JPH01230697A - Lubricant for metal working - Google Patents

Abstract

PURPOSE:To obtain the title lubricant which has excellent lubricating properties and is stable against disturbances, such as contamination with dissimilar oils, and water-soluble by incorporating a product of addn. reaction of an alkylene oxide to a mixture of a natural fat or oil with a polyhydric alcohol. CONSTITUTION:This lubricant for metal working is obtd. by incorporating as an essential component a product of addn. reaction of an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) to a mixtures of a natural fat or oil (e.g., coconut oil, beef tallow, soybean oil, etc.) with a trihydric or higher polyhydric alcohol (e.g., glycerin, pentaerythritol, etc.) in such proportions that 10-100mol of the alkylene oxide is used per mol of the natural fat or oil. The reaction product has a structure similar to the triglyceride structure of beef tallow, palm oil, etc., which are excellent conventional lubricants, and accordingly it is useful as a water-soluble lubricant for metal working. Further, when this reaction product is combined with conventional lubricants, an emulsion-type lubricant for metal working having improved lubricating performance attributed to the lubricities of both can be obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a lubricant for metal working.

[Conventional technology and its problems]

In the plastic working of metals such as steel and aluminum, that is, hot and cold rolling, pressing, cutting, drawing, etc., we aim to reduce the coefficient of friction between the processing tool and the material during processing, Various lubricants are used for the purpose of smoothing the process, and these are often used as a machining oil emulsion using water for the purpose of suppressing the heat generation of the metal during plastic working.

Here, the lubricants used in these processes include norilafin or naphthenic mineral oil, esters of fatty acids and monohydric or polyhydric alcohols, fatty acids, higher alcohols, etc., and one type of lubricant is used depending on the purpose. Alternatively, two or more types have been mixed and prepared.

These lubricants are pre-mixed with an emulsifier (Emulsion V!4 stabilizer) in the entire lubricant so that they can be made into emulsions when used, and problems such as separation may occur in the emulsions during processing. In order not to impair processing properties, one type of emulsifier or a mixture of two or more types of emulsifiers used to measure emulsion stability have been used.

The stabilization of processed oil emulsions is achieved by a technique that has already been known in the past, namely the HLB (Hydrophilic/Lipophilic Balance) of an emulsifier.
lance ) value for the lubricant and stabilize it? A method of measuring this has been adopted. The emulsifier used is mainly nonionic, for example, an aliphatic alcohol, nonylphenol, or octylphenol with an HLB value in the range of about 2 to 19, and ethylene oxide or ethylene oxide and both fo and oxide added. Norpitan fatty acid ester, aliphatic amine or aliphatic acid amide with ethylene oxide added,
Ethylene oxide/7°o% lene oxide block? Limers, fatty acids and glycerin or sorbitol esters, etc. have been used.

In addition to these nonionic surfactants, anionic surfactants such as metal salts of fatty acids or alkanolamine salts may also be used as emulsifiers.

The purpose of these emulsifiers is simply to turn the lubricant into oil particles in water, that is, to make it into an emulsion. In actual processing operations, the required HLB of the emulsifier changes due to the mixing of viscous substances such as processed oil degraded products and metal powder, which are called It was discovered and became a problem.

Furthermore, among these lubricants, mineral oils that do not contain functional groups in their structure have no polarity, so great efforts have been made in selecting emulsifiers in order to turn them into oil particles and stabilize the emulsion. This is the current situation.

On the other hand, in view of these problems, water-soluble lubricants that do not use "water-insoluble lubricants" and are not "emulsion" types have been developed and are already in use. However, the performance of these water-soluble lubricants was not fully satisfactory.

[Means to solve the problem]

As a result of intensive research in order to obtain a compound with excellent lubricating properties for metal processing, the present inventors discovered a reaction product obtained by adding an alkylene oxide to a mixture of natural oils and fats and a polyhydric alcohol of trihydric or higher valence. It is soluble in water in any proportion, and has lubricating properties itself, and allows lubricants such as mineral oil to exist as stable oil particles in water, and is resistant to external disturbances (mixture of foreign materials, etc.). They found that it is stable and completed the present invention.

That is, the present invention is characterized in that it contains as an essential component a reaction product obtained by adding 10 to 100 moles of alkylene oxide per 1 mole of natural fats and oils to a mixture of natural fats and oils and polyhydric alcohols having a valence of 3 or more. The present invention provides a lubricant for metal processing.

The reaction product (
(hereinafter abbreviated as "reaction product"), the oils and fats used as raw materials include vegetable oils such as coconut oil, gnome oil, olive oil, soybean oil, rapeseed oil, and linseed oil, beef tallow, pork fat, and bone oil. Examples include animal oils such as fish oils, hydrogenated oils and semi-hardened oils thereof, and recovered oils obtained in the refining process of these oils and fats.

In addition, trivalent or higher polyhydric alcohols used as raw materials include glycerin, trimethylolethane, trimethylolethane, 1,2,4-butanetriol,
Examples include 1,2.6-hexanetriol, 1,1.1-)limethylolhexane, pentaerythritol, tetramethylolcyclohexanol, zoglycerin, and triethanolamine.

To obtain the reaction product, it is sufficient to add an alkylene/oxide to a mixture of natural oils and fats and polyhydric alcohols having a valence of 3 or more.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. The alkylene oxide can be added by mixing (random addition) or by sequential addition (block addition), but random addition or sequential addition of ethylene oxide and alkylene/oxide other than ethylene oxide is preferred.

In addition, the molar ratio of natural oils and fats to trihydric or higher polyhydric alcohol in the mixture is 1:0.1 to 1:3, preferably 1:0.3 to 1:2, and the alkylene oxide is In the mixture of natural fat and oil and polyhydric alcohol, it is used in an amount of 10 to 100 mol, preferably 20 to 40 mol, per mol of natural fat.

The addition reaction of alkylene oxide is not particularly limited, and can be carried out under the conditions commonly used for addition reactions of alkylene oxide to compounds having active hydrogen. That is, a catalytic amount of an alkaline substance is added to a mixture of natural oils and fats and polyhydric alcohol prepared in the above molar ratio, and then about 100 to 200 ('C), 1 to 3 (k, /cfn
2) can be achieved by reacting alkylene oxide for several hours.

For example, when glycerin is used as the polyhydric alcohol, the reaction product obtained as described above is as follows (1)
A mixture having the structure shown in ~(lii) is obtained.

(1) CHz-0 (CHzCHzO) +AO)
n, -Xl CH-0+ CHz CHzO+ +AO) n2-x
CHz -0+ CH2CHt O+ (7AO)n
3- X(1) X -0(CH2CHz O+a
(AO leakX(fil) H-(AO) (CH2CH
IOchi, (AO)e -H The metalworking lubricant of the present invention is a water-soluble metalworking lubricant in which each component, such as a lubricating component, is dissolved in water, and a lubricating oil component, etc., as emulsified particles. The lubricant can be any type of emulsified metalworking lubricant containing the lubricant.

When obtaining a water-soluble metalworking lubricant, for example, the reaction product of the formation is preferably made into an aqueous solution of 1 to 90% by weight (hereinafter simply referred to as "%"), particularly 2 to 60% by weight. It is prepared. In addition, when using an emulsified type lubricant for metal processing, preferably 1 to 20%, especially 2 to 15%
and preferably 99 to 80%, especially 98 to 85%, of a known lubricant and adding this to water.

As a lubricant, for example, the viscosity at 40°C is 10 to 5.
It is in the range of 00 centistokes. Q Rough-in or naphthenic mineral oil, monohydric or polyhydric alcohol, and carbon number 6
-22 fatty acid esters, aliphatic alcohols having 8 to 22 carbon atoms, and fatty acids having 6 to 22 carbon atoms.

Among more specific lubricants, examples of the rough-in or naphthenic mineral oil include spindle oil, machine oil, turbine oil, and cylinder oil.

Concubine → Aliphatic alcohols include hexyl alcohol, octyl alcohol, decyl alcohol, dodecyl alcohol, etc., with a carbon number of 4 and a branched alkyl group.
Fatty acid esters up to 0 include casillonic acid,
6 carbons from caprylic acid, capric acid to tocosanoic acid
~22 fatty acids and diols such as ethylene glycol, diethylene glycol, triethylene glycol, soropyrene glycol, and zoderopyrene glycol as monohydric or polyhydric alcohols, ranging from methyl alcohol with 1 carbon number to eicosanol with 20 carbon atoms Carbon number 1-20
aliphatic alcohols in the range of trihydric alcohols, glycerin, trimethylolethane, trimethylolethane, 1°2,4-butanetriol, 1,2
．． Those obtained from 6-hexanetriol, 1,1.1-) lyncholhexane, zoglycerin, pentaerythritol, tetramethylolcyclohexanol, and sorbitol as polyhydric alcohols, and caproic acid and caprylic acid as esteric acids. , 2 carbons from capric acid
Examples include those leading to No. 2 tocosanoic acid.

Furthermore, the metal working lubricant of the present invention may further contain various optional components as required. Examples of optional components for water-soluble metal processing lubricants include 2,
Antioxidants such as phenolics such as 4-zot-butyl-p-cresol or aromatic amines such as phenylminaphthylamine, alkenylsuccinic acids having 12 or more carbon atoms and their wire conductors, benzotriazole, mercaptobenzotriazole, etc. Rust inhibitors, extreme pressure agents such as phosphorus compounds such as phosphates or phosphites having mono, zo or triphenyl or mono, zo or trialkyl alkyl groups or organometallic compounds such as zinc dialkyldithiophosphate, triethanol All examples include pH adjusters such as amines, 2-bromo-2-nitro-1,3-7'lono-Q-enzool, and antifungal agents.

In addition, even if the lubricant is water-soluble, the water-soluble lubricant must be maintained in order to maintain the desired lubricity in various processing methods such as rolling of aluminum, stainless steel, steel, copper, etc. One or more types selected from the group consisting of aliphatic alcohols having 6 to 40 carbon atoms, fatty acids having 6 to 22 carbon atoms, monohydric or polyhydric alcohols, and fatty acid esters having 6 to 22 carbon atoms. It is also possible to add lubricant components.

When water-soluble metal processing lubricants are applied to processing methods that require extremely severe lubricity, one or more of the various lubricant components listed above are added to ensure smooth processing. The purpose is achieved by doing this, but what if the addition produces water-soluble females? Liethylene glycol or broken propylene glycols, aliphatic alcohols with 8 or more carbon atoms, alkylphenol A sorbitan fatty acid esters with 8 or more carbon atoms, or 3 moles or more of ethylene oxide added to alkyl amines with 8 or more carbon atoms, Reaction product of aliphatic amine or aliphatic acid amide having 8 or more carbon atoms and monochloroacetic acid or monochlorozolopionic acid or a salt thereof, ethylene oxide delobylene oxide block co? Rimmer, carbon number 6
It is also possible to add a substance selected from the above fatty acid Na, ammonium salt, etc. to the product of the present invention as a solubilizer for the above-mentioned lubricant components, thereby maintaining water-soluble performance. I can do things.

In addition to lubricant components and solubilizers such as aliphatic alcohols, fatty acid esters, and fatty acids, known ionic or HLB components of 20 to
19.0 nonionic surfactants or ionic polymeric dispersants, such as dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, aliphatic alcohols having 6 to 22 carbon atoms as monomers There is no problem in adding a single metal such as methacrylic acid or acrylic ester, acrylamide, a copolymer of two or more thereof, or a salt thereof to the product of the present invention in advance.

These various components may be added as antioxidants in the water-soluble metal processing lubricant of the present invention at a concentration of 0.1%, if necessary.
= 5. O%% Preferably 0.5-3.0%, as extreme pressure agent 0.1-5.0%, preferably 0.3-5.
0%, 0.1 to 5.0% as a rust and corrosion inhibitor, preferably 0.3 to 3.0%, and 0.1 to 10% as a pH adjuster.
0%, preferably 0.3 to 5.0%, and 0.0% as a fungicide.
It is possible to add 0.01 to 1.0%, preferably 0.01 to 0.5%.

In addition, in the metal processing lubricant of the present invention, lubricant components other than water-soluble reaction products, that is, aliphatic alcohols, fatty acid esters, or fatty acids, and solubilizers necessary for maintaining water solubility, are each Although it is possible to use the aliphatic alcohol in the lubricant of the present invention if necessary, the amount of aliphatic alcohol in the lubricant is 50% or less, preferably 40% or less,
Fatty acid ester is contained in the lubricant in an amount of 50% or less, preferably 40%.
% or less, the fatty acid content in the lubricant is 10% or less, preferably 8%
The following is desirable, and one or more of these Fi types are selected and used.

On the other hand, the solubilizer is used as an improvement method when the above-mentioned lubricant component is added and the water-soluble metalworking oil of the present invention loses its characteristic of being ``soluble in water.'' The formulation tf'i may be within the lowest concentration range that provides stable water solubility.

The emulsified metal processing lubricant can also contain the same arbitrary components as described above, and the amounts thereof are also approximately the same.

In preparing the emulsified metalworking lubricant of the present invention, the above-mentioned various lubricants are added to a metalworking oil containing 1.0 to 1.0%
In actual use, a method is adopted in which 20%, preferably in the range of 2.0 to 15.0%, is added, mixed uniformly, and then diluted with water to prepare an emulsion of a predetermined concentration.
There is no problem in preparing the emulsion by adding the lubricant components separately.

In addition, when using the water-soluble lubricant for metal processing of the present invention, firstly, a highly concentrated water bath solution that has been homogenized by stirring and mixing with water is poured into a141A, and then, when used, it is necessary for the specified metal processing. The lubricant of the present invention may be diluted with water to a desired concentration, or the lubricant itself of the present invention may be diluted directly with water to a concentration required for a given metal processing.

〔Effect of the invention〕

The reaction product used in the lubricant for metal processing of the present invention is:
When viewed from its structure, it has a triglyceride structure similar to that of beef tallow, gnome oil, etc., which are excellent lubricants conventionally known in the field of plastic processing, so the reaction product itself It has pressure resistance against loads during processing, that is, lubricity, and is useful as a water-soluble lubricant for metal processing. Furthermore, when this reaction product is combined with a known lubricant, an emulsified metalworking lubricant with improved lubrication performance due to the anti-lubrication ability of both can be obtained.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A water-soluble metalworking lubricant was prepared according to the composition shown in Table-1. The reaction products blended into this are shown in Table-
2.

Notes in the margin below (1); Lubricating oil component A-1; lauryl alcohol (aliphatic alcohol) E-1; toIJ methylol derono-Q trioleate (fatty acid ester) E-2; zoetelene glycol zono-9 lumitate (fatty acid) Ester) F-1; Oleic acid (fatty acid) (2); Values in parentheses in Table 1 indicate weight % (3);
US IAC = Rust and corrosion inhibitor (benzotriazole) Takashi 2I:
p = extreme pressure agent (triphenyl 7 osphite) 43 S1 = solubilizer (hexylene glycol) S2
= Solubilizer (N-coconut alkyl-β-iminozozolopion tIRNa) S3 = Solubilizer (polyoxyethylene (p=6) lupitan monooleate) s4 = Solubilizer (laurylamine, ethylene oxide (5 mol) Adduct) 4PH = pH adjuster (triethanolamine) *sD
= Polymer dispersant (sesquibutyl phosphate salt of dimethylaminoethyl methacrylate/sodium acrylate (molar ratio 6/1) copolymer, 2QOOO in MW), makes metal powder generated during metal processing more hydrophilic used for the purpose.

(4); The solubilizer was added in advance to the lubricant of the present invention.

This is intended to maintain water solubility when these lubricants are diluted with water to a predetermined concentration during processing.

Downstream margin Example 2 Friction coefficient by Soda pendulum type oil tester: (Test method) Using the present invention 8th floor 1 to 11 shown in Table-1,
The friction coefficient at °C was measured using a Soda pendulum type oil testing machine (load 200F, maximum Hertzian pressure on the friction contact surface = 111 k).
y/xx”sThe friction pin and ball are made of steel (SUJ
-2)) was evaluated.

(Evaluation results) Table-3 Friction coefficient measurement results Note: Composition of comparative products 1 to 3 Comparative product 1: Mineral oil (200cSt/40C)
83.5wt% oleic acid
5.0 Triethanolamine 1.
0 Antifungal agent, etc. 0.5 Comparative product 2: Mineral oil (150cst/40℃) 81
．． 5w″% oleic acid 5
．． 0 Potassium oleate 5.0 Hexylene glycol 8.0 Antifungal agents, etc.
0.5 Comparative product 3: Mineral oil (10
0 cS t/40 C) 74.5 w'thi 2-xf hexyl stearate 200 oleic acid 4.0 triphenyl phosphorite 1.0? lyoxyethylene (EO=
6) 5.0 Nonyl Phenyl Ether These Comparative Products 1 to 3 were subjected to the test in the form of an emulsion with water.

Example 3 Cleanability of drawn-shidoki-processed cans (tin-plated steel plate): (Formation of drawn-shidoki-processed cans) Invention products N shown in Table 1 [L1 to 11 and Comparative 8 1 to 1] Adjust the processing fluids of various concentrations in 3 using water,
The temperature was set at 0°C.

Drawing) - Ironing was performed using a tin-plated steel plate with a thickness of 0.301 m and a hardness of 55.0 according to Rockwell 30T.
First, cup molding was carried out under the following conditions.

Tin plating on the surface that should be the outside surface of the can: 2-99/m" Amount of tin plating on the surface that should be the inside surface of the can; 2.9 ? 7m
2 Inner diameter of drawing can; Height of 71ur; 34 Recommended molding speed; Applicable lubricant equivalent to a speed of 100 cans/min; Products of the present invention m1 to 11. Comparison products 1 to 3 (see Table 4 for applied concentration) Next, using the drawn cup formed under the above conditions, the drawn cup was re-drawn using a known ironing device, and the first stage ironing (thickness reduction rate of 3
8.2%), second stage ironing (plate thickness reduction rate 13.6%),
Performed third stage ironing (plate thickness reduction rate 39.4%), inner diameter 52.6711J, height 145IIJ.

A can with a can body thickness of 0.100 u% was molded.

(Cleanability of Squeezed-Squeezed Molded Cans) After 1 hour, the cans molded under the conditions described above were heated at a temperature of 60°C and a pressure of '1. Cleaning was performed with water at 7 cm" for 1 minute.

Spray cleaning was performed using a nozzle (CER-JET 5035) from two locations, the bottom and the opening of the molded can.

(Cleanability evaluation method) After drying the washed molded can, it was immersed in tap water, and after being pulled up, the area of the water-wetted part (clean surface) on the outer surface of the can was determined.

(Evaluation Results) v1 Lower Margin Table-4 Example 4 Draw-Paper Formability: Evaluated at the same time as Actual Example 3. As a result, both Invention 8 Ugly 1 to 11 and Comparative 8 Ugly 1 to 3 were normal, with no breakage or surface flaws in the molded cans.

Example 5 An emulsion type lubricant for metal processing was prepared according to the composition shown in Table-5. The reaction products blended therein are the same as those in Table 2 of Example 1.

Margin below *Lubricating oil content Emulsifier Example 6 Add 10 t of the emulsified metal processing lubricant obtained in Example 5 to water.
ts, and 2t was stirred at 400 rpm for 20 minutes at 5000 rpm using a homomixer (Model 9M manufactured by % Soukika Kogyo Co., Ltd.).

Immediately thereafter, 500 d of emulsion was collected into a separating funnel, and after being left for 1 hour, the concentration of processing oil in the upper layer and the lower 1 ton each was examined.

Next, the emulsion stirred with a homomixer is subjected to actual aluminum drawing-shidoki processing (DI processing).
A viscous sludge (processing oil 42%, aluminum 4%, moisture 43%, balance 11%) is a mixture of aluminum powder and processing oil (mineral oil), which is 30% by weight of the processing oil. The mixture was added in the same manner as above, stirred under the same conditions as above, and the concentrations of upper and lower r- were examined in the same manner after 1 hour. The results are shown in Table-6.

Here, the stability index of the processed oil emulsion was determined by the following calculation method.

Table 6 Example 7 Frictional lubrication properties: The effect of improving the frictional lubrication properties of the emulsified metalworking lubricant of the present invention was evaluated using a Soda-type photographic oil tester (load load 200F,
The friction coefficient was investigated by evaluating the friction coefficient using the maximum Hertz pressure on the friction surface = 111 kp/m''.

The test was conducted using the present invention 8 No. 12 to No. 15 shown in Table 5 and the comparative product Na.
4 to Nl16 at 40°C. The results are shown in Table-7.

Table-7 that's all

Claims (1)

[Claims] 1. A mixture of natural oils and fats and polyhydric alcohol of trihydric or higher valence,
A metalworking lubricant characterized by containing as an essential component a reaction product obtained by adding 10 to 100 moles of alkylene oxide per mole of natural oil or fat. 2. The lubricant for metal working according to item 1, wherein the mixing ratio of the mixture of natural oil and fat and polyhydric alcohol having a valence of 3 or more is from 1:0.1 to 1:3 in terms of molar ratio. 3. The metalworking lubricant according to item 1 or 2, which is water-soluble. 4. Furthermore, aliphatic alcohol having 6 to 40 carbon atoms, 6 carbon atoms
~22 fatty acids, monohydric or polyhydric alcohols and 6 carbon atoms
4. The metalworking lubricant according to item 3, wherein one or more lubricant components selected from the group consisting of 22 fatty acid esters are added. 5. It further contains as an essential ingredient an oil selected from beef tallow, lard, bone oil, fish oil, coconut oil, palm oil, rapeseed oil, linseed oil, and their hydrogenated or semi-hardened oils, and is in an emulsified form. The metalworking lubricant according to item 1 or 2.