JP2010007033A - Lubricant for chlorine-free plastic working for hard-to-work metallic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new lubricant for use in chlorine-free plastic working for hard-to-work metallic materials which has an enhanced lubricity without adding an extreme-pressure additive. <P>SOLUTION: The lubricant for chlorine-free plastic working for hard-to-work metallic materials includes. (A) 5-90 pts.mass of an organic carbonate expressed by formula (I) and having a boiling point of over 265°C under normal pressure, wherein R<SP>1</SP>and R<SP>2</SP>are each independently a hydrocarbon group or an alkoxy-alkoxy-alkoxy group and the total number of carbons in R<SP>1</SP>and R<SP>2</SP>is 14 to 30, (B) 5-95 pts.mass of the total of a basic metal sulfonate having a basic value of ≥300 mgKOH/g and/or a metal dithiophosphate, (C) 0-90 pts.mass of a base oil for lubrication oil based on 100 pts.mass of the total amount of the component (A) and the component (B). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a non-chlorine lubricant used when plastically processing difficult-to-work metal materials such as stainless steel, titanium, titanium alloys, and high-tensile steel plates. More specifically, the present invention relates to a lubricant for plastic working of difficult-to-work metal materials that exhibits good lubricity and seizure resistance without blending a chlorine-based compound such as chlorinated paraffin, which is a chlorine-based extreme pressure agent.

  When processing metal, the friction generated between the mold and the workpiece (metal) is reduced to prevent seizure and reduce the wear of the mold due to friction to improve the mold life. Lubricants are used for this purpose. Lubricants for metal processing usually contain additives such as anti-wear agents that reduce wear and extreme pressure additives that are useful for preventing seizures in base oils such as animal and vegetable oils and synthetic oils. Has been. The extreme pressure additive means one having excellent reactivity with metals under high pressure and high temperature, and is composed of chemically active sulfur-based, chlorine-based, and phosphorus-based compounds.

  In particular, when processing difficult-to-process metal materials such as stainless steel, a lubricant having a higher kinematic viscosity is used than when processing easily-processable metal materials. In addition, a lubricant having a high kinematic viscosity is also used when performing plastic processing with high processing difficulty such as deep drawing, ironing, wire drawing, and drawing. This is because when a lubricant having a high kinematic viscosity is used, oil film breakage during processing is prevented, and plastic processing of difficult-to-work metal materials becomes easy. In addition, if the seizure cannot be suppressed only by controlling the kinematic viscosity, the above extreme pressure additive is often blended in order to improve the seizure resistance of the lubricant. Are preferably used. For example, extreme pressure additives are used to prevent friction and seizure on contact surfaces with extremely high load pressures on metal contact surfaces such as hypoid gear oils and cutting oils in addition to plastic working oils. .

  In recent years, non-chlorine lubricants that do not contain chlorine compounds have been actively developed in consideration of adverse effects on the human body and the environment such as generation of dioxins and carcinogenicity by chlorine compounds. For example, Patent Documents 1 and 2 disclose a lubricant containing a sulfur-based extreme pressure additive and a phosphorus-based extreme pressure additive such as zinc dialkyldithiophosphate without using a chlorine-based extreme pressure additive. Patent Document 3 discloses a method for preventing seizure flaws between a rolling roll and a steel material using a lubricant containing a highly basic Ca sulfonate having a base number of 40 mgKOH / g or more.

On the other hand, the present applicant discloses, in Patent Document 4, an organic carbonate-containing compound that can reduce the degreasing load after processing and is excellent in lubrication performance. In Patent Document 4, specifically, an organic carbonate having a flash point of 30 ° C. or higher and a boiling point of 100 to 250 ° C. under normal pressure is used. Since this organic carbonate volatilizes at room temperature and normal pressure with almost no residue, using this compound as a base oil eliminates the step of cleaning the press oil adhering to the metal plate after processing. Can prevent friction and seizure.
JP 2007-262371 A JP 2004-75883 A Japanese Patent No. 2689827 Japanese Patent No. 3533423

  An object of the present invention is to provide a novel non-chlorine plastic working lubricant for difficult-to-work metal materials that has improved lubricity and seizure resistance without the addition of a chlorine-based extreme pressure additive. .

The non-chlorine plastic working lubricant for difficult-to-work metal materials according to the present invention that can solve the above problems has the gist in that it contains the following (A) to (C).
(A) Organic carbonate represented by the following formula (I) and having a boiling point under normal pressure of more than 265 ° C .: 5 to 90 parts by mass,

... (I)
In the above formula,
R ¹ and R ² are each independently a hydrocarbon group or an alkoxyalkoxyalkoxy group, and the total number of carbon atoms of R ¹ and R ² is 14 or more and 30 or less.
(B) Total of basic sulfonic acid metal salt and / or dithiophosphoric acid metal salt having a base number of 300 mgKOH / g or more: 5-95 parts by mass,
(C) Lubricating base oil: 0 to 90 parts by mass with respect to 100 parts by mass of the total amount of component A and component B.

  The lubricant preferably further contains (D) a sulfur-based extreme pressure additive and / or a phosphorus-based extreme pressure additive.

  The present invention also includes a metal processed product obtained using any of the above-described lubricants.

  The lubricant of the present invention is excellent in lubricity and seizure resistance although it basically does not contain a chlorine compound or an extreme pressure additive. Therefore, the lubricant of the present invention is suitably used for plastic working difficult-to-work metal materials such as stainless steel, for example, cutting oil, rolling oil, press oil, squeezing used at room temperature (cold). It is useful as a lubricating oil for processing oil, drawing oil, punching oil, forging oil, and the like.

  This inventor examined in order to provide the non-chlorine type lubricant which does not contain a chlorine type compound and is useful for plastic processing of a difficult-to-work metal material. In particular, the study was conducted from the viewpoint of providing a lubricant that basically does not contain sulfur-based or phosphorus-based extreme pressure additives as well as chlorine-based extreme pressure additives widely used in the above-mentioned applications. As a result, when a predetermined organic carbonate compound is used in combination with a basic sulfonic acid metal salt or dithiophosphate metal salt, the intended purpose is achieved; preferably, a sulfur-based or phosphorus-based non-chlorine extreme pressure It was found that if the additive was further blended, the lubricity and seizure resistance were further improved, and the present invention was completed.

  The organic carbonate used in the present invention is extremely useful as a substitute for lubricating base oils represented by animal / vegetable oils, mineral oils and the like. As demonstrated in the Examples section which will be described later, the organic carbonate used in the present invention and the conventional lubricating base oil both have the same lubricating performance (anti-seizure resistance), and the additives and A remarkable difference was observed between the two in terms of the degree of the characteristic improvement effect by the combination. In addition, if the lubricant of the present invention is used, a chlorine-based extreme pressure additive-containing lubricant is used without blending a chlorine-based extreme pressure additive that is widely used for plastic working applications of difficult-to-work metal materials. It was also confirmed that the same good lubrication performance was obtained. Therefore, the lubricant of the present invention is very useful as a non-chlorine lubricant used for the above-mentioned applications.

  The organic carbonate used in the present invention has a boiling point of more than 265 ° C. under normal pressure as compared with the organic carbonate of formula (I) disclosed in Patent Document 4 described above. This is mainly due to the fact that the total number of carbon atoms of the organic carbonate used in the present invention is larger than that of Patent Document 4, and the carbon number of alkyl groups, alkoxy groups, etc. is long.

  Hereinafter, the lubricant of the present invention will be described in detail. In this specification, for convenience of explanation, the organic carbonate of formula (I) is referred to as component A, a basic sulfonic acid metal salt or dithiophosphate metal salt having a base number of 300 mgKOH / g or more is referred to as component B, and a lubricant group. Oil is referred to as component C, and sulfur-based or phosphorus-based extreme pressure additives other than chlorine are referred to as component D. The A component and the B component are essential components, and the C component and the D component are selective components.

(A) Organic carbonate First, the organic carbonate used in the present invention will be described.

  The organic carbonate used in the present invention is a compound represented by the following formula (I) and having a boiling point of more than 265 ° C. under normal pressure.

... (I)
In the above formula,
R ¹ and R ² are each independently a hydrocarbon group or an alkoxyalkoxyalkoxy group, and the total number of carbon atoms of R ¹ and R ² is 14 or more and 30 or less.

  As described above, the organic carbonate used in the present invention is different from the organic carbonate disclosed in Patent Document 4 in physical properties (boiling point and flash point under normal pressure), and both are different compounds. That is, Patent Document 4 discloses an organic carbonate having a boiling point of substantially 100 to 250 ° C. under a normal pressure and a flash point of 30 ° C. or more and having volatility at normal temperature and normal pressure. In contrast, the organic carbonate used in the present invention has a boiling point under normal pressure of over 265 ° C., which is higher than that disclosed in Patent Document 4, has a flash point of 60 ° C. or higher, and is volatile at normal temperature and normal pressure. do not do.

  The difference in physical properties between the two leads to a difference in use. The low-boiling organic carbonate used in Patent Document 4 is suitably used as a lubricating base oil for press working that volatilizes at room temperature and normal pressure, whereas the high-boiling organic carbonate used in the present invention is difficult to process. It is suitably used as an oil for plastic working of metal materials. A compound that easily volatilizes at room temperature will cause deterioration of the working environment due to volatilization of the lubricant, if used in processing that involves processing heat generated by plastic processing (generally when the temperature of the mold is 60 ° C or higher). It is easy to do and there is a concern about safety. Therefore, the organic carbonate disclosed in Patent Document 4 cannot be used for plastic working of difficult-to-work metal materials. In addition, Patent Document 4 does not intend to provide a high boiling point compound that does not volatilize at normal temperature and normal pressure, and this is a matter of course, and this is a lubricant base oil used for plastic working of difficult-to-work metal materials. Means no consideration of the provision of

  The preferable boiling point of the organic carbonate used in the present invention is generally 265 to 450 ° C, more preferably 300 to 450 ° C. Moreover, the preferable flash point of the said organic carbonate is 60-300 degreeC in general, More preferably, it is 160-230 degreeC.

In the above formula (1), R ¹ and R ² are the same or different and are a hydrocarbon group or an alkoxyalkoxyalkoxy group, and the total number of carbon atoms of R ¹ and R ² (excluding C carbon constituting carbonate) .) Is 14 or more and 30 or less, and a preferable total number of carbon atoms is 17 or more and 30 or less.

  Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group; an aromatic hydrocarbon group such as an aryl group (for example, a phenyl group) and an aralkyl group. The aliphatic hydrocarbon group may be linear, branched or cyclic. The aromatic hydrocarbon group includes a heterocyclic group. Furthermore, a hydrocarbon group (for example, an aromatic hydrocarbon group, particularly an aryl group) may be substituted with a group containing an element other than carbon and hydrogen, for example, a halogen atom, a hydroxy group, or an amino group. Among these, a preferable hydrocarbon group is an alkyl group, and examples thereof include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group.

  Further, the above alkoxyalkoxyalkoxy group may be either linear or branched. The alkoxy in the “alkoxyalkoxyalkoxy group” is, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy Groups and the like.

Specifically, in the organic carbonate used in the present invention, R ¹ and R ² may all be composed of the above hydrocarbon groups. The types of hydrocarbon groups may be the same or different. For example, R ¹ and R ² may be composed of the same hydrocarbon group. Alternatively, in the organic carbonate used in the present invention, R ¹ and R ² may all be composed of the above alkoxyalkoxyalkoxy groups. The types of alkoxyalkoxyalkoxy groups may be the same or different, and R ¹ and R ² may be composed of the same alkoxyalkoxyalkoxy group. In any case, the total carbon number of the hydrocarbon group or alkoxyalkoxyalkoxy group is 14 or more and 30 or less, and preferably 17 or more and 30 or less.

Preferred organic carbonates, for example, R ¹ and R ² are the same, the number of carbon atoms in R ¹ and R ² are organic carbonates consisting of alkyl groups of 7 to 15; R ¹ and R ² are identical, and R ¹ Examples thereof include organic carbonates composed of alkoxyalkoxyalkoxy groups having R ² to 7 carbon atoms. These organic carbonates may be a mixture, such as a mixture of an organic carbonate having a C14 alkyl group and an organic carbonate having a C15 alkyl group, as in the examples described later. It is done. Moreover, these may use a commercial item.

The organic carbonate used in the present invention can be typically produced by the following method. For example, when R ¹ and R ² are all composed of hydrocarbon groups, (a) in the presence of a catalyst, a lower dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate or the like and R ¹ or R ² Process for producing ester carbonate by transesterification with alcohol (R ¹ OH or R ² OH): (I) R ¹ or R ² alcohol (R ¹ OH or R ² ) in the presence of organic base or inorganic base ² OH) and phosgene are reacted to produce a carbonate ester. Further, when all of R ¹ and R ² are composed of alkoxyalkoxyalkoxy groups, for example, in the method (a) above, not the alcohol of R ¹ or R ² but a predetermined group is obtained ( Produced by transesterification in the same manner as in (a) above, except that alcohol such as OCaH2a) x (OCbH2b) yOH (wherein a, b, x and y are the same or different and are integers) is used. be able to. For example, the compound a1 in Examples described later can be produced using methoxydipropylene glycol as an alcohol.

(B) Basic sulfonic acid metal salt and / or dithiophosphoric acid metal salt having a base number of 300 mgKOH / g or more In the present invention, the above B component is included as an essential component. As demonstrated in the column of Examples described later, by blending the B component with the A component, the lubricity and seizure properties are remarkably improved as compared with the case where the B component is blended with the conventional lubricating base oil.

  The component B is composed of a basic sulfonic acid metal salt (referred to as component B1) having a base number of 300 mgKOH / g or more and a dithiophosphate metal salt (referred to as component B2). Any of these may be included or used in combination.

  First, the basic sulfonic acid metal salt (B1 component) will be described. Basic sulfonic acid metal salt is a difficult-to-process metal material because the metal carbonate contained in the basic sulfonic acid metal salt exhibits the properties of a solid lubricating film and is excellent in lubricity under severe processing conditions. It is a compound that is suitably used for plastic processing. For example, in Patent Document 3 described above, a preparation method, a mechanism for improving lubricity, and the like are described in detail for basic Ca sulfonate, which is a representative example of a basic sulfonic acid metal salt.

  The sulfonic acid metal salt used in the present invention is not particularly limited as long as it has a basicity (alkali value) of 300 mgKOH / g or more, and includes those usually used. As demonstrated in the examples described later, even when a neutral sulfonic acid metal salt was added to the component A, no effect of improving lubricity or seizure was observed. In order to ensure good lubricity and seizure resistance, the higher the base number, the better. Generally, it is preferably 300 mgKOH / g or more, more preferably 400 mgKOH / g or more, and the upper limit is not particularly limited. Considering the stability of separation and precipitation due to the combination of agents, it is generally preferable that it is 450 mgKOH / g or less. The base number may be measured according to a conventional method, and may be measured using hydrochloric acid or perchloric acid as a titration reagent and using an indicator or potentiometer. For example, the base number can be measured using a potentiometric titration method defined in JIS K2501.

Examples of the basic sulfonic acid metal salt include alkali metal salts of sulfonic acid (Na salt, K salt, etc.) and alkaline earth metal salts (Mg salt, Ca salt, Ba salt, etc.). Such a basic sulfonic acid metal salt is obtained by, for example, neutralizing an alkyl aromatic sulfonic acid to obtain an alkali metal or alkaline earth metal salt, and then reacting with a basic substance such as CaO or Ca (OH) _2. Can be obtained. As the raw material alkyl aromatic sulfonic acid, for example, a hydrocarbon group sulfonic acid mixture (petroleum sulfonic acid) produced as a by-product during the purification of sulfuric acid in a petroleum fraction is used. As the alkyl aromatic, for example, a lubricating oil fraction of mineral oil or a synthetic compound such as alkylbenzene or dinonylnaphthalene is used. As the basic sulfonic acid metal salt, for example, a commercially available product may be used as shown in Examples described later.

  Next, the dithiophosphate metal salt (B2 component) used in the present invention will be described. Dithiophosphoric acid metal salts are compounds containing both S (sulfur) and P (phosphorus), which are highly reactive with metals, and are widely used as antiwear agents. It is said that the metal salt of dithiophosphate itself decomposes and forms a solid lubricating film on the surface, and this film is more easily sheared than the base metal (working material), so that friction and wear can be reduced.

  The dithiophosphate metal salt used in the present invention is not particularly limited as long as it is usually added to the lubricant, and examples thereof include dialkyldithiophosphate metal salts, dialkenyl dithiophosphates, and diaryl dithiophosphate metal salts. . Examples of the metal include zinc and molybdenum. The performance of dithiophosphate metal salt varies depending on the number of carbons such as alkyl, alkenyl, aryl, etc. and the structure (straight or branched), etc., so appropriate dithiophosphate metal salt should be used to achieve the desired characteristics. Just choose. In the present invention, those having a total carbon number of 8 or more and 24 or less are preferably used, and in general, those having 12 or more and 16 or less are more preferably used. As the metal salt of dithiophosphoric acid metal salt, for example, a commercially available product may be used as shown in Examples described later.

  Typically, zinc dialkyldithiophosphate (Zn-DTP) is used. This is known as a multifunctional additive such as having not only wear resistance and seizure resistance but also antioxidant and corrosion resistance. In Zn-DTP, the smaller the number of carbon atoms, the better the wear resistance, but the thermal stability tends to deteriorate. The preferred total number of carbon atoms is the same as above. Alternatively, the molybdenum thiophosphate compound described in Patent Document 3 may be used.

  The blending ratio of the above component A (organic carbonate) and component B (basic sulfonic acid metal salt and / or dithiophosphate metal salt) is 5 to 90 parts by mass for component A and 5 to 95 parts by mass for component B. To do. Below this range, the lubricity improving effect due to the blending of the organic carbonate is weakened, and when exceeding this range, the lubricity improving effect due to the blending of the organic carbonate is not effectively shown. A preferable blending ratio is 10 to 30 parts by mass of the A component and 10 to 90 parts by mass of the B component, and more preferably 10 to 30 parts by mass of the A component: 50 to 85 parts by mass.

  The lubricant of the present invention may be composed of only the above-mentioned A component and B component, but the following C component and D component may be further blended for further improvement in lubricity and the like.

(C) Lubricating base oil In the present invention, a lubricating base oil that is usually added as a metalworking oil (hereinafter abbreviated as base oil) may be further blended. The base oil is a useful component for adjusting the viscosity of the lubricating oil (proportional to the thickness of the lubricating film). The component A (organic carbonate) used in the present invention is useful as a substitute for this base oil, but the above-mentioned action is further improved by the combined use with the base oil.

  The base oil used in the present invention is not particularly limited, and animal / vegetable oil, mineral fat, synthetic oil and the like are used. Specifically, for example, animal oils such as beef tallow, lard, fish oil (hardened); linseed oil, safflower oil, soybean oil, sesame oil, corn oil, rapeseed oil, cottonseed oil, olive oil, rice bran oil, coconut oil, palm oil, Castor oil and other vegetable oils; spindle oil, machine oil, dynamo oil, aromatic lubricating oil, naphthenic lubricating oil, paraffinic lubricating mineral oil; synthetic ester oil such as fatty acid ester, polyether oil, silicone oil, poly Examples include synthetic oils such as alpha olefins. What is used as a base oil of metalworking oil can be illustrated. These may be used alone or in combination of two or more arbitrarily selected.

  When mix | blending said base oil, it is preferable that the compounding quantity of base oil shall be 0.1-90 mass parts generally with respect to 100 mass parts of total amounts of A component and B component mentioned above, 5-20 Part by mass is more preferable.

(D) Sulfur-based extreme pressure additive and / or phosphorus-based extreme pressure additive In the present invention, an extreme pressure additive other than chlorine-based additives may be further blended. As demonstrated in the Examples section described later, if the lubricant of the present invention is used, good lubricity and seizure resistance can be obtained without blending the extreme pressure additive, but the addition of the extreme pressure additive This further enhances this characteristic.

  The extreme pressure additive used in the present invention is not particularly limited as long as it is a commonly used sulfur-based or phosphorus-based additive. Specifically, sulfur-based extreme pressure additives include, for example, sulfurized fats and oils such as sulfurized rapeseed oil, sulfurized palm oil, and sulfurized lard oil; sulfurized esters such as sulfurized fatty esters; di (mono) benzyldi (mono) sulfide, dioctyl Examples thereof include alkyl polysulfides such as polysulfide and sulfides such as olefin polysulfide. Examples of the phosphorus extreme pressure additive include phosphoric acid esters such as tricresyl phosphate (TCP), tridecyl phosphite, and lauric acid phosphate; and phosphites such as tributyl phosphite and dilauryl phosphite. It is done. These amine salts (for example, amine salts of phosphate esters, ethylamine salts, hexylamine salts, etc.) are also used. Or you may use what is indicated by the patent document mentioned above as an extreme pressure additive. In the present invention, the above sulfur-based or phosphorus-based extreme pressure additives may be used alone, or two or more of them may be used in combination.

  When blending the above extreme pressure additive, the blending amount of the extreme pressure additive is preferably about 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of component A and component B described above. -30 mass parts is more preferable. Or it is preferable to set it as 5-50 mass parts in general with respect to 100 mass parts of total amounts of A component, B component, and C component mentioned above, and 10-40 mass parts is more preferable.

  In this invention, you may mix | blend the well-known additive normally used for metalworking oil. Specific examples include antioxidants, preservatives, colorants, antifoaming agents, fragrances, and surfactants. What is necessary is just to set these compounding ratios suitably in the range which does not impair the effect of this invention.

  The lubricant of the present invention is suitably used when plastically processing difficult-to-work metal materials. Examples of difficult-to-work metal materials that are the subject of the present invention include stainless steel, titanium, titanium alloys, high-tensile steel plates, Inconel, chromium molybdenum steel, and the like. Examples of plastic working include deep drawing, wire drawing, drawing, drawing, forging, punching, bending, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and may be implemented with appropriate modifications within a range that can meet the purpose described above and below. These are all possible and are within the scope of the present invention. In the following description, all compounding amounts mean “parts by mass”.

Example 1
In this example, the organic carbonate-containing non-chlorine lubricant of the present invention was studied mainly on the fact that it has better seizure resistance than conventional base oil-containing lubricant skins.

  The components used in this example are summarized in Table 1.

Details of each component in Table 1 are as follows. In the component A of Table 1, the "total number of carbon atoms" means the total number of carbon atoms of R ¹ and R ² (carbon of C constituting the carbonate is excluded.).

(1) Component A (organic carbonate): a1, a2, and a3 are used. “A1” = di (methoxydipropoxy) carbonate,
_{CH 3 O (C 3 H 6} O) 2 -CO-CH 3 O (C 3 H 6 O) 2,
A total of 14 carbon atoms, boiling point 266-270 ° C, flash point 172 ° C,
"DIALCARB H-2" manufactured by Mitsui Chemical Fine Co., Ltd.
“A2” = C ₁₄ -C ₁₅ alkyl such as di (2-methyltetradecyl) carbonate
Carbonate having a group; more particularly, a car having a C ₁₄ H ₂₈ group in the side chain
A mixture of a bonate and a carbonate having a C ₁₅ H ₃₀ group in the side chain;
C _14-15 H _28-30 O—CO—C _14-15 H _28-30 O, _28-30 in total,
Boiling point 300-337 ° C, flash point 224 ° C,
"LIALCARB SR-1000 / R" manufactured by Mitsui Chemical Fine Co., Ltd.
“A3” = bis (2-ethylhexyl) carbonate,
_{C 8 H 17 O-CO-} C 8 H 17 O,
Total number of carbons 16, boiling point 280-290 ° C, flash point 162 ° C,
"DIALCARB H-1" manufactured by Mitsui Chemical Fine Co., Ltd.

(2) Component B [(B-1) Basic sulfonic acid calcium salt] + C component (base oil)
“B1-1” = basic sulfonic acid calcium salt (base number 400 mgKOH / g)
Mixture with mineral oil,
Lubrizol: Lubrizol 5347LC
“B1-2” = basic sulfonic acid calcium salt (base number 300 mgKOH / g)
Mixture with mineral oil, "300 BASIC" manufactured by WITCO
CALCIUM PETROGATE "

(3) Component B [(B-2) dithiophosphate metal salt]
“B2” = zinc dialkyldithiophosphate (9.9% zinc content),
Made by Line Chemie: ADDITIN 3180

(4) Component C (base oil)
"C1" = vegetable oil, "FS oil" manufactured by Showa Sangyo Co., Ltd.
“C2” = mineral oil, “Diana Fresia P-430” manufactured by Shin Nippon Oil & Fats Co., Ltd.
“C3” = fatty acid ester, “Yunistar M-182A” manufactured by NOF Corporation

(5) Component D (sulfur-based extreme pressure additive / phosphorus-based extreme pressure additive)
“D1” = dioctyl polysulfide (sulfur content 40%),
"GS-440" manufactured by DIC Corporation
“D2” = tridecyl phosphite, “JP-213D” manufactured by Johoku Chemical Industry Co., Ltd.

Further, in Table 1, in addition to the constituent components (components A to D) used in the present invention, a column “Other” is provided for comparison, and two types of components (e1 to e2) are described. . Among these, chlorinated paraffin (e1) is a widely used chlorine-based extreme pressure additive and is a compound containing chlorine. In addition, the chlorine value of calcium sulfonate (neutral) is 0.1 mgKOH / g or less, which does not satisfy the requirements of the present invention (base value of 300 mgKOH / g or more).
“E1” = chlorinated paraffin, “Toyoparax 150” manufactured by Tosoh Corporation
“E2” = calcium sulfonate (neutral, base number 0.1 mg KOH / g or less),
“Thruhole CA45N” manufactured by Matsumura Oil Co., Ltd.

  First, the sample which mix | blended the component shown in Table 1 with the ratio (all mass parts) shown in Tables 2-4 was prepared. In Tables 2-4, the kinematic viscosity in 40 degreeC of the prepared sample was written together. The kinematic viscosity was measured using a Canon-Fenske viscometer specified in JISK2283.

  The lubricating performance (seizure resistance) of the sample was evaluated by conducting a friction test using the friction test apparatus shown in FIG. 1 and measuring the maximum load at which no seizure occurs.

  The apparatus shown in FIG. 1 is disclosed by the present applicant as an apparatus capable of simulating a lubrication state during plastic working with a very large surface pressure. If this apparatus is used, the lubrication state on the friction surface between the tool and the work material during plastic working can be reproduced, and the lubrication performance of the lubricant can be evaluated easily and quantitatively.

  Details of the above apparatus are described in Japanese Patent Application No. 2007-5097. The outline of the apparatus is as follows.

  As shown in FIG. 1, the friction test apparatus 1 includes an upper backing plate (movable member) 2 and a lower backing plate (fixed member) 3 that are arranged to face each other in the vertical direction. A holder plate 4 is attached to the lower surface of the upper backing plate 2, and a ball holder 6 for fixing the test ball 5 is fixed to the lower surface of the holder plate 4, and the test plate is used for the test downward from the lower surface of the ball holder 6. The sphere 5 protrudes in a hemispherical shape. On the other hand, a test plate holder 7 is attached to the upper surface of the lower backing plate 3. A concave portion is formed on the test plate holder 7 in accordance with the shape of the test plate (test fixing material) 8, and the test plate 8 is detachably mounted in the concave portion. Between the test ball 5 and the test plate 8, a strip-shaped test piece 9 assuming a work material is inserted in the horizontal direction, and one end of the strip-shaped test piece 9 is a load cell (pulling force detection means). The chuck 11 is held by a chuck 11 with which the strip 11 can be pulled in the direction of arrow B.

  For example, in the case of ironing, which is a forming process, in FIG. 1, the test ball 5 corresponds to a die as a tool, the test plate 8 corresponds to a die (punch), and a strip-shaped test piece. 9 corresponds to a workpiece processed by being sandwiched between a die and a mold.

  Further, the upper backing plate 2 can apply a desired vertical load P downward. Therefore, when the strip test piece 9 is pulled out in the direction of arrow B with the vertical load P applied in the friction test apparatus 1, the vertical load P is measured by the load cell 12, and the test ball 5 and the test plate 8 are The frictional force generated on both surfaces of the strip-shaped test piece 9 sandwiched therebetween is detected by the load cell 10.

  When the friction test is performed, a lubricant to be evaluated is applied to both the upper and lower surfaces or one of the strip-shaped test pieces 9.

  According to the configuration of the friction test apparatus 1, the strip plate-like test piece 9 is moved linearly in one direction, so that friction is not repeatedly applied by rotation or sliding as in the conventional friction test apparatus. In addition, the material of the test balls 5 and the test plate 8 are made to correspond to the tools and molds in the actual machine, and the material of the strip-shaped test piece 9 is matched to the actual processing material, thereby resembling the actual molding process. It is possible to perform a friction test in a state where

  In this embodiment, the above-mentioned lubricant is applied to both surfaces of the strip-shaped test piece 9, inserted between the test ball 5 and the test plate 8, and pressurized in the direction of arrow P with the chuck 11. A friction test was performed by pulling the strip-shaped specimen 9 in the direction of arrow B.

The detailed conditions of the friction test are as follows.
Test ball: SUJ2 ball, 3/8 inch diameter
Test plate: Carbide strip Test piece: SUS430 test piece
Size (W x t x L) 25mm x 1mm x 100mm
Friction speed: 170mm ² / sec Friction distance: 0.5m
Measurement item: Load applied in the direction of arrow P (N)

  After the friction test, the maximum load (load bearing capacity, N) at which seizure did not occur on the surface of the strip test piece 3 was measured, and the seizure resistance of the lubricant was evaluated. It can be evaluated that the larger the maximum load obtained by this method, the better the seizure resistance and the better the lubricating performance. In general, seizure means a phenomenon in which two surfaces cause excessive adhesion or fusion due to frictional heat, and the friction suddenly increases or sticks and does not slip. It is known that seizure hardly occurs. Therefore, seizure resistance and lubrication performance are generally considered to have a good correlation.

Load carrying capacity (seizure resistance) is affected by the kinematic viscosity of the lubricant. As shown in Table 1, the kinematic viscosities of the components used in the present invention vary greatly depending on the type. The viscosity is very high compared to the component A (organic carbonate). In this example, in order to eliminate the influence of kinematic viscosity as much as possible, the kinematic viscosity (40 ° C.) of each sample was adjusted to be approximately 30 mm ² / s or 200 mm ² / s. However, depending on the combination of components, there are some samples in which the dynamic viscosity of the sample is about 20 mm ² / s or 500 mm ² / s. In this example, a maximum load of about 1300 N or more (kinematic viscosity 30 mm ² / s) or a maximum load of about 2000 N or more (kinematic viscosity 200 mm ² / s) was evaluated as excellent in seizure resistance.

  These results are also shown in Tables 2-4. No. in Table 2 1-10, No. 4 in Table 4. 1, 3, 5, and 7 are examples that satisfy the requirements of the present invention; All of 11 to 14 and Table 3, and 2, 4, 6, and 8 in Table 4 are comparative examples that do not satisfy the requirements of the present invention. For reference, Tables 2 to 4 are provided with a remarks column, in which an example including an A component and a B component (AB), an example including an A component, a B component, and a C component are described as an (ABC) component. Also in the following description, an example including the A component and the B component is described as an (A + B) component, and an example including the A component, the B component, and the C component is described as an (A + B + C) component.

(About Table 2)
First, refer to Table 2. Table 2 shows an example in which an organic carbonate of “a2” in which both R ¹ and R ² are alkyl groups is used as the A component. Nos. 1 to 10 are examples of the present invention containing at least a B component. 11 to 14 are comparative examples not including the B component.

  No. In 1-11, as shown in Table 2, the compounding quantity of the organic carbonate (A component) was changed in the range of 6-100 mass parts. Among these, No. in which the compounding quantity of A component satisfies the requirements of this invention. In Nos. 1 to 10, good seizure resistance was obtained regardless of the kinematic viscosity, whereas No. 1 containing only the A component and no B component was obtained. No. 11 has a kinematic viscosity of about the same. The seizure resistance was also lower than 7. No. No. 12 is a comparative example in which “e2” (neutral calcium sulfonate) was blended without containing the B component. The seizure resistance was reduced as compared with 1-3.

  More specifically, No. 1 satisfying the requirements of the present invention. Consider 1-7. These contain at least organic carbonate (component A) and basic sulfonic acid metal salt / dithiophosphate metal salt (component B). Other than 3, 6, and 7, the base oil (C component) is further included.

Of these, No. 1-3 (kinematic viscosity 200mm < ² > / s) is an example which changed the compounding quantity of A component, and changed the combination and the compounding quantity of B component or (B + C) component. These are examples of very high kinematic viscosity, but the maximum load was high and good seizure resistance was observed. No. 4 to 6 (kinematic viscosity 30 mm ² / s) is an example in which the blending amount of the A component is made constant and the combination or blending amount of the B component or the (B + C) component is changed. Obtained. No. 7 (kinematic viscosity of about 20 mm ² / s) is an example in which the blending amount of component A is increased to the upper limit (95 parts by mass). Compared with 11, the maximum load increased markedly. From these examination results, it was confirmed that a lubricant having excellent seizure resistance can be obtained within the range of the blending ratio defined in the present invention.

Next, No. further containing a phosphorus-based or sulfur-based extreme pressure additive (component D). Consider 8-10. Of these, No. No. 8 (kinematic viscosity about 200 mm ² / s) No. No. Compared with 1-3, it increased significantly. Similarly, no. The maximum load of 9, 10 (kinematic viscosity about 30 mm ² / s) is No. with no kinematic viscosity and no D component. Increased compared to 4-6. In particular, no. The maximum load of No. 8 is very high, and No. 1 in Table 3 containing chlorinated paraffin which is a chlorinated extreme pressure additive. It was about the same as 11. From these examination results, it was confirmed that the seizure resistance of the lubricant of the present invention is remarkably increased by the addition of the D component.

(Contrast between Table 2 and Table 3)
Furthermore, the usefulness of the organic carbonate (component A) used in the present invention will be examined in comparison with the examples in Table 3 not containing the organic carbonate (component A).

First, consider an example where the kinematic viscosity is about 30 mm ² / s. First, No. 2 in Table 2. 1 (invention example) and No. 1 in Table 3. Contrast 1 (comparative example). No. in Table 3 1 is No. 1 in Table 2. 1 is different only in that the same amount of C component is included instead of A component. When comparing the maximum loads of the two, the No. of Table 2 containing the A component. No. 1 in Table 3 containing conventional base oil (C component). Increased compared to 1. A similar trend is shown in Table 2. 2 (invention example) and No. 2 in Table 3. 2 (Comparative Example), No. 2 in Table 2. 3 (examples of the present invention) and No. 3 in Table 3. 3 (comparative examples) were also recognized, and the increase rate of the maximum load was more noticeable. Therefore, it was found that the organic carbonate used in the present invention can be replaced with a conventional base oil.

A tendency similar to the above was also confirmed in an example of about 200 mm ² / s with a high kinematic viscosity. That is, in Table 2, No. 4 (Example of the present invention) and No. 4 in Table 3. 4 (Comparative Example), No. 2 in Table 2. 5 (invention example) and No. 5 in Table 3. 5 (comparative example), No. 2 in Table 2. 6 (examples of the present invention) and No. 3 in Table 3. When comparing 6 (comparative examples), the maximum load of each inventive example in Table 2 containing the organic carbonate (component A) used in the present invention is compared to each comparative example in Table 3 containing the conventional base oil. It was found to be high and excellent in seizure resistance.

  From the above examination results, it was confirmed that the organic carbonate used in the present invention is extremely useful as a base oil that can be substituted for the conventional base oil regardless of the kinematic viscosity.

  The above-mentioned examples of the present invention in Table 2 are examples of the (A + B) component or the (A + B + C) component, but the usefulness of the organic carbonate (A component) used in the present invention is No. in Table 2 further including the D component. . Similar results were observed for 8-10. For example, in Table 2, No. No. 8 (example of the present invention) and No. 3 in Table 3. 8 (Comparative Example), these are all examples containing the D component, but in Table 2 containing the organic carbonate (A component). No. 8 includes N component in Table 3 in addition to D. Compared to 8, the maximum load increased. A similar trend is shown in Table 2. Nos. 9 and 10 (both examples of the present invention) and No. 3 in Table 3. This was also observed when 9 (Comparative Example) was compared.

  From the above examination results, it was confirmed that the usefulness of the organic carbonate used in the present invention is recognized even when the component D is further included.

  Furthermore, the seizure resistance improving effect of the organic carbonate (component A) used in the present invention is remarkably exhibited at least in combination with the component B, and is effective even when combined with additives other than the component B. The fact that it was not demonstrated will be discussed with reference to Table 3.

  No. in Table 2 13 is a comparative example (A + C) in which the conventional base oil (C component) is blended with the A component, but the maximum load is No. 1 in Table 3 including only the C component and having the same kinematic viscosity. It was exactly the same as No. 15, and the desired seizure resistance was not obtained. A similar tendency is shown in No. 2 of Table 2 where the kinematic viscosity is low. 14 and No. 3 in Table 3. No. 16 was recognized, and the desired seizure resistance was not obtained.

  Moreover, No. of Table 2 which mix | blended neutral calcium sulfonate with A component. No. 12 in Table 3 which contains the same amount of C component instead of A component. No change to 14.

  From these examination results, it was proved that the above-mentioned characteristics of the organic carbonate (component A) used in the present invention are effectively exhibited by the combined use with the component B.

(About Table 4)
Table 4 shows the results when organic carbonates (a1 or a3) other than “a2” used in Table 2 were used. For details, see No. 4 in Table 4. Nos. 1 and 5 are examples using the organic carbonate of “a1” in which both R ¹ and R ² are alkoxyalkoxyalkoxy groups. 1 is an example further including a D component. No. in Table 4 3 and 7 are examples using an organic carbonate of “a3” in which both R ¹ and R ² are alkyl groups. No. in Table 4 2, 4, 6, and 8 are comparative examples that do not contain any organic carbonate.

  First, the organic carbonate a1 will be examined. No. in Table 4 No. 1 (invention example) and no organic carbonate. 2 (comparative example), No. 2 No. 5 (Example of the present invention) and No. Comparing 6 (comparative example), it can be seen that the inventive example containing organic carbonate is superior in seizure resistance compared to the comparative example.

  Similarly, when the organic carbonate a3 is examined, No. 1 in Table 4 is obtained. 3 (Example of the present invention) and No. 6 (Comparative Example), No. 7 (invention example) and No. As for 8 (comparative example), all of the examples of the present invention containing an organic carbonate improved the seizure resistance as compared with the comparative example.

  From the above examination results, it was confirmed that the seizure resistance improving action by the organic carbonate was also observed when an organic carbonate other than “a2” was used. Therefore, it was demonstrated that the seizure resistance is improved by using the organic carbonate defined in the present invention. In Table 4, in order to clarify the optimum blending amount of each organic carbonate, the blending amount of the organic carbonate was set to 5 parts by mass as the lower limit value. It was confirmed by experiment that it was recognized over the range of the blending amount specified in 1.

FIG. 1 is a perspective view showing the configuration of a friction test apparatus used for evaluating the lubrication performance (seizure resistance) of a lubricant for metal working.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Friction test apparatus 2 Upper backing plate 3 Lower backing plate 4 Holder plate 4a Keyway 4b Fixing screw 5 Test ball 6 Ball holder 6a Projection 7 Test plate holder 8 Test plate (Test fixture)
9 Strip specimen 10 Load cell 11 Chuck 12 Load cell

Claims (3)

A lubricant for non-chlorine plastic working of difficult-to-work metal materials, comprising the following (A), (B), and (C).
(A) Organic carbonate represented by the following formula (I) and having a boiling point under normal pressure of more than 265 ° C .: 5 to 90 parts by mass,
... (I)
In the above formula,
R ¹ and R ² are each independently a hydrocarbon group or an alkoxyalkoxyalkoxy group, and the total number of carbon atoms of R ¹ and R ² is 14 or more and 30 or less.
(B) Total of basic sulfonic acid metal salt and / or dithiophosphoric acid metal salt having a base number of 300 mgKOH / g or more: 5 to 95 parts by mass.
(C) Lubricating base oil: 0 to 90 parts by mass with respect to 100 parts by mass of the total amount of component A and component B.   The non-chlorine plastic working lubricant according to claim 1, further comprising (D) a sulfur-based extreme pressure additive and / or a phosphorus-based extreme pressure additive.   A metal processed product obtained by using the non-chlorine plastic working lubricant according to claim 1.