WO2006068270A1

WO2006068270A1 - Lubricant composition for cold working and cold working method using same

Info

Publication number: WO2006068270A1
Application number: PCT/JP2005/023750
Authority: WO
Inventors: Keishi Matsumoto; Yasunobu Murai; Masaki Nakane; Hidenori Ogawa; Yasunari Oshimoto; Kazuyoshi Ohashi; Masahiko Fukuhara; Yuji Mishima
Original assignee: Sumitomo Metal Industries, Ltd.
Priority date: 2004-12-24
Filing date: 2005-12-26
Publication date: 2006-06-29
Also published as: BRPI0519409B1; EP1835012A4; JP2006182809A; BRPI0519409A2; ES2805345T3; JP4611014B2; EP1835012B1; EP1835012A1

Abstract

Disclosed is a flame-retardant lubricant composition for cold working which contains no chlorine compound and exhibits good lubricity and welding resistance. Also disclosed is a cold working method using such a lubricant composition. Specifically disclosed is a lubricant composition for cold working which contains, in a lubricant base oil, at least one carbonate selected from alkali metal carbonates and alkaline earth metal carbonates, and at least one hydroxide selected from alkali metal hydroxides and alkaline earth metal hydroxides. This lubricant composition contains no chlorine compound. The carbonate content in the composition is not less than 10% by mass and less than 100% by mass, and the hydroxide content is more than 0 part by mass and not more than 5 parts by mass per 100 parts by mass of the carbonate.

Description

Specification

Cold plastic molding method and lubricant composition therefor

Technical field

[0001] The present invention relates to a lubricant composition for cold plastic working and a cold plastic working method using the same. More specifically, cold forging and cold pipe forming (hereinafter referred to as such processing) that are difficult to seize due to severe lubrication conditions without containing a chlorinated compound having problems such as carcinogenicity and dioxin generation. A lubricant composition for cold plastic cache that exhibits good lubricity and seizure resistance and is difficult to ignite, and a cold plastic working method using the same .

Background art

[0002] Conventionally, lubricating oils for cold plastic working such as cold forging are provided with an oily agent such as fats and oils, fatty acids, esters, and / or sulfur-based, chlorine-based, phosphorus-based lubricants for the purpose of imparting lubricity. An extreme pressure additive (EP agent) is added. Among extreme pressure additives, chlorinated extreme pressure additives such as chlorinated paraffin and chlorinated fatty acid esters are less expensive than other extreme pressure additives, and have excellent lubrication performance and flammability. Because of its difficulty, it has been added to lubricant compositions that are used in difficult applications such as cold forging.

[0003] However, as described below, chlorine compounds have problems of carcinogenicity and dioxin generation.

Regarding carcinogenicity, for example, certain chlorinated paraffins have been designated by the IARC (International Cancer Organization) as 2B (a non-carcinogenic substance). In addition, in the EU, the launch of products containing the same substances at concentrations exceeding 1% is restricted for specific chlorinated paraffins for metal processing, in view of the need to take measures to limit risks to aquatic organisms. Has been.

[0004] When incinerating waste liquids of lubricating oils containing chlorinated compounds, dioxin may be generated depending on the generation of hydrogen chloride (HC1), which causes air pollution during combustion, or the combustion temperature during incineration. It has been pointed out that it may cause environmental pollution. [0005] Due to such health and global environmental problems, in many countries, the use of metal processing lubricants containing chlorinated compounds such as chlorinated paraffin is being avoided. Accordingly, a lubricant composition for cold plastic working that does not contain a chlorinated compound such as chlorinated paraffin has been developed.

[0006] For example, JP-A-8-333594 proposes a forging die lubricant in which a highly basic alkaline earth metal salt (phenate, carboxylate or sulfonate) is dispersed in a base oil. . Japanese Patent Application Laid-Open No. 8-34988 proposes a lubricating oil in which a base oil is added with a highly basic petroleum sulfonate and an extreme pressure additive such as a calcium salt of a phosphate ester or a sulfur-based fat. Japanese Patent Laid-Open No. 6-256784 proposes a lubricating oil in which a coating enhancer such as ZnDTP (zinc dithiophosphate) and sulfided lard and a carbohydrate such as starch or a derivative thereof are dispersed in a base oil.

Disclosure of the invention

[0007] However, the lubricant composition that does not contain an organic chlorine-based compound proposed in the above-mentioned patent document does not exhibit sufficient lubricity and seizure resistance, even if it is difficult to process. There is a problem. Therefore, there is still a need for a metal processing lubricant composition that prevents environmental contamination by chlorine-based compounds, exhibits excellent seizure resistance even in difficult processing, and is difficult to ignite.

[0008] The present invention relates to cold forging and cold pipe forming (that is, seizure is likely to occur due to severe lubrication conditions without containing a chlorinated compound having problems such as carcinogenicity and dioxin generation (ie Provides a lubricant composition for cold plastic processing that exhibits good lubricity and seizure resistance, is suitable for the environment and is not easily flammable, and a cold plastic processing method using the same. To do.

[0009] The present invention specifies an alkali metal and a carbonate of Z or alkaline earth metal (particularly a carbonate having a specific crystal structure) and an alkali metal and a hydroxide of Z or alkaline earth metal. This is based on the knowledge that the lubricant composition contained in this ratio exhibits excellent seizure resistance and lubricity even if it does not contain a chlorine compound.

[0010] In plastic processing with severe processing conditions, the temperature of the lubricating oil may be 150 ° C or higher, but the content of carbonates of alkali metals and / or alkaline earth metals is increased. Thus, the content ratio of the combustible substance can be reduced, and as a result, it becomes difficult to ignite.

[0011] The lubricant composition for cold plastic working according to the present invention comprises, in a lubricating base oil, at least one carbonate selected from alkali metal carbonates and alkaline earth metal carbonates, and an alkali metal. Contains at least one hydroxide selected from hydroxides and alkaline earth metal hydroxides, and does not contain chlorine compounds. In this cold plastic cache lubricant composition, the carbonate content in the composition is 10% by mass or more and less than 100% by mass, and the hydroxide content is 100 parts by mass of the carbonate. It is more than 0 parts by mass and 5 parts by mass or less.

[0012] This lubricating composition for cold plastic casings is good even in cold forging and cold pipe forming (for example, cold pilger rolling), which is liable to cause seizure under severe lubrication conditions. Can exhibit excellent lubricity and seizure resistance. Also, this composition is difficult to ignite. Furthermore, this composition exhibits excellent performance even if it does not contain chlorine-based compounds having problems such as carcinogenicity and dioxin, and is adapted to the environment.

[0013] The lubricant composition for cold plastic working of the present invention includes the following preferred embodiments.

'It further contains at least one metal salt selected from sulfonates, salicylates, phenates and carboxylates of alkali metals or alkaline earth metals. In this way, it is possible to impart a cleaning and dispersing action to the lubricant composition. The content of the metal salt is preferably 1 to 50 parts by mass per 100 parts by mass of the carbonate.

[0014] · Further containing an organic sulfur compound having a carbon atom in which a sulfur atom and a nitrogen atom or an oxygen atom are bonded, and the content of the organic sulfur compound in the composition is 0.:! To 50 mass% is there. Thus, more excellent lubricity can be obtained.

[0015] The crystal structure of the carbonate is an amorphous type. Excellent seizure resistance can be obtained.

• The average particle size of the carbonate is 0.5 x m or less. After all, it is possible to obtain better seizure resistance.

[0016] The alkali metal is sodium and the alkaline earth metal is calcium. The material used is inexpensive, and the lubricant composition can be supplied stably.

• The flash point is 150 ° C or higher. As a result, the processing conditions at which the lubricant composition becomes hot It can be used safely even in severe plastic cages.

[0017] The organic sulfur compound is preferably at least one selected from compounds represented by the following formulas (1) to (12):

[0018] [Chemical 1]

[Wherein X is an integer of 2 to 4]

[0021] [Chemical 3]

[In the formula, R and R are each —CH or —CH, and they may be the same or different.

1 2 3 2 5

May be)

[0023] [Chemical 4]

[Wherein X is 1 or 2]

2

[0025] [Chemical 5]

[In the formula, R is —C (CH 3) or —C H]

3 3 3 6 11

[0027] [Chemical 6]

[0028] [Chemical 7]

[In the formula, χ and x are each an integer of 24 and may be the same or different from each other.

3 4

R and R are each --C H-C H or _C (S) N (C H) and

4 5 8 17 12 25 2 5 2

[0030] [Chemical 8]

[In the formula, R and R are each —CH—CH—CH—CH—CH or —CH.

6 7 3 2 5 3 7 4 9 6 5

C H, which may be the same or different from each other M is Na K or l / 2Ca

6 5

is there〕

[0032] [Chemical 9]

[Wherein, R is H or —CH, and R is —CH 2 NH or —CH (CH 2) 2 C H NH

8 3 9 5 10 2 3 4 8)

[0034] [Chemical 10]

^RW , N input ^ Ν, ¹

(Ten)

[Wherein RRR and R are each —CH 2 CHCHCH or —C H CH (CH) CH, which may be the same or different from each other X is:

(2 2 5 4 9 5 is an integer)

[0036] [Chemical 11]

[Wherein X is an integer of 1 to 4]

6

[0038] [Chemical 12]

2)

[Wherein R 1 and R 2 are each H, 1 CH, or 1 C H, and may be the same or different from each other.

14 16 3 2 5

R and R may be —CH, —CH or —CH, and are the same as each other.

15 17 3 2 5 6 5

Even if it ’s one, it ’s different.

[0040] According to the present invention, there is also provided a cold plastic working method characterized by performing cold plastic working of a workpiece using the cold plastic working lubricant composition. According to this method, since the lubricant composition for cold plastic working used is excellent in seizure resistance and lubricity, the workpiece can be plastically processed well.

[0041] According to the cold plastic casing method of the present invention, a material strength S stainless steel, high alloy steel, aluminum, copper, titanium, Eckenole, or an alloy thereof is satisfactorily plasticized. The power to do S.

[0042] Further, since the above-described lubricant composition for cold plastic working having excellent seizure resistance and lubricity is used,

• Stable production of plastic casings such as metal tubes, metal wires, metal bars or billets, or

• Cold plastic casing such as cold forging or cold pipe forming can be stably performed. Brief Description of Drawings [0043] FIG. 1 is an explanatory view schematically showing a testing machine used in an ironing test.

BEST MODE FOR CARRYING OUT THE INVENTION

[0044] (1) Lubricant composition for cold plastic working

The lubricant composition for cold plastic working of the present invention comprises an alkali metal and a carbonate of Z or alkaline earth metal (hereinafter simply referred to as “carbonate”), an alkali metal and / or an alkali in a lubricating base oil. It contains earth metal hydroxides (hereinafter simply referred to as “hydroxides”) and does not contain chlorine compounds. Both of these carbonates and hydroxides are present in a dispersed state in the base oil, but may be partially dissolved.

The type of “lubricating base oil” is not particularly limited, and a known lubricating base oil can be used. Examples of the lubricating base oil include mineral oil, fat and oil, and synthetic lubricating oil. Examples of mineral oil include kerosene, light oil, spindle oil, machine oil, neutral oil, turbine oil, cylinder oil, and liquid paraffin. Examples of fats and oils include beef tallow, lard, rapeseed oil, coconut oil, palm oil, nuka oil, and hydrogenated oils thereof. Synthetic lubricating oils include fatty acids obtained from the above oils, esters of fatty acids and alcohols, poly-alpha-olefins such as polybutene, polyols such as polyethylene glycol and polyol esters, polyetherols or polyesters and higher alcohols. . A “lubricating base oil” can comprise one or more component forces.

[0046] The content of the lubricating base oil in the cold plastic additive lubricant composition is not particularly limited. However, in order to ensure good lubricity and excellent seizure resistance, the composition ( 1 to 90% by mass based on the total amount of all components constituting the composition, the same shall apply hereinafter), more preferably 5 to 80% by mass, still more preferably 10 to 70% by mass, particularly preferably 10-60% by mass

[0047] Examples of the "alkali metal" of the carbonate include lithium, sodium, and potassium, and examples of the "alkaline earth metal" include magnesium, calcium, and barium. Specific examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, and sodium carbonate. Of these, sodium carbonate and / or calcium carbonate, which are inexpensive and can stably supply a lubricant composition, are preferred when considered as a substitute for an inexpensive chlorine-based compound. 1 carbonate Species or two or more can be used.

[0048] The crystal structure of the carbonate is not particularly limited, and in the case of an alkaline earth metal carbonate, examples include a patelite type, a calcite type, and an amorphous type. It is preferable to use a carbonate having a crystal structure of the amorphous structure because a cold plastic lubricant composition having excellent seizure resistance can be obtained. Of course, two or more carbonates having different crystal structures may be used in combination.

[0049] The average particle size of the carbonate is not particularly limited, but is preferably 0. or less (usually 0.001 zm or more), more preferably 0.3 xm or less, and still more preferably 0. Less than lzm. The average particle size is preferably 0.5 × m or less because a cold plastic lubricant composition having better seizure resistance can be obtained.

[0050] The carbonate content is 10% by mass or more and less than 100% by mass based on the composition (usually 95% by mass or less), preferably 10 to 90% by mass, more preferably 10 to 80% by mass. , more preferably 10 to 70 weight ^_0/0, and particularly preferably 15 to 65 wt%. When this content is less than 10% by mass, a lubricant composition for cold plastic working having good lubricity and excellent seizure resistance cannot be obtained. In addition, the flash point of the lubricant composition cannot be made sufficiently high.

[0051] Examples of the "alkali metal" and "alkaline earth metal" in the hydroxide include those similar to the carbonates described above. The alkali metal and / or alkaline earth metal constituting the hydroxide may be the same as or different from the alkaline metal and / or alkaline earth metal constituting the carbonate. Specific examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydroxy hydroxide, barium hydroxide, and the like. One or more hydroxides can be used.

[0052] The hydroxide content is the amount of hydroxide with respect to 100 parts by mass of carbonate, more than 0 parts by mass and not more than 5 parts by mass (usually 0.01 parts by mass or more), preferably 0. 05 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and particularly preferably 0.09 to 3.5 parts by mass. If the content of this hydroxide exceeds 5 parts by mass, sufficient seizure resistance cannot be obtained. The hydroxide content can be determined by a general titration method such as neutralization titration with acid. The

[0053] The content of the hydroxide is usually more than 0% by mass and less than 5% by mass, preferably 0.05 to 4% by mass, more preferably 0.05 to 3% by mass based on the composition. %, More preferably 0.05 to 2% by mass, particularly preferably 0.:! To 1% by mass.

[0054] By setting the hydroxide content in the above range, a cold plastic cache lubricant composition having good lubricity and excellent seizure resistance can be obtained.

Carbonates and hydroxides may be synthetic or commercially available. Commercial products can be obtained as powders. Alternatively, a solution in which an alkali metal and / or alkaline earth metal carbonate and hydroxide are uniformly dissolved or dispersed in an appropriate medium (an inorganic solvent or an organic solvent, particularly an oil used as a lubricating base oil) or It can also be obtained as a dispersion.

[0055] The lubricant composition for cold plastic working of the present invention does not contain a chlorine compound. “Chlorine compounds” are inorganic compounds and organic compounds containing chlorine atoms. Specifically, for example, chlorine-based extreme pressure additives such as chlorinated paraffin and chlorinated fatty oil, carbon tetrachloride, trichlorethylene And chlorine-based solvents such as methylene chloride, chlorine-containing fluorine-based solvents such as black fluorocarbon, and inorganic chlorine compounds such as ammonium chloride.

[0056] The lubricant composition for cold plastic working of the present invention "contains no chlorine-based compound" is ideal for the content of the chlorine-based compound to be 0% by mass. A composition containing a small amount of a chlorine-based compound depending on the product is also included in the present invention. In the present invention, it is not excluded that the lubricant composition for cold plastic working contains more than 0% by mass and less than 1% by mass of a chlorine-based compound based on the composition. In this case, the content of the chlorine-based compound is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, and most preferably 0.001% by mass. % Or less.

[0057] The lubricant composition for cold plastic working of the present invention further contains at least one metal salt selected from sulfonates, salicylates, phenates and carboxylates of alkali metals or alkaline earth metals. Can do. Thereby, a clean dispersion action can be imparted to the lubricant composition.

[0058] Regarding the "alkali metal" and "alkaline earth metal" of this metal salt, The same thing as the above can be mentioned. The “alkaline metal” and “alkaline earth metal” of the metal salt may be the same as or different from the alkali metal and / or alkaline earth metal constituting the carbonate and / or hydroxide.

[0059] "Sulfonate" includes alkyl aromatic sulfonic acids such as petroleum sulfonic acid and alkylbenzene sulfonic acid, alkali metal salts and alkaline earth metal salts of sulfonic acids such as alkyl sulfonic acid and polyisobutenyl sulfonic acid. Is mentioned. Examples of “salicylate” include alkali metal salts and alkaline earth metal salts of salicylic acids such as alkyl salicylic acid. “Phenates” include alkali metal salts and alkaline earth metal salts of phenates such as phenol and alkylphenol. Examples of the “carboxylate” include alkali metal salts and alkaline earth metal salts of carboxylic acids such as maley polybutene, fatty acids, and carboxy-modified acrylic resins. One or more metal salts can be used.

[0060] Metal salts, such as sulfonates, salicylates, phenates or carboxylates of alkali metals and / or alkaline earth metals, in base oils in which the corresponding acids, ie sulfonic acids, salicylic acids, phenols or carboxylic acids, are dissolved. Further, it can be produced by blowing carbon dioxide into a system containing alkali metal and / or alkaline earth metal hydroxide (and / or oxide).

[0061] Usually, an excessive amount of alkali metal and / or alkaline earth metal hydroxide is used. In that case, the produced metal salt contains alkali metal and / or alkaline earth metal carbonate, and optionally unreacted alkali metal and / or alkaline earth metal hydroxide, and thus has basicity. Show. The base number of the metal salt depends on the amount of alkali metal and / or alkaline earth metal hydroxide contained in the system. In some cases, the base number of the base salt is higher than that of a highly basic metal salt with a base number of 100 mg-KOHZg or more. Become. The base number of the metal salt used in the present invention is not particularly limited.

[0062] The lubricant composition for cold plastic working of the present invention contains a metal salt such as sulfonate, and the metal salt contains an alkali metal and Z or alkaline earth metal carbonate and / or hydroxide. In the case where it is contained, the amount of the carbonate, Z and hydroxide contained in this metal salt is also the above-mentioned “carbonate” which is an essential component in the composition of the present invention. And / or " Included in the "hydroxide" amount.

[0063] The content of metal salt (alkali metal and / or alkaline earth metal sulfonate, salicylate, phenate and / or carboxylate) is the mass of metal salt relative to 100 parts by mass of carbonate (metal salt is carbonate and In the case of containing a hydroxide and / or a hydroxide, the mass is excluded): preferably 50 to 50 parts by mass, more preferably 1 to 40 parts by mass, More preferably, it is 5-30 mass parts. When the content is in the above range, the stability of the lubricant composition is excellent and the seizure resistance can be improved.

[0064] The lubricant composition for cold plastic cache of the present invention has an organic sulfuration having a carbon atom in which a sulfur atom and a nitrogen atom or an oxygen atom are bonded in order to further improve lubricity. A compound can be further contained. As this organic sulfur compound, for example, N = C-S, N—C = S, N—C_S, N = C = S, ○ = C_S, ○ _C = S, ○ _C_S and ○ = C = Organic compounds having a structural part such as S can be mentioned. Preferable specific examples of this organic sulfur compound are compounds represented by the above formulas (1) to (12), and it is possible to surely obtain a lubricant composition having better lubricity. One or more organic sulfur compounds can be used.

[0065] The content of the organic sulfur compound is not particularly limited, but is preferably 0.:! To 50% by mass based on the composition, more preferably 1 to 40% by mass, and even more preferably 5 to 5% by mass. 30% by mass. When this content is within the above range, it is possible to obtain a lubricant composition having superior lubricity.

[0066] In addition to the above components, the lubricant composition for cold plastic working of the present invention may appropriately contain various additives that are added to a general plastic additive. . For example, oily agents such as hindered esters and alkylamines; extreme pressure additives including organic sulfur compounds such as polysulfides and sulfurized fats and oils, organic phosphorous compounds such as (sub) phosphate esters and acidic (sub) phosphate esters; Examples thereof include organic metal salts such as zinc dithiophosphate and molybdenum dithiocarbamate; solid lubricants such as graphite and molybdenum disulfide; antioxidants, antifungal agents, and anticorrosives. It is preferable to refrain from using solid lubricants such as graphite and molybdenum disulfide because they may deteriorate the working environment. [0067] Since the lubricant composition for cold plastic working of the present invention does not contain a chlorine-based compound, an optional additive other than the chlorine-based compound is used. However, the use of a chlorinated compound in an optional additive used in a trace amount is not excluded as long as it does not cause harmful effects due to the inclusion of the chlorinated compound.

[0068] The form of the lubricant composition for cold plastic working of the present invention is liquid or gel at normal temperature (about 25 ° C). The flash point of this composition is preferably 150 ° C or higher, more preferably 170 ° C or higher, and further preferably 200 ° C or higher. When the flash point is 150 ° C or higher, the lubricant composition can be used safely even in severe plastic molding where the processing conditions are high and the processing temperature is high. (2) Cold plastic working method

When performing cold plastic working of a workpiece using the lubricant composition for cold plastic working of the present invention, the material of the force-bearing material is not particularly limited. Examples of the material to be supported include stainless steel, high alloy steel, aluminum, copper, titanium, nickel, and alloys thereof. The shape of the workpiece is not particularly limited because it is possible to process a shape (such as a gear shaft) after hot forging using only a bar or block material. There is no particular limitation on the plastic processed product obtained by the cold plastic processing method. Specific examples of the plastic processed product include a metal tube, a metal wire, a metal rod, and a billet.

[0069] Specific examples of cold plastic working include sheet rolling, tube rolling, strip steel (section steel, bar wire, wire rod) rolling, drawing (drawing), forging, and the like. Particularly preferred cold plastic working is cold forging or cold pipe making. The conditions and methods of cold plastic working such as cold forging and cold pipe forming are not particularly limited, and can be performed by appropriately setting conditions using a known apparatus or the like.

Example

[0070] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. In the description of this example, “%” represents “mass%” and “part” represents “part by mass”.

[0071] [1] Preparation of lubricant composition for cold plastic working

The carbonate dispersions of No .:! To 5 shown in Table 1 were mixed with the indicated alkali metal or alkaline earth metal carbonate and hydroxide, and metal sulfonate (alkylbenzene sulfone). (Calcium salt or sodium salt of acid) was dispersed in mineral oil (refined mineral oil; manufactured by Nippon Oil Corporation) so as to have the indicated content. Table 1 also shows the average particle size and crystal structure of the alkali metal or alkaline earth metal carbonate used, and the appearance of the dispersion. In each dispersion, the metal species of carbonate, hydroxide, and sulfonate were the same.

[table 1]

Mineral oil (refined) with the carbonate dispersion selected from the above No.:! 5 and the organic sulfur compounds selected from the following No. 1 to: 12 to the contents shown in Table 2 and Table 3. Mineral oil; The lubricant composition for cold plastic working of Examples:! To 18 and Comparative Examples:! To 2 was prepared. Tables 2 and 3 also indicate the alkali metal or alkaline earth metal carbonate content, crystal structure and average particle size, and hydroxide content relative to the alkali metal or alkaline earth metal carbonate. did. “*” In Table 3 indicates that it is outside the scope of the present invention.

[0074] Organic sulfur compounds used:

No. 1 Compound of formula (1),

No. 2 Compound of general formula (2) (X = 2),

1

No. 3 The compound of the general formula (3) (R = R = —C H),

1 2 2 5

No. 4 Compound of the above general formula (4) (X = 2),

2

No. 5 Compound [R = -C (CH)] of the general formula (5),

3 3 3

No. 6 The compound of the formula (6),

No. 7 The compound of the general formula (7) (X = x = 2 and R = R = C H),

3 4 4 5 8 17

No. 8 Compound of the above general formula (8) (R = R = —CH and M = l / 2Ca),

6 7 4 9

No. 9 Compound of the above general formula (9) (R = H and R = —C H NH),

8 9 5 1C 2

No. 10: Compound of the above general formula (10) [x = 2, and R to R = CH 2 CH 2 (CH 3)

5 10 13 2 2 5

C H,

4 9

No. 11: Compound of the above general formula (11) (x = 4),

6

No. 12: Compound of the above general formula (12) (R = R = H and R = RCH).

14 16 15 17 6 5

[0075] As Comparative Example 3, a water-insoluble lubricating oil (main component: fatty acid ester 15%, sulfurized fat and oil 70%) was used.

[2] Performance evaluation of lubricant composition

The performance evaluation of each plastic working lubricant composition of Examples:! To 18 and Comparative Examples:! To 3 was carried out by the methods described below.

[0076] (1) Cold drawing test of steel pipe with small drawing machine

A steel pipe (material: SUS304) having an outer diameter of 21.5 mm, an inner diameter of 16.04 mm, and a length of 750 mm was used as a workpiece. This steel pipe was subjected to a solution treatment in advance and then a surface roughening treatment by pickling. The diameter of the die of the small drawing machine is 17.5 mm, and the plug is A semi-float type with an outer diameter of 13.2 mm was used. The area reduction after cold drawing with this small drawing machine is 35.6%.

[0077] The plastic working lubricant compositions of the above Examples:! To 18 and Comparative Examples:! To 3 were applied to the inner and outer surfaces of the steel pipe, and were also applied to the inner and outer surfaces of the steel pipe immediately before drawing. Example: Cold drawing was performed by supplying the plastic working lubricant compositions of! -18 and Comparative Examples 1-3.

[0078] The surface of the steel pipe after drawing was visually observed, and the performance was evaluated by examining the presence or absence of seizure. The results are shown in Table 2 and Table 3, respectively. In each table, “©” indicates that there was no seizure, “◯” indicates that slight seizure occurred, and “△” indicates that slight seizure occurred. “X” indicates that severe seizure occurred.

[0079] (2) Ironing test

Using the testing machine for evaluating lubricity shown in Fig. 1, the ironing test was conducted as follows. The test machine T has a die placed on the base 7 (concave tool, material: carbide tool, diameter: 20.85 mm) 1 and a steel ball [convex tool, material: 3¾12 (bearing steel), Diameter: 1 9111111] 4, and a press machine 5 disposed above the die 1 and capable of vertical stroke operation.

[0080] A test plate (material: SUS304, plate thickness: 2. Omm, shape: disc shape) 2 in which a hole 6 having a diameter of 10 mm was formed at the center was used as a workpiece. The lubricant compositions for plastic working of Examples:! To 18 and Comparative Examples:! To 3 were sufficiently applied to both surfaces of the test plate 2. Thereafter, the test plate 2 was fixed to the center of the die 1 by the plate presser 3. Next, the steel ball 4 was placed on the hole 6 in the center of the test plate 2. This placement was performed so that the axes of the die 1, the test plate 2, the steel ball 4, the press machine 5, and the cylinder rod 8 coincided. After that, the lower end 81 of the cylinder rod 8 of the press machine 5 was applied to the steel ball 4 with a force S, the hydraulic cylinder was extended downward, and ironing was performed to form the boss part. The ratio (scoring rate) between the die 1 and the steel ball 4 that the test plate 2 is squeezed by one-time machining was 45%. An electric furnace was used, and the die 1 and the steel ball 4 were preheated to 100 ° C. before the test.

[0081] The performance evaluation was performed by visually observing the processed boss and examining the presence or absence of seizure. The results are also shown in Table 2 and Table 3, respectively. In each table, “◎” indicates that no seizure occurred, “◯” indicates that slight seizure occurred, and “△” indicates half-surface seizure. “X” indicates that severe seizure has occurred.

[0082] (3) Evaluation of flammability

Examples:! To 18 and comparative examples:! To 3, the flash point of each plastic working lubricant composition is JIS

According to K2265, measurement was performed using a Cleveland open flash point measuring device. The results are shown in Tables 2 and 3.

[0083] [Table 2]

As shown in Table 3, in comparative examples that are outside the scope of the present invention:! To 3, severe seizure occurred on the inner surface of the tube after cold drawing, and seizure at the boss in the ironing test described above. On the other hand, as shown in Table 2 and Table 3, in Examples:! To 18, which are within the scope of the present invention, all can be drawn without causing surface flaws such as seizure, In the test, it was confirmed that surface defects such as seizure occurred on the boss part. [0086] Further, the flash points of the lubricant compositions of Examples:! To 18 are 150 to 260 ° C, and the lubricant composition that is as high as 150 to 260 ° C should be used safely even during severe plastic processing where the processing conditions are high. I was able to confirm that

[0087] The present invention is not limited to those shown in the specific examples, and various modifications can be made within the scope of the present invention according to the purpose and application.

Claims

The scope of the claims

[1] In lubricating base oil, selected from at least one carbonate selected from alkali metal carbonate and alkaline earth metal carbonate, and from alkali metal hydroxide and alkaline earth metal hydroxide. A lubricant composition for cold plastic working containing at least one hydroxide and not containing a chlorine-based compound, wherein the carbonate content in the composition is 10% by mass or more and 100% by mass. %, And the hydroxide content is more than 0 parts by mass and not more than 5 parts by mass per 100 parts by mass of the carbonate.

[2] The lubricant composition for cold plastic working according to claim 1, further comprising at least one metal salt selected from sulfonates, salicylates, phenates and strong lpoxylates of alkali metals or alkaline earth metals.

[3] It further contains an organic sulfur compound having a carbon atom in which a sulfur atom and a nitrogen atom or an oxygen atom are bonded, and the content of the organic sulfur compound in the composition is 0.:! To 50% by mass The lubricant composition for cold plastic working according to claim 1 or 2.

[4] The lubricant composition for cold plastic working according to any one of claims 1 to 3, wherein the crystal structure of the carbonate is an amorphous type.

[5] The lubricant composition for cold plastic working according to any one of [1] to [4], wherein the carbonate has an average particle size of 0.5 × m or less.

6. The cold plastic cache lubricant composition according to any one of claims 1 to 5, wherein the alkali metal is sodium and the alkaline earth metal is calcium.

[7] The lubricant composition for cold plastic cache according to any one of claims 1 to 6, having a flash point of 150 ° C or higher.

8. The cold plastic working lubricant composition according to claim 2, wherein the content of the metal salt is 1 to 50 parts by mass per 100 parts by mass of the carbonate.

[9] The lubricant composition for cold plastic working according to claim 3, wherein the organic sulfur compound is at least one selected from compounds represented by the following formulas (1) to (: 12): :

[Chemical 1]

[Chemical 2]

[Wherein X is an integer of 2 to 4]

[Chemical 3]

[In the formula, R and R are each CH or CH, and they may be the same or different.

1 2 3 2 5

May be)

[Chemical 4]

[Wherein X is 1 or 2]

2

[Chemical 5]

[Wherein R is _C (CH) or _C H]

3 3 3 6 11

[Chemical 6]

[Chemical 7]

[Wherein x and x are each an integer of 24 and may be the same or different from each other.

3 4

R and R are each --C H-C H or _C (S) N (C H) and

4 5 8 17 12 25 2 5 2

Even if it ’s one, it ’s different.

[Chemical 8]

[Wherein R and R are each —CH—CH—CH—CH—CH or CH

6 7 3 2 5 3 7 4 9 6 5 2

C H, which may be the same or different from each other M is Na K or l / 2Ca

6 5

is there〕

[Chemical 9]

[Wherein, R is H or —CH, and R is —C H NH or —CH (CH 2) C H NH

8 3 9 5 10 2 3 4 8 2)

[Chemical 10]

[Wherein R R R and R are each —CH C H C H C H or — C

10 11 12 13 3 2 5 3 7 4 9

H CH (C H) C H, which may be the same or different from each other X is 14

(2 2 5 4 9 5 is an integer)

[Chemical 11]

[Wherein x is an integer of 14]

6

[Chemical 12]

2)

[Wherein R and R are each H—CH or —CH, and they may be the same or different.

14 16 3 2 5

R and R may be —CH—CH or —CH, and are the same as each other.

15 17 3 2 5 6 5

Even if it ’s one, it ’s different.

[10] A cold plastic working method comprising performing cold plastic working of a material to be caloeed using the lubricant composition for cold plastic working according to any one of claims 19 to 19.

11. The cold plastic caching method according to claim 10, wherein the workpiece material is stainless steel, high alloy steel, aluminum, copper, titanium, nickel or an alloy thereof.

12. A metal tube, a metal wire, a metal bar or a billet is manufactured by the cold plastic working.

The cold plastic processing method according to 0 or 11.

[13] The cold plastic working method according to any one of [10] to [12], wherein the cold plastic working is a cold forging cage or cold pipe forming.