JP5704921B2 - Preparation of metal working fluid - Google Patents

Description

Related Applications N / A Federal Sponsored Research or Development N / A Microfiche / Copyright Citation N / A

BACKGROUND OF THE INVENTION This invention relates to oil-free metalworking fluids, also known as synthetic metalworking fluids.

  Metalworking is defined as shaping a metal workpiece and conforming to a desired set of geometric standards. Metalworking consists of two basic categories of machining and forming. Machining includes grinding, turning, milling, tapping, broaching and hobbing. Forming includes hot and cold rolling, drawing, forging, embossing and stamping.

  Metalworking fluids are essentially used in both machining and forming processes. This metalworking fluid must provide lubrication between the workpiece and the tool, and must also provide cooling by the removal of heat generated during machining.

  Lubrication is defined as reducing the friction between two moving surfaces. The two main types of lubrication in machining are hydrodynamic and have interfacial or extreme pressure (EP). Hydrodynamic lubrication involves the separation of moving surfaces by a liquid lubricant coating. Interfacial lubrication or extreme pressure (EP) lubrication minimizes the wear experienced when multiple surfaces are rubbed together. Polymer lubricants can provide both types of lubrication.

  Metalworking fluids are classified into two main categories: oil containing and non-oil containing. The oil containing segments include straight oils, water soluble oils and semi-synthetic oils, all of which utilize mineral oil as the primary lubricant. The oil-free section is known as a synthetic oil, which contains a composition of additives that produce lubricity in an aqueous transport system or diluent. Water-soluble oils and semi-synthetic products occupy an 80% share of the market, and the non-aqueous reduced straight oil category occupies a 10% share, while synthetic oils occupy a 10% share of the market.

  Existing types of metalworking fluids have advantages and disadvantages. Oil-containing products have the advantages of excellent lubricity, wide application, and barrier protection of drainage from corrosion. The disadvantages of oil-containing metalworking fluids are that the hardness of water often affects the stability of the fluid, and foaming is often a problem due to the inclusion of the fluid in a high detergency emulsifier, which can cause significant contamination of the fluid. It entails a material load, the fluid requires more expense for tank disposal and cleaning, and the fluid has significant microbial problems.

  The use of synthetic oils is encouraged because of various factors derived from the environment for microbial benefits. However, most consumers continue to use oil-containing products. This is because, at a relatively low cost, the lubricity of oil-containing products is good and the corrosion-related maintenance associated with synthesis is increased. Synthetic drainage that lacks the protective barrier coating provided by the oil can corrode and "freeze" the bolts of the machining system, making maintenance difficult. Additionally, synthetic products with high lubricity performance are expensive when compared to oil-containing products with the same lubricity performance. The reduced physical lubricity of the synthetic product as a function of the cost of the semi-synthetic product limits the use of the synthetic product in heavy duty operation.

SUMMARY OF THE INVENTION One aspect of the present invention relates to an entirely new class of metalworking fluid products. With this new chemistry, synergistic blends of carboxylates, fatty acids of boundary lubricants and EO / PO polymers are intimately mixed, where these components react and optionally increase in one embodiment. Forming one component that can have a controlled particle size, exceptional lubricity, or both. Additionally, the diluent used for one embodiment is opaque and resembles the appearance of an oil-based solution.

In one embodiment, the metalworking fluid composition can have a volume average diameter of 120 nm or more when diluted to 0.1 to 50% by volume. This composition has the following ingredients:
(A) one or more polymer lubricants;
(B) one or more carboxylates;
(C) contains one or more emulsifiers or dispersants; and (d) a transport component.

  One embodiment can be a synthetic metalworking fluid that demonstrates a technical increase in lubricity while still providing corrosion resistance and microbial control.

Brief description of the drawings

DETAILED DESCRIPTION OF THE INVENTION In one embodiment, a metalworking lubricant according to the present invention can have a volume average diameter of 125 nm or more when diluted to 0.1 to 50% by volume. In one embodiment, the composition comprises the following ingredients:
(A) one or more polymer lubricants;
(B) one or more carboxylates;
(C) one or more emulsifiers or dispersants; and (d) a transport component.

More specifically, the composition comprises the following components:
(A) 1-80% by volume of one or more block copolymers as polymer lubricants;
(B) 1-40% by volume of one or more carboxylates;
(C) one or more emulsifiers or dispersants 1-20% by volume; and (d) transport components 1-97% by volume.

In another embodiment, the composition comprises the following ingredients:
(A) 5-40% by volume of one or more block copolymers as polymer lubricant;
(B) 3-30% by volume of one or more carboxylates;
(C) one or more emulsifiers or dispersants 2-12 vol%; and (d) a transport component 18-90 vol%.

In yet another embodiment, the composition comprises the following ingredients:
(A) 15-25% by volume of one or more block copolymers as polymer lubricant;
(B) 5-15% by volume of one or more carboxylates;
(C) one or more emulsifiers or dispersants 3-8% by volume; and (d) transport components 52-77% by volume.

  Examples of each component and the components are further described below.

Polymer lubricant The polymer lubricant can be, for example, an EO / PO copolymer. The EO / PO polymer can have, for example, one or more of the following: The EO / PO copolymer can be a block copolymer having a central polyoxypropylene block with a polyoxyethylene chain at each end. The EO / PO copolymer can be a block copolymer having a central polyoxyethylene block with a polyoxypropylene chain at each end. The EO / PO copolymer can be a tetrablock copolymer derived from the continuous addition of ethylene oxide and propylene oxide to ethylenediamine. The EO / PO copolymer can be an ethylene oxide / propylene oxide copolymer having at least one terminal hydroxyl group. The EO / PO copolymer can be a water-soluble lubricant base material of a random copolymer of ethylene oxide and propylene oxide. The EO / PO copolymer can be a water-soluble polyoxyethylene alcohol or polyoxypropylene alcohol, or a water-soluble carboxylic acid ester of such an alcohol. The EO / PO copolymer can be a base material with an alcohol initiator of all polyoxypropylene groups having one terminal hydroxyl group. EO / PO copolymers are monobasic or dibasic acid esters, polyol esters, polyalkylene glycol esters, polyalkylene glycols grafted with organic acids, phosphate esters, polyisobutylene, polyacrylonitrile, polyacrylamide, polyvinylpyrrolidone , Polyvinyl alcohol, or a copolymer of acrylic acid or methacrylic acid and an acrylate ester.

  The polymers discussed in detail include polypropylene glycol block copolymers, polyethylene glycol block copolymers, or polyethylene glycol / polypropylene glycol block copolymers.

Carboxylates Partially neutralized carboxylates are being considered to provide lipophilic components for polymer lubricants for reticulation and to define large particle size designs. The salts can be formed, for example, by partially neutralizing free carboxylic acids, fats or oils with any alkaline agent described herein. The cations discussed in detail for the salts include alkali metal salts or alkanolamine salts, such as sodium salts (formed by treating the acid with sodium hydroxide). The pH of partial neutralization depends on the alkaline agent used. Many of the carboxylates additionally provide sufficient boundary lubrication.

  The carboxylic acid used as a raw material can be a linear or branched saturated or unsaturated free carboxylic acid. The acid may be saturated or unsaturated, and the site of unsaturation may be configured in cis or trans form. The acid can be a dicarboxylic acid, a tricarboxylic acid, or an ester, amine, amide or ethoxylated derivative of a carboxylic acid. According to other selectable methods, fats or oils derived from animals or vegetables can be directly neutralized to provide carboxylates.

  The following are examples of carboxylic acids studied or examples of sources of the carboxylic acids: caproic acid (also known as hexanoic acid), enanthic acid (also known as heptanoic acid), caprylic acid (also known as octanoic acid) , Pelargonic acid (also known as nonanoic acid), isononanoic acid, capric acid (also known as decanoic acid), neodecanoic acid, lauric acid (also known as dodecanoic acid), stearic acid (also known as octadecanoic acid), arachidic acid ( Also known as eicosanoic acid), palmitic acid (also known as hexadecanoic acid), erucic acid, oleic acid, arachidonic acid, linoleic acid, linolenic acid, myristic acid (also known as tetradecanoic acid), behenic acid (also known as docosanoic acid) ), Α-linolenic acid, docosahexanoic acid, ricinoleic acid, butyric acid, lard oil, tallow oil, butter , Coconut oil, palm oil, cottonseed oil, wheat germ oil, soybean oil, olive oil, corn oil, sunflower oil and rapeseed oil or canola oil.

Emulsifier or Dispersant Dilution of the metalworking fluid composition with water forms an opaque emulsion. When the concentration exceeds 10%, the emulsion may require stabilization. Emulsifiers or dispersants are being considered to provide designed large particle emulsion stabilization.

The emulsifier or dispersant can be one or more of the following: alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amides and amine soaps, block copolymers, carboxylated alcohols, carboxylic acids or fatty acids. Ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines or amides, ethoxylated fatty acids, ethoxylated fatty acid esters and oils, ethoxylated phenols, fatty amines and esters, glycerol esters, glycol esters, imidazoline and imidazoline derivatives, lignin and lignin derivatives , Maleic anhydride or succinic anhydride, methyl ester, monoglyceride and derivatives, naphthenic acid, olefin sulfonate Phosphate ester, polyalkylene glycol, polyethylene glycol, polyol, polymer (polysaccharide, acrylic acid, acrylamide), propoxylated or ethoxylated fatty acid, alcohol or alkylphenol, quaternary surfactant, sarcosine derivative, soap, sorbitan derivative, sucrose And glucose esters and derivatives, oil and fatty acid sulfates and sulfonates, ethoxylated alkylphenol sulfates and sulfonates, alcohol sulfates, ethoxylated alcohol sulfates, or fatty acid ester sulfates, dodecylbenzene and tridecylbenzene sulfonates, naphthalene sulfonates Alkyl naphthalenes, sulfonates, petroleum sulfonates, Succinamates, sulfosuccinates and derivatives or tridecyl benzenesulfonic acid and dodecylbenzenesulfonic acid.

Corrosion Inhibiting Components Oil-containing products are highly dependent on the oil itself and form a rust-preventing barrier coating. A product that does not contain oil can achieve rust prevention of the product, optionally by chemical means. Corrosion inhibitors are compounds that stop or slow the corrosion of metals and alloys when added at low concentrations.

  Some mechanisms of corrosion inhibitors are the formation of a passivating layer (thin film on the surface of the material that stops the access of the corrosive substance to the metal), suppression of the oxidized or reduced portion of the redox corrosion system (anodic suppression). And scavengers of dissolved oxygen).

There are a number of different substances included in the group. Some examples are alkali metal salts and alkanolamine salts of carboxylic acid, undecanoic diacid, or dodecanedioic acid or salts thereof, C ₄ -C ₂₂ carboxylic acid or a salt thereof, boric acid and its salts, tolytriazole and its salts , Benzotriazole and its salts, imidazoline and its salts, alkanolamines and amides, sulfonates, alkali metal and alkanolamine salts of naphthenic acid, phosphate ester amine salts, alkali metal nitrites, alkali metal carbonates, carboxylic acid derivatives, alkyl Sulfonamide carboxylic acids, arylsulfonamide carboxylic acids, fatty sarkosides, phenoxy derivatives and sodium molybdate.

Alkaline agent The alkaline agent provides the desired pH of the product, and in some cases provides reservations for alkalinity and pH buffering. Examples of alkaline agents are primary alkanolamines, secondary alkanolamines and tertiary alkanolamines, aminomethylpropanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicyclohexylamine (DCHA), diethanolamine (DEA), butyldiethanolamine (NBDEA), triethanolamine (TEA), alkali metal hydroxide, potassium hydroxide, sodium hydroxide, water Magnesium oxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate. A preferred alkaline agent for one embodiment is an alkali metal hydroxide.

  The investigated pH for the composition is optionally 3 or more, optionally 3 to 10, optionally 4 to 9, optionally 4 to 8.

Other Components The composition may contain antifoams and / or biocides or fungicides as well as any other conventional or novel additive.

Transport Component A preferred transport component, also referred to as a dispersion medium or vehicle, is predominantly water, in some cases entirely. However, optionally, the composition may contain one or more oils, preferably less than 10% by volume. The oil can be any conventional lubricating oil. When complex oils and water transport components are considered, emulsifiers may be used to form stable emulsions of oils with water.

  The commonly available positive attributes of oil-free products are optionally maintained in the composition, and optionally include one, more than one, or all the following attributes: Environment Friendly, good cooling, good tip removal or installation characteristics, long drainage life and good biological resistance.

In the present invention, the metalworking fluid composition can have a lubricity of less than 8000 Newton-cm ^{−1 as} measured by a tapping torque meter when diluted to 0.1-50 volume%.

The composition optionally includes one or more of the following in a formulation that contains a small amount of oil (ie, up to 10% by volume oil), or a formulation that contains essentially no oil or no oil at all: Can have the following preferred properties:
Lubricity of oil-containing products,
Lubricity / cost performance aimed at products containing oil,
Reduced irritation to researchers (this irritation is associated with high pH products),
Anti-rust or other anti-rust effect for oil-containing products, or alkanolamine free chemistry.

Particle size Compositions prepared according to the present invention contain particles and are described in the examples below. Large particles have been considered to provide high lubricity, but the invention is not limited to this exact theory. The particles discussed according to any embodiment optionally have a volume average diameter of 120-100000 nanometers (nm), and according to other selectable methods, have 120-100,000 nm, other selectable According to other methods, it has 120-10000 nm, according to other selectable methods, it has 120-5000 nm, according to other selectable methods, it has 125-10000 nm, other options According to possible methods have 125-5000 nm, according to other selectable methods have 125-2000 nm, according to other selectable methods have 140-10000 nm, other According to the selectable method, it has 140-5000 nm, according to other selectable methods, it has 140-2000 nm, and according to other selectable methods, it has 200-1000 nm. other selectable methods have 200-5000 nm, other selectable methods have 200-2000 nm, and other selectable methods have 220-200 nm. According to other selectable methods, it has 220-5000 nm, according to other selectable methods, it has 220-2000 nm, according to other selectable methods, According to another selectable method, it has 350-5000 nm, and according to another selectable method, it has 350-2000 nm.

EXAMPLES The foregoing description can be better understood with reference to the following examples, which are intended to illustrate the methods for practicing the present invention. It is not intended to limit the scope.

Example 1

  Materials A to E in Table 1 were used for tapping torque operations including 6061 aluminum tapping. The concentrate was first diluted into a 7.5% by volume solution prior to testing. The tapping torque test is a quantitative measurement of the lubricity performance of a metal working fluid. This tapping torque test has the ASTM standard method shown in D5619. Tapping torque affects industrial machining processes better than other tests typically performed by rubbing two metal surfaces together. This tapping torque is an excellent way to identify the machining performance of a metalworking fluid (MWF) product in a laboratory. The tapping torque results proved to be well correlated with on-site machining performance.

  This tapping torque measuring instrument is designed to measure the lubricity of MWFs while actual cutting is performed. During the tapping operation, the tapping torque meter measures 250 instantaneous torques as tap progress through the cutting depth. In addition, specialized software simplifies data analysis. The tapping torque is expressed in units of Nm (Newton-meter) or N-cm (Newton-centimeter). Products with high lubricity will generate low torque values. Conversely, a low lubricity product will produce a high torque value. Thus, the instrument quantifies the difference in lubrication performance between products.

One drawback of the tapping torque meter is that the measured absolute torque value depends on the diameter of the tap used and can vary with this diameter. Therefore, it is effective to express the degree of lubrication as torque per unit area in order to cancel the geometric effect, and the energy for one rotation of one tap is described. The formula for this is
E / A = (2'r) / r2
And
In the above formula, t = torque value, r = radius of tap, E / A = energy amount per unit area, and the unit is Nm ^-1 (Newton per meter) or N-cm ^-1 ( Newton per centimeter).

  Lubricity data is presented in Table 1 and is identified as E / A. The lower the E / A value, the better the lubricity and machining performance. All samples were diluted to 7.5% by volume with water prior to testing.

Example 2:
The materials in Table 1 were used for particle size manipulation, including measurement of volume average diameter in nanometers. The concentrate was first diluted with water to a 7.5% by volume solution prior to testing. The particle sizer uses high performance dynamic light scattering to quantify a particle size of 20-100,000 nanometers.

  All samples were diluted to 7.5% by volume prior to testing. The resulting particle size is shown in Table 1.

Example 3
Material C from Table 1 was tested for particle size at two different concentrations and evaluated for appearance and emulsion stability at each concentration. The results are shown in Table 2, which shows a large average particle size, opaque appearance and excellent stability at each concentration. Larger particle sizes indicate even better lubricant properties. Typical synthetic MWFs form a clear solution having a particle size of less than 100 nanometers when diluted. Diluted Sample C has a particle size that is 3.5-20 times larger than the maximum particle size found in typical synthetic MWFs.

  Examples 1-3 show that optimum lubricity and particle size are obtained with Sample C, which combines 10% alkali metal carboxylate and 20% Pluronic "R" block copolymer. This ratio yields the maximum volume average diameter and maximum lubricity.

  Also, from the above examples, it becomes apparent that the lubricity of the composition is a function of the volume average diameter. An increase in volume average diameter results in an increase in lubricity.

  From Example 3, it can be seen that the increased concentration of Sample C results in a significantly larger volume average diameter. This explains the need for an emulsifier to stabilize the high concentration of Sample C. In the absence of an emulsifier, it is certain that agglomeration continues in an unstable state due to the high concentration of particle size. It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Accordingly, such modifications and variations are intended to be covered by the appended claims.

Claims (17)

A metalworking fluid composition free of alkanolamines, the metalworking fluid composition comprising:
(A) 5 to 40 vol% of one or more block copolymers that are polymeric lubricants;
(B) 3-30% by volume of one or more carboxylates;
(C) one or more emulsifiers from 2 to 12% by volume; and (d) a transport component,
Dilution of the metalworking fluid composition with water forms an opaque emulsion having a volume average particle size of 125 nm or greater when diluted to 0.1 to 50% by volume, wherein the block copolymer is at each end. A block copolymer having a central polyoxyethylene block having a polyoxypropylene chain in part, the transport component containing water ,
The carboxylate is: butyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, linoleic acid, Linolenic acid, α-linolenic acid, ricinoleic acid, eicosanoic acid, docosanoic acid, docosahexanoic acid, erucic acid, arachidonic acid, lard oil, tallow oil, butter, coconut oil, palm oil, cottonseed oil, malt oil, soybean oil, olive oil A metalworking fluid composition obtained from one or more of corn oil, sunflower oil and rapeseed oil or canola oil .   2. A composition according to claim 1, wherein the pH is 3 or above 3.   The composition according to claim 1 or 2, comprising less than 10% by volume of one or more oils.   The composition according to any one of claims 1 to 3, comprising a corrosion inhibiting component. Those corrosion inhibiting component is the following: undecane diacid or dodecanedioic acid, C ₄ -C ₂₂ carboxylic acids, boric acid and its salts, tolytriazole and its salts, benzotriazoles and its salts, imidazolines and its salts, alkanolamides, sulphonates 5, containing at least one of phosphoric ester amine salt, alkali metal nitrite, alkali metal carbonate, alkylsulfonamide carboxylic acid, arylsulfonamide carboxylic acid, fatty sarcoside, phenoxy derivative and sodium molybdate. Composition.   The composition according to any one of claims 1 to 5, wherein the pH is 3 to 9.   The composition according to any one of claims 1 to 6, comprising an alkaline agent.   Alkaline agents include: dicyclohexylamine (DCHA), alkali metal hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonate and metal bicarbonate, sodium carbonate, sodium bicarbonate 8. The composition of claim 7, wherein the potassium carbonate and potassium bicarbonate are one or more.   The composition according to claim 7 or 8, wherein the alkaline agent is an alkali metal hydroxide.   The composition according to any one of claims 1 to 9, comprising an antifoaming agent.   The composition according to any one of claims 1 to 10, comprising a biocide and / or a fungicide. Carboxylate having an alkali metal salt of C ₄ -C ₂₂ carboxylic acid, Composition according to any one of claims 1 to 11. 13. A composition according to any one of claims 1 to 12 , wherein the carboxylate is obtained from one or more selected from the group consisting of: isononanoic acid and neodecanoic acid. The emulsifiers are: alkanolamides, alkylaryl sulfonates, alkylaryl sulfonic acids, amine oxides, amides and amine soaps, carboxylated alcohols, carboxylic acids or fatty acids, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated amines or amides, Ethoxylated fatty acids, ethoxylated fatty acid esters and oils, ethoxylated phenols, fatty esters, glycerol esters, glycol esters, imidazolines and imidazoline derivatives, lignin and lignin derivatives, maleic anhydride or succinic anhydride, methyl esters, monoglycerides and derivatives , Naphthenic acid, olefin sulfonate, phosphate ester, polyethylene glycol, polyol, polymer (polysaccharide, (Crylic acid, acrylamide), propoxylated or ethoxylated fatty acids, alcohols or alkylphenols, quaternary surfactants, sarcosine derivatives, soaps, sorbitan derivatives, sucrose and glucose esters and derivatives, sulfates and sulfonates of oils and fatty acids, ethoxylated Alkylphenol sulfates and sulfonates, alcohol sulfates, ethoxylated alcohol sulfates, fatty acid ester sulfates, dodecylbenzene and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, petroleum sulfonates, sulfosuccinates, sulfosuccinates And derivatives, or tridecylbenzenesulfonic acid and dodecylbenzenesulfonic acid It is one or more of in composition according to any one of claims 1 to 13. 15. A metalworking fluid composition according to any one of claims 1 to 14 , wherein the metalworking fluid composition has a lubricity of less than 8000 Newton-cm- ^{1 as} measured by a tapping torque meter when diluted to 0.1-50% by volume. 2. The composition according to item 1. (A) 15-25% by volume of one or more block copolymers;
(B) 5-15% by volume of one or more carboxylates;
(C) 3-8% by volume of one or more emulsifiers;
The metalworking fluid composition according to any one of claims 1 to 15 , comprising (d) a transport component. 17. The metalworking fluid composition of any one of claims 1 to 16 , having a volume average diameter of 125 to 100,000 nanometers (nm).