Patent Description:
A metal working fluid (MWF) is an oil or other liquid that is used to cool and/or lubricate metal work pieces when the metal work pieces are being machined, ground, milled, and the like. In this regard, metal working fluids are configured to reduce the heat and friction between the cutting tool and the metal work piece. In addition, the use of a metal working fluid also helps to improve the quality of the work piece by continuously removing the fines, chips, and swarfs (small pieces of metal removed from a work piece by a cutting tool) from the tool being used and the surface of the work piece.

While there are many different components and additives in metal working fluids, there are generally four basic classes of metal working fluids. A "straight oil" (also called a "cutting" or "neat" oil) is a type of metal working fluid that is comprised of mineral (e.g., petroleum), animal, marine, vegetable, or synthetic oils. Straight oils are not diluted with water, but other additives may be present. A "soluble oil" (also called an "emulsifiable" oil) is a type of metal working fluid that contains <NUM> to <NUM> percent of a refined petroleum oil, as well as emulsifier(s) to disperse the oil in water. A "semi-synthetic fluid" is a type of metal working fluid that contains <NUM> to <NUM> percent of a refined petroleum oil, <NUM> to <NUM> percent water, and a number of additives. Lastly, a "synthetic fluid" is a type of metal working fluid that does not contain a petroleum oil. Instead, the synthetic fluid uses detergent-like components and other additives to assisting in "wetting" the work piece.

Each of the above-noted metal working fluids may contain additives such as Sulphur-containing, phosphorus-containing, or chlorinated compounds; corrosion inhibitors (e.g., calcium sulfonate, sodium sulfonates, fatty acid soaps, amines, boric acid); extreme pressure additives (e.g., sulfurized fatty materials, chlorinated paraffins, phosphorus derivatives); anti-mist agents (e.g., polyisobutylene polymer); emulsifiers (e.g., triethanolamine, sodium petroleum sulphonates, salts of fatty acids, and non-ionic surfactants); biocides (e.g., triazine compounds, oxazolidine compounds); stabilizers; dispersants; de-foaming agents; colorants; dyes; odorants; fragrances; and other additives known to one skilled in the art.

Semi-synthetic metal working fluids are regarded as having the best all-round properties, as this type of metal working fluid simultaneously provides good cooling, lubricity, and corrosion protection. Straight or neat oils typically have better lubricity, but worse cooling; and fully synthetic fluids may have better cooling, but often have worse lubricity and corrosion protection.

In use, metal working fluids (especially those including water) can become susceptible to bacterial contamination. The bacteria can degrade the emulsions and change the properties of the metal working fluid. In this regard, the bacteria can cause the emulsion to degrade to an extent that the oil drops out of the emulsion and sits on the fluid surface, can cause a pH of the metal working fluid to drop (i.e., become acidic) which can lead to increased corrosion, can reduce lubricity of the metal working fluid which adversely affects tool life, and can potentially cause skin and respiratory conditions for anyone exposed to the metal working fluid having the increased bacterial content.

While biocides can be added to reduce the amount of microbial growth and prolong the useful life of the metal working fluid, the biocide products themselves may have hazardous properties. As a result, the number of biocides that are available for use has been reduced, especially in Europe. In addition, biocides may degrade in time either by hydrolysis or bacterial attack, which will eventually decrease the efficacy of the metal working fluid. Once the efficacy of the metal working fluid has been reduced, or the amount of bacteria in the metal working fluid is too great, it must be removed from the machine tool, which is then cleaned and replenished with fresh metal working fluid. This can take several hours of machine tool downtime, which will adversely affect productivity. As a result, a need has been identified for a metal working fluid that can resist bacteria for longer periods of time to increase productivity of the machine tools that use the metal working fluid, as well as provide a safer environment for users of the machine tools.

<CIT> and <CIT> disclose metal working composition comprising amines and analyse putrefaction resistant properties.

The invention is set out in the appendeded claims.

According to the present invention, the present disclosure provides a metal working fluid including a cross-linked polymeric ester emulsifier; an amine having at least two primary amine groups represented by the following formula (<NUM>): (H<NUM>N)a-Q-(NH<NUM>)b.

In the metal working fluid, X may be a cyclic ring system including <NUM> to <NUM> carbon atoms.

Alternatively, X may be a cyclic ring system including <NUM> carbon atoms.

In the metal working fluid according to the first embodiment, the cyclic ring system may be an aromatic ring or an aliphatic ring.

In the metal working fluid according to the first embodiment, the Y and Z groups may include alkylene chains (-CH<NUM>)n where n is an integer between <NUM> and <NUM>.

In the metal working fluid, the primary amine groups may be located at a terminal end of the alkylene chains.

In the metal working fluid, the metal working fluid may further include a biocide, wherein the biocide is selected from the group consisting of N,N'-methylenebismorpholine (MBM); <NUM>,<NUM>'-methylene bis [<NUM>-methyloxazolidine] (MBO); α,α',α"-trimethyl-<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>(<NUM>,<NUM>,<NUM>)-triethanol (HPT); hexahydrotriazine (HHT); (ethylenedioxy)dimethanol (EDDM); benzisothiazolinone (BIT); methylisothiazolinone (MIT, MI); chloromethylisothiazolinone (CMIT, CMI, MCI); octylisothiazolinone (OIT, OI); dichlorooctylisothiazolinone (DCOIT, DCOI); and butylbenzisothiazolinone (BBIT).

In the metal working fluid, the amine does not include secondary or tertiary amine groups.

The present disclosure provides a metal working fluid that sufficiently resists contamination by bacteria during use thereof. The metal working fluid according to the present disclosure is a semi-synthetic type of metal working fluid that includes an oil, water, and various additives and emulsifiers. To increase resistance to bacterial growth and lengthen the useful life of the metal working fluid, one of the additives of the metal working fluid is an amine that includes at least two primary amine groups (-NH<NUM>). The amines that include at least two primary amine groups according to the present disclosure are those that include a cyclic ring system.

In addition, one of the additives of the metal working fluid is an amide that is formed from one of the above-noted amines.

With respect to the present invention, example amines that include at least two primary amine groups that include a cyclic ring system include <NUM>,<NUM>'-methylene-bis-cyclohexylamine.

The above amines can be described using the following formula (<NUM>):.

where a and b are integers, and Q is represented by Y-X-Z, where X is a cyclic ring system including <NUM> to <NUM> carbon atoms, Y and Z are groups that include at least one carbon atom directly attached to the cyclic ring system, and the amine groups are attached to the Y and Z groups, respectively.

The amines according to the present disclosure include at least two primary amine groups and a cyclic ring system, and the primary amine groups are located in a side chain off the cyclic ring system. Amines comprising only secondary or tertiary amine groups do not form part of the present disclosure.

More preferably, the amines according to the present disclosure include at least two primary amine groups and a cyclic ring system, wherein each of the two primary amine groups are located in side chains off the cyclic ring system. Amines of this type are represented by the following formula (<NUM>):.

(H<NUM>N)a-Y-X-Z-(NH<NUM>)b     (<NUM>),.

where a and b are each integers; a+b ≥ <NUM>; X is a cyclic ring system including <NUM> to <NUM> carbon atoms, more preferably <NUM> to <NUM> carbon atoms, and even more preferably <NUM> carbon atoms; and Y and Z are groups that include at least one carbon atom directly attached to the cyclic ring system.

The cyclic ring system (X) may be an aromatic ring or an aliphatic ring. For example, if X is an aromatic ring containing six carbon atoms, X may be a benzene ring. Similarly, if X is an aliphatic ring including six carbon atoms, X may be a cyclohexane ring. For ring systems that exhibit isomerism, the present disclosure contemplates the use of either cis or trans configurations, or any combination thereof.

Example (Y) and (Z) groups include alkylene chains (-CH<NUM>)n where n is an integer between <NUM> and <NUM>, wherein the primary amine groups can be located at any position of the chain. Although the primary amine groups can be located at any position of the chain, it is preferable that the primary amine group be located at a terminal end of the chain. The cyclic ring (X) and side chains (Y and Z) may also comprise other functional groups known in organic chemistry, such as halogen, oxygen, phosphorus, nitrogen, and Sulphur-containing groups.

An example of a particularly preferred amine that comprises two primary amine groups that are both located in side chains attached to a cyclohexane ring system is <NUM>,<NUM>-bis(aminomethyl)cyclohexane, which can be the cis or trans configuration, or any combination thereof.

Although not required, it is preferred that the amines of the present disclosure that comprise at least two primary amine groups are those that exhibit excellent pH buffering properties in a metal working fluid formulation. It is also preferable that the amine assist in inhibiting ferrous corrosion and reducing aluminum staining.

The metal working fluids according to the present disclosure may include various additives. For example, the metal working fluid according to the present disclosure may include at least one emulsifier; at least one lubricant; at least one extreme pressure additive that may be a compound that is halogen-, phosphorus-, Sulphur-, or molybdenum-based; at least one corrosion inhibitor including compounds that may be boron-based or a boron-free amine carboxylate; at least one metal passivator; at least one anti-foam agent; at least one fungicide or biocide; at least one anti-misting agent; at least one chelating agent; at least one dye; and the like. It should be understood that the above-noted compounds for the extreme pressure additive and the corrosion inhibitor are examples only, and other materials known to one skilled in the art may be used without limitation.

Example emulsifiers that may be used in the metal working fluid of the present disclosure include cross-linked polymeric esters, examples of which are disclosed in <CIT>. The emulsifiers disclosed therein are commercially available from Italmatch Chemicals GB Ltd. as the Polartech® EA 7xx series of products, which includes Polartech® EA <NUM> / <NUM> / <NUM> / <NUM><NUM>.

Example biocides that may be used in the metal working fluids according to the present disclosure include formaldehyde releasers such as, for example, N,N'-methylenebismorpholine (MBM); <NUM>,<NUM>'-methylene bis [<NUM>-methyloxazolidine] (MBO); α,α',α"-trimethyl-<NUM>,<NUM>,<NUM>-triazine-<NUM>,<NUM>,<NUM>(<NUM>,<NUM>,<NUM>)-triethanol (HPT); hexahydrotriazine (HHT); and (ethylenedioxy)dimethanol (EDDM). Other biocides include substances that do not release formaldehyde including, for example, isothiazolinone compounds such as benzisothiazolinone (BIT); methylisothiazolinone (MIT, MI); chloromethylisothiazolinone (CMIT, CMI, MCI); octylisothiazolinone (OIT, OI); dichlorooctylisothiazolinone (DCOIT, DCOI); and butylbenzisothiazolinone (BBIT).

Next, an reference example metal working fluid (Reference Example <NUM>) was manufactured. In addition, a pair of comparative examples (Comparative Examples <NUM> and <NUM>) were manufactured. The metal working fluids according to Reference Example <NUM> and Comparative Examples <NUM> and <NUM> each have the below formula shown in Table <NUM>.

The "test amine" used in Reference Example <NUM> was <NUM>,<NUM>-bis(aminomethyl)cyclohexane in an amount equal to about <NUM> wt%. In addition, the "test emulsifier" was Polartech® EA <NUM> (i.e., a cross-linked polymeric ester) in an amount equal to about <NUM>%.

The "test amine" used in Comparative Example <NUM> included monoethanolamine in an amount equal to about <NUM> wt%, and triethanolamine in an amount equal to about <NUM> wt%. In addition, the "test emulsifier" was Polartech® EA <NUM> in an amount equal to about <NUM>%.

The "test amine" used in Comparative Example <NUM> included <NUM>,<NUM>-bis(aminomethyl)cyclohexane in an amount equal to about <NUM> wt%. In addition, the "test emulsifier" was PET Sulphonate <NUM> in an amount equal to about <NUM> wt%.

Reference Example <NUM> and Comparative Examples <NUM> and <NUM> were each formulated to the same approximate level of alkalinity.

Next, Reference Example <NUM> and Comparative Examples <NUM> and <NUM> were subjected to fluid life testing to determine each formulation's ability to withstand bacterial degradation and prolong the life of a metal working fluid. In this regard, the three semi-synthetic metal working fluid concentrates prepared in Reference Example <NUM>, Comparative Example <NUM>, and Comparative Example <NUM> were converted into aqueous oil-in-water emulsions for fluid life testing by mixing each of the concentrates with tap water such that the resultant metal working fluids each included about <NUM>% of the respective concentrate and <NUM>% of the tap water. About five liters of each of the metal working fluids were prepared, and each metal working fluid was placed into a <NUM> Perspex bath. Each bath contained a recirculation pump and a heater so that the metal working fluids could be continuously recirculated at a constant <NUM>±<NUM>. The bath also contained a nylon mesh filter bag into which cast iron chips (<NUM>) were placed. The baths were each arranged so that the metal working fluids were constantly recirculated through the cast iron chips.

Once the baths were set up, a dose (<NUM>) of spoiled emulsion (i.e., an emulsion containing bacteria) was added to each of the baths. In this regard, adding spoiled emulsion containing ><NUM><NUM> CFU/ml bacteria to a metal working fluid is known to encourage bacterial degradation. The metal working fluids were then left recirculating continuously at <NUM>, <NUM> hours a day / <NUM> days a week. After one week had passed, each of the metal working fluids were then tested for bacterial contamination using agar dip slides. Specifically, after the dip slide had been treated with each respective metal working fluid and placed into the incubator, another dose (<NUM>) of spoiled emulsion was added to each of the remaining amounts of metal working fluids and left to recirculate in the respective bath for another week at <NUM>, after which time the dip slide testing and dosing procedure was repeated. This process was continuously repeated until a bacterial contamination of <NUM><NUM> CFU/ml was recorded in the metal working fluids. At this point the metal working fluid was deemed to have reached the end of its useful life, and the test was stopped.

Table <NUM> below shows the results of the tests conducted on the metal working fluids of Reference Example <NUM>, Comparative Example <NUM>, and Comparative Example <NUM>. As can be seen in Table <NUM>, the metal working fluid of Reference Example <NUM> yielded a superior resistance to bacteria growth. Indeed, the amount of time required to yield <NUM><NUM> bacterial per CFU/ml was over double the amount of time required for each of Comparative Example <NUM> and Comparative Example <NUM>. As a result, the combination of the amine <NUM>,<NUM>-bis(aminomethyl)cyclohexane and emulsifier Polartech® EA <NUM> has provided an unexpectedly long fluid life.

Reference example <NUM> is not according to the invention.

The amines were also tested to determine whether each sample was sufficient in inhibiting corrosion. This was assessed using an IP <NUM> test method for determination of rust prevention characteristics of water mix metal working fluids, as follows. Solutions of the test amines in 200ppm water were applied to PERA cast iron test chips (<NUM>) on a piece of Whatman No. <NUM> filter paper <NUM> diameter. The fluid remained in contact with the cast iron chips on the filter paper for <NUM> hours, after which time the fluid covered chips were removed and the staining of the paper assessed visually. The result is the minimum concentration needed to produce a completely stain free piece of filter paper. The amines according to the present disclosure that were tested included <NUM>,<NUM>-bis(aminomethyl)cyclohexane and <NUM>,<NUM>-diaminopentane as a reference. Comparative amines included monoethanolamine and <NUM>-amino-<NUM>-octanol. The minimum concentration required for the amines according to the present disclosure required a concentration of <NUM>%. Meanwhile, monoethanolamine required a concentration of <NUM>%, and <NUM>-amino-<NUM>-octanol required a concentration of <NUM>%. This in indicates that in addition to prolonging the service life of the metal working fluid, the amines according to the present disclosure also exhibit good ferrous corrosion inhibition properties.

The amides for use in the metal working fluids according to the present disclosure are formulated by reacting the above-noted amines with a carboxylic acid, which react at high temperature via a condensation reaction with the elimination of water. Because the amides are based on the above-noted primary amines, the amides will include at least one NHCO- group. Example carboxylic acids include mono-valent compounds and polyvalent compounds such as di- and tri-carboxylic acids. The term "carboxylic acid," however, should also be understood to include carboxylic acid derivatives such as acid halides, acid anhydrides, and esters.

The carboxylic acid group or groups can be attached to a carbon atom that is part of a chain system. The chain system can be hydrocarbon or can comprise other functional groups known in organic chemistry such as those including O, N, P or S atoms. The chain system can be saturated or unsaturated, include straight chains or branched chains, and/or include ring systems that can be aliphatic, aromatic, homocyclic, or heterocyclic.

Examples of suitable monocarboxylic acids include those represented by the formula R-COOH, where R is a saturated, linear, or branched hydrocarbon chain represented by CnH2n+<NUM>, where n is an integer in the range of <NUM> to <NUM>. Example compounds having such a formula include dodecanoic acid and stearic acid. Other examples of suitable monocarboxylic acids include tall oil fatty acids; ricinoleic acid; oleic acid; erucic acid; isononanoic acid; <NUM>,<NUM>,<NUM>-trimethylhexanoic acid; neodecanoic acid; naphthenic acid; undecenoic acid; undecynoic acid; alkoxylated ether carboxylic acids such as alkoxylated alkyl ether carboxylic acids; amino acids; and Sulphur-containing carboxylic acids such as <NUM>-[[(<NUM>-methylphenyl)sulphonyl]amino]hexanoic acid.

Examples of suitable di-carboxylic acids include those represented by the formula R-(COOH)<NUM>, where R is a saturated, linear, or branched hydrocarbon chain represented by CnH2n, where n is an integer in the range of <NUM> to <NUM>. Example compounds having such a formula include azelaic acid; adipic acid; sebacic acid; undecanedioic acid; and dodecanedioic acid. Other suitable examples include unsaturated chains such as maleic acid and aromatic rings such as benzenedicarboxylic acid.

Examples of suitable tri-carboxylic acids include citric acid; isocitric acid; aconitic acid; propane-<NUM>,<NUM>,<NUM>-tricarboxylic acid; trimesic acid; trimellitic acid; and <NUM>,<NUM>,<NUM>-tri-(<NUM>-aminocaproic acid)-<NUM>,<NUM>,<NUM>-triazine, known commercially as Irgacor L190 Plus manufactured by BASF.

Reaction of the amines of the present disclosure with at least <NUM> carboxylic acid comprising <NUM> or more carboxylic acid groups yields a polyamide species according to the present disclosure.

For example, to manufacture a metal working fluid including an amide (Reference Example <NUM>), one mole (<NUM>) of <NUM>,<NUM>-diaminopentane (Dytek EP) and <NUM> moles (<NUM>) <NUM>,<NUM>,<NUM>-tri-(<NUM>-aminocaproic acid)-<NUM>,<NUM>,<NUM>-triazine (Irgacor L190 Plus (<NUM>% active), (tri-carboxylic acid = <NUM> mol carboxylic acid groups)) were added to a suitable reaction vessel. The reaction mixture was then heated to <NUM> over a period of <NUM> hours and then held at this temperature. The elimination of water was monitored and when it appeared that no further water was being eliminated the reaction mixture temperature was raised to <NUM> over a time period of <NUM> hours. The reaction mixture was then held at this increased temperature until the acid value had decreased to around 20mgKOH/g. The reaction mixture was then left stirring to cool. When the temperature had reached <NUM>, <NUM> of water was added to the reaction vessel. The reaction mixture was then left stirring to cool for a further hour by which time its temperature had decreased to <NUM>. The final reaction mixture amide had a pH of <NUM> (<NUM>% solution in deionized water), the total alkalinity was <NUM>%, and the acid value was about <NUM> KOH/g.

Next, a comparative amide (Comparative Example <NUM>) was made using <NUM>-amino-<NUM>-octanol, which is an alkanolamine commonly used in water-based metal working fluid. The <NUM>-amino-<NUM>-octanol was reacted with <NUM>,<NUM>,<NUM>-tri-(<NUM>-aminocaproic acid)-<NUM>,<NUM>,<NUM>-triazine using the same stoichiometric ratios and method as Reference Example <NUM>.

The synthesized amides were each formulated into metal working fluid semi-synthetic concentrates according to Table <NUM>:.

Next, Reference Example <NUM> and Comparative Example <NUM> were subjected to fluid life testing to determine each formulation's ability to withstand bacterial degradation and prolong the life of a metal working fluid. In this regard, the two semi-synthetic metal working fluid concentrates prepared in Reference Example <NUM> and Comparative Example <NUM> were converted into aqueous oil-in-water emulsions for fluid life testing by mixing each of the concentrates with tap water such that the resultant metal working fluids each included about <NUM>% of the respective concentrate and <NUM>% of the tap water. About five liters of each of the metal working fluids were prepared, and each metal working fluid was placed into a <NUM> Perspex bath. Each bath contained a recirculation pump and a heater so that the metal working fluids could be continuously recirculated at a constant <NUM>±<NUM>. The bath also contained a nylon mesh filter bag into which cast iron chips (<NUM>) were placed. The baths were each arranged so that the metal working fluids were constantly recirculated through the cast iron chips.

Table <NUM> below shows the results of the tests conducted on the metal working fluids of Reference Example <NUM> and Comparative Example <NUM>. As can be seen in Table <NUM>, the metal working fluid of Reference Example <NUM> yielded a superior resistance to bacteria growth. Indeed, the amount of time required to yield <NUM><NUM> bacterial per CFU/ml was over double the amount of time required for Comparative Example <NUM>.

Reference Example <NUM> and Comparative Example <NUM> were also tested to determine whether each sample was sufficient in inhibiting corrosion. This was assessed using the IP <NUM> test method for determination of rust prevention characteristics of water mix metal working fluids, as follows. Solutions of the test amide in <NUM> ppm water were applied to PERA cast iron test chips (<NUM>) on a piece of Whatman No. <NUM> filter paper <NUM> diameter. The fluid remained in contact with the cast iron chips on the filter paper for <NUM> hours, after which time the fluid covered chips were removed and the staining of the paper assessed visually. The result is the minimum concentration needed to produce a completely stain free piece of filter paper.

While the amide of Reference Example <NUM> produced a similar level of ferrous corrosion resistance as the amide of Comparative Example <NUM>, the amide of Reference Example <NUM> provided a superior fluid life.

Lastly, it should be understood that the amines according to the present disclosure can also be used in a carbamate form where the above-noted amines are reacted with carbon dioxide.

Claim 1:
A metal working fluid, comprising:
a cross-linked polymeric ester emulsifier; and
an amine having at least two primary amine groups represented by the following formula (<NUM>):

        (H<NUM>N)a-Q-(NH<NUM>)b     (<NUM>),

where a and b are each integers; a+b ≥ <NUM>, and Q is represented by Y-X-Z, where X is a cyclic ring system including <NUM> to <NUM> carbon atoms, Y and Z are groups that include at least one carbon atom directly attached to the cyclic ring system, and the amine groups are attached to the Y and Z groups, respectively, and
an amide, the amide being formed through a reaction between the amine having the formula (<NUM>) with a carboxylic acid.