CA2166300C

CA2166300C - Aqueous lubricant and surface conditioner for formed metal surfaces

Info

Publication number: CA2166300C
Application number: CA002166300A
Authority: CA
Inventors: James P. Bershas; Timm L. Kelly; Gary L. Rochfort; Henry A. Rossmaier
Original assignee: Henkel Corp
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-07-13
Filing date: 1994-01-04
Publication date: 2003-10-21
Anticipated expiration: 2014-01-04
Also published as: JPH09500408A; CN1203265A; EP0708812A1; SG79190A1; PL180724B1; BR9407122A; CN1066483C; CN1127010A; AU6082094A; AU683047B2; CA2166300A1; PL312564A1; EP0708812A4; CN1044716C; WO1995002660A1

Abstract

A lubricant and surface conditioner for formed metal surfaces, particularly aluminum and tin beverage containers, reduces the coefficient of static friction of said metal surfaces and enables drying sai d metal surfaces at a lower temperature. The conditioner includes (i) a water-soluble organic material selected from amine oxides and quaterna ry ammonium salts, ethoxylated castor oil derivatives, a nd imidazoline moiety-containing phosphonates and preferably also includes (ii) at least one of fluozirconate, fluohafnate, or fluotita nate ion, and (iii) phosphate and/or nitrate ions. Good resistance to damaging the fri ction reducing effect by overheating and to staining of the domes of treated containers during pasteurization can be achieved.

Description

WO 95/02660 , ' , ~ ' ; 216 b 3 Q ~ PCT/US94/00024 Description AQUEOUS LUBRICANT AND SURFACE CONDITIONER FOR
FORMED METAL SURFACES
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to processes and compositions which accomplish at least one, and most preferably all, of the following related objectives when applied s to formed metal surfaces, more particularly to the surfaces of cleaned aluminum and/or tin plated cans: (i) reducing the coefficient of static friction of the treated surfaces after drying of such surfaces, without adversely affecting the adhesion of paints or lacquers applied thereto; (ii) promoting the drainage of water from treated WO 95/02660 ~ ~ ~ PCT/US94/00024 surfaces, without causing "water-breaks", i.e., promoting drainage that results in a thin, continuous film of water on the cans, instead of distinct water droplets separat-ed by the relatively dry areas called "water-breaks" between the water droplets; and (iii) lowering the dryoff oven temperature required for drying said surfaces after they s have been rinsed with water.
Discussion of Related Art The following discussion and the description of the invention will be set forth primarily for aluminum cans, as these represent the largest volume area of applica-tion of the invention. However, it is to be understood that, with the obviously neces-,o sary modifications, both the discussion and the description of the invention apply al-so to tin plated steel cans and to other types of formed metal surfaces for which any of the above stated intended purposes of the invention is practically interesting.
Aluminum cans are commonly used as containers for a wide variety of prod-ucts. After their manufacture, the aluminum cans are typically washed with acidic ,s cleaners to remove aluminum fines and other contaminants therefrom.
Recently, en-vironmental considerations and the possibility that residues remaining on the cans following acidic cleaning could influence the flavor of beverages packaged in the cans has led to an interest in alkaline cleaning to remove such fines and contami-nants. However, the treatment of aluminum cans with either alkaline or acidic clean-ers generally results in differential rates of metal surface etch on the outside versus on the inside of the cans. For example, optimum conditions required to attain an aluminum fme-free surface on the inside of the cans usually leads to can mobility problems on conveyors because of the increased roughness on the outside can sur-face.
is Aluminum cans that lack a low coefficient of static friction (hereinafter often abbreviated as "COF") on the outside surface usually do not move past each other and through the trackwork of a can plant smoothly. Clearing the jams resulting from failures of smooth flow is inconvenient to the persons operating the plant and costly because of lost production. The COF of the internal surface is also important when the cans are processed through most conventional can decorators. The operation of these machines requires cans to slide onto a rotating mandrel which is then used to transfer the can past rotating cylinders which transfer decorative inks to the exterior WO 95102660 j ~ ~ PCT/LTS94/00024 surface of the cans. A can that does not slide easily on or off the mandrel can not be decorated properly and results in a production fault called a "printer trip". In ad-dition to the misloaded can that directly causes such a printer trip, three to four cans before and after the misloaded one are generally lost as a consequence of the me-s chanics of the printer and conveyor systems. Jams and printer trips have become in-creasingly troublesome problems as line speed have increased during recent years to levels of about 1200 to 1500 cans per minute that are now common. Thus, a need has arisen in the can manufacturing industry, particularly with aluminum cans, to modify the COF on the outside and inside surfaces of the cans to improve their mo-,o bility.
An important consideration in modifying the surface properties of cans is the concern that such modification may interfere with or adversely affect the ability of the can to be printed when passed to a printing or labeling station. For example, after cleaning the cans, labels may be printed on their outside surface, and lacquers may be sprayed on their inside surface. In such a case, the adhesion of the paints and lacquers is of major concern. It is therefore an object of this invention to im-prove mobility without adversely affecting adhesion of paints, decorating inks, lac-quers, or the like.
In addition, the current trend in the can manufacturing industry is directed to-ward using thinner gauges of aluminum metal stock. The down-gauging of alumi-num can metal stock has caused a production problem in that, after washing, the cans require a lower drying oven temperature in order to pass the column strength pressure quality control test. However, lowering the drying oven temperature result-ed in the cans not being dry enough when they reached the printing station, and is caused label ink smears and a higher rate of can rejects.
One means of lowering the drying oven temperature would be to reduce the amount of water remaining on the surface of the cans after water rinsing.
Thus, it is advantageous to promote the drainage of rinse water from the treated can surfaces.
However, in doing so, it is generally important to prevent the formation of surfaces with water-breaks as noted above. Such water-breaks give rise to at least a percep-lion, and increase the possibility in reality, of non-uniformity in practically important properties among various areas of the surfaces treated.

WO 95/02660 . ~ 216 6 3 0 0 PCTIUS94/00024 Thus, it is desirable to provide a means of improving the mobility of alumin-um cans through single filers and printers to increase production, reduce line jam-mings, minimize down time, reduce can spoilage, improve or at least not adversely affect ink laydown, and enable. lowering the drying oven temperature of washed s cans.
In the most widely used current commercial practice, at least for large scale operations, aluminum cans are typically subjected to a succession of six cleaning and rinsing operations as described in Table 1 below. (Contact with ambient temperature tap water before any of the stages in Table 1 is sometimes used also; when used, this ,o stage is often called a "vestibule" to the numbered stages.) Table 1 STAGE ACTION ON SURFACE DURING STAGE
NUMBER

1 Aqueous Acid Precleaning 2 Aqueous Acid and Surfactant Cleaning 3 Tap Water Rinse 4 Mild Acid Postcleaning, Conversion Coating, or Tap Water Rinse Tap Water Rinse 6 Deionized ("DI") Water Rinse It is currently possible to produce a can which is satisfactorily mobile and to which subsequently applied inks and/or lacquers have adequate adhesion by using suitable surfactants either in Stage 4 or Stage 6 as noted above. Preferred treatments for use in Stage 6 are described in U. S. Patents 4,944,889 and 4,859,351, and some of them are commercially available from the Parker+Amchem Division of Henkel Corporation (hereinafter often abbreviated as "P+A") under the name "Mobility Enhancer~'~'' 40" (herein often abbreviated "ME-40~").
However, many manufacturers have been found to be reluctant to use chemi-cals such as ME-40~ in Stage 6. In some cases, this reluctance is due to the pres-ence of a carbon filter for the DI water (normal Stage 6) system, a filter that can be-come inadequately effective as a result of adsorption of lubricant and surface condi-WO 95/02660 216 6 3 PCT~S94/00024 UO
tioner forming additives such as those in ME-40~; in other cases, it is due to a re-luctance to make the engineering changes necessary to run ME-40.
For those manufacturers that prefer not to add any lubricant and surface con-ditioner material to the final stage of rinsing but still wish to achieve the advantages s that can be obtained by such additions, alternative treatments for use in Stage 4 as described above have been developed and are described in U. S. Patents 5,030,323 and 5,064,500. Some of these materials are commercially available from P+A
under the name FIXODINE~ 500.
However, the reduction in coefficient of friction provided by prior art treat-,o ments in either Stage 4 or Stage 6 can be substantially reduced, often to an unaccept-able level, if the treated cans are subjected to extraordinary heating after completion of the six process stages described above. Such extraordinary heating of the cans in the drying oven occurs whenever a high speed production line is stalled for even a few minutes, an event that is by no means rare in practice. In practical terms, the ,s higher COF measurements correlate with the loss of mobility, thereby defeating the purpose of introducing mobility enhancing surfactants into can washing formulations.
Accordingly, it is an object of this invention to provide means of improving the mo-bility of aluminum cans and/or one of the other objects stated above that are superior to means taught in the prior art, particularly with respect to stability of the beneficial effects to heating well beyond the minimum extent necessary for drying the treated surfaces.
Also, some beverages packaged in aluminum cans are pasteurized, and unless the temperature and the compositions) of the aqueous solutions) with which cans are contacted during pasteurization are very carefully controlled, staining of the is dome of the can often occurs during pasteurization. It is a further object of this in-vention to provide compositions and methods suitable for use in reducing coefficient of friction that will also resist such dome staining during pasteurization.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all num-bers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about" in describing the broad-est scope of the invention. Practice within the numerical limits given, however, is generally preferred.
Also, unless there is an explicit statement to the contrary, the description be-low of groups of chemical materials as suitable or preferred lfor a particular ingred-ient according to the invention implies that mixtures of two or more of vthe individual s group members are equally as suitable or preferred as the indiividual members of the group used alone. Furthermore, the specification of chemical materials in ionic form should be understood as implying the presence of some counterions as necessary for electrical neutrality of the total composition. In general, such counterions should first be selected to the extent possible from the ionic materials specified as part of ,o the invention; any remaining counterions needed may generall~~ be selecvted freely, ex-cept for avoiding any counterions that are detrimental to the objects of the invention.
Summary of the Invention In accordance with this invention, it has been found that a lubricant and sur-face conditioner applied to aluminum cans after washing enhances their mobility and, ~s in a preferred embodiment, improves their water film drainage; and evaporation char-acteristics as to enable lowering the temperature of a drying oven by from about 25°
to about 38° C without having any adverse effect on the label, printing process. The lubricant and surface conditioner reduces the coefficient of stiitic friction on the out-side surface of the cans, enabling a substantial increase in production line speeds, 2o and in addition, provides a noticeable improvement in the rate of water film drainage and evaporation resulting in savings due to lower energy demands vvhile meeting quality control requirements.
Various embodiments of the invention include a concentrated lubricant and surface conditioner forming composition as described above; a solution of such a 2s composition in water, optionally with additional acid or base to adjust the pH value, suitable as the complete composition for contacting a metal surface;, in Stage and/or Stage 6 of a six stage cleaning and rinsing process a<c describe;d above; and processes including contacting a metal surface, particularly an aluminum surface, with an aqueous composition including the ingredients of thE; lubricant and surface conditioner forming composition specified in detail above.

According to one aspect of the p;=esent invention, there is provided a process comprising steps of (i) cleaning a formed metal container, preferably an aluminum can or tin-plated steel can, with an aqueous acidic or alkaline cleaning solution, (ii) subsequently contacting a.t least one exterior surface of the cleaned metal container with an aqueous lubricant and surface conditioner i=orming composition, (iii) drying the metal container after steps (i) and (ii), and (iv) subsequently conveying the cleaned and dried can via automatic conveying equipment to a location where it is lacquered or decorated by printing or both, characterized in that the aqueous lubricant and surface conditioner comprises at least one of the following groups of constituents: (I) fluozirconic acid and one or more ethoxylated castor oil derivatives in amounts sufficient to impart to the dome of a can treated therewith staining resistance during subsequent pastE:urization of the contents of the can; (II) (A) a dissolved phosphorus containing surfactant component that is a mixture of molecules conforming to the general formula I:
/( 0-Y-R ) x 0=p (I) , \(OM)y where M is selected from the group consisting of H, alkali metal rations, monovalent fractions of alkaline earth metal rations, and monovalent fractions of ammonium and substituted ammonium rations; x = 1 or 2 and y = 3-x; Y is an alkylene or alkylene ether group, which may be branched or unbranched, with its open valences on carbon atoms and with from 2 to 12 carbon atoms and up to 3 oxygen atoms; and R is an imidazoline moiety conforming to general f=ormula II:
6a (II) , N ~ N~

R -~-R

where each of R1 and R2 is independently selected, except that R1 and R2 may not both be hydrogen, from the group consisting of hydrogen, a moiety derived from propionitrile by removing a hydrogen atom from the -CH3 group thereof, and moieties of the general formula ILI:
-CHzCHzll Q
O (III), where Q is selected from the group concisting of -OM, -NH2, and -OR4, where M has the same meaning as defined above and R4 represents a C2-la alkyl, alkyl aryl, or al_kylcycloaliphatic moiety; and R3 is selected from the group consisting of unsubstituted and hydroxy substituted aliphatic and cycloaliphatic and alkylaryl moieties having from 2 to 22 carbon atoms; (B) a component selected from the group of water soluble salts containing ions that comprise atoms selected from the group consisting of Zr, Ti, Sn, Al, and Fe; (C) a metal etching component; and (D) "free fluoride ions"; and, optionally, any one or more of the fo~Llowing:
(E) a component selected from molecules conforming to general formula IV:

R6-0-(-C H-C H 2-0 ) s-X ( Iv) , 6b wherein R6 is a linear, cyclic, or branched. saturated monovalent aliphatic hydrocarbon moiety containing from 1 to 25 carbon atoms; X is selected from the group consisting of hydrogen, halogen, phenyl, and R5; s is an integer from 1 to 50; and R5 is selected from the group consisting of hydrogen and alkyl groups containing 1 - 4 carbon atoms; (F) a component selected from molecules conforming to general formula V:

1o R~ (C6H4)-0-(-CH-CHz-0) s-H (v) .
wherein R' is a linear, cyclic, or branched saturated monovalent aliphatic hydrocarbon moiety containing from 4 to 25 carbon atoms; (C6H4) is an ortho-, meta-, or para-phenylene nucleus; and RS and s have the same meaning as for formula IV; (G) a component selected from molecule s conforming to general formula VI:

R$-C-0-(-C H-C H z-0 ) s-H ( VI ) , wherein R$ is a linear or branched, saturatE:d or unsaturated monovalent aliphatic hydrocarbon moiety containing from 1 to carbon atoms; and RS and s have the same meaning as in formula IV; (H) a component selected from clzelating agents for the metal containing ions of component (II)(B); and (J) an antimicrobial agent; (III) (A) a component selected from 25 the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I:

R2-N+ R3 fX )a R4 (I) , 6c where R1 is a monovalent aliphatic moiety, which 'may be saturated or unsaturated and contains from 8 to 22 carbon atoms; each of R2 and R3 is a monovalent moiety independently selected from the group consisting of (i) alkyl a.nd hydroxyalkyl moieties having from 1 to 8 carbon atoms and (ii) aryl and arylalkyl moieties having from 6 to 10 carbon atoms; R4 is a monovalent moiety selected from the same group as for RZ and R3 plus the -O- moiety; X- is a monovalent anion or monovalent fraction of an anion with a zralence higher than 1; and a = 0 i f R4 i s -O- and = 1 i f R'~ i s not -O- ; and (B) a component of complex fluoride anions; and, optionally but preferably, (C) a component of phosphate ions, optionally also including sulfate or nitrate ions or both;
and, optionally, (D) aluminate anions, including fluoroaluminate anions; and, optionally (E) aluminum canons, including complex fluoroaluminum cations, and, optionally, one or both of: (F) a water soluble a:nd/or water dispersible polymer including amino-substituted vinyl phenolic moieties; and (G) a foam reducing component; and (IV) dissolved organic material, said material being selected from the group consisting of alkox:ylated and non-alkoxylated castor oil triglycerides and hydrogenated castor oil derivatives, oxa-acid esters, and amine oxides with at least one hydroxyethyl group bonded to the amine oxide forming nitrogen atom, said material being present in sufficient amount that the coefficient of static :Friction of the treated metal container increases less upon heating of the treated metal container beyond the minimum decree of heating needed for drying than does the coefficient of friction of a comparison container treated in the same way, except for substituting ethoxylated isostearic acid for all the alkoxylated and non-alkoxylated castor oil triglycerides and hydrogenated castor oil derivatives, oxa-acid esters, 6d and amine oxides with at least one hydroxyethyl group bonded to the amine oxide forming nitrogen atom treat are present in the lubricant and surface conditioner forms.ng composition.
According to another aspect of tree present invention, there is provided a concentrate additive suitable for dilution with water to form a lubricant. and surface conditioner forming aqueous composition for treating metal surfaces to reduce the coefficient of friction thereof, said additive consisting essentially of water and: (A) a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I:

z I+ 3 R -N-R { X- } a R4 (I) .
where R1 is a monovalent aliphatic moiety, which may be saturated or unsaturated and contains from 8 to 2<? carbon atoms; each of R2 and R3 is a monovalent moiety independently selected from the group consisting of (e) alkyl and hydroxyalkyl moieties having from 1 to 8 carbon atoms and (ii) aryl and arylalkyl moieties having from 6 to 10 carbon atoms; R4 is a monovalent moiety selected from the same group as for R2 and R3 plus the -0- moiety; X- is ~~ monovalent anion or monovalent fraction of an anion with a v<~lence higher than 1; and a = 0 if R4 is -O- and = 1 if R4 is not: -O-; and (B) a component of complex fluoride anions; and, optionally but preferably, (C) a component of phosphate ions, optionally also including sulfate or nitrate ions or both;
and, optionally, (D) aluminate anions, including fluoroaluminate anions; and, optionally (E) aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of: (F) a water soluble an.d/or water 6e dispersible polymer including amino-substi~~uted vinyl phenolic moieties; and (G) a foam reducing component.
Brief Description of the Drawings Figures 1 (a) - 1 (d) illustrate the effect of fluoride activity during cleaning of 6f WO 95/02660 ' ' , v ~;'~ 2 ~ 6 ~ 3 ~ p PCTIUS94/00024 cans before applying a lubricant and surface conditioner according to this invention on the characteristics of the cans after processing.
Description of Preferred Embodiments More particularly, in accordance with one preferred embodiment of this in-s vention, it has been found that application of a thin organic film to the outside sur-face of aluminum cans serves as a lubricant inducing thereto a lower coefficient of static friction, which consequently provides an improved mobility to the cans, and al-so increases the rate at which the cans may be dried and still pass the quality control column strength pressure test. It has also been found that the degree of improved ,o mobility and drying rate of the cans depends on the thickness or amount of the or-ganic film, and on the chemical nature of the material applied to the cans.
The lubricant and surface conditioner for aluminum cans in accordance with this invention may, for example, be selected from water-soluble alkoxylated surfact-ants such as organic phosphate esters; alcohols; fatty acids including mono-, di-, tri-, ,s and poly-acids; fatty acid derivatives such as salts, hydroxy acids, amides, esters, particularly alkyl esters of 2-substituted alkoxylated fatty alkyloxy acetic acids (brief-ly denoted hereinafter as "oxa-acid esters") as described more fully in U. S.
Appli-cation Serial No. 843,135 filed February 28, 1992; ethers and derivatives thereof;
and mixtures thereof.
The lubricant and surface conditioner for aluminum cans in accordance with this invention in one embodiment preferably comprises a water-soluble derivative of a saturated fatty acid such as an ethoxylated stearic acid or an ethoxylated isostearic acid, or alkali metal salts thereof such as polyoxyethylated stearate and polyoxyethyl-ated isostearate. Alternatively, the lubricant and surface conditioner for aluminum cans may comprise a water-soluble alcohol having at least about 4 carbon atoms and may contain up to about 50 moles of ethylene oxide. Excellent results have been obtained when the alcohol comprises polyoxyethylated oleyl alcohol containing an average of about 20 moles of ethylene oxide per mole of alcohol.
In another preferred aspect of this invention, the organic material employed to ~o form a film on an aluminum can following alkaline or acid cleaning and prior to the last drying of the exterior surface prior to conveying comprises a water-soluble or-ganic material selected from a phosphate ester, an alcohol, fatty acids including WO 95/02660 216 6 3 0 0 PCT~S94100024 mono-, di-, tri-, and poly-acids fatty acid derivatives including salts, hydroxy acids, amides, alcohols, esters, ethers and derivatives thereof and mixtures thereof.
Such organic material is preferably part of an aqueous solution comprising water-soluble organic material suitable for forming a film on the cleaned aluminum can to provide s the surface after drying with a coefficient of static friction not more than 1.5 and that is less than would be obtained on a can surface of the same type without such film coating.
In one embodiment of the invention, water solubility can be imparted to or-ganic materials by alkoxylation, preferably ethoxylation, propoxylation or mixture ,o thereof. However, non-alkoxylated phosphate esters are also useful in the present in-vention, especially free acid containing or neutralized mono-and diesters of phos-phoric acid with various alcohols. Specific examples include Tryfac~ 5573 Phos-phate Ester, a free acid containing ester available from Henkel Corp.; and Triton H-55, Triton" H-66, and Tritons QS-44, all available from Union Carbide Corp.
,s Preferred non-ethoxylated alcohols include the following classes of alcohols:
Suitable monohydric alcohols and their esters with inorganic acids include water soluble compounds containing from 3 to about 20 carbons per molecule.
Spe-cific examples include sodium lauryl sulfates such as Duponol~ WAQ and Dupon-of~ QC and Duponol~ WA and Duponoh'"' C available from Witco Corp. and pro-prietary sodium alkyl sulfonates such as Alkano1~189-S available from E.I. du Pont de Nemours & Co.
Suitable polyhydric alcohols include aliphatic or arylalkyl polyhydric alcohols containing two or more hydroxyl groups. Specific examples include glycerine, sorbi-tol, mannitol, xanthan gum, hexylene glycol, gluconic acid, gluconate salts, glucohep-tonate salts, pentaerythritol and derivatives thereof, sugars, and alkylpolyglycosides such as APG"~300 and APG"~325, available from Henkel Corp. Especially pre-ferred polyhydric alcohols include triglycerols, especially glycerine or fatty acid es-ters thereof such as castor oil triglycerides.
In accordance with the present invention, we have discovered that employing alkoxylated, especially ethoxylated, castor oil triglycerides as lubricants and surface conditioners results in further improvements in can mobility especially where opera-tion of the can line is interrupted causing the cans to be exposed to elevated temper-WO 95/02660 ~ PCTIUS94/00024 atures for extended periods. Accordingly, especially preferred materials include Try-lox~''' 5900, TryloxTM 5902, TryloxTM 5904, Trylox~ 5906, Trylox'z''~ 5907, Trylox"''s 5909, Trylox~ 5918, and hydrogenated castor oil derivatives such as Trylox"~

and Trylox'~ 5922, all available from Henkel Corp.
s Preferred fatty acids include butyric, valeric, caproic, caprylic, capric, pelar-gonic, lauric, myristic, palmitic, oleic, stearic, linoleic, and ricinoleic acids; malonic, succinic, glutaric, adipic, malefic, tartaric, gluconic, and dimer acids; and salts of any of these; iminodipropionate salts such as Amphoteric N and Amphoteric 400 availa-ble from Exxon Chemical Co.; sulfosuccinate derivatives such as Texapon~SH-135 ,o Special and Texapon"~SB-3, available from Henkel Corp.; citric, nitrilotriacetic, and trimellitic acids; Versenol"~ 120 HEEDTA, N-(hydroxyethyl)ethylenediaminetri-acetate, available from Dow Chemical Co.
Preferred amides generally include amides or substituted amides of carboxylic acids having from four to twenty carbons. Specific examples are Alkamide~ L203 ,s lauric monoethanolamide, Alkamide"~ L7DE lauric/myrisdc alkanolamide, Alka-mide~ DS 280/s stearic diethanolamide, Alkamide"~ CD coconut diethanolamide, Alkamide~ DIN 100 lauric/linoleic diethanolamide, Alkamidez"'' DIN 295/s linoleic diethanolamide, Alkamide"~ DL 203 lauric diethanolamide, all available from Rhone-Poulenc; Monamid~ 150-MW myristic ethanolamide, Monamid~ 150-CW
capric ethanolamide, Monamid~'~'' 150-IS isostearic ethanolamide, all available from Mona Industries Inc.; and Ethomidz'"' HT/23 and Ethomid"~ HT60 polyoxyethylated hydrogenated tallow amines, available from Akzo Chemicals Inc.
Preferred anionic organic derivatives generally include sulfate and sulfonate derivatives of fatty acids including sulfate and sulfonate derivatives of natural and synthetically derived alcohols, acids and natural products. Specific Examples:
do-decyl benzene sulfonates such as Dowfax"~ 2A1, Dowfaxz'''I 2A0, Dowfax~ 3B0, and Dowfax~'~'' 3B2, all available from Dow Chemical Co.; Lomar~ LS condensed naphthalene sulfonic acid, potassium salt available from Henkel Corp.;
sulfosuccinate derivatives such as Monamate'~'' CPA sodium sulfosuccinate of a modified alkanola-ao mide, Monamate~ LA-100 disodium lauryl sulfosuccinate, all available from Mona Industries; Triton's GR-SM sodium dioctylsulfosuccinate, available from Union Car-bide Chemical and Plastics Co.; Varsult'""~ SBFA 30, fatty alcohol ether sulfosuccin-WO 95/02660 216 6 3 Q p PCT~S94/00024 ate, Varsul~M SBL 203, fatty acid alkanolamide sulfosuccinate, Varsult''~'' S
1333, ri-cinoleic monoethanolamide sulfosuccinate, all available from Witco Chemical Co.
Another preferred group of organic materials comprise water-soluble alkoxyl-ated, preferably ethoxylated, propoxylated, or mixed ethoxylated and propoxylated s materials, most preferably ethoxylated, and non-ethoxylated organic materials se-lected from amine salts of fatty acids including mono-, di-, tri-, and poly-acids, amino fatty acids, fatty amine N-oxides, and quaternary salts, and water soluble pol-ymers.
Preferred amine salts of fatty acids include ammonium, quaternary ammoni-,o um, phosphonium, and alkali metal salts of fatty acids and derivatives thereof con-taming up to 50 moles of alkylene oxide in either or both the cationic or anionic species. Specific examples include Amphoteric N and Amphoteric 400 iminodipro-pionate sodium salts, available from Exxon Chemical Co.; DeriphatTM 154 disodium N-tallow-beta iminodipropionate and DeriphatTM 160, disodium N-lauryl-beta imino-,s dipropionate, available from Henkel Corp.
Preferred amino acids include alpha and beta amino acids and diacids and salts thereof, including alkyl and alkoxyiminodipropionic acids and their salts and sarcosine derivatives and their salts. Specific examples include Armeen"''I Z, N-coco-beta-aminobutyric acid, available from Akzo Chemicals Inc.; Amphoteric N, Amphoteric 400, Exxon Chemical Co.; sarcosine (N-methyl glycine); hydroxyethyl glycine; Hamposyl~ TL-40 triethanolamine lauroyl sarcosinate, Hamposyl~''' O
oleyl sarcosinate, Hamposyl~ AL-30 ammoniumlauroyl sarcosinate, Hamposyl~ L laur-oyl sarcosinate, and Hamposyl'~'' C cocoyl sarcosinate, all available from W.R. Grace & Co.
~s Preferred amine N-oxides include amine oxides where at least one alkyl sub-sdtuent contains at least three carbons and up to 20 carbons. Specific examples in-chide Aromox~ C/12 bis-(2-hydroxyethyl)cocoalkylamine oxide, Aromox~'~'' T/12 bis-(2-hydroxyethyl)tallowalkylamine oxide, Aromox~'~M DMC dimethylcocoalkyla-mine oxide, Aromox~'~'' DMHT hydrogenated dimethyltallowalkylamine oxide, Aro-mox"~DM-16 dimethylheaxdecylalkylamine oxide, all available from Akzo Chemi-Gals Inc.; and Tomah~ AO-14-2 and Tomah'~'' AO-728 available from Exxon Chem-ical Co.

WO 95/02660 . 2 ~ 6 6 3 0 0 pCT/US94100024 Preferred quaternary salts include quaternary ammonium derivatives of fatty amines containing at least one substituent containing from 12 to 20 carbon atoms and zero to 50 moles of ethylene oxide and/or zero to 15 moles of propylene oxide where the counter ion consists of halide, sulfate, nitrate, carboxylate, alkyl or aryl s sulfate, alkyl or aryl sulfonate or derivatives thereof. Specific examples include Ar-quadTM 12-37W dodecyltrimethylammonium chloride, Arquad~ 18-SO octadecyltri-methylammonium chloride, Arquad"~ 210-50 didecyldimethylammonium chloride, Arquad~ 218-100 dioctadecyldimethylammonium chloride, Arquad'~ 316(W) trihex-adecylmethylammonium chloride, Arquad"~ B-100 benzyldimethyl(C,2_,8)alkylam-yo monium chloride, Ethoquad"~ G12 cocomethyl[POE(2)]ammonium chloride, Etho-quadTM C/25 cocomethyl[POE(15)]ammonium chloride, Ethoquad"~ C/12 nitrate salt, Ethoquad"''~ T/13 Acetate tris(2-hydroxyethyl)tallowalkyl ammonium acetate, Duo-qaud'z''~ T-50 N,N,N',N',N'-pentamethyl-N-tallow-1,3-diammonium dichloride, Propo-quadTM 2HT/11 di(hydrogenated tallowalkyl)(2-hydroxy-2-methylethyl)methylam-,s monium chloride, Propoquad"~T/12 tallowalkylmethyl-bis-(2-hydroxy-2-methylethyl)-ammonium methyl sul-fate, all available from Akzo Chemicals Inc.; Monaquat~ P-TS stearamidopropyl PG-diammonium chloride phosphate, available from Mona In-dustries Inc.; Chemquaf'~'' 12-33 lauryltrimethylammonium chloride, Chemquat~

50 Cetyltrimethylammonium chloride available from Chemax Inc.; and tetraethylam-monium pelargonate, laurate, myristate, oleate, stearate or isostearate.
A combination of fluoride ions with either amine oxide or quaternary am-monium salts as described above, preferably the latter, is a major part of one espe-cially preferred embodiment of the invention when good resistance of the friction re-duction to overheating and/or resistance to dome staining during pasteurization is needed. More particularly, a suitable additive to satisfy these objectives preferably comprises, more preferably consists essentially of, or still more preferably consists of:
(A) a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I:

WO 95/02660 Q ~ PCT/US94/00024 R2-N+-R3 {X }a ~I).

where R' is a monovalent aliphatic moiety, which may be saturated or unsat-urated and contains from 8 to 22 carbon atoms, or preferably from 12 to 18 carbon atoms, preferably arranged in a straight chain; each of RZ and R3 is a monovalent moiety independently selected from the group consisting of (i) al-,o kyl and hydroxyalkyl moieties having from 1 to 8, preferably from 1 to 4, more preferably 1 or 2, carbon atoms and (ii) aryl and arylalkyl moieties hav-ing from 6 to 10, or preferably from 6 to 8, carbon atoms; R4 is a monoval-ent moiety selected from the same group as for RZ and R3 plus the -O- moi-ety; X' is a monovalent anion or monovalent fraction of an anion with a ~s valence higher than 1; and a = 0 if R4 is -O', and a = 1 if R4 is not -O';
(B) a component of complex fluoride anions, with anions selected from the group consisting of fluotitanate, fluohafnate, and fluozirconate preferred and fluozir-conate alone most preferred; and, optionally but preferably, (C) a component selected from the group consisting of phosphate, sulfate, and ni-2o trate ions, with phosphate or a mixture of phosphate with one or both of sul-fate and nitrate preferred; and, optionally, (D) aluminate anions, including fluoroaluminate anions; and, optionally (E) aluminum cations, including complex fluoroaluminum cations, and, optional-1y, one or both of:
25 (F) a water soluble andlor water dispersible polymer including amino-substituted vinyl phenolic moieties, as described in detail in one or more of U. S.
Patents 5,116,912, 5,068,299, 5,063,089, 4,944,812, 4,517,028, 4,457,790, 4,433,015, and 4,376,000; and (G) a foam reducing (antifoam) component.
For component (A) as defined above, quaternary salts are preferred over amine oxides when dome staining resistance is desired. Independently, it is pre-ferred that at least two, or more preferably all three, of the moieties Rz, R3, and R°
be hydroxyalkyl groups, most preferably 2-hydroxyethyl groups.
For economy and commercial availability, it is preferred that the R' moieties WO 95/02660 2 ~ 6 6 3 ~ 0 PCT/US94/00024 in the materials used for component (A) be mixtures of the alkyl groups correspond-ing to the mixture of alkyl groups present in the fatty acid mixtures derived from hy-drolysis of natural fats and oils, such as coconut oil, palm kernel oil, animal tallow, and the like. Alkyl groups from animal tallow are particularly preferred.
s For component (B), fluozirconate ions added as fluozirconic acid are most preferred. The optimal amount of fluoride can conveniently be monitored during use if desired by means of fluoride sensitive electrode as described in U. S.
Patent 3,431,182 and commercially available from Orion Instruments. "Fluoride activity" as this term is used herein was measured relative to a 120E Activity Standard Solution, ,o commercially available from the P+A, by a procedure described in detail in P+A
Technical Process Bulletin No. 968. The Orion Fluoride Ion Electrode and the reference electrode provided with the Orion instrument are both immersed in the noted Standard Solution and the millivolt meter reading is adjusted to 0 with a Standard Knob on the instrument, after waiting if necessary for any initial drift in ,s readings to stabilize. The electrodes are then rinsed with deionized or distilled water, dried, and immersed in the sample to be measured, which should be brought to the same temperature as the noted Standard Solution had when it was used to set the meter reading to 0. The reading of the electrodes immersed in the sample is taken directly from the millivolt (hereinafter often abbreviated "mv") meter on the 2o instrument. With this instrument, lower positive my readings indicate higher fluoride activity, and negative my readings indicate still higher fluoride activity than any positive readings, with negative readings of high absolute value indicating high fluoride activity.
The initial millivolt reading of a well operating freshly prepared working is composition according to this embodiment of the invention ideally should be at least approximately maintained throughout the use of the composition. The my reading for free fluoride activity in such a working composition according to this embodi-ment of the invention, including components (A), (B), and (C) as defined above, preferably should lie, with increasing preference in the order given, within the range from -30 to -120, -50 to -100, -60 to -85, -68 to -80, or -68 to -72, mv.
The anions specified for component (C) above are preferably added to the mixtures according to the invention in the form of the corresponding acids.
When WO 95/02660 ~ PCT/US94/00024 resistance to dome staining is desired, component (C) preferably includes phosphate anions. Because of the preferred values for pH and for the ratio of the phosphpate content of component (C) to components (A) and (B) when component (C) includes phosphate, which are considered further below, usually some other acid than phos-s phonic acid is required to bring the pH within the preferred ranges without exceeding the preferred ratio of phosphate to the other components. In such cases, nitric acid is preferably used when dome staining resistance is desired; otherwise, any other suf ficiently strong acid that does not interfere with the attainment of the objects of the invention may be used; in such cases, sulfuric acid is normallly preferred primarily ,o because it is less expensive than other strong acids.
Components (D) and (E) normally are not added deliberately to the stage 4 composition (except for testing purposes), but normally accumulate in it as it is used under practical conditions for treating aluminum surfaces. While aluminum is un-likely to have any beneficial effect, experience has indicated that a normal equilibri-um concentration in commercial aluminum can cleaning lines will be within the range from 100 - 300 parts per million by weight (hereinafter often abbreviated "ppm"), and satisfactory results can be obtained with compositions including this much, or even more, aluminum. Preferably the total concentration of components (D) and (E) is, with increasing preference in the order given, not more than 1000, ?00, 500, 450, 400, 370, 340, 325, or 315 ppm.
In a complete Stage 4 working composition according to the embodiments of this invention including amine oxide or quaternary ammonium salts as a necessary component, the pH is preferably maintained in the range from 2.3 to 3.3, more pref-erably from 2.5 to 3.1, still more preferably from 2.70 to 2.90. Values of pH
lower is than those stated usually result in less resistance than is desirable to dome staining, while pH values higher than those stated tend to result in inadequate etching of the surface to assure good adhesion of subsequently applied lacquers and/or inks.
Addi-tion of acid during prolonged operation is generally required to maintain these values of pH, because acidity is consumed by the process that forms the lubricant and sur-face conditioner coating. If the surfaces being treated are predominantly aluminum as is most common, it is preferable to include in the replenishment acid, which is added during prolonged use of the lubricant and surface conditioner forming compo-WO 95/02660 ~ ~ PCTIUS94/00024 sition, a sufficient amount of hydrofluoric acid to complex the aluminum dissolved into the lubricant and surface conditioner forming composition during its use.
When component (C) includes phosphate ions as is generally preferred, the molar ratio between components (CP):(B):(A), where "CP" denotes the phosphate s content only of component (C) as defined above, is preferably, with increasing pref-erence in the order given, in the range from 1.0:(0.5 - 4.0):(0.25 - 8.0), 1.0:(0.5 -2.0):(0.5 - 6.0), 1.0:(0.7 - 1.3):(0.8 - 1.5), 1.0:(0.8 - 1.2):(0.90 - 1.40), 1.0:(0.90 -1.10):(1.05 - 1.25), or 1.0:(0.95 - 1.05):(1.05 - 1.15). If component (C) is not used or does not contain phosphate, the ratio of (B):(A), with respect to those two com-,o ponents, preferably falls within the same ranges as stated above for cases in which phosphate is included in the compositions. Independently, the concentration of component (A) in a working Stage 4 composition preferably is, with increasing pref-erence in the order given, in the range from 0.14 to 2.25, 0.42 to 1.50, 0.56 to 1.12, 0.67 to 0.98, or 0.77 to 0.88, millimoles per liter (hereinafter often abbreviated ,s "mM"); the concentration of component (B) in a working Stage 4 composition pref-erably is in the range from 0.20 to 2.0, or more preferably from 0.40 to 1.0, mM;
and the concentration of component (CP) in a working Stage 4 composition prefer-ably is in the range from 0.20 to 2.0, more preferably from 0.40 to 1.0, or still more preferably from 0.60 to 0.84, mM. [In these numerical specifications, for component (CP), the stoichiometric equivalent as phosphate ion of any unionized phosphoric acid or anions produced by any degree of ionization of phosphoric acid is to be con-sidered as phosphate anions.]
Higher concentrations of component (A) within the stated ranges improve the dome staining resistance during pasteurization but also increase the foaming tenden-cy of the composition and often must be avoided for that reason. The lower the con-centration of component (A), the higher should be the concentration of component (CP) within the stated ranges when dome staining resistance is important, because component (CP) appears to act synergistically with component (A) to promote dome staining resistance. Higher concentrations of component (B) within the stated ranges are preferred when the concentration of components (D) and/or (E) is relatively high.
Under some conditions of operation, it is preferred that the compositions according to this invention that include amine oxides and/or quaternary ammonium salts do not contain certain materials that are useful for mobility enhancement, even in other embodiments of this invention, and also do not contain certain other materi-als with various disadvantageous properties. Specifically, independently for each possible component listed below, with increasing preference in the order given, s amine oxide and/or quaternary ammonium salt based compositions according to this invention for use in Stage 4 as defined above, either as such or after dilution with water, preferably contain no more than 5, 1.0, 0.2, 0.05, 0.01, 0.003, 0.001, or 0.0005 % by weight of any of the following materials (other than those specified as necessary or optional components (A) - (G) above]: (a) surfactants such as (a.1) ,o organic phosphate esters, (a.2) alcohols, (a.3) fatty acids including mono-, di-, tri-, and poly-acids and their derivatives (a.4) such as (a.4.1) salts, (a.4.2) hydroxy acids, (a.4.3) amides, (a.4.4) esters, and (a.4.5) ethers; (b) surfactants that are alkoxylated but are otherwise as described in part (a); (c) alkoxylated castor oil triglycerides; (d) sulfate and sulfonate derivatives of natural and synthetically derived alcohols, acids, and/or natural products; (e) amino acids; (fj water-soluble homopolymers and/or het-eropolymers of ethylene oxide, propylene oxide, butylene oxide, acrylic acid and its derivatives, malefic acid and its derivatives, and/or vinyl alcohol; and (g) salts of or-ganic acids containing a total of at least two carboxyl and hydroxyl groups.
Preferred water-soluble polymers include homopolymers and heteropolymers of ethylene oxide, propylene oxide, butylene oxide, acrylic acid and its derivatives, malefic acid and its derivatives, vinyl phenol and its derivatives, and vinyl alcohol.
Specific examples include Carbowax~ 200, Carbowax"~ 600, Carbowax~ 900, Car-bowax'~'' 1450, Carbowax~ 3350, Carbowaxz"'' 8000, and Compound 20Mz'''s, all available from Union Carbide Corp.; Pluronic'~ L61, Pluronic~ L81, Pluronic~
3181, Pluronic"''' 2582, Tetronicz'''s 304, Tetronic""' 701, TetronicT"'' 908, Tetronicz'"' 9084, and Tetronic~ 15081, all available from BASF Wyandotte Corp.; Acusol~
410N sodium salt of polyacrylic acid, Acusoh''' 445 polyacrylic acid, Acusol~
460ND sodium salt of malefic acid/olefin copolymer, and Acusol"~ 479N sodium salt of acrylic acid/maleic acid copolymer, all available from Rohm & Haas Company;
and N-methylglucamine adducts of polyvinylphenol and N-methylethanolamine ad-ducts of polyvinylphenol.
Additional improvements are achieved by combining in the process of this in-vention the step of additionally contacting the exterior of an aluminum can with an inorganic material selected from metallic or ionic zirconium, titanium, cerium, alumi-num, iron, vanadium, tantalum, niobium, molybdenum, tungsten, hafnium or tin to produce a film combining one or more of these metals with one or more of the s above-described organic materials. A thin film is produced having a coefficient of static friction that is not more than 1.5 and is preferably less than the coefficient without such film, thereby improving can mobility in high speed conveying without interfering with subsequent lacquering, other painting, printing, or other similar dec-orating of the containers.
,o The technique of incorporating such inorganic materials is described, in par-ticular detail with reference to zirconium containing materials, in U.S.
Patents 5,030,323 of July 9, 1991 and 5,064,500 of November 1:Z, 1991 .
The substitution of other metallic materials ,s for those taught explicitly in one of these patents is within the scope of those skilled in the art.
In a further preferred embodiment of the process of the present invention, in order to provide improved water solubility, especially for the non-e;thoxylated organ-ic materials described herein, and to produce a suitable filin on the; can surface hav-ing a coe~cient of static friction not more than 1.5 after drying, one employs a mix-_ ture of one ~r more surfactants, preferably alkoxylated arid most preferably ethoxyl-ated, along with such non-ethoxylated organic material to contact the cleaned can surface prior to final drying and conveying. Preferred surfactants include ethoxyl-ated and non-ethoxylated sulfated or sulfonated fatty alcohols, such as lauryl and coco alcohols. Suitable are a wide class of anionic, non-ionic, cationic, or amphoteric surfactants. Alkyl polyglycosides such as C$ - Cl8 alkyl polyglycosides having aver-age degrees of polymerization between 1.2 and 2.0 are also suitable. Other classes of surfactants suitable in combination are ethoxylated no~nyl and octyl phenols con-taining from 1.5 to 100 moles of ethylene oxide, preferably a nony;lphenol condensed with from 6 to SO moles of ethylene oxide such as Igepal""" CO-x87 available from Rhone-Poulenc; alkyllaryl polyethers, for example, Tritan~ DF-:16; and phosphate esters of which Tritons H-66 and Tritons QS-44 are examples, ,all of the TritonT'''' WO 95/02660 2 i 6 b 3 0 0 PCT/US94I00024 products being available from Union Carbide Co., and Ethox~ 2684 and Ethfac"~
136, both available from Ethox Chemicals Inc., are representative examples;
polyeth-oxylated and/or polypropoxylated derivatives of linear and branched alcohols and de-rivatives thereof, as for example Trycoh''' 6720 (Henkel Corp.), Surfonic~ LF-s (Texaco) and Antarox"''I LF-330 (Rhone-Poulenc); sulfonated derivatives of linear or branched aliphatic alcohols, for example, NeodolTM 25-3S (Shell Chemical Co.);
sul-fonated aryl derivatives, for example, Dyasulf"~ 9268-A, Dyasulf~ C-70, Lomar"''t D (all available from Henkel Corp.) and Dowfax~ 2A1 (available from Dow Chemi-cal Co.); and ethylene oxide and propylene oxide copolymers, for example, Pluron-IcTM L-61, Pluronic~ 81, Pluronic'~ 3181, Tetronic~ 701, Tetronic~ 9084 and Te-tronic~ 15081, all available from BASF Corp.
Further, the lubricant and surface conditioner for aluminum cans in accord-ance with this invention may comprise a phosphate acid ester or preferably an ethox-ylated alkyl alcohol phosphate ester. Such phosphate esters are commercially availa-,s ble under the tradename Rhodafac~ PE 510 from Rhone-Poulenc Corporation, Wayne, NJ, and as Ethfacz'''' 136 and Ethfac~ 161 from Ethox Chemicals, Inc., Greenville, SC. In general, the organic phosphate esters may comprise alkyl and aryl phosphate esters with and without ethoxylation.
The lubricant and surface conditioner for aluminum cans may be applied to the cans during their wash cycle, during one of their treatment cycles such as clean-ing or conversion coating, during one of their water rinse cycles, or more preferably (unless the lubricant and surface conditioner includes a metal cation as described above), during their final water rinse cycle. In addition, the lubricant and surface conditioner may be applied to the cans after their final water rinse cycle, i.e., prior to oven drying, or after oven drying, by fine mist application from water or another volatile non-inflammable solvent solution. It has been found that the lubricant and surface conditioner is capable of depositing on the aluminum surface of the cans to provide them with the desired characteristics. The lubricant and surface conditioner may be applied by spraying and reacts with the aluminum surface through chemi-sorption or physiosorption to provide it with the desired film.
The method of contact and the time of contact between the aqueous treating compositions and the metal substrates to be treated and the temperature of the com-WO 95/02660 ' ~ ~ PCT/US94100024 positions during treatment are generally not critical features of the invention; they may be taken from the known state of the art. However, for large scale operations, power spraying is the preferred method of contact, and times of contact in stage 4 in the range from 5 to 60 seconds ("sec"), or more preferably from 10 to 30 sec, and a s temperature of 20 to 60 ° C, or more preferably 30 to 48 ° C, are generally used.
Generally, in the cleaning process of the cans, after the cans have been washed, they are typically exposed to an acidic water rinse. In accordance with this invention, the cans may thereafter be treated with a lubricant and surface conditioner comprising an anionic surfactant such as a phosphate acid ester. The pH of the treat-,o ment composition is important and generally should be acidic, that is between about l and about 6.5, preferably between about 2.5 and about 5. If the cans are not treat-ed with the lubricant and surface conditioner of this invention next after the acidic water rinse, the cans are often exposed to a tap water rinse and then to a deionized water rinse. In such event, the deionized water rinse solution is prepared to contain ,s the lubricant and surface conditioner of this invention, which may comprise a non-ionic surfactant selected from the aforementioned polyoxyethylated alcohols or poly-oxyethylated fatty acids, or any of the other suitable materials as described above.
After such treatment, the cans may be passed to an oven for drying prior to further processing.
2o The amount of lubricant and surface conditioner remaining on the treated surface after drying should be sufficient to result in a COF value not more than 1.5, or with increasing preference in the order given, to a value of not more than 1.2, 1.0, 0.80, 0.72, 0.66, 0.60, 0.55, or 0.50. Generally speaking, such amount should be on the order of from 3 mg/m2 to 60 mg/m2 of lubricant and surface conditioner on the outside surface of the cans. For reasons of economy, it is generally preferred that the aqueous lubricant and surface conditioner forming composition contain, with increasing preference in the order given, not more than 2.0, 1.0, 0.8, 0.6, 0.4, 0.30, or 0.20 grams per liter (often abbreviated hereinafter as "g/L,") of the necessary organic materials) to form the lubricant and surface conditioner film on the treated can surface after drying.
Embodiments of the Invention with Desirable Special Characteristics In accordance with a particular preferred embodiment of this invention, it has been found that the coefficient of friction of a surface treated with a lubricant and surface conditioner is less easily damaged by heating when the lubricant and surface conditioner composition includes at least one of the following organic nnaterials: al-koxylated or non-alkoxylated castor oil trigIycerides and hydrogenated castor oil de-s rivatives; alkoxylated and non-alkoxylated amine salts of a fatty aciid including mono-, dl-; tri-, and poly-acids; aikoxyiated and non-alkoxylated amino fatty acids;
alkoxylated and non-alkoxylated fatty amine N-oxides, alkoxylated and non-alkoxyl ated quaternary ammonium salts, alkyl esters of 2-substituted alkoxylated fatty alkyl oxy acetic acids (briefly denoted hereinafter as "oxa-acid esters") as described more ~o fully elsewhere, and water-soluble alkoxylated and non-alkoxylated polymers. Furthermore, if the lubricant ar.~d surface conditioner is not applied to the surface from the last aqueous composition with which the sur-face is contacted before the last drying of the surface before automatic:
conveying, ,s the composition including the organic materials preferably also includes a metallic element selected from the group consisting of zirconium, titanium, cerium, alumin-um, iron, tin, vanadium, tantalum, niobium, molybdenum, tungsten, and hafnium in metallic or ionic form, and the film formed on the surface as part of the lubricant and surface conditioner in dried form should include some of this metallic element along with organic material.
For a fuller appreciation of the invention, reference should be made to the following examples, which are intended to be merely descriptive, illustrative, and not limiting as to the scope of the invention, except to the extent that their-limitations may be incorporated into the appended claims.
is Example Group 1 This example illustrates the amount of aluminum can lubricant and surface conditioner necessary to improve the mobility of the cans through the tracks and printing stations of an industrial can manufacturing facility, and also shows that the lubricant and surface conditioner does not have an adverse effect on the adhesion of labels printed on the outside surface as well as of lacquers sprayed on the:
inside sur-face of the cans.
Uncleaned aluminum cans obtained from an industrial ca.n manufacturer were WO 95/02660 ~ ~ PCT/US94/00024 washed clean with an alkaline cleaner available from the P+A, employing that company's Ridoline~ 3060/306 process. The cans were washed in a CCW process-ing 14 cans at a time. The cans were treated with different amounts of lubricant and surface conditioner in the final rinse stage of the washer and then dried in an oven.
s The lubricant and surface conditioner comprised about a 10 % active concentrate of _ polyoxyethylated isostearate, an ethoxylated nonionic surfactant, available under the tradename Ethox~ MI-14 from Ethox Chemicals, Inc., Greenville, SC. The treated cans were returned to the can manufacturer for line speed and printing quality evaluations. The printed cans were divided into two groups, each consisting of 4 to 6 cans. All were subjected for 20 minutes to one of the following adhesion test solutions:
Test Solution A: 1 % Joy's' (a commercial liquid dishwashing detergent, Proc-ter and Gamble Co.) solution in 3:1 deionized wateraap water at a temperature of 82° C.
~s Test Solution B: 1% Joys detergent solution in deionized water at a tempera-ture of 100° C.
After removing the printed cans from the adhesion test solution, each can was cross-hatched using a sharp metal object to expose lines of aluminum which showed through the paint or lacquer, and tested for paint adhesion. This test included apply-ing Scotches transparent tape No. 610 firmly over the cross-hatched area and then drawing the tape back against itself with a rapid pulling motion such that the tape was pulled away from the cross-hatched area. The results of the test were rated as follows: 10, perfect, when the tape did not peel any paint from the surface;
8, accept-able; and 0. total failure. The cans were visually examined for any print or lacquer pick-off signs.
In addition, the cans were evaluated for their coefficient of static friction us-ing a laboratory static friction tester. This device measures the static friction associ-ated with the surface characteristics of aluminum cans. This is done by using a ramp which is raised through an arc of 90° by using a constant speed motor, a spool and a cable attached to the free swinging end of the ramp. A cradle attached to the bottom of the ramp is used to hold 2 cans in horizontal position approximately 0.5 inches apart with the domes facing the fixed end of the ramp. A third can is laid WO 95/02660 ~ ~ ~ PCTIUS94/00024 upon the 2 cans with the dome facing the free swinging end of the ramp, and the edges of all 3 cans are aligned so that they are even with each other.
As the ramp begins to move through its arc, a timer is automatically actuated.
When the ramp reaches the angle at which the third can slides freely from the 2 low-s er cans, a photoelectric switch shuts off the timer. It is this time, recorded in sec-onds, which is commonly referred to as "slip time". The coefficient of static friction is equal to the tangent of the angle swept by the ramp at the time the can begins to move. This angle in degrees is equal to [4.84 + (2.79~t)], where t is the slip time.
In some cases the tested cans were subjected to an additional bake out at 210° C for ,0 5 minutes and the COF redetermined; this result is denoted hereinafter as "COF-2".
The average values for the adhesion test and coefficient of static friction eval-uation results are summarized in Table 2. In brief, it was found that the lubricant and surface conditioner concentrate as applied to the cleaned aluminum cans provid-ed improved mobility to the cans even at very low use concentrations, and it had no ,s adverse effect on either adhesion of label print or internal lacquer tested even at 20 to 100 times the required use concentration to reduce the coefficient of static friction of the cans.
Example Group 2 These examples illustrate the use of the aluminum can lubricant and surface 2o conditioner of Example Group 1 in an industrial can manufacturing facility when passing cans through a printing station at the rate of 1260 cans per minute.
Aluminum can production was washed with an acidic cleaner (Ridoline ~
125 CO, available from P+A), and then treated with a non-chromate conversion coat-ing (Alodine'~'' 404, also available from the Parker+Amchem Division, Henkel Cor-is poration, Madison Heights, MI). The aluminum can production was then tested for "slip" and the exterior of the cans were found to have a static coefficient of friction of about 1.63. During processing of these cans through a printer station, the cans could be run through the printer station at the rate of 1150 to 1200 cans per minute without excessive "trips", i.e., improperly loaded can events. In such case, the cans are not properly loaded on the mandrel where they are printed. Each "trip"
causes a loss of cans which have to be discarded because they are not acceptable for final stage processing.

WO 95/02660 ~ ~ PCT/US94/00024 Table 2 Lubricant and Adhesion Evaluation Surface Con-ditioner Con- Test Coefficient of Test centrate Solu- Static Friction No. (%/vol.) tion OSW ISW ID

Control (no 1 treatment) --- --- --- --- 1.42 2 0.1 B 10 10 10 0.94 3 0.25 A 10 10 10 ---4 0.5 B 9.5* 10 10 0.80 0.75 A 10 10 10 0.63 6 1.0 B 10 10 10 0.64 7 2.0 A 10 10 10 0.56 8 5.0 B 10 10 10 0.55 9 10.0 A 9.8* 10 10 0.56 Notes for Table *Littlepick-off was on the , mainlyat the contact visually noticed outside walls marks.

"OSW"stands for ISW" standsfor outside sidewall, inside " sidewall, and "ID"

stands for inside dome.

About 1 ml/liter of aluminum can lubricant and surface conditioner was add-ed to the deionized rinse water system of the can washer, which provided a reduction of the static coefficient of friction on the exterior of the cans to a value of 1.46 or a reduction of about 11 percent from their original value. After passing the cans s through the printer, it was found that the adhesion of both the interior and exterior coatings were unaffected by the lubricant and surface conditioner. In addition, the printer speed could be increased to its mechanical limit of 1250 to 1260 cans per minute without new problems.
In similar fashion, by increasing the concentration of the aluminum can lubri-WO 95/02660 , 216 6 3 p p PCT/US94/00024 cant and the surface conditioner to the deionized rinse water system, it was possible to reduce the coefficient of static friction of the cans by 20 percent without adversely affecting the adhesion of the interior and exterior coatings of the cans.
Further, it was possible to maintain the printer speed continuously at 1250 cans per minute for s a 24-hour test period.
Example and Comparison Example Grog 3 These examples illustrate the use of other materials as the basic component for the aluminum can lubricant and surface conditioner.
Aluminum cans were cleaned with an alkaline cleaner solution having a pH
,o of about 12 at about 41 ° C for about 35 seconds. The cans were rinsed, and then treated with three different lubricant and surface conditioners comprising various phosphate ester solutions. Phosphate ester solution 1 comprised a phosphate acid ester (available under the tradename Rhodafac~ PE 510 from Rhone-Poulenc, Wayne, NJ) at a concentration of 0.5 g/1. Phosphate ester solution 2 comprised an ,s ethoxylated alkyl alcohol phosphate ester (available under .the tradename Ethfac"~
161 from Ethox Chemicals, Inc., Greenville, SC) at a concentration of 0.5 g/1.
Phos-phate ester solution 3 comprised an ethoxylated alkyl alcohol phosphate ester (avail-able under the tradename Ethfac~'~'' 136 from Ethox Chemicals, Inc., Greenville, SC) at a concentration of 1.5 g/1.
The mobility of the cans in terms of coefficient of static friction was evaluat-ed and found to be as follows in Table 3:
Table 3 Phosphate ester solution pH Coefficient of static friction 1 3.6 0.47 2 3.3 0.63 3 2.6 0.77 None --- 1.63 The aforementioned phosphate ester solutions all provided an acceptable mo-bility to aluminum cans, but the cans were completely covered with "water-break".

It is desired that the cans be free of water-breaks, i.e., have a thin, continuous film of water thereon, because otherwise they contain large water droplets, and the water film is non-uniform and discontinuous. To determine whether such is detrimental to printing of the cans, they were evaluated for adhesion. That is, the decorated cans s were cut open and boiled in a 1 %a liquid dishwashing detergent solution (Joys) comprising 3:1 deionized wateraap water for ten minutes. The cans were then rinsed in deionized water and dried. As in Example Group 1, eight cross-hatched scribe lines were cut into the coating of the cans on the inside and outside sidewalls and the inside dome. The scribe lines were taped over, and then the tape was snapped ,o off. The cans were rated for adhesion values. The average value results are sum-marized in Table 4, in which the acronyms have the same meaning as in Table 2.
Table 4 Phosphate Ester Adhesion Ratin~on:
,s Solution Used OSW ISW ID
control 10 10 10 1 9.8 6.8 1.0 2 9.8 10 10 so For the control, it was observed-that there was no pick-off (loss of coating adhesion) on either the outside sidewall, the inside sidewall or the inside dome of the cans. For phosphate ester solution 1, it was observed that there was almost no pick-s off on the outside sidewall, substantial pick-off on the inside sidewall, and complete failure on the inside dome of the cans. For phosphate ester solution 2, it was observed that there was almost no pick-off on the outside sidewall, and no pick-off on the inside sidewall and no pick-off on the inside dome of the cans.
For phosphate ester solution 3, it was observed that there was no pick-off on the outside sidewall, the inside sidewall, or the inside dome of the cans.
Example Grau~ 4 This example illustrates the effect of the lubricant and surface conditioner of this invention on the water draining characteristics of aluminum cans treated there-WO 95/02660 ~ ~ ~ PCT/US94/00024 with.
Aluminum cans were cleaned with acidic cleaner (Ridoline~ 125 CO fol-lowed by Alodine ~ 404 treatment or Ridoline"~ 125 CO only) or with an alkaline cleaner solution (Ridoline"''~ 3060/306 process), all the products being available from s the Parker+Amchem Division, Henkel Corporation, Madison Heights, MI, and then rinsed with deionized water containing about 0.3% by weight of the lubricant and sur-face conditioner of this invention. After allowing the thus-rinsed cans to drain for up to 30 seconds, the amount of water remaining on each can was determined.
The same test was conducted without the use of the lubricant and surface conditioner.
The results are summarized in Table 5. It was found that the presence of the lubri-cant and surface conditioner caused the water to drain more uniformly from the cans, and that the cans remain "water-break" free for a longer time.
Table 5 ~s Drain Time Grams ner Can of Water Remainin~n~
in Seconds DI Water DI Water + 0.3 % Conditioner 6 2.4 - 3.0 nd 12 2.1 - 3.5 2.8 18 2.2 - 3.5 2.3 2o 30 1.8 - 3.4 2.3 Example Group 5 This example illustrates the effect of the oven dryoff temperature on the side-wall strength of aluminum cans. This test is a quality control compression test which determines the column strength of the cans by measuring the pressure at which they buckle. The results are summarized in Table 6.
It can be seen from Table 6 that at an oven drying temperature of 193° C, a 2 psi increase was obtained in the column strength test compared to the value ob-tained at 227° C oven temperature.

Table 6 Oven Temperature (° C) Column Strength (PSI) 227 86.25 204 87.75 193 88.25 182 89.25 ,o The higher column strength test results are preferred and often required be-cause the thin walls of the finished cans must withstand the pressure exerted from within after they are filled with a carbonated solution. Otherwise, cans having weak sidewalls will swell and deform or may easily rupture or even explode. It was found that the faster water film drainage resulting from the presence therein of the lubricant ,s and surface conditioner composition of this invention makes it possible to lower the temperature of the drying ovens and in turn obtain higher column strength results.
More specifically, in order to obtain adequate drying of the rinsed cans, the cans are allowed to drain briefly before entry into the drying ovens. The time that the cans reside in the drying ovens is typically between 2 and 3 minutes, dependent to some extent on the line speed, oven length, and oven temperature. In order to obtain ade-quate drying of the cans in this time-frame, the oven temperature is typically about 227° C. However, in a series of tests wherein the rinse water contained about 0.3 °lo by weight of organic material to form a lubricant and surface conditioner of this in-vention, it was found that satisfactory drying of the cans could be obtained wherein the oven temperature was lowered to 204° C, and then to 188° C, and dry cans were still obtained.
Examples Group 6 Uncleaned aluminum cans from an industrial can manufacturer are washed clean in examples Type A with alkaline cleaner available from Parker+Amchem Di-3o vision, Henkel Corporation, Madison Heights, Michigan, employing the Ridoline"~
3060/306 process and in Examples Type B with an acidic cleaner, Ridoline~ 125 CO from the same company. Following initial rinsing and before final drying, the cleaned cans are treated with a lubricant and surface conditioner comprised of about 216b30~

a 1 % by weight active organic (I) in deionized water as specified in Table 7 below.
In a separate set of examples, following initial rinsing and before final drying, the cleaned cans are treated with a reactive lubricant and surface conditioner comprised of about a 1% active organic (I) in deionized water plus about 2 g/L (0.2wt%) of the s inorganic (II) as specified in Table 7, below. In yet another set of examples, follow-ing initial rinsing and before final drying, the cleaned cans are treated with a lubri-cant and surface conditioner comprised of about 1 % active organic (I) in deionized water plus about 0.5 % by weight of surfactant (III) specified in Table 7 below. In a further set of examples, following initial rinsing and before final drying, the cleaned cans are treated with a reactive lubricant and surface conditioner forming component, in deionized water, comprised of about 1 % active organic (I), about 0.2 % inorganic (II), about 0.5 % surfactant (III) as specified in Table 7 below.
In all cases in this group of examples, the COF produced on the surface is less than 1.5.
Examples and Comparison Examples Group 7 ,s In this group, various candidate materials for forming a lubricant and surface conditioner were tested at lower concentrations than in Group 6.
7.1 General Procedures. Mobility enhancer/rinse aid process solutions were pre pared using deionized water with a conductivity less than 5 usiemens; unless other wise noted, all other solutions were prepared in tap water. Drawn and wall ironed 2o aluminum cans were obtained from commercial factory production.
Most cans were tested on a pilot scale beltwasher, a single track seven stage conveyor belt type washer (hereinafter denoted "BW") at its highest speed of 6.2 feet per minute ("fpm"). Alternatively, the CCW already noted, which processes 14 cans in a sequence of batch steps under microprocessor control, was employed. Both types of washer were capable of simulating the sequences, dwell and blow off char-acteristics of full scale production washers.
Free Acidity and Fluoride Activities of the cleaner baths were determined as described in the P+A Technical Process Bulletin (No. 968) for Ridoline 124C.
The cleaned and treated cans were dried in an electric forced air oven as described be-low. Can mobility was tested as in Group 1.

n 2~~~~0 Ex- Active InorganicSurfactant (III)pH
Organic (I) am- (B) ple Trade Chemical Type N~,e Description A Emery 657 Caprylic acidA12(S04)3IGEPAL CO-887 2.2 B Emery 659 Capric acid HzZrF6 TRITON X-101 2.2 A Emery 651 Lauric acid FeF3 NEODOL 25-5-3 2.3 B Emery 655 Myristic acidSnCl4 TERGITOL 2.3 A Emersol Palmitic acidCe(N03)4 TRITON DF-16 2.6 143 91 %

B Emersol Stearic acid H2TiF6 TRYCOL 6720 2.6 153 NF 92%

A Emersol Isostearic HZHfFb ANTAROX LF- 2.6 acid B Emersol Oleic acid (NH4)ZZrFbTRITON H-55 2.6 75%

A Empol Dimer acid Fe2(S04)3TRITON H-66 2.6 1014 95%

B Emery Azelaic acid Al(N03)3 TRTTON QS-44 2.6 B Ethox MI5 Ethoxylated TiCl4 TRYCOL 6720 3.0 iso-stearic acid A Emulphor Polyoxyethylat-CeI3 SURFONIC LF- 3.0 VN 430 ed oleic acid 17 B Ethox Polyoxyethylat-FeF3 LOMAR D 3.0 MOS ed oleic acid A Monamide Lauric alkanol-FeCl3 DOWFAX 2A1 2.0 150 LW amide B Monamide Myristic alka-FeBr3 DYASULF 9268- 3.0 150 MW nolamide A

~' Monamide Isostearic HZZrF6 DYASULF C-70 4.0 A alka-150 IS nolamide ... Table continued on next page ...

21 ~~~fl~

Ex- Active InorganicSurfactant (III)pH
Organic (I) am- (II) Pie Trade Chemical Type Name Description B Monamide Stearic alkanol-HZTiFb IGEPAL CO-887 5.0 718 amide A Rhodafac Aliphatic Fe(N03)3 POLYTERGENT 2.0 phos-BH 650 phate ester, SLF-18 acid form B Ethox Aromatic phos-(NH4)ZZrFbPLURONIC L-61 3.0 PP16 phate ester A Rhodafac Aliphatic TaFS TETRONIC 701 6.0 phos-BL 750 phate ester, acid form B Rhodafac Aromatic phos-NbFS PLURONIC 3181 5.0 PE510 phate ester, acid form A Ethfac Aliphatic HZZrFb PLURONIC 4.0 phos-142W phate ester 15081 B Rhodafac Aliphatic (NH4)ZMo04APG 300 6.0 phos-RA 600 phate ester, acid form A Armeen N-Coco-B- HZTiF6 TRITON CF-21 6.0 Z

aminobutyric acid B Hamposyl Lauroyi sarcos-VF4 TRITON DF-18 5.0 L ine A Hamposyl Cocoyl sarcos-FeF3 TRITON GR-7M 4.0 C ine B Hamposyl Oleoyl sarcos-SnCl4 TRITON H-55 3.0 O ine A Hamposyl Stearyl sarcos-A12(SO4)3TRTTON X-100 2.0 S ine B Acusol Polyacrylic HZZrF6 TRITON X-120 4.0 410N acid, sodium salt, ... Table continued on next page ...

WO 95/02660 ~ ~ ~ ~ ~ PCT/(TS94/00024 Ex- Active InorganicSurfactant (III)pH
Organic (I) am- (B) Ple Trade Chemical Type Name Description B Triton Dioctylsulfo-Al(N03)3 TRYCOL 5882 6.0 GR-SM succinate A Avanel Sodium alkyl-VOS04 TRYCOL 5887 5.0 S

70 ether sulfonate B Igepon Sodium N-co- VFS TRYCOL 5964 4.0 TC-42 conut and N-methyl taurate A Igepon Sodium N- VF3 IGEPAL CO-887 3.0 TK-32 methyl-N-tall oil acid taurate B Neodol Sulfonated (NH4)zWO4IGEPAL CO-630 3.0 25- line-3A ar alcohol, am-monium salt A Aromox Bis(2-hydroxy-(NH4)zZrF6NEODOL 25-3 3.0 C/12 ethyl) cocamine oxide B Aromox Dimethylcoc- FeF3 NEODOL 25-35 3.0 DMC amine oxide A Ethoquad Oleyl Fez(S04)3NEODOL 25-9 2.0 0/25 [POE( 15)]

ammonium chloride B Ethoquad Cocomethyl Alz(S04)3NEODOL 91-25 3.0 C/12 [POE(2)]

ammonium chloride A Ethoquad Octadecyl Sn(S04) TRITON QS-15 3.0 1815 [POE( 15)]

ammonium chloride ... Table continued on next page ...

216b3~O

Ex- Active InorganicSurfactant (III)pH
Organic (I) am- (B) Pie Trade Chemical Type Nee Description B Propoquad Tallowalkyl- Ce2(SO4)3TRITON DF-12 2.0 T/12 methyl-bis-(2-hydroxy-2-methylethyl) ammonium methyl sulfate A Ethfac Phosphate HZZrF6 IGEPAL CO-887 2.3 136 ester B Ethox Phosphate HZZrF6 IGEPAL CO-887 2.7 ester A Trylox Ethoxylated HZZrF6 IGEPAL CO-887 2.3 5922 hydrogenated castor oil B Trylox " HZTiF6 IGEPAL CO-887 2.7 A Trylox " HZZrF6 TRITON H-66 2.7 Foam heights were determined by placing 50 milliliters (hereinafter "mL") of the process solution in a 100 mL stoppered graduated cylinder and shaking vigorous-ly for 10 seconds. The total volume of fluid, liquid plus foam, was determined im-mediately and after 5 minutes of standing. These "foam heights" will be referred to hereinafter as "IFH" (initial foam height) and "PFH" (persistent foam height) respectively.
The water break characteristics of cans treated with candidate final rinse mo-bility enhancers ("FRME's) were evaluated by visually rating the amount of water-break on each of the four major surfaces of the can: interior dome and sidewall and 1o exterior dome and sidewall. In this rating scheme a value of 2 is assigned to a com-pletely waterbreak free surface, zero to a completely waterbroken surface and inter-mediate values to waterbreaks in between. Four cans are evaluated in this way and the scores totaled to give a number between 32 and 0, the waterbreak free (WBF) rating number.

WO 95/02660 ~ ~ PCT/US94/00024 7.2 Effect of Cleaner Bath Fluoride Activity On COF and Reflectivity. The CCW
and subsequent drying oven were used as follows:
Stage 1 tap water, 54.4° C, 30 sec.
Stage 2 RIDOLINE~ 124C, 15 mL Free Acid, 3.4 g total of s surfactant, Fluoride Activity 10 to -20 mV in 10 mV
increments, 60° C, 60 sec.
Stage 3 tap water, 30 sec.
Stage 4 deionized water, 90 sec.
Stage 5 optional application of 0.4% ME-40~, 20 sec.
,o Stage 6 not used Oven 5 minutes at 210° C
The "fluoride activity" noted for Stage 2 above is defined and can conven-iently be measured by means of a fluoride sensitive electrode as described above and ~s in more detail in U. S. Patent 3,431,182.
Effectiveness of soil removal was measured by use of the "brightness tester."
This device consisted of a power stabilized high intensity lamp and a fiber optic bundle conveying the light to the can surface. The light reflected from the can im-pinged on a photocell whose current output was amplified and converted to a digital readout by an International Microtronics Inc. Model 350 amplifier; the number dis-played was recorded as the brightness of the surface. The instrument is calibrated with a back silvered plane minor to a measured reflectivity of 440. Once calibrated, the reflectivides of fourteen cans were measured and averaged. With this device it was possible to measure the overall interior reflectivity and exterior dome reflectivi-ty. Results are shown in Figures 1(a) - 1(d).
These results indicate that brightness increases monotonically within the range shown with increasing fluoride activity. COF values, in contrast, appear to peak at fluoride activities corresponding to about +10 my readings and decrease slightly with either increases or decreases from that range. The variation of COF
3o with fluoride activity level in these experiments is actually of relatively little practi-cal importance, compared to the substantial improvement obtained by using a suita-ble FRME material.
If the results shown in Figures 1 (a) - 1 (d) were the only practically important considerations, they would favor the highest fluoride activity levels. For several rea-~s sons, however, this has not been found to be true in commercial practice.
High WO 95/02660 ' 21 b b 3 0 0 pCT~S94/00024 fluoride levels are more costly and promote high etching rates that may increase pol-lution abatement costs or even damage an etched container's ability to contain pres-surized contents such as carbonated beverages. Also, in integrated commercial oper-ations where there is a relatively short time between can formation and cleaning, the oily residues from can forming are easier to remove than in the laboratory experi-ments, where at least a few hours of time normally elapses between forming a set of cans and cleaning them. As a result of these factors, fluoride activity levels corre-sponding to electrode readings of from +50 to -10 my have been found to be gener-ally preferred, with electrode readings from +5 to 0 most preferred. As would be 1o expected from the results shown in Figures 1 (b) and 1 (d), higher fluoride activities within these ranges are preferred when high brightness of the cans is required.
7.3 Screening of Diverse Materials For FRME Activity. The CCW was operated ac-cording to the following scheme, in which the extended Stage 3 rinse time simulated a production sequence wherein the normal Stage 3, 4, and 5 applications were used as nnseS:
Stage 1 sulfuric acid, pH 2.0, 30 sec., 54.4° C
Stage 2 RIDOLINE~ 124C, 15 mL Free Acid, 3.4 g/L total of surfactant, Fluoride Activity -10 mV, 90 sec., 54.4° C
Stage 3 deionized water, 150 sec. (ca. 17.7 L) 2o Stage 4 as noted in Table 8, 30 sec., 29.4° C temperature Stage 5 not used Stage 6 not used For this work Macamine~'~'' SO was predissolved by adding 15 % isopropanol.
For the compositions containing Igepah'''' 430 or polyvinyl alcohol, 1.6 g/L of Igepal'~'"I
z5 CO-887 was added to obtain a homogeneous solution. Results are shown in Table 8.
Among the candidate materials shown in Table 8, oxa-acid esters such as those identified in the table as OAE 1 - 4, are preferred lubricant and surface conditioner formers, as are the ethoxylated castor oil derivatives and amine oxides with hydroxy-ethyl groups bonded to the amine oxide nitrogen, such as Aromox~ C/12 and T/12.
Quaternary ammonium salts, such as the ETHOQUADTM materials exemplified in Table 7 are also in the preferred group. The ethoxylated castor oil derivatives, amine oxides, and quaternary salts are all considered in more detail below.
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Ew ~"w E"'w ~ C7 C ,r" N T..' >, E..' ~ ~ y o U N
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G~LIC~ooUC7x~c,c.v~E-~~Gv~E-~C.~G~xz '-_"w ~a WO 95/02660 ~ ~ .~ PCT/US94/00024 applied for 130 sec and the first oven treatment was performed at 200°
C rather than 150° C. The Stage 4 compositions were as shown in Table 9. The experiment using TryloxTM 5921 included 0.2 g/L of Igepal~'~'' CO-887 in an unsuccessful attempt to clarify the solution; a slight cloudiness persisted even in the presence of the cosur s factant.
Table 9 ETHOXYLATED HYDROGENATED CASTOR OIL DERIVATIVES AND
COMPARISONS AS FINAL RINSE MOBILITY ENHANCERS
~o Product Grams/ COF COF-2 IFH PFH

Name 8 Liters Mean StD Mean StD

None 0 1.231 .149 - - _ _ TryloxTM 5922 1.6 .479 .072 .503 .085 69 65 Trylox~''' 5922 0.4 .974 .161 1.055 .151 60 56 ~s Tryiox"" 59220.8 1.007 .117 1.131 .132 70 60 Trylox~" 5921 1.6 .511 .108 .548 .093 74 68 TryloxTM 5921 0.4 1.072 .144 1.034 .201 63 59 Trylox'~' 5921 0.8 .883 .154 .958 .152 62 54 Trylox'~'' 5925 3.2 .914 .140 1.139 .157 67 62 2o Trylox'~"' 6.4 1.020 .149 1.231 .122 74 67 TryloxTM 5925 9.6 .965 .180 1.007 .122 73 63 EthoxT"' MI-i4 1.6 .621 .118 1.059 .144 75 70 7.5 The Effect of Ethylene Oxide Content On The Properties of Isostearyl FRME's And Binary Mixtures With Other Surfactants. The CCW was charged and operated as described in ~ 7.3 with the Stage 4 variations shown in Table 10. The results in Table 10 indicate that only very slight defoaming at best was achievable with these defoamers. However, lower amounts of ethoxylation of the primary ethoxylated iso-stearic acid lubricant and surface conditioner forming composition result in less foam, with COF values that are fully adequate for most applications. Mixtures of the "defoamers" Pluronic"~ 3181 and Trycol"~ 6720 with Ethox"~ MI-9 produced somewhat more foam than compositions with an equal total amount of Ethox~ MI-9 WO 95/02660 2 I 6 b 3 0 0 PCT/US94/00024 Table IO
EFFECT OF VARIATION OF DEGREE OF ETHOXYLATION IN PRIMARY LUBRICANT
AND SURFACE CONDITIONER (ETHOXYLATED ISOSTEARIC ACID) AND OF
s VARIATION OF COSURFACTANT ADDED AS ATTEMPTED DEFOAMER
COF Ethoxylated Defoamer IFH PFH

Isostearic Acid Mean StD ~/8L # of ~ Name EO

~o per Molecule 1.139 .170 0 - 0 - - -1.159 .181 0 - 0 - - -15 1.069 .165 0 - 0 - - -1.190 .158 0 - 0 - -1.154 .198 0 - 0 - - -1.142 .174 (Averageof resultwithabove five lots) can 20 .587 .170 0 - 1.60Pluronic~" 77 50 .817 .155 0 - 1.60Triton'' DF-1679 55 .659 .175 0 - 1.60Trycoh" LF-1 50 50 .499 .099 1.60 9 0 - 55 55 25 .478 .072 1.20 9 .40 Pluronic''~ 61 58 .479 .093 1.20 9 .40 Triton'' DF-1663 62 .423 .027 1.20 9 .40 Trycoh" LF-1 69 67 .408 .038 .80 9 .80 Pluronic'''r' 65 63 .576 .172 .80 9 .80 Triton" DF-16 72 69 30 .467 .103 .80 9 .80 Trycol'~' LF-165 63 .496 .122 .40 9 1.20Pluronic'M 67 64 .628 .176 .40 9 1.20Triton'' DF-1678 76 .656 .194 .40 9 1.20Trycol~'' LF-173 66 s5 .457 .074 1.60 10.5 0 - 60 60 .465 .121 1.20 10.5 .40 Pluronic'''' 60 59 .531 .108 1.20 10.5 .40 Triton'' DF-1667 66 .566 .186 1.20 10.5 .40 Trycol''~ LF-165 65 .583 .114 .80 10.5 .80 Pluronic'~'' 58 57 40 .564 .142 .80 10.5 .80 Triton'' DF-1672 72 .550 .114 .80 1-0.5 .80 Trycol'~' LF-169 65 .539 .111 .40 10.5 1.20Pluronic''r' 55 53 .685 .205 .40 10.5 1.20Triton'' DF-1675 70 .644 .133 .40 10.5 1.20TrycolT~' LF-177 62 .444 .104 1.60 14 0 - 76 75 .477 .098 1.60 14 0 - 77 75 .534 .093 1.20 14 .40 Pluronic'~' 74 71 .456 .121 1.20 14 .40 Triton" DF-16 80 75 50 .516 .148 1.20 14 .40 Trycol'~' LF-181 80 .505 .106 .80 14 .80 Pluronic~'' 82 79 .532 .128 .80 14 .80 Triton'' DF-1685 84 .456 .078 .80 14 .80 Trycol~'' LF-186 83 .681 .178 .40 14 1.20Pluronic'M 82 79 55 .615 .149 .40 14 1.20Triton'' DF-1681 78 .538 .106 .40 14 1.20Trycoh" LF-1 80 76 WO 95/02660 ~ ~ PCT/US94100024 alone, but also give further reductions in the COF. The interactions are evidently complex and difficult to predict.
7.6 Final Rinse Mobility Enhancers and Water Drainage Aids. The BW was op-erated as follows:
s Stage 1 sulfuric acid, pH 2.0, 54.4° C
Stage 2 RIDOLINE 124C, 15 mL Free Acid, 3.4 g/L of total surfactant, Fluoride Activity -10 mV, 60° C
Stage 3 tap water Stage 4 not used ,o Stage 5 deionized water Stage 6 as noted in Table 11, 0.2 g/L total active additive.
Table 11 VARIATION OF WATER DRAINAGE WITH LINE SPEED AND ADDITIVE
,5 TO FINAL RINSE
Lubricant and/or Water Line Water Retention COF COF-2 Drainage Promoting Additive Speed Mean StD Mean StD e~
S
2o None 100 31.72 - - - -None 100 30.44 - - - -None 70 28.40 - - - -None 70 28.29 .81 1.446 .071 -None 70 27.02 1.00 - - -25 None 40 23.34 - - - -Ethox't" MI-14 40 19.11 - - - -Neodol'~'' 91-2.5 70 15.65 .37 1.356 .211 -Pluronic'''''' L-81 70 17.44 .14 1.124 - -PluronicT" L-61 70 17.71 .09 1.206 - -3o Neodol~ 91-6 70 20.83 .27 1.201 .175 -EthoxT''' MI ~4/

70 21.02 .53 .728 - .970 Pluronic L-81 (1:1) Ethox~''' MI

X 70 21.63 .32 .725 - .832 Pluronic L-61 (1:1) 35 Ethal's' OA-23 70 21.64 .72 .919 - 1.141 Ethox'~'' MI-14 70 21.68 .18 - - -Ethox''t'' MI-14 70 21.69 - - - -Ethox'1'r' MI-10.5 70 21.93 .38 .550 - .727 Neodol~'' 91-8 70 22.55 .30 1.009 .204 -4o Ethox~" MI-14/

Trylox~" 5922 (1:1) 70 24.07 1.00 .581 - .707 TryloxT~' 5925 70 24.62 .92 1.090 - -Trylox~'' 5922 70 25.21 .97 .581 - .680 Trylox''~ 5921 70 25.88 .26 .546 - .645 a5 Ethox''r" MI-14 100 26.60 - - - -WO 95/02660 ~ ~ ~ PCTIUS94/00024 The line speed of this washer was controlled by a rheostat with the following approximate relationship between percentage of output and line speed in feet per minute:
Setting: 100% Speed: 6.2 fpm 70 3.4 "
40 1.8 " .
Three sets of 14 cans each were treated and collected at the end of the washer using tongs. The cans were stacked on a light gauge aluminum baking pan and weighed with the tongs taking care to lose as little water as possible during the manipulations.
,o The cans, tongs and tray were then dried at 210° C for ten minutes and reweighed.
The average of three replicate runs was taken as an estimation of the water retention of the finished cans. A fourth set of cans was collected, dried at 210°
C for 3 min-utes and tested to determine their COF. For those cases where the COF was less than 1.00 the COF-2 was determined. Results are shown in Table 11. Some sur-,s factants were found that are better at promoting water drainage than the ethoxylated isostearic acids that are very effective in providing lubricant and surface conditioner films. However, the surfactants that are exceptionally good at promoting water drain-age are much poorer than ethoxylated isostearic acids in reducing COF. Mixing the two types permits improvement in water drainage, while retaining the ability to achieve COF values that are adequate in many applications.
7.7. Amine Oxide and/or Quaternary Ammonium Salt Combinations with Fluoride.
General Conditions for the Examples and Comparison Examples in & 7 7 All the process examples and comparison examples described below in this section used aluminum cans as substrates and a laboratory prototype simulation of a is commercial six stage processor. Each run was made with 14 cans. The process se-quence used is described in Table 12.
Stage 4 compositions were prepared either by dilution of concentrate or di-rectly from the ingredients. In order to simulate what happens in a commercial can washing operation, the aluminum level (i.e., the stoichiometric equivalent as alumin-um of the total of components (D) and (E) above) was adjusted to about 100 ppm, to account for Stage 3 drag-out into Stage 4. Additionally, the pH, fluoride activity, and concentrations of other components varied with the particular experiment, as WO 95/02660 PCTlUS94/00024 Table 12 Times in seconds for: Temp., Spray Dwell Blow-Off ° C Composition 1 30 10 30 54.4 Aqueous H2S04 to give pH = 2.
2 90 10 30 60.0 See Notes for this table below.
3 30 10 30 22~4 Tap Water 4 20 20 30 37.8 Varies; see details below.
5 30 0 0 22~4 Tap water rinse 6 90 0 30 22~4 DI water rinse Notes for Table 12 The composition for Stage 2 contained (i) a commercially available sulfuric acid and surfactant cleaner (RmOLINE~ 124-C from P+A) at a concentration to give 3.4 grams per liter of total surfactant and (ii) hydrofluoric acid, and if needed, additional 2o sulfuric acid to give a free acid value of 15 points and a fluoride ion activity reading of -10 mv, using the Orion instrument and associated electrodes as described in the main text above. The free acid points are determined by titrating a 10 mL
sample of the composition, dissolved in about 100 ml of distilled water, with 0.10 N
NaOH so-lution, using a phenolphthalein indicator after dissolving a large excess of sodium is fluoride (about 2 - 3 ml in bulk volume of powdered dry reagent) in the sample be-fore titrating. The points of free acid are equal to the number of mL of titrant re-quired to reach a faint pink end point.
described specifically below.
Cans washed and rinsed according to the six stage process described above were dried for 5 minutes at 150° C under normal conditions, except that when heat resistant mobility was being tested, the cans were subsequently placed in a 200° C
oven for an additional 5 minutes. These conditions were identified as single and double baked cans, respectively.
All determinations of coefficient of friction (hereinafter often abbreviated as "COF") were made in the manner described in lines 44 - 65 of U. S. Patent 4,944, 889 and were the average of 15 individual measurements.

WO 95/02660 ' w 216 6 3 0 0 pCT/US94/00024 The domes were removed from the cans using a can opener. Once this was done, they were placed in a 66° C water bath containing 0.2 grams of sodium tetra-borate decahydrate per 1000 mL of deionized water. Following immersion for 30 minutes, the domes were rinsed with DI water and dried in an oven. The quality of s resistance to dome staining was judged on a visual basis with cleaned only (non treated) cans as a negative control and cans treated with Alodine~ 404 as a positive control. Both the exterior and interior dome surfaces were inspected.
Example and Comparison Example Group 7 7 1 In this group, component (A) as described above was Aromox~ C/12, which ,o according to its supplier is an amine oxide with a chemical structure represented by:
Cocoa-N(O)(CHZCHZOH)2, where "Cocoa" represents the mixture of alkyl groups that would result by substitut-ing a -CHZ moiety for each -COOH moiety in the mixture of fatty acids obtained upon hydrolysis of natural coconut oil.
,s The values of the variables in this group of experiments are shown in Table 13, and the particular combinations of these variables tested and the resulting coeffi-cients of friction on the cans treated are shown in Table 14.

Variable yalues of the Variables:

High Medium Low H2ZrF61 0.0099 0.0069 0.0040 pH 4.50 3.50 2.50 Molar Ratio of 2.0 1.0 0.0 H3P04 to H2ZrF6 Molar Ratio of A02 to H2ZrF6 1.0 0.75 0.5 Notes for Table 13 ao 1 Values shown are moles in 8 liters of composition.
2 "AO" means "amine oxide", in this case Aromox~ C/12.

WO 95/02660 ~ ~ ~ PCTILJS94/00024 Run No. Values in Run COF-8B2 COF-DB3 for Variable with This Number:

s HZZrF6__PH Ix3po41~ LAOI~

LZZrF61 L2zrF61 1 0 0 0 0 0.739 0.874 2 -1 +1 +1 +1 1.421 -~0 3 +1 +1 -1 +1 0.728 0.712 4 -1 -1 -1 +1 1.065 1.189 +1 -1 -1 +1 0.565 0.638 6 0 0 0 0 0.582 0.578 7 +1 -1 +1 -1 1.366 -~s 8 -1 -1 +1 +1 1.410 -9 +1 -1 +1 +1 0.605 0.581 -1 +1 -1 +1 0.781 0.885 11 0 0 0 0 1.046 -12 -1 -1 +1 -1 1.547 -zo 13 +1 +1 +1 +1 1.459 -14 -1 -1 -1 -1 1.312 -+1 +1 -1 +1 0.609 0.588 16 0 0 0 0 0.606 0.647 17 -1 +1 +1 -1 1.410 -2s 18 +1 +1 +1 -1 1.470 -19 +1 -1 -1 -1 0.550 0.593 -1 +1 -1 -1 1.400 -21 0 0 0 0 0.828 0.880 Footnotes for Table 1 The value is expressed as high ("+1"), medium ("0"), or low ("-1"), with the numerical meanings for these values given in Table 13.
2 "SB" = single bake.
3 "DB" = double bake ~s Example and Comparison Example Group 7 7 2 In this group quaternary ammonium salts were used instead of the amine oxide in Group 1. The particular salts used are shown in Table 15.

TABLE 15: QUATERNARY AMMONIUM BALTB
Trademark Name Chemical Structure of:
Cation Counter Ion ETHOQUAD~ C-12 Cocoa-N-(CH3)(CH2CH20H)2 C1-~o ETHOQUAD~ C-12B Cocoa-N-(CH2~)(CH2CH20H)2 C1-ETHOQUAD~ T-13/50 Tallow-N-(CH2CH20H)3 -OC(0)CH3 Notes for Table 15 "Cocoa" here means the same mix of alkyl groups as already noted in the main text, while "Tallow" means the same as "Cocoa" except that animal tallow is substituted for coconut oil in the definition given. "c~" represents a phenyl moiety.
All the Stage 4 compositions in this group contained 9.6 crams of A12(SO4)3 ~ 151/2H20 (which corresponds to 104 ppm of Al+3), 2.05 grams of HZZrF6, and 0.0099 ~ 0.0001 mole of quaternary ammonium salt; those compositions desig-nated with "/PA" in Table 16 below also had 0.97 grams of H3P0,,, all in 8 liters of total composition. The compositions all had a pH value of 2.5. The results of the treatments as described are shown in Table 16 below.
Example and Comparison Example Group 7 7 3 In this group, only ETHOQUAD~ T-13/50 was used as component (A), and only HZZrF6 was used as component (B). In addition to concentration of the ETHO-QUAD~ T-13/50, the other variables investigated were H2ZrF6 concentration, pH, and nitrate versus sulfate anions in solution. In order to adjust pH and free F~, it was found advantageous to use sodium aluminate as a partial source of aluminum. In all compositions in this group, sodium aluminate at a concentration of 50 ppm as Al was used along with phosphoric acid in an amount equimolar with the HzZrF6 used;
fluoride activity was adjusted to a reading of -90 my on fluoride sensitive electrode as described above. An additional 50 ppm of A1 was added as (l) aluminum sulfate, in which case sulfuric acid was used to adjust the pH; (ii) as aluminum nitrate, in which case nitric acid was employed to adjust the pH; or (ii) both aluminum nitrate WO 95/02660 ~ ~ PCT/US94/00024 Quat in Composition Free F-1 COF-SB COF-DB -DS
ETHOQUAD~ C-12 -89.0 1.12 1.28 3 s ETHOQUAD~ C-12/PA -90.0 0.69 0.87 3 ETHOQUAD~ C-12B -93.1 0.98 1.21 3 ETHOQUAD~ C-12B/PA -89.9 0.90 0.94 3 ETHOQUAD~ T-13/50 -84.0 0.85 0.98 3 ETHOQUAD~ T-13/50/PA -90.3 0.49 0.53 2 _____________________________ Notes for Table 16 The column headed "Free F'" gives the readings for the composition in milli-volts, using an Orion Fluoride Sensitive Electrode and apparatus standardized with 120E Activity Standard Solution as described above. The column headed "DS"
,s gives dome stain resistance evaluations on the following scale: 1 = Better (less staining) than with ALODINE~ 404; 2 = Equal staining as when using ALODINE~
404; 3 = As much staining as with no additive in Stage 4 (worse than with ALO-DINE~ 404. "COF-SB" = coefficient of friction with single bake, and "COF-DB" -coefficient of friction with double bake.
and aluminum sulfate were added, in which case both acids, in the same molar ratio as their corresponding aluminum salts, were used to adjust the pH. The results are reported in detail below. The four variables tested and the three values of each such is variable are shown in Table 17, and the combinations of the values of the three variables and the results are shown in Table 18.

yariable Values and Designator for Variable:

BiQh Medium Low Moles of H2ZrF6 X1 = ~in 8 liters of 0.009 0.00675 0.0045 ~

composition X2 = pH 3.1 2.8 2.5 Molar percent of the X3 = aluminum salts) 100 50 0 that was aluminum nitrate Molar ratio of , X4 = ~ ETHOQUAD~ T-13/50 1 1.00 0.75 0.5 l to H2ZrF
,6 Run No. X1 X2 X3 X4 COF-8B COF-DB _D8 1 1 -1 -1 -1 0.513 0.531 2 s 2 1 1 1 1 0.544 0.700 3 3 1 1 -1 -1 1.274 1.406 3 4 0 0 0 0 0.499 0.629 3 -1 -1 1 -1 0.508 0.517 2 6 0 0 0 0 0.572 0.731 2 7 0 0 0 -1 1.229 1.257 3 8 -1 1 1 -1 1.421 1.397 3 ~9 0 0 1 0 0.516 0.700 2 -1 1 -1 -1 1.451 1.458 3 11 1 1 1 -1 1.311 1.412 3 is 12 1 1 -1 1 0.976 1.149 3 13 0 0 0 1 0.501 0.549 2 14 -1 1 1 1 0.762 1.049 3 1 -1 1 -1 0.552 0.553 1 16 0 -1 0 0 0.537 0.553 2 17 1 -1 1 1 0.559 0.592 1 18 0 1 0 0 1.158 1.346 3 19 1 -1 -1 1 0.522 0.561 1 20 0 0 0 0 0.599 0.813 3 21 -1 0 0 0 0.484 0.518 2 2s 22 0 0 0 0 0.619 0.732 3 23 -1 1 -1 1 0.738 0.998 3 24 1 0 0 0 0.732 0.913 3 0 0 0 0 0.581 0.875 3 26 -1 -1 -1 1 0.520 0.546 2 27 -1 -1 1 1 0.511 0.518 2 28 -1 -1 -1 -1 0.503 0.532 2 29 0 0 0 0 0.610 0.673 2 Notes for Table In the mns X2", ", and the entry+1"
colu headed "X3 "X4", " indicates "X1", the "

high valuefor variable specifiedin Table ; the "0"
the as 17 entry indicates the middle ; and try value the en "-1"
for the indicates variable as specified in Table the low ue Other val for column the headings variable and as specified in Table 17.

meanings are the same as in Table 16.

216b300 WO 95/02660 ' PCTIUS94/00024 Example and Comparison Example Group 7 7 4 In this group, the general conditions and materials used were the same as for Group 7.7.3 except that in all cased in this group, aluminum sulfate and sulfuric acid were used and no aluminum nitrate or nitric acid was used, but the values of the s some of the variables were different. The various combinations and the resulting performance are shown in Table 19.

Run QH Concentration in Mil- Molar OF-SB COF-DB DS
C

No. moles ver Ratiosl Liters of:

H ZrFs H PO, T13' 1 CLEAN ONLY 1.155 - 3.0 2 2.00 9.00 9.00 4.50 1:1:0.5 0.543 0.582 3.0 3 2.20 9.00 9.00 4.50 1:1:0.5 0.546 0.551 2.0 i5 4 2.50 9.00 9.00 4.50 1:1:0.5 0.505 0.492 2.0 2.50 9.00 0.00 4.50 1:0:0.5 0.584 0.576 3.0 6 2.50 9.00 4.50 2.25 1:0.5:0.250.512 0.557 3.0 7 2.50 9.00 4.50 9.00 1:0.5:1 0.522 0.545 2.0 8 2.50 9.00 4.50 18.00 1:0.5:2 0.479 0.509 2.0 20 9 2.50 9.00 18.00 2.25 1:2:0.25 0.511 0.531 2.0 2.50 9.00 18.00 9.00 1:2:1 0.514 0.513 2.0 11 2.50 9.00 18.00 18.00 1:2:2 0.466 0.491 1.5 12 2.50 4.50 2.25 1.13 1:0.5:0.250.481 0.496 2.5 13 2.50 4.50 2.25 4.50 1:0.5:1 0.485 0.528 3.0 25 14 2.50 4.50 2.25 9.00 1:0.5:2 0.468 0.509 3.0 2.50 4.50 9.00 1.13 1:2:0.25 0.531 0.577 2.5 16 2.50 4.50 9.00 4.50 1:2:1 0.475 0.480 2.0 17 2.50 4.50 9.00 9.00 1:2:2 0.458 0.503 2.0 18 2.50 13.50 6.75 3.38 1:0.5:0.250.515 0.529 2.0 19 2.50 13.50 6.75 13.50 1:0.5:1 0.497 0.544 1.5 2.50 13.50 6.75 27 1:0.5:2 0.470 0.519 1.5 21 2.50 13.50 27.00 3.38 1:2:0.25 1.453 1.338 2.0 22 2.50 13.50 27.00 13.50 1:2:1 0.535 0.595 2.0 23 2.50 13.50 27.00 27 1:2:2 0.479 0.514 1.5 35 24 2.80 9.00 9.00 4.50 1:1:0.5 0.568 0.733 2.0 ALODINE~ 1.463 - 2.0 Footnotes for Table 19 1 The ratios are shown in the order: HZZrF6:H3P04:T13.
4° 2 "T13" means ETHOQUAD~ T-13/50.
Other Notes for Table 19 The column headings "COF-SB", "COF-DB", and "DS" and the entries in these columns have the same meanings as in Table 16.

A preferred group of concentrates according to this embodiment of the inven-tion has the following compositions, with water forming the balance of each compo-sition not specified below:
In redient Grams of Ingredient per Kilogram of Concentrate Composition Inorganic Make-Up Concentrate 45 % Fluozirconic acid solution in water 32.3 75 % Phosphoric acid solution in water 9.1 Aqueous nitric acid, 42 ° Baum~ 25.5 Organic Make-Up and Replenisher Concentrate ETHOQUAD~ T-13/50 70.0 SURFYNOL~ 104 23.8 Inorganic Replenisher Concentrate 45 % Fluozirconic acid solution in water 44.4 ~s 75 % Phosphoric acid solution in water 12.6 70 % Hydrofluoric acid solution in water 4.6 Aqueous nitric acid, 42 ° Baum~ 38.7 The SURFYNOL~ 104 noted above was added for its antifoam activity; it is a commercial product of Air Products and Chemicals Co. and is reported by its sup-plier to be 2,4,7,9-tetramethyl-5-decyn-4,7-diol.
In a preferred process embodiment of this invention, a working composition was prepared by adding 1 % of each of the above noted Make-Up Concentrates to de-ionized water, and the resulting solution, which had a pH within the range from 2.7 to 2.9 and a fluoride activity value between -60 and -80 my relative to Standard So-lution 120E was used in stage 4 to treat commercially supplied D & I aluminum cans for mobility enhancement by spraying the cans for 25 sec at 43° C. The resulting cans had COF-SB values in the range from 0.5 to 0.6 and dome staining resistance equal to that achieved with ALODINE~ 404, particularly when the aluminum cation concentration in the treating composition was in the range from 100 - 300 ppm.
As the treating composition is used, replenisher compositions as described above are added as needed to maintain the COF and dome staining resistance.
If a one package make-up concentrate is required, the following is an examp-1e of a preferred concentrate, with water forming the balance not otherwise stated:
Ingredient Grams of Ingredient per Kilogram of Concentrate Composition Aqueous sulfuric acid, 66 ° Baum~ 13.0 s 45 % Fluozirconic acid solution in water 41.4 75 % Phosphoric acid solution in water 11.6 70 % Hydrofluoric acid solution in water 7.7 ETHOQUAD~ T-13/50 40.9 In a preferred process embodiment using this concentrate, 50 mL of concen ,o trate was diluted to form 8 liters of working composition, with the pH
adjusted if necessary to 2.4 - 2.6 and the free fluoride activity to -85 to -95 mv. A COF
value of less than 0.6 was obtained in several experimental trials over a thirteen week per iod of storage of the concentrate.
Examples and Comparison Examples Group 8 The combination of ethoxylated castor oil derivatives and fluozirconic acid shown in Table 8 above has been found to have an unexpected additional advantage, which is illustrated further in this group.
An FRME combining fluozirconic acid and hydrogenated castor oil deriva-tives in proper concentrations has been found to provide both protection against dome staining during pasteurization and adequate lowering of the COF for most pur-poses.
The can washing setup for this group of examples was:
Stage 1 sulfuric acid, pH 2.0, 30 sec., 54.4° C
Stage 2 RIDOLINE~ 124C, 15 mL Free Acid, 3.4 g/L total of surfactant, Fluoride Activity -10 mV, 90 sec., 54.4° C
Stage 3 deionized water, 150 sec. (ca. 17.7 L) Stage 4 as noted in Table 7 and below, 20 sec. spray + 20 sec.
dwell, 29.4° C temperature Stage 5 not used Stage 6 not used In addition to the ingredients listed in Table 7, the solutions were all adjusted to pH 4.5 by addition of aqueous ammonia or nitric acid as required.

WO 95/02660 ' 216 b 3 0 0 PCT/US94/00024 Dome staining was evaluated by first removing the domes from the treated cans with a can opener. The domes were then placed in a water bath containing 0.2 g/L of borax at 65.6° C for 30 minutes, then rinsed in deionized water and dried in an oven. Staining resistance was evaluated visually by comparison with known sat-s isfactory and unsatisfactory standards. Results are shown in Table 20. The last two conditions shown in Table 20 are highly satisfactory with respect to both COF
and dome staining resistance during pasteurization.
Table 20 '° EFFECT OF CONCENTRATIONS OF ETHOXYLATED CASTOR OIL
DERIVATIVE AND OF FLUOZIRCONIC ACID ON DOME STAINING
RESISTANCE AND COEFFICIENT OF FRICTION
Grams of Grams of COF Pasteurization H ZrF iter Trylox"~ Protection Rating 5921/Liter 0 0 1.16 Fail 0 0.2 0.57 Fail 0.14 0.2 0.52 Fail 0.29 0.2 0.61 Marginal 0.58 0.2 0.63 Pass 1.16 0.2 0.70 Pass Examples and Comparison Examples Group 9 This group illustrates use with tin cans. Three types of materials were tried 2s as lubricant and surface conditioner forming and water drainage promoting agents for tin cans: (i) Ethox""t MI-14; (ii) a combination of 1 part by weight of Pluronic'~
3181 and 4 parts by weight of Plurafac'~ D25; and (iii) Tergitol"~ Min-Foam'~"'r 1X.
Of these, the Ethox"~, Tergitol"~, and Plurafac~ products are ethoxylated fatty acids or alcohols, with a poly{propylene oxide} block cap on the end of the poly{ethylene oxide } block in some cases, while the Pluronic~ is a block copolymer of ethylene and propylene oxides, with poly { propylene oxide } block caps on the ends of the pol ymers. All were used at a concentration of 0.2 g/L of active material with deionized water in a final rinse before drying, after an otherwise conventional tin can washing WO 95/02660 216 6 3 p 0 PCT/~JS94/00024 sequence. Water retention and COF values were measured as generally described above. Results are shown in Table 21.
Table 21: RESULTS WITH TIN-PLATED STEEL D&I CANS
Additive to Final Rinse Mean COF Value Percent Water Retention None 1.04 100 % (Defined) Ethox~ 0.70 83.6 Pluronic"~/Plurafac'~ 0.81 77.3 Tergitol"''t 0.82 78.6 ,o

Claims

CLAIMS:

1. A process comprising steps of (i) cleaning a formed metal container, preferably an aluminum can or tin-plated steel can, with an aqueous acidic or alkaline cleaning solution, (ii) subsequently contacting at least one exterior surface of the cleaned metal container with an aqueous lubricant and surface conditioner forming composition, (iii) drying the metal container after steps (i) and (ii), and (iv) subsequently conveying the cleaned and dried can via automatic conveying equip-ment to a location where it is lacquered or decorated by printing or both, character-ized in that the aqueous lubricant and surface conditioner comprises at least one of the following groups of constituents:
(I) fluozirconic acid and one or more ethoxylated castor oil derivatives in amounts sufficient to impart to the dome of a can treated therewith staining resistance during subsequent pasteurization of the contents of the can;
(II) (A) a dissolved phosphorus containing surfactant component that is a mix-ture of molecules conforming to the general formula I:

(I), where M is selected from the group consisting of H, alkali metal cat-ions, monovalent fractions of alkaline earth metal cations, and mono-valent fractions of ammonium and substituted ammonium cations; x =
1 or 2 and y = 3-x; Y is an alkylene or alkylene ether group, which may be branched or unbranched, with its open valences on carbon atoms and with from 2 to 12 carbon atoms and up to 3 oxygen atoms;
and R is an imidazoline moiety conforming to general formula II:

(II), where each of R1 and R2 is independently selected, except that R1 and R2 may not both be hydrogen, from the group consisting of hydrogen, a moiety derived from propionitrile by removing a hydrogen atom from the -CH3 group thereof, and moieties of the general formula III:

(III), where Q is selected from the group concisting of -OM, -NH2, and -OR4, where M has the same meaning as defined above and R4 repre-sents a C2-12 alkyl, alkylaryl, or alkylcycloaliphatic moiety; and R3 is selected from the group consisting of unsubstituted and hydroxy sub-sdtuted aliphatic and cycloaliphatic and alkylaryl moieties having from 2 to 22 carbon atoms;
(B) a component selected from the group of water soluble salts containing ions that comprise atoms selected from the group consisting of Zr, Ti, Sn, Al, and Fe;
(C) a metal etching component; and (D) "free fluoride ions"; and, optionally, any one or more of the following:
(E) a component selected from molecules conforming to general formula IV:

(IV), wherein R6 is a linear, cyclic, or branched saturated monovalent ali-phatic hydrocarbon moiety containing from 1 to 25 carbon atoms; X
is selected from the group consisting of hydrogen, halogen, phenyl, and R5; s is an integer from 1 to 50; and R5 is selected from the group consisting of hydrogen and alkyl groups containing 1 - 4 carbon atoms;
(F) a component selected from molecules conforming to general formula V:
(V), wherein R7 is a linear, cyclic, or branched saturated monovalent ali-phatic hydrocarbon moiety containing from 4 to 25 carbon atoms;
(C6H4) is an ortho-, meta-, or para-phenylene nucleus; and R5 and s have the same meaning as for formula IV;
(G) a component selected from molecules conforming to general formula VI:

(VI), wherein R8 is a linear or branched, saturated or unsaturated monoval-ent aliphatic hydrocarbon moiety containing from 1 to 25 carbon at-oms; and R5 and s have the same meaning as in formula IV;
(H) a component selected from chelating agents for the metal containing ions of component (II)(B); and (J) an antimicrobial agent;
(III) (A) a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I:

(I), where R1 is a monovalent aliphatic moiety, which may be saturated or unsaturated and contains from 8 to 22 carbon atoms; each of R2 and R3 is a monovalent moiety independently selected from the group con-sisting of (i) alkyl and hydroxyalkyl moieties having from 1 to 8 car-bon atoms and (ii) aryl and arylalkyl moieties having from 6 to 10 carbon atoms; R4 is a monovalent moiety selected from the same group as for R2 and R3 plus the -O- moiety; X? is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a = 0 if R4 is -O- and = 1 if R4 is not -O; and (B) a component of complex fluoride anions; and, optionally but preferably, (C) a component of phosphate ions, optionally also including sulfate or ni-trate ions or both; and, optionally, (D) aluminate anions, including fluoroaluminate anions; and, optionally (E) aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of:
(F) a water soluble and/or water dispersible polymer including amino-sub-stituted vinyl phenolic moieties; and (G) a foam reducing component; and (IV) dissolved organic material, said material being selected from the group consisting of alkoxylated and non-alkoxylated castor oil triglycerides and hy-drogenated castor oil derivatives, oxa-acid esters, and amine oxides with at least one hydroxyethyl group bonded to the amine oxide forming nitrogen atom, said material being present in sufficient amount that the coefficient of static friction of the treated metal container increases less upon heating of the treated metal container beyond the minimum degree of heating needed for drying than does the coefficient of friction of a comparison container treated in the same way, except for substituting ethoxylated isostearic acid for all thealkoxylated and non-alkoxylated castor oil triglycerides and hydrogenated castor oil derivatives, oxa-acid esters, and amine oxides with at least one hy-droxyethyl group bonded to the amine oxide forming nitrogen atom that are present in the lubricant and surface conditioner forming composition.

2. A process according to claim 1, characterized in that the lubricant and surface conditioner forming composition comprices constituent group (III), wherein each of R2 and R3 is selected from the group consisting of hydroxyalkyl moieties having from 1 to 4 carbon atoms and component (C) is present and includes phosphate ions.

3. A process according to claim 2, wherein all of R2, R3, and R4 are 2-hydroxy-ethyl groups and component (B) includes fluozirconate ions.

4. A process according to claim 3, wherein the mixture of R1 moieties in com-ponent (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of coconut oil, palm kernel oil, or animal tallow, and component (C) in-cludes both phosphate and nitrate ions.

5. A process according to claim 4, wherein the mixture of R1 moieties in com-ponent (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of animal tallow.

6. A process according to claim 5, wherein the molar ratio of the phosphate content of component (C) to component (B) to component (A) is within the range from 1.0:(0.90 - 1.10):(1.05 - 1.25).

7. A process according to claim 4, wherein the molar ratio of the phosphate content of component (C) to component (B) to component (A) is within the range from 1.0:(0.8 - 1.2):(0.90 - 1.40).

8. A process according to claim 3, wherein the molar ratio of the phosphate content of component (C) to component (B) to component (A) is within the range from 1.0:(0.7 - 1.3):(0.8 - 1.5).

9. A process according to claim 2, wherein the molar ratio of the phosphate content of component (C) to component (B) to component (A) is within the range from 1.0:(0.5 -2.0):(0.5 - 6.0).

10. A process according to claim 1, characterized in that the lubricant and surface conditioner forming composition comprises constituent group (III), wherein the molar ratio of component (B) to component (A) is within the range from (0.5 - 4.0):(0.25 -8.0).

11. A process according to claim 10, wherein the aqueous lubricant and surface conditioner forming composition has a pH in the range from 2.3 to 3.3, a fluoride activity corresponding to a reading of -30 to -120 mv on a fluoride sensitive electrode, and contains component (A) in an amount from 0.14 to 2.25 mM, component (B) in an amount from 0.4 to 2.0 mM, from 0.28 to 3.4 mM of phosphate ions.

12. A process according to claim 9 wherein the pH of the aqueous lubricant and surface conditioner forming composition is in the range from 2.5 to 3.1, the fluoride activity corresponds to a reading of -50 to -100 mv on a fluoride sensitive electrode, each of R2 and R3 is selected from the group consisting of hydroxyalkyl moietieshaving from 1 to 4 carbon atoms, the concentration of component (A) is within the range from 0.42 to 1.50 mM, and component (C) includes from 0.56 to 3.4 mM of phosphate ions.

13. A process according to claim 8, wherein the pH of the aqueous lubricant and surface conditioner forming composition is in the range from 2.5 to 3.1, the aqueous lubricant and surface conditioner forming composition has a fluoride activity corresponds to a reading of -60 to -85 mv on a fluoride sensitive electrode, all of R2, R3, and R4 are 2-hydroxyethyl groups, the concentration of component (A) is within the range from 0.56 to 1.12 mM, component (B) includes fluozirconate ions, and component (C) includes from 0.56 to 2.2 mM of phosphate ions.

14. A process according to claim 7, wherein the pH of the aqueous lubricant and surface conditioner forming composition is in the range from 2.5 to 3.1, the aqueous lubricant and surface conditioner forming composition has a fluoride activity corresponds to a reading of -68 to -80 mv on a fluoride sensitive electrode; themixture of R1 moieties in component (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of coconut oil, palm kernel oil, or animal tallow; all of R2, R3, and R4 are 2-hydroxyethyl groups; the concentration of com-ponent (A) is within the range from 0.56 to 1.12 mM; component (B) includes fluozirconate ions, and component (C) includes from 0.56 to 2.2 mM of phosphate ions.

15. A process according to claim 6 wherein the pH of the aqueous lubricant and surface conditioner forming composition is in the range from 2.5 to 3.1, the aqueous lubricant and surface conditioner forming composition has a fluoride activity corresponds to a reading of -68 to -80 mv on a fluoride sensitive electrode; themixture of R1 moieties in component (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of animal tallow; all of R2, R3, and R4 are 2-hydroxyethyl groups; the concentration of component (A) is within the range from 0.67 to 0.87 mM; component (B) includes from 0.56 to 1.69 mM of fluozirconate ions; component (C) includes from 0.56 to 2.2 mM of phosphate ions; and the total of the concentrations of components (D) and (E) is not greater than 340 ppm.

16. A process according to claim 1, characterized in that the lubricant and surface conditioner forming composition has a pH from 1 to 8 and comprises constituent group (II), wherein the amount of component (A) is such as to provide from 0.000012 to 0.005 gram atoms of phosphorus per liter of composition; the amount of component (B) is such as to provide from 0.00002 to 0.005 gram atoms of a total of Zr, Ti, Sn, Al, and Fe per liter of composition; the fluoride ion activity is such as to result in a fluoride ion activity meter reading within the range from -50 to -130 mv;
component (A) is selected from molecules conforming to general formula I when the "Y" groups contain from 2 to 4 carbon atoms and no oxygen atoms, R1 and R2 are selected from the group consisting of hydrogen and moieties of general formula III
when Q = OM and M is hydrogen or an alkali metal, and at least 50 mole percent of the total R3 groups in the composition have from 8 to 20 carbon atoms.

17. A process according to claim 16, wherein the amount of component (A) is such as to provide at least 0.000025 gram atoms of phosphorus per liter of compo-sition; the amount of component (B) is such as to provide at least 0.000042 gramatoms of the total of Zr, Ti, Sn, Al, and Fe per liter of composition; the fluoride ion activity is such as to result in a fluoride ion activity meter reading within the range from -60 to -120 mv; and the concentration of fluorine atoms in ingredients of the composition selected from the group consisting of fluoride ions, bifluoride salts, and hydrogen fluoride is at least 0.000051 gram atoms per liter of fluorine atoms.

18. A process according to claim 17, whelein the pH is in the range from 2.0 to 5.0; the amount of component (A) is such as to provide from 0.000051 to 0.001 gram atoms of phosphorus per liter of composition; component (B) includes dissolved fluozirconic acid, fluozirconate ions, or both fluozirconic acid and fluozirconate ions; and the amount of component (B) is such as to provide at least 0.000097 gram atoms of Zr per liter of composition.

19. A process according to claim 18, wherein component (A) is selected from molecules conforming to general formula I when Y is an ethylene group and at least 76 mole percent of the total R3 groups have from 10 to 14 carbon atoms and are un-substituted and unbranched alkyl groups; the amount of component (A) is such as to provide at least 0.00019 gram atoms of phosphorus per liter of composition; the amount of component (B) is such as to provide at least 0.00038 gram atoms of Zr per liter of composition; the amount of component (C) is such as to provide from0.001 to 0.025 gram atoms per liter of hydrogen ions and from 0.002 to 0.050 gram atoms per liter of fluoride atoms; and the amount of component (D) is in the range from 0.001 to 0.01 % by weight.

20. A process according to claim 19, wherein the amount of component (B) is such as to provide no more than 0.00059 gram atoms of the total of Zr, Ti, Sn, Al, and Fe per liter of composition, and the fluoride ion activity is such as to result in a fluoride ion activity meter reading within the range from -75 to -105 mv.

21. A process according to claim 20, wherein the nature and amount of compon-ent (B) are such as to provide from 0.00038 to 0.00059 gram atoms of Zr per liter of composition, and the amount of component (C) is such as to provide from 0.006 to0.014 gram atoms per liter of fluoride atoms.

22. A process according to claim 1, characterized in that the aqueous lubricant and surface conditioner forming composition comprises at least one of constituent groups (I) and (IV); the pH of the aqueous lubricant and surface conditioner forming composition is from 1 to 6.5, preferably from 2 to 5; the content of organic material in the aqueous lubricant and surface conditioner forming composition is not greater than 1.0 g/L, preferably not greater than 0.6 g/L; and the treated metal container after drying has a coefficient of friction that is not greater than 1.2, preferably not greater than 1Ø

23. A process according to any one of claims 1 to 22, characterized in that the cleaning of the metal container is accomplished by contact with an acidic cleaning composition having a fluoride ion activity indicated by a fluoride sensitive electrode reading in the range from +50 to -10 mv.

24. A concentrate additive suitable for dilution with water to form a lubricant and surface conditioner forming aqueous composition for treating metal surfaces to re-duce the coefficient of friction thereof, said additive consisting essentially of water and:
(A) a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I:

(I), where R1 is a monovalent aliphatic moiety, which may be saturated or unsat-urated and contains from 8 to 22 carbon atoms; each of R2 and R3 is a mono-valent moiety independently selected from the group consisting of (i) alkyl and hydroxyalkyl moieties having from 1 to 8 carbon atoms and (ii) aryl and arylalkyl moieties having from 6 to 10 carbon atoms; R4 is a monovalent moiety selected from the same group as for R2 and R3 plus the -O- moiety; X-is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a = 0 if R4 is -O- and = 1 if R4 is not -O-; and (B) a component of complex fluoride anions; and, optionally but preferably, (C) a component of phosphate ions, optionally also including sulfate or nitrate ions or both; and, optionally, (D) aluminate anions, including fluoroaluminate anions; and, optionally (E) aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of:
(F) a water soluble and/or water dispersible polymer including amino-substituted vinyl phenolic moieties; and (G) a foam reducing component.

25. An additive according to claim 24, wherein each of R2 and R3 is selected from the group consisting of hydroxyalkyl moieties having from 1 to 4 carbon atoms and component (C) is present and includes phosphate ions.

26. An additive according to claim 25, wherein all of R2, R3, and R4 are 2-hy-droxyethyl groups and component (B) includes fluozirconate ions.

27. An additive according to claim 26, wherein the mixture of R1 moieties in component (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of coconut oil, palm kernel oil, or animal tallow, and component (C) includes both phosphate and nitrate ions.

28. An additive according to claim 27, wherein the mixture of R1 moieties in component (A) corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of animal tallow.

29. An additive according to claim 28, wherein the molar ratio of the phosphate content of component (C) to component (B) to component (A) is within the range from 1.0:(0.90 - 1.10):(1.05 - 1.25).

30. A liquid composition of matter consisting essentially of water and:
(A) a dissolved phosphorus containing surfactant component that is a mixture of molecules conforming to the general formula I:
(I), where M is selected from the group consisting of H, alkali metal cations, monovalent fractions of alkaline earth metal cations, and monovalent fractions of ammonium and substituted ammonium cations; x = 1 or 2 and y = 3-x; Y is an alkylene or alkylene ether group, which may be branched or unbranched, with its open valences on carbon atoms and with from 2 to 12 carbon atoms and up to 3 oxygen atoms; and R is an imidazoline moiety conforming to general formula II:

(II), where each of R1 and R2 is independently selected, except that R1 and R2 may not both be hydrogen, from the group consisting of hydrogen, a moiety derived from propionitrile by removing a hydrogen atom from the -CH3 group thereof, and moieties of the general formula III:

(III), where Q is selected from the group consisting of -OM, -NH2, and -OR4, where M has the same meaning as defined above and R4 represents a C2-12 alkyl, alkylaryl, or alkylcycloaliphatic moiety; and R3 is selected from the group consisting of unsubstituted and hydroxy substituted aliphatic and cycloaliphatic and alkylaryl moieties having from 2 to 22 carbon atoms;
(B) a component selected from the group of water soluble salts containing ions that comprise atoms selected from the group consisting of Zr, Ti, Sn, Al, and Fe;
(C) a metal etching component; and (D) "free fluoride ions"; and, optionally, any one or more of the following:
(E) a component selected from molecules conforming to general formula IV:

(IV), wherein R6 is a linear, cyclic, or branched saturated monovalent aliphatic hy-drocarbon moiety containing from 1 to 25 carbon atoms; X is selected from the group consisting of hydrogen, halogen, phenyl, and R5; s is an integer from 1 to 50; and R5 is selected from the group consisting of hydrogen and alkyl groups containing 1 - 4 carbon atoms;
(F) a component selected from molecules conforming to general formula V:

(V), wherein R7 is a linear, cyclic, or branched saturated monovalent aliphatic hy-drocarbon moiety containing from 4 to 25 carbon atoms; (C6H4) is an ortho-, meta-, or para-phenylene nucleus; and R5 and s have the same meaning as for formula IV;
(G) a component selected from molecules conforming to general formula VI:

(VI), wherein R8 is a linear or branched, saturated or unsaturated monovalent ali-phatic hydrocarbon moiety containing from 1 to 25 carbon atoms; and R5 and s have the same meaning as in formula IV;
(H) a component selected from chelating agents for the metal containing ions of component (B); and (J) an antimicrobial agent.

31. A composition according to claim 30, wherein the amount of component (A) is such as to provide from 0.000060 to 5 gram atoms of phosphorus per liter of composition; the amount of component (B) is such as to provide from 0.00010 to 5gram atoms of the total of Zr, Ti, Sn, Al, and Fe per liter of composition; component (A) is selected from molecules conforming to general formula I when the "Y" groups contain from 2 to 4 carbon atoms and no oxygen atoms, R1 and R2 are selected from the group consisting of hydrogen and moieties of general formula III when Q = OMand M is hydrogen or an alkali metal, and at least 50 mole percent of the total R3 groups in the composition have from 8 to 20 carbon atoms.

32. A composition according to claim 31, wherein the amount of component (A) is such as to provide at least 0.0010 gram atoms of phosphorus per liter of compo-sition; the amount of component (B) is such as to provide at least 0.0017 gram atoms of the total of Zr, Ti, Sn, Al, and Fe per liter of composition; and the concentration of fluorine atoms in ingredients of the composition selected from the group consisting of fluoride ions, bifluoride salts, and hydrogen fluoride is at least 0.0020 gram atoms per liter of fluorine atoms.

33. A composition according to claim 32, wherein the amount of component (A) is such as to provide from 0.0010 to 0.40 gram atoms of phosphorus per liter of composition; component (B) includes dissolved fluozirconic acid, fluozirconate ions, or both fluozirconic acid and fluozirconate ions; and the amount of component (B) is such as to provide at least 0.0039 gram atoms of Zr per liter of composition.

34. A composition according to claim 33, wherein component (A) is selected from molecules conforming to general formula I when Y is an ethylene group and at least 76 mole percent of the total R3 groups have from 10 to 14 carbon atoms andare unsubstituted and unbranched alkyl groups; the amount of component (A) is such as to provide at least 0.020 gram atoms of phosphorus per liter of composition; the amount of component (B) is such as to provide at least 0.0040 gram atoms of Zr per liter of composition; the amount of component (C) is such as to provide from 0.21 to 11 gram atoms per liter of fluoride atoms; and the amount of component (D) is inthe range from 0.10 to 2.2 % by weight.

35. A composition according to claim 34, wherein the nature and amount of com-ponent (B) are such as to provide from 0.057 to 0.103 gram atoms of Zr per liter of composition, and the amount of component (C) is such as to provide from 0.9 to 2.4 gram atoms per liter of fluoride atoms.