JPH07118682A - Cold forging processing oil composition - Google Patents

Abstract

PURPOSE:To obtain the processing oil composition capable of carrying out cold forging processing without treatment with a phosphoric acid coating film even under a severe processing condition by blending a lube base oil comprising a mineral oil, a synthetic oil, etc., with specific amounts of zinc dithiophosphate, a sulfur-based extreme-pressure agent and a dispersant. CONSTITUTION:A lube base oil comprising a mineral oil (e.g. paraffinic oil) and/or a synthetic oil (e.g. poly-alpha-olefin) is blended with (A) 1-50wt.% based on the whole amount of a composition of one or more of organometallic compounds such as zinc dithiophosphate, zinc dithocarbamate, molybdenum dithiophoshate and molybdenum dithocarbamate, (B) 0.1-10wt.% calculated as sulfure content of a sulfur-based extreme-pressure agent (e.g. di-butyl- pentasulfide) and (C) an ash-free dispersant (e.g. bis type alkenylsuccinic acid imide) to give the cold forging processing oil composition having excellent processing performances.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold forging oil composition, and more particularly to a cold forging oil composition having good working performance even under severe extrusion (backward extrusion) conditions such as punch breakage. Regarding things.

[0002]

2. Description of the Related Art In the field of cold forging of metals, particularly cold forging of steel materials, for many years, forging work is performed to prevent seizure between a work material and a tool and to reduce a working load. A method of subjecting a material to be processed to a chemical conversion treatment in advance to form a phosphate film on the surface has been frequently used.

On the other hand, if cold forging can be performed only with lubricating oil without using such a pretreatment, the process can be simplified, and it can be integrated with other processing steps, which is a great advantage. To be Therefore, in recent years, researches on cold forging oils have been actively conducted, and as cold forging oils that do not require phosphate coating treatment, metal soap, sulfur-based extreme pressure agents, chlorine-based extreme pressures are used as lubricating base oils. Various cold forging oils containing a chemical agent and a phosphorus-based extreme pressure agent have been developed and used.

[0004]

However, these cold forging oils have the drawbacks that they have poor oil film retention and are prone to seizure, so their range of use has been limited. Therefore, it was not possible to use the cold forging oil alone without the phosphoric acid coating treatment under the severe conditions of backward extrusion where breakage of the punch occurs. INDUSTRIAL APPLICABILITY The present invention provides a cold forging oil composition having excellent processability, which enables cold forging without phosphoric acid coating treatment even under severe extrusion (backward extrusion) conditions in which punch damage occurs. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of repeated studies to overcome the drawbacks of the above-mentioned conventional cold forging oils, the present inventors have found that an organometallic compound having a specific structure and a sulfur-based extreme pressure agent. It has been found that a cold forging oil containing as an essential component exhibits extremely excellent processing performance as compared with a conventional cold forging oil, and has completed the present invention.

The first invention of the present invention relates to (A) zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate and a lubricant base oil comprising a mineral oil and / or a synthetic oil, based on the total amount of the composition. One or more organometallic compounds selected from the group consisting of molybdenum dithiocarbamates, 1 to 50% by weight, and (B) a sulfur-based extreme pressure agent as a sulfur component, 0.1 to 10% by weight. The present invention provides a cold forging processing oil composition.

The second invention of the present invention is based on the total amount of the composition, based on the total amount of the composition (A) zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate for a lubricating base oil comprising mineral oil and / or synthetic oil. One or two or more organometallic compounds selected from the group consisting of a fate and molybdenum dithiocarbamate, 1 to 50% by weight, (B) a sulfur-based extreme pressure agent as a sulfur content, 0.1 to 10% by weight, and ( C) An ashless dispersant, which provides a cold forging oil composition containing 0.1 to 10% by weight. Hereinafter, the content of the present invention will be described in more detail.

The lubricating base oil for use in the present invention is not particularly limited, and any mineral oil or synthetic oil can be used as long as it is commonly used as a lubricating base oil. As the mineral oil-based lubricating base oil, for example,
Lubricating oil fractions obtained by distilling crude oil under atmospheric pressure and vacuum distillation are used for solvent degassing, solvent extraction, hydrocracking, solvent dewaxing,
Oils such as paraffin-based and naphthene-based oils that are refined by appropriately combining purification treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment can be used.

Examples of synthetic lubricating base oils include poly-α-olefins (polybutene, 1-octene oligomer, 1-decene oligomer, etc.), alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-decene). Ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di2-
Ethylhexyl sebacate etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-
Ethyl hexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, polyphenyl ether, silicone oil, perfluoroalkyl ether, etc. can be used. These base oils may be used alone or in combination of two or more.

Although the viscosity of the lubricating base oil used in the present invention is arbitrary, the kinematic viscosity at 40 ° C. is usually 5 to 300 mm ² / because of its excellent cooling performance for the processed material during cold forging. s is preferably used, and 5
It is more preferably 0 to 200 mm ² / s.

On the other hand, the component (A) which is an essential additive in the cold forging oil composition of the present invention is selected from the group consisting of zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate and molybdenum dithiocarbamate. It is one kind or two or more kinds of organometallic compounds.

The zinc dithiophosphate as used herein is specifically represented by the following general formula (1) (chemical formula 1),
The zinc dithiocarbamate is specifically, for example, the following general formula (2) (chemical formula 2), and the molybdenum dithiophosphate is specifically, for example, the following general formula (3) (chemical formula 3), and molybdenum The dithiocarbamate is specifically a compound represented by the following general formula (4) (formula 4).

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

In the above general formulas (1) to (4), R ¹ and R
² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each has 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, a cycloalkyl group, It represents an alkylcycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group. Also, a, b, c and d are a + b = 4 and c + d = 4
Respectively, and in particular a = 1 to 3,
The numbers b = 1 to 3, c = 1 to 3 and d = 1 to 3 are preferred.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
^{As 7} and R ⁸ , specifically, for example, a methyl group,
Ethyl group, propyl group (including all branched isomers),
Butyl group (including all isomers), pentyl group (including all isomers), hexyl group (including all isomers), heptyl group (including all isomers) ), An octyl group (including all fractional isomers),
Nonyl group (including all division isomers), decyl group (including all division isomers), undecyl group (including all division isomers), dodecyl group (including all division isomers) ), Tridecyl group (including all fractional isomers),
Tetradecyl group (including all isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers) ), Octadecyl group (including all divisional isomers), nonadecyl group (including all divisional isomers), eicosyl group (including all divisional isomers), heneicosyl group (all divisional isomers) An alkyl group such as docosyl group (including all divisional isomers), tricosyl group (including all divisional isomers), tetracosyl group (including all divisional isomers); cyclopentyl group, Cycloalkyl groups such as cyclohexyl group and cycloheptyl group; methylcyclopentyl group (including all substitution isomers), ethylcyclopentyl group (including all substitution isomers) ), Including dimethylcyclopentyl group (including all isomers), propylcyclopentyl (all partial skill isomers and substituted isomers),
Methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers), butylcyclopentyl group (including all divisional isomers and substituted isomers), methylpropylcyclopentyl group ( (Including all divisional isomers and substitution isomers),
Diethylcyclopentyl group (including all substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers) ), Dimethylcyclohexyl group (including all substitution isomers), propylcyclohexyl group (including all division isomers and substitution isomers), methylethylcyclohexyl group (including all substitution isomers),
Trimethylcyclohexyl group (including all substitution isomers), butylcyclohexyl group (all division isomers,
(Including substituted isomers), methylpropylcyclohexyl group (including all partial isomers and substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers) ), Methylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group ( All divisional isomers, including substitution isomers, methylethylcycloheptyl group (including all divisional isomers), trimethylcycloheptyl group (including all substitutional isomers), butylcycloheptyl group (all Isomers, including substituted isomers), methylpropylcycloheptyl group (all isomers, substituted isomers) ), An alkylcycloalkyl group such as a diethylcycloheptyl group (including all substituted isomers) and a dimethylethylcycloheptyl group (including all substituted isomers); an aryl group such as a phenyl group and a naphthyl group; Tolyl group (including all substitution isomers), xylyl group (including all substitution isomers), ethylphenyl group (including all substitution isomers), propylphenyl group (all division isomers, substitution isomers) Body), methylethylphenyl group (including all substitution isomers), trimethylphenyl group (including all substitution isomers), butylphenyl group (including all division isomers and substitution isomers), Methylpropylphenyl group (including all divisional isomers and substitution isomers), diethylphenyl group (including all substitution isomers), dimethyl ether Ruphenyl group (including all substitution isomers), pentylphenyl group (including all division isomers and substitution isomers), hexylphenyl group (including all division isomers and substitution isomers), heptylphenyl Group (including all divisional isomers and substitution isomers), octylphenyl group (including all divisional isomers and substitution isomers), nonylphenyl group (including all divisional isomers and substitution isomers) ), Decylphenyl group (including all divisional isomers and substitution isomers), undecylphenyl group (including all divisional isomers and substitution isomers), dodecylphenyl group (all divisional isomers, (Including substituted isomers), tridecylphenyl group (including all divisional isomers and substitutional isomers), tetradecylphenyl group (including all divisional isomers and substitutional isomers), pentadecylphenyl Group (including all division isomers and substitution isomers), hexadecylphenyl group (all division isomers,
Alkylaryl groups such as substituted isomers), heptadecylphenyl groups (including all divisional isomers and substitutional isomers), octadecylphenyl groups (including all divisional isomers and substitutional isomers); benzyl Examples thereof include arylalkyl groups such as a group, a phenethyl group, a phenylpropyl group (including all isomers), a phenylbutyl group (including all isomers), and the like.

As the component (A) of the present invention, the organometallic compounds represented by the above-mentioned general formulas (1) to (4) and mixtures thereof are used, but the processing performance during cold forging is used. Zinc dithiophosphate represented by the general formula (1) is preferably used from the viewpoint of excellent
Zinc dialkyldithiophosphates in which R ¹ and R ² in the formula are alkyl groups having 4 to 18 carbon atoms are often used preferably, and R ¹ and R in the formula (1) are used.
Zinc dialkyldithiophosphate in which ² is a secondary alkyl group (secondary alkyl group) having 4 to 18 carbon atoms is particularly preferably used.

As the component (A) of the present invention, a compound represented by the general formula (1)
As long as it is an organometallic compound represented by the formulas (4) to (4), only an organometallic compound having a single structure may be used, or a mixture of two or more organometallic compounds having different structures may be used.

In the present invention, the content of the component (A) is
1 to 50% by weight, preferably 20 to 4 based on the total amount of the composition
It is 5% by weight. When the content of the component (A) is less than 1% by weight, the effect of improving the workability due to the synergistic effect with the component (B) is insufficient and the punch damage increases during cold forging, while If the content exceeds 50% by weight, the effect of improving the processing performance commensurate with the content cannot be obtained, and it is economically disadvantageous, and therefore it is not preferable.

On the other hand, the component (B) which is an essential additive in the cold forging oil composition of the present invention is a sulfur-based extreme pressure agent. Specific examples of the sulfur-based extreme pressure agent used herein include sulfurized whale oil, sulfurized lard oil, sulfurized vegetable oil, sulfurized fish oil, sulfurized oils and fats such as sulfurized esters; by reacting an olefin such as 1-butene with sulfur. The resulting olefin polysulfide; and dihydrocarbyl sulfide and the like. Among these sulfur-based extreme pressure agents, sulfurized fats and oils are preferably used in the present invention, in particular, because the fats and oils in the molecule can also be expected to improve the oiliness.

When a sulfurized fat or oil is used as the sulfur-based extreme pressure agent in the present invention, the sulfur content is preferably 1 to 30% by weight, more preferably from the viewpoint of easily adjusting the sulfur content in the lubricating oil composition. Is preferably 5 to 25% by weight.

The content of the component (B) in the present invention is 0.1 to 10% by weight, preferably 0.5 to 6% by weight, as a sulfur content, based on the total amount of the composition. When the content of the component (B) is less than 0.1% by weight as sulfur content, (A)
The effect of improving the workability due to the synergistic effect with the components is insufficient, and the punch breakage increases during cold forging. On the other hand, when the content of sulfur exceeds 10% by weight, it is commensurate with the content. It is not preferable because the effect of improving the processing performance is not obtained and it is economically disadvantageous. When sulfurized fats and oils are used as the sulfur-based extreme pressure agent in the present invention, this content is usually 2 to 50 based on the total amount of the composition as sulfurized fats and oils.
%, Preferably 3 to 30% by weight.

In the present invention, as described above, it is necessary to use a specific amount of (A) an organometallic compound and (B) a sulfur-based extreme pressure agent in combination with a lubricating base oil to obtain a cold work which is particularly excellent in processing performance. A forging oil composition can be obtained. However, this composition has a risk of causing gelation under severe conditions such as long-term use at high temperature, and has some problems in use under severe conditions. Therefore, when this composition is used under severe conditions of high temperature and long time use, it is preferable to further use (C) an ashless dispersant for the purpose of preventing this gelation.

The ashless dispersant (C) as used herein is a compound having an amino group and a long-chain alkyl group or alkenyl group in the same molecule. Specifically, for example, succinimide or its derivative, benzyl. Examples include amines, polyalkenylamines and aminoamides.

More specifically, as the succinimide or its derivative, a polyolefin such as polybutene having a molecular weight of 300 to 3000 is reacted with maleic anhydride, and then a polyamine such as tetraethylenepentamine or pentaethylenehexamine is used. Imidized alkenyl (alkyl) succinimide; the obtained alkenyl succinimide is reacted with an aromatic polycarboxylic acid such as phthalic acid, trimellitic acid or pyromellitic acid, and the remaining amino groups are partially amides. The obtained alkenyl succinimide or the amidated product thereof is further modified with boric acid; or a mixture thereof.

The alkenyl succinimide imidized with polyamine is a so-called mono-type in which maleic anhydride is added to one end of polyamine, and a so-called bis-type in which maleic anhydride is added to both ends of polyamine. However, any of them can be preferably used as the component (C) in the present invention.

Benzylamine has a molecular weight of 3
Examples include those produced by a so-called Mannich reaction in which a polyolefin such as propylene orimagomer of 0 to 3000 or polybutene is reacted with phenol to form an alkylphenol, and then formaldehyde and polyamine are reacted with this.

Examples of the polyalkenylamine include those obtained by chlorinating a polyolefin such as polybutene having a molecular weight of 300 to 3000 and reacting this with ammonia, polyamine or the like.

As the aminoamide, a polyalkylenepolyamine such as tetraethylenepentamine is reacted with a saturated or unsaturated monofatty acid having 8 to 30 carbon atoms to amidate a part or all of the amino group of the polyalkylenepolyamine. The ones that have been done are listed.

When the component (C) is used in the present invention, the content of the component (C) is 0.1 based on the total amount of the composition.
10 to 10% by weight, preferably 1.0 to 5.0% by weight. When the content of the component (C) is less than 0.1% by weight, the effect of preventing gelation of the composition by blending the component (C) at high temperature is insufficient, while when the content exceeds 10% by weight. Does not have a gel prevention effect that is commensurate with the content,
It is economically disadvantageous and therefore not preferable.

The cold forging oil composition of the present invention may be used alone or in combination with several known lubricating oil additives for the purpose of further enhancing various performances thereof.

Specific examples of these additives include phosphoric acid esters such as tricresyl phosphate, oils and fats such as lard oil, and lubricity improvers typified by fatty acids; neutrality, basicity or superactivity. Metal-based detergents represented by basic sulfonates, phenates, salicylates, and phosphonates; benzotriazole;
Examples include metal deactivators such as thiadiazole; defoaming agents such as methyl silicone, fluorosilicone, and polyacrylate. Although the addition amount of these known additives is arbitrary, the content of the lubricity improver and the metal-based detergent is usually 1 to 30% by weight, and the content of the metal deactivator is usually based on the total amount of the composition. The content of 0.005 to 1% by weight and the content of the defoaming agent are usually 0.0001 to 0.5% by weight.

The cold forging oil composition according to the present invention is used for cold forging of steel such as carbon steel, alloy steel, and stainless steel, specifically, for example, upsetting,
Extrusion, forward extrusio
n), backwardextrusion, cutting (trimm
ing), cold forging such as piercing.

[0036]

EXAMPLES Hereinafter, the contents of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these contents. (Example 1) With the composition shown in Table 1, a cold forging working oil composition according to the present invention was prepared. The following performance tests were conducted on this composition, and the results are also shown in Table 1.

(Examples 2 to 6) According to the composition shown in Table 1,
A cold forging processing oil composition according to the present invention was prepared. The following performance test was conducted on this composition in the same manner as in Example 1,
The results are also shown in Table 1.

(Comparative Example 1) For comparison, a cold forging oil composition having the composition shown in Table 1 was prepared without using the component (B). The following performance tests were conducted on this composition in the same manner as in Example 1, and the results are also shown in Table 1.

Comparative Example 2 Table 1 without using the component (A)
A cold forging processing oil composition was prepared according to the composition shown in. The following performance tests were conducted on this composition in the same manner as in Example 1, and the results are also shown in Table 1.

(Comparative Examples 3 and 4) Similar performance tests were carried out when other extreme pressure agents were used instead of the component (A), and the results are also shown in Table 1.

[Four-ball test] JIS K 2519 "Lubricant oil load capacity test method" 5. According to the “Soda-type four-ball method” defined in paragraph 1, the acceptable limit load at a rotation speed of 750 rpm was measured. Also, using the same testing machine, the rotation speed is 200 rp
The test was conducted for 5 minutes under m and a load of 5 kgf, and the wear scar diameter of the hard sphere after the test was measured.

[Ball insertion test] Inner diameter 15 mm, outer diameter 2
The pushing load required when pushing the bearing shaft having a diameter of 16 mm into the cylindrical carbon steel of 9.8 mm (area reduction rate: 4.6%) was measured. (For details of this ball threading test, see, eg, "38th Plastic Working Joint Lecture Preliminary Collection" (1987).
, Pp. 649-652. )

[Thermal stability test] 120 ° C. according to “Lubricating oil thermal stability test method” specified in JIS K 2540
The thermal stability test was performed under two conditions of 48 hours at 130 ° C. and 48 hours at 130 ° C., and the state of the sample oil after the test was visually observed.

The components used in the examples and comparative examples are as follows. Lubricating base oil A: refined paraffin mineral oil (kinematic viscosity 22.4 mm ² /
s (@ 40 ℃))

Component (A) A: Zinc didodecyl dithiophosphate B: Zinc dipentyl dithiocarbamate C: Molybdenum dioctyl dithiophosphate D: Molybdenum alkyldithiocarbamate (alkyl group = mixture of alkyl groups having 8 to 13 carbon atoms) [ Mo content: 29.1% by weight, S content 25.2% by weight]

Component (B) A: Sulfurized fats and oils (S content: 11.2% by weight) B: Di-t-butyl-pentasulfide (S content: 3)
7.0% by weight)

Component (C) A: Bis-type alkenyl succinimide (weight average molecular weight: 1470, N content 4.8% by weight) B: benzylamine (weight average molecular weight: 107, N content 13.1% by weight)

Other extreme pressure agents A: lead naphthenate (Pb content: 30% by weight) B: tricresyl phosphate

[0049]

[Table 1]

As is clear from the results shown in Table 1, the cold forging oil composition according to the present invention has good results in the four-ball test and the ball-through test, and shows excellent processing performance. Moreover, the compositions of Examples 5 and 6 in which the component (C) was used in combination were compared with the compositions of Examples 1 to 4 in Examples 1 to 4.
The gelation-preventing effect at high temperature is further improved while maintaining the excellent performance of the composition of (C).
The effects of the ingredients are clearly visible. On the other hand, (B)
Comparative Example 1 using no component, Comparative Example 2 using no component (A), Comparative Example 3 using another extreme pressure agent in place of the component (A)
Also, the compositions of Comparative Example 4 are much inferior to the composition of the present invention in the results of the four-ball test and the ball threading test, and it is understood that the composition of the composition of the present invention is inferior to the composition of the present invention.

[0051]

The cold forging oil composition of the present invention contains a specific organometallic compound (A) and a sulfur-based extreme pressure agent (B) in specific amounts with respect to a lubricating base oil such as mineral oil or synthetic oil. However, the severe machining (backward
Even under the conditions of (extrusion), it has an excellent processing performance that enables cold forging without phosphoric acid film treatment. Further, another cold forging oil composition of the present invention further containing a specific amount of the ashless dispersant (C) with respect to the cold forging oil composition of the above composition, maintains the above excellent performance. Further, it has an effect of preventing gelation under high temperature.

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Claims (2)

[Claims] 1. A lubricating base oil comprising a mineral oil and / or a synthetic oil, based on the total amount of the composition, (A) selected from the group consisting of zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate and molybdenum dithiocarbamate. Cold forging oil composition comprising one or more selected organometallic compounds, 1 to 50% by weight, and (B) 0.1 to 10% by weight of a sulfur-based extreme pressure agent as a sulfur content. object. 2. A lubricating base oil comprising a mineral oil and / or a synthetic oil, based on the total amount of the composition, selected from the group consisting of (A) zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiophosphate and molybdenum dithiocarbamate. One or more selected organometallic compounds, 1 to 50% by weight, (B) 0.1 to 10% by weight of sulfur-based extreme pressure agent as a sulfur content, and (C) Ashless dispersant 0.1 to A cold forging processing oil composition containing 10% by weight.