WO2000056845A1

WO2000056845A1 - Metal working aid composition containing dialkyl thiodipropionate and method of metal working

Info

Publication number: WO2000056845A1
Application number: PCT/JP2000/001684
Authority: WO
Inventors: Norie Hoshi; Kazuki Katsuyama; Kazuhiro Matsuzaki
Original assignee: Yoshitomi Fine Chemicals, Ltd.
Priority date: 1999-03-19
Filing date: 2000-03-17
Publication date: 2000-09-28
Also published as: JP4415494B2

Abstract

A metal working aid composition comprising a dialkyl thiodipropionate having an average particle diameter of 10 νm or smaller and represented by the general formula (1): R1OOCCH2CH2SCH2CH2COOR2 (wherein R?1 and R2¿ may be the same or different and each represents C¿12-18? linear or branched alkyl) and at least one emulsifier/dispersant selected from the group consisting of basic sulfates of higher alcohols, polyoxyethylene derivatives, and salts of fatty acids. The composition combines lubricating properties, suitability for extreme-pressure lubrication, and anticorrosive properties, and is hence useful as a metal working aid in, e.g., the cutting, grinding, plastic working, or forming (deep drawing, squeezing forming, etc.) of a metallic material. The dialkyl thiodipropionate has been ascertained to be safe and is an excellent lubricant from the standpoint of global environmental protection. It is excellent also from the standpoint of energy saving because degreasing/cleaning is easy.

Description

Description Metal working agent composition containing dialkylthiodipropionate and metal working method

TECHNICAL FIELD The present invention relates to a metal processing agent composition and a metal processing method which are excellent in lubricity, extreme pressure properties and heat resistance, and are preferably emulsion-type and dispersion-type metal processing agents. More specifically, water washing used for cutting, grinding, plastic working, forming (metal deep drawing, metal ironing, etc.) of metal materials such as aluminum, aluminum alloy, iron, zinc, and copper The present invention relates to an easy metal working agent composition and a metal working method for a metal as described above. Background art

Conventionally, metal cutting agents have been used for cutting, polishing, and plastic working of metal materials to prevent seizures and reduce the coefficient of friction.

For example, oil-based metal processing agents such as superbasic calcium salts and superbasic calcium sulfonates as disclosed in International Publication WO087 / 01723 are used. However, these are problems under the Fire Service Law due to the danger of fire caused by containing a large amount of non-aqueous solvents, the deterioration of the work environment due to smoking and scattering, and environmental pollution when mixed into wastewater. There was.

Also, for example, Japanese Patent Application Laid-Open No. 2-55794 discloses a fatty acid having 6 to 10 carbon atoms and a cationic surfactant, and Japanese Patent Publication No. 167575/1994 discloses an alkyl phosphate ester. An emulsion-type metalworking agent composition containing a chloroethylene adduct and an amphoteric surfactant, and Japanese Patent Application Laid-Open No. 1986/9898, respectively, contains an alkyl phosphate salt and a cationic surfactant. It has been disclosed. However, these known compositions have problems such as seizure during metal working due to insufficient lubrication, damage to products due to lack of extreme pressure properties, and a low anticorrosive effect.

In addition, it has been known that chlorine-containing organic compounds such as chlorinated paraffins and chlorinated fatty acid esters have excellent extreme pressure properties as extreme pressure additives for improving the performance of metalworking oils. However, using these chlorine-containing organic compounds Metalworking II has problems such as corrosion of processed materials due to slight hydrochloric acid generated during processing and the problem of the global environment due to hydrochloric acid gas generated by decomposition after disposal after use.

Conventionally, sulfur-containing organic compounds such as sulfurized oils and fats, sulfurized refins, and dialkyl borosulfides are also known as extreme pressure agents. Chemical compounds have little effect on the human body and the environment, but the use of such compounds with mercapto groups is discouraged due to the odor of the extreme pressure agent itself and the problem of corrosion of the work material. .

As a measure for solving these problems, Japanese Patent Publication No. Hei 4-5 716 discloses a disulfide group (R—S—S—S— which has no mercapto group (one SH group) which causes odor and has extreme pressure. R) (wherein, R represents a CH ₂ CH ₂ COOH group). In the extreme pressure agent with these structures, the sulfur content in one molecule is higher than that of the hydrocarbon structure in one molecule and the activity is strong, so when added to metalworking fluids for heavy working However, if the added amount is too small, it leads to the corrosion of the workpiece and the tool, which causes a problem. Further, there is a problem that it is necessary to further add a lubricant because of lack of lubricity.

Also, JP-A-5-43886 describes that R—SR′—COOH (wherein R represents an alkyl group or cycloalkyl group having 6 to 20 carbon atoms, and R ′ represents carbon An extreme pressure additive consisting of a water-soluble salt of an acid represented by the formula: and a water-soluble metalworking oil containing the additive. . These extreme pressure additives are excellent in extreme pressure properties, but lack lubricity and protection properties, so that there is a problem that it is necessary to further add a lubricant or a protection agent. By the way, Japanese Patent Application Laid-Open No. 5-658481 discloses a method selected from alkylthiodipropionate having an average particle diameter of 10 nm or less, a sulfate-basic salt of a higher alcohol, a polyoxyethylene derivative and a fatty acid salt. It describes an anti-oxidation deterioration inhibitor dispersion characterized by containing an emulsifier, but does not disclose or suggest that they can be used as a metal working agent.

In addition, after deep-drawing (cupping) a metal plate such as aluminum or iron, the body and the bottom part are manufactured by further processing such as ironing. Metal forming agents are used for metal forming such as cans (also called DI cans or drawn cans) that have an integrated structure without any seams.

Aluminum and iron DI cans are widely used as containers for beer and soft drinks.

These cans are made by punching an aluminum sheet into a disc and fixing it with a wrinkle holding device, and then using a tool consisting of a combination of punch and die to produce a cup-shaped bottom with an integrated structure. After the process (deep drawing 5 mm processing), it is manufactured by applying a process (ironing forming) to stretch the side wall of the cup protruding piece long.

In such deep drawing, re-drawing, and ironing processes, it is possible to reduce the failure rate due to rupture of the nip and reduce the occurrence of scratches due to excessive friction between the nip and the tool. For this purpose, deep drawing agents and ironing agents are used as lubricants.

Emulsion-type preparations are used as these metal forming agents, that is, deep drawing agents and ironing agents, and these agents are also called tubing ¾ij or coolant. .

When the metal forming agent is emulsion, how to selectively and efficiently adhere the oil in the emulsion to the lubricating portion becomes a problem. Even lubricants with excellent lubricity, even those with poor adhesion, may crack or break or break in the wrought molding during deep drawing from the part where it does not adhere.

Even if cracks and breaks do not occur, excessive friction generated between the metal material and tools such as punches and dies causes damage to the surface of the cup-shaped molded product, causing breakage, It can not be practically used because the aesthetic appearance of the can is significantly impaired due to scratches caused by friction between them, which significantly reduces the commercial value. Even if an oil-based agent is used as the deep-drawing forming agent due to the problem of adhesion, if the lubricating property is insufficient, as in the case of the above-described poorly-adhering lubricant, the deep drawing process However, cracks in the cup β-piece may cause breakage and breakage, and even if cracks or breakage do not occur, excessive friction generated between the metal material and tools such as punches and dies may cause the cup-shaped molded product to break. Same as emulsion type, such as scratches on the surface / JP00 / 01684

There was a problem. The scratches generated in this way remain on the surface even after squeezing during the manufacture of DI cans, significantly impairing the aesthetics of the cans and greatly reducing their commercial value.

In addition, the lubricant used for deep drawing left on the surface of the cup-shaped molded product was used in the ironing process, which is a post-process in the manufacture of D1 cans. As a lubricant, it also contributes to friction reduction, but does not have sufficient lubricity. In this case, the surface of the lip-shaped molding is also damaged.

On the other hand, if the lubricity of the deep drawing forming agent is excessively pierced, the fixing property deteriorates due to slipping between the plate and the wrinkle holding portion at the fixed portion of the plate during deep drawing forming, so that the deep opening forming can be performed at the opening of the can. When wrinkles are generated or a partial strength <elongation, protrusions called ears are formed. As described above, when wrinkles are generated or ears are formed, the thickness of the opening of the can becomes uneven, and the post-process is performed. The ironing process increases the thickness of the plate and increases the ironing rate in some parts, resulting in seizure due to insufficient lubrication and surface defects. In addition, the eared cups may be caught by the transfer equipment for the ironing process, which is a later process, and may cause a significant decrease in productivity.

The cans after deep drawing or ironing are usually degreased and washed with an aqueous detergent containing a surfactant, and are subjected to surface treatment to prevent corrosion, followed by painting. · Through the printing process, the opening is subjected to draw forming called the necking process and edge forming called flange forming. Depending on the components of the deep drawing forming agent and the ironing forming agent, the degree of difficulty in the degreasing and cleaning steps varies, and the surfactant and alkali concentrations of the cleaning agent also vary. When a lubricant that is difficult to clean is used, it takes a long time to clean, and it is necessary to use a high-concentration surfactant, which increases the load on wastewater treatment.

In addition, it is possible to remove frictional powder caused by metal friction generated during deep drawing and ironing during degreasing and cleaning.However, in the case of a lubricant that is difficult to clean, a small amount of metal powder can be removed. Remaining on the surface of the can can cause soiling of the can. Disclosure of the invention

The present invention solves the above problems, and provides aluminum, aluminum alloy, iron, and zinc. It is an object of the present invention to provide a metal working agent composition for a metal material such as copper and a metal working method using such a composition.

In particular, metal processing agents that are used for cutting, grinding, plastic working, etc. for metal materials are excellent in lubricity, extreme pressure, and protection, and are easy to clean, especially emulsion-type and dispersion-type metal processing agents. And a metal working method using such a composition.

In addition, it is easy to use not only for lubrication but also for degreasing and cleaning after molding, and good drainage treatment of cleaning wastewater, especially for deep drawing and ironing used in the production of D-cans. It is an object of the present invention to provide a metal additive composition, particularly an emulsion-type and dispersion-type metal processing agent composition, and a metal processing method using such a composition. The present inventors have conducted intensive studies to develop a metal working agent composition having excellent lubricating properties, extreme pressure properties, and corrosion resistance in cutting, grinding, plastic working, and the like of metal materials in order to achieve the above object. A dialkylthiodipropionate having a fast-average particle size of 10 or less, and at least one emulsifier and dispersant selected from the group consisting of sulfate base salts of higher alcohols, polyoxyethylene derivatives and fatty acid salts. It is surprising that a metal additive composition containing, particularly, a metal processing agent composition in an emulsion type and a dispersion type has both lubricity, extreme pressure, and water resistance, and is easy to clean. They have found and completed the present invention.

In addition, the present inventors use the above-mentioned composition, particularly its emulsion or dispersion, and if necessary, a metal-forming agent composition diluted with water at the time of deep drawing or ironing to obtain high quality. In addition to producing aluminum and iron DI cans with excellent properties, the composition was found to be easily degreased / washed and had good drainage treatment properties, and the present invention was completed.

That is, the present invention is as follows.

1. General formula (1)

R'OOCCH ₂ CH ₂ SCH ₂ CH ₂ COOR ² (1) (Wherein, R ¹ and R ² represent a linear or branched alkyl group having 12 to 18 carbon atoms, and R ¹ and R ² may be the same or different from each other.) A metalworking composition containing a dialkylthiodipropionate to be prepared.

2. The metal working agent composition according to the above 1, wherein in the general formula (1), R ′ and R ² are a linear or branched alkyl group having 18 carbon atoms.

3. The metal working agent composition according to the above 1 or 2, wherein the average particle diameter of the dialkylthiodipropionate is 10 / m or less.

4. In addition, the above-mentioned 1-3, which is an emulsion type or a dispersion type containing at least one emulsifier selected from the group consisting of a sulfated basic salt of a higher alcohol, a polyoxyethylene derivative and a fatty acid salt and a dispersant and water. The metalworking agent composition according to any one of the above.

5. The method according to any one of the above items 1 to 4, wherein the mixing ratio (based on the total amount of the composition) of the metal working agent composition of the dialkylthiodiprobionet when used is 0.05 to 10% by weight. Metalworking composition.

6. The method according to any one of 1 to 4 above, wherein the mixing ratio of the dialkylthiodipropionate during storage of the metal processing composition (based on the total amount of the composition) is 25% by weight or more and less than 70% by weight. Metalworking composition.

7. The metal working agent composition according to any one of the above 1 to 6, wherein the metal working is cutting, polishing, plastic working or metal forming of a metal material.

8. The metal working agent composition according to the above 7, wherein the metal forming process is a metal deep drawing process and a Z or metal ironing process.

9. General formula (1)

R ¹ OOCCH ₂ CH ₂ SCH ₂ CH2COOR ² (1)

(Wherein, R ¹ and R ² represent a linear or branched alkyl group having 12 to 18 carbon atoms, and R ¹ and R ² may be the same or different from each other.) A metal working method comprising working a metal in the presence of a metal working agent composition containing a dialkylthiodiprobionate to be prepared.

6

Corrected form (Rule 91) 10. The metal working method according to the above 9, wherein in the general formula (II), R ¹ and R ² are a linear or branched alkyl group having 18 carbon atoms.

11. The metal working method according to any one of 9 to 11 above, wherein the average particle diameter of the dialkylthiodipropionate is 1 or less.

12. The metal working composition is at least one emulsifier selected from the group consisting of a sulfated basic salt of a higher alcohol, a polyoxyethylene derivative, and a fatty acid salt. • Emulsion type or dispersed type containing a fraction and water. A metal working method according to any one of the above items 9 to 11.

13. The mixing ratio of the dialkylthiodipropionate in the metal working composition when the metal working composition is used (based on the total amount of the composition). The metal working method according to any one of the above.

14. The above-mentioned 9 wherein the mixing ratio (based on the total amount of the composition) of the dialkylthiodipropionate in the metal processing composition during storage of the metal processing composition is 25% by weight or more and less than 70% by weight. 13. The metal working method according to any one of to 12.

15. The metal working method according to any one of 9 to 14 above, wherein the metal working is cutting, polishing, plastic working, or metal forming of a metal material.

16. The metal working method according to the above item 15, wherein the metal forming is metal deep drawing and Z or metal ironing. BEST MODE FOR CARRYING OUT THE INVENTION

R ¹ and R ^{2 in} the general formula (1) may be the same or different and each have a carbon number of from 12 to 18, preferably a linear or branched C 18, 12, 14 or 13 carbon atom. Alkyl groups (especially, linear alkyl groups), more preferably, linear or branched alkyl groups having 18 or 12 carbon atoms (among others, linear alkyl groups), particularly preferably 18 carbon atoms A straight-chain or branched alkyl group (among others, a straight-chain alkyl group), specifically, lauryl group, tridecyl group, myristyl group, cetyl group, stearyl group, isostearyl group and the like. However, a linear alkyl group such as a lauryl group, a myristyl group, and a stearyl group is preferable, and a stearyl group is particularly preferable. Further, it is preferable that R ¹ and R ² are the same. Di represented by the general formula (1)

7 Corrected Form (Rule 91) Only one alkylthiodipropionate may be used, or two or more compounds may be used in combination.

— The dialkylthiodipropionates represented by the general formula (1) include diperylthiodipropionate, dimyristylthiodipropionate, distearyl thiodipropionate, and ditridecylthiodione. Powers, such as propionate, laurinole. Stearylthiodipropionate, myristyl. Stearylthiodipropionate, etc., are not limited to these.

According to the present invention, in the case of a water-dispersible preparation, the average particle size of the dialkyldipropionate dipropionate dispersed in the water dispersant is preferably 10 m or less, more preferably 8 m in terms of excellent storage stability. The following is preferable. The lower limit of the average particle diameter is preferably 1; / m. If the diameter is smaller than 1, it is not preferable because it tends to be viscous and difficult to handle at a high concentration.

In the case of the emulsion type preparation, the average particle size of the dialkylthiodipropionate Shandrop emulsified in water is preferably 10 m or less, and more preferably 2 m or less from the viewpoint of excellent storage stability. The lower limit of the average particle diameter is preferably 0.01 m. If the diameter is smaller than 0.01 / m, stirring during production takes too much time, and it is necessary to increase the blending amount of the emulsifier.

Here, the average diameter of the abalone refers to the particle diameter (volume average diameter) when the volume reaches 50%.

The measurement of the average particle size of the aqueous dispersion-type preparation is performed as follows. That is, a developing solution dissolved in pure water was prepared so that the dispersing agent used for dispersion was 0.1% by weight, a small amount of the sample was mixed with the developing solution using a spatula, and the particle size was determined while observing the absorbance. This is performed by adding a sample to a concentration at which measurement is possible, and then measuring the average particle size using a SALD-200J laser diffraction particle size distribution device manufactured by Shimadzu Corporation.

The average particle size of the emulsion-type preparation is determined by dispersing the emulsion-type preparation to be measured on a slide glass as uniformly and sparsely as possible, and using a scanning electron microscope to reduce the average particle size to about 30 particles in one visual field. Measures all measurable particle sizes, 1 Determine the average value per cycle, repeat the operation three times, and determine the average value.

Linear alkyl compounds having both 1,2,14, and 18 carbon atoms in the dialkylthiodibutene pionate of the general formula (1) are compounds having excellent safety and hygiene properties. It has been approved by the Food and Drug Administration (FDA) as a plastic stabilizer that can be used in contact with food, and those with a straight-chain carbon number of 12 have been approved as food additives that can be added directly to food. I have.

In addition, compounds having both straight-chain carbon atoms of 12 and 18 in which the alkyl group of the dialkylthiodipropionate of the general formula (1) is used are regulated by the Ministry of International Trade and Industry and the Ministry of Health and Welfare in Japan under the “Regulations on the Examination and Manufacture of Chemical Substances”. Has been evaluated as a highly degradable compound by a microbial degradation test of chemical substances, and is easily degraded by naturally occurring microorganisms and is safe as carbon dioxide and water. Since it is a substance that has been shown to decompose into a simple substance, the metalworking molding agent of the present invention is also excellent from the viewpoint of protecting the global environment.

The concentration (based on the total amount of the composition) of the alkylthiodiprobionate during storage of the metalworking composition of the present invention is 25% by weight or more and less than 70% by weight, and particularly 30% by weight or more and 50% by weight. The following is preferred, but not limited to this concentration. When the concentration during storage is less than 25% by weight, separation tends to occur easily during storage, and when the concentration is 70% by weight or more, the viscosity of the drug product tends to increase, making it difficult to handle. Is not preferred.

In the present specification, the term “storage” means not only the time of storage of the metal working agent composition, but also the time other than the time of use, including the time of transportation and sale.

The concentration of alkylthiodipropionate (based on the total amount of the composition) when the metal working composition is used is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight. However, the present invention is not limited to this. When the concentration at the time of use is less than 0.05% by weight, the effect tends to vary, and when it exceeds 10% by weight, it takes time for cleaning and the like, and the amount of the cleaning agent is increased. It is not preferable because it tends to cause economical and environmental problems such as necessity.

The metal working agent composition of the present invention contains sulfur derived from dialkylthiodipropionate. When used, the amount (based on the total amount of the composition) is preferably 0.002 to 0.6% by weight, more preferably 0.05 to 0.3% by weight, and the sulfur content is less than 0.002% by weight. In the case of ¾, the effect, especially the extreme pressure property, tends not to be sufficiently exerted. When the content exceeds 0.6% by weight, the concentration of the compound represented by the general formula (1) becomes high, and it takes a long time for washing, etc. It is not preferable because it tends to cause economic and environmental problems such as the need to perform The sulfur content at the time of storage (based on the total amount of the composition) is preferably 1.0 to 4.5% by weight, and particularly preferably 1.5 to 3.5% by weight. If it is less than 1.0% by weight, it tends to be easily separated during storage, and if it exceeds 4.5% by weight, the viscosity of the preparation tends to be high, making it difficult to handle.

As the sulfate basic salt of a higher alcohol used as the emulsifier / min t ^ j, a sulfate basic salt of a higher alcohol having a carbon number of 10 to 20 is suitable.Specifically, sodium dodecyl sulfate, dodecyl Examples thereof include ammonium sulfate, triethanolamine dodecyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium stearate, ammonium stearate sulfate, and triethanolamine stearate.

As the polyoxyethylene derivative used as the emulsifier-diamine C¾ij, ethers of polyoxyethylene and higher alcohols having 10 to 20 carbon atoms, or ethers of polyoxetylene and alkylphenol are preferable. Specific examples thereof are as follows. Polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, poly And oxyethylene nonylphenyl ether.

Emulsifiers-Examples of the fatty acid salts used as dispersants include potassium oleate, semi-hardened tallow fatty acid potassium, castor oil potassium and the like having 6 to 30, preferably 8 to 20 carbon atoms. Earth metal salts.

These milky dispersants may be used alone or in combination.

The ratio of emulsifier and dispersant in the dispersion (based on the total amount of the composition) is preferably from 0.1 to 10% by weight, more preferably from 1 to 8% by weight, as the amount of the active ingredient compound when stored. . If the proportion of emulsifier / dispersion ^ j in the dispersion exceeds 10% by weight, the viscosity increases and the chemical oxygen demand (C 0 D) at the time of drainage increases, which is not preferable. If it is less than 0.1% by weight, a sufficient emulsification / dispersion effect cannot be obtained.

The metal working composition of the present invention is usually formulated as an emulsion-type preparation or a dispersion-type preparation.

Here, the emulsion type formulation is usually an oil-in-water type emulsion, and the compound represented by the general formula (1) having an average particle diameter of 10 / m or less <, emulsifier It is a formulation dispersed in water in the form of a liquid oil (drops). The average particle diameter of the compound represented by the general formula (1) in the emulsion-type preparation is the average particle diameter in the form of a liquid oil (oil droplets) dispersed in water.

Further, the dispersion-type preparation is a preparation in which the above-mentioned powdery compound having an average diameter of 10 m or less is dispersed in water.

In the present invention, the water for the aqueous medium in the emulsion-type preparation and the dispersion-type preparation is not particularly limited, and deionized water and distilled water are desirably used, and ordinary industrial water may be used.

Metalworking compositions of the invention may also aspects der connexion to a dispersion type and Emarujon type are mixed _π

An emulsification / dispersion stabilizing aid can be added to the metalworking agent composition of the present invention. Dispersion stabilizing aids include gum arabic, gelatin, cellulose derivatives (methyl cellulose, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose), starch derivatives (sodium starch glycolate, sodium starch phosphate, carboxylate). Methyl starch, etc.), acrylic acid or polyacrylic acid and their salts (such as sodium salts), polyhydric alcohols (such as polyethylene glycol and polypropylene glycol), polyvinyl alcohol, maleic anhydride-styrene copolymer, Water-soluble polyesters and the like can be mentioned, and the amount added during storage (based on the total amount of the composition) is usually 0.5% by weight or less, preferably 0.05% to 0.4% by weight. Is usually up to 0.2 % By weight or less.

As the metal working agent composition of the present invention, a composition comprising only the above-described base is used. For example, a base obtained by adding an additive to a base may be used.

Examples of such additives include carboxylic acids, fats and oils, extreme pressure additives, various amines, alcohols, antioxidants, defoamers, non-ferrous metal anticorrosives, antioxidants, preservatives, metal sealants Agents and the like can be blended.

Examples of the carboxylic acids of the above additives include aliphatic carboxylic acids having 8 to 24 carbon atoms, and may be monobasic acids or dibasic acids, linear or branched ones, or saturated ones. However, it may be unsaturated. Specific examples of such a carboxylic acid include saturated carboxylic acids such as caprylic acid, nonanoic acid, capric acid, lauric acid, palmitic acid, sebacic acid and dodecanoic acid, and oleic acid and linoleic acid. And unsaturated carboxylic acids such as linolenic acid and ricinoleic acid. The carboxylic acid may be used as a carboxylic acid as a complexing agent described later depending on its type.

Examples of the fats and oils of the above additives include animal oils such as beef tallow and lard, vegetable oils such as soybean oil, rapeseed oil, coconut oil, palm oil, and nuka oil, and hydrogenated products thereof.

The extreme pressure additives of the above additives include chlorinated paraffins, chlorinated fatty acids, sulfuric acid fatty acids, polysulfides, alkyl phosphates, zinc dialkyldithiophosphates, and molybdenum dialkyldithiophene additives. And zinc dialkyldithiocarbamate, molybdenum dialkyldithiocarbamate and the like. Examples of the various additives include alcohols, alkylamines, and the like.Alcohols include linear or branched alcohols having 10 to 18 carbon atoms or various glycols. Examples of the alkyl include straight-chain or branched alkyl having 3 to 20 carbon atoms. Specific examples of such an amine include dodecanol amine, lauryl alcohol amine, and stearyl alcohol amine. Styrene, isostearyl alcoholamine, polyethylene glycol laurylamine, polyethylene glycol stearylamine, ethylene glycol laurylamine, ethylene glycol stearylamine, propylamine, n-butylamine, 2-phenylene Tylhexylamine, n-octylamine, dodecylamine, laurylamine, Myristylamine, stearylamine, g-propylamine, g-n-butyl Amin, G2-ethylhexylamine, Gn-octylamine, didodecylamine, dilaurylamine, dimyristylamine, distearylamine, tree η—propylamine, tree: η—butylamine, tree2 —Ethylhexylamine, tri-η—S-octylamine, tridodecylamine, trilaurylamine, trilithristylamine, tristearylamine and the like.

Carboxylic acids (such as lauric acid, myristic acid, panolemitic acid, stearinic acid, arachinic acid, behenic acid, naphthenic acid, alkenyl succinic acid, etc.), carboxylate salts and naphthenic acids include Acid, abietic acid, lanolin fatty acid, alkenyl succinic acid, metal salt of carboxylic acid such as amino acid derivative, such as calcium, magnesium, aluminum, zinc, lead, etc., salt of the above carboxylic acid and amine, sulfonate Sodium acid, petroleum sulfonic acid, dinonyl naphthalene sulfonic acid, heavy alkylbenzene sulfonic acid, etc., salts such as sodium, calcium, sodium, etc., carboxylic acids such as oleic acid, radium acid and sorbitol, pen Even esters of polyhydric alcohols such as erythritol, sucrose, and glycerin can be mentioned. It is not limited to these.

Examples of the antifoaming agent of the above additives include silicone compounds, higher alcohols and the like, but are not limited thereto.

Examples of the non-ferrous metal anticorrosive of the above additives include, but are not limited to, benzotriabul, mercaptobenzothiazole, sodium salt of mercaptobenzothiazole, and trinoletriazole.

Examples of the antioxidant of the additive include a phenolic antioxidant, but are not limited thereto.

Examples of the preservatives of the above additives include thiazole, isothiazole, ο-phenylphenol, ο-sodium phenylphenol, 2,3,4.6-tetrachlorophenol and the like. Phenolic compounds, 2-hydroxymethyl-2--2-tro 1,3-propanediol, hexahydr 1,3,5 — tris (2-hydric quichetyl) 1 (s) — trialdehyde and other formaldehyde Donor compounds, halogen-based additives such as tribromosalicylanilide dibromosalicylanilide, etc., and pyrithione such as sodium pyrithione, sodium pyrithione, copper pyrithione, etc. Examples include, but are not limited to, on-type compounds.

Examples of the metal sequestering agent of the above additive include ethylenediaminetetraacetate and the like, but are not limited thereto.

The content of each of these additives (based on the total amount of the composition) is preferably 5% by weight or less, and preferably 1% by weight or less when stored.

In the present invention, examples of the metal to be processed include aluminum, aluminum alloy (such as aluminum-manganese alloy), steel plate, surface-treated steel plate (zinc plated steel plate, tin plated plate), and copper. It is not something to be done.

Regarding the present invention, as a method for producing an emulsion-type and dispersion-type metal working agent composition (hereinafter, also referred to as the present production method), for example, as exemplified in JP-A-5-64881, Emulsifiers and dispersants such as dialkylthiodiprobionet represented by the general formula (1) and sodium lauryl sulfate, water such as ion-exchanged water, and glass beads are cooled while keeping the internal temperature within 30 ° C. An example is a method in which stirring is performed at a high speed between 20 and 30 B temples, particularly for about 26 hours, and then the beads and the dispersion are separated by filtration. This method is usually used when manufacturing a dispersion type. The emulsion-type metalworking agent composition uses the dialkylthiodipropionate in the present invention even when the dialkylthiodipropionate represented by the general formula (1) is a liquid at room temperature and has a relatively high melting point. Min ij 'emulsifier type, carboxylic acid, fats and oils, extreme pressure additives, various amines, alcohols, antioxidants, defoamers, metal anticorrosives, antioxidants, preservatives, metal sealants, etc. Depending on the additive, crystals of dialkylthiodiprobionet may be dissolved in the additive and exist as a liquid at room temperature. In such a case, it can be produced by stirring with water. In the case of a powdery dialkyl thiodipropionate, the compound can be produced by a melt dispersion method in which the compound is melted at a temperature higher than the melting point, stirred, dispersed, and cooled to room temperature.

In the present invention, when the dialkylthiodiprobionet is present in the form of liquid particles dissolved in an additive, the average particle diameter of the dialkylthiodiprobionet in the emulsion-type metalworking agent composition, The particle diameter of the particles is treated as the average particle diameter of the dialkylthiodipropionate in the present invention. The method for producing the metal working composition of the present invention will be described from another viewpoint. The wet emulsification method in which the specific emulsifier used in the present invention, water, and other additives are stirred and dispersed together with a grinding medium (eg, glass beads, titania), A melt dispersion method in which diprobionet is melted and stirred at a temperature equal to or higher than the melting point, dispersed, and cooled to room temperature can be applied. In the wet dispersion method, when the concentration of the dialkylthiodipropionate generally exceeds 50% by weight (based on the total amount of the composition), the fluidity is poor and the dispersion efficiency is reduced. Emulsification and dispersion can be performed efficiently even at a concentration, which is a preferable method. In the present invention

The powdered or oily or liquid alkylthiodiprobionet dissolved in additives having an average particle size of 10 / m or less is substantially water-soluble with a specific emulsifier and, if necessary, a dispersion-stabilizing rib. It can be prepared by a known method such as a batch system or a continuous system.

For example, in the case of the wet dispersion method, a bowl mill, a tube mill, a dyno mill, a bisco mill, a sand grinder, etc., and in the case of the melt dispersion method, a homomixer, a homogenizer, a colloid mill, a jet flow mixer, an ultrasonic homogenizer, etc. The force used is not limited to these, and various devices are used.

A mixed preparation of an emulsion type and a dispersion type can be produced in the same manner as the dispersion type. At this time, the mixing ratio of the dialkylthiodiprobionet represented by the general formula (1) in the form of a powder or a liquid at room temperature is adjusted. Thereby, the mixed preparation can be easily obtained.

The metalworking agent composition of the present invention is subjected to a metalworking method as follows, for example, in the case of cutting and grinding, the metalworking agent composition at the time of storage is diluted and processed while flowing to the machined portion. This enhances lubrication as well as cooling, and reduces friction.

In the case of DI cans, diluting liquid is applied during cutting (deep drawing), and processing is performed while flowing when ironing, thereby improving lubricity while cooling and reducing friction. In the process of drawing, which is a type of plastic processing, in which a metal rod is drawn through a die and the diameter of the rod is reduced, after the metal rod is passed through a container containing a diluent, Introduced into dies, improve lubricity between dies and metal rods to reduce friction. _

PCT / JP00 / 01684

Hereinafter, the metal working agent composition of the present invention will be described more specifically with reference to Production Examples, Examples and Specific Examples, but the present invention is not limited thereto.

Production Example 1

The average particle size measured with a laser diffraction type particle size distribution device (manufactured by Shimadzu Corporation, SAL D-200.J) is 100 // m or more (that is, the average particle size is 100 m). Take 40 g of diazirylthiodipropionate, 8 g of sodium lauryl sulfate, 52 g of ion-exchanged water and 150 g of 1.5 mm-diameter spherical glass beads into a 300 ml 1 volume beaker. that the internal temperature 3 0 ⁿ cooled C so as not to exceed 2 6 hours stirring at a high speed at a three-one motor evening while was濾别beads and dispersion by a sieve of 8 0 mesh. The sulfur content of the obtained aqueous dispersion was 2.49% by weight.

The average particle diameter of the obtained aqueous dispersion was 4.3 m, as measured by the above-mentioned laser-diffraction type distribution apparatus, and was measured by a B-type rotational viscometer (manufactured by TOK I ME CI NC). The viscosity was 350 cp sZ20. Also, the dispersion stability was good even after standing at room temperature for 2 months.

Production Example 2

Same as Production Example 1, except that 4 g of polyoxyethylene diaryl ether was used instead of sodium lauryl sulfate used in Production Example 1 and 66 g of ion-exchanged water and 30 g of dilauryl thiodipropionate were used. A wet-pulverized dispersion was obtained by the method described in (1). The sulfur content of the resulting dispersion was 1.86% by weight.

As a result of measuring the obtained aqueous dispersion in the same manner as in Production Example 1, the average particle size was 4.1, and the viscosity measured with the B-type rotary viscometer was 400 cp sX20. Also, the dispersion stability was good even after being left at room temperature for one month.

Production Example 3

A dispersion liquid wet-ground was obtained in the same manner as in Production Example 2, except that 30 g of distearyl thiodipropionate was used instead of dilauryl thiodipropionate used in Production Example 2. The sulfur content of the resulting dispersion was 1.40% by weight. As a result of measuring the obtained aqueous dispersion in the same manner as in Production Example 1, the average particle diameter was 4.1 μm, and the viscosity measured with the above-mentioned B-type rotational viscometer was 400 cp sZ20. Was. In addition, the dispersion stability was good even when allowed to stand at room temperature for 2 months.

Production Example 4

40 g of ditridecylthiodipropionate, 10 g of sodium lauryl sulfate, and 5 Og of ion-exchanged water are cooled by a homomixer for 2 hours while cooling so that the internal temperature does not exceed 30 ° C. The mixture was stirred to obtain an emulsion liquid.

The sulfur content of the obtained dimulsion liquid was 2.3 (3% by weight. The obtained emulsion was measured by a scanning electron microscope. As a result, the average particle diameter was 0.8 μm. The viscosity measured with a 回 -type viscometer was 50 cps / 20, and the stability of the emulsion was good even after standing at room temperature for one month.

Example 1

A test sample (hereinafter referred to as “DL-AJ”) was prepared by diluting the composition of Production Example 1 11 times with water, and a test sample (hereinafter referred to as “DL-AJ”) was diluted 7 times. Below, it is called "DS-A." The extreme pressure property was evaluated by examining the welding load (Weld Point) by increasing the load using a FAL EX tester (manufactured by FAL EX) at a rotational speed of 500 rotations until burning. .

Example 1

A test sample (hereinafter, referred to as “Commercial 1A”) was prepared by diluting the stock solution of emulsion-based metal working agent “SS-11” manufactured by Nitto Oil Co., Ltd. 20 times with water.

Example 2

A test sample (hereinafter, referred to as “commercially-B”) was manufactured by diluting the stock solution of water-soluble metal processing agent “SW-400S” manufactured by Nitto Oil Co., Ltd. 20 times with water.

table 1

Compared with the composition of the comparative example, it was found that the composition of the present invention was high and did not cause seizure even under a load, and had excellent extreme pressure properties. In addition, the friction of the test piece was also low, indicating good lubricity.

Example 2

Using a cold-rolled steel plate, a steel plate, a zinc plate, a copper plate and an aluminum plate, an anti-complexity test was performed under the following conditions. The test plate was immersed in a test solution diluted to a specified magnification with distilled water for 30 seconds, air-dried for 2 hours, and then sprayed with 5%: water for 72 hours.

Table 2

Waterproofing: (Good) 〇> 〇> △> ▲> <(Poor) From the results of Example 2, it can be seen that the composition of the present invention is more excellent in waterproofing than the composition of the comparative example.

Example 3

Detergency of plates used in applications requiring degreasing After spraying alkaline water (20% sodium hydroxide solution) at high pressure for 30 seconds, washing with distilled water, air drying, and visually observing the surface cloudiness Detergency was evaluated.

Table 3

The symbols shown in Table 3 indicate the ease of cleaning, and the best one is indicated by “©”, and the factory is indicated as “、”, “△”, “▲”, and the lowest one is “x”.

From the results of Example 3, it can be seen that the composition of the present invention has the same ease of cleaning as that of the completely water-soluble metal working agent as a comparative composition.

Example 4

The composition obtained in Production Example 1 was diluted 8-fold with water to produce a metal forming agent “DL-1” used for performance evaluation of deep forming and ironing.

Example 5

The composition obtained in Production Example 3 was diluted 8-fold with water to produce a metal forming agent “DS-1” used for performance evaluation of deep drawing and ironing.

Comparative Example 3

Nitto Oil Co., Ltd. Emulsion-based metal processing agent stock solution (trade name “SS-11”) is diluted 20 times with water and used to evaluate the performance of deep drawing and ironing processing. Commercially available C "was manufactured.

Comparative example 4 Said Toyo Oil Co., Ltd., a water-soluble metal working agent stock solution (trade name “SW-400S”) was diluted 20 times with water and used for performance evaluation of deep drawing and ironing. Manufactured a metal forming agent “Commercial I-D”.

Performance test 1

In order to evaluate the performance of the deep drawing process, use a deep drawing tester (SAS-200D, manufactured by JT Toshi) and increase the ratio of the diameter of the metal disk to the diameter of the punch. It was evaluated by finding the diameter ratio (hereinafter, also referred to as the limit drawing ratio) at which forming was impossible due to the above. The larger the limit drawing ratio, the better the performance of the “deep drawing J” machining.

The test conditions are shown below.

Molding material: Cold rolled steel plate (SPCC)

Punch speed: 40 mm min

Punch diameter: 40 mm

Die diameter: 4 2 mm

Wrinkle pressure: 4 kN Table 4 persons Limit drawing ratio

D L-1 2.18

OS-1.20 on the market 1 C 2.18 on the market D 2.09 From the results shown in Table 4, it can be seen that the metal forming agent of the present invention has a higher limit drawing ratio and is superior to the commercially available product D.

Comparative Example 5

We diluted the stock solution for deep drawing lubricant manufactured by Kyuichi Isshiki Co., Ltd. to 4 times the actual working concentration, and manufactured a metal forming agent “Commercial I-E” used for evaluating the performance of deep drawing metal forming. Example 6

The composition obtained in Example 1 was diluted 10 times with water to produce a metal forming agent “DL-2” used for evaluation of the performance of deep drawing.

Example 7

The composition obtained in Example 3 was diluted 5-fold, 10-fold, 15-fold and 20-fold with water, respectively, and used as a metal forming agent "DS-2" for evaluating the performance of deep drawing. , "DS-3", "DS-4" and "DS-5".

Performance test 2

Use the same deep drawing tester as in Performance Test 1. Use a pure aluminum plate and No. 304 aluminum plate (alloy containing 1% by weight of manganese and 1% by weight of magnesium). ) And the limiting aperture ratio was measured.

The test conditions are shown below.

Material to be molded: Pure aluminum and No. 304 Aluminum Punch speed: SmmZ seconds

Punch diameter: 28.4 mm

Die diameter: 30.0mm

Wrinkle pressure: 10KN

twenty two

Corrected form (Rule 91) Table 5

Pure aluminum

Sample name Active ingredient Limit drawing ratio Commercially available E 25 wt% 2.0.07

DL- 2 4 w t% 2.04 2

D S-26 w t% 2.04 2

D S- 3 3wt% 2.0 4 2

D S-4 2 t% 2.0 4 2

DS-5 1 wt% 2.04 2

Table 6

No. 304 Aluminum

Industrial applicability

For example, emulsion-type and dispersion-type metal processing agents containing the metal processing agent composition of the present invention have lubricating properties, extreme pressure properties, and P-orientation properties, and are particularly suitable as lubricants. It is. In addition, the dialkylthiodibutene bioione represented by the general formula (1), which is a component, has been confirmed to be safe, is an excellent lubricant from the viewpoint of global environmental protection, and is easy to degrease and clean. It is also excellent in resource saving. Therefore, it is used as a metal working agent in metal material cutting, polishing, plastic working, forming (metal deep drawing, ironing, etc.).

The present application is based on Japanese Patent Application No. Hei 7-17672 and Japanese Patent Application No. Hei 05-27676 filed in Japan, the contents of which are incorporated in full herein. It is.

twenty four

Corrected form (Rule 91)

Claims

The scope of the claims

1. General formula (1)

R ¹ OOCCH ₂ CH ₂ S CH ₂ CH ₂ COOR ² (1)

(Wherein, R ¹ and R ² represent a linear or branched alkyl group having 12 to 18 carbon atoms, and R ¹ and R ² may be the same or different from each other.) A metalworking composition comprising a dialkylthiodiprobionate.

2. The metal working composition according to claim ¹ , wherein in formula (1), R ¹ and R ² are linear or branched alkyl groups having 18 carbon atoms.

3. The metalworking composition according to claim 1, wherein the average particle diameter of the dialkylthiodipropionate is 10 / m or less.

4. An emulsion or dispersion containing at least one emulsifier selected from the group consisting of a sulfated basic salt of a higher alcohol, a polyoxyethylene derivative and a fatty acid salt and water. 4. The metal working agent composition according to any one of 3.

5. The method according to any one of claims 1 to 4, wherein a mixing ratio (based on the total amount of the composition) of the metalworking agent composition of the dialkylthiodipropionate in use is 0.05 to 10% by weight. The metalworking agent composition according to item 1.

6. Mixing ratio of dialkylthiodiprobionet in storage of the metal working agent composition (based on the total amount of the composition) Force << 25% by weight or more and less than 70% by weight Claims 1 to 4 The metal working agent composition according to any one of the above.

7. The metal working agent composition according to any one of claims 1 to 6, wherein the metal working is cutting, polishing, plastic working or metal forming of a metal material.

8. The metal working composition according to claim 7, wherein the metal forming process is a metal deep drawing process and a Z or metal ironing process.

9. "^ formula (1)

twenty five

Corrected form (Rule 91) ROOCCH2CH2SCH2CH2COOR ² (1)

(In the formula, R ′ and R ² represent a linear or branched alkyl group having 12 to 18 carbon atoms, and R ¹ and R ² may be the same or different from each other.) A metal working method comprising working a metal in the presence of a metal working agent composition containing a dialkylthiodipropionate to be prepared.

10. The metal working method according to claim 9, wherein in the general formula (1), R ¹ and R ² are a linear or branched alkyl group having 18 carbon atoms.

1 1. The metal processing method according to any one of claims 9 to 11, wherein the average particle diameter of the dialkylthiodipropionate is 10 // m or less.

1 2. The metal processing agent composition may be an emulsion type or a dispersion type containing at least one emulsifier selected from the group consisting of a sulfated basic salt of a higher alcohol, a polyoxyethylene derivative and a fatty acid salt, and water and water. The metal working method according to any one of claims 9 to 11.

1 3. The compounding ratio of the dialkylthiodipropionate in the metal working composition at the time of use of the metal working composition (based on the total amount of the composition) is 0.05 to 10% by weight. 13. The metal working method according to any one of to 12.

1 4. The claim that the mixing ratio (based on the total amount of the composition) of the dialkylthiodipropionate in the metal processing composition during storage of the metal processing composition is not less than 25% by weight and less than 70% by weight. 13. The metal working method according to any one of ranges 9 to 12.

1 5. The metal working method according to any one of claims 9 to 14, wherein the metal working is cutting, polishing, plastic working, or metal forming of a metal material.

16. The metal working method according to claim 15, wherein the metal forming is metal deep drawing and / or ironing.

2 6 Ordered paper (Rule 91)