CA2200747A1 - Aqueous metal cleaner - Google Patents

Abstract

An aqueous metal cleaning composition is provided which comprises an alkalinity providing agent such as alkali metal carbonate and/or bicarbonate salts and a low emulsifying, low foaming surfactant, the aqueous cleaning solution having specified foam height and foam collapse characteristics.

Description

W096/09366 ~ ~ ~ n n 7 4 ;7~ PCT/US95/08976 AOUEOUS METAL CLEANER
BACKGROUND OF THE lN~.J~-lON
The present invention relates generally to aqueous metal cleAni ng compositions. In particular, this invention is directed to aqueous metal cleaning compositions useful in so-called parts washers which are particularly adapted to be used for industrial cleaning, as well as for domestic use.
Parts washers of various kinds are known to those skilled in the art as having great utility for mechanics and others working in a variety of occllpAtions, particularly those working in industrial plants, maint~nAnce and repair services, and the like. The parts washers referred to herein include soak tanks, so-called hot tanks, immersion type parts cleaners with or without air agitation, spray washers (continuous or batch) and ultrasonic baths. Generally, parts washers are used to remove all types of contaminants adhered to the metal surface including greases, cutting fluids, drawing fluids, machine oils, antirust oils such as cosmoline, carbonaceous soils, sebaceous soils, particulate matter, waxes, paraffins, used motor oil, fuels, etc.
Until recently, metal surfaces were cleaned of most oily and greasy contamination by use of solvents. Existing solvents, with or without special additives, are adequate to achieve good cleaning of most dirty, greasy, metal parts. A
great number of solvents have been employed to produce metallic surfaces free from contamination.
These wash solvents generally include various halogenated hyd~o~arbons and non-halogenated hydrocarbons, of significant quantity industry wide -W096/09366 ~ PcT~sgslo8s76 for cleaning and degreasing of the metal surfaces, and the degree of success with each of these wash solvents is generally dependent upon the degree of cleanliness required of the resultant surface.
Recently, however, the various hydrocarbon and halogenated hydrocarbon metal cleaning solvents previously employed have come under scrutiny in view of the materials employed, and in particular, the environmental impact from the usage of the various materials. This is particularly so in the case of parts cleaning which is done in closed environments such as garages and the like or for even home usage in view of the close human contact. Even the addition of devices to parts washers which can reduce spillage, fire and excessive volatilization of the cleaning solvent are not sufficient to alleviate present environmental concerns.
Although the halogenated hydrocarbon solvents such as chlorofluorocarbons (CFCs) and trichloromethane, methylene chloride and trichloroethane (methyl chloroform) are widely used in industry for metal cleaning, their safety, environmental and cost factors coupled with waste disposal problems are negative aspects in their usage. A world-wide and U.S. ban on most halogenated hydlG~arbon solvents is soon in the offing by virtue of the Montreal Protocol, Clean Air Act and Executive and Departmental directives.
The non-halogenated hydrocarbon solvents such as toluene and Sto~rd solvent and like organic compounds such as ketones and alcohols on the other hand are generally flammable, have high volatility and dubious ability to be recycled for continuous use. These, plus unfavorable safety, environmental and cost factors, put this group of wog6l09366 2 ~ n n 7 4 7 PCT/US95108976 ._ solvents in a category which is unattractive for practical consideration. Most useful organic solvents are classified as volatile organic com~ou,.ds (VOCs) which pollute the atmosphere, promote formation of toxic ozone at ground level, and add to the inventory of greenhouse gases.
In order to eliminate the various negative aspects of the known chemical washing and degreasing systems, it has, therefore, been suggested that an aqueous detergent system be used so as to overcome some of the inherent negative environmental and health aspects of prior art solvent cleaning systems. Unfortunately, aqueous cleaning systems are not without their own problems as related to use thereof in metal cleaning systems including use in parts washers as described above. For example, certain of the aqueous cleaners are exceedingly alkaline having pHs of 13 and above such as sodium hyd~oxide or include organic solvents such as alkanolamine, ethers, alcohols, glycols, ketones and the like. Besides being highly ~o~ L G~-ive, the exc~e~i ngly high alkaline aqueous solutions are highly toxic and can be dangerous to handle requiring extreme safety measures to avoid contact with skin. Organic solvent-containing aqueous cleaners present the problems regarding toxicity, volatility or the environment as expressed previously. On the other hand, it is most difficult to obtain an aqueous detersive solution at moderate pH which is effective in removing the greases and oils which contaminate metal including metal engine - parts and which would not be corrosive to the metal substrate.
one particular disadvantage of using aqueous systems to clean metal surfaces is the W096/09366 ~ 7 ~ 1 PCT~Ss5/08s76 potential to ~oL~ode or discolor the surfaces.
While aqueous cleaning solutions having a high pH
such as formed from sodium hydroxide are often more ~0~ L Gf-ive than aqueous solutions having a relatively low pH such as formed by mildly alkaline detergents, ~oLLo_ion and discoloration are still problematic with the more mild solutions. Various corrosion inhibitors are known and have been used to prevent ~LGf-ion of surfaces which come into contact with aqueous alkaline solutions. Probably, the most effective and least costly of the known corrosive inhibitors are the silicates, such as alkali metal silicates. Unfortunately, the alkali metal silicates begin to precipitate from aqueous solution at pHs below 11, thus, greatly reducing the effectiveness of these materials to prevent corrosion of the contacted surfaces when used in aqueous cleaning solutions having a lower pH.
Accordingly, to be as effective and be able to replace the halogenated and hydrocarbon solvents now widely used, aqueous metal cleaning compositions will have to be formulated to solve the problems associated therewith including efficacy of detersive action at moderate pH levels and the corrosiveness inherent in aqueous based systems, in particular, on metal substrates.
One particular problem with respect to ~LLGsion using aqueous metal cleaning solutions is manifest in the cleaning of iron-based metals.
Thus, it has been found that iron-based metals treated with aqueous based systems and then removed from the aqueous solution begin to rust almost immediately. This phenomenon has been characterized as flash rusting. Inasmuch as it takes longer for metal parts to dry subsequent to treatment with 2 2 ~ ~ 7 4 7 PCI/US95/08976 _ aqueous based cleaners as compared to the drying times of organic solvent-based cleaners due to the high surface tension of water, the potential for flash rusting to occur with iron-containing metal substrates is a serious drawback to the use of aqueous based cleaners to clean such metal surfaces.
It is al~o important that the aqueous metal cleaners be reusable to render such cleaners economically viable. Thus, it is not practical on an industrial scale to sewer an aqueous cleaning bath upon a single usage thereof. Many of the aqueous based cleaners now available use detersive agents which are effective in removing the dirt, grease or oil from the metal surface but unfortunately readily emulsify the contaminants such that the contaminants are highly dispersed or solubilized throughout the aqueous solution. These highly emulsified cleaning solutions are difficult to treat to separate contaminants from the aqueous cleaner and, accordingly, the cleaning solution gets spent in a relatively short period of time and must be replaced to again achieve effective cleaning of the metal parts and the like. It would be worthwhile to provide an aqueous metal cleaner which could effectively remove the contaminants from the metal surface but which would allow the ready separation of such contaminants from the cleaning solution to allow effective and prolonged reuse of the cleaning solution.
Still another disadvantage of the use of aqueous cleaners again stems from the high surface - tension of water and the propensity of the detersive agents in the aqueous cleaner to foam upon agitation of the cleaning bath such as induced in the bath or by the use of spray nozzles to apply the cleaning W096/09366 PcT~sg5lo8s76 7 ~ ~

solution to the metal components being cleaned. The presence of foam often renders the use of machines with high mechAnical agitation impractical due to e~reCcive foaming. Also, the pr~-enr~ of foam can cause pump cavitation problems and the overflow of liquids onto floors as well as cause difficulties with viewing the cleaning process through vision ports and the like contained in the machinery.
Accordingly, it is an object of this invention to provide an aqueous metal cleAning composition which is effective to clean grease, oil, dirt or any other contaminant from a metal surface and yet have a relatively moderate pH so as to not be excessively corrosive to the substrate and irritating to human skin.
Another object of the invention is to provide an aqueous metal cleaning composition which can be used effectively in immersion and impingement type parts washers so as to effectively remove dirt, grease, oil and other contaminants from metal parts and which is safe to use and not a hazard to the environment in use or upon disposal.
Still another object of the present invention is to provide an aqueous metal cleaning composition which is not ~o~osive to metal parts in general and, in particular, can greatly reduce flash rusting of iron-containing metal components.
Still yet another object of the present invention is to provide an aqueous metal cleaning composition of moderate pH which has effective detersive action and is low foaming to maintain the cleaning efficacy of the composition in aqueous solution.

wog6/09366 ~ 7 4 7 PcT~ss5/o8s76 A further object of the present invention i6 to provide an aqueous metal cleaning composition which does not readily emulsify and solubilize the contaminants removed from a metal surface such that the contaminants can be separated from the aqueous cleaning solution and the solution continuously reused.
Yet another object of this invention is to provide an aqueous cleaning concentrate which when diluted to cleaning concentration can be an effective and environmentally sound aqueous cleaner.
These and other objects of the invention can be readily ascertained from the description of the invention which follows.
SUMMARY OF THE lNv~NllON
In accordance with the present invention, an aqueous alkaline metal cleaning solution is provided which has a pH of up to 11.0 but a sufficiently high pH to effectively clean dirt, grease, oil and the like from any metal surface.
The aqueous metal cleaning solutions of the present invention are formed from compositions which contain an alkali metal salt electrolyte and one or more surfactants which do not readily emulsify or solubilize the contaminants which are removed from the metal surface and which are low foaming.
Accordingly, aqueous cleaning solutions of this invention can be treated to separate the contaminants which have been removed from the metal substrates such as by skimming, filtration and the like to yield a cleaning solution which is - essentially free from contamination and can be continuously reused to clean additional metal WO g6/09366 PCTIUS95/08976 7 ~ ~

substrates. Unlike the halogenated or hydrocarbon solvents of the prior art, the aqueous alkaline cleaning solutions of this invention are environmentally safe in use and can be safely handled, stored and disposed of without the environmental problems caused by eYceccive amounts of volatile and toxic organics or the hazards of extremely high alkaline aqueous compositions which have been previously suggested.
The metal cleaning compositions of this invention also optionally include a corrosion inhibitor, a polycarboxylated polymer to maintain any corrosion inhibitor in solution in the mildly alkaline solutions of this invention, and a hydrotrope to maintain the surfactant in aqueous solution.
It has further been found that the treatment of iron-based metal surfaces with carbonates, bicarbonates or mixtures thereof is effective in greatly reducing, if not eliminating the phenomenon of flash rusting and, accordingly, the present invention is also concerned with a method of treating iron-based parts and surfaces with carbonate or bicarbonate salts or mixtures thereof either as part of the aqueous cleaning solution of this invention or in a post treatment step so as to prevent the flash rusting of the iron components and allowing such components to be stored without rusting until use.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph comparing the foaming characteristics of the aqueous cleaner of the W096/09366 ~ 2 ~ O ~ ~ ~ PCT~S95/08976 ~e_ont invention with those of several commercially available metal cleaners.
Figure 2 is a graph comparing the cleaning efficacy of the aqueous cleaner of the present invention with that of commercially available metal cleaners.
D~TATT~n D~CRIPTION OF T~ lNv~lTION
The aqueous cleaning compositions of the present invention comprise an alkalihity providing agent which comprises an alkaline salt electrolyte and a low emulsifying, low foaming surfactant or mixture of surfactants. The metal cleaning compositions of the present invention are useful for removing any type of contaminant from a metal surface including greases, cutting fluids, drawing fluids, machine oils, antirust oils such as cosmoline, carbonaceous soils, sebaceous soils, particulate matter, waxes, paraffins, used motor oil, fuels, etc. Any metal surface can be cleaned including iron-based metals such as iron, iron alloys, e.g., steel, tin, aluminum, copper, ~ul~y~en, titanium, molybdenum, etc., for example.
The structure of the metal surface to be cleaned can vary widely and is unlimited. Thus, the metal surface can be as a metal part of complex configuration, sheeting, coils, rolls, bars, rods, plates, disks, etc. Such metal components can be derived from any source including for home use, for industrial use such as from the aerospace industry, automotive industry, electronics industry, etc., wherein the metal surfaces have to be cleaned.
- The aqueous alkaline metal cleaning solutions of this invention comprising the cleaning W096/09366 ~ 4 ~ PCT~S95/08976 eomposition in water have a pH above 7.5 and up to 11.0 so as to render these solutions substantially less harmful to use and handle than highly alkaline aqueous eleaners sueh as those formed from sodium h~oxide or aqueous alkanolamine solutions. The solutions preferably have a pH of at least 8.0 to less than 11.0 to effeetively elean the typieal metal substrates. Most preferably, the aqueous alkaline eleaning solutions have a pH from about 8.0 to 10.0 which is effeetive to remove the dirt, grease, oil and other eontaminants from the metal surfaee without eausing tarnishing or diseoloration of the metal substrate and yet allow the solutions to be used, handled and disposed of without burning or irritating human skin. It is preferable that the eompositions and resultant aqueous eleaning solutions formed therefrom be free of organie solvents ineluding hydroearbon, halohydroearbon and oxygenated hydrocarbon solvents.
The alkalinity providing agent of the aqueous metal eleaning eompositions of the present invention is provided to aehieve the desired pH in aqueous solution as well as to provide a suffieient reservoir of alkalinity to maintain the eleaning ability of the eleaning solution. Useful agents ean be provided by one or more alkaline salts. Suitable alkaline salts or mixLu.e~ thereof useful in the present invention are those eapable of providing the desired pH. Most suitable are the electrolyte salts whieh appear to aid in the separation of the contaminants from aqueous solution. Preferred salts are those of potassium and sodium. Especially preferred are the potassium and sodium earbonates wog6/09366 ~ ~ ~ o ~ ~ 7 PCI/US95/08976 and bicarbonates which are economical, safe and environmentally friendly. The carbonate salts include potassium carbonate, potassium carbonate dihydrate, potassium carbonate trihydrate, sodium carbonate, sodium carbonate decahydrate, sodium carbonate heptahydrate, sodium carbonate monohydrate, sodium sesquicarbonate and the double salts and mixtures thereof. The bicarbonate salts include potassium bicarbonate and sodium bicarbonate and mixtures thereof. Mixtures of the carbonate and bicarbonate salts are also especially useful.
The carbonate and bicarbonate salts are also especially useful inasmuch as it has been surprisingly found that treatment of iron-containing substrates with aqueous solutions of carbonate and/or bicarbonate salts greatly reduces the rusting of the substrates subsequent to when the substrates are removed from the aqueous cleaning solution and stand for either drying and/or storage. Thus, these preferred salts not only provide the desired pH and alkalinity to the aqueous cleaning solution, but also provide a measure of corrosion protection to iron-b~ substrates. The carbonate and bicarbonate salts are preferably used in the cleaning solution but can also be used in a post treatment step such as a rinsing step which contains an aqueous solution of such salts to provide the resistance to flash rusting for the iron-based substrates. Such a post treatment step can use the potassium and sodium carbonate and bicarbonate salts described above but can also include ammonium salts.
- Although not preferred, other suitable alkaline salts which can be used include the alkali W096/09366 PcT~ssslo8s76 metal ortho or complex phosphates. Examples of alkali metal orthopho~r~Ates include trisodium or tripotassium orthophosphate. The complex phosphates are especially effective because of their ability to chelate water hardness and heavy metal ions. The complex pho~phates include, for example, sodium or potassium pyrophosphate, tripolyphosphate and hexametaphosphates. It is preferred to limit the amount of phosphates contained in the cleaners of lo this invention to less than 1 wt.% (phosphorus) relative to the total alkaline salts used inasmuch as phosphates are ecologically undesirable being a major cause of euLro~hication of surface waters.
Additional suitable alkaline salts useful in the metal cleaning compositions of this invention include the alkali metal borates, acetates, citrates, tartrates, succinates, edates, etc. It is preferred to maintain the compositions of this invention silicate-free due to the resultant high pH
and difficulty in formulating a composition which will remain soluble in aqueous solution at pH's of 11.0 or less when silicates are present.
To improve cle~n~ng efficacy of the cleaning compositions of the present invention, it is needed to add one or more surfactants. Nonionic surfactants are preferred as such surfactants are best able to remove the dirt, grease and oil from the metal substrates. The surfactants utilized in the cleaning compositions of the present invention must also be characterized as ones which do not readily emulsify the contaminants in aqueous solution so as to form a substantially uniform phase with the aqueous solution in the cleaning bath.

wog6/09366 ~ ~ ~ o 7 4 7 PCT~S95/08976 Thus, the surfactants of this invention must be such as to penetrate the contaminants on the surface of the metal so as to remove same from the surface but at the same time the compositions of this invention in aqueous solution allow the formation of a distinct and separated contaminant phase or phases within solution so as to allow the separated contaminant phase to be readily removed from solution such as by filtration, skimming and the like. The cleaning compositions of the present invention are meant to include any surfactant or combination thereof which do not substantially emulsify the dirt, grease, oil, etc., removed from the metal substrate and accordingly, any of such surfactants are to be considered within the scope of the pL~-?nt invention. It is relatively easy to determine whether a surfactant or surfactant combination will emulsify the contaminant.
Preferably, it is believed that the alkoxylated surfactants are best capable of improving the detersive action of the alkaline solution without substantially emulsifying the contaminants to prevent their ready separation from the aqueous cleaning solution and bath containing same. In general, ethoxylated alcohol, ethylene oxide-~G~ylene oxide block copolymers, ethoxylated-propoxylated alcohols, alcohol alkoxylate phosphate esters, ethoxylated amines and alkoxylated thioethers are believed to be useful surfactants either alone or in combination in the cleaning compositions and solutions of the present invention.
Among the most useful surfactants in view of the ability thereof to remove grease and oil are 7 4 ~

the nonionic alkoxylated thiol surfactants. The nonionic alkoxylated (ethoxylated) thiol surfactants of the present invention are known and are described for example in U.S. Pat. Nos. 4,575,569 and 4,931,205, the contents of both of which are herein incorporated by reference. In particular, the ethoxylated thiol is prepared by the addition of ethylene oxide to an alkyl thiol of the formula R-SH
wherein R is alkyl in the presence of either an acid or base catalyst. The thiol reactant that is suitable for producing the surfactant used in the practice of the present invention comprises, in the broad sense, one or more of the alkane thiols as have heretofore been recognized as suitable for alkoxylation by reaction with alkylene oxides in the pre~^nce of basic catalysts. Alkane thiols in the 6 to 30 carbon number range are particularly preferred reactants for the preparation of thiol alkoxylates for use as surface active agents, while those in the 7 to 20 carbon number range are considered more preferred and those in the 8 to 18 carbon number range most preferred.
Broadly, the thiol surfactant can be formed from reaction of the above alkyl thiol and one or more of the several alkylene oxides known for use in alkoxylation reactions with thiols and other com~oul.ds having active hydrogen atoms.
Particularly preferred are the vicinal alkylene oxides having from 2 to 4 carbon atoms, including ethylene oxide, 1,2-propylene oxide, and the 1,2-and 2,3-butylene oxides. Mixtures of alkylene oxides are suitable in which case the product will be mixed thiol alkoxylate. Thiol alkoxylates WO 96109366 ~ ~ ~I n 7 4 7 PCT/US95/08976 prepared from ethylene or propylene oxides are recognized to have very advantageous surface active properties and for this reason there is a particular preference for a reactant consisting essentially of ethylene oxide which is considered most preferred for use in the invention.
The relative quantity of thiol and alkylene oxide reactants determine the average alkylene oxide number of the alkoxylate product. In the alkoxylated thiol surfactant of this invention an adduct number in the range from about 3 to 20, particularly from about 3 to 15 is preferred.
Accordingly, preference can be expressed in the practice of the invention for a molar ratio of alkylene oxide reactant to thiol reactant which is in the range from about 3 to 20, particularly from about 3 to 15. Especially preferred is an ethoxylated dodecyl mercaptan with about 6 ethylene oxide units. Such a surfactant is a commercial product known as ALCODET 260 marketed by Rhone-Poulenc.
Preferred examples of other alkoxylated surfactants include com~ounds formed by condensing ethylene oxide with a hyd~o~hobic base formed by the ron~enr~tion of propylene oxide with ~o~ylene glycol. The hydrophobic portion of the molecule which exhibits water insolubility has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50 percent of the WOg6/09366 PCT~S95/08976 7 4 ~

total weight of the eondensation produet. Examples of ~uch eompositions are the "Pluronics" ~old by BASF.
Other suitable surfaetants inelude: those derived from the eondensation of ethylene oxide with the product resulting from the reaetion of propylene oxide and ethylene-diamine or from the product of the reaction of a fatty acid with sugar, starch or eellulose. For example, compounds containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about ll,OOo resulting from the reaetion of ethylene oxide groups with a hydrophobic base constituted of the reaction produet of ethylene diamine and excess propylene oxide, and hydrophobie bases having a moleeular weight of the order of 2,500 to 3,000 are satisfaetory.
In addition, the eondensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched ehain eonfiguration, with ethylene oxide and propylene oxide, e.g., a eoeonut aleohol-ethylene oxide propylene oxide eonAe~C~te having from 1 to 30 moles of ethylene oxide per mole of eoeonut aleohol, and 1 to 30 moles of propylene oxide per mole of ~v~GnU~
aleohol, the Cv~vllU- aleohol fraetion having from 10 to 14 earbon atoms, may also be employed.
Also useful are alkoxylated aleohols which are ~old under the tradename of "Polytergent S~-Series" surfactants by Olin Corporation or "Neodol"
by Shell Chemical Co. The polycarboxylated ethylene oxide condensates of fatty alcohols manufactured by Olin under the tradename of "Polytergent CS-1" are W096/09~6 ,~ 4 ~ PcT~sgslo8s76 also believed to be effective such as in combination with the above Polytergent SL-Serie~ surfactants.
An effective surfactant which also provides antifoam properties is "Polytergent SLF-18" also manufactured by Olin.
Polyoxyethylene condensates of sorbitan fatty aeids, alkanolamides, such as the monoalkoanolamides, dialkanolamides, and amines; and aleohol alkoxylate phosphate esters, such as the "Klearfac" series from 8ASF are also useful surfaetants in the compositions of this invention.
The polyethylene oxide/polypropylene oxide condensates of alkyl phenols are believed to be low emulsifying but are not effectively biodegradable to be particularly useful surfactants and in most cases should be avoided.
Another useful surfactants are those derived from N-alkyl pyrrolidone. This surfactant iR one whieh ean be used alone to achieve exeellent eleaning or used in eombination with the ethoxylated thiol surfaetant. Partieularly preferred is N-(n-alkyl)-2-pyrrolidone wherein the alkyl group eontains 6-15 carbon atoms. These eompounds are deseribed in U.S. Pat. No. 5,093,031, assigned to ISP Investments, Inc., Wilmington, DE and whieh diseloses surfaee active lactams and is herein ~ ated by referenee. The above N-alkyl pyrrolidone products having a molecular weight of from about 180 to about 450 are conveniently prepared by several known processes ineluding the reaction between a laetone having the formula J~

Wos6/o9~6 PCT~S95/08976 4 ?

wherein n is an integer from 1 to 3, and an amine having the formula R'-NH2 wherein R' is a linear alkyl group having 6 to 20 carbon atoms. The amine reactant having the formula R'-NH2 includes alkylamines having from 6 to 20 carbon atoms; amines derived from natural products, such as coconut amines or tallow amines distilled cuts or hyd~o~enated derivatives of such fatty amines.
Also, mixL~le-~ of amine reactants can be used in the process for preparing the pyrrolidone compounds.
Generally, the C6 to C14 alkyl pyrrolidones have been found to display primarily surfactant properties.
It is also important that the surfactant or mixture of surfactants which are utilized are low foaming such that the aqueous cleaning solution formed from the aqueous compositions of the present invention are overall low foaming. It is important also that any foam which is formed swiftly coll~p~e~. The present applicants have developed a foam test which is described in the examples which can be used to determine which compositions are useful in aqueous solution and can be characterized as low foaming. This test is easily performed with conventional equipment and can be utilized to form a foaming and foam collapse scale to characterize the cleaning solutions of the present invention. Figure 1 sets forth in the shaded area between points X, Y, and Z, the foaming characteristics of the useful cleaners of this invention. In general, aqueous solutions containing up to 20 wt.% of the composition of this invention should have maximum foam height of about 250 ml and collapse within 5 W096/09~6 ~ 7 ~ ~ PCT~S95108976 minutes according to the foaming and foam collapse test described in Example I below.
The aqueous metal cleaning compositions of the present invention comprising the alkalinity providing agent and the surfactant or mixture of surfactants also preferably include other adjuvants such as co~o~ion inhibitors, polymeric stabilizing agents and hyd~uLropes to maintain the active ingredients of the composition in aqueous solution.
Particularly useful corrosion inhibitors which can be added to the aqueous metal cleaning compositions of this invention include magnesium and/or zinc ions. Preferably, the metal ions are provided in water soluble form. Examples of useful water soluble forms of magnesium and zinc ions are the water soluble salts thereof including the chlorides, nitrates and sulfates of the respective metals. If the alkalinity providing agents are the alkali metal carbonates, bicarbonates or mixtures of such agents, magnesium oxide can be used to provide the Mg ion. The magnesium oxide is water soluble in such solutions and is a preferred source of Mg ions.
The magnesium oxide appears to reduce coloration of the metal substrates even when compared with the chloride salt.
In order to maintain the dispersibility of the magnesium and/or zinc corrosion inhibitors in aqueous solution, in particular, under the mildly alkaline pH conditions most useful in this invention and in the presence of agents which would otherwise cause precipitation of the zinc or magnesium ions, e.g., carbonates, phosphates, etc., it has been Wos6/o9366 PCT~S95/08976 found advantageous to include a carboxylated polymer to the solution.
The carboxylated polymers may be generically categorized as water-soluble carboxylic acid polymers such as polyacrylic or polymethacrylic acids or vinyl addition polymers. Of the vinyl addition polymers contemplated, maleic anhydride copolymers as with vinyl acetate, styrene, ethylene, isobutylene, acrylic acid and vinyl ethers are examples.
All of the above-described polymers are water-soluble or at least colloidally dispersible in water. The molecular weight of these polymers may vary over a broad range although it is preferred to use polymers having average molecular weights ranging between 1,000 up to 1,000,000. In a preferred emho~iment of the invention these polymers have a molecular weight of lOO,OoO or less and, most preferably, between 1,000 and 10,000.
The water-soluble polymers of the type described above are often in the form of copolymers which are contemplated as being useful in the practice of this invention provided they contain at least 10% by weight of -C-OM
y~ G~ where M is hydrogen, alkali metal, ammonium or other water-solubilizing radicals. The polymers or copolymers may be prepared by either addition or hydrolytic techniques. Thus, maleic anhydrided copolymers are prepared by the addition polymerization of maleic anhydride and another comonomer such as styrene. The low molecular weight Wog6109366 ~ 7 4 7 PCT~S95/08976 acrylic acid polymers may be prepared by addition polymerization of acrylic acid or its salts either with itself or other vinyl comonomers.
Alternatively, such polymers may be prepared by the alkaline hydrolysis of low molecular weight acrylonitrile homopolymers or copolymers. For such a preparative tec-hnique see Newman U.S. Pat.
No. 3,419,502.
Especially useful maleic anhydride polymers are selected from the group consisting of homopolymers of maleic anhydride, and copolymers of maleic anhydride with vinyl acetate, styrene, ethylene, isobutylene, acrylic acid and vinyl ethers. These polymers can be easily prepared according to standard methods of polymerization.
The carboxylated polymers aid in maintAin1ng the magnesium and zinc compounds in solution, thereby preventing the precipitation of the corrosion inhibitor from solution and consequent degradation of ~o~lG-ion protection. Further, the carboxylated polymer aids in preventing water-ha~ln-~c precipitation and scaling on the cleaning equipment surfaces when the cleaning compositions of this invention are used in hard water.
The hydrotropes useful in this invention include the sodium, potassium, ammonium and alkanol ammonium salts of xylene, toluene, ethylbenzoate, isG~Lu~ylbenzene, naphthalene, alkyl naphthalene sulfonates, phosphate esters of alkoxylated alkyl phenols, phosphate esters of alkoxylated alcohols and sodium, potassium and ammonium salts of the - alkyl sarcosinates. The hydrotropes are useful in maintaining the organic materials including the w096/09366 PCT~S95/08976 2 ~ ~ ~ 7 ~ 7 surfactant readily dispersed in the aqueous cleaning ~olution and, in particular, in an aqueous concentrate which is an especially preferred form of packaging the compositions of the invention and allow the user of the compositions to accurately provide the desired amount of cleaning composition into the aqueous wash solution. A particularly preferred hydrotrope is one that does not foam.
Among the most useful of such hydrotropes are those which comprise the alkali metal salts of intermediate chain length monocarboxylic fatty acids, i.e., C7-C13. Particularly preferred are the alkali metal octanoates and nonanoates.
The metal cleaning compositions of this invention comprise from about 20 to 80 wt.% based on the dry components of the alkalinity providin~
agent, 5 to 50 wt.%, preferably, 10 to 30 wt.%
surfactant, 0 to 10 wt.%, preferably, 0.5 to 5 wt.%
of the corrosion inhibitor compound, 0-5 wt.%, preferably, 0.3 to 2 wt.% of the carboxylated polymer and 0-30 wt.%, preferably, 2-25 wt.% of the hyd.o~.ope. The dry composition is used in the aqueous wash solution in amounts of about 0.1-20 wt.%. preferably from about 0.2-5 wt.%.
Most preferably, the metal cleaning compo~itions of the present invention are provided and added to the wash bath as an aqueous concentrate in which the dry components of the composition comprise from about 5-40 wt.% of the concentrate and, most preferably, from about 10-20 wt.%.
The aqueous concentrates of this invention preferably comprise 60-90% deionized water, 5-15 wt.% alkaline salts, and 2-10 wt.% surfactant, along W096/09366 ~ PCT~S95/08976 , _ with the optional ingredients comprising 1-5 wt.% of the hydLoLLupe, 0.05-5 wt.% of the corrosion inhibitor and 0.05-1 wt.% of any polymeric A i ~srersant .
The aqueous metal cleaning solutions of the ~L~-~nt invention are useful in removing a variety of contaminants from metal substrates as previously described. A useful method of cleaning such metal parts is in a parts washer. In parts washers the metal parts are contacted with the aqueous solution either by immersion or some type of impingement in which the aqueous cleaning solution is circulated or continuously agitated against the metal part or is sprayed thereon. Alternatively, agitation can be provided as ultrasonic waves. The cleaning solution is then filtered and recycled for reuse in the parts washer.
For best use, the aqueous cleaning solutions of this invention should be at an elevated temperature typically ranging from about 90-180F.
The contact time of the aqueous cleaning solution with the metal substrates including metal engine parts will vary deren~ing upon the degree of contamination but broadly will range between about 1 minute to 30 minutes with 3 minutes to 15 minutes being more typical.
F~YAMPLE 1 In this example, the foaming characteristics of compositions within the scope of the present invention were compared with the foaming characteristics of a control composition and several commercial aqueous cleaners. The control and test samples (wt.%) are set forth in Table 1 below. The commercial cleaners were Brulin 815 GD and QR~, phQcr~te-based cleaners containing a high level of Wos6/o9366 PCT~S95/08976 ~ 2 ~Q ~ 7 ~ 7 surfactant and Daraclean 235 and 282~ (W.R. Grace) which contain organic solvents.

A B C
(Control) DI water 82.47582.475 82.475 Sodium bicarbonate 4.5 4.5 4.5 Potassium carbonate 3.0 3.0 3.0 Sodium carbonate 2.2 2.2 2.2 Magnesium oxide 0.0750.075 0.075 Acrylic acid polymer~ 0.25 0.25 0.25 Sodium nonanoate 3.0 3.0 3.0 Ethoxylated thioether2 - 1.0 (Alcodet 260) 15 Ethoxylated-propoxylated 3.0 l.0 alcohol (LF-92) E0-P0-E0 Block copolymer - 1.0 (LF-120) N-octyl pyrrolidone 1.5 1.5 3.0 (LP-100) 1. A polycarboxylated copolymer containing acrylic and maleic acid units and having a molecular weight of about 4,500.
2. Ethoxylated dodecyl mercaptan (6 ethylene oxide units).

A foam test was devised which represents the agitation which would be found in a particular preferred method utilizing the solution in which the cleaning solution is in agitated contact with the metal substrates. The results of the foam testing are set forth in Figure 1. The shaded area between points X, Y, and Z, represents the desired foaming WO g6/09366 ~ ~ PCT/US95/08976 characteristics of aqueous cleaning compositions useful in the present invention when used in amounts of 0.5-20 wt.% in aqueous solution.
The foam and foam collapse test was as follows:
A 500ml graduated cylinder was placed inside a 2000ml beaker which contained a water level higher than the 100ml mark on the graduated cylinder. This apparatus was placed on a digital Cole-Parmer stir/hot plate, which contained a temperature probe. The temperature probe was immersed in the test solution within the graduated cylinder and heated to the desired temperature (160F-180F). An air cylinder equipped with a medical regulator (2-50 l/min), a flow meter (0.02-2.1 l/min) and a length of Tygon tubing rigged with a gas dispersion tube, fitted with a fritted glass disc (coarse porosity), was used to disperse the air in a stream of fine bubbles.
In the 500ml graduated cylinder was added 100ml of test solution diluted (10X) with water (vol.). The temperature probe was inserted and heated to the desired temperature (160-180F).
Once the temperature had been reached, the air was ~;r~nced at a rate of 3 l/min, in order to generate foam.
Foam height was measured by reading the total milliliters of foam at specified timed inter~als. Each lOOml of foam height is equivalent to 2.31 inches.
As can be seen from Figure 1, the cleaners of the present invention designated as B and C had a foam height less than about 25 ml. and were fully coll~p~e~ in 1 min. subsequent to the turnoff of the air. In comparison, the Brulin~ commercial cleaners WO g6/Og366 PCI~/US95108976 7 ~ 7 were substantially greater foaming and took a substantially longer time for the foam collapse.
The Daraclean 282~ cleaner was also very low foaming. Daraclean 235~ had high initial foaming with a fast foam collapse time. However, it is noted that the Daraclean cleaners contain organic solvents and substantially emulsify the dirt, grease or oil removed from treated substrates and are, therefore, not as useful as the cleaners of the present invention. Control Sample A using only an ethoxylated-propoxylated alcohol as surfactant foamed too much and had a long collapse time.

In this Example, aqueous cleaning formulations B and C of Example 1 were tested for cleaning ability and again compared with the cleaning ability of the two commercial cleaners Brulin 815 GD~ and Daraclean 235~ and control A of Example I.
The formulations A, B and C of Table 1 and the commercial cleaners received as concentrates were diluted (lOx) with water and the solutions heated to 160F.
A soil mix was made of 1/2 part used motor oil and 1/2 part axle grease and a small amount of carbon black. Approximately 1 gram of the mixed soil was applied to a metal mesh screen. The metal mesh screen was immersed in the heated cleaning solutions and periodically taken from these solutions and weighed to determine the amount of soil removal. The results are shown in Figure 2 in which each of the data points represents the mean of three measurements.
As can be seen from Figure 2, the aqueous cleaners of the present invention yielded wo g6/09366 ~ 7 Pcr~US95/08976 substantially improved results after the two minutes of eleAn1ng, eompared with the eontrol and the two eommereial produets.

In this Example, the Sample B whieh is set forth in Table 1 of Example 1 was tested to determine its ability to elean after repeated treatments to remove eontaminants.
A soil mix was made of 1/2 part used motor oil and 1/2 part axle grease and a small amount of earbon blaek. Approximately 1 gram of the mixed soil was applied to a metal mesh screen.
lOOml of the eoncentrate (Sample B) was diluted (lOX) to lOOOml with tap water and heated to about 160F. The metal mesh screen was immersed in the heated cleaning solution for approximately 3 to 4 min. and taken from the solution for weighing to determine the amount of soil removal. This is represented by the "initial oil removal"-set forth in Table 2 below.
20 grams of WD 40 motor oil and 20 grams of the soil mix described above was added to the heated test solution. The amount of eontaminants added to the solution represents approximately 4-6 weeks of heavy eleaning. The metal mesh was again immer~ed in the solution for 3-4 min., removed and weighed to determine the amount of oil removal.
This re~ ?nts the "final oil removal" as set forth in Table 2 below.
The solution was allowed to eool to room temperature and the top oil layer was removed. The - solution was then filtered through a eombination of Celite, PM-100~ and Polymin PR 8515~ (a BASF
eationie polymer). The treated solution was then Le~ ded for weight, pH, and conductance. Makeup W096/~366 P~l/u~5S/08976 ~ ~ ~ V 7 4 7 solution was then added based on a 1/10 dilution with tap water to 1000ml and heated to working temperature. The above represents one cleaning cycle. Four of such cleaning cycles were repeated and the results of cleaning are set forth in Table 2 below.
TART~ 2 Initial % Final % Solution oil oil Conductivity cycle # removal removal Mills-Siemans pH
1 99 50 12 9.4 2 93 42 13.6 9.3 3 90 39 18.2 9.3 4 97 35 20.3 9.3 lg The addition of the oil and soil mix to the cleaning solution for each cycle was meant to simulate approximately 4-6 weeks of cleaning. As can be seen, the solution was able to maintain its cleaning ability throughout the test.

In this example, the emulsification properties of various cleaning solutions were compared. All solutions were diluted (10X) in DI
water. The following products were tested:
(D) Brulin 815 GD~, (E) Brulin 815 QR~, (F) invention cleaner (see Table 3), (G) Grace Daraclean 235~ and (H) Grace Daraclean 282~. The solutions were heated to 120F and 94 mls of liquid were drawn off and directed into a preheated 100 ml graduated cylinder. 6 mls of 10W40 Motor Oil were added to the cylinder and the cylinder capped. The capped cylinder was vigorously shaken for 30 seconds and allowed to stand. Mls. of the layers that formed at 3, 6, and 10 minutes were recorded. Results are shown in Table 4.

wo g6/09366 ~ 7 PCT~S95/~97~

TART~ 3 S~MPT~ F
wt%
Deionized water 79.580 5 Sodium bicarbonate 4.480 Potassium carbonate 2.900 Sodium carbonate 2.220 Magnesium oxide 0.074 Carboxylated Polymer1 0.250 10 Sodium nonanoate 6.000 Alcodet 260 3.000 LP 100 1.500 Acrylic acid/Maleic anhydride copolymer having a molecular weight of about 4,500.

Samples D E F G H
LaYer voLume in mls 3 min.
Top 7-cloudy 3-cloudy 7-cloudy 3-cloudy 4-cloudy Bottom 92 96 93 97 96 Foamy Foamy 6 m~n.
Top 10-cloudy 6-cloudy 7-cloudy 4-cloudy 4-cloudy Bottom 90 93 93 96 96 Foamy Foamy 10 min.
Top 10-cloudy 10-cloudy 7-cloudy 4-cloudy 6-cloudy Bottom 90 93 96 94 Foamy Foamy The results show that 3 minutes after mixing 6 mls of Motor Oil with present inventive Sample F, a 7 ml oily layer, which represents essentially all of the oil added, separates off. It may be noted that because of the increased oil W096/09366 ~ 7 PCT~S95/08976 volume over the amount added it appears that about 14% water remains trapped in the oil phase.
In ~nLLast, 3 minutes after mixing with water solutions of either Brulin 815 QR~, Daraclean 235~ or Daraclean 282~, only about 1/2 of the oil separates off, the balance of the oil remaining emulsified in the water phase.
With Brulin 815 GD~, 7 mls of oil separates off after 3 minutes. However, an additional 3 mls of oil phase separates off after a further 3 minutes to a final volume of 10 mls. This indicates that the oil remains trapped in the water phase for a longer period than with the formula of the present invention. It also shows that once the oil does separate off, it contains about 3 times as much water emulsified in it as compared to the amount obtained with the inventive formulation.
This will make the oil phase more difficult to treat, i.e., there will be a greater volume to dispose of as waste, or it will take more treatment to recover the pure oil from the oil phase if so desired.

Claims

WHAT IS CLAIMED:
2. The composition of claim 46 providing a pH of from 8.0 to less than 11.0 when present in amounts of 0.5 to 20 wt.% in aqueous solution.
3. The composition of claim 2 providing a pH of from about 8.0 to 10.0 when present in amounts of 0.5 to 20 wt.% in aqueous solution.
4. The composition of claim 46 wherein said alkaline salts comprise alkali metal carbonates, alkali metal bicarbonates or a mixture thereof.
5. The composition of claim 46 wherein said surfactants consist essentially of an ethoxylated compound and an ethoxylated-propoxylated compound.
6. The composition of claim 46 being silicate free.
7. The composition of claim 46 further containing magnesium and/or zinc ions and 0 to 2 wt.% of a carboxylated polymer.
9. The solution of claim 47 having a pH
of from 8.0 to less than 11Ø
10. The solution of claim 9 having a pH
of from about 8.0 to 10Ø
11. The solution of claim 47 wherein said alkaline salts comprise alkali metal carbonates, alkali metal bicarbonates or mixtures thereof.
12. The solution of claim 47 wherein said surfactants consist essentially of an ethoxylated compound and an ethoxylated-propoxylated compound.

13. The solution of claim 47 being silicate free.
14. The solution of claim 47 further containing magnesium and/or zinc ions and 0 to 2 wt.% of a carboxylated polymer.
16. The concentrate of claim 48 having a pH of from 8.0 to less than 11Ø
17. The concentrate of claim 16 having a pH of from about 8.0 to 10Ø
18. The concentrate of claim 48 wherein said alkaline salts comprise alkali metal carbonates, alkali metal bicarbonate or a mixture thereof.
19. The concentrate of claim 48 wherein said surfactants consist essentially of an ethoxylated compound and an ethoxylated-propoxylated compound.
20. The concentrate of claim 19 wherein said surfactants consist essentially of an ethoxylated thiol surfactant having 3-20 ethylene oxide groups.
21. The concentrate of claim 20 wherein said ethoxylated thiol has 7-20 carbon atoms and is ethoxylated with 3-15 ethylene oxide units.
22. The concentrate of claim 48 comprising 60-90 wt.% water, 5-15 wt.% of said alkaline salts and 2-10 wt.% of said surfactant.
23. The concentrate of claim 22 further including a corrosion inhibitor.
24. The concentrate of claim 23 wherein said corrosion inhibitor is selected from the group consisting of magnesium ions, zinc ions and mixtures thereof.
25. The concentrate of claim 24 wherein said corrosion inhibitor comprises magnesium ions.
26. The concentrate of claim 25 wherein said magnesium ions are provided in the form of magnesium oxide and said alkaline salts comprise alkali metal carbonate salts, alkali metal bicarbonate salts or mixtures of said salts.
27. The concentrate of claim 22 further including a hydrotrope.
28. The concentrate of claim 27 wherein said hydrotrope comprises an alkali metal salt of a linear C7-C13 carboxylic acid.
29. The concentrate of claim 48 being silicate free.
30. The concentrate of claim 28 wherein said surfactants consist essentially of an N-alkylpyrrolidone.
31. A method of cleaning metal substrates so as to remove contaminants therefrom comprising:
contacting said metal substrates with an aqueous cleaning solution comprising 0.5-5 wt.% of an organic solvent-free cleaning composition containing at least one alkaline salt and 10-30 wt.% of surfactants based on dry components of the cleaning composition, said surfactants consisting essentially of non-phenolic alkoxylated nonionic surfactants, N-alkyl pyrrolidones and mixtures thereof, said solution being characterized as having a pH of between about 7.5 and 11, being low emulsifying so as to allow the ready formulation of distinct and substantially complete separated contaminant phase from said aqueous solution, and having a foam height and foam collapse time within the area bounded by points X, Y and Z of Figure 1, said contacting being for a sufficient time to remove said contaminants from said substrate and removing said substrate from said solution.
32. The method of claim 31 wherein said solution has a pH of from 8.0 to less than 11Ø
33. The method of claim 32 wherein said solution has a pH of from about 8.0 to 10Ø
34. The method of claim 31 wherein said alkaline salts comprise alkali metal carbonates, alkali metal bicarbonates and mixtures thereof.
35. The method of claim 31 wherein said surfactants consist essentially of an ethoxylated and an ethoxylated-propoxylated compound.
36. The method of claim 34 wherein said surfactants consist essentially of an ethoxylated and an ethoxylated-propoxylated compound.
37. The method of claim 31 wherein said metal substrates are contacted with said cleaning solution by immersion, impingement or both.
38. The method of claim 37 wherein said metal substrates are separated from said cleaning solution and said aqueous cleaning solution is reused to clean additional metal substrates.
39. The method of claim 37 wherein said metal substrates are sprayed with said aqueous cleaning solution.

40. The method of claim 31 wherein said aqueous cleaning solution is at a temperature of from about 90-180°F.
41. The method of claim 31 wherein after said substrates are removed from said cleaning solution, said cleaning solution is treated to separate from said aqueous solution contaminants removed from said metal substrates and said aqueous solution is then contacted with additional metal substrates.
42. The method of claim 41 wherein said aqueous solution is treated to remove said contaminants by filtering said aqueous cleaning solution.
43. The method of claim 31 wherein said composition is silicate free and essentially free of phosphate.
45. he method of claim 31 wherein said composition further includes a hydrotrope comprising an alkali metal salt of a linear C7-C13 carboxylic acid.
46. An organic solvent-free metal cleaning composition comprising at least one alkaline salt and 10-30 wt.% of total surfactants based on dry components of the cleaning composition, said surfactants consisting essentially of non-phenolic alkoxylated nonionic surfactants, N-alkyl pyrrolidones and mixtures thereof, an aqueous solution containing 0.5 to 20 wt.% by dry weight of said composition being characterized as having a pH
of between about 7.5 an 11, being low emulsifying so as to allow the ready formation of a distinct and substantially complete separated contaminant phase from said aqueous solution and having a foam height and foam collapse time in the area bounded by points X, Y, and Z of Figure 1, wherein the aqueous cleaning composition is free of phosphate.
47. An aqueous cleaning solution comprising 0.5 to 20 wt.% by dry weight of an organic solvent-free metal cleaning composition containing at least one alkaline salt and 10-30 wt.%
of total surfactants based on the dry weight of the cleaning composition, said surfactants consisting essentially of non-phenolic alkoxylated nonionic surfactants, N-alkyl pyrrolidones and mixtures thereof, said solution being characterized as having a pH of between about 7.5 and 11, being low emulsifying so as to allow the ready formation of a distinct and substantially complete separated contaminant phase from said aqueous solution and having a foam height and foam collapse time in the area bounded by points X, Y, and Z of Figure 1, wherein the aqueous cleaning solution is free of phosphate.
48. An aqueous cleaning concentrate comprising 60 to 90 wt.% water and 10-40 wt.% by dry weight of an organic solvent-free metal cleaning composition containing at least one alkaline salt and 10-30 wt.% of total surfactants based on the dry weight of the cleaning composition, said surfactants consisting essentially of non-phenolic alkoxylated nonionic surfactants, N-alkyl pyrrolidones and mixtures thereof, an aqueous solution containing 0.5 to 20 wt.% of said composition being characterized as having a pH of between about 7.5 and 11, being low emulsifying so as to allow the ready formation of a distinct and substantially complete contaminant phase from said aqueous solution and having a foam height and form collapse time in the area bounded by points X, Y, and Z of Figure 1, wherein the aqueous cleaning concentrate is free of phosphate.