularly to improving the formability of a metal tube by hydroforming. It has excellent emulsion resistance during molding by the hydroforming method, excellent rust resistance after molding, and its lubricating film has excellent water resistance to water drops such as rainwater, and also manufactures automotive parts. The present invention relates to a solid lubricant for hydroforming and a metal tube having a solid lubricating layer, which is also capable of being easily and completely removed in a pretreatment step of a chemical conversion treatment line.

[0002]

2. Description of the Related Art A metal tube has a straight initial shape basically having a uniform cross section. This is cut, bent, crushed, or expanded / contracted to perform secondary processing into a desired shape. However, there are cases where it is effective to finish in a tubular shape in advance and cases where it is difficult. From the standpoint of parts design and processing, the technology to replace with new pipe material was a development issue.

[0003] In recent years, the secondary processing technology using a material such as an electric resistance welded steel pipe has advanced, and among them, bulge processing and Tube Hydro-formi related to a processing method of an automobile part for forming a curved pipe into an irregular cross section have been developed.
ng technology is attracting attention. In such a processing method, as an influencing factor for defects such as breakage, wrinkles, and buckling,
It is considered that the bulge characteristics, mold shape, preforming state, hydraulic forming conditions, etc. of the raw tube are important.

[0004] Further, in various fields including the automobile industry, there is a growing expectation for hydroforming, which is a secondary molding technique for pipes, as one of the techniques for reducing the weight. In the case of forming mechanical structural parts by hydroforming, In order to ensure strength reliability, it is very important to control the thickness reduction of the product and make the thickness distribution uniform. The better the lubrication, the more the material supply, and the greater the processing, the greater the difference. . It is also reported that the better the lubricity, the more the reduction in wall thickness can be suppressed.

[0005] However, the solid lubricant for hydroforming is inevitably required to have a high lubricating property, and furthermore, it has resistance to the emulsion used for maintaining the hydraulic pressure during processing and degreasing after the pressing step. There is a problem with sex, causing various troubles.

Then, in order to cope with such a situation,
For example, Japanese Patent Application Laid-Open No. Hei 10-137863 proposes a surface-treated steel pipe for hydraulic bulging which is excellent in anti-seizure performance and lubricity which can be removed after forming.

However, in these techniques,
The viewpoint regarding the emulsion resistance at the time of molding is missing, and satisfactory performance has not been obtained. In hydroforming, a working fluid (emulsion liquid) for applying an internal pressure during processing is almost widely adhered to a mold. When a steel pipe is set in the mold, the emulsion liquid adheres to the outer surface of the steel pipe.

When the emulsion liquid adheres to the solid lubricating layer, the film is melted and it becomes impossible to maintain sufficient performance for processing. The effect is pronounced. In some cases, the mold is provided with a drain hole, but the emulsion liquid attached to the mold cannot be removed by itself. Further, if the workability is reduced and breakage occurs, the emulsion liquid flows out further into the mold, and a vicious cycle occurs in which the workability is reduced. Therefore, further improvement of this solid lubricant is necessary to maintain production stability in continuous processing.

[0009] The inventors of the present invention have investigated the disadvantages of lubricity and water resistance with respect to solid waxes such as higher alcohol esters of higher fatty acids and glycerides of higher fatty acids disclosed in JP-A-58-6579. Utilizing the technology of organic synthetic chemistry and polymer chemistry, we succeeded in synthesizing a new polymer synthetic wax with good water resistance, degreasing and lubricity. The used solid lubricant for metal plates is proposed in JP-A-6-299180.

However, the solid lubricant proposed in Japanese Patent Application Laid-Open No. 6-299180 using this high molecular weight synthetic wax could not obtain the performance required for the solid lubricant for hydroforming of the present invention.

[0011]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional solid lubricants and provides a hydroform having excellent properties in terms of high lubricity, emulsion resistance, degreasing property and other properties. It is an object to provide a solid lubricant and a metal tube having the solid lubricant layer.

[0012]

The present inventors have focused on the disadvantage of high lubricity, which is a disadvantage of the polymer synthetic wax proposed in JP-A-6-299180, and a metal stearate having a hydroxy group. The salt was successfully dissolved in water without deteriorating various properties, and the present invention was completed.

That is, according to the present invention, the organic polymer (A) -based rust preventive (a) is 0.5 to 3.5 in terms of mass percentage in terms of solid content.
%, Higher fatty acid having a hydroxy group (B) and / or a salt thereof (b) 2 to 9%, higher fatty acid amide (C) -based lubricant (c) 0.5 to 2.5%, number average molecular weight 6000
Salt (J) of terpolymer (G) of α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F), which is the above-mentioned high molecular weight synthetic wax (d).
A hydro-polymer comprising a water-soluble or water-dispersible film-forming component comprising from 22 to 87% of an organic polymer compound (H) having a carboxyl group and / or a salt thereof (e) from 10 to 75%. It is a solid lubricant for foam, and the polymer synthetic wax (d) has the following chemical formula

[0014]

Embedded image

[0015]

[Outside 2]

Is an alkyl alcohol having 4 to 14 carbon atoms, and an alkylene oxide having 2 to 3 carbon atoms,
These are the residues of the hydroxyl group of the polyoxyalkylene alkyl ether to which about 5 moles have been added, and may be the same or different.

M represents a residue of a basic substance, and m, n and t represent natural numbers. ) Is preferably a salt (J) of a terpolymer (G) of an α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F), and The present invention is a metal tube coated with the solid lubricant in a thickness of 0.4 to 15 g / m ² .

More specifically, the present invention provides the following (1) to
(29) is achieved.

(1) Organic polymer (A) -based rust preventive (a) 0.5 to 3.5% in terms of solid content mass percentage, higher fatty acid (B) having hydroxy group and / or salt thereof ( B) 2 to 9%, higher fatty acid amide (C) based lubricant (c) 0.5 to 2.5%, α-olefin (D) which is a high molecular weight synthetic wax having a number average molecular weight of 6000 or more (d) -Maleic acid monoester (E)-Maleic acid monoester salt (F), terpolymer (G) salt (J) 2
2 to 87%, a water-soluble or water-dispersible film-forming component comprising 10 to 75% of an organic polymer compound having a carboxyl group (H) and / or a salt thereof (e) (10). Solid lubricant for foam.

(2) The organic polymer (A) comprises an unsaturated alkyl and / or alkylene ester (a), an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) and an unsaturated carboxylic acid N, N
-The solid lubricant for hydroform according to the above (1), which comprises a dialkylaminoalkylene ester (c).

(3) The solid lubricant for hydroform according to the above (1) or (2), wherein the organic polymer (A) has a number average molecular weight of 8,000 to 50,000.

(4) The organic polymer (A) has 1 to 1 carbon atoms.
18 alkyl alcohols and / or 2-1 carbon atoms
8 alkylene alcohol (i) and an unsaturated carboxylic acid alkyl and / or alkylene ester (a) composed of an unsaturated carboxylic acid (filtrate) and 1 mole of an alkyl alcohol (ha) having 1 to 4 carbon atoms and ethylene oxide (Ni). )
And an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) composed of an unsaturated carboxylic acid (filtrate) having 9 to 30 moles of An unsaturated carboxylic acid N, N-dialkylaminoalkylene ester (c) comprising an N, N-dialkylaminoalkylene alcohol having an alkylene group having 2 to 3 carbon atoms and an unsaturated carboxylic acid (filtrate). The solid lubricant for a hydroform according to any one of the above (1) to (3).

(5) The organic polymer (A) is an alkyl alcohol having 1 to 18 carbon atoms and / or
Or an unsaturated alkyl carboxylate and / or alkylene ester (a) comprising an alkylene alcohol (i) having 2 to 18 carbon atoms and an unsaturated carboxylic acid (filtrate) 55 to 7
0%, a polyoxyethylene alkyl ether obtained by adding 9 to 30 mol of ethylene oxide to 1 mol of an alkyl alcohol having 1 to 4 carbon atoms, and an unsaturated carboxylic acid (filtrate). Saturated carboxylic acid polyoxyethylene alkyl ether ester (b) 5 to 20%
And an unsaturated carboxylic acid N comprising an N, N-dialkylaminoalkylene alcohol (having an alkylene group having 2 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms) and an unsaturated carboxylic acid (filtrate). Any one of the above (1) to (4), which is a terpolymer comprising 10 to 40% of an N-dialkylaminoalkylene ester (c).
The solid lubricant for hydroform according to any one of the above.

(6) The organic polymer rust preventive (a) comprises an organic polymer (A) having a number average molecular weight of 8,000 to 50,000 and an anticorrosive (d). The solid lubricant for a hydroform according to any one of (5).

(7) The anticorrosive (d) is at least one selected from the group consisting of polyphenolic carboxylic acids (e), azole compounds (f) and aromatic carboxylic acids having nitro groups (g). The solid lubricant for a hydroform according to the above (6), which is characterized in that:

(8) The organic polymer rust preventive (a) is selected from the group consisting of polyphenol carboxylic acids (e), azole compounds (f) and aromatic carboxylic acids having nitro groups (g). The solid lubricant for hydroform according to any one of the above (1) to (36), comprising at least one kind of anticorrosive agent (d) and an organic polymer (A).

(9) The organic polymeric rust inhibitor (a) comprises an alkyl alcohol having 1 to 18 carbon atoms and / or an alkylene alcohol having 2 to 18 carbon atoms (i) and an unsaturated carboxylic acid (filtrate). Polyoxyethylene alkyl ether (h) obtained by adding 9 to 30 moles of ethylene oxide to 1 mole of an alkyl and / or alkylene ester of an unsaturated carboxylic acid (a) and 1 mole of an alkyl alcohol having 1 to 4 carbon atoms. And an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) comprising an unsaturated carboxylic acid (filtrate) and N, N having an alkyl group having 1 to 4 carbon atoms and having an alkylene group having 2 to 3 carbon atoms. -Unsaturated carboxylic acid N, N-dialkylaminoalkylene comprising -dialkylaminoalkylene alcohol (he) and unsaturated carboxylic acid (filtrate) An organic polymer (A) having a number average molecular weight of 8,000 to 50,000, composed of an ester (c), a polyphenolic carboxylic acid (e), an azole compound (f), and an aromatic carboxylic acid having a nitro group (G) a solid lubricant for a hydroform according to any one of the above (1) to (8), which is a salt with at least one anticorrosive agent (d) selected from the group consisting of: Agent.

(10) The higher fatty acid (B) having a hydroxy group is replaced by stearic acid (h) having a hydroxy group.
And / or hydroxyalkylcarbamyl stearic acid (i) derived from stearic acid having an amino group, wherein the solid lubrication for a hydroform according to any one of the above (1) to (9), Agent.

(11) The higher fatty acid (B) having a hydroxy group and / or a salt thereof (b) is a hydroxyalkyl carboxy derivative derived from stearic acid (h) having a hydroxy group and / or stearic acid having an amino group. The hydroform according to any one of the above (1) to (10), which is a salt of an alkali metal (j) and / or an alkaline earth metal (k) of mil stearic acid (i). Solid lubricant.

(12) The solid lubricant for hydroform according to any one of the above (1) to (11), wherein the higher fatty acid amide (C) comprises a higher fatty acid and an amino acid (p). .

(13) The hydroform according to any one of the above (1) to (12), wherein the amino acid (p) forming the higher fatty acid amide (C) is L-lysine. Solid lubricant.

(14) The hydroid according to any one of the above (1) to (13), wherein the higher fatty acid amide (C) -based lubricant is N-ε-lauroyl-L-lysine. Solid lubricant for foam.

(15) Polymeric synthetic wax (d)
Has a melting point of 58 to 76 ° C according to the JIS K-0064 method.
The solid lubricant for hydroform according to any one of the above (1) to (14), wherein

(16) Polymeric synthetic wax (d)
Has a carboxyl group, and the amount of the carboxyl group is 55 to 80 KOHmg / g in terms of an acid value determined by an oil and fat analysis method.
The solid lubricant for hydroform according to any one of the above (1) to (15), wherein

(17) The above-mentioned (1) to (1), wherein the α-olefin (D) is a polymer synthetic wax (d) which is an α-olefin having 22 to 48 carbon atoms.
6) The solid lubricant for hydroform according to any one of 6).

(18) Maleic acid monoester (E)
Is a polyoxyalkylene alkyl ether obtained by adding 1 to 5 mol of an alkyl alcohol having 2 to 3 carbon atoms to an alkyl alcohol having 4 to 14 carbon atoms, and maleic acid comprising maleic acid. The solid lubricant for hydroform according to any one of the above (1) to (17), which is a polymer synthetic wax (d) which is an acid monopolyoxyalkylene alkyl ether ester (r).

(19) The maleic acid monoester salt (F) is an alkyl alcohol having 4 to 14 carbon atoms (C)
And an alkylene oxide having 2 to 3 carbon atoms
It is a salt (J) of maleic acid monopolyoxyalkylene alkyl ether ester (r) comprising 5 moles of polyoxyalkylene alkyl ether (ri) and maleic anhydride, wherein the salt (J) is an alkali metal (s) and The polymer synthetic wax (d), which is one or a mixture of two or more selected from alkaline earth metals (u), is described in any one of the above (1) to (18). Solid lubricant for hydroforms.

(20) Ternary copolymer (G) of α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F) constituting high-molecular synthetic wax (d) α-olefin (D) has 22 to 4 carbon atoms.
And maleic acid monoester (E) has 4 carbon atoms
Monoalkylene maleate monopolyoxyalkylene consisting of polyoxyalkylene alkyl ether (G) obtained by adding 1 to 5 moles of alkylene oxide (C) having 2 to 3 carbon atoms to (C) alkyl alcohol (C) and maleic anhydride The alkyl ether ester (r), the maleic acid monoester (E) salt (F) is a salt (J) of a maleic acid monopolyoxyalkylene alkyl ether ester (r), and the salt (J) is an alkali metal (S)
And a mixture of two or more selected from alkaline earth metals (u), and having a number average molecular weight of 6000 or more, according to any one of the above (1) to (19). Solid lubricant for hydroforms.

(21) The organic polymer compound (H) having a carboxyl group has a number average molecular weight of 50,000 to 300.
The solid lubricant for a hydroform according to any one of the above (1) to (20), wherein the solid lubricant is 000.

(22) Any one of the above (1) to (21), wherein the organic polymer compound (H) having a carboxyl group is a copolymer of an unsaturated carboxylic acid (filtrate). The solid lubricant for a hydroform according to the above.

(23) Unsaturated carboxylic acid (filtrate) constituting the organic polymer compound (H) having a carboxyl group
Is one or a mixture of two or more selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, wherein any one of the above (1) to (22) is used. Solid lubricant for hydroforms.

(24) The salt (e) of the organic polymer compound (H) having a carboxyl group is one or two selected from an alkali metal (s) and an alkaline earth metal (u).
(1) to (1) to (4) above, wherein
(23) The solid lubricant for hydroform according to any one of (23).

(25) The organic polymer compound (H) having a carboxyl group is an unsaturated carboxylic acid (filtrate), an unsaturated carboxylic acid ester (R), an unsaturated nitrile (O), and a hydroxyl group-containing unsaturated carboxylic acid ester. (1) to (2), which is a quaternary copolymer (K).
The solid lubricant for hydroform according to any one of 4).

(26) The organic polymer compound (H) having a carboxyl group contains 10 to 25% of an unsaturated carboxylic acid (filtrate), 50 to 85% of an unsaturated carboxylic acid ester (R), Saturated nitrile (O) 5-15
%, A quaternary copolymer (K) consisting of 5% or less of a hydroxyl group-containing unsaturated carboxylic acid ester (W), wherein the hydroform according to any one of (1) to (25) above. For solid lubricants.

(27) The organic polymer compound (H) having a carboxyl group contains 10 to 25% of an unsaturated carboxylic acid (filtrate), 50 to 85% of an unsaturated carboxylic acid ester (R), Saturated nitrile (O) 5-15%
And 5% of hydroxyl group-containing unsaturated carboxylic acid ester (W)
Number average molecular weight 50,000-3000 composed of
00, and the unsaturated carboxylic acid (filtrate) is one or a mixture of two or more selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. , Quaternary copolymer (K) salt (e)
Represents an alkali metal (s) and an alkaline earth metal (u)
The solid lubricant for hydroform according to any one of the above (1) to (26), which is one or a mixture of two or more kinds selected from the group consisting of:

(28) High-molecular synthetic wax (d)
Is the following general formula

[0047]

Embedded image

[0048]

[Outside 3]

Is an alkyl alcohol having 4 to 14 carbon atoms and an alkyl alcohol having 2 to 3 carbon atoms, respectively.
These are the residues of the hydroxyl group of the polyoxyalkylene alkyl ether to which about 5 moles have been added, and may be the same or different.

M represents a residue of a basic substance, and m, n and t represent natural numbers. A) a terpolymer (G) salt (J) of an α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F) represented by Polymer compound (H)
And / or its salt (e) has a number average molecular weight of 5000
(1) to (3), which are 0 to 300000
(27) The solid lubricant for a hydroform according to any one of (27).

(29) The solid lubricant according to any one of the above (1) to (28) is applied to the outer surface of the metal pipe in an amount of from 0.4 to
A metal pipe coated at a thickness of 15 g / m ² .

In the present invention, the sum of the water-soluble or water-dispersible film-forming components of the solid lubricant for hydroforms is 100% by mass in terms of solid content in any combination. It is.

[0053]

DETAILED DESCRIPTION OF THE INVENTION The organic polymer (A) used in the present invention has the following general formula:

[0054]

Embedded image

(Wherein, R^FourAre each independently
Hydrogen atom or CH_ThreeR represents a group ^FiveHas 1 to 18 carbon atoms
Alkyl group and / or alkylene having 2 to 18 carbon atoms
R represents⁶Is R^TenO ｛CH_TwoCH_TwoO｝_nGroup (here
And R^TenIs an alkyl group having 1 to 4 carbon atoms, and n is 9 to
It is a positive number of 30. ) And R⁷Represents a group having 2 to 3 carbon atoms.
A alkylene group;⁸And R⁹Are each independently
Represents an alkyl group having 1 to 4 carbon atoms, and expressed as a percentage by mass,
x / y / z is 55-70% / 5-20% / 10-40%
It is. ) Is an unsaturated alkyl carboxylate and / or
Or an alkylene ester (a) and an unsaturated carboxylic acid
Lioxyethylene alkyl ether ester (b),
N, N-dialkylaminoalkylene unsaturated carboxylic acid
Consisting of ester (c), having a number average molecular weight of 8000
It is preferably from 50,000 to 50,000.

On the other hand, the organic polymer-based rust preventive (a) comprises the organic polymer (A) and the anticorrosive (d).
Is at least one selected from a polyphenol carboxylic acid (e), an azole compound (f), and an aromatic carboxylic acid (g) having a nitro group.

The organic polymer-based rust preventive (a) comprises a polyphenol-based carboxylic acid (e) and an azole-based compound (f).
And at least one anticorrosive (d) selected from aromatic carboxylic acids having a nitro group (g);
18 alkyl alcohols and / or 2-1 carbon atoms
8 alkylene alcohol (i) and an unsaturated carboxylic acid alkyl and / or alkylene ester (a) composed of an unsaturated carboxylic acid (filtrate) and 1 mole of an alkyl alcohol (ha) having 1 to 4 carbon atoms and ethylene oxide (Ni). )
And an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) composed of an unsaturated carboxylic acid (filtrate) having 9 to 30 moles of And an unsaturated carboxylic acid N, N-dialkylaminoalkylene ester (c) comprising an N, N-dialkylaminoalkylene alcohol having an alkylene group having 2 to 3 carbon atoms and an unsaturated carboxylic acid. Organic polymer (A)
And 0.5 to 3.5 parts by mass per 100 parts by mass of the solid lubricant for hydroform in terms of solid content mass percentage.
%, Particularly preferably 0.6 to 2%.

[0058]

[Outside 4]

The organic polymer (A) has 1 to 1 carbon atoms.
8 alkyl alcohols and / or 2 to 18 carbon atoms
If the alkyl and / or alkylene alcohol of the unsaturated alkyl carboxylate and / or alkylene ester (a) comprising the alkylene alcohol (i) and the unsaturated carboxylic acid (filtrate) has 19 or more carbon atoms, the organic polymer and The organic polymer-based rust preventive, which is a salt with the anticorrosive, cannot be dissolved in water.

Further, it comprises polyoxyethylene alkyl ether (ho) obtained by adding 9 to 30 moles of ethylene oxide to 1 mole of alkyl alcohol (ha) having 1 to 4 carbon atoms and unsaturated carboxylic acid (filtrate). The unsaturated carboxylic acid polyoxyethylene alkyl ether ester is
When the number of moles of ethylene oxide added is less than 9 moles, the water-soluble performance of the organic polymer-based rust preventive (a) of the present invention is low, so that the solid lubricant for hydroform of the present invention must be produced. Can not be done.

Further, when the number of moles of added ethylene oxide exceeds 30 moles, the water solubility of the produced organic polymer rust inhibitor (a) becomes too large,
The dry lubricating film produced and mixed with the solid lubricant for hydrofoam of the present invention and applied and dried on a metal plate has poor drying properties, causing stickiness and the like, peeling of the lubricating film, and pressing. This may cause trouble during processing.

Further, when the alkyl group constituting the N, N-dialkylaminoalkylene alcohol (H) has 5 or more carbon atoms, the basicity of the N, N-dialkylaminoalkylene alcohol itself becomes low, and this is naturally reduced. The basicity of the unsaturated carboxylic acid N, N-dialkylaminoalkylene ester itself synthesized using the compound also becomes low, and it takes a long time to prepare a salt with the anticorrosive agent later. In some cases, the salt cannot be produced.

Next, the unsaturated alkyl and / or alkylene ester (a) / unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) / unsaturated carboxylic acid N, constituting the organic polymer (A) N
-The percentage by mass of the dialkylaminoalkylene ester (c) is 55 to 70%, 5 to 20%,
-40%, especially 58-65%, 7-15%, 2
0-35% is preferred.

In the case of the unsaturated carboxylic acid alkyl ester (a), when the percentage by mass is less than 55%, the water solubility of the organic polymer-based rust inhibitor becomes high and the hydroform of the present invention is used. If the solid lubricant has poor emulsion resistance, and if it exceeds 70%, it may be difficult or impossible to make the organic polymer rust preventive itself water-soluble.

When the content of the unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) is less than 5%, it may be difficult or impossible to make the high molecular weight rust preventive agent water-soluble. If it exceeds 20%, the water solubility of the solid lubricant for hydroforming of the present invention becomes high, and the emulsion resistance becomes poor.

Next, in the case of the unsaturated carboxylic acid N, N-dialkylaminoalkylene ester (c), if it is less than 10%, the portion constituting the rust-preventive performance of the organic polymer-based rust-preventive agent itself becomes insufficient. However, when the solid lubricant for hydroforming of the present invention itself is poor in rust prevention and is applied to a metal pipe, it becomes a cause of a problem of causing rust on the metal pipe.

If it exceeds 40%, a salt with an anticorrosive is formed to increase the water solubility of the polymeric rust inhibitor of the present invention itself, and the water resistance of the solid lubricant for hydroform of the present invention itself is increased. Insufficiency in emulsion resistance causes insufficient emulsion resistance.

Next, the corrosion inhibitor (d) will be described.

The anticorrosive agent (d) includes a polyphenol carboxylic acid (e), an azole compound (f) and an aromatic carboxylic acid having a nitro group (g). The polyphenol carboxylic acid includes gallic acid, Protocatechuic acid and ferric acid and the like, azole compounds,
Examples include benzotriazole, tolyltriazole, 5-aminotetrazole, and indazole, and examples of the carboxylic acid having a nitro group include nitrobenzoic acid and nitrophthalic acid.

Higher fatty acid having hydroxy group (B)
Is stearic acid (h) having a hydroxy group and / or
Or a hydroxyalkylcarbamyl stearic acid (i) derived from stearic acid having an amino group, and a salt of a higher fatty acid (B) having a hydroxy group (b)
Is stearic acid (h) having a hydroxy group and / or
Or an alkali metal (j) and / or an alkaline earth metal (k) of hydroxyalkylcarbamyl stearic acid (i) derived from stearic acid having an amino group
There is also a divalent or trivalent salt, and the compounding ratio thereof is preferably 2 to 9% based on 100 parts by mass of the solid lubricant for hydroforming in terms of solid content in terms of mass percentage, Particularly, 4 to 7.5% is preferable.

When the salt (b) of the higher fatty acid (B) having a hydroxy group is less than 2% in terms of solid content based on 100 parts by mass of the solid lubricant for hydroform, the solid for hydroform of the present invention is used. Insufficient lubricity of lubricant,
This may cause trouble in the subsequent molding process. In addition, 9
%, It causes poor dispersion when the solid lubricant is solubilized in water, causes uneven coating in the coating process, and results in poor degreasing in the subsequent degreasing and washing process, resulting in poor coating. Cause trouble.

The higher fatty acid amide (C) has the following chemical formula

[0073]

Embedded image

Is represented by

Further, the higher fatty acid amide (C) comprises a higher fatty acid and L-lysine (p), and the higher fatty acid amide-based lubricant (c) is N-ε-lauroyl-L-lysine.

The compounding amount is 0.5% by mass conversion with respect to 100 parts by mass of the solid lubricant for hydroform.
The higher fatty acid amide-based lubricant (c) is suitable for the present invention that exhibits the high lubricity required by the solid lubricant for hydroforms of the present invention. It is a component that has been made possible.

When the compounding amount is less than 0.5%, the high lubricity of the solid lubricant for hydroforming of the present invention is insufficient, which causes poor molding in a subsequent molding step. . Further, when it exceeds 2.5%, insufficient degreasing is caused in a degreasing and washing step in a subsequent step, and a trouble occurs in which a coating failure occurs in a subsequent coating step.

The terpolymer (G) of α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F) of the high molecular weight synthetic wax (d) used in the present invention is , The following general formula

[0079]

Embedded image

[0080]

[Outside 5]

Is an alkyl alcohol having 4 to 14 carbon atoms and an alkyl alcohol having 2 to 3 carbon atoms, respectively.
These are the residues of the hydroxyl group of the polyoxyalkylene alkyl ether to which about 5 moles have been added, and may be the same or different.

M represents a residue of a basic substance, and m, n and t represent natural numbers. The structural units forming the terpolymer (G) are described in detail below.

First, the proviso in parentheses described in the above chemical formula [Formula 5] will be described.

[0084]

[Outside 6]

Further, α constituting the terpolymer (G)
The olefin (D) is preferably an α-olefin having 22 to 48 carbon atoms, preferably 32 to 48 carbon atoms. If the α-olefin has less than 22 carbon atoms, the resulting terpolymer is waxy. It is difficult to become a substance and becomes a substance having resin-like properties, which causes poor lubrication.

In the case of an α-olefin having more than 48 carbon atoms, it was not possible to synthesize a synthetic polymer wax.

Next, R ² and R ³ may be the same or different, and in the case of R ² , the maleic acid monoester (E) is a straight-chain or side-chain monomer having 4 to 14 carbon atoms. A branched monovalent alkyl or alkylene alcohol having a chain and an alkylene oxide having 2 to 3 carbon atoms
A compound obtained by adding 5 moles, that is, a monoester obtained by using a polyoxyalkylene alkyl or an alkylene ether as a monoesterifying agent and performing a mole / mole reaction with maleic acid or maleic anhydride.

When the alcohol which is a monoesterifying agent is a compound having 1 to less than 4 carbon atoms, the terpolymer synthesized therefrom does not show the desired wax property. In addition, alcohols having 15 or more carbon atoms have two or more carbon atoms.
The ternary copolymer synthesized by using a maleic acid monoester derived from a polyoxyalkylene alkyl ether obtained by adding 6 mol or more of the alkylene oxide 3 has a melting point as described below, It will be lower than 60 ° C or higher. Therefore, the blocking property of the lubricating film is deteriorated, so that the solid lubricating film is easily peeled before molding or easily adheres to a mold during molding, which causes trouble.

As a method for producing such a novel polymer synthetic wax, for example, an α-olefin-maleic anhydride copolymer (for example, Diacarna # 30 manufactured by Mitsubishi Chemical Corporation) and a carbon number Polyoxyalkylene alkyl or alkylene ether obtained by adding 1 to 5 moles of alkylene oxide having 2 to 3 carbon atoms to linear or branched monovalent alkyl or alkylene alcohol having 4 to 14 Is produced by converting a waxy substance synthesized by a reaction into an alkali metal salt and / or an alkaline earth metal salt by a conventional method (for example, the method described in JACS, Vol. 70, p3952). be able to.

Next, the production of maleic acid monoester salt (F) of maleic acid monoester salt (F) in the case of R ³ is the same as that of maleic acid monoester (E). Basic substance (the above chemical formula [Chemical Formula 5]
M in the following is described as a residue of a basic substance. When the basic substance is sodium of an alkali metal, it is Na, but when the basic substance is calcium of an alkaline earth metal, Ca is
And / or CaOH, it was simply expressed as M. Specific examples thereof include alkali metals such as lithium, sodium, and potassium, and hydroxides such as alkaline earth metals such as magnesium, calcium, and barium. In the case of (a), sodium and potassium are preferred, and in the case of an alkaline earth metal, magnesium and calcium are preferred.

In the production of salts, hydroxides of various metals are preferred, and it is preferable to use them as aqueous solutions or dispersed in water.

The high molecular weight synthetic wax (d) used in the present invention has a number average molecular weight of 6000 or more, preferably 8 or more.
The melting point is from 000 to 12000, and the melting point according to the JIS K-0064 method is from 58 to 76C, preferably from 66 to 73C.

When the number average molecular weight of the high molecular weight synthetic wax (d) is less than 6000, the wax is a wax-like substance similar to the high molecular weight synthetic wax used in the present invention and has a melting point of 58 ° C. As a result, the melting point of the dry lubricating film of the solid lubricant for hydroforming of the present invention itself becomes low, which causes a problem that the solid lubricating layer is blocked.

Further, if the melting point exceeds 76 ° C., the problem of insufficient degreasing and washing in the subsequent degreasing step occurs, which is not preferable because it causes coating failure.

The polymer-based synthetic wax (d) includes:
It is necessary to leave an acid component (carboxylic acid: COOH), and this acid component has a function of exhibiting degreasing properties in a later step. ~ 8
What is 0 KOHmg / g is good, and preferably 60 to
It is preferably 75 KOHmg / g.

Next, m, represented by the above chemical formula [Formula 5],
n and t will be described.

M, n, and t are the mixing ratios of three types of monomers that exhibit the wax performance of the high molecular weight synthetic wax (d) as the skeleton component of the solid lubricant for hydroforming of the present invention.

In the case of m = α-olefin (D), n = maleic acid monoester (E), and t = maleic acid monoester salt (F) of three kinds of raw materials, m / n / t is α-α
Olefin = m is 10 parts by mass, maleic acid monoester (E) = n is 3 to 10 parts by mass, maleic acid monoester salt (F) = t is 1.5 to 4.5 parts by mass. M / n / t is preferably 10 parts by mass / 5.5 to 5.5 parts by mass.
7.5 parts by mass / 2.5 to 3.5 parts by mass is preferred.

When the compounding ratio n of the maleic acid monoester (E) is less than 3 parts by mass with respect to 10 parts by mass of the α-olefin (D), the polymer synthesis Insufficient resin performance of the wax (d), resulting in insufficient strength of the lubricating film at the time of press working, and lack of acid groups contained in the maleic acid monoester (E). The water-soluble effect of the high molecular weight synthetic wax (d) in the production of the lubricant is reduced, and the solid lubricant itself cannot be produced.

Next, the compounding ratio n of the maleic acid monoester (E) is such that the compounding ratio m of the α-olefin (D) is 10%.
When the amount exceeds 10 parts by mass with respect to the parts by mass, insufficient wax performance is caused, and insufficient lubrication performance at the time of press working causes trouble in press working.

The mixing ratio t of the maleic acid monoester salt (F) is such that when the mixing ratio m of the α-olefin (D) is less than 1.5 parts by mass with respect to 10 parts by mass, a solid lubricant is used. The production of solid lubricants caused by a decrease in water solubility of the synthetic synthetic wax (d), the solid lubricant itself could not be produced, or the shortage of alkaline earth metal salts to be compounded during the production of the solid lubricant caused a lubricating film Insufficiency in the drying property of the oil causes a sticky trouble.

Next, when the amount exceeds 4.5 parts by mass, the polar portion in the salt (J) of the high molecular weight synthetic wax increases, so that
Insufficient lubricity causes press working trouble during press working.

Next, the unsaturated carboxylic acid (filtrate) -unsaturated carboxylic acid ester (る) -unsaturated nitrile (お) -hydroxyl group-containing unsaturated compound of the organic polymer compound (H) having a carboxyl group used in the present invention. The constituent units forming the quaternary copolymer (K) of the saturated carboxylic acid ester (W) are described in detail below.

The unsaturated carboxylic acid (filtrate) / unsaturated carboxylic acid ester (ru) constituting the quaternary copolymer (K) of the organic polymer compound (H) having a carboxyl group of the present invention /
The compounding ratio of unsaturated nitrile (O) / hydroxyl-containing unsaturated carboxylic acid ester (W) is 10 to 25%, 50 to 85%, 5 to 15%, and 5% or less, respectively, in terms of mass conversion. , 13-22%, 55-75%, 8-10
%, And 2 to 4% are preferable.

Further, when the carboxylic acid (filtrate) constituting the quaternary copolymer (K) is less than 10% based on 100 parts by mass of the quaternary copolymer (K), the processing step Insufficient acid groups in the lubricating film formed on the metal surface in the subsequent degreasing step may cause a problem of insufficient cleaning. On the other hand, if it exceeds 25%, the drying time in the drying step after coating may be too long, or moisture may be introduced into the dried film, which may cause rusting.

Next, the unsaturated carboxylic acid ester
Is less than 50% based on 100 parts by mass of the quaternary copolymer (K), the organic polymer compound (H) having a carboxyl group of the present invention (H) The strength of its own resin film is reduced, and the formed lubricating film formed by applying and drying the solid lubricant for hydroforming of the present invention on a metal surface is insufficient in film strength, resulting in poor molding in a subsequent molding process. Cause troubles.

Further, when it exceeds 85%, the quaternary copolymer (based on the mixing ratio of unsaturated carboxylic acid and hydroxyl group-containing unsaturated carboxylic acid ester / unsaturated carboxylic acid ester), which is a component contributing to water solubility, is used. K) Since the polarity of the solid lubricant itself is low, the solid lubricant itself cannot be dissolved in water.

Next, when the blending amount of the unsaturated nitrile (O) is less than 5% based on 100 parts by mass of the quaternary copolymer (K), the organic polymer having a carboxyl group of the present invention can be used. The quaternary copolymer (K) of the molecular compound (H) has a reduced adhesiveness to the metal surface of the resin film, and also has a reduced lubricity-imparting property due to the nitrile group contained in the unsaturated nitrile. The solid lubricant for use causes insufficient lubrication of the lubricating film formed on the metal surface, which causes troubles such as poor processing.

When the content exceeds 15%, the brittleness of the lubricating film itself increases due to the extremely large polarity of the nitrile group, the lubricating film breaks in the working process, and causes a processing trouble in the working process. Also.

When the mixing ratio of the hydroxyl group-containing unsaturated carboxylic acid ester (W) is more than 5% based on 100 parts by mass of the quaternary copolymer (K), the amount of the quaternary copolymer itself is reduced. It is not preferable because the polarity decreases and the solid lubricant cannot be made water-soluble, or the drying property of the film deteriorates.

The unsaturated carboxylic acid (filtrate) constituting the quaternary copolymer (K) is one or a mixture of two or more selected from acrylic acid, methacrylic acid, crotonic acid and maleic acid. , The salt of the quaternary copolymer (e) is an alkali metal (s) and / or an alkaline earth metal (u)
It is preferable to use one or a mixture of two or more selected from the group consisting of

The salt of the unsaturated carboxylic acid constituting the quaternary copolymer of the present invention is an alkali metal salt which is a salt for making the organic polymer compound (H) having a carboxyl group soluble in water. In the case of an earth metal, it has both roles of enhancing the lubricity of the solid lubricant for hydroforming of the present invention and enhancing the drying property of the formed lubricating film.

Therefore, when the alkali metal is used alone, the lubricating property of the solid lubricant for hydroforming of the present invention itself is insufficient, and the drying property of the lubricating film becomes slow. In addition, when only an alkaline earth metal is blended, the organic polymer compound (H) having a carboxyl group may cause gelation, or may not be sufficiently water-soluble to be water-soluble.

Next, the salt (e) of the organic polymer compound (H) having a carboxyl group is converted into a solid content-based mass percentage,
For 100 parts by mass of solid lubricant for hydroform,
It is blended in an amount of 10 to 75%.

Further, when the amount of the salt (e) of the organic polymer compound having a carboxyl group is less than 10%,
The solid lubricant for hydroforms of the present invention is insufficient in film strength of the lubricating film formed on the surface of the metal tube, and does not produce the target lubricating performance, which causes trouble in the molding process.

When the content exceeds 75%, even if the strength of the lubricating film is good, the lubricity itself becomes insufficient, which similarly causes a trouble in the molding process.

Next, the organic polymer compound (H) having a carboxyl group has a number average molecular weight of 50,000 to 30,000.
When the number average molecular weight is less than 50,000, the solid lubricant for hydroforming of the present invention is applied to the surface of a metal tube and dried to form a lubricating film having insufficient strength. This causes troubles due to insufficient lubrication in the process. Further, if it exceeds 300,000, the lubricating film may break in the molding process due to insufficient elongation of the lubricating film, which may cause a trouble.

In order to apply the solid lubricant for hydroforming of the present invention to the surface of a metal tube to form a solid lubricating layer, for example, a 3 to 12.5% aqueous solution is prepared depending on the desired thickness of the dry film. The solution is applied to the surface of the metal tube by a method such as a spray method or a roll coater method using a grooved roll, and dried at a temperature between room temperature and 60 ° C. after the application.

At this time, the lower limit of the thickness of the dry solid lubricating layer is 0.4 g / m ² in view of the effect of securing rust prevention and the effect of moldability.
In consideration of weldability, blocking resistance, lubricity, emulsion resistance, and the like, the upper limit is preferably 15 g / m ² . In particular, 0.5 to 3.5 g / m ² is preferable.

[0120] In the present invention, the term "metal pipe" includes an electric resistance welded pipe, a steel pipe, a seamless steel pipe, a non-ferrous metal pipe such as aluminum and the like, and a solid pipe formed on the surface of the metal pipe. The lubricating layer may be formed with the same thickness on the outer surface of the metal tube or with different thicknesses.

By coating the solid lubricant for hydroforming of the present invention on a metal tube, a solid lubricating layer (lubricating film) having high lubricity is formed.

This high lubricity is attributable firstly to the long-chain alkyl group introduced into the molecule of the terpolymer of α-olefin / maleic acid monoester / maleic acid monoester salt. is there.

Secondly, the higher fatty acid present in the molecule of the higher fatty acid having a hydroxy group is also caused by the long-chain alkyl group, and the higher fatty acid amide is also present in the molecule of the higher fatty acid also present in the molecule. In addition to the alkyl groups, particularly in the case of higher fatty acid amides, the state of solidification exerts an effect of improving lubricity by a sliding action between molecules of a scaly layered crystal structure.

The lubricating film formed by the terpolymer of α-olefin / maleic acid monoester / maleic acid monoester salt has a high lubricating property, that is, an oily property. Thus, while maintaining a certain degree of hydrophilicity, a large hydrophilicity of the remaining carboxyl groups or salts thereof forms a lubricating film that can be washed with warm water or a dilute alkaline liquid. This means that the lubricating film can be washed and removed with an aqueous cleaning solution after the forming process.

Furthermore, the high lubricity indicates that the solid lubricant for hydroforms of the present invention has high oiliness, and moreover, the α-olefin which contributes to the lubricating performance of the lubricating film. The terpolymer of maleic acid monoester-maleic acid monoester salt has a melting point of 60 ° C. or higher, and the higher fatty acid salt having a hydroxy group is 145.
It is a solid with a high melting point of at least ℃.

Further, the higher fatty acid amide N-ε-lauroyl-L-lysine is a solid having a high melting point of 200 ° C. or higher, and the boundary kinetic friction coefficients of various powder lubricants are shown in FIG. As shown in FIG. 1, N-ε-lauroyl-
L-lysine has a lower boundary kinetic friction coefficient than other powders, has remarkably excellent lubricity, and has good blocking resistance of a lubricating film. Further, due to the water resistance due to high oiliness, the lubricating film does not fall off due to rainwater or the like, and the coated metal pipe can be stored and transported without any trouble.

Further, the emulsion resistance is described in JP-A-6-2.
No. 99180 discloses a plastic working solid lubricant and a lubricant proposed for a metal plate having a solid lubricating layer are the same as those of the lubricating substance of the present invention, the same α-olefin-maleic acid monoester-maleic acid monoester salt. This is a terpolymer, and the method of making the terpolymer water-soluble has succeeded by blending 5 to 25% of a nonionic surfactant.

However, the nonionic surfactant is
Because it has the property of being dispersed or emulsified in water,
It has been found that when used in the lubricant of the present invention which requires emulsion resistance, the emulsion resistance is significantly deteriorated.

Therefore, the present inventors, as described above, did not use or blend these nonionic surfactants and the like to make water-soluble substances having high oiliness and high lubricity into water as lubricating substances α -High oiliness by assembling the olefin-maleic acid monoester-maleic acid monoester salt terpolymer into a substance having the performance of a surfactant,
In addition, we succeeded in making a highly lubricating substance water soluble.

Further, the substances having the performance of a surfactant assembled from the terpolymer of the present invention include higher fatty acid salts and higher fatty acid amides having a hydroxy group as second and third lubricating substances. The inventors have found that the lubricant is also made water soluble, and succeeded in the present invention.

[0131]

The present invention will be specifically described below based on examples and comparative examples. Table 1 shows the organic polymer rust inhibitor of the present invention, Table 2 shows a higher fatty acid salt having a hydroxy group, Table 3 shows a terpolymer, and Table 4 shows an organic polymer compound having a carboxyl group. Table 5 shows the solid lubricant according to the example of the present invention, Table 6 shows the solid lubricant according to the comparative example, and the results are shown in Table 7 and the result of the comparative example is shown in Table 7. Are respectively shown.

The production of the organic polymer-based rust preventive is described below by taking composition No. 1 in Table 1 as an example. Raw material of the following composition No. 1 in a nitrogen stream at 68 to 75 ° C
For 24 hours to obtain a transparent viscous substance. Further, an anticorrosive agent was added to the transparent viscous substance, and the mixture was reacted at the same temperature for 12 hours. Then, water was added to the transparent viscous substance at 65 to 70 ° C. while removing the solvent under reduced pressure to make water soluble. I got

(Ingredients of Composition No. 1) n-butyl methacrylate 60 parts by mass methoxypolyoxyethylene ether methacrylate (1000 ^{* 1} ) 10 parts by mass N, N-dimethylaminoethyl methacrylate 30 parts by mass Isopropyl alcohol 400 parts by mass Azobisisobutyronitrile 3 parts by mass Gallic acid 32.5 parts by mass Deionized water 400 parts by mass Note that the number * 1 indicates the molecular weight of polyoxyethylene in methoxypolyoxyethylene ether, Composition Nos. 2 to 6 were produced in the same manner.

[0134]

[Table 1]

The method of producing the higher fatty acid (B) having a hydroxy group is different from that of Compound Nos. 1 and 2 in Table 2 and that of Compound Nos. 3 to 5.

However, since the production method of the higher fatty acid (B) having a hydroxy group of Compound Nos. 1 and 2 is the same, the method of producing the higher fatty acid having a hydroxy group of Compound No. 1 will be mainly described. The higher fatty acid (B) having a hydroxy group of Compound Nos. 3 to 5 uses a commercially available product, and Compound Nos. 1 to 5 separately produce various salts by a usual method for producing metal soap. The mixture was used as a compound.

(Formulation of Raw Materials and Production Method of Higher Fatty Acid Having Hydroxy Group of Compound No. 1) 232 parts by mass of oleic acid 123 parts by mass of acetonitrile 338 parts by mass of concentrated sulfuric acid 2,000 parts by mass of water 50% diluted sulfuric acid 1000 parts by mass 48% caustic soda (Sodium hydroxide) aqueous solution 2,000 parts by mass Dimethylolpropionic acid 110 parts by mass The above-mentioned oleic acid, acetonitrile and concentrated sulfuric acid were added to 27 parts by mass.
The mixture was reacted at で 30 ° C. for 3 hours, poured into water, stirred for 5 hours, and the obtained solid was separated by filtration, washed with water and dried to obtain acetylaminostearic acid.

Next, acetylaminostearic acid was boiled with a 50% by weight aqueous solution of sulfuric acid for 6 hours, and the sulfate of aminostearic acid obtained was dissolved in a 48% by weight aqueous solution of sodium hydroxide, and then obtained with hydrochloric acid at pH 5-6. A higher fatty acid having a hydroxy group of a waxy substance as a pale yellow solid was obtained by a conventional amide production method from aminostearic acid and dimethylolpropionic acid.

[0139]

[Table 2]

The production of the salt (J) of the terpolymer (G), which is a high molecular weight synthetic wax (d), was carried out according to composition No. 1 in Table 3.
Will be described as an example.

(Mixing and Production of Raw Materials for Polymeric Synthetic Wax of Composition No. 1) α-olefin 1.0 mol Maleic acid mono n-butyl ester 1.0 mol Toluene 500 g Lauroyl peroxide 175 g The polymerization reaction is carried out at 75 to 80 ° C. for 24 hours in an air stream, and the solvent and unreacted raw materials are distilled off under reduced pressure. The number average molecular weight is 7000 and the melting point is 69 ° C. (JIS K-0064)
Terpolymer (G) as a pale yellow solid having an acid value of 56 was obtained.

Next, the obtained high molecular weight synthetic wax of Composition No. 1, ion-exchanged water, sodium hydroxide and calcium hydroxide were heated and stirred for several hours, and gradually cooled under stirring to obtain a milky white paste-like composition. The salt (J) of the terpolymer (G), which is the high molecular weight synthetic wax (d) of No. 1, was obtained.

The compositions Nos. 2 to 15 were produced in the same manner.

Regarding the terpolymer, the “monomer (molar ratio)”, the “carbon content of α-olefin”, the “monomeric maleate” of the α-olefin, maleic acid monoester, and maleic acid monoester salt used therein. The “ester component of the ester” and the “molecular weight (number average molecular weight by GPC method)” are further defined as “residue of a basic substance constituting a salt” used in the synthesis of the terpolymer, and "Concentration of lubricating component in composition (% by mass)", i.e., the percentage of solid content of polymer synthetic wax (d) with respect to 100 parts by mass of solid lubricant for hydroforms.

[0145]

[Table 3]

The production of the polymer compound having a carboxyl group will be described below with reference to the composition No. 1 in Table 4 as an example. The following materials are placed in a nitrogen stream 68 to 7
When a polymerization reaction was performed at 0 ° C. for 16 hours, a milky white viscous liquid was obtained. Sodium hydroxide and magnesium hydroxide were added, and after measuring the concentration, ion-exchanged water was added to 40% by mass.

(Ingredients of Composition No. 1) Crotonic acid 20 parts by mass Acrylic acid 5 parts by mass Lauryl methacrylate 10 parts by mass Methyl methacrylate 50 parts by mass Acrylonitrile 15 parts by mass 2-hydroxyethyl methacrylate 5 parts by mass Aqualon RS-10 15 parts by mass Ammonium persulfate 1 part by mass Ion exchange water 225 parts by mass However, methacrylic ester is manufactured by Kyoeisha Chemical Co., Ltd., crotonic acid and ammonium persulfate are manufactured by Wako Pure Chemical Industries, Ltd. Nippon Shokubai, Aqualon RS
-10 is manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

Incidentally, Composition Nos. 2 to 6 were produced in the same manner.

[0149]

[Table 4]

The solid lubricant of the embodiment shown in Table 5 and the solid lubricant of the comparative example shown in Table 6 were mixed with a metal tube having an outer diameter of 60.5 mm.
φ, plate thickness 1.6mm, length 300mm JIS standard S
After coating on a TKM11A steel pipe for machine structure, it was left at room temperature and dried to obtain a coated metal pipe having a solid lubricating layer. Each of these coated metal tubes was tested and measured for lubricity, rust prevention, blocking properties, emulsion resistance, mold adhesion and adhesion amount. Table 7 shows the results for the solid lubricants of Examples shown in Table 5, and Table 8 shows the results for the solid lubricants of Comparative Examples shown in Table 6.

As for lubricity, a T-forming test by hydroforming as shown in FIG. 2 was performed. Die hole diameter of T overhang is 60.5mm, shoulder radius is 20mm
Using the split molds 3 and 4 with the maximum internal pressure of 39MP
a, The cylinder stroke was performed at 40 mm on one side. The mold was wiped off with a rag after each test and tested in a dry state. The overhang height h of the branch pipe was measured, and when h = 50 mm or more, ○, 45 mm or more and less than 50 mm, Δ;
And

The evaluation of emulsion resistance was carried out by T-molding in a state where the wiping of the mold was stopped and the emulsion was adhered to the mold. Other molding conditions and evaluation methods are the same as in the evaluation of lubricity.

The degreasing property was evaluated by using a fine cleaner FCL-446 manufactured by Nippon Parker Rising Co., Ltd.
0, using a 3% solution, a liquid temperature of 45 ° C., and an immersion time of 120 seconds, followed by a water leak rate of 60 seconds after water washing. % And less than 50% were evaluated as x.

The rustproofing properties were evaluated by evaluating the solid content-based mass concentration of each of the solid lubricants of Examples and Comparative Examples by 1%, 5% and 1%.
A 0% aqueous solution was prepared, and the test pieces were immersed in these solid lubricant aqueous solutions. The rusting state was visually observed for 14 days, and the results were as follows: ○: no rusting, Δ: partial rusting observed , Rusting is remarkable, and evaluated in three stages.

The evaluation of the blocking property was 100 mm × 1
The test pieces of 00 mm were overlapped, a load of 12.5 kgf was applied, and after several hours at 50 ° C. in that state, the state of adhesion between the test pieces was visually observed. The results were evaluated on a three-point scale: 付 着: no adhesion, Δ: partial adhesion peeling, ×: entire adhesion.

[0156]

[Table 5]

[0157]

[Table 6]

[0158]

[Table 7]

[0159]

[Table 8]

As is clear from the results in Table 7, the solid lubricants for hydroforms of the present invention have excellent performances in lubricity, degreasing property, rustproofing property, emulsion resistance, blocking property and mold adhesion. Having. On the other hand, in the results of the comparative examples in Table 8, the solid lubricants of lubricant numbers 1 to 12 all had some poor performance.

[0161]

According to the present invention, lubricating properties, degreasing properties, emulsion resistance, and other properties required for other solid lubricants for hydroforms, such as rustproofing properties, blocking properties, mold adhesion, etc. Thus, a solid lubricant for hydroforming having excellent performance can be provided. Further, the metal tube having a solid lubricating layer formed using the solid lubricant for hydroforming of the present invention has a solid lubricating layer due to rainwater, etc. , And can be stored and transported without any trouble.

[Brief description of the drawings]

FIG. 1 is a diagram showing boundary dynamic friction coefficients of various powders.

FIG. 2 is a cross-sectional view showing a hydroforming method to which the present invention is applied.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Metal tube, 2 ... Molded product, 3,4 ... Mold, 5,6 ... Cylinder, 7 ... Liquid introduction hole.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 129/36 C10M 129/36 129/54 129/54 133/28 133/28 133/32 133/32 135 / 18 135/18 145/12 145/12 145/16 145/16 145/38 145/38 149/02 149/02 149/08 149/08 // C10N 10:02 C10N 10:02 10:04 10: 04 20:00 20:00 Z 20:04 20:04 30:00 30:00 AC 30:12 30:12 40:24 40:24 Z 50:02 50:02 50:08 50:08 (72) Inventor Yukihisa Kuriyama 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Headquarters (72) Inventor Chihiro Masago 5-2-2 Nishikujo-cho, Nara-shi, Nara 5 (72) Inventor Yasuhiro Takahara 5-2, Nishikujo-cho, Nara-shi, Nara 5 K-Seisha Co., Ltd. Research Headquarters F-term (reference) 4H104 BB19C BB24C BE11A BE17C BE19C BG1 0C CB07C CB08A CB08C CB09A CB09C CB14C CE01C CE04A CE04C EA03A EA03C FA01 FA02 LA06 LA11 LA13 PA23 QA02 QA08 QA11

Claims (29)

[Claims] 1. An organic polymer (A) -based rust inhibitor (a) in an amount of 0.5 to 3.5% in terms of mass percentage in terms of solid content, a higher fatty acid having a hydroxy group (B) and / or a salt thereof (b) ) 2-9%, higher fatty acid amide (C) -based lubricant (c) 0.5-2.5
%, A terpolymer (G) of α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F) which is a high molecular weight synthetic wax (d) having a number average molecular weight of 6000 or more A water-soluble or water-dispersible film-forming component consisting of 22 to 87% of a salt (J) of an organic polymer compound (H) having a carboxyl group and / or 10 to 75% of a salt thereof (e). A solid lubricant for hydroforming, characterized by that: 2. An organic polymer (A) comprising: an unsaturated alkyl and / or alkylene ester (a);
The solid lubricant for hydroform according to claim 1, comprising an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) and an unsaturated carboxylic acid N, N-dialkylaminoalkylene ester (c). 3. The organic polymer (A) has a number average molecular weight of 80.
The solid lubricant for a hydroform according to claim 1 or 2, wherein the solid lubricant is in the range of 00 to 50,000. 4. The organic polymer (A) is an unsaturated alkyl carboxylate comprising an alkyl alcohol having 1 to 18 carbon atoms and / or an alkylene alcohol having 2 to 18 carbon atoms (i) and an unsaturated carboxylic acid (filtrate). And / or an alkylene ester (a), a polyoxyethylene alkyl ether obtained by adding 9 to 30 mol of ethylene oxide to 1 mol of an alkyl alcohol having 1 to 4 carbon atoms, and an unsaturated carboxylic acid. (B) an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b), an N, N-dialkylaminoalkylene alcohol having an alkyl group having 1 to 4 carbon atoms and an alkylene group having 2 to 3 carbon atoms (N) and an unsaturated carboxylic acid N, N-dialkylaminoalkylene ester of unsaturated carboxylic acid (filtrate) (c Hydroforming a solid lubricant according to any one of claims 1 to 3, characterized in that it consists of. 5. The organic polymer (A) comprises an alkyl alcohol having 1 to 18 carbon atoms and / or an alkylene alcohol having 2 to 18 carbon atoms (i) and an unsaturated carboxylic acid (filtrate) in terms of mass conversion. Polyoxyethylene alkyl obtained by adding 55 to 70% of an unsaturated alkyl carboxylate and / or alkylene ester (a) and 9 to 30 mol of ethylene oxide to 1 mol of an alkyl alcohol having 1 to 4 carbon atoms. 5 to 20% of an unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) comprising an ether (ho) and an unsaturated carboxylic acid (filtrate), having an alkyl group having 1 to 4 carbon atoms, and having 2 to 3 carbon atoms. Unsaturated carboxylic acids N, N comprising an N, N-dialkylaminoalkylene alcohol having an alkylene group The solid lubricant for hydroform according to any one of claims 1 to 4, wherein the solid lubricant is a terpolymer composed of 10 to 40% of -dialkylaminoalkylene ester (c). 6. The method according to claim 1, wherein the organic polymer rust inhibitor (a) comprises an organic polymer (A) having a number average molecular weight of 8,000 to 50,000 and a corrosion inhibitor (d). The solid lubricant for a hydroform according to any one of claims 1 to 7. 7. The anticorrosive (d) is at least one selected from the group consisting of polyphenolic carboxylic acids (e), azole compounds (f) and aromatic carboxylic acids having nitro groups (g). The solid lubricant for hydroforming according to claim 6, which is a lubricant. 8. The organic polymer rust preventive (a) is selected from the group consisting of polyphenol carboxylic acid (e), azole compound (f) and nitro group-containing aromatic carboxylic acid (g). At least one corrosion inhibitor (d)
And a solid lubricant for hydroforming according to any one of claims 1 to 6, comprising an organic polymer (A). 9. An organic polymer-based rust inhibitor (a) comprising an alkyl alcohol having 1 to 18 carbon atoms and / or an alkylene alcohol having 2 to 18 carbon atoms (i) and an unsaturated carboxylic acid (filtrate). A saturated alkyl carboxylate and / or alkylene ester (a), and a polyoxyethylene alkyl ether (ho) obtained by adding 9 to 30 moles of ethylene oxide to 1 mole of an alkyl alcohol having 1 to 4 carbon atoms. An unsaturated carboxylic acid polyoxyethylene alkyl ether ester (b) comprising an unsaturated carboxylic acid (filtrate); and N, N- having an alkyl group having 1 to 4 carbon atoms and having an alkylene group having 2 to 3 carbon atoms. Unsaturated carboxylic acid N, N-dialkylaminoalkylenes comprising dialkylaminoalkylene alcohol (he) and unsaturated carboxylic acid (filtrate) The number average molecular weight composed of ter (c) is 800
0 to 50,000 organic polymer (A), and at least one selected from the group consisting of polyphenolic carboxylic acids (e), azole compounds (f), and aromatic carboxylic acids having nitro groups (g). 9. A salt with an anticorrosive (d).
The solid lubricant for a hydroform according to any one of the above. 10. A hydroxyalkylcarbamyl stearic acid (i) wherein the higher fatty acid (B) having a hydroxy group is derived from stearic acid (h) having a hydroxy group and / or stearic acid having an amino group.
The solid lubricant for hydroforming according to any one of claims 1 to 9, wherein 11. A hydroxyalkylcarbamyl wherein the higher fatty acid (B) having a hydroxy group and / or its salt (b) is derived from stearic acid (h) having a hydroxy group and / or stearic acid having an amino group. The solid lubricant for hydroforming according to any one of claims 1 to 10, wherein the solid lubricant is a salt of an alkali metal (j) and / or an alkaline earth metal (k) of stearic acid (i). 12. The higher fatty acid amide (C) comprising a higher fatty acid and an amino acid (p).
12. The solid lubricant for hydroform according to any one of items 11 to 11. 13. The solid lubricant for hydroform according to claim 1, wherein the amino acid (p) forming the higher fatty acid amide (C) is L-lysine. 14. The higher fatty acid amide (C) -based lubricant comprises:
The solid lubricant for hydroform according to any one of claims 1 to 13, wherein the lubricant is N-ε-lauroyl-L-lysine. 15. The high molecular weight synthetic wax (d) is a product of JI
The solid lubricant for hydroforming according to any one of claims 1 to 14, wherein the melting point according to the SK-0064 method is 58 to 76 ° C. 16. The high-molecular synthetic wax (d) has a carboxyl group, and the amount of the carboxyl group is 55 to 80 KOH mg / g as an acid value by a fat analysis method. The solid lubricant for hydroforms according to any one of claims 15 to 15. 17. The α-olefin (D) has 22 carbon atoms.
The solid lubricant for hydroforming according to any one of claims 1 to 16, wherein the solid lubricant is a high-molecular synthetic wax (d) which is an α-olefin of No. 1 to No. 48. 18. A maleic acid monoester (E) is obtained by adding an alkyl alcohol having 4 to 14 carbon atoms to a C 2-14 alkyl alcohol.
And a polyoxyalkylene alkyl ether (g) obtained by adding 1 to 5 moles of an alkylene oxide (II) and a maleic acid monopolyoxyalkylene alkyl ether ester (r) composed of maleic acid (r). The solid lubricant for hydroform according to any one of claims 1 to 17, wherein d). 19. The maleic acid monoester salt (F) is
Monopolyoxy maleate comprising maleic anhydride and polyoxyalkylene alkyl ether obtained by adding 1 to 5 mol of alkylene oxide having 2 to 3 carbon atoms to alkyl alcohol having 4 to 14 carbon atoms. A polymer (J) which is a salt (J) of an alkylene alkyl ether ester (r), wherein the salt (J) is one or a mixture of two or more selected from an alkali metal (s) and an alkaline earth metal (u); The solid lubricant for hydroforming according to any one of claims 1 to 18, which is a synthetic wax (d). 20. The α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F) terpolymer (G) constituting the polymer synthetic wax (d) -The olefin (D) has 22 to 48 carbon atoms.
Is a polyoxyalkylene obtained by adding 1 to 5 mol of an alkyl alcohol having 2 to 3 carbon atoms to an alkyl alcohol having 4 to 14 carbon atoms (C), Maleic acid monopolyoxyalkylene alkyl ether ester (r) comprising an alkyl ether (ri) and maleic anhydride, wherein maleic acid monoester (E) salt (F) is a maleic acid monopolyoxyalkylene alkyl ether ester (r) A salt (J), wherein the salt (J) is one or a mixture of two or more selected from an alkali metal (s) and an alkaline earth metal (u), and has a number average molecular weight of 6,000 or more The solid lubricant for hydroform according to any one of claims 1 to 19, characterized in that: 21. The organic polymer compound (H) having a carboxyl group has a number average molecular weight of 50,000 to 300,000.
The solid lubricant for hydroforming according to any one of claims 1 to 20, wherein: 22. The hydropolymer according to claim 1, wherein the organic polymer compound (H) having a carboxyl group is a copolymer of an unsaturated carboxylic acid (filtrate). Solid lubricant for foam. 23. The unsaturated carboxylic acid (filtrate) constituting the organic polymer compound (H) having a carboxyl group is one or two selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid. The solid lubricant for hydroforming according to any one of claims 1 to 22, which is a mixture of two or more kinds. 24. The salt (e) of the organic polymer compound (H) having a carboxyl group is one or a mixture of two or more selected from an alkali metal (s) and an alkaline earth metal (u). The solid lubricant for a hydroform according to any one of claims 1 to 23, characterized in that: 25. An organic polymer compound having a carboxyl group (H) is an unsaturated carboxylic acid (filtrate), an unsaturated carboxylic acid ester (R), an unsaturated nitrile (O), and a hydroxyl group-containing unsaturated carboxylic acid ester (H). 25. The solid lubricant for hydroform according to claim 1, which is the quaternary copolymer (K). 26. The organic polymer compound (H) having a carboxyl group is an unsaturated carboxylic acid (filtrate) of 10 to 25% and an unsaturated carboxylic acid ester (R) in mass conversion percentage.
2. A quaternary copolymer (K) comprising 50 to 85%, unsaturated nitrile (O) 5 to 15%, and hydroxyl group-containing unsaturated carboxylic acid ester (W) 5% or less.
26. The solid lubricant for hydroforms according to any one of items 25 to 25. 27. The organic polymer compound (H) having a carboxyl group is an unsaturated carboxylic acid (filtrate) in an amount of 10 to 25% and an unsaturated carboxylic acid ester (R) in mass conversion percentage.
A quaternary copolymer (K) having a number average molecular weight of 50,000 to 300,000, comprising 50 to 85%, 5 to 15% of an unsaturated nitrile (O) and 5% or less of a hydroxyl group-containing unsaturated carboxylic acid ester (W). The unsaturated carboxylic acid (filtrate) is one or a mixture of two or more selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and a salt of the quaternary copolymer (K) ( E) is an alkali metal (s)
And one or a mixture of two or more selected from alkaline earth metals (u).
7. The solid lubricant for a hydroform according to any one of 6 above. 28. The high molecular weight synthetic wax (d) has the following general formula: [Outside 1] Is an alkyl alcohol having 4 to 14 carbon atoms,
It is a residue of a hydroxyl group of a polyoxyalkylene alkyl ether to which 1 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms are added, and may be the same or different. M
Represents a residue of a basic substance, and m, n and t represent natural numbers. Α-olefin (D) -maleic acid monoester (E) -maleic acid monoester salt (F)
Wherein the organic polymer compound (H) having a carboxyl group and / or a salt thereof (e) has a number average molecular weight of 50,000 to 300,000. The solid lubricant for a hydroform according to any one of claims 1 to 27. 29. The solid lubricant according to any one of claims 1 to 28, wherein the solid lubricant is applied to the outer surface of the metal tube in an amount of 0.4 to 15 g / m ^2.
A metal tube characterized by being coated with a film thickness of: