AU683047B2 - Aqueous lubricant and surface conditioner for formed metal surfaces - Google Patents

Description

OPI DATE 13/02/95 AOJP DATE 23/03/95 APPLN. ID 60820/94 |l|li|11lff1lllllilli1 1 II PCT NUMBER PCT/US94/00024 1 1 11 1111 1 AU9460820 (51) International Patent Classification 5 (11) International Publication Number: WO 95/02660 C1OM 173/02, B21B 45/02 Al M 173/02, B21B 45/02 (43) International Publication Date: 26 January 1995 (26.01.95) (21) International Application Number: PCT/US94/00024 (81) Designated States: AU, BR, CA, CN, JP, PL, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, (22) International Filing Date: 4 Jmnuary 1994 (04.01.94) NL, PT, SE).

Priority Data: Published 08/090,724 13 July 1993 (13.07.93) US With international search report.

08/109,791 23 September 1993 (23.09.93) US 08/143,803 27 October 1993 (27.10.93) US (71) Applicant: HENKEL CORPORATION [US/US]; Suite 150, 140 Germantown Pike, Plymouth Meeting, PA 19462 (US).

(72) Inventors: BERSHAS, James, 2284 Strader, West Bloomfield, MI 48324 KELLY, Timm, 998 Suffield, Birmingham, MI 48009 ROCHFORT, Gary, 2770 Northampton, Troy, MI 48083 ROSSMAIER, Henry, 34408 Sandpebble Drive, Sterling Heights, MI 48310

(US).

(74) Agent: WISDOM, Norvell, Jr.; Henkel Corporation, Suite 150, 140 Germantown Pike, Plymouth Meeting, PA 19462

(US).

(54) Title: AQUEOUS LUBRICANT AND SURFACE CONDITIONER FOR FORMED METAL SURFACES (57) 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 said metal surfaces at a lower temperature. The conditioner includes a water-soluble organic material selected from amine oxides and quaternary ammonium salts, ethoxylated castor oil derivatives, and imidazoline moiety-containing phosphonates and preferably also includes (ii) at least one of fluozirconate, fluohafnate, or fluotitanate ion, and (iii) phoss ',ate and/or nitrate ions. Good resistance to damaging the friction reducing effect by overheating and to staining of the domes of treated containers during pasteurization can be achieved.

U

WO 95102660 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 to formed metal surfaces, more particularly to the surfaces of cleaned aluminum and/or tin plated cans: 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 ~arr~ara~ilsslr~ l la; -rmP-a-- WO 95/02660 PCT/US94/00024 surfaces, without causing "water-breaks", promoting drainage that results in a thin, continuous film of water on the cans, instead of distinct water droplets separated 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 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 application of the invention. However, it is to be understood that, with the obviously necessary modifications, both the discussion and the description of the invention apply also 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 products. After their manufacture, the aluminum cans are typically washed with acidic cleaners to remove aluminum fines and other contaminants therefrom. Recently, environmental 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 finea and contaminants. However, the treatment of aluminum cans with either alkaline or acidic cleaners 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 fine-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 surface.

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 lcl I- I al~ WO 95/02660 PCT[US94/00024 surface of 'de 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 addition 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 mechanics of the printer and conveyor systems. Jams and printer trips have become increasingly 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 molo 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 improve mobility without adversely affecting adhesion of paints, decorating inks, lacquers, or the like.

In addition, the current trend in the can manufacturing industry is directed toward using thinner gauges of aluminum metal stock. The down-gauging of aluminum 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 resulted in the cans not being dry enough when they reached the printing station, and 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 perception, and increase the possibility in reality, of non-uniformity in practically important properties among various areas of the surfaces treated.

WO 95/02660 PCT/US94/00024 Thus, it is desirable to provide a means of improving the mobility of aluminum cans through single filers and printers to increase production, reduce line jammings, minimize down time, reduce can spoilage, improve or at least not adversely affect ink laydown, and enable, lowering the drying oven temperature of washed 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 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 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 under the name "Mobility Enhancer M 40" (herein often abbreviated However, many manufacturers have been found to be reluctant to use chemicals such as ME-40 m in Stage 6. In some cases, this reluctance is due to the presence of a carbon filter for the DI water (normal Stage 6) system, a filter that can become inadequately effective as a result of adsorption of lubricant and surface condi- WO 95102660 PCTIUS94/00024 tioner forming additives such as those in ME-40'; in other cases, it is due to a reluctance to make the engineering changes necessary to run For those manufacturers that prefer not to add any lubricant and surface conditioner material to the final stage of rinsing but still wish to achieve the advantages 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 T 500.

However, the reduction in coefficient of friction provided by prior art treatments in either Stage 4 or Stage 6 can be substantially reduced, often to an unacceptable 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 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 mobility 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 ar.. pasteurized, and unless the temperature and the composition(s) of the aqueous solution(s) with which cans are contacted during pasteurization are very carefully controlled, staining of the dome of the can often occurs during pasteurization. It is a further object of this invention 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 numbers 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 broadest scope of the invention. Practice within the numerical limits given, however, is I 1- 6 generally preferred.

Also, unless there is an explicit statement to the contrary, the description below of groups of chemical materials as suitable or preferred for a particular ingredient according to the invention implies that mixtures of two or more of the individual group members are equally as suitable or preferred as the individual members of the group used alone. Furthermore, the specification of chernmical 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 the invention; any remaining counterions needed may generally be selected freely, except 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 surface conditioner applied to aluminum cans after washing enhances their mobility and, in a preferred embodiment, improves their water film drainage and evaporation characteristics as to enable lowering the temperature of a drying oven by from about 250 to about 380 C without having any adverse effect on the label printing process. The lubricant and surface conditioner reduces the 20 coefficient of static friction on the outside surface of the cans, enabling a substantial increase in production line speeds, and in addition, provides a noticeable improvement in the rate of water film drainage and evaporation resulting in savings due to lower energy demands while meeting quality control requirements.

In particular, the present invention provides a process comprising steps of 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 and and (iv) subsequently conveying the Scleaned and dr.=d can via automatic convti:ing Gc-i ipment to a location where it is lacquered or decorated by printing or both, characterized in that the aqueous lubricant and surface conditioner comprises: a component selected from the group consisting of quaternary

II

6a ammonium salt and amine oxide surfactants conforming to general formula I:

R

1 R2_ N+ R 3 {X)a

(I)

R

4 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 alkyl and hydroxyalkyl moieties having fruin 1 to 8 carbon atoms and (ii) aryl and arylalkyl moieles having from 6 to 10 carbon atoms; R4 is a monovalent moiety selected from the same group as for R2 and R3 plus the moiety; X- is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a 0 if R4 is and 1 if R4 is not and a component of complex fluoride anions; and, optionally but preferably, a component of phosphate ions, optionally also including sulfate or nitrate ions or both; and, optionally, aluminate anions, including fluoroaluminate anions; and, optionally aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of: *9 9 a water soluble and/or water dispersible polymer including aminosubstituted vinyl phenolic moieties; and 20 a foam reducing component.

Various embodiments of the invention include a concentrated lubricant and surface conditioner forming composition as described above; a solution of such a composition in water, optionally with additional acid or base to adjust the 9 pH value, suitable as the complete composition for contacting a metal surface, in Stage 4 and/or Stage 6 of a six stage cleaning and rinsing process as described 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 dtaii a;bove.

Brief Description of the Drawings Figures 1(a) 1(d) illustrate the effect of fluoride activity during cleaning of 1 I WO 95/02660 PCT/US94/00024 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 invention, it has been found that application of a thin organic film to the outside surface 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 also 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 mobility and drying rate of the cans depends on the thickness or amount of the organic film, and on the chemical nature of the material applied to the cans.

The lubricant and surface conditioner for aluminum cans in accordance with nvention may, for example, be selected from water-soluble alkoxylated surfactants such as organic phosphate esters; alcohols; fatty acids including mono-, di-, tri-, and poly-acids; fatty acid derivatives such as salts, hydroxy acids, amides, esters, particularly alkyl esters of 2-substituted alkoxylated fatty alkyloxy acetic acids (briefly denoted hereinafter as "oxa-acid esters") as described more fully in U. S. Agppiic :S-S l -l 195 ,eai 84 ~.S/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 polyoxyethylated 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 so 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 organic material selected from a phosphate ester, an alcohol, fatty acids including ~T I WO 95/02660 PCT/US94/00024 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 materiel 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 organic materials by alkoxylation, preferably ethoxylation, propoxylation or mixture thereof. However, non-alkoxylated phosphate esters are also useful in the present invention, especially free acid containing or neutralized mono-and diesters of phosphoric acid with various alcohols. Specific examples include Tryfac' 5573 Phosphate Ester, a free acid containing ester available from Henkel Corp.; and Triton T M Triton T M H-66, and Triton T QS-44, all available from Union Carbide Corp.

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. Specific examples include so,.Nm lauryl sulfates such as Duponolf WAQ and Duporol M QC and Duponol T M WA and Duponol T M C available from Witcc Corp. and proprietary sodium alkyl sulfonates such as Alkanolm189-S available from E.I. du Pont de Nemours Co.

Suitable polyhydric alcohols include aliphatic or aiylalkyl polyhydric alcohols containing two or more hydroxyl groups. Specific examples include glycerine, sorbitol, mannitol, xanthan gum, hexylene glycol, gluconic acid, gluconate salts, glucoheptonate salts, pentaerythritol and derivatives thereof, sugars, and alkylpolyglycosides such as APGM300 and APGM325, available from Henkel Corp. Especially preferred polyhydric alcohols include triglycerols, especially glycerine or fatty acid esters 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 operation of the can line is interrupted causing the cans to be exposed to elevated temper- 8 WO 95/02660 PCT/US94/00024 atures for extended periods. Accordingly, especially preferred materials include Trylox M 5900, TryloxTM 5902, TryloxTM 5904, Trylox m 5906, Trylox 5907, Trylox

T

5909, Trylox T 5918, and hydrogenated castor oil derivatives such as Trylox T 5921 and Trylox T 5922, all available from Henkel Corp.

s Preferred fatty acids include butyric, valeric, caproic, caprylic, capric, pelargonic, lauric, myristic, palmitic, oleic, stearic, linoleic, and ricinoleic acids; malonic, succinic, glutaric, adipic, maleic, tartaric, gluconic, and dimer acids; and salts of any of these; iminodipropionate salts such as Amphoteric N and Amphoteric 400 available from Exxon Chemical Co.; sulfosuccinate derivatives such as TexaponSH-135 Special and TexaponMSB-3, available from Henkel Corp.; citric, nitrilotriacetic, snd trimellitic acids; Versenol M 120 HEEDTA, N-(hydroxyethyl)ethylenediaminetriacetate, 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 T L203 is lauric monoethanolamide, AlkamideT m L7DE lauric/myristic alkanolamide, AlkamideTM DS 280/s stearic diethanolamide, Alkamide' CD coconut diethanolamide, Alkamide' DIN 100 lauric/linoleic diethanolamide, Alkamide DIN 295/s linoleic diethanolamide, Alkamide T DL 203 lauric diethanolamide, all available from Rh6ne-Poulenc; MonamidM 150-MW myristic ethanolamide, Monamid M 150-CW capric ethanolamide, Monamid 150-IS isostearic ethanolamide, all available from Mona Industries Inc.; and EthomidT HT/23 and Ethomid M 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: dodecyl benzene sulfonates such as Dowfax T 2A1, Dowfax T M 2AO, Dowfax T 3BO, and Dowfax T 3B2, all available from Dow Chemical Co.; Lomar LS condensed naphthalene sulfonic acid, potassium salt available from Henkel Corp.; sulfosuccinate derivatives such as Monamate T CPA sodium sulfosuccinate of a modified alkanolamide, Monamate T LA-100 disodium lauryl sulfosuccinate, all available from Mona Industries; TritonTM GR-5M sodium dioctylsulfosuccinate, available from Union Carbide Chemical and Plastics Co.; Varsulf

M

SBFA 30, fatty alcohol ether sulfosuccin- I WO 95102660 PCTIUS94/00024 ate, VarsulfrM SBL 203, fatty acid alkanolamide sulfosuccinate, Varsulf' S1333, ricinoleic monoethanolamide sulfosuccinate, all available ai Witco Chemical Co.

Another preferred group of organic materials comprise wate-soluble alkoxylated, preferably ethoxylated, propoxylated, or mixed ethoxylated and propoxylated materials, most preferably ethoxylated, and non-ethoxylated organic materials selected 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 polymers.

Preferred amine salts of fatty acids include ammonium, quaternary ammonium, phosphonium, and alkali metal salts of fatty acids and derivatives thereof containing up to 50 moles of alkylene oxide in either or both the cationic or anionic species. Specific examples include Amphoteric N and Amphoteric 400 iminodipropionate sodium salts, available from Exxon Chemical Co.; Deriphat TM 154 disodium N-tallow-beta iminodipropionate and DeriphatTM 160, disodium N-lauryl-beta iminodipropionate, 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 Armeena Z, Ncoco-beta-aminobutyric acid, available from Akzo Chemicals Inc.; Amphoteric N, Amphoteric 400, Exxon Chemical Co.; sarcosine (N-methyl glycine); hydroxyethyl glycine; Hamposylf TL-40 triethanolamine lauroyl sarcosinate, HamposyM 0 oleyl sarcosinate, HamposyfM AL-30 ammoniunmlauroyl sarcosinate, HamposylP L lauroyl sarcosinate, and Hamposylfm C cocoyl sarcosinate, all available from W.R. Grace Co.

Preferred amine N-oxides include amine oxides where at least one alkyl substituent contains at least three carbons and up to 20 carbons. Specific examples include Aromoxm C/12 bis-(2-hydroxyethyl)cocoalkylamine oxide, AromoxM T/12 bis-(2-hydroxyethyl)tallowalkylamine oxide, AromoxM DMC dimethylcocoalkylamine oxide, Aromoxm DMHT hydrogenated dimethyltallowalkylamine oxide, AromoxmDM-16 dimethylheaxdecylalkylamine oxide, all available from Akzo Chemicals Inc.; and TomahP AO-14-2 and Tomah'm AO-728 available from Exxon Chemical Co.

i L WO 95/02660 PCT/US94/00024 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 sulfate, alkyl or aryl sulfonate or derivatives thereof. Specific examples include ArquadTM 12-37W dodecyltrimethylammonium chloride, 'Arquad" 18-50 octadecyltrimethylammonium chloride, Arquad T 210-50 didecyldimethylammonium chloride, Arquad T M 218-100 dioctadecyldimethylammonium chloride, Arquad T 316(W) trihexadecylmethylammonium chloride, Arquad T B-100 benzyldimethyl(C 1 218 )alkylam- 1o monium chloride. Ethoquad T C/12 cocomethyl[POE(2)]ammonium chloride, Ethoquad T M C/25 cocomethyl[POE(15)]ammonium chloride, Ethoquad T C/12 nitrate salt, Ethoquad T T/13 Acetate tris(2-hydroxyethyl)tallowalkyl ammonium acetate, Duoqaud T M T-50 N,N,N',N',N'-pentamethyl-N-tallow-1,3-diammonium dichloride, Propoquad T M 2HT/11 di(hydrogenated tallowalkyl)(2-hydroxy-2-methylethyl)methylam- 1i monium chloride, PropoquadrT/12 tallowalkylmethyl-bis-(2-hydroxy-2-methylethyl)ammonium methyl sul-fate, all available from Akzo Chemicals Inc.; Monaquat T M

P-

TS stearamidopropyl PG-diammonium chloride phosphate, available from Mona Industries Inc.; Chemqua T M 12-33 lauryltrimethylammonium chloride, Chemquat T 16- Cetyltrimethylammonium chloride available from Chemax Inc.; and tetraethylammonium pelargonate, laurate, myristate, oleate, stearate or isostearate.

A combination of fluoride ions with either amine oxide or quaternary ammonium salts as described above, preferably the latter, is a major part of one especially preferred embodiment of the invention when good resistance of the friction reduction to overheating and/or resistance to dome staining during pasteurization is needed. More particularly, a suitable additive to satisfy these objectives preferably comprises, more pi-ferably consists essentially of, or still more preferably consists of: a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula I: WO 95/02660 PCT/US94/00024

R

2

-N+-R

3

I

R-

where R' is a monovalent aliphatic moiety, which may be saturated or unsaturated and contains from 8 to 22 carbon atoms, or preferably from 12 to 18 carbon atoms, preferably arranged in a straight chain; each of R 2 and R 3 is a monovalent moiety independently selected from the group consisting of alkyl 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 having from 6 to 10, or preferably from 6 to 8, carbon atoms; R 4 is a monovalent moiety selected from the same group as for R' and R 3 plus the -0O moiety; X is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a 0 if 1 4 is -O0, and a 1 if R" is not a component of complex fluoride anions, with anions selected from the group consisting of fluotitanate, fluohafnate, and fluozirconate preferred and fluozirconate alone most preferred; and, optionally but preferably, a component selected from the group consisting of phosphate, sulfate, and nitrate ions, with phosphate or a mixture of phosphate with one or both of sulfate and nitrate preferred; and, optionally, aluminate anions, including fluoroaluminate anions; and, optionally aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of: a water soluble and/or 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 a foam reducing (antifoam) component.

For component as defined above, quaternary salts are preferred over amine oxides when dome staining resistance is desired. Independently, it is preferred that at least two, or more preferably all three, of the moieties R 2

R

3 and R 4 be hydroxyalkyl groups, most preferably 2-hydroxyethyl groups.

For economy and commercial availability, it is preferred that the R' moieties 111119~I~lslli~W WO 95102660 PCTIUS94/00024 in the materials used for component be mixtures of the alkyl groups corresponding to the mixture of alkyl groups present in the fatty acid mixtures derived from hydrolysis 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.

For component 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, 1o 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 is 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 meter on the instrument. With this instrument, lower positive mv 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 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 embodiment of the invention, including components and 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, my.

The anions specified for component above are preferably added to the mixtures according to the invention in the form of the corresponding acids. When -U~a WO 95/02660 PCT/US94/00024 resistance to dome staining is desired, component preferably includes phosphate anions. Because of the preferred values for pH and for the ratio of the phosphpate content of component to components and when component includes phosphate, which are considered further below, usually some other acid than phosphoric 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 sufficiently 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 because it is less expensive than other strong acids.

Components and 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 unlikely to have any beneficial effect, experience has indicated that a normal equilibriis um concentration in commercial aluminum can cleaning lines will be within the range from 100 300 parts per million by weight (hereinafter often abbreviated and satisfactory results can be obtained with compositions including this much, or even more, aluminum. Preferably the total concentration of components and is, with increasing preference in the order given, not more than 1000, 700, 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 quaternm y ammonium salts as a necessary component, the pH is preferably maintained in the range from 2.3 to 3.3, more preferably from 2.5 to 3.1, still more preferably from 2.70 to 2.90. Values of pH lower 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 surface 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 PCT/US94/00024 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 includes phosphate ions as is generally preferred, the molar ratio between components where "Cp" denotes the phosphate content only of component as defined above, is preferably, with increasing preference in the order given, in the range from 1.0:(0.5 4.0):(0.25 1.0:(0.5 1.0:(0.7 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 is not used or does not contain phosphate, the ratio of with respect to those two components, preferably falls within the same ranges as stated above for cases in which phosphate is included in the compositions. Independently, the concentration of component in a working Stage 4 composition preferably is, with increasing preference 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 "mMf); the concentration of component in a working Stage 4 composition preferably 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 preferably 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 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 considered as phosphate anions.] Higher concentrations of component within the stated ranges improve the dome staining resistance during pasteurization but also increase the foaming tendency of the composition and often must be avoided for that reason. The lower the concentration of component 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 to promote dome staining resistance. Higher concentrations of component within the stated ranges are preferred when the concentration of components and/or 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 slslPlsll~-~irorrrara~c WO 95/02660

PC

T

/US94/00024 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 materials with various disadvantageous properties. Specifically, independently for each possible component listed below, with increasing preference in the order given, 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 above]: surfactants such as (a.1) organic phosphate esters, alcohols, fatty acids including mono-, di-, tri-, and poly-acids and their derivatives such as salts, hydroxy acids, amides, esters, and ethers; surfactants that are alkoxylated but are otherwise as described in part alkoxylated castor oil triglycerides; (d) sulfate and sulfonate derivatives of natural and synthetically derived alcohols, acids, ard/or natural products; amino acids; water-soluble homopolymers and/or heteropolymers of ethylene oxide, propylene oxide, butylene oxide, acrylic acid and its derivatives, maleic acid and its derivatives, and/or vinyl alcohol; and salts of organic 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, maleic acid and its derivatives, vinyl phenol and its derivatives, and vinyl alcohol.

Specific examples include CarbowaxT M 200, Carbowax T M 600, Carbowax M 900, Carbowax T M 1450, Carbowax T 3350, Carbowax 8000, and Compound 20M T M all available from Union Carbide Corp.; PluronicTM L61, Pluronic T L81, Pluronic 31R1, Pluronic' 25R2, Tetronic" 304, Tetronic M 701, Tetronic T 908, Tetronic 90R4, and Tetronic 150R1, all available from BASF Wyandotte Corp.; Acusol

M

410N sodium salt of polyacrylic acid, Acusol M 445 polyacrylic acid, Acusolf 460ND sodium salt of maleic acid/olefin copolymer, and Acusol M 479N sodium salt of acrylic acid/maleic acid copolymer, all available from Rohm Haas Company; and N-methylglucamine adducts of polyvinylphenol and N-methylethanolamine adducts of polyvinylphenol.

Additional improvements are achieved by combining in the process of this ini 1 ~IIIBIH~I~IC--~- WO 95102660 PCT/US94/00024 vention the step of additionally contacting the exterior of an aluminum can with an inorganic material selected from metallic or ionic zirconium, titanium, cerium, aluminum, 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 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 decorating of the containers.

The technique of incorporating such inorganic materials is described, in particular detail with reference to zirconium containing materials, in U.S. Patents 5,030,323 of July 9, 1991 and 5,064,500 of November 12, 1991, the entire disclosures of which, to the extent not inconsistent with any explicit statement herein, are hereby incorporated herein by reference. The substitution of other metallic materials 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-ethoxylated organic materials described herein, and to produce a suitable film on the can surface having a coefficient of static friction not more than 1.5 after drying, one employs a mixture of one or more surfactants, preferably alkoxylated and most preferably ethoxylated, along with such non-ethoxylated organic material to contact the cleaned can surface prior to final drying and conveying. Preferred surfactants include ethoxylated 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, C 8 alkyl polyglycosides having average degrees of polymerization between 1.2 and 2.0 are also suitable. Other classes of surfactants suitable in combination are ethoxylated nonyl and octyl phenols containing from 1.5 to 100 moles of ethylene oxide, preferably a nonylphenol condensed with fiom 6 to 30 moles of ethylene oxide such as Igepal T CO-887 available from Rhone-Poulenc; alkyl/aryl polyethers, for example, Triton T DF-16; and phosphate esters of which Triton' H-66 and Triton

T

QS-44 are examples, all of the Triton

T

c WO 95/02660 PCT/US94/00024 products being available from Union Carbide Co., and Ethox T M 2684 and Ethfac m 136, both available from Ethox Chemicals Inc., are representative examples; polyethoxylated and/or polypropoxylated derivatives of linear and branched alcohols and derivatives thereof, as for example Trycol M 6720 (Henkel Corp.), Surfonic" LF-17 (Texaco) and Antarox' m LF-330 (Rh6ne-Poulenc); sulfonated derivatives of linear or branched aliphatic alcohols, for example, NeodolTM 25-3S (Shell Chemical sulfonated aryl derivatives, for example, Dyasulf M 9268-A, Dyasulf T C-70, Lomar m D (all available from Henkel Corp.) and Dowfaxm 2A1 (available from Dow Chemical and ethylene oxide and propylene oxide copolymers, for example, PluronicTM L-61, Pluronic T M 81, Pluronic T 31R1, Tetronic T 701, Tetronic T 90R4 and Tetronic T 150R1, all available from BASF Corp.

Further, the lubricant and surface conditioner for aluminum cans in accordance with this invention may comprise a phosphate acid ester or preferably an ethoxylated alkyl alcohol phosphate ester. Such phosphate esters are commercially available under the tradename Rhodafac T PE 510 from Rhone-Poulenc Corporation, Wayne, NJ, and as Ethfac T 136 and Ethfac T 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 cleaning 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, 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 chemiso 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/US94/00024 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 or more preferably from 10 to 30 sec, and a temperature of 20 to 60 0 C, or more preferably 30 to 48 0 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 treatment composition is important and generally should be acidic, that is between about 1 and about 6.5, preferably between about 2.5 and about 5. If the cans are not treated 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 is the lubricant and surface conditioner of this invention, which may comprise a nonionic surfactant selected from the aforementioned polyoxyethylated alcohols or polyoxyethylated 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.

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 or with increasing preference in the order given, to a value of not more than 1.2, 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/in 2 to 60 mg/m 2 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 of the necessary organic material(s) 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 a ~L Lr- Is P WO 95/02660 PCT/US94!00024 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 materials: alkoxylated or non-alkoxylated castor oil triglycerides and hydrogenated castor oil des rivatives; alkoxylated and non-alkoxylated amine salts of a fatty acid including mono-, di-, tri-, and poly-acids; alkoxylated and non-alkoxylated amino fatty acids; alkoxylated and non-alkoxylated fatty amine N-oxides, alkoxylated and non-alkoxylated quaternary ammonium salts, alkyl esters of 2-substituted alkoxylated fatty alkyloxy acetic acids (briefly denoted hereinafter as "oxa-acid esters") as described more -1 I's fully in U. S. pea o. 8430lS filed February 28, 1992, the disclosure of which is hereby incorporated herein by reference, and water-soluble alkoxylated and non-alkoxylated polymers. Furthermore, if the lubricant and surface conditioner is not applied to the surface from the last aqueous composition with which the surface is contacted before the last drying of the surface before automatic conveying, the composition including the organic materials preferably also includes a metallic element selected from the group consisting of zirconium, titanium, cerium, aluminum, 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.

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 surface of the cans.

Uncleaned aluminum cans obtained from an industrial can manufacturer were i I WO 95/02660 PCTIUS94/1'8024 washed clean with an alkaline cleaner available from the P+A, employing that company's Ridoline T M 3060/306 process. The cans were washed in a CCW processing 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.

The lubricant and surface conditioner comprised about a 10 active concentrate of poiyoxyethylated isostearate, an ethoxylated nonionic surfactant, available under the tradename Ethox T 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 1o 6 cans. All were subjected for 20 minutes to one of the following adhesion test solutions: Test Solution A: 1% Joy M (a commercial liquid dishwashing detergent, Procter and Gamble Co.) solution in 3:1 deionized water:tap water at a temperature of 820 C.

Test Solution B: 1% Joy T detergent solution in deionized water at a temperature of 1000 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 applying Scotch T 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, acceptable; 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 using a laboratory static friction tester. This device measures the static friction associated with the surface characteristics of aluminum cans. This is done by using a ramp which is raised through an arc of 900 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 inches apart with the domes facing the fixed end of the ramp. A third can is laid

-I-

WO 95/02660 W'CT/US94/00024 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 lower cans, a photoelectric switch shuts off the timer. It is this time, recorded in seconds, 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 where t is the slip time.

In some cases the tested cans were subjected to an additional bake out at 210° C for 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 eva!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 provided improved mobility to the cans even at very low use concentrations, and it had no is adverse effect on either adhesion of label print or internal lacquer tested even at 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 conditioner of Example Group 1 in an industrial can manufacturing facility when paiag cans through a printing station at the rate of 1260 cans per minute.

Aluminum can production was washed with an acidic cleaner (Ridoline T M 125 CO, available from and then treated with P non-chromate conversion coating (Alodine T M 404, also available from the Parker+Amchem Division, Henkel Corporation, 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 can; 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", 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.

~II WO 95/02660 PCT/US94/00024 Table 2 Test No.

1 2 3 4 6 7 8 9 Lubricant and Surface Conditioner Concentrate Control (no treatment) 0.1 0.25 0.5 0.75 1.0 2.0 5.0 10.0 Test Solution OSW ISW ID 10 10 10 10 10 9.5* 10 10 10 10 10 10 10 10 10 10 10 10 10 10 9.8* 10 10 Adhesion Evaluation Coefficient of Static Friction 1.42 0.94 0.80 0.63 0.64 0.56 0.55 0.56 Notes for Table 2 *Little pick-off was visually noticed on the outside walls, mainly at the contact marks.

"OSW" stands for outside sidewall, "ISW" stands for inside sidewall, and "ID" stands for inside dome.

About 1 ml/liter of aluminum can lubricant and surface conditioner was added 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-

I

WO 95/02660 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 a 24-hour test period.

Example and Comparison Example Group 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 of about 12 at about 410 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 M PE 510 from Rhone-Poulenc, Wayne, NJ) at a concentration of 0.5 g/1. Phosphate ester solution 2 comprised an ethoxylated alkyl alcohol phosphate ester (available under the tradename Ethfac

T

161 from Ethox Chemicals, Inc., Greenville, SC) at a concentration of 0.5 g/l. Phosphate ester solution 3 comprised an ethoxylated alkyl alcohol phosphate ester (available under the tradename Ethfac T 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 evaluated 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 mobility to aluminum cans, but the cans were completely covered with "water-break".

g- WO 95/02660 PCT/US94100024 It is desired that the cans be free of water-breaks, 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 were cut open and boiled in a 1 liquid dishwashing detergent solution (Joy

M

comprising 3:1 deionized water:tap 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 off. The cans were rated for adhesion values. The average value results are summarized in Table 4, in which the acronyms have the same meaning as in Table 2.

Table 4 Phosphate Ester Adhesion Rating on: Solution Used OSW ISW ID control 10 10 1 9.8 6.8 2 9.8 10 3 10 10 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 pickoff 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 phos- 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 Group 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- I WO 95/02660 PCT/US94/00024 with.

Aluminum cans were cleaned with acidic cleaner (Ridoline M 125 CO followed by Alodine T 404 treatment or Ridoline M 125 CO only) or with an alkaline cleaner solution (Ridoline T 3060/306 process), all the products being available from 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 surface 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 lubricant 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 Drain Time Grams per Can of Water Remaining Using: in Seconds 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 30 1.8 3.4 2.3 Example Group This example illustrates the effect of the oven dryoff temperature on the sidewall 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 1930 C, a 2 psi increase was obtained in the column strength test compared to the value obtained at 2270 C oven temperature.

WO 95/02660 PCT/US94/00024 Table 6 Oven Temperature C) Column Strength (PSI) 227 86.25 204 87.75 193 88.25 182 89.25 The higher column strength test results are preferred and often required because 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 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 adequate drying of the cans in this time-frame, the oven temperature is typically about 2270 C. However, in a series of tests wherein the rinse water contained about 0.3 by weight of organic material to form a lubricant and surface conditioner of this invention, it was found that satisfactory drying of the cans could be obtained wherein the oven temperature was lowered to 204° C, and then to 1880 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 Division, Henkel Corporation, Madison Heights, Michigan, employing the Ridoline T M 3060/306 process and in Examples Type B with an acidic cleaner, Ridoline

T

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 l-r WO 95102660 PCT/US94/00024 a 1 by weight active organic 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 in deionized water plus about 2 g/L (0.2wt%) of the inorganic (II) as specified in Table 7, below. In yet another set of examples, following initial rinsing and before final drying, the cleaned cans are treated with a lubricant and surface conditioner comprised of about 1 active organic 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 about 0.2 inorganic 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 Examples and Comparison Examples Group 7 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 prepared using deionized water with a conductivity less than 5 psiemens; unless otherwise noted, all other solutions were prepared in tap water. Drawn and wall ironed 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 at its highest speed of 6.2 feet per minute 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 characteristics 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- 3o low. Can mobility was tested as in Group 1.

I

WO 95/02660 PTU9/02 PCT/US94/00024 TABLE 7 Ex- Active Organic Inorganic Surfactant (III) PH1 pie Trade Chemical LType Name Description A Emery 657 Caprylic acid A1 2 (S0 4 3 IGEPAL CO-887 2.2 B Emery 659 Capric acid H2ZrF 6 TRITON X-101 2.2 A Emery 651 Lauric acid FeF 3 NEODOL 25-5-3 2.3 B Emery 655 Myristic acid SnC1 4 TERGITOL 2.3 A Emersol Palmitic acid Ce(N0 3 4 TRITON DF-16 2.6 91% B Emersol Stearic acid H 2 TiF 6 TRYCOL 6720 2.6 153 NF 92% A Emersol Isostearic acid H 2 HfF 6 ANTAROX LF- 2.6 871 B Emersol Oleic acid 75% (NH 4 ).,ZrF 6 TRITON H-55 2.6 6313 NF A Empol Dimer acid Fe 2 (S0 4 3 TRITON H-66 2.6 ___1014 13. Emery Azelaic acid AI(N0 3 3 TRITON QS-44 2.6 1110__ B Ethox M15 Ethoxylated iso- TiC1 4 TRYCOL 6720 stearic acid A Emuiphor Polyoxyethylat- Gel 3 SURFONIC LF 430 ed oleic acid 17 B Ethox Polyoxyethylat- FeF 3 LOMAR D ed oleic acid A Monamide Lauric alkanol- FeC1 3 DOWFAX 2A1 LW B Monamide Myristic alka- FeBr 3 DYASULF 9268- MW nolamide A A Monamide Isostearic alka- H 2 ZrF 6 DYASIJLF C-70 150 IS Table continued on next page..

WO 95/02660 WO 95/2660 CT/US94/00024 Ex- Active Organic 1Inorganic Surfactant (111) pH am- pie Trade Chemical LType Name Description B Monamide Stearic alkanol- H 2 TiF 6 IGEPAL CO-887 718 amide A Rhodafac Aliphatic phos- Fe(N0 3 3 POLYTERGENT BH 650 phate ester, acid SLF-18 form B Ethox Aromatic phos- (NH 4 2 ZrF 6 PLTJRONIC L-61 ____PP16 phate ester A Rhodafac Aliphatic phos- TaF. TETRONIC 701 BL 750 phate ester, acid B Rhodafac Aromatic phos- NbF 5 PLURONIC 31R1 10 phate ester, acid form A Ethfac Aliphatic phos- H 2 ZrF6 PLUPONIC ____142W phate ester B Rhodafac Aliphatic phos- (NH 4 ),MoO 4 APG 300 RA 600 phate ester, acid form A Armeen Z N-Coco-B- H 2 TiF 6 TRITON CF-21 aminobutyric acid B Hamposyl Lauroyl sarcos- VF 4 TRITON DF-18 L me A Hamposyl Cocoyl sarcos- FeF 3 TRITON GR-7M C mne B Hamposyl Oleoyl sarcos- SnCl 4 TRITON H-55 0 mne A Hamposyl Stearyl sarcos- A1 2 (S0 4 3 TRITON X-100 S B Acusol Polyacrylic H 2 ZrF 6 TRITON X- 120 41ON acid, sodium .Table continued on next page..

WO 95/02660 J3CT[US94100024 Ex- j Active Organic Inorganic Surfactant (HII) pH a me Trade Chemnicat i Type Name Description B Triton GR- Dioctylsulfo- AI(N0 3 3 TRYCOL 588-2 A 5M succinate A Avanel S Sodium alkyl- VOS4 TRYCOL 5887 ether sulfonate B Igepon Sodium N-co- VF 5 TRYCOL 5964 TC-42 conut and N- ______methyl taurate A Igepon Sodium N- VF 3 IGEPAL CO-887 TK-32 methyl-N-tall oil acid taurate B Neodol 25- Sulfonated line- (NH 4 2 W0 4 IGEPAL CO-630 3A ar alcohol, ammonium salt A Aromox Bis(2-hydroxy- (NH 4 2 ZrF 6 NEODOL 25-3 C/12 ethyl) cocamine oxide B Aromox Dimethylcoc- FeF 3 NEODOL 25-35 DMC amine oxide A Ethoquad Oleyl Fe 2 (S0 4 3 NEODOL 25-9 0/25 amnmonium chloride B Ethoquad Cocomethyl A1 2 (S0 4 3 NEODOL 9 1-25 C/12 [POE(2)] ammonium chloride A Ethoquad Octadecyl Sn(S0 4 TRITON QS-15 18/5 [POE( ammonium chloride Table continued on next page..

WO 95/02660 PCT/US94/00024 Ex- Active Organic Inorganic Surfactant (II) pH am- (IH) pie Trade Chemical Type Name Description B Propoquad Tallowalkyl- Ce 2

(SO

4 3 TRITON DF-12 T/12 methyl-bis-(2hvdroxy-2methylethyl) ammonium methyl sulfate A Ethfac 136 Phosphate ester H2ZrF 6 IGEPAL CO-887 2.3 B Ethox Phosphate ester H 2 ZrF, IGEPAL CO-887 2.7 2684 A Trylox Ethoxylated HZrF 6 IGEPAL CO-887 2.3 5922 hydrogenated castor oil B Trylox H 2 TiF 6 IGEPAL CO-887 2.7 5921 A Trylox H" HZrF 6 TRITON H-66 2.7 5925___ Foam heights were determined by placing 50 milliliters (hereinafter of the process solution in a 100 mL stoppered graduated cylinder and shaking vigorously for 10 seconds. The total volume of fluid, liquid plus foam, was determined immediately and after 5 minutes of standing. These "foam heights" will be referred to s hereinafter as "IFH" (initial foam height) and "PFH" (persistent foam height) respectively.

The water break characteristics of cans treated with candidate final rinse mobility enhancers ("FRME's) were evaluated by visually rating the amount of waterbreak on each of the four major surfaces of the can: interior dome and sidewall and exterior dome and sidewall. In this rating scheme a value of 2 is assigned to a completely waterbreak free surface, zero to a completely waterbroken surface and intermediate values to waterbreaks in between. Four cans sae 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, 54.40 C, 30 sec.

Stage 2 RIDOLINE T 124C, 15 mL Free Acid, 3.4 g total of s surfactant, Fluoride Activity 10 to -20 mV in 10 mV increments, 600 C, 60 sec.

Stage 3 tap water, 30 sec.

Stage 4 deionized water, 90 sec.

Stage 5 optional application of 0.4% ME-40

T

20 sec.

Stage 6 not used Oven 5 minutes at 2100 C The "fluoride activity" noted for Stage 2 above is defined and can conveniently be measured by means of a fluoride sensitive electrode as described above and 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 impinged on a photocell whose current output was amplified and converted to a digital readout by an International Microtronics Inc. Model 350 amplifier; the number displayed was recorded as the brightness of the surface. The instrument is calibrated with a back silvered plane mirror to a measured reflectivity of 440. Once calibrated, the reflectivities of fourteen cans were measured and averaged. With this device it was possible to measure the overall interior reflectivity and exterior dome reflectivi- 2s ty. Results are shown in Figures l(a) l(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 mv readings and decrease slightly with either increases or decreases from that range. The variation of COF with fluoride activity level in these experiments is actually of relatively little practical importance, compared to the substantial improvement obtained by using a suitable FRME material.

If the results shown in Figures l(a) l(d) were the only practically important considerations, they would favor the highest fluoride activity levels. For several reasons, however, this has not been found to be true in commercial practice. High

I

WO 95/02660 PCT/US94/00024 fluoride levels are more costly and promote high etching rates that may increase pollution abatement costs or even damage an etched container's ability to contain pressurized contents such as carbonated beverages. Also, in integrated commercial operations 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 experiments, 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 corresponding to electrode readings of from +50 to -10 my have been found to be generally preferred, with electrode readings from +5 to 0 most preferred. As would be expected from the results shown in Figures l(b) and 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 according 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 rinses: Stage 1 sulfuric acid, pH 2.0, 30 sec., 54.40 C Stage 2 RIDOLINE M 124C, 15 mL Free Acid, 3.4 g/L total of surfactant, Fluoride Activity -10 mV, 90 sec., 54.40 C Stage 3 deionized water, 150 sec. (ca. 17.7 L) Stage 4 as noted in Table 8, 30 sec., 29.40 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 Igepalf 430 or polyvinyl alcohol, 1.6 g/L of Igepal

M

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 hydroxyethyl groups bonded to the amine oxide nitrogen, such as Aromox T C/12 and T/12.

Quaternary ammonium salts, such as the ETHOQUAD T materials exemplified in Table 7 are also in the preferred group. The ethoxylated castor oil derivatives, amine oxides, and quaternary salts are all ccasidered in more detail below.

7.4 Ethoxylated Castor Oil FRME's. The CCW was charged and operated as described in 7.3 with the exceptions that the Stage 3 deionized water rinse was I I- Table 8: CANDIDATE FINAL RINSE MOBILITY ENHANCERS AND COMPARISONS Candidate Chemical Class or Comparison Hydroho Hydrophile Molecular HLB COF COF -2 IUFH PFH WBF Wei~ght Mean StD Mean StD None None None None None None Surfynoff m 420 Surfynolh 440 Surfyno t 465 Dimethylforamide Monamin~m AD-100 M.Pyrolmh Macamin6h C-10 Triethanolamine ArmoxCm T112 AromoTM C112 Aromoxeh DM-16 MacamineiM CAO Macamine~h CO Macaminem SO Triton~m RW-100 TritonP RW-50 ThtorP RW-75 TEA Oleate AnneenTm Z APG~h 300 APGm 325 Hostacor7M BP~ Acetylenic-EO Acetylenic-EO Acetylenic-EO Amide Amide Amine Amine Amine Amine Oxide Amine Oxide Amine Oxide Amine Oxide Amine Oxide Amine Oxide Amine-(EO)1O Amine-(EO)5 Amine-(EO)7.5 Amine-Fatty Amphoteric Glycoside Glycoside Borate

TMDD

TMDD

TMDD

(EO)1.3 (EO)3.5 (EO)10 C12 (tallow) C12 (coco) C16 Cocamidopropyl Cocamine Stearamine N=0/2-hydroxyethyl N=0/2-hydroxyethyl

N=O

N=O

N=O

73.1 366 1.168 .108 1.126 .071 1.098 .129 1.141 .151 1.331 .263 1.362 .194 1.295 .197 4 1.363 .201 8 1.404 .276 13 1.623 .549 1.371 .181 -457 .020 .645 .127 1.184 .172 1.645 .476 1.134 .120 .548 .129 .672 .107 .527 .090 1.005 .190 1.519 .202 1.532 .468 1.329 .222 1.180 .116 16 .802 .179 1.136 .132 13 1.099 .096 15 1.001 .130 1.496 -430 1.214 .438 1A430 .315 .660 .182 1I463 .299 1.146 .201- 1.015 .251 1.211 .183 1.211 .157 32 32 32 32 32 32 32 31.8 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32 32

RCOOH/N

-Table continued on next page..

Candidate or Comparison Chemical Class Hydrophobe Hydrophile Molecular HLB COF COF -2 IFHR PFH WBF Weipght M ean SOD Mean StO Hostacorf' BS OAE-1 OAE-2 OAE-3 OAE-4 Acrysolf "LMW-45 Aininohexanoic Acid Citric Acid Gantrez'm S-95 Gluconic acid Isoascorbic Acid NIiraweimh B Cn Potassiam Biphthalate Sodium Glutoheptonate Sodium Gluconate Tartaric Acid COiemquaf' SP-10 Tatronic~h 701 Hfenkef'" SF-w7063 Ethoirm MI-14 Ethoxrm MI-14 EthoX)hm MI-14 Ethoi'm MI-14 Ethoixm MI-14 Etloxih MI-14 Ethoi' MI-14 Brif'" 30 ChemaP'm 2EH5 Chemal' PA-5P38 Ethaff~ 2EH2 Ethaff' CSA-10 Borate C-18 EO/PO C16-18 EQ C8-10 EQ C8-18 EQ Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxylic Acid Carboxyi3c Acid Carboxylic Acid Cationic

EOIPO

EOJPOIMe-ester Ester Ester Ester Ester Ester Ester Ester Fatty Alcohol Fatty Alcohol, Fatty Alcohol Fatty Alcohol Fatty Alcohol C-iS/POdl) C16&18 C8-10 C8-18 n/a C6 (EQ)5 (EQ)5 (EQ)5 (EQ)5

RCOO(-)

RCOOH/NH2

CQQH/C-OH

4500- 191.1 204.2 249.2 218 1.339 .231 .315 .040 .343 .305 .030 .386 .602 .149 .687 .282 .017 .483 1.102 .112- 1.491 .495 1.334 .110 1353 .356 1.551 .316 1.251 .201 1 .299 .294 1. S 0 .6 1.238 .122 1.329 .147

C-OHIRCQO(-)

C-OH/RCOO(-)

(P0)2.04 C13/CH 2 -C(=0)OCH, C18 C18 C18 C18 C18 C18 C18 C12 2-ethylhexanol C-10 LAIPO 2-ethyl hexanol C16-18 CEO)13.7 (EO)8.5 (EQ)14 (EO)14 (F0).4 (EO'14 (EO)14 (EG!)4 (EO)14 (EO)4 (EO)2

EQ

EO)2 (EO)12 1.5,01 .322 .990 .125 1.538 .162 3600 1-7 .972 .244 2.129 .363 .287 .038 .374 -049 13 .402 .044 .474 .0-48 13 .492 .076 .558 -146 13 .426 .042 .708 .133 11 .458 .080 .841 .241 13 .455 .087 .841 .274 13 .432 .061 13 .468 .090- .890 .161 1,013 .076 1.032 .068 1.075 .103 .815 .200-.725 .132 8.1 1.167 .118 1.149 .146 .748 .164 .761 .166 58 54 32 32 28 32 16 53 50 32 50 50 32 55 50 32 59 52 32 50 50 32 51 50 32 59 52 32 53 50 32 51 51 32 51 50 32 52 50 32 56 51 32 64 51 32 32 70 67 32 32 68 67 32 67 63 32 66 64 32 67 63 -1 32 32 57 50 32 32 high 32 Table ontinued on next page..

Candidate or Comparison Ethaff CSA-17 Ethai'" DA-6 Ethal'f OA-23 Ethiaff TDA-6 Sandoxylate T m SX-408 Sandoxylate h SX-424 Sandoxylate m SX-602 Tritoni XL-80N Varonic6h MT-42 Varonic74 IMT-48 Varonic~m MT-65 Fluorad'" FC-126 Kelig'r' 100 KeligTm 400 Igepafhm 660 lgepa t m 710 Igepaff' 720 IgepafPm 430 Igepa t 610 Carbowax'" Methoxy PEG Ct.rbowai' Methoxy PEG CarL~owax'" Methoxy PEG Carbowaiht Methoxy PEG Carbowai'm PEG 20M Carbowaxm PEG-1450 Carbowax~m PEG-200 Carbowax 7 m PEG-3 350 Carbowax~m PEG-8000 Carbowaxih PEG-900 Deques TM 2000 Deques7

M

2006 Chemical Clas Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fatty Alcohol Fluorosurfactant.

Ligno-Sulfonate Ligno-Sulfonate NP-(EQ)10 NP-(EO)10.4 NP-(EO)12 NP-(EQ)4 NP-(EQ)7.5

PEG

PEG

PEG

PEG

PEG

PEG

PEG

PEG

PEG

PEG

Phosphonate Phosphonate Hydrophobe Hydrophile Molecular HLB COF COF -2 Iff1 PFH WBF Weight Mean SOD Mean SO) C16-18 Cl0 C18 C13 LAP i-C1O-12 LAJPO i-C10-12 LAIPO C8-10 EQ/PO/EO C12-18 CH3 cap C12-18 CH3 cap C12-18 CH3 cap C7FlS Nonyl Phemol Nonyl Phenol Nonyl Phenol Nonyl Phenyl Nonyl Phenyl Q-CH3 Q-CH3 Q-CH3 O-CH3 (EO)17 .726 .177 .677 .167 (EQ)6 12.4 .931 .201 1.045 .155 (EQ)23, 15.8 .698 .175 .749 .192 (EQ)6 11.4 .764 .179 .930 .163 EQ 11 .913 .107 .885 .105 EQ 15 .688 .160 .676 IV EQ 8 .966 .132 1.145 EQ 42C- .801 .187 .776 J EQ .549 .093 .581 EQ 5 953 .146 .692 .1-60 EQ O .814 .171; 862 .122 R-CQONa 1.335 .233 1.450 .473 53 2.022 .773 54 (EQ)10 660 13.2 1.527 .555 (EQ)10.4 678.5 13.6 1.330 .329 (EO)12 748 14.2 1.524 .423 76 (EO)4 396 8.8 .516 .064 .815 .195 63 (EO)7.5 570.9 12.2 .693 .170 1.021 .176 63 (EQ)44.7 2000 .766 .222 .886 .199 (EQ)7.3 350 .955 .126 1.047 .113 (EO)112.8 5000 .739 .158 .839 .118 (E)16.3 750 .927 .236 .915 -190 (EQ)n 17500 .663 .149 .934 .155 (EO)32.5 1450 .778 .158 .854 .229 (EO)4.15 200 1.122 .140 1.050 .114 (EO)75.7 3350 .747 .105 .921 .149 (EO)181.2 8000 .778 .188 .840 .162 (EO)19.5 900 .819 .199 .865 .212 N[CH2-P=O(OH)2j 3 299 1.506 .203 52 NasN[CH 2 7-=O(OH) 2 3 409 1.327 .095 51 Table continued on next page.- Candidate or Comparison Dequesr m 2016 DequestP 2054 DequestP 2066 Belzakm AC Cerelosemh 2001 Glycerine Hexylene glycol Methocefh 40-200 Pentaerythritol Polylvinyl alcohol) Sorbitol Tripropylene Glycol Xanthan Gum SOMATrm TweenT' 20 Dodecylbenzene Sulfonate Dowfax~m 2A1 Heptane Sulfonate Nacconoifh 90F Chemica Class Phosphonate Phosphonate Phosphonate Polyhydric Polyhydric Polyhydric Polyhydric Polyhydric Polyhydric Polyhydric Polyhydric Polyhydric Hydropho HEydrophile Molecular 'HLI3 COP COF -2 EIH PFH WBF -Weig~ht Mean StD Mean SID

[(C-CH

3 OH)][P=O(Na)] 2 294

HMDA[CH

2 721 TrienIICH-P=-O(Na)j 683

R-OH

2-Me,2,4-C5 diol (C-QH)2

C-OH

1.271 .209 1.095 .225 1.176 .150 1.211 .098 1.318 .095 1.335 .134 1.886 .130 SO01 .076 1.193 .252 1.133 .088 .479 .067 .982 .420 1.239 .091 1.266 .125 1.059 .139 .714 .161 .601 .100 1.146 .498 .396 .029 .616 .182 .614 .112 .793 .109 1.214 .436 .387 .021 .462 .065 51 51 51 51 52 51 51 58 60 54 54 52 71 67 51 60 52 52 51 59 68 100 82 71 68 52 100 Polyhydric Proprietary Sorbitan ester-(EO)zD C12 Sulfonate C12-Ph Sulfonate iso-C12-Ph (bis) Sulfonate C6 Sulfonate-

EO

S03(-) [S03(-)12 C6-COOH Notes for Table 8 "SLD" here and in subsequent tables means "standard deviation from the mean." "WBF means "waterbreak free rating". The multiple entries for "None" and for Ethox"h MI-14 represent determinations with different lots of cans. The "OAE-" products have the general chemical formula:

RO-(C

3

H

6 1

-(C

2

HO).-CH,-C(O)O-CH,

with the straight chain alkyl group R ranging from 8 to 18 carbon atoms in length, "in" being 0 or 1, and ranging from 5 to an average of WO 95/02660 PCT/US94/00024 applied for 130 sec and the first oven treatment was performed at 2000 C rather than 1500 C. The Stage 4 compositions were as shown in Table 9. The experiment using Trylox T M 5921 included 0.2 g/L of IgepalT CO-887 in an unsuccessful attempt to clarify the solution; a slight cloudiness persisted even in the presence of the cosurfactant.

Table 9 ETHOXYLATED HYDROGENATED CASTOR OIL DERIVATIVES AND COMPARISONS AS FINAL RINSE MOBILITY ENHANCERS Product Grams/ Name 8 Liters

COF

None TryloxTM 5922 Trylox T M 5922 Trylox TM 5922 Trylox T M 5921 TryloxTM 5921 TryloxTM 5921 Trylox T 5925 Trylox T 5925 Trylox T M 5925 Ethox T M MI-14 Mean 1.231 .479 .974 1.007 .511 1.072 .883 .914 1.020 .965 .621 StD .149 .072 .161 .117 .108 .144 .154 .140 .149 .180 .118 COF-2 Mean StD .503 .085 1.055 .151 1.131 .132 .548 .093 1.034 .201 .958 .152 1.139 .157 1.231 .122 1.007 .122 1.059 .144 IFH PFH L 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 isostearic 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 T 31R1 and Trycol T 6720 with Ethox T MI-9 produced somewhat more foam than compositions with an equal total amount of Ethox

M

MI-9 -I I, WO 95/02660 PCT/US94/00024 Table EFFECT OF VARIATION OF DEGREE OF ETHOXYLATION IN PRIMARY LUBRICANT AND SURFACE CONDITIONER (ETHOXYLATED ISOSTEARIC ACID) AND OF VARIATION OF COSURFACTANT ADDED AS ATTEMPTED DEFOAMER COF Ethoxylated Defoamer IFH PFH Isostearic Acid StD /8L of EO /8L Mean Name Molecule 1.139 1.159 1.069 1.190 1.154 1.142 .587 .817 .659 .499 .478 .479 .423 .408 .576 .467 .496 .628 .656 .457 .465 .531 .566 .583 .564 .550 .539 .685 .644 .444 .477 .534 .456 .516 .505 .532 .456 .681 .615 .538 .170 .181 .165 .158 .198 .174 .170 .155 .175 .099 .072 .093 .027 .038 .172 .103 .122 .176 .194 .074 .121 .108 .186 .114 .142 .114 .111 .205 .133 .104 .098 .093 .121 .148 .106 .128 .078 .178 .149 .106 0 0 0 0 0 (Average 0 0 0 0 0 result with above five can lots) 1.60 1.20 1.20 1.20 .80 .80 .80 .40 .40 .40 1.60 1.20 1.20 1.20 .80 .80 .80 .40 .40 .40 1.60 1.60 1.20 1.20 1.20 .80 .80 .80 .40 .40 .40 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 14 14 14 14 14 14 14 14 14 14 14 1.60 1.60 1.60 0 .40 .40 .40 .80 .80 .80 1.20 1.20 1.20 0 .40 .40 .40 .80 .80 .80 1.20 1.20 1.20 0 0 .40 .40 .40 .80 .80 .80 1.20 1.20 1.20 Pluronic 31R1 TritonT DF-16 Trycol m LF-1 PluronicT 31Ri Triton T DF-16 Trycol" LF-1 PluronicT 31R1 Triton T DF-16 Trycol" LF-1 PluronicT 31R1 Triton T DF-16 TrycolT LF-1 Pluronic" 31R1 Triton DF-16 Trycol T LF-1 Pluronic™ 31R1 Triton T DF-16 Trycol T LF-1 Pluronic™ 31R1 Triton T DF-16 TrycolT LF-1 Pluronic M 31R1 Triton T DF-16 Trycol T LF-1 Pluronic™ 31R1 Triton T DF-16 Trycol m LF-1 Pluronic™ 31R1 Triton DF-16 Trycol T m LF-1 I WO 95102660 PTU9/02 PCT/US94/00024 alone, but also give further reductions in the GOF. The interactions are evidently complex. and difficult to predict.

7.6 Final Rinse Mobility Enhancers and Water Drainage Aids. The BW WaS Operated as follows: 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, 600 C Stage 3 tap water Stage 4 not used Stage 5 deionized water Stage 6 as noted in Table 11, 0.2 g/L total active additive.

Table 11I VARIATION OF WATER DRAINAGE WITH LINE SPEED AND ADDITIVE TO FINAL RINSE Lubricant and/or Water Drainage Promoting Additive Line Speed Setting Water Retention COF COF-2 Mean SOD Mean Sti (Mean) None None None None None None Ethox'h MI-14 Neodoilh 91-2.5 Pluronic~m L-81 Pluronic'h L-61 Neodoim 91-6 Ethox7'm 14-14/ Pluronic'h L-81 (1:1) EthoxT1 241-14/ Pluronic7'm L-61 (1:1) Ethafn' OA-23 Ethoxlh MI-14 EthoxTh MI1-14 Ethox" 14-10. 5 Neodoilh 91-8 EthoxT' 141-14/ TryloxTh 5922 (1:1) Trylox tm 5925 Trylox tm 5922 Trylox tm 5921 Ethox7 141-14 100 100 70 70 70 40 40 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 100 21. 72 30.44 28.40 28.29 27.02 23.34 19.11 15.65 17.44 17.71 20.83 1.00 .37 .14 .09 .27 1.446 1.356 1.124 1.206 1.201 .071 .211 .175 21.02 .53 .728 .970 21.63 21. 64 21.68 21.69 21.93 22.55 24.07 24.62 25.21 25.88 26.60 .32 .72 .18 .38 .30 1.00 .725 .919 .550 1.009 .581 .832 .204 1.141 .727 .707 .680 .645 .92 1.090 .97 .581 .26 .546 WO 95/02660 PCT/US94/00024 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" 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.

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 minutes 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 surfactants 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 drainage 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 commercial six stage processor. Each run was made with 14 cans. The process sequence used is described in Table 12.

Stage 4 compositions were prepared either by dilution of concentrate or directly from the ingredients. In order to simulate what happens in a commercial can washing operation, the aluminum level the stoichiometric equivalent as aluminum of the total of components and 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 I ~I WO 95/02660 PCT/US94/00024 Table 12 Times in Seconds for: Stae Sray Dwell Blow-Off 0 C 10 30 10 30 10 30 20 30 54.4 60.0 22+4 37.8 22+4 Composition Aqueous H 2

SO

4 to give pH 2.

See Notes for this table below.

Tap Water Varies; see details below.

Tap water rinse DI water rinse 0 6 6 90 0 30 22+4 Notes for Table 12 The composition for Stage 2 contained a commercially available sulfuric acid and surfactant cleaner (RIDOLINE® 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 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 solution, using a phenolphthalein indicator after dissolving a large excess c' sodium fluoride (about 2 3 ml in bulk volume of powdered dry reagent) in the sample before titrating. The points of free acid are equal to the number of mL of titrant required to reach a faint pink end point.

o3 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 2000 C oven for an additional 5 minutes. These conditions were identified as single an' 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.

I

WO 95/02660 PCT/US94/00024 The domes were removed from the cans using a can opener. Once this was done, they were placed in a 660 C water bath containing 0.2 grams of sodium tetraborate decahydrate per 1000 mL of deionized water. Following immersion for minutes, the domes were rinsed with DI water and dried in an oven. The quality of 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 as described above was Aromox@ C/12, which according to its supplier is an amine oxide with a chemical structure represented by: Cocoa-N(O)(CH2CH 2

OH)

2 where "Cocoa" represents the mixture of alkyl groups that would result by substituting a -CH- moiety for each -COOH moiety in the mixture of fatty acids obtained upon hydrolysis of natural coconut oil.

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 coefficients of friction on the cans treated are shown in Table 14.

Variable TABLE 13 Values of the Variables: Medium Higi

H

2 ZrF 6 1 0.0099 0.0069 pH 4.50 3.50 Molar Ratio of 2.0 1.0

H

3 P0 4 to H 2 ZrF 6 Molar Ratio of 1 7

AO

2 to H 2 ZrF 6 10 075 Notes for Table 13 1 Values shown are moles in 8 liters of composition.

2 "AO" means "amine oxide", in this case Aromox@ C/12.

0.

Low .0040 2.50 ).0 ~eeL~p, WO 95102660 P1-"TfUS94/00024 TABLE 14 Run No. Value 1 for Variable in Run COF-BB 2

COP-D-B

3 with This Number: H2z-F6 pH EH 3

PO

4 J/ [AO]/ 1 0 0 0 0 0.739 0.874 2 -1 +1 +1 +1 1.421 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 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 13 +1 +1 +1 +1 1.459 14 -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 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 soFootnotes for Table 14 1 The value is expressed as high medium or low (1),with the numerical meanings for these values given in Table 13.

2 "SB" =single bake.

3 "DB" =double bake 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 WO 95/02660 PCT/US94/00024 TABLE 15: QUATERNARY AMMONIUM SALTS Trademark Name Chemical Structure of: Cation Counter Ion ETHOQUAD® C-12 Cocoa-N- (CH 3

(CH

2 CH20H) 2 Cl ETHOQUAD® C-12B Cocoa-N- (CH 2

(CH

2 CH20H) 2 C1- ETHOQUAD® T-13/50 Tallow-N- (CH 2

CH

2 0H) 3 -OC (0)CH 3 Notes for Table "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. represents a phenyl moiety.

All the Stage 4 compositions in this group contained 9.6 grams of A1 2

(SO

4 3 152H 2 0 (which corresponds to 104 ppm of A1+3), 2.05 grams of H 2 ZrF and 0.0099 0.0001 mole of quaternary ammonium salt; those compositions designated with in Table 16 below also had 0.97 grams of H 3

PO

4 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 and only H 2 ZrF 6 was used as component In addition to concentration of the ETHO- QUAD® T-13/50, the other variables investigated were H 2 ZrF 6 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 H 2 ZrF 6 used; fluoride activity was adjusted to a reading of -90 my on fluoride sensitive electrode as described above. An additional 50 ppm of Al was added as 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 TABLE 16 Ouat in Composition Free F 1 COF-SB COF-DB DS ETHOQUAD® C-12 -89.0 1.12 1.28 3 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 millivolts, using an Orion Fluoride Sensitive Electrode and apparatus standardized with 120E Activity Standard Solution as described above. The column headed "DS" is 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 variable are shown in Table 17, and the combinations of the values of the three variables and the results are shown in Table 18.

TABLE 17 Variable and Designator Values for Variable: High Medium Low Moles of H2ZrF XI in 8 liters of 0.009 0.00675 0.0045 composition X2 pH 3.1 2.8 3 5 Molar percent of the X3 aluminum salt(s) that 100 50 0 was aluminum nitrate Molar ratio of X4 ETHOQUAD® T-13/50 1.00 0.75 to H2ZrF 6

J

_I

WO 95/02660 PCT/US94/00024 TABLE 18 Run No. X1 X2 X3 X4 COF-SB COF-DB DS 1 1 -1 -1 -1 0.513 0.531 2 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 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 0 0 0 0 0.599 0.813 3 21 -1 0 0 0 0.484 0.518 2 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 18 In the columns headed and the entry indicates the high value for the variable as specified in Table 17; the entry indicates the middle value for the variable as specified in Table 17; and the entry indicates the low value for the variable as specified in Table 17. Other column headings and meanings are the same as in Table 16.

WO 95/02660 WO 9502660P CTUS94/00024 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 ac~id was used, but the values of the some of the variables were different. The various combinations and the resulting performance are shown in Table 19.

TABLE 19 Run No.

1 H Concentration in Mulmoles per 8 Liters of: 1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24

CLEAN

2.00 2.20 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2 2,0 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.80

ONLY

9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 9.00 4.50 4.50 4.50 4.50 4.50 4.50 13.50 13.50 13.50 13.50 13.50 13.50 9.00 9.00 9.00 9.00 0.00 4.50 4.50 4.50 18.00 18.00 18.00 2.25 2.25 2.25 9.00 9.00 9.00 6.75 6.75 6.75 27.00 27.00 27.00 9.00 T132 4.50 4.50 4.50 4.50 2.25 9.00 18.00 2.25 9.00 18.00 1.13 4.50 9.00 4.50 9.00 3.38 13.50 27 3.38 13.50 27 4.50 Molar Ratios' 1:1:0.5 1:1:0.5 1:1:0.5 1:0:0.5 1: 0. 5:0. 25 1:0.5:1 1:0.5:2 1:2:0.25 1:2:1 1:2:2 1:0.5:0.25 1:0.5:1 1:0.5:2 1:2:0.25 1:2:1 1:2:2 1:0.5 25 1:0.5:1 1:0.5:2 1:2: 0.25 1:2:1 1:2:2 1:1:0.5 COF-SZ C!OP-DB DS 1.155 0.543 0.546 0.505 0.584 0.512 0.522 0.479 0.511 0.514 0.466 0.481 0.485 0.468 0.531 0.475 0.458 0.515 0.497 0.470 1.453 0.535 0.479 0.568 1.463 0.582 0.551 0.492 0.576 0.557 0.545 0.509 0.531 0.513 0.491 0.496 0.528 0.509 0.577 0.480 0.503 0.529 0.544 0.519 1.338 0.595 0.514 0.733 340 ALODINEM 404 Footnotes for Table 19 1 The ratios are shown in the order: H 2 ZrF 6

:H

3 P0 4 :TI3, 2 '713" means ETHOQUAD® T-13/50.

Other Notes for Table 19 The column headings "COP-SB", "COF-DB", and "DS" and the entries in these columns have the same meanings as in Table 16.

WO 95/02660 PCT/US94/00024 A preferred group of concentrates according to this embodiment of the invention has the following compositions, with water forming the balance of each composition not specified below: Ingredient Grams of Ingredient per Kilogram of SConcentrate Composition Inorganic Make-Up Concentrate Fluozirconic acid solution in water 32.3 Phosphoric acid solution in water 9.1 Aqueous nitric acid, 42 Baum6 25.5 Organic Make-Up and Replenisher Concentrate ETHOQUAD® T-13/50 70.0 SURFYNOL® 104 23.8 Inorganic Replenisher Concentrate Fluozirconic acid solution in water 44.4 75 Phosphoric acid solution in water 12.6 Hydrofluoric acid solution in water 4.6 Aqueous nitric acid, 42 o Baum6 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 supplier 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 deionized 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 Solution 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 430 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- WO 95/02660 PCT/US94/00024 le of a preferred co. entrate, with water forming the balance not otherwise stated: Ingredient Grams of Ingredient per Kilogram of Concentrate Composition Aqueous sulfuric acid, 66 o Baum6 13.0 45 Fluozirconic acid solution in water 41.4 Phosphoric acid solution in water 11.6 Hydrofluoric acid solution in water 7.7 ETHUQUAD@ T-13/50 40.9 In a preferred process embodiment using this concentrate, 50 mL of concentrate 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 my. A COF value of less than 0.6 was obtained in several experimental trials over a thirteen week period 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 derivatives in proper concentrations has been found to provide both protection against dome staining during pasteurization and adequate lowering of the COF for most purposes.

The can washing setup for this group of examples was: Stage 1 sulfuric acid, pH 2.0, 30 sec., 54.40 C 2 Stage 2 RIDOLINET 124C, 15 mL Free Acid, 3.4 g/L total of surfactant, Fluoride Activity -10 mV, 90 sec., 54.40 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.

i II WO 95/02660 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 65.60 C for 30 minutes, then rinsed in deionized water and dried in an oven. Staining resistance was evaluated visually by comparison with known satisfactory 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 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 ZrFELiter Trylox T 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 as lubricant and surface conditioner forming and water drainage promoting agents for tin cans: EthoxT m MI-14; (ii) a combination of 1 part by weight of Pluronic'

T

31R1 and 4 parts by weight of Plurafac6 D25; and (iii) Tergtol Min-Foam m 1X.

Of these, the Ethox T M 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 T is a block copolymer of ethylene and propylene oxides, with poly{propylene oxide) block caps on the ends of the polymers. 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 PCT/US94/00024 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 Pluronicm/Plurafac'T 0.81 77.3 Tergitolf 0.82 78.6

Claims (17)

1. A process comprising steps of 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 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: a component selected from the group consisting of quaternary ammonium salt and amine oxide surfactants conforming to general formula z: R 1 I R 2 N R 3 (X)a R* *4 0 S 15 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 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 20 selected from the same group as for R2 and R3 plus the moiety; X- is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a 0 if R4 is and 1 if R4 is not and 0 a component of complex fluoride anions: and, optionally but preferabiy, a component of phosphate ions, optionally also including sulfate or nitrate ions or both; and, optionally, aluminate anions, including fluoroaluminate anions; and, optionally aluminum cations, including complex fluoroaluminum cations, and, optionally, one or both of: a water soluble and/or water dispersible polymer including amino- substituted vinyl phenolic moieties; and a foam reducing component.

2. A process according to claim 1, wherein each of R2 and R3 is selected from the group consisting of hydroxyalkyl moieties having from 1 to 4 carbon atoms and component is present and includes phosphate ions.

3. A process according to claim 2, wherein all of R2, R2, and R4 are 2- hydroxyethyl groups and component includes fluozirconate ions.

4. A process according to claim 3, wherein the mixture of R1 moieties in component 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 includes both phosphate and nitrate ions.

5. A process according to claim 4, wherein the mixture of R1 moieties in 15 component corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of animal tallow. a

6. A process according to claim 5, wherein the molar ratio of the phosphate content of component to component to component is within the range from 1.0:(0.90- 1.10):(1.05- 1.25). A* 20 7. A process according to claim 4, wherein the molar ratio of the phosphate content of component to component to component is within the range :00.0: 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 to component to component is within the range from

9. A process according to claim 2, wherein the molar ratio of the phosphate content of component to component to component is within the range from 1.0:(0.5 A process according to claim 1, wherein the molar ratio of component (B) to component is within the range from (0.5 4.0):(0.25

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 in an amount from 0.14 to 2.25 mM, component 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 my on a fluoride 15 sensitive electrode, each of R2 and R3 is selected from the group consisting of hydroxyalkyl moieties having from 1 to 4 carbon atoms, the concentration of component 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 20 and surface conditioner forming composition is in the range from 2.5 to 3.1, the S.e aqueous lubricant and surface conditioner forming composition has a fluoride activity corresponding to a reading of -60 to -85 my on a fluoride sensitive electrode, all of R2, R3, and R4 are 2-hydroxyethyl groups, the concentration of S. component is within the range from 0.56-to 1.12 mM compoi-.nt (B) includes fluozirconate ions, and component includes from 0.56 to 2.2 mM of phosphate ions. i _Mm~l I~

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 corresponding to a reading of -68 to -80 mv on a fluoride sensitive electrode; the mixture of R1 moieties in component 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 component is within the range from 0.56 to 1.12 mM; component includes fluozirconate ions, and component includes from 0.56 to 2.2 mM of phosphate ions. 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 corresponding to a reading of -68 to -80 my on a fluoride sensitive 15 electrode; the mixture of R1 moieties in component 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 is within the range from 0.67 to 0.87 mM; component includes from 0.56 to 1.69 mM of fluozirconate ions; component includes from 0.56 to 2.2 mM 20 of phosphate ions; and the total of the concentrations of components and (E) is not greater than 340 ppm.

16. A concentrate additive suitable for dilution with water to form a lubricant 0. 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 component selected from the group consisting of quaternary ammoiium salt arid amine oxide surfactants conforming to general formnuia T: I r I- R 2 N+ R 3 {Xa R 4 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 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 moiety; X- is a monovalent anion or monovalent fraction of an anion with a valence higher than 1; and a 0 if R4 is and 1 if R4 is not and S: a component of complex fluoride anions; and, optionally but preferably, a component of phosphate ions, optionally also including sulfate or nitrate ions or both; and, optionally, 40 aluminate anions, including fluoroaluminate anions; and, optionally aluminum cations, including complex fluoroaluminum cations, and, to optionally, one or both of: a water soluble and/or water dispersible polymer including amino- substituted vinyl phenolic moieties; and a foam reducing component. 0*

17. An additive according to claim 16, wherein each of R2 and R3 is selected from the group consisting of hydroxyalkyl moieties having from 1 to 4 carbon atoms and component is present and includes phosphate ions.

18. An additive according to claim 17, wherein all of R2, R3 and R4 are 2- hydroxyethyl groups and component includes fiuozirconate ions.

19. An additive according to claim 18, wherein the mixture of R1 moieties in i 1 59 component 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 includes both phosphate and nitrate ions. An additive according to claim 19, wherein the mixture of R1 moieties in component corresponds to the mixture of alkyl groups in the fatty acids derived from hydrolysis of animal tallow.

21. An additive according to claim 20, wherein the molar ratio of the phosphate content of component to component to component is within the range from 1.0:(0.90 1.10):(1.05 1.25). DATED this 23rd day of June, 1997 HENKEL CORPORATION WATERMARK PATENT TRADEMARK ATTORNEYS 4TH FLOOR, "DURACK CENTRE" 263 ADELAIDE TERRACE PERTH W.A. 6000 AUSTRALIA ••8 0o00 00 *0 c L~ R ~1~1 I INTERNATIONAL SEARCH REPORT International application No. PCT/US94/00024 A. CLASSIFICATION OF SUBJECT MATTER C10M 173/02; B21B 45/02 US CL :252/25, 26, 34, 49.3, 49.5, 49.9; 72/42 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. 252/25, 26, 34, 49.3, 49.5, 49.9; 72/42; CO1M 173/02 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US,A, 5,139,586 (Das) 18 August 1992, see col. 3, line 62- 1-35 col. 4, line 32 and cols. 5-6 Y US,A, 5,064,500 (Awad) 12 November 1991, see col. 1, 1-36 line 60 to col.5, line Y USA, 5,030,323 (Awad) 09 July 1991, see col. 1, line 51 1-35 to col. 4, line Y US,A, 4,490,536 (Corti et al) 25 December 1984, see col. 1, 1,16-23,30-35 line 22 to col. 3, line A USA, 5,061,389 (Reichgott) 29 October 1991, see col. 2, 1-35 liine 28-68. SFurther documents are listed in the continuation of Box C. See patent family annex. Special categories of cited documents: "T later document published after the intemational filing date or priority date and not in confict with the application but cited to understand the documentdefining the general ntate of the art which is not conaidered principle or theory underlying the invention to be of particular relevance S earlier document publhed on or afr the intetion fiing dte document of particular relevance; the claimed invention cannot be E' earlier document publishd on or ftr the intetional iling date conide novel or cannot be considered to involve an inventiv step document which may throw doubts on priority claim(s) or which is when the document is taken alone cited to establish the publication date of another citation or other apccial reason (as specified) document of particular relevance; the claimed invention cannot be considered to involve an inventive step when the document is document referring to an oral disclosure, use. exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the ar documentpublihed prior to the international filing date but ater than document member of the same patent family the priority date claimed Date of the actual completion of the international search Date of mailing of the international search report 14 MARCH 1994 14 JUN 1994 Name and mailing address of the ISA/US Au1oriz Commissioner of Patents and Trademarks Box PCT cAvoy Washington, D.C. 20231 Facsimile No. (703) 305-3230 Telephone No. (703) 308-2510 Form PCT/ISA/210 (second sheet)(July 1992)* s a l M INTERNATIONAL SEARCH REPORT International application No. PCT/US94/00024 C (Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Rlvntoclaim No. US,A, 4,921,552 (Sander et al) 01 May 1990, see col. 2, line I11 to col. 4, line 16. 1-35 I I Form PCT/ISAJ21O (continuation of second sheet)(July 1992)*