JPH11158484A - Lubricating oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating oil compsn. having excellent plastic forming properties, especially anti-scorching in pipe enlarge work, and excellent in the reduction effect of working force for pipe enlarge work. SOLUTION: This compsn. comprises 10-99.7 mass % 1 or not less than 2 kinds of oils selected from a mineral oil and a synthetic oil as a base oil (A), 0.1-30 mass% 1 or not less than 2 kinds of phosphorus compds. (B), 0.1-30 mass% 1 or not less than 2 kinds of sulfur compds. (C), and 0.1-30 mass% 1 or not less than 2 kinds of metal salts selected from metal stearates or metal oleates (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lubricating oil composition having excellent pipe expandability.

[0002]

2. Description of the Related Art It is difficult to manufacture a bent pipe by bending a circular pipe. Simply bending a circular pipe may cause the pipe to collapse or buckle. As a processing method of manufacturing a bent pipe from a straight circular pipe, in a straight circular pipe,
There is known an expanding pipe bending method in which a spherical plug having a diameter larger than the inner diameter of the circular pipe is inserted and passed through the circular pipe, and the circular pipe is plastically deformed and expanded at the plug portion while expanding the pipe. ing. The method of pushing the plug includes a fixed plug method using a fixed plug, an eccentric plug method using an eccentric plug, and a floating plug method using a floating plug.

[0003] In these pipe expansion bending and pipe expansion processes, a lubricant has conventionally been used for the purpose of reducing the problem of seizure or the like due to a decrease in lubricity between the plug and the inner surface of the circular pipe. As this lubricant, grease is mainly used,
In particular, when processing conditions are severe, molybdenum-based grease having excellent lubricity is used.

[0004]

However, conventional molybdenum-based greases may not satisfy seizure resistance and reduction in working force due to a decrease in lubricity, and it is desired to develop a lubricant having excellent lubricity. Was rare.

[0005] Accordingly, an object of the present invention is to provide a lubricating oil composition which is excellent in seizure resistance at the time of expanding a pipe and is excellent in reducing the working force in the expanding of the pipe.

[0006]

Under these circumstances, the present inventors have conducted intensive studies and have found that a lubricating oil composition comprising a base oil, a phosphorus compound, a sulfur compound and a specific fatty acid metal salt in combination. It has been found that if is used for pipe bending, the seizure resistance due to a decrease in lubricity is improved and the working force can be reduced, and the present invention has been completed.

That is, the present invention provides (A) a base oil comprising:
10 or more kinds selected from mineral oil and synthetic oil
-99.7% by mass, 0.1-30% by mass of one or more selected from (B) phosphorus compounds, 0.1-30% by mass of one or more selected from (C) sulfur compounds. It is intended to provide a lubricating oil composition comprising 0.1 to 30% by mass of (D) one or more selected from metal stearates or metal oleates. .

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the base oil of component (A) used in the lubricating oil composition of the present invention, mineral oil and synthetic oil may be mentioned, and these may be used alone or in combination of two or more. Can be. Examples of the mineral oil include, but are not particularly limited to, white kerosene, spindle oil, machine oil, turbine oil, cylinder oil, and the like.Synthetic oils are not particularly limited, but include, for example, polybutene,
Examples thereof include poly-α-olefins (PAO) and esters. Of these base oils, polybutene, poly-α-olefin, machine oil, turbine oil, cylinder oil and the like are preferably combined and blended at an appropriate ratio, since the finished viscosity of the composition can be appropriately adjusted, which is preferable. As the viscosity range of the base oil, the viscosity at 25 ° C is usually 1.
0 to 200,000 cP, preferably 40 to 100,000 cP
P, more preferably 1,000 to 100,000 cP
Range.

The phosphorus compound (B) used in the lubricating oil composition of the present invention is not particularly restricted but includes, for example, secondary phosphites, tertiary phosphites, and acidic phosphates. , Acidic phosphoric acid ester amine salts, acidic phosphoric acid ester metal salts, thiophosphates, phosphates and the like. These are 1
Species can be used alone or in combination of two or more.

The secondary phosphite has a general formula: (R ¹ O) ₂
A compound represented by PHO, wherein R ¹ is an alkyl group,
An organic group such as an aromatic hydrocarbon group, preferred R ¹ a linear or branched alkyl group having 12 to 18 carbon atoms; phenyl or the like, alkylphenyl group, carbon atoms. Examples of particularly preferred R ¹ 12 ~ 18 linear or branched alkyl groups. Specific examples of the secondary phosphites include:
For example, di-2-ethylhexyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite and the like can be mentioned.

The tertiary phosphite has a general formula: (R ² O) ₃
A compound represented by P 1, wherein R ² represents an organic group such as an alkyl group or an aromatic hydrocarbon group, and preferred R ² is a linear or branched alkyl group having 12 to 18 carbon atoms; Group, an alkylphenyl group, etc., and is particularly preferable.
R ² is a linear or branched alkyl group having 12 to 18 carbon atoms. Specific examples of the tertiary phosphites include, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, triisooctyl phosphite,
Examples include diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tristearyl phosphite, trioleyl phosphite, and trilauryl trithiophosphite.

The acidic phosphates are also called acid phosphates, and are represented by diesters (general formula: [(R ³ O) ₂ P
(O) OH]) and a monoester (general formula: [R ⁴ OP (O) (O
H) ₂ ]), wherein R ³ and R ⁴ represent an organic group such as an alkyl group or an aromatic hydrocarbon group, and preferred R ³ and R ⁴ have 1 to 20 carbon atoms, preferably 10 carbon atoms. ~ 18,
Particularly preferred are a linear or branched alkyl group having 12 to 18 carbon atoms; a phenyl group, an alkylphenyl group, and the like;
Particularly preferred R ³ and R ⁴ are linear or branched alkyl groups having 12 to 18 carbon atoms. The proportion of diester and monoester is usually equimolar or greater for monoester. In addition, these acidic phosphates may contain a small amount of a pyro-type compound and a poly-type compound generated in the production stage.

Specific examples of the acid phosphates include:
For example, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid Phosphate, oleyl acid phosphate, di-2-ethylhexyl acid phosphate and the like can be mentioned.

Examples of the amine salts of acidic phosphate esters include, for example, the above-mentioned acidic phosphate esters represented by the following general formula (1): NR ⁵ R ⁶ R ⁷ (1) (wherein R ⁵ , R ⁶ and R ⁷ are Each represents a monovalent hydrocarbon group or a hydrogen atom, at least one of which is a hydrocarbon group).
R ⁵ , R ⁶ and R ⁷ represent a hydrocarbon group such as an alkyl group or an aromatic hydrocarbon group, and preferred R ⁵ , R ⁶ and R ⁷ are straight-chain or branched alkyl groups having 12 to 18 carbon atoms; Phenyl group,
An alkylphenyl group and the like, and particularly preferred R ⁵ , R ⁶ and R ⁷ are linear or branched alkyl groups having 12 to 18 carbon atoms.

Specific examples of the amine include dibutylamine, octylamine, dioctylamine, laurylamine, dilaurylamine, coconutamine and tallowamine. As the amine salt of the acidic phosphoric acid ester, for example, commercially available products such as Ortholeumu535 (trade name, manufactured by DuPont), Vanlube672 (trade name, manufactured by Vandabuild), Irgalube349 (trade name, manufactured by Ciba Geigy) can be used. .

Examples of the metal salts of the acid phosphate include, for example, the periodic table Ia of the acid phosphate described above.
And metal salts of Group IIa, Group Ib, Group Ib, Group IIb and Group IIIb. Preferred examples of the metal salt include, for example, magnesium stearyl acid phosphate, aluminum stearyl acid phosphate, calcium stearyl acid phosphate, zinc stearyl acid phosphate, barium stearyl acid phosphate, zinc behenyl acid phosphate, and the like. , Of which, aluminum stearyl acid phosphate, calcium stearyl acid phosphate,
Zinc stearyl acid phosphate is preferred.

The thiophosphates have the general formula: PS (SR ⁸ ) ₃
Wherein R ⁸ represents an organic group such as an alkyl group or an aromatic hydrocarbon group, and preferred R ⁸ is a linear or branched alkyl group having 12 to 18 carbon atoms; a phenyl group , An alkylphenyl group and the like, and particularly preferred R ⁸
Is a linear or branched alkyl group having 12 to 18 carbon atoms. Specific examples of the thiophosphates include, for example, tripropyl thiophosphate, tributyl thiophosphate, trihexyl thiophosphate, tridecyl thiophosphate, and the like.

The phosphates such of the general formula: PO is (OR ⁹⁾ a compound represented by _3, wherein, R ⁹ represents an alkyl group, an organic group such as an aromatic hydrocarbon group, preferred R ⁹ is A straight-chain or branched alkyl group having 12 to 18 carbon atoms; a phenyl group, an alkylphenyl group and the like, and particularly preferable R ⁹ is a straight-chain or branched alkyl group having 12 to 18 carbon atoms. Specific examples of the phosphates include, for example, tributyl phosphate, trihexyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate, and the like.

Among these phosphorus compounds, preferred are secondary phosphites, tertiary phosphites,
Acidic phosphates and metal salts of acidic phosphates are mentioned, and more preferred phosphorus compounds include acid phosphates and metal salts of acid phosphates. These phosphorus compounds may be used alone or in a combination of two or more.

The combination of the phosphorus compound is preferably a combination of a metal salt of an acid phosphate and another type of phosphorus compound, and more preferably a combination of a metal salt of an acid phosphate and an acid phosphate. Are preferable, and the weight ratio is 1: 4 to 4: 1, preferably 1: 2 to
2: 1.

The sulfur compound (C) component used in the lubricating oil composition of the present invention, for example, (i) the general formula ^{(2); R 1 0 -S} x - (R 11 -S x) m -R ¹² (2) (wherein, R ¹⁰ and R ¹² are the same or different and each represents a monovalent hydrocarbon group; R ¹¹ represents a divalent hydrocarbon group; x is an integer of 1 or more; , Each x in the repeating unit may be the same or different, and m is 0 or an integer of 1 or more.)

(B) sulfurized fats and oils, which are reaction products of fats and sulfur, and (c) general formula (3);

(Wherein R ¹³ and R ^{14 each} represent a divalent hydrocarbon group, y is an integer of 1 or more, and each y in the repeating unit may be the same or different; Is an integer of 0 or 1 or more.).

In the general formula (2) of the above (a), R ¹⁰ and R
¹² are the same or different and each represents a monovalent hydrocarbon group, and examples of the hydrocarbon group include a linear or branched saturated or unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms (eg, alkyl Group, alkenyl group) and an aromatic hydrocarbon group having 6 to 26 carbon atoms. Specific examples of these hydrocarbon groups include ethyl, propyl, butyl, nonyl, dodecyl, propenyl, butenyl, benzyl, phenyl, tolyl, hexylphenyl and the like. R ¹¹ is a divalent hydrocarbon group, and examples of the hydrocarbon group include an aliphatic hydrocarbon group having 2 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 26 carbon atoms. Specific examples of these divalent hydrocarbon groups include an ethylene group, a propylene group, a butylene group, and a phenylene group.

Typical sulfur compounds of the general formula (2) are sulfurized olefins and the general formula: R ¹⁰ -S _x -R ¹²
(X is an integer of 2 or more). Specific examples of the sulfur compound represented by the general formula (2) include, for example, diisobutyl disulfide, dioctyl polysulfide, di-tert-nonyl polysulfide, di-tert-nonylphenyl polysulfide, di-ter
t-butyl polysulfide, dibenzyl polysulfide, and sulfurized olefins obtained by sulfided olefins such as polyisobutylene and terpenes with a sulfurizing agent such as sulfur; a compound of isobutylene and sulfur;

[0026]

Embedded image

Or the general formula (5):

[0028]

Embedded image

And the like.

The component (C) (ii) is a sulfurized oil / fat which is a reaction product of oil / fat and sulfur.
There are animal and vegetable fats and oils such as beef tallow, whale oil, palm oil, coconut oil, and rapeseed oil. The reaction product is not a single chemical structure but various mixtures, and the chemical structure itself is not clear.

The component (C) (C) is a hydrocarbon sulfide represented by the general formula (3). In this cyclic sulfur compound, the groups R ¹³ and R ¹⁴ are divalent hydrocarbon groups, and examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 2 to 20 carbon atoms, An aromatic hydrocarbon group having the number of 6 to 26 is exemplified. Specific examples of these divalent hydrocarbon groups include an ethylene group, a propylene group, a butylene group, and a phenylene group. As specific examples of the sulfur compound of the general formula (3), the following general formula (6);

[0032]

Embedded image

Compounds of the formula This cyclic sulfur compound can be prepared, for example, by a synthesis method described in U.S. Pat.No. 3,925,414, and is obtained by further reacting a reaction product obtained from an olefin such as isobutylene with a sulfur monohalide with an alkali mercaptide. . A preferred compound selected from the group consisting of the components (A), (B) and (C) of the component (C) is the sulfurized fat or oil (B).

The metal (D) stearate or metal oleate used as the component (D) in the lubricating oil composition of the present invention includes, for example, calcium stearate, aluminum stearate, sodium stearate, potassium stearate, and stearin. Lithium oxide, zinc stearate, calcium oleate, aluminum oleate, sodium oleate, potassium oleate, lithium oleate, zinc oleate. Preferred of these metal salts include calcium stearate, aluminum stearate, calcium oleate, aluminum oleate, and zinc oleate. These metal stearates or metal oleates may be used alone or in combination of two or more.

In the lubricating oil composition of the present invention, (A)
The compounding amount of the base oil as a component is 10 to 99.7% by mass, and preferably 40 to 97% by mass. The compounding amount of the phosphorus compound (B) is 0.1 to 30% by mass, and preferably 1 to 10% by mass. If the blending amount of the component (B) is less than 0.1% by mass, the pipe expandability is poor, and
If the amount is more than 0% by mass, the effect does not change and it is economically disadvantageous. The compounding amount of the sulfur compound (C) is 0.1 to
It is 30% by mass, preferably 1 to 20% by mass.
When the amount of the component (C) is less than 0.1% by mass, the expandability of the tube is poor. When the amount is more than 30% by mass, corrosion tends to be promoted. The compounding amount of the metal salt of stearic acid or metal oleate as the component (D) is 0.1 to 30% by mass, and preferably 1 to 10% by mass. (D)
If the compounding amount of the component is less than 0.1% by mass, the effect of improving the pipe expandability cannot be obtained, and if it is more than 30% by mass, the degreasing performance after processing is undesirably reduced.

Further, in the lubricating oil composition of the present invention,
In addition to the above components, components used in ordinary lubricating oil compositions, for example, various additives such as a rust inhibitor, an antioxidant, and an antifoaming agent can be appropriately added. As the rust inhibitor, for example, alkenyl succinic acid and its derivatives, esters such as sorbitan monooleate, wax oxide, neutral barium sulfonate, sorbitan triol, paraffin or other amines, and the like, as an antioxidant, For example, phenolic compounds such as 2,4-di-tert-butyl-p-cresol, aromatic amines such as phenyl-α-naphthylamine, and the like.Examples of the antifoaming agent include polydimethylsiloxane and polymethacrylic acid. No. The addition amount of these additives may be appropriately selected, but usually the rust inhibitor is 0.01 to 30% by mass, and the antioxidant is 0.1 to 30% by mass.
1% by mass, 10 to 100 ppm of antifoaming agent may be added.

The viscosity of the lubricating oil composition of the present invention at 25 ° C. is usually in the range of 1 to 200,000 cP, preferably
100 to 100,000 cP, more preferably 1,000 cP
It is in the range of ~ 100,000 cP. If the viscosity is too high, handling during use tends to be difficult, and the degreasing property in the post-processing step decreases. On the other hand, if the viscosity is too low, the processability decreases, which is not preferable.

The lubricating oil composition of the present invention can be produced by appropriately mixing and mixing predetermined amounts of the above essential components and various additives as necessary. The mixing method and the adding method of the various essential components and the various additives are not particularly limited, and can be performed by various methods, and the mixing order and the adding order can be performed in various mixing orders and the adding order.

The lubricating oil composition of the present invention can be formed by pultrusion molding,
It can be used for various types of plastic working such as bending, press forming, and drawing, but it works particularly effectively for pipe expansion. The pipe expansion is not particularly limited, and includes pipe expansion and pipe expansion and bending involving both pipe expansion and bending. For example, fixed plug bending, eccentric plug bending, floating plug bending, and the like can be listed. . In this pipe expansion, to apply the lubricating oil composition of the present invention, for example, apply an appropriate amount to the inner wall of the circular pipe of the workpiece,
After that, there is a method in which a plug is inserted and processed.
As a material used for various processing, it can be used for extruded pipes such as aluminum, aluminum alloy, copper, copper alloy, carbon steel, alloy steel, stainless steel, etc., and especially for expanding and bending carbon steel, alloy steel and stainless steel. Suitable for processing.

[0040]

Next, the present invention will be described in more detail with reference to examples, but this is merely an example and does not limit the present invention. Examples 1 to 14 A lubricating oil composition was prepared by blending a base oil, a phosphorus compound, a sulfur compound, a metal salt of stearic acid or a metal salt of oleic acid and other additives shown in Tables 1 to 3 below. ,
Pipe expansion was performed by the test method described below, and the workability was evaluated. The viscosity of the obtained lubricating oil composition is shown in the middle part of the table, and the evaluation test result is shown in the lower part of the table.

Base oil (component A) Mixed oil of polybutene and mineral oil (viscosity 25,000 cP at 25 ° C.) Polybutene (viscosity 25,000 cP at 25 ° C.) Phosphorus compound (component B) Acidic phosphate: stearyl acid phos with 18 carbon atoms Mixture of fate and oleyl acid phosphate Phosphate: tricresyl phosphate Metal salt of acid phosphate: Al stearyl acid phosphate Ca stearyl acid phosphate Zn stearyl acid phosphate Sulfur compound (component C) Lard oil and sulfur Sulfurized oils and fats which are the reaction products of sulfided olefins: Compounds having the following structural formula (6) synthesized by further reacting the reaction product of isobutylene and sulfur monochloride with Na mercaptide.

[0042]

Embedded image

Metal stearate or metal oleate (D component) Metal stearate: aluminum stearate Calcium stearate Metal oleate: calcium oleate Zinc oleate

Other additives Antifoaming agent: polymethacrylic acid Rust inhibitor: alkenyl succinic acid derivative

(Evaluation Method of Expandability) In the evaluation test, the processing force at the time of expansion, the surface condition of the plug and the inner surface of the circular pipe after expansion, and the contamination degree of the processing die and the processed material after expansion were evaluated.
The evaluation methods and evaluation criteria are shown below.

(1) Pipe Expansion Workability Evaluation Test An expansion workability evaluation test apparatus 10 shown in FIGS. 1 and 2 is used. The pipe expandability evaluation test apparatus 10 includes a table 6, a frame 7, a workpiece support 11 and a workpiece 12, and the workpiece support 11 is provided with bearing retainers 8a and 8b.
A cylindrical space for supporting the workpiece is formed by b, 8c, and the bearing 9. The work material in an upright posture composed of the plug 2 and the plug support 13 is fixed to the base 6 by the holding plate 5. First, an appropriate amount of a lubricant is applied to the inner surface of a straight pipe 1 having the following specifications. Next, the straight pipe 1 is set from above the expanding die apparatus 10 so as to be in contact with the upper surface of the plug 2, and is pushed from above through the bush rod 4 so as to insert the plug 2 by a hydraulic press. To obtain an expanded circular pipe indicated by a two-dot chain line. The expansion ratio and plug specifications are shown below. In addition, the maximum value of the processing force during the pipe expansion was defined as the processing force. The smaller the value of the working force, the easier the work forming is.

Plug (working material): Material: SUJ2 (high carbon chrome bearing steel) Surface TD treatment: Dimensions: φ 17.46 mm Circular pipe (working material): Material SUS304 Seamless pipe: Dimensions Outer diameter φ16 mm Inner diameter φ13 mm Wall thickness φ1 0.5 mm length 200 mm Expansion ratio: 34.3%

(2) Surface Condition of Worked Material and Workpiece after Pipe Expansion Process The surface condition of the workpiece (plug) after processing and the workpiece (circular pipe) after processing are cut in half lengthwise. The surface condition of the tube wall was observed. The following criteria were used to evaluate the degree of image sticking. Evaluation ：: No seizure occurred. ：: A small amount of seizure is observed. Δ: Image sticking is slightly observed. ×: Many seizures are observed.

(3) Degree of contamination of the mold and the processed material after pipe expansion In FIG. 1, the presser plate 5, the base 6, and the plug support 7 of the processed die are wiped with gauze, and the mold and the processed material with the lubricant are used. Was evaluated as follows. Evaluation ◎: No stain is seen at all. ：: A trace amount of dirt is observed. Δ: Some stains are observed. ×: Very dirty and black.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

Comparative Examples 1 to 8 The base oil, phosphorus compound, sulfur compound, metal stearate or metal oleate and other additives shown in Examples were blended in the proportions shown in Tables 4 and 5 to form a lubricating oil composition. An article was prepared, and the pipe expandability was evaluated in the same manner as in the examples. The viscosity of the obtained lubricating oil composition is shown in the middle part of the table, and the evaluation test result is shown in the lower part of the table.

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

The lubricating oil composition of the present invention acts on the adhered portion between the plug and the inner wall of the circular pipe by using it for various plastic workings, especially for expanding the pipe, thereby improving the lubricity. For this reason, the pipe expanding force can be reduced, and the seizure resistance is excellent. Further, the degree of contamination of the mold and the processing material can be reduced.
The lubricating oil composition of the present invention is extremely useful in practical use.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a pipe expandability evaluation test apparatus for evaluating pipe expandability.

FIG. 2 is an enlarged cross-sectional view around the plug of FIG. 1 (dashed line).

[Description of Signs] 1 Circular tube 2 Plug 4 Bush rod 5 Pressing plate 6 Units 7 Frame 8a, 8b, 8c Bearing holder 9 Bearing 10 Expanding workability evaluation test device 11 Workpiece support part 12 Workpiece part 13 Plug support

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B21D 39/08 B21D 39/08 Z C10N 40:24

Claims (1)

[Claims] (1) 10 to 99.7% by mass of (A) one or more selected from mineral oil and synthetic oil as a base oil;
(B) One or two or more selected from phosphorus compounds may be used in 0.1.
1 to 30% by mass, 0.1 to 30% by mass of one or more selected from (C) sulfur compounds, and one or two selected from (D) metal stearate or metal oleate A lubricating oil composition comprising 0.1 to 30% by mass of the above.