CN1066483C - Aqueous lubricant and surface conditioner for formed metal surfaces - Google Patents

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 (i) 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) phosphate 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.

Description

The aqueous lubricant and the surface conditioner that are used for formed metal surfaces

The present invention relates to method and composition, when said composition is applied to formed metal surfaces, especially during the clean surface of aluminium and/or washpot, can realize at least one and all purposes that relate to below most preferably: (ⅰ) after the dry tack free, reduce the confficient of static friction for the treatment of surface, to be coated with thereon coating or the bonding force of lacquer have no adverse effect; (ⅱ) promote water to discharge from the surface of having processed, do not cause " moisture film damaged ", namely promote to be created in the discharge of the thin continuous film (rather than each water droplet (being called " moisture film is damaged ") that is separated by relatively dried zone between the water droplet) of water on the tank; (ⅲ) these tanks reduce the oven drying temperature that dry described surface needs after with water rinse.

Following discussion of the present invention and description will be mainly from aluminium pots, because these tanks represent largest application areas of the present invention. Yet, should know that by apparent necessary the variation discussion of the present invention and describe the formed metal surfaces that also is applicable to zinc-plated cylinder of steel and other type is actually interesting to the predetermined purpose of this invention described above.

Aluminium pot generally is used as the packing container of variety of products. After it is made, usually wash therefrom remove aluminum dust and other dirt with acidic cleaner. Recently, consider that the residue impact of staying after environment and acid are cleaned on the tank is packaged in the possibility of the smell of the beverage in the tank, causes people to remove the interest of these dust and dirt with alkaline cleaner. Yet, no matter be to process aluminium pot with alkaline cleaner or acidic cleaner, generally all cause etch in various degree on the outer and tank inner metal surface of tank. For example, for the desired optimal conditions of tank inner surface that reaches without aluminum dust causes the mobility problem of tank on conveying equipment usually, reason has been to increase the roughness of tank outer surface.

The aluminium pot that outer surface does not have low confficient of static friction (following often referred to as " COF ") generally can not move and the conveyer belt that passes through reposefully tank equipment one by one. Remove because evenly raising for manually-operated equipment inconvenience and owing to lost units makes cost by the obstruction that unsuccessfully causes. When tank adds man-hour by the canned decorations equipment of vast majority of conventional, the COF of inner surface also is important. The service requirement tank of these machines slides on the axle of rotation, then with this axle tank is carried the cylinder that passes through rotation, and these cylinders print decorative ink to the outer surface of tank. The difficult tank of sliding upward or skid off axle can not suitably be decorated and be caused fault in production to be referred to as " printing machine tripping operation ". Except the mistake that directly causes this printing machine tripping operation is carried the tank, before or after mistake is carried a tank, since the mechanical breakdown of printing machine and induction system, three to four tanks of General Loss. Along with streamline speed in recent years increases to the level of about 1200 to 1500 tanks of quotidian per minute, stop up and printing machine trips and more and more becomes two concerned hang-ups. Therefore, in tank, especially aluminium pot manufacturing industry, more need to improve COF on the tank surfaces externally and internally to improve its mobility.

In improving the tank surface nature, a major issue that relates to be when tank by printing or when going up label workshop section, can the performance of the tank that will print be counteracted or adverse effect. For example, after the cleaning tank, the marking label spray paint at inner surface on its outer surface. To this, the bonding force of coating and lacquer is most critical. Therefore the object of the invention is to improve mobility and the bonding force of coating, decorative ink, lacquer or analog is not had adverse effect.

In addition, in the tank manufacturing industry, present trend is the aluminum metal blank that used thickness is thinner. The problem that reduction aluminium pot metal stock thickness has brought is after this tank washing, to need to reduce the temperature of baking oven so that by post intensity pressure quality control inspection. Yet reducing that the drying oven temperature causes when tank arrives printing workshop section can not be by abundant drying, and causes label printing ink stain thereby can't two-forty production tank.

A kind of method that reduces oven temperature is to reduce the lip-deep surplus water of tank behind water rinse. Therefore, it is favourable impelling washings to discharge from the surface of having processed. Yet, in the case, usually importantly prevent from forming the surface with above-mentioned moisture film breakage. This moisture film breakage causes a kind of sensation at least, and has in fact also increased in each zone for the treatment of surface the inhomogeneous possibility for the critical nature of practicality.

Therefore; in order to increase output, reduce the production line obstruction, reduce downtime to greatest extent, to reduce the waste product tank, improve ink deposition or at least do not cause adverse effect that the oven temperature of washed tank is reduced to ink deposition, need to provide a kind of aluminium pot that improves by the mobility of single-row production line and printing machine.

In present the most widely used industrial practice, at least for large-scale operation, aluminium pot will carry out successively generally that as shown in following table 1 six times are cleaned and rinsing operates. (before any step in table 1, sometimes also use with room temperature under the running water contact procedure; When using, the step of this step for mark usually is called one " passage ".

Table 1
		Step	The effect of effects on surface when step is carried out
1	Aqueous acids prerinse
2	Aqueous acids and surfactant washing
3	The running water rinsing
4	Clean behind the weak acid, conversion coated, or the running water rinsing
5	The running water rinsing
6	Deionization (" DI ") water rinse

Might produce the mobile tank of to be satisfied with at present, in step 4 or step 6, use suitable surfactant to make printing ink and/or lacquer to subsequently coating have enough bonding forces by above-mentioned. The preferred process agent of using in step 6 is disclosed in US 4944889 and 4859351, and some in them can be from the Parker+Amchem Division (following often referred to as " P+A ") of Henkel company with trade name " Mobility Enhancer^TM40 " (often be reduced to " ME-40 here^TM") bought.

Yet, found that a lot of manufacturing firms are unwilling to use chemicals such as ME-40 in step 6^TM In some cases, thisly be unwilling to have the carbon filter material by DI water (conventional steps 6) system, this filter material absorption forms the additive of lubricant and surface conditioner, such as ME-40^TMIn the result of those reagent, make it become not too effective; For other situation, be owing to be unwilling to change technique, and these changes are to use ME-40 necessary.

Be unwilling any lubricant and surface conditioner are added last rinse step for those, but still hope obtains the producer by the obtainable advantage of these additives, developed other processing methods for above-mentioned steps 4, kept a little processing methods and be disclosed in US 5030323 and 5064500. In these materials some can be from P+A with trade name FIXODINE^TM500 have bought.

Yet, if the tank of processing additionally heats, for the reduction of the coefficient of friction that provides by the prior art processing method in step 4 or the step 6, often can substantially be reduced to unacceptable level after finishing above-mentioned six step process. Whenever even if high-speed production lines is stopped a few minutes, the extra heating of this tank in baking oven always occurs, and such situation is often run in actual production. Therefore in fact, higher COF numerical value and the reduction of mobility interrelate, and it is still inadequate to add the surfactant that improves mobility in the batching of washing tank. Therefore, one object of the present invention is to provide a kind of method of improving the aluminium pot mobility, and/or one of above-mentioned other purpose of the present invention is to provide a kind of especially to heating the method that is better than prior art aspect beneficial effect when far exceeding the required minimum degree of dry treatment surface stable.

In addition, some beverage that is packaged in the aluminium pot will carry out pasteurize, unless therefore in pasteurization processes, carefully control the composition of temperature and the aqueous solution that contacts with tank, otherwise the often corrosion of generation tank top cover in pasteurization processes. Further aim of the present invention is to provide composition and the method that is suitable for reducing coefficient of friction, and these compositions and method also can stop the top cover corrosion in the pasteurization processes.

Except in operation embodiment, or except being otherwise noted, this paper is used for the amount of expression component or all numerical value of reaction condition, when describing wide region of the present invention, is interpreted as in all cases by the term " about " correction. Yet in the number range that provides, implement normally preferred.

In addition, unless opposite offering some clarification on arranged, the following describes be fit to or be preferably used as specific components of the present invention respectively organize chemical substance refer to two or more mixture in each composition the same with each single component in the group of using separately be fit to or preferably. Simultaneously, it should be noted that the chemical substance that is ionic state is to exist as some required equilibrium ions of the total composition of charge neutrality. Usually, these equilibrium ions should be chosen from the ionic state material as the present invention's part at first as far as possible; The equilibrium ion of required various remainders generally can freely be chosen, but should avoid selecting to the disadvantageous equilibrium ion of the object of the invention.

Aqueous lubricant for formed metal surfaces of the present invention is basically by water and the following fluid composition that becomes to be grouped into surface conditioner:

(A) the phosphorous surface active agent composition of dissolving, this component is the mixture that meets the molecule of general formula I:

Wherein M is the group that is selected from monovalence part and the ammonium of H, alkali metal cation, alkaline earth metal cation and replaces the monovalence part of ammonium cation; X=1 or 2 and y=3-x; Y is alkylidene or alkylene ether group, it can be with the key that stretches out on its carbon atom branching or nonbranched and have 2 to 12 carbon atoms and up to 3 oxygen atoms; R is the imidazoline part that meets the general formula II:

R wherein¹And R²Except not being the hydrogen simultaneously, all can be selected from hydrogen, by from propionitrile-CH₃The part of removing a hydrogen atom in the group and deriving and the group with part of general formula III:

Wherein, Q be selected from-OM ,-NH₂With-OR₄, wherein M is identical with meaning defined above, R⁴Expression C_2-12Alkyl, alkaryl or alkyl cyclic aliphatic part; R³Be selected from the aliphatic series with 2 to 22 carbon atoms and cyclic aliphatic and alkaryl part that not replacement or hydroxyl replace;

Wherein the amount of component (A) reaches every liter of composition provides 0.00060 to 5 mole phosphorus;

(B) be selected from the component that contains the water soluble salt that comprises the ion that is selected from Zr, Ti, Sn, Al and Fe atom,

Wherein the amount of component (B) reaches every liter of composition provides 0.00010 to 5 mole total Zr, Ti, Sn, Al and Fe;

(C) metal etch component, wherein the amount of component (C) reaches every liter of degree that 0.21 to 11 mole fluorine atom is provided; With

(D) " free fluorine ion ", the amount of component (D) are 0.10 to 2.2 % by weight, and one or more nonessential following components:

(E) be selected from the component that molecule meets following general formula IV:

R wherein⁶For having the saturated monovalence aliphatic hydrocarbon of straight chain, ring-type or the side chain part of 1 to 25 carbon atom; X is selected from hydrogen, halogen, phenyl and R⁵ S is 1 to 50 integer; R⁵Be selected from hydrogen and the alkyl group that contains 1 to 4 carbon atom;

(F) be selected from the component that molecule meets the general formula V:

R wherein⁷Be straight chain, ring-type or the side chain monovalence aliphatic hydrocarbon that contains 4 to 25 carbon atoms; (C₆H ₄) be adjacent, or to penylene ring, R⁵Identical with meaning in the general formula IV with s;

Wherein component (E) and component (F) weight ratio are 1.7: 1.00 to 1.00: 1.4, and component (E) and (F) weight ratio of total amount and component (A) be 3.3: 1.00 to 1.00: 2.0.

(G) the surface-active effective dose be selected from the component that molecule meets the general formula VI:

R wherein⁸Be the straight or branched with 1 to 25 carbon atom, saturated or undersaturated monovalence aliphatic hydrocarbon part; R⁵Have and meaning identical in the general formula IV with s;

(H) the chelating effective dose is selected from chelator component for the metal ion of component (B); With

(I) bactericidal agent of sterilization effective dose.

In a preferred embodiment, component (A) is selected from and meets the general formula I and " Y " group contains 2 to 4 carbon atoms but the molecule of anaerobic atomic time, R¹And R²Being selected from hydrogen and general formula III and Q=OM and M is hydrogen or alkali-metal part, and total at least R³50 % by mole in composition, have 8 to 20 carbon atoms.

In a more preferred, the amount of component (A) reaches every liter of composition provides at least 0.0010 mole of phosphorus; The amount of component (B) reaches every liter of composition provides at least 0.0017 mole total Zr, Ti, Sn, Al and Fe; Fluorine atom concentration is lacked 0.0020 mole fluorine atom for whenever rising in the component that is selected from fluorine ion, difluoride salt and hydrofluoric acid of composition.

In preferred embodiment again and again, component (A) reaches every liter of composition provides 0.0010 to 0.40 mole phosphorus; Component (B) comprises fluorine zirconic acid, fluorine zirconate ion or fluorine zirconic acid and the fluorine zirconate ion of dissolving; The amount of component (B) reaches every liter of composition provides at least 0.0039 mole Zr.

In preferred embodiment again and again, component (A) is selected from and meets the general formula I and Y is ethylidene group and total R³At least 76 % by mole of group have 10 to 14 carbon atoms and for not replacing or molecule during nonbranched alkyl group; The amount of component (A) reaches every liter of composition provides at least 0.02 mole phosphorus; The amount of component (B) reaches every liter of composition provides at least 0.0040 mole Zr.

In a most preferred embodiment, every liter of composition provides 0.057 to 0.103 mole Zr and 0.9 to 2.4 mole fluorine atom.

Various embodiments of the present invention comprise the composition that forms above-mentioned concentrated lubricant and surface conditioner; The aqueous solution of this composition that is adapted at being used as in step 4 in above-mentioned 6 cleanings and the rinse cycle and/or the step 6 the complete combination thing on contacting metal surface is not necessarily regulated the pH value with other acid or alkali); With the Aquo-composition contacting metal surface, the especially method on aluminium surface that comprise with the composition component that comprises the formation lubricant that describes in detail above and surface conditioner.

Fig. 1 (a)-1 (d) illustrated before coating lubricant of the present invention and surface conditioner in the purge tank process, the fluoride activity for processing after the impact of characteristic of tank.

More particularly, according to a preferred embodiment of the invention, can be used as the lubricant that causes surface friction factor to reduce at the thin organic film of aluminium pot outer surface coating, it finally provides improved mobility to tank, and has improved drying chamber and the speed of post intensity pressure test by the control quality. Find that also the improvement mobility of tank and the degree of rate of drying depend on thickness or the amount of organic film, and depend on the chemical property that is applied to the material on the tank.

According to the present invention, be used for aluminium pot lubricant and surface conditioner, for example can be selected from water soluble alkoxylated surfactant such as organic phosphoric acid ester; Alcohols; Comprise one, two, three and the fatty acid of polyacid; Derivative of fatty acid such as salt, hydroxyl acids, amide-type, ester class, the especially alkyl esters (being designated hereinafter simply as " oxa-esters of gallic acid ") of 2-substituted alkoxyization fat alkoxy acetic acid are in 843135 the U.S. Patent application those as more completely being described in the serial number of submitting on February 18th, 1992; Ethers and its derivative; And composition thereof.

According to one embodiment of the invention, the soluble derivative that is used for the isostearic acid of the lubricant of aluminium pot and stearic acid that surface conditioner preferably includes saturated fatty acid such as ethoxylation or ethoxylation, or its alkali metal salt such as the ethylating stearate of polyoxy and the ethylating isostearate of polyoxy. In addition, lubricant and the surface conditioner for aluminium pot can comprise that the water-soluble alcohol that has at least about 4 carbon atoms also can contain up to about 50 moles oxirane. When alcohol comprises the polyoxy ethylization oleyl alcohol that contains average about 20 moles of ethylene oxide/1 mol of alcohol, obtain excellent result.

The present invention another preferred aspect, be used for organic substance at aluminium pot formation film before the outer surface final drying after alkali or acid are cleaned and before conveying and comprise and be selected from phosphate, alcohol, comprise one, two, three and the Water-soluble Organic Substances of the fatty acid of polyacid derivative of fatty acid (comprising salt, hydroxyl acids, amide-type, alcohols, ester class, ethers and its derivative) and composition thereof. This organic substance is preferably and comprises the partially aqueous solution that is adapted at cleaning the Water-soluble Organic Substances of formation film on the aluminium pot, have confficient of static friction after the drying and be no more than 1.5 surface in order to be provided at, this confficient of static friction is lower than the confficient of static friction that is not coated with this film and obtains on similar tank surface.

In one embodiment of the invention, can pass through alkoxylate, it is water-soluble that preferred ethoxylation, propoxylation or its mixed form are given organic substance. Yet, non-oxyalkylated phosphate, especially phosphoric acid and various alcohol contain list free acid or neutral and diester also is used for the present invention. Object lesson comprises Tryfac^TM5573 phosphates, it is the ester that contains free acid available from Henkel company; And Triton^TMH-55、Triton ^TMH-66 and Triton^TMQS-44, they all can be available from Union Carbide Corporation.

Preferred non-ethoxylated alcohols comprises following all kinds of alcohol:

The ester class of suitable unary alcohol and itself and inorganic acid comprises that per molecule contains 3 water soluble compounds to about 20 carbon atoms. Concrete example comprises that NaLS is such as the Duponol available from Witco company^TM WAQ、Duponol ^TM QC、Duponol ^TMWA and Duponol^TMC, and the sodium alkyl sulfonate of sale monopoly is such as the AlRanol available from E.I.du Pont de Nemours ﹠ Co.^TM189-S。

Suitable polyalcohol comprises aliphatic series or the aralkyl polyalcohol that contains two or more oh groups. Object lesson comprises glycerine, D-sorbite, mannitol, synthesising biological polymeric gel, hexylene glycol, gluconic acid, gluconic acid salt, glucoheptonic acid salt, pentaerythrite and its derivative, and carbohydrate and alkylpolyglycosides class are as can be available from the APG of Henkel company ^TM300 and APG^TM325. Especially preferred polyalcohols comprises three alcohols, particularly glycerine or its fatty acid ester such as castor oil triglyceride.

According to the present invention, we find to use alkoxylate, especially ethoxylated castor oil triglyceride to cause the further improvement of tank mobility as lubricant and surface conditioner, and particularly wherein the operation of tank production line causes tank to be exposed to the improvement of the tank mobility of lower long period of high temperature when being interrupted. Therefore, especially preferred material comprises Trylox^TM 5900、 Trylox ^TM 5902、Trylox ^TM 5904、Trylox ^TM 5906、Trylox ^TM 5907、Trylox ^TM 5909、Trylox ^TM5918 and rilanit special derivative such as Trylox^TM5921 and Try-lox^TM5922, they all can be available from Henkel company.

Preferred aliphatic acid comprises butyric acid, valeric acid, caproic acid, sad, capric acid, n-nonanoic acid, dodecoic acid, tetradecylic acid, hexadecylic acid, oleic acid, stearic acid, linoleic acid and castor oil acid; Malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, tartaric acid, gluconic acid and dimeric dibasic acid; And any salt in these acid, the imino-diacetic propionate compound is as can be available from Amphoterie N and the Amphoteric 400 of Exxon chemical company; The sulfonation butanedioic acid derivative is as can be available from the Texapon of Henkel company^TMSH-135 Special and Texapon^TMSB-3; Citric acid, NTA and TMLA; Can be available from the Versenol of Dow Chemical^TM120 HEEDTA, N-(ethoxy) ethylenediamine triacetic acid ester.

Preferred acid amides generally comprises acid amides or the substituted amide of the carboxylic acid with 4 to 20 carbon atoms. Object lesson is can be available from the Alkamide of Rh_ne-Poulenc^TML203 lauric monoethanolamide, Alkamide^TML7DE laurate/tetradecylic acid alkanolamide, Alka-mide^TMDS 280/S Stearic acid diethanolamine salt, Alkamide^TMCD coconut diethanolamide, Alamide^TMDIN 100 laurate/linoleic acid diglycollic amide, Alkamide^TMDIN 295/S linoleic acid diglycollic amide, Alkamide^TMDL 203 lauric acid diethyl amides; Can be available from the Monamid of Mona industrial group^TM150-MW tetradecylic acid glycollic amide, Mon-amid^TM150-CW capric acid glycollic amide, Monamid^TM150-IS isostearic acid glycollic amide and can be available from the Ethomid of AKZO chemical company^TMHT/23 and Ethomid^TMHT60 polyoxy ethylization hydrogenated tallow acid amides.

Preferred anion organic derivative generally comprises sulfate and the sulfonate derivatives of aliphatic acid, comprises the sulfate of natural and synthetic alcohols of deriving, acids and natural products and the derivative of sulfonate. Concrete example is: dodecyl benzene sulfonate is as can be available from the Dowfax of Dow Chemical^TM 2Al、Dowfax ^TM 2AO、Dowfax ^TM3BO and Dowfax^TM3B2; Can be available from the Lomar of Henkel company^TMLS polycondensation naphthalene sulfonic acids, sylvite; Sulfo-succinate derivative is as can be available from the Monamate of Mona industrial group^TMSulfo-sodium succinate, the Monamate of CPA modification alkanolamide^TMLA-100 lauryl sulfo-disodium succinate can be available from the Triton of Union Carbide Corporation and Plastics company^TMGR-5M dioctyl sulfo-sodium succinate; Can be available from the Varsulf of Witco chemical company^TMSBFA 30 (fatty alcohol ether sulfo-succinate), Varsulf^TMSBL 203 (Marlamid sulfo-succinate), Varsulf^TMS 1333 (castor oil acid single ethanol amide sulfo-succinate).

Another kind of preferred organic substance comprises and is selected from fatty acid, comprises one, two, three and the water soluble alkoxylated of the amine salt of polyacid, amino aliphatic acid, fatty amine n-oxide and quaternary salt, preferred ethoxylation, propoxylation or mixed ethoxylated and propoxylation material, most preferably ethoxylation and non-ethoxylated organic substance and water-soluble polymer.

Preferred aliphatic acid amine salt comprises fatty acid and all contains ammonium, quaternary ammonium, Phosphonium and alkali metal salt up to the derivative of 50 moles of alkylidene oxygen at cation or anionicsite or cation and anionicsite. Object lesson comprises can be available from Am-photeric N and the Amphoteric 400 imino-diacetic propionic acid sodium salts of Exxon chemical company; Can be available from the Deriphat of Henkel company^TM154 N-tallow-β imino group disodium beclomethasone and Deriphat^TM160 (N-lauryls-β imino group disodium beclomethasone).

Preferred amino acids comprises α and beta amino acids class and two acids and salt thereof, comprises alkyl and Alkoximino dipropyl acids and salt thereof, comprises alkyl and Alkoximino dipropyl acids and salt thereof and sarcosine derivative and salt thereof. Concrete example comprises can be available from the Armeen of Akao chemical company^TMZ (N-coconut-beta-aminobutyric acid); Can be available from Amphoteric N, the Amphoteric 400 of Exxon chemical company, methyl amimoacetic acid (sarcosine); The ethoxy glycine; Can be available from the Hamposyl of W.R.Grace ﹠ Co.^TMTL-40 triethanolamine lauroyl sarcosine salt, Hamposyl^TMO oleoyl sarcosinate, Hamposyl^TMAL-30 lauroyl sarcosine ammonium, Hamposyl^TML lauroyl sarcosine salt and Hamposyl^TMC cocoyl sarcosinate.

Preferred amine n-oxide class comprises that at least one alkyl substituent wherein contains at least three carbon atoms and up to the amine oxide class of 20 carbon atoms, concrete example comprises can be available from the Aromox of Akzo chemical company^TMC/12 bis oxide-(2-ethoxy) cocounut oil alkylamine, Aromox^TMT/12 bis oxide-(2-ethoxy) tallow alkyl amine, Aromox^TMDMC cacodyl oxide base cocounut oil alkylamine, Aromox^TMDMHT oxidation hydrogenation dimethyl tallow alkyl amine, Aromox^TMDM-16 cacodyl oxide base cetyl alkylamine; With can be available from the Tomah of Exxon chemical company^TMAO-14-2 and Tomah^TM AO-728。

Preferred quaternary salt comprises the quaternary ammonium salt derivative that contains at least one substituent fatty amines, this substituting group contains the expoxy propane of 12 to 20 carbon atoms and 0 to 50 moles of ethylene oxide and/or 0 to 15 mole, and wherein counter ion counterionsl gegenions are comprised of halogen, sulfate radical, nitrate anion, carboxylate radical, alkyl or aryl sulfate radical, alkyl or aryl sulfonate radical or derivatives thereof ion. Object lesson comprises can be available from the Arzuad of Akzo chemical company^TM12-37W chlorination dodecyl trimethyl ammonium, Arguad^TM18-50 chlorination Octadecyl trimethylamine, Arquad^TM210-50 chlorination didecyldimethyl ammonium, Arquad^TMThe two octadecyl Dimethyl Ammonium Arquad of 218-100 chlorination^TM316 (W) chlorination, 31 cetyl ammonium methyls, Arquad^TMB-100 zephiran chloride dimethyl (C_12-18) alkylammonium, Ethoquad^TMC/12 chlorination cocounut oil methyl [POE (2)] ammonium, Ethoquad^TMC/25 chlorination cocounut oil methyl [POE (15)] ammonium, Ethoquad^TMC/12 nitrate, Ethoquad^TMT/13 Acetate acetic acid three (2-ethoxy) tallow alkyl ammonium, Duoqaud^TMT-50 dichloride N, N, N ', N ', N '-pentamethyl-N-tallow-1,3-two ammoniums, Propoquad^TM2HT/11 chlorination two (hydrogenated tallow alkyl) (2-hydroxy-2-methyl ethyl) ammonium methyl, Propoquad^TMT/12 methylsulfuric acid tallow alkyl methyl-two (2-hydroxy-2-methyl ethyl) ammonium; Can be available from the Monaquat of Mona industrial group^TMP-TS chlorination stearyl propyl group PG-di-basic ammonium phosphate; Chemquat available from Chemax company^TM12-33 Trimethyllaurylammonium chloride, Chemquat^TMThe 16-50 cetyltrimethylammonium chloride; And n-nonanoic acid, laurate, tetradecylic acid, oleic acid, stearic acid or isostearic acid tetraethyl ammonium.

When need to be overheated lower still keep low COF and/or anti-top cover corrosion the time in pasteurization processes, it be the major part of a particularly preferred embodiment according to the invention that fluorine ion combines with above-mentioned amine oxide or quaternary ammonium salt (the preferably latter). More specifically, for reaching these purposes, applicable additive preferably includes following substances and more preferably substantially is comprised of following substances, or further more preferably is comprised of following substances, and these materials are:

(A) be selected from the quaternary ammonium salt that meets the general formula I and the component of amine oxide surfactant:

R wherein¹Be monovalence aliphatic series part, it can be saturated or undersaturated and contain 8 to 22 carbon atoms, or preferably contains 12 to 18 carbon atoms, and preferred arrangement is straight chain; R²And R³Be the monovalence part respectively, be selected from respectively (ⅰ) and have 1 to 8, preferred 1 to 4, the more preferably alkyl of 1 or 2 carbon atom and hydroxyalkyl part and (ⅱ) have 6 to 10, or aryl and the aralkyl moiety of preferred 6 to 8 carbon atoms; R⁴To be selected from and R²And R³Identical group adds-O^-The monovalence part; X^-Be univalent anion or have the monovalence part that valence state is higher than the anion of 1 valency, and if R⁴And-O^-, if a=0 then is R⁴Be not-O^-, a=1 then;

(B) compound fluorine anion component, wherein the compounding ingredients of the anion of preferred fluotitanate, hafnifluoride and fluozirconate most preferably only has the fluozirconate anionic group; And not necessarily but preferred;

(C) be selected from phosphate radical, the component of sulfate radical and nitrate ion, the mixture of one or both in preferably phosphoric acid radical ion or phosphate radical and sulfate radical and the nitrate anion; And nonessential;

(D) aluminate anion comprises the fluoaluminate anion; And nonessential;

(E) aluminium cations comprises clad aluminum fluorine cation, and nonessential one or both;

(F) comprise the water-soluble and/or aqueous dispersion polymers of the amino vinyl phenol part that replaces, be disclosed in detail in one or more among the US 5116912,5068299,5063089,4944812,4517028,4457790,4433015 and 4376000;

(G) component (defoamer) of minimizing foam.

For component defined above (A), when the anti-top cover corrosion of needs, quaternary ammonium salt is better than amine oxide. R preferably²,R ³And R⁴In the part at least two kinds, or more preferably all three kinds all be hydroxyalkyl group, preferred 2-hydroxyethyl groups.

From economy and sale, at the material R that is used for component (A)¹Part preferably be present in fatty acid mixt in the mixture of the consistent alkyl group of the mixture of alkyl group, wherein fatty acid mixt is derived from natural fat and oils, such as coconut oil, palm-kernel oil, animal tallow etc. The alkyl group that comes from the animal tallow is particularly preferred.

For component (B), the fluorine zirconate ion that adds in fluorine zirconic acid mode is most preferred. The optimization consumption of fluoride in use easily (if needs) also can be monitored from the fluoride sensitive electrode that Orion Instruments has bought by being disclosed among the US 3431182. " fluoride is active " that use as term herein measured with respect to the 120E Activity Standard Solution (active standard liquid) available from P+A by being described in detail in the method among the P+A Technical Process Bulletin No.88. Orion fluoride ion electrode (Orion Fluoride Ion Electrode) and reference electrode that Orion Instrument is provided all immerse in the described standard liquid, if need, wait a moment so that the various initial drifts of reading stable after, with the Standard Knob on the instrument millivolt gage readings is transferred to 0. Then with electrode with deionized water or distilled water rinsing, drying and immerse in the testing sample, it is the identical temperature of 0 standard liquid that sample should transfer to being used for setting measurement instrument reading. The reading that immerses the electrode in the sample directly millivolt (following often referred to as " the mv ") measuring instrument from the instrument reads. Use this instrument, the higher fluoride of lower positive mV readings signify is active, and also high fluoride is active than positive mV reading for negative mV readings signify, and the high negative mV readings signify fluoride of absolute value is active high.

According to this embodiment of the present invention, appropriately operate freshly prepd working group compound and the first millivolt reading that makes should be in the use procedure of whole this composition at least substantially keep. For the composition that comprises said components (A), (B) and this embodiment of the present invention (C), the mV reading of free fluorine compound activity should be in-30 to-120 ,-50 to-100 ,-60 to-85 ,-68 to-80 or-68 to-72mV scope, with the increase of the preferred property of the order that provides.

The anion definite for top component (C) preferably adds in the mixture of the present invention with corresponding sour form. When the anti-top cover corrosion of needs, component (C) preferably includes phosphate anion. When component (C) when comprising phosphate, because pH and the phosphate content of component (C) and the preferred value (will further consider below) of component (A) and ratio (B), usually need to transfer to the pH value in the preferable range with some other acid except phosphoric acid and don't exceed phosphoric acid and the preferable range of other component. In the case, when the anti-top cover corrosion of needs, preferably use nitric acid; In addition, any do not hinder realize the object of the invention other enough strong acid can use; To this, usually main preferably sulfuric acid is because it is more cheap than other strong acid.

Component (D) and (E) can optionally adding in the composition of step 4 (except test purpose), but generally under physical condition, produce accumulation at this during for the treatment of the aluminium surface. Yet aluminium unlikely has any beneficial effect. Empirical evidence normal equilibrium concentration in industrial aluminium pot cleaning product line is 100-300 weight portion/1000,000 weight portions (following often referred to as " ppm "), can be many by comprising this, or even the composition of more aluminium obtain satisfied result. Component (D) and concentration (E) preferably are no more than 1000,700,500,450,400,370,340,325 or 315ppm, with the increase of the preferred property of the order that provides.

In comprising that amine oxide or quaternary ammonium salt are as the effect composition in the whole step 4 of embodiment of the present invention that must component, pH value preferably remains on 2.3 to 3.3, and more preferably 2.5 to 3.1, in further preferred 2.70 to 2.90 scopes. The pH value is lower than described value and usually causes being lower than the required rust resistance of top cover, is tending towards producing lacquer and/or the printing ink good adhesion of inadequate etch surface to guarantee to be coated with subsequently and the pH value is higher than described value. In long-time process, generally need to add acid to keep the pH value, because acidity has consumption in forming lubricant and surface conditioner coating procedure. If just processed surface mainly is modal aluminium surface, preferably in the acid that replenishes, comprise q.s hydrofluoric acid so that the aluminium of dissolving in the composition use procedure, cooperate with the composition that forms lubricant and surface conditioner. Described supplemental acid adds in the process of the composition of long-time use formation lubricant and surface conditioner.

When component (C) comprises usually preferred phosphate anion, component (Cp): (B): the mol ratio between the A is preferably (with the increase of the preferred property of the order that provides) 1.0: (0.5-4.0): (0.25-8.0), 1.0: (0.5-2.0): (0.5-6.0), 1.0: (0.7-1.3): (0.8-1.5), 1.0: (0.8-1.2): (0.90-1.40), 1.0: (0.90-1.10): (1.05-1.25) or 1.0: (0.95-1.05), wherein " Cp " only represents the phosphate content of said components (C). Do not use or do not conform to phosphate such as fruit component (C), then for this two component, ratio (B): (A) preferably fall into above-mentioned wherein within composition comprises the identical scope of phosphatic situation. Separately, the concentration of component (A) in the composition of the step 4 of effect is preferably (with the increase of the preferred property of the order that provides) 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 mM/l (following often referred to as " mM "), the concentration of component (B) in the composition of step 4 of effect is preferably 0.20 to 2.0, or more preferably 0.40 to 1.0mM; Reach the concentration of component (Cp) in the composition of the step 4 of effect and be preferably 0.20 to 2.0, more preferably 0.40 to 1.0, or further preferred 0.60 to 0.84mM. [in these data declarations, for component (Cp), the Chemical Calculation equivalent of the anion that produces as the phosphate anion of any unionized phosphoric acid or the phosphoric acid ionization by any degree is used as phosphate anion and considers. ]

Higher component (A) concentration has been improved the top cover rust resistance but has also been increased the trend that composition bubbles in pasteurization processes in above-mentioned scope, must often avoid for this reason. When anti-top cover corrosion was important, the concentration of component in above-mentioned scope (A) was lower, and then the concentration of component (Cp) just should be higher, because for improving the top cover rust resistance, component (Cp) shows the synergy with component (A). When component (D) and/or relative concentration (E) were high, in above-mentioned scope, higher component (B) concentration was preferred.

Under some operating condition, preferably, the composition of the present invention that comprises amine oxide and/or quaternary ammonium salt does not contain even can be used for strengthening ambulant Cucumber in other embodiment of the present invention, does not also contain some other material with various unfavorable character simultaneously. Particularly, for the following various possibility components (increasing preferred property with the order that provides) of listing separately, the composition based on amine oxide and/or quaternary ammonium salt for above-mentioned steps 4 (or with behind itself or dilute with water) of the present invention, preferably contain any following material that is no more than 5,1.0,0.2,0.05,0.01,0.003,0.001 or 0.0005 % by weight [except as those materials that must stipulate or the nonessential said components (A)-(G)]: (a) surfactant as (a.1) organophosphorus compounds, (a.2) alcohols, (a.3) fatty acid comprise one, two, three and polyacid and derivative (a.4) thereof such as (a.4.1) salt, (a.4.2) hydroxyl acids, (a.4.3) amide-type, (a.4.4) ester class and (a.4.5) ethers; (b) oxyalkylated (but except describing as part (a) is middle) surfactant; (c) oxyalkylated castor is sheltered oily triglyceride, (d) natural and synthetic alcohols of deriving. The sulfate of acids and/or natural products and sulfonate derivatives; (e) amino acids; (f) water-soluble homopolymer of oxirane, expoxy propane, epoxy butane, acrylic acid and derivative thereof, maleic acid and derivative thereof and/or vinyl alcohol and/or heteropolymer; (g) contain altogether the organic acid salt of at least two carboxyls and oh group.

Preferred water-soluble fluidity polymer comprises homopolymers and the heteropolymer of oxirane, expoxy propane, epoxy butane, acrylic acid and derivative thereof, maleic acid and derivative thereof, phenol ethylene and derivative thereof and vinyl alcohol, and concrete example comprises can be available from the Carbowax of Union Carbide Corporation ^TM 200、Carbowax ^TM 600、Carbowax ^TM 900、Carbowax ^TM 1450、 Carbowax ^TM 3350、Carbowax ^TM8000 and Compound 20M^TM Can be available from the Pluronic of BASF Wyandotte company^TM L61、Pluronic ^TM L81、Pluronic ^TM 31R1、 Pluronic ^TM 25R2、Tetronic ^TM 304、Tetronic ^TM 701、Tetronic ^TM 908、Tetron- ic ^TM90R4 and Tetronic^TM150R1; Can be available from the Acusol of Rohm ﹠ Haas Corp^TMThe polyacrylic sodium salt of 410N, Acusol^TM445 polyacrylic acid, Acusol^TMThe sodium salt of 460ND maleic acid/olefin copolymer, and Acusol^TMThe sodium salt of 479N acrylic acid/maleic acid; And the N-METHYL-ALPHA-L-GLUCOSAMINE adduct of polyvinyl phenol and the N-methyl ethanol amine adduct of polyvinyl phenol.

Can pass through in the method for the invention, the step that contacts with the inorganic material that is selected from metallic state or ion state zirconium, titanium, cerium, aluminium, iron, vanadium, tantalum, niobium, molybdenum, tungsten, hafnium or tin in conjunction with the aluminium pot outer surface again realizes further improving to produce the film of one or more combinations in one or more and the above-mentioned organic material in these metals. The film that produces has the confficient of static friction when being no more than 1.5 confficient of static friction and preferably being lower than without this film, improves thus the mobility of tank in carrying at a high speed and does not hinder container japanning, other coating, printing or other similar decoration subsequently.

Add these inorganic material, especially refer in detail to and add the method contain zirconia material and be disclosed among the US5030323 and the US 5064500 on November 12nd, 1991 on July 9th, 1991, complete open (the clearly statement with this paper does not meet to a certain extent) of the method here is incorporated herein as a reference. Replace the scope that those materials that clearly provide in one of these patents belong to those skilled in that art with other metal material.

In the further preferred embodiment of the inventive method, in order to provide improved water-soluble, especially water-soluble for non-ethoxylated organic substance as herein described, simultaneously to have confficient of static friction and be no more than the surfactant of 1.5 suitable thin baseization and the mixture of the organic material of non-ethoxylated in order to produce on the tank surface after drying, in final drying and conveying before with the tank Surface Contact that cleans. Preferred surfactant comprises sulphation or the sulfonated aliphatic alcohols of ethoxylation and non-ethoxylated, such as laruyl alcohol and lauric alcohol. Each anionoid, nonionic, cation or amphoteric surfactant all are suitable. The alkylpolyglycosides class is as having the C of average degree of polymerization between 1.2 and 2.0₈-C ₁₈The alkylpolyglycosides class also is suitable. Other various surfactants that is suitable for mixing is nonyl and the octyl phenol that contains the ethoxylation of 1.5 to 100 moles of ethylene oxide, preferably with the nonyl phenol of 6 to 50 moles of ethylene oxide condensations as can be available from the Igepal of Rh_ne-Poulenc^TMCO-887; The alkyl/aryl polyethers is such as Triton^TMDF-16; Phosphate is such as the Triton available from Union Carbide Corporation^TMProduct is such as Triton^TMH-66 and Triton^TMQS-44 and can be available from the Ethox of Ethox chemical company^TM2684 and Ethfac^TM136 all is representative example; The polyvinyl of straight chain and side chain alcohols and derivative thereof and/or poly-propoxylated derivative, for example Trycol^TM6720 (Henkel companies), Surfonic^TMLF-17 (Texaco) and An-tarox^TMLF-300 (Rhone-Poulenc); The sulfonated derivative of straight or branched aliphatic alcohol class is such as Neodol^TM25-3S (shell chemical company); Sulfonated aryl derivatives is such as Dyasulf^TM 9268-A、Dyasulf ^TM C-70、Lomar ^TMD (but all structure from Henkel company) and Dowfox^TM2Al (can available from Dow Chemical); And the copolymer of oxirane and expoxy propane, for example Pluronic^TM L-61、Pluronic ^TM 81、Pluronic ^TM 31R1、 Tetronic ^TM 701、Tetronic ^TM90R4 and Tetronic^TM150R1 can be available from BASF Corp.

In addition, according to the present invention, be used for the lubricant of aluminium pot and the alkyl acid phosphate alcohol ester that surface conditioner can comprise phosphate or preferred ethoxylation. These phosphates can trade name Rhodafac^TMPE 510 is from Rh_ne-Poulenc company, Wayne, and NJ has bought. And with trade name Ethfac^TM136 and Ethfac^TM161 from Ethox chemical company, Greenville, SC trade name Ethfac^TM136 and Ethfac^TM161 from Ethox chemical company, Greenville, and SC has bought. Usually, these organophosphorus esters can comprise alkyl and the aryl phosphate ester of ethoxylation or non-ethoxylated.

The lubricant and the surface conditioner that are used for aluminium pot can be in its washing operation cycles, one of its treatment cycle as clean or the conversion coated process in, in one of its water rinse cycle process, or more preferably (unless lubricant and surface conditioner comprise above-mentioned metal cation) in its last water rinse periodic process, be applied on the tank. In addition, lubricant and surface conditioner can after it is at last with the water rinse operation, before namely drying, or after the oven dry, be applied on the tank in the solution of water or another volatile solvent that does not fire by thin spraying rubbing method. Found that lubricant and surface conditioner can be deposited on the aluminium surface of tank so that it has required characteristic. Lubricant and surface conditioner can by spraying coating and by chemistry or physical absorption and aluminium surface reaction so that its required film to be provided.

The temperature of composition is not key features of the present invention usually in contact method between aqueous treatment composition and the metallic matrix to be processed and time of contact and the processing procedure, and they can be chosen from the known level of prior art. Yet for large-scale operation, powder spray is preferred contact method, and be 5 to 60 seconds (" sec ") time of contact in the step 4, or more preferably 10 to 30sec, 20 to 60 ℃ of temperature, or more preferably 30 to 48 ℃, be normally used.

Usually, in the cleaning process of tank, after tank cleaned, they generally were exposed to rinsing in the acid water. According to the present invention, available lubricant and the surface conditioner process tank that comprises anion surfactant such as phosphate. The pH value for the treatment of compositions is important and should is acid usually that namely the pH value is between about 1 to about 6.5, preferred about 2.% to about 5. If tank then need not lubricant of the present invention after the acid water rinsing and surface conditioner process, then often tank is exposed to rinsing in the running water, then use rinsed with deionized water. To this, preparation contains the rinsed with deionized water solution of lubricant of the present invention and surface conditioner, this solution can comprise and is selected from the ethylating alcohols of above-mentioned polyoxy or the ethylating fatty acid of polyoxy, or the non-ionic surface active agent of above-mentioned any other suitable substance, after this processed, tank can pass through oven drying in further first being processed.

Remaining in lubricant on the treatment surface and the amount of surface conditioner after the drying should be enough to cause the COF value to be no more than 1.5, or is enough to cause the COF value to be no more than (with the increase of the preferred property of the order that provides) 1.2,1.0,0.80,0.72,0.66,0.60,0.55 or 0.50. Generally speaking, lubricant and the surface conditioner amount on the tank outer surface should be about 3 milligrams/square metre to about 60 milligrams/square metre. Because generally preferred containing (with the increase of the preferred property of the order that provides) is no more than the necessary organic substance of 2.0,1.0,0.8,0.6,0.4,0.30 or 0.20 grams per liter (following often referred to as " g/ L ") to form lubricant and surface conditioner film on the tank surface of processing after drying for economic cause, the composition that aqueous lubricant and surface conditioner form.

The particularly preferred embodiment according to the present invention, found when lubricant and surface conditioner composition comprise at least a following organic substance, the skin-friction coefficient of processing with this lubricant and surface conditioner is difficult for by adding heat damage, these organic substances are: oxyalkylated or non-oxyalkylated castor oil triglyceride and rilanit special derivative oxyalkylatedly and non-oxyalkylatedly comprise one, two, three and the amine salt of the aliphatic acid of polyacid; Alkoxylate and non-oxyalkylated amino fatty acid; Alkoxylate and non-oxyalkylated aliphatic amine n-oxide, alkoxylate and non-oxyalkylated quaternary ammonium salt, (they are disclosed in the serial number of submitting on February 28th, 1992 more completely is in 843135 the U.S. Patent application to the Arrcostab of 2-substituted alkoxy aliphatic alkoxy acetic acid (being designated hereinafter simply as " oxa-acid esters "), the disclosed content of this application here is incorporated herein as a reference), and water soluble alkoxylated and non-Alkoxylated polymers. In addition, if before lubricant and the surface conditioner last dry tack free before automatic transport, not from the final Aquo-composition of Surface Contact be applied to the surface, the composition that then comprises these organic substances preferably also comprises the metallic element that is metallic state or ionic state of selected among zirconium, titanium, cerium, aluminium, iron, tin, vanadium, tantalum, niobium, molybdenum, tungsten and hafnium, and the film that is drying regime as lubricant and surface conditioner part that forms from the teeth outwards should comprise some and organic substance in this metalloid element.

For a more complete understanding of the present invention, should be with reference to the following example, these embodiment only are as describing and illustrative, be not limited to scope of the present invention, except the scope of its restriction can be introduced in the appended claim.

Embodiment group 1

Present embodiment explanation improves tank by the required aluminium pot lubricant of the mobility of the guide rail of industrial tank manufacturing equipment and printing workshop section and the amount of surface conditioner, and proves that lubricant and surface conditioner have no adverse effect to the bonding force that is printed in the label on the tank outer surface and is sprayed at the lacquer on the tank inner surface.

To use alkaline cleaner available from P+A from the unwashed aluminium pot that industrial tank factory obtains, adopt the Ridoline of company^TMThe washing of 3060/306 method is dry. Process the mode washing tank of 14 tanks by each CCW. With lubricant and the surface conditioner process tank of different amounts, then dry in baking oven in the last rinse step of washing facility. Comprise the ethylating isostearate of polyoxy of about 10% active concentration in lubricant and the surface conditioner, it is a kind of non-ionic surface active agent of ethoxylation, can be by trade name Ethox^TMMI-14 is from Ethox chemical company, Greenville, and SC has bought. Send the tank of processing back to tank factory, line speed and printing quality are identified. All tanks were put into following binding power test solution 20 minutes:

Testing liquid A: the deionized water at 3: 1: the 1%Joy in the running water^TMThe solution of (a kind of washing agent of commercial liquid dishwashing, P﹠G produces), temperature is 82 ℃.

Testing liquid B: the 1%Joy in deionized water^TMDetergent solution, temperature are 100 ℃.

After from binding power test solution, taking out the tank printed, with sharp metal object each tank is crossed hachure to expose the aluminum steel seen through coating or lacquer and tank is tested paint adhesion. This test comprises Scotch^TMAdhesive tape NO.610 is bonded on the cross hachure zone securely, then by ripping rapidly action adhesive tape is pulled open facing to itself, so adhesive tape is shut down from cross hachure zone. Result of the test is by following classification: 10, perfection, when adhesive tape not from any coating of sur-face peeling; 8, qualified; 0, fall flat. Any seal China ink of tank or the vestige that comes off of lacquer detect by an unaided eye.

In addition, use laboratory static friction test instrument to measure the confficient of static friction of tank. The confficient of static friction that this device measuring is relevant with the aluminium pot surface characteristic. Hold the hawser that be connected to do this test through inclined-plane, coil that 90 ° of arcs rise with freely swinging with the inclined-plane by adopting by constant velocity motors. With fixing the be separated by tank of about 1.27 centimetres (0.5 inches) of two horizontal positioned with the support that is connected at the bottom of the inclined-plane, top ends of cans is in the face of the stiff end on inclined-plane. The 3rd tank is placed on two tanks, and the top cover of this tank is in the face of the end that freely swings on inclined-plane, and the limit of three tanks is arranged in a straight line, and it is alignd mutually.

Along with the inclined-plane begins to move through arc, meter is automatically opened when the inclined-plane arrives wherein the 3rd tank and hangs down the angle that tanks are free to slide from 2, and optoelectronic switch cuts out timer. This time in second is commonly referred to " sliding time " just. When confficient of static friction equals the tank setting in motion by the tangent value of the inswept angle in inclined-plane. This angle (with the degree metering) equals [4.84+(2.79.t)], and wherein t is sliding time. In some cases, proof tank toasted under 210 ℃ 5 minutes again and remeasure COF, this as a result following table be shown " COF-2 ".

The mean value of binding power test and confficient of static friction measured value are generally listed in the table 2. In brief, the aluminium pot that discovery was cleaned for coating, even lubricant and surface conditioner concentrate are when very low concentrations, also can provide improved mobility to tank, even use 20 to 100 times simultaneously to the concentration that reduces tank confficient of static friction requirement use, label seal China ink or the interior lacquer of testing also had no adverse effect.

Embodiment group 2

These embodiment explanation when tank with 1260 tanks/minute speed when printing workshop section, the aluminium pot lubricant of embodiment 1 and the surface conditioner operating position in industrial tank production equipment.

With aluminium pot product acidic cleaner (Ridoline^TM125 CO are available from P+A) washing, then use Chrome-free convertion coating (Alodine^TM404, with the hurdle available from Parker+Amchem Division, Henkel company, Madison Heights, MI) process. Then this aluminium pot product is carried out " slip " test, find the confficient of static friction about 1.63 that the tank outer surface has. Pass through in the printing workshop section process at these tanks, tank can with 1150 to 1200 tanks/minute speed by printing workshop section without too much " tripping operation ", be the accident of inappropriate load tank, in the case, tank is loaded on the axle of printing tank inadequately. At every turn " tripping operation " all cause tank loss, these tanks have to abandon, because they are not accepted by last procedure of processing.

About 1 milliliter/liter aluminium pot lubricant and surface conditioner are added in the deionization washings system of tank rinsing maching, it makes the confficient of static friction on the tank outer surface be down to 1.46, or reduce about 11% of its former confficient of static friction, after tank passed through printing machine, the bonding force of rustproof lacquer was not affected by lubricant and surface conditioner in finding. In addition, press speed can increase to 1250 to 1260 tanks of its mechanical limit/minute and without new problem.

By same way as, by increasing the concentration of deionized water name aluminium pot lubricant and surface conditioner, might reduce the confficient of static friction 20% of tank and the bonding force of the interior rustproof lacquer of tank is had no adverse effect. Can in 24 hours test periods, keep continuously in addition 1250 tanks of press speed/minute.

Embodiment and comparative example group 3

These embodiment illustrate and use other material as the solvent of aluminium pot lubricant and surface conditioner.

Under about 41 ℃, clean aluminium pot about 35 seconds with the alkaline cleaner solution of pH value about 12. With this aluminium pot rinsing, then process with three kinds of different lubricants that comprise various phosphate solution and surface conditioner. Phosphate solution 1 comprises that concentration is that the phosphate of 0.5 grams per liter is (with trade name Rhodafac^TMPE 510 is available from Rhone-Poulenc, Wayne, NJ). Phosphate solution 2 comprises that concentration is that the alkylol phosphate of ethoxylation of 0.5 grams per liter is (with trade name Ethfac^TM161, available from Ethox chemical company, Greenville, SC). Phosphate solution 3 comprises that concentration is that the ethoxylated alkyl alcohol phosphate of 1.5 grams per liters is (with trade name Eth-fac^TM136 available from Ethox chemical company, Greenville, SC).

Measure the mobility with the confficient of static friction measurement of tank, the results are shown in following table 3. Table 3 phosphate pH value of solution confficient of static friction

1        3.6    0.47

2        3.3    0.63

3        2.6    0.77

Nothing---1.63

Above-mentioned phosphate solution all can provide aluminium pot qualified mobility, but aluminium pot is covered fully by " moisture film is damaged ". And what need is that aluminium pot is damaged without moisture film, namely has thin continuous moisture film thereon, because otherwise they contain larger water droplet, and moisture film is inhomogeneous and discontinuous simultaneously. Whether this moisture film breakage is printed with harm to tank in order to measure, and measures the bonding force of these tanks. Here it is, this decorative pot cut and at the deionization that comprises 3: 1: the detergent solution (Joy of the liquid dishwashing of running water^TM) in boiled 10 minutes. Then with the rinsing and dry in deionized water of these tanks. The same with embodiment group 1, carve 8 cross hachures at the interior lateral wall of tank and the coating of internal head cover. This score line is pasted adhesive tape. Then tear adhesive tape off. These tanks are carried out the bonding force classification. Its mean value is generally listed in the table 4, and abbreviation wherein is identical with meaning in the table 2. The phosphate solution bonding force classification that table 4 uses

      OSW   ISW   ID

Contrast 10 10 10

1     9.8   6.8   1.0

2     9.8   10    10

3     10    10    10

In order to contrast, observation does not exist come off (loss of paint adhesion) for phosphate solution 1 on lateral wall, madial wall or the internal head cover of tank, observe on the tank lateral wall, to exist hardly and come off, on the madial wall of tank, substantially do not exist to come off, and entirely ineffective on the tank internal head cover. For phosphate solution 2, observe on the lateral wall of tank to exist hardly and come off, on the madial wall of tank, do not exist to come off, on the tank internal head cover, do not exist to come off. For phosphate solution 3, observe on tank lateral wall, madial wall or internal head cover, not exist and come off.

Embodiment group 4

Present embodiment illustrates that lubricant of the present invention and surface conditioner are on the impact of the characteristic of the discharge water of the aluminium pot processed with its.

Aluminium pot (is used first Ridoline with acidic cleaner^TM125 CO then use Alodine^TM404 process, or only use Ridoline^TM125 CO process) or alkaline cleaner solution (Rido-line^TM3060/306 method) clean, all products all can be available from Parker+Amchem Di-vision, Henkel company, and Madison Heights, MI is then with containing the lubricant of the present invention of about 0.3 % by weight and the rinsed with deionized water of surface conditioner. When the tank draining that makes rinsing like this after 30 seconds, be determined at the remaining water yield on each tank. Do not make with lubricator and carry out same test with surface conditioner. The result generally lists in the table 5. Discovery exists lubricant and surface conditioner to cause water to be discharged from tank more equably, and these tanks of while are not residual " moisture film is damaged " in a long time. Table 5

The grams of the residual water of each tank is used: drain time (second) DI water DI water+0.3% conditioning agent

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

Embodiment group 5

Present embodiment explanation oven drying temperature is on the impact of aluminium pot side wall strength. This test is the quality control applied voltage test of the piezometry tank post degree when measuring flat tin of tank. The result who obtains generally lists in the table 6.

As can be seen from Table 6, the value that the value that the value that obtains in the post strength test when oven temperature is 193 ℃ obtains when being 227 ℃ with oven temperature obtains when being 227 ℃ with oven temperature is compared increases by 1.38 * 10⁴Handkerchief (2psi). Table 6 oven temperature (℃) post intensity (handkerchief) 227 5.94 * 10⁵ 204           6.05×10 ⁵ 193           6.08×10 ⁵ 182           6.15×10 ⁵

Higher post strength test result preferably and usually needs, because the thin-walled of final tank must bear applied pressure in the tank after tank is full of the solution of carbonic acid gas. Otherwise the poor tank of sidewall matter can expand and be out of shape or break easily or be even sudden and violent fried. Found because the quick discharge moisture film that wherein exists lubricant of the present invention and surface conditioner to cause might make oven temperature reduce and also obtain thus higher post intensity results. More specifically, for the tank of dry rinsing fully, make tank before entering baking oven, make its a little draining. Tank is stayed time in the baking oven generally between 2 to 3 minutes, and this time is somewhat dependent upon line speed, baking oven length and oven temperature. In order to obtain fully dry tank in the section between at this moment, general about 227 ℃ of oven temperature. Yet, in series of experiments (wherein washings contain the organic substance of 0.3 % by weight of having an appointment to form lubricant of the present invention and surface conditioner), found the drying chamber that when oven temperature is low to moderate 204 ℃, can be satisfied with, even when oven temperature is down to 188 ℃, still can obtain dry tank.

Embodiment group 6

To in embodiment type A, use the Division available from Parker+Amchem from the unwashed aluminium pot of industrial tank factory, Henkel company, Madison Heights, the alkaline cleaner of Michigan utilizes Ridolne^TM3060/306 method washes clean is used the acidic cleaner (Ridoline available from same company in the embodiment type B^TM125 CO) washes clean. Then carry out preliminary rinsing and before final drying, the tank that cleaned is used in the lubricant of the acitve organic matter matter (I) that comprises about 1 % by weight in the deionized water and surface conditioner is processed, these acitve organic matter matter (I) are listed in the table below in 7. In another kind of embodiment, after the initial rinsing and before final drying, the tank usefulness of cleaning is included in reactive lubricant and the surface conditioner processing of the inorganic matter (II) (listing in the table 7) of about 1% acitve organic matter (I) in the deionized water and about 2 grams per liters (0.2 % by weight). In another kind of embodiment, before drying after the initial rinsing and in the end, the tank usefulness of cleaning is included in lubricant and the surface conditioner processing of the acitve organic matter (I) of about 1% in the ionized water and the surfactant (III) of about 0.5 % by weight (be listed in the table below 7 in). In a class embodiment again, before drying after the initial rinsing and in the end, the tank that cleaned is used in reactive lubricant and the processing of surface conditioner component that comprises about 1% acitve organic matter (I), about 0.2% inorganic matter (II), about 0.5% surfactant (III) (be listed in the table below 7 in) formation in the deionized water. For all situations in this group embodiment, the COF value that produces in its surface is lower than 1.5.

Embodiment and comparative example group 7

In this group, will be used to form with the concentration test that is lower than the 6th group the various candidate substances of lubricant and surface conditioner. 7.1 general process. The deionized water of using electric conductivity to be lower than 5 μ siemens prepares mobility reinforcing agent/help the solution of rinsing, and except as otherwise noted, all other solution prepare in running water. From factory, obtain drawing and the boiling hot aluminium pot processed of tank skin.

The most of tanks of test in pilot-scale belt rinsing maching, this belt rinsing maching is single-rail seven step conveyor belt type rinsing machings (following usefulness " BW " expressions), its maximum speed is 1.890 m/mins (6.2 inch per minute clocks). In addition, use aforesaid CCW, this equipment is being processed 14 tanks under the microcomputer control in an order pilgrim-step. Two types rinsing maching can be simulated order, pause and the emission performance that large examination scale rinsing maching is produced.

Measure free acidity and the fluoride activity that cleaning agent is bathed by the method that is described in for Ridoline 124C among the P+A Technical Process Bulletin (NO. 968). Drying in the electrothermal air baking oven that the tank that cleans and processed is described below. The same with embodiment group 1, the mobility of test tank.

Table 7

The embodiment type	Acitve organic matter (I)		Inorganic matter (II)	Surfactant (III)	pH
						Trade name	Chemical name
	A	Emery657						Sad	Al 2(SO 4) 3	IGEPALCO-887	2.2
B			Emery659	Capric acid	H 2ZrF 6	TRITONX-101	2.2
	A	Emery651						Laurate	FeF 3	NEODOL25-5-3	2.3
B			Emery655	Tetradecylic acid	SnCl 4	TERGITOL  TMN-6	2.3
	A	Emersol  143						Palmitic acid 91%	Ce(NO 3) 4	TRITONDF-16	2.6
B			Emersol  153NF	Stearic acid 92%	H 2TiF 6	TRYCOL6720	2.6
	A	Emersol  871						Isostearic acid	H 2HfF 6	ANTAROXLF-  330	2-6
B			Emersol  6313NF	Oleic acid 75%	(NH 4) 2ZrF 6	TRITONH-55	2.6
	A	Empol  1014						Dimeric dibasic acid 95%	Fe 2(SO 4) 3	TRITONH-66	2.6
B			Emery  1110	Azelaic acid	AI(NO 3) 3	TRITONQS-44	2.6
	B	EthoxM15						The ethoxylation isostearic acid	TiCl 4	TRYCOL6720	3.0
A			EmuIphor  VN430	Polyoxy ethylization oleic acid	CeI 3	SURFONICLF-  17	3.0
	B	Ethox  MO5						Polyoxy ethylization oleic acid	FeF 3	LOMARD	3.0
A			Monamide  150LW	The laurate alkanolamide	FeCl 3	DOWFAX2Al	2.0
	B	Monamide  150 MW						The tetradecylic acid alkanolamide	FeBr 3	DYASULF9268-  A	3.0
A			Monamide  150IS	The isostearic acid alkanolamide	H 2zrF 6	DYASULFC-70	4.0

* table continued on next page

The embodiment type	Acitve organic matter: (I)		Inorganic matter (II)	Surfactant (III)	pH
						Trade name	Chemical name
	B	Monamide  718						The stearic acid alkanolamide	H 2TiF 6	IGEPALCO-887	5.0
A			Rhodafac  BH 650	Aliphatic series phosphoric acid fat, sour form	Fe(NO 3) 3	POLYTERGENT SLF-18	2.0
	B	Ethox  PP16						Aromatic phosphate acid ester	(NH 4) 2zrF 6	PLURONICL-61	3.0
A			Rhodafac  BL750	Aromatic phosphate acid ester, sour form	TaF 5	TETRONIC701	6.0
	B	Rhodafac  PE510						Aromatic phosphate acid ester, sour form	NbF 5	PLURONIC31R1	5.0
A			Ethfac  142W	Aromatic phosphate acid ester	H 2ZrF 6	PLURONIC 150R1	4.0
	B	Rhodafac  RA600						Aromatic phosphate acid ester acid form	(NH 2) 2MoO 4	APG300	6.0
A			ArmeenZ	N-cocounut oil-B-aminobutyric acid	H 2TiF 6	TRITONCF-21	6.0
	B	Hamposyl  L						Lauroyl sarcosine	VF 4	TRITONDF-18	5.0
A			Hamposyl  C	The cocoyl methyl amimoacetic acid	FeF 3	TRITONGR-7M	4.0
	B	Hamposyl  O						Oleoylsarcosine	SnCl 4	TRITONH-55	3.0
A			Harnposyl  S	Stearyl sarcosine:	Al 2(SO 4) 3	TRITONX-100	2.0
	B	AcusoI  410N						Polyacrylic acid sodium salt	H 2zrF 6	TRITONX-120	4.0

* table continued on next page

The embodiment type	Live and give birth to organic matter (I)		Inorganic matter (II)	Surfactant (III)	pH
						Trade name	Chemical name
	B	TritonGR-  5M						Dioctyl sulfo-methyl amimoacetic acid	Al(NO 3) 3	TRYCOL5882	6.0
A			AvanelS  70	The alkyl ether sodium sulfonate	VOSO 4	TRYCOL5887	5.0
	B	Igepon  TC-42						N-coconut and N-N-methyltaurine (taurate) sodium	VF 5	TRYCOL5964	4.0
A			Igepon  TK-32	N-methyl-N-tall oil acid taurine (taurate) sodium	VF 3	IGEPALCO-887	3.0
	B	Neodol25-  3A						The sulfonation linear alcohol, ammonium salt	(NH 4) 2WO 4	IGEPALCO-630	3.0
A			Aromox  C/12	Bis oxide (2-hydroxyl-ethyl) α-ample former times cocaine	(NH 4) 2zrF 6	NEODOL25-3	3.0
	B	Aromox  DMC						Cacodyl oxide base cocamine	FeF 3	NEODOL25-35	3.0
A			Ethoquad	0/25	Chlorinated oil acyl group (POE (15)) ammonium	Fe 2(SO 4) 3	NEODOL25-9					2.0
	B	Ethoquad  C/12						Chlorination cocounut oil methyl (POE (2)) ammonium	Al 2(SO 4) 3	NEODOL91-25	3.0
A			Ethoquad  18/5	Chlorination octadecyl (POE (15)) ammonium	Sn(SO 4)	TRITONQS-15	3.0

* table continued on next page

The embodiment type	Acitve organic matter (I)		Inorganic matter (II)	Surfactant (III)	pH
						Trade name	Chemical name
	B	Propoquad  T/12						Methylsulfuric acid tallow alkyl-methyl-two-(2-hydroxy-2-methyl ethyl) ammonium	Ce 2(SO 4) 3	TRITONDF-12	2.0
A			Ethfac136	Phosphate	H 2zrF 6	IGEPALCO-887	2.3
	B	Ethox  2684						Phosphate	H 2ZrF 6	IGEPALCO-887	2.7
A			Trylox  5922	The rilanit special of ethoxylation	H 2zrF 6	IGEPALCO-887	2.3
	B	Trylox  5921						″	H 2TiF 6	IGEPALCO-887	2.7
A			Trylox  5925	″	H 2ZrF 6	TRITONH-66	2.7

Foam height is by putting into 50 milliliters of (being designated hereinafter simply as " ml ") treatment fluids 100ml with 10 seconds of the also violent jolting of graduated cylinder of stopper. Leave standstill the cumulative volume of measuring immediately fluid, liquid and foam after 5 minutes. These are called " IFH " (initial foam height) and " PFH " (stable foam height) below " foam height ".

Processed the damaged characteristic of moisture film of tank with candidate's final rinsing mobility reinforcing agent (" FRME ' S), by each four main surfaces of range estimation classification tank: the method estimation of the moisture film breakage of internal head cover and madial wall and outer top cover and lateral wall. In this hierarchy system, without the surface of moisture film breakage, 0 represents the surface of complete moisture film breakage fully in numerical value 2 expressions, and the moisture film that median represents to be in therebetween is damaged. Estimate in this way four tanks and amount to the result to provide the number between 32 to 0, without moisture film damaged (WBF) minute progression.

7.2 cleaning agent is bathed the fluoride activity to the impact of COF and reflectivity. Use following CCW and last baking oven.

Step 1 running water, 54.4 ℃, 30sec

Step 2 RIDOLINR^TM124C, the 15ml free acid, total surfactant is

3.4 gram, fluoride activity 10 increases progressively with 10mv to-20mv),

         60℃，60sec

Step 3 running water, 30sec

Step 4 deionized water, 90sec

0.4%ME-40 is used on the nonessential property of step 5 ground^TM，20sec

Step 6 need not

210 ℃ in baking oven is lower 5 minutes

Defining as mentioned above step 2 described " fluoride is active " also can measure and see for details among the US3431182 with the fluoride sensitive electrode easily.

Except the effect of crude removal is measured by use " brightness test instrument ". This equipment is comprised of the power supply of stable high-strength lamp and the transmission light fibre bundle to the tank surface. Illumination from the tank reflection is mapped on the photoelectric tube, and its output current is by International Microtronics company, and Model 350 amplifiers amplify and are converted into numeral to be read. Shown in digital record be surface brightness. It is 440 that this instrument is calibrated to measurement of reflectivity with the level crossing of backing silver. Once calibration, can measure reflectivity and the calculating mean value of 14 tanks. Use this equipment, might measure whole internal head cover reflectivity and outer top cover reflectivity. The result is shown in Fig. 1 a to 1d.

These results show, brightness shown in the scope with the increase of fluoride activity monotone increasing. On the contrary, the COF value is equivalent to pact+10mv place in the fluoride activity and peak value and certainly slowly increase or reduction herein occur. In these experiments, COF is with the variation of fluoride activity value, and compares by the substantial improvements of using suitable FRME material to obtain, and in fact actual importance is quite little.

If the result shown in Fig. 1 (a)-1 (d) only considers from actual importance, then tends to the highest fluoride activity value. Yet because a variety of causes is not also found to reach in industrial reality. High fluoride amount expense is higher and impel etch rate fast, and this can increase the cost of pollution abatement or even damage the ability be subjected to etch container splendid attire pressurization material such as carbonated drink. Simultaneously; form therein in the large-scale industrial production that has the suitable short time between tank and the cleaning; from the tank that forms remove the oily residue than the experiment in laboratory easily, in the experiment in laboratory, form one group of tank and clean between them and generally will spend a few hours. Because these factors, it generally is preferred having found to be equivalent to electrode reading+50 to the fluoride activity value of-50mv, and most preferably the electrode reading is+5 to 0. As desired from the result shown in Fig. 1 (b) and 1 (d), when requiring the high tank of brightness, in these scopes is preferred than the high fluoride activity. 7.3 screen various FRAM active materials. According to following scheme operation CCW, the conventional steps 3 as rinse application, 4 and 5 production routine are wherein used in the rinsing time simulation that wherein prolongs step C3:

Step 1 sulfuric acid, pH2.0,30sec, 54.4 ℃

Step 2 RIDOLINE^TM124C, 15ml free acid, 3.4 grams per liter total surfaces are lived

Property agent, activator activity-10mv, 90sec, 54.4 ℃

Step 3 deionized water, 150sec. (about 17.7L)

Step 4 described in table 8,30sec, 29.4 ℃ of temperature

Step 5 need not

Step 6 need not be tested this, by adding 15% isopropyl alcohol predissolve Macamine^TMCO. Containing Igepal^TM430 or the composition of polyvinyl alcohol in, add 1.6 grams per liter Igepal^TMCO-887 obtains homogeneous solution. The result is as shown in table 8. In the candidate substances shown in the table 8, oxa-acid is preferred lubricant and surface conditioner formation such as those materials that are labeled as OAE 1-4 in table. They are ethoxylated castor oil derivatives and have hydroxyethyl groups and be bonded in amine oxide such as Aromox on the nitrogen-atoms of amine oxide^TMC/12 and T/12. Quaternary ammonium salt is as being illustrated in the ETHOQUAD in the table 7^TMMaterial also is a preferred class. Ethoxylated castor oil derivative, amine oxide and quaternary ammonium are all with below more detailed addressing. 7.4 ethoxylated castor oil FRME ' S. By described in 7.3 to CCW batching and operation, that different is the rinsed with deionized water 130sec of step 3, the first time, oven was at 200 ℃ rather than carry out under 150 ℃. The composition of step 4 is as shown in table 9. Repay in the examination the unsuccessful of settled solution, use Trylox^TM5921 experiment comprises 0.2 grams per liter Igepal^TMCO-887; Even in the presence of cosurfactant, still have slight haze.

Table 8

Candidate's the removable reinforcing agent of last rinsing and comparison
											Material standed for or comparison	Chemical classification	Hydrophobe	Hydrophile	Molecular weight	HLB	COF average StD	COF-2 average StD	IFH	PFH	WBF
Nothing nothing nothing nothing nothing is without SurfynolTM420 Surfynol TM440 Surfynol TM465 dimethyl formamide MonamineTMAD-100 M-Pyrol TM Macamine TMC-10 triethanolamine ArmoxTMT/12 Aromox TMC/12 Aromox TMDM-16 Macamine TMCAO Macanine TMCO Macamine TMSO Triton TMRW-100 Triton TMRW-50 Triton TMRW-75 TEAOleate Armeen TMZ APG TM300 APG TM325 Hostacor TMBF	------the glycosides glycosides borate of 7.5 amine-fatty both sexes of 5 amine of 10 amine of acetylene series-EO acetylene series-EO acetylene series-EO acid amides acid amides acid amides acid amides acid amides amine oxide amine oxide amine oxide amine oxide amine oxide amine oxide amine-(EO)-(EO)-(EO)	--------------C12 tallow C12 coconut C16 a-cocaine propyl group of ample former times (cocamidopropyl) coconut oleoyl amine stearmide-------	------(EO) 1.3 (EO) 3.5 (EO) 10----N=O/2-ethoxy N=O/2-ethoxy N=O N=O N=O---RCOOH/NH---	-     -     -     -     -     -     -     -     -     73.1     -     -     -     -     366     -     -     -     -     -     -     -     -     -     -     -	- - - - - - 4 8 13 - - - - - - - - - - - 16 13 15 - - - -	1.168 .108 1.098 .129 1.141 .151 1.331 .263 1.362 .194 1.295 .197 1.363 .201 1.404 .276 1.623 .549 1.371 .181 .457  .020 1.184 .172 1.645 .476 1.134 .120 .548  .129 .527  .090 1.519 .202 1.532 .468 1.329 .222 1.180 .116 .802  .179 1.099 .096 1.001 .130 1.214 .438 .660  .182 1.146 .201 1.015 .251 1.211 .157	1.126 .071  -     -  -     -  -     -  -     -  -     -  -     -  -     -  -     -  -     - .645  .127  -     -  -     -  -     - .672  .107 1.005 .190  -     -  -     -  -     -  -     - 1.136  .132  -     - 1.496  .430 1.430  .315 1.463  .299 1.211  .183  -      -	-     -     -     -     -     -     59     56     70     56     74     53     64     53     -     77     54     70     51     76     69     69     71     52     71     75     72     53	-     -     -     -     -     -     50     51     53     50     73     51     50     51     -     71     54     64     50     73     61     66     62     50     64     66     70     51	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

Material standed for or chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 IFH PFH WBF comparison average StD average StD HostacorTMBS borate--1.339 .231--58 54 32 OAE-1 C-18EO/PO C-18/PO (1) (EO) 5--.315 .040 .343 .032--32 OAE-2 C16-18EO C16-18 (EO) 5--.305 .030 .386 .066--28 OAE-3 C3-10EO C8-10 (EO) 5--.602 .149 .687 .118--32 OAE4 C8-18EO C8-18 (EO) 5--.282 .017 .483 .071--16 Acrysol^TMLMW-45 carboxylic acid n/a RCOO (-) 4500-1.02 .112--53 50 32 aminocaproic acid carboxylic acid C6 RCOOH/NH2--1.491 .495--50 50 32 citric acid carboxylic acid--191.1-1.334 .110--55 50 32 Gantrez^TMS-95 carboxylic acid----1.353 .356--59 52 32 gluconic acid carboxylic acid-COOH/C-OH--1.551 .316--50 50 32 arabo-ascorbic acid carboxylic acids----1.251 .201--51 50 32 Mimwet^TMB carboxylic acid C4---1.299 .294--59 52 32 potassium hydrogen phthalate carboxylic acid--204.2-1.500 .406--53 50 32 sodium glucoheptonate carboxylic acid-C-OH/RCOO (-) 249.2-1.238 .122--51 51 32 gluconic acid sodium salt carboxylic acid-C-OH/RCOO (-) 218-1.329 .147--51 50 32 tartaric acid carboxylic acids----1.501 .322--52 50 32 Chemquat^TMSP-10 is cationic----.990 .125 1.538 .162 56 51 32 Tetronic^TM701     EO/PO           (PO)2.04           (EO)13.7     3600  1-7   .972  .244  2.129 .363 64 51 32 Henkel ^TMSF-7063   EO/PO/Me-ester  Cl3/CH2-C(=O)OCH3  (EO)8.5       -    -     .287  .038  .374  .049 -  -  32 Ethox ^TMMI-14 ester C18 (EO) 14-13 .402 .044 .474 .048 70 67 32 Ethox^TMMI-14 ester C18 (EO) 14-13 .492 .076 .558 .146--32 Ethox^TMMI-14 ester C18 (EO) 14-13 .426 .042 .708 .133 68 67 32 Ethox^TMMI-14 ester C18 (EO) 14-13 .458 .080 .841 .241 67 63 32 Ethox^TMMI-14 ester C18 (EO) 14-13 .455 .087 .841 .274 66 64 32 Ethox^TMMI-14 ester C18 (EO) 14-13 .432 .061--67 63 32 Ethox^TMMI-14 ester C18 (EO) 14-13 .468 .090-----Brij^TM30 fatty alcohol C12 (EO) 4--.890 .161 1.013 .076--32 Chemal^TM2EH5 fatty alcohol 2-Ethylhexyl Alcohol (EO) 2--1 .032 .068 1.075 .103--32 Chemal^TMPA-5P8 fatty alcohol C-10LA/PO EO--815 .200 .725 .132 57 50 32 Ethal^TM2EH2 fatty alcohol 2-Ethylhexyl Alcohol (EO) 2-8.1 1.167 .118 1.149 .146--32 Etha^TMCSA-10 fatty alcohol C16-18 (EO) 12--.748 .164 .761 .166 high-32 chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 (FH WRF material standed for or average StD average StD comparison Ethal^TMCSA-17 aliphatic alcohol C16-18 (EO) 17--.726 .177 .677 .167--32 Ethal^TMDA-6 aliphatic alcohol C10 (EO) 6-124 .931 .201 1.045 .155--32 Ethal^TMOA-23 aliphatic alcohol C18 (EO) 23-15.8 .698 .175 .749 .192--32 Ethal^TMTDA-6 aliphatic alcohol C13 (EO) 6-11.4 .764 .179 .930 .163--32 Sandoxylate^TMSX-408 aliphatic alcohol i-C10-12LA/PO EO-11 .913 .107 .885 .105--32 Sandoxylate^TMSX-24 aliphatic alcohol i-C10-12LA/PO EO-15 .688 .160 .676 .137--32 Sandoxylate^TMSX-602 aliphatic alcohol i-C10-12LA/PO EO-8 .966 .132 1.145 .175--32 Triton^TMXL-80N aliphatic alcohol C8-10EO/PO/EO EO 420-.801 .187 .776 .156--32 Varonic^TMMT-42 aliphatic alcohol C12-18 CH3 cap EO--.549 .093 .581 .156--32 Varonic^TMMT-48 aliphatic alcohol C12-18 CH3 cap EO--.583 .146 .692 .180--32 Varonic^TMMT-65 aliphatic alcohol C12-18 CH3 cap EO--.814 .171 .862 .122--32 Fluorad^TMFC-126 fluorine surfactant C7F15 R-COONa--1.335 .233--65 50 0 Kelig^TM100 lignosulphonic acid esters-----1.450 .473--53 50 32 Kelig^TM400 lignosulphonic acid esters-----2.022 .773--54 51 32 Igepal^TM660 NP-(EO), 10 nonyl phenols (EO), 10 660 13.2 1.527 .555--70,65 32 Igepal^TM710 NP-(EO), 10.4 nonyl phenols (EO), 10.4 678.5 13.6 1.330 .329--75,67 32 Igepal^TM720 NP-(EO), 12 nonyl phenols (EO), 12 748 14.2 1.524 .423--76,71 32 Igepal^TM430 NP-(EO), 4 nonyl phenyl (EO), 4 396 8.8 .516 .064 .815 .195,63 60 32 Igepal^TM610 NP-(EO), 7.5 nonyl phenyl (EO)) 7.5 570.9 12.2 .693 .170,1.021 .176,63 60 32 Carbowax^TMMethoxy PEG    PEG           O-CH3          (EO)44.7            2000 -    .766  .222   .886  .199  -  -    32 Carbowax ^TMMethoxy PEG    PEG           O-CH3          (EO)7.3             350  -    .955  .126   1.047 .113  -  -    32 Carbowax ^TMMethoxy PEG    PEG           O-CH3          (EO)112.8           5000 -    .739  .158   .839  .118  -  -    32 Carbowax ^TMMetboxy PEG    PEG           O-CH3          (EO)16.3            750  -    .927  .236   .915  .190  -  -    32 Carbowax ^TMPEG20M         PEG           -              (EO)n              17500 -    .663  .149   .934  .155  -  -    32 Carbowax ^TMPEG-1450       PEG           -              (EO)32.5            1450 -    .778  .158   .854  .229  -  -    32 Carbowax ^TMPEG-200        PEG           -              (EO)4.15            200  -    1.122 .140   1.050 .114  -  -    32 Carbowax ^TMPEG-3350       PEG           -              (EO)75.7            3350 -    .747  .105   .921  .149  -  -    32 Carbowax ^TMPEG-8000       PEG           -              (EO)181.2           8000 -    .778  .188   .840  .162  -  -    32 Carbowax ^TMPEG-900        PEG           -              (E0)19.5            900  -    .819  .199   .865  .212  -  -    32 Dequest ^TM2000 phosphonate esters-N[CH₂-P=0(OH) ₂l ₃    299  -    1.506 .203    -    -     52 50   32 Dequest ^TM2006 phosphonate esters-Na₂N[CH ₂-P=O(OH) ₂] ₃409-1.327 .095--51,51 32 material standed fors or chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 IFH PFH WBF comparison average StD average StD Deques^TM2016 phosphonate esters-[(C-CH₃OH)][P=O(Na) ₂] ₂ 294  -   1.27   1.209    -        -      51 51 32 Dequest ^TM2054 sour fat-HMDA[CH₂-P=O(Na) ₂]4721  -    -   1.095  .225     -        -      51 50 32 Dequest ^TM2066 phosphonate esters-Trien[CH₂-P=O(Na) ₂]683  -    -   1.176  .150     -        -      51 50 32 Belzak ^TMAC is polyhydric-R-OH--1.211 .098--52 50 32 Cerelose^TMThe polyhydric 2-Me of polyhydric----1.335 .134--51 50 32 hexylene glycols of 2001 polyhydric----1.318 .095--51 50 32 glycerine, 2,4-C5 glycol (C-OH)₂                   -    -   1.886  .130     -        -      58 50 32 Methocel ^TM40-200 is polyhydric----polyhydric----1.133 .088--54 52 32 poly-{ vinyl alcohol } of .901 .076 1.193 .252 60 54 32 pentaerythrites are polyhydric----.479 .067 .982 .420 71 67 32 sorbs (sugar) alcohol is polyhydric-C-OH 182-1.239 .091--51 50 32 3 polyhydric----1.059 .139--52 51 32 SOMA of polyhydric----1.266 .125--60 52 32 synthesising biological polymeric gel of polypropylene glycol^TnSpecial-purpose----.714 .161-----Tween^TM20 dehydration sorb (sugar) C12 EO--.601 .100 1.146 .498 59 68 32 alcohol esters-(EO)₂₀Neopelex sulphonic acid ester Cl2-Ph SO3 (-)--.396 .029 .616 .182 100 82 85 Dowfax^TM2A1 sulphonic acid ester iso-C12-Ph (bis) [SO3 (-)] 2 576-.614 .112 .793 .109 71 68 0 heptanesulfonic acid salt sulphonic acid ester C6 C6-COOH--1.214 .436--52 50 32 Nacconol^TMThe 90F sulphonic acid ester----.387 .021 .462 .065 100 95 9

The note of table 8

Ben Biao and below table in " StD " refer to " standard deviation of average ", " wBF " refers to " nothing

The damaged minute progression of moisture film ". Multinomial " nothing " and EXthox^TMM1-14 represents the tank with different amounts

Measure. " OAE-" product has following chemical general formula: RO-(C₃H ₆O) _m-(C ₂H ₄O) _n-CH ₂-C(O)O-CH ₃，

Wherein straight chained alkyl radicals R length is 8-18 carbon atom, and " m " is 0 or 1, " n "

Be 5 to average 8.5. Table 9 is as rilanit special derivative and the comparison of the ethoxylation of the mobility reinforcing agent of last rinsing

/ 8 liters of COF COF-2 IFH PFH of ProductName gram

Mean value StD mean value StD

Nothing 0 1.231 .149----Trylox^TM5922 1.6    .479      .072   .503   .085  69    65 Trylox ^TM5922 0.4    .974      .161   1.055  .151  60    56 Trylox ^TM5922 0 8    1.007     .117   1.131  .132  70    60 Trylox ^TM5921 1.6    .511      .108   .548   .093  74    68 Trylox ^TM5921 0.4    1.072     .144   1.034  .201  63    59 Trylox ^TM5921 0.8    .883      .154   .958   .152  62    54 Trylox ^TM5925 3.2    .914      .140   1.139  .157  67    62 Trylox ^TM5925 6.4    1.020     .149   1.231  .122  74    67 Trylox ^TM5925 9.6    .965      .180   1.007  .122  73    63 Ethox ^TMMI-14 1.6 .621 .118 1.059 .144 75 70 7.5 oxirane are on the impact of the binary mixture of isostearoyl base FRME ' s and other surfactant. Press reaching step 4 variation shown in the table 10 to the CCW batching and operating CCW of describing in 7.3. Result in the table 10 points out only only to obtain at most very little froth breaking effect with these defoamers. Yet the composition that the preliminary ethoxylation isostearic acid lubricant of small amount ethoxylation and surface conditioner form causes less foam and is fit to the COF value of most of purposes fully. " defoamer " Pluronic^TM31R1 and Trycol^TM6720 and Ethox^TMThe mixture of MI-9 is than the only Ethox of uniform amt^TMMI-9 produces more more foams, but also further reduces the COF value, and the interaction between them obviously is complicated and is difficult to prediction. Table 10 degree of ethoxylation in initial lubricant and surface conditioner (ethoxylation isostearic acid) change and on probation the cosurfactant variation that adds of defoamer affect COF ethoxylation defoamer IFH PFH

Isostearic acid average StD restrains/8 liters of EO#/gram/8 liter titles

Molecule 1 .139 .170 0-0---1.159 .181 0-0---1.069 .165 0-0---1.190 .158 0-0---1.154 .198 0-0---1.142 .174 (with the average result of top five groups of tanks) .587 .170 0-1.60 Pluronic^TM31R1  77    50 .817    .155    0      -    1.60  Triton ^TMDF-16   79    55 .659    .175    0      -    1.60  Trycol ^THLF-1    50    50 .499    .099    1.60   9    0     -                55    55 .478    .072    1.20   9    .40   Pluronic ^TM31R1  61    58 .479    .093    1.20   9    .40   Triton ^TMDF-16   63    62 .423    .027    1.20   9    .40   Trycol ^TMLF-1    69    67 .408    .038    .80    9    .80   Pluronic ^TM31R1  65    63 .576    .172    .80    9    .80   Triton ^TMDF-16   72    69 .467    .103    .80    9    .80   Trycol ^TMLF-1    65    63 .496    .122    .40    9    1.20  Pluronic ^TM31R1  67    64 .628    .176    .40    9    1.20  Triton ^TM DF-16  78    76 .656    .194    .40    9    1.20  Trycol ^TMLF-1    73    66 .457    .074    1.60   10.5  0    -                60    60 .465    .121    1.20   10.5  .40  Pluronic ^TM31R1  60    59 .531    .108    1.20   10.5  .40  Triton ^TMDF-16   67    66 .566    .186    1.20   10.5  .40  Trycol ^TMLF-1    65    65 .583    .114    .80    10.5  .80  Pluronic ^TM31R1  58    57 .564    .142    .80    10.5  .80  Triton ^TMDF-16   72    72 .550    .114    .80    10.5  .80  Trycol ^TMLF-1    69    65 .539    .111    .40    10.5  1.20 Pluronic ^TM31R1  55    53 .685    .205    .40    10.5  1.20 Triton ^TMDF-16   75    70 .644    .133    .40    10.5  1.20 Trycol ^TMLF-1    77    62 .444    .104    1.60   14    0    -                76    75 .477    .098    1.60   14    0    -                77    75 .534    .093    1.20   14    .40  Pluronic ^TM31R1  74    71 .456    .121    1.20   14    .40  Triton ^TMDF-16   80    75 .516    .148    1.20   14    .40  Trycol ^TMLF-1    81    80 .505    .106    .80    14    .80  pluronic ^TM31R1  82    79 .532    .128    .80    14    .80  Triton ^TMDF-16   85    84 .456    .078    .80    14    .80  Trycol ^TMLF-1    86    83 .681    .178    .40    14    1.20 Pluronic ^TM31R1  82    79 .615    .149    .40    14    1.20 Triton ^TMDF-16   81    78 .538    .106    .40    14    1.20 Trycol ^TMThe mobility reinforcing agent of LF-1 80 76 7.6 last rinsings and the auxiliary agent of discharge water are by following operation BW

Step 1 sulfuric acid, pH2.0,54.4 ℃

Step 2 RIDOLINE 124C, the 15ml free acid, 3.4 grams per liter total surfaces are lived

The property agent, fluoride activity-10mV, 60 ℃

Step 3 running water

Step 4 need not

Step 5 deionized water

Step 6 described in table 11,0.2 grams per liter gross activity additive

Table 11
							Variation for last rinsing discharge water and line speed and additive
The additive of lubricant and/or promotion discharge water	The line speed of setting	Hydropexis mean value	StD	COF		COF-2 (mean value)
							Mean value	StD
				Nothing nothing nothing nothing nothing is without EthoxTMMI-14 Neodol TM91-2.5 Pluronic TML-81 Pluronic TML-61 Neodol TM91-6 Ethox TMMI-14/ pluronic TML-81(1∶1) Ethox TMMI-14/ pluronic TML-61(1∶1) Etha1 TMOA-23 Ethox TMMI-14 Ethox TMMI-14 Ethox TMMI-10.5 Neodol TM91-8 Ethox TMMI-14/ Trylox TM5922(1∶1) Trylox TM5925 Trylox TM5922 Trylox TM5921 Ethox TMMI-14	100     100     70     70     70     40     40     70     70     70     70     70     70     70     70     70     70     70     70     70     70     70     100				31.72     30.44     28.40     28.29     27.02     23.34     19.11     15.65     17.44     17.71     20.83     21.02     21.63     21.64     21.68     21.69     21.93     22.55     24.07     24.62     25.21     25.88     26.60	-  -  - .81 1.00  -  - .37 .14 .09 .27 .53 .32 .72 .18  - .38 .30 1.00 .92 .97 .25  -	-      -      -     1.446      -      -      -     1.356     1.124     1.206     1.201     .728     .725     .919       -       -     .550     1.009     .581     1.090     .581     .546      -	-   -   - .071   -   -   - .211   -   - .175   -   -   -   -   -   - .204   -   -   -   -   -	-     -     -     -     -     -     -     -     -     -     .970     -     .832     1.141     -     -     .727     -     .707      -     .680     .645      -

The linear velocity of cleaning machine is controlled by variable rheostat, output percentage with have following approximation relation with the speed of m/min expression: set: 100% speed: 1.890 m/mins (6.2 feet per minute clock) 70 1.036 m/mins (3.4 feet per minute clock) 40 0.549 m/mins (1.8 feet per minute clock)

Process and collect three groups of tanks of every group of 14 tanks with pliers in the cleaning machine end. These tanks are deposited on the slim aluminium drip pan and with the pliers weighing, are careful in the operating process and reduce as far as possible the loss of water. Then with tank, pliers and dish dry 10 minutes and again weighings under 210 ℃. The mean value of triplicate test is as the estimated value of whole tank hydropexis amount. The 4th group of tank collected, in 210 ℃ of dryings 3 minutes and test to measure their COF value. COF value wherein is lower than 1.00 situation and measures the COF-2 value. The result is given in the table 11. Found for promoting discharge water than the good surfactant of ethoxylation isostearic acid (they are more effective for lubricant and surface modulation agent film are provided). Yet, poorer than ethoxylation isostearic acid on reduction COF value for promoting the particularly preferred surfactant of discharge water. This two classes material mixing can be improved drainage, keep reaching simultaneously performance 7.7 amine-oxides of the COF value that is suitable for many-sided purposes and/or the combination of quaternary ammonium salt and fluoride

Use aluminium pot to simulate on a small scale six industrial step procedures as matrix and with the laboratory in all processing and implementation examples of describing with this joint and comparative example. 14 tanks of each processing. The processing sequence of using is described in the table 12.

The composition of step 4 or by the dilution concentrate or directly by the preparation of each component.

In order to simulate situation about occurring in the industrial cleaning of evaporator operation, with the aluminium amount (component namely

Table 12
						Step	Time (second) spray quinoline	Pause	Blowdown	Temperature ℃	Composition
1  2  3  4  5  6	30     90     30     20     30     90	10  10  10  20  0  0	30     30     30     30     0     30	54.4     60.0     22±4     37.8     22±4     22±4	Make moisture H2SO 4PH=2 sees that the note running water below this table changes; See following running water rinsing DI water rinse for details
						The composition of the note step 2 of table 12 contains (ⅰ) commercial sulfuric acid and surfactant washing agent (RIDOLINE_124-C. available from P+A). its concentration makes total surfactant reach 3.4 grams per liters, (ⅱ) hydrofluoric acid, to make free acid value be 15 and fluorine ion activity readings if (needs) add sulfuric acid in addition is-10mV, uses the relevant electrode of describing in Orion instrument and the above-mentioned text. By using 0.10N NaOH solution, use phenolphthalein indicator, the 10ml composition sample that titration is dissolved in about 100 ml distilled waters is measured free acid value, dissolves excessive a lot of sodium fluoride (the Powdered drying test of about 2-3 milliliter cumulative volume) before the titration in sample. The free acid point equals to arrive the required titrant milliliter number of lightpink terminal point.

Table 13
				Change	Changing value
	High	In	Low
				H 2ZrF 6 1 pH H 3PO 4With H2ZrF 6Mol ratio AO2With H2ZrF 6Mol ratio	0.0099     4.50     2.0     1.0	0.0069     3.50     1.0     0.75	0.0040     2.50     0.0     0.5
Value shown in the note 1 of table 13 is molal quantity 2 " AO " expression " amine oxide " in 8 liters of compositions, refers to Aromox here_C/12。

(D) and (E) chemical equivalent of the aluminium of total amount) transfer to about 100ppm (include in the step 4 calculate step 3). In addition, as following specific descriptions, the concentration of pH value, fluoride activity and other component changes with particular experiment.

Will be according to the tank of the washing of above-mentioned six step method and rinsing under the normal condition under 150C dry 5 minutes, and in the time will testing heat-resisting mobility, drying 5 minutes again in the baking oven in the time of then tank being placed on 200 ℃. These conditions are called as respectively once and the secondary baking tank.

The mean value of 15 independent measurements is carried out and is in the measurement of all confficients of static friction (following often referred to as " COF ") according to the capable disclosed method of 44-65 of US 4944889.

With can opener top cover is removed from tank. After so finishing, these top covers are put into per 1000 milliliters of water-baths of going block of wood water to contain 0.2 gram tetraboron decahydride acid sodium, bath temperature is 66 ℃. After soaking 30 minutes, will cover with DI water rinse and dry in baking oven. Top cover rust stable performance contrasts as reverse side based on the tank that only cleans (being untreated), uses Alodine^_404 tanks of processing contrast as the front, estimate judgement. The top cover surfaces externally and internally is all judged.

Embodiment and comparative example group 7.7.1

In this group, said components (A) is Aromox^_C/12 provides according to supplier, and it is the amine oxide with chemical constitution that following formula represents:

          Cocoa-N(O)(CH ₂CH ₂OH) ₂Wherein " Cocoa " expression is by usefulness-CH₂-part replace in the fatty acid mixt that is obtained by the natural coconut oil hydrolysis each-the alkyl group mixture of COOH part gained.

Changing value in this group experiment is as shown in table 13, the particular combinations of these variations of test and as shown in table 14 to the coefficient of friction result of process tank test.

Table 14
							The experiment number	With the changing value in the experiment of this numerical value1				COF-8B 2	COF-DB 3
	H 2ZrF 6	pH	[H 3PO 4】/ [H 2ZrF 6】	[AO】/ [H 2zrF 6】
							1     2     3     4     5     6     7     8     9     10     11     12     13     14     15     16     17     18     19     20     21	0     -1     +1     -1     +1     0     +1     -1     +1     -1     0     -1     +1     -1     +1     0     -1     +1     +1     -1     0	0 +1 +1 -1 -1 0 -1 -1 -1 +1 0 -1 +1 -1 +1  0 +1 +1 -1 +1  0	0     +1     -1     -1     -1     0     +1     +1     +1     -1     0     +1     +1     -1     -1     0     +1     +1     -1     -1     0	0     +1     +1     +1     +1     0     -1     +1     +1     +1     0     -1     +1     -1     +1     0     -1     -1     -1     -1     0	0.739     1.421     0.728     1.065     0.565     0.582     1.366     1.410     0.605     0.781     1.046     1.547     1.459     1.312     0.609     0.606     1.410     1.470     0.550     1.400     0.828	0.874  -  0.712  1.189  0.638  0.578    -    -  0.581  0.885    -    -    -    -  0.588  0.647    -    -  0.593    -  0.880
Note 1 these values of table 14 are with (" 0 ") or low (" 1 ") expression in high ("+1 "), and its numerical value meaning provides in table 13. 2 " SB "=once toast 3 " DB "=secondary bakings

Embodiment and comparative example group 7.7.2

In this group, with the amine oxide in the quaternary ammonium salt replacement group 1, the specific salts of use is as shown in Table 15.

Table 15 quaternary ammonium salt
			Trade (brand) name	Chemical constitution
	Anion	Counter ion counterionsl gegenions
			ETHOQUAD _C-12 ETHOQUAD _C-12B ETHOQUAD _T-13/50	+ Cocoa-N-(CH3)(CH 2CH 2OH) 2     + Cocoa-N-(CH 2Φ)(CH 2CH 2OH) 2     + Tallow-N-(CH 2CH 2OH) 3	Cl -     Cl -     -OC(O)CH 3
The note of table 15 " CoCoa " refers to identical with the mixture of the alkyl group of having pointed out in text here, and that " Tal-low " refers to except coconut oil is replaced by the animal tallow in the definition that provides is identical with " Cocoa ", and " Φ " represents phenyl moiety.

In this group in steps 4 composition contain 9.6 the gram Al₂(SO ₄) ₃·151/2H ₂(it is equivalent to the A of 104ppm to O⁺³), 2.05 the gram H₂ZrF ₆With 0.0099 ± 0.0001 mole of quaternary ammonium salt; The composition that is expressed as "/PA " in following table all also contains 0.97 gram H in 8 liters of total compositions₃PO ₄ Composition pH value all is 2.5. By the results are shown in the following table 16 of described processing.

Table 16
					Qual ETHOQUAD in the composition_C-12  ETHOQUAD _ C-12/PA  ETHOQUAD _C-12B  ETHOQUAD _C-12B/PA  ETHOQUAD _T-13/50  ETHOQUAD _T-13/50/pA	Free F-1 -89.0 -90.0 -93.1 -89.9 -84.0 -90.3	COF-BB     1.12     0.69     0.98     0.90     0.85     0.49	COF-DB     1.28     0.87     1.21     0.94     0.98     0.53	DB     3     3     3     3     3     2

The note gauge outfit of table 16 is " free F^-1" row provide composition reading with millivoltmeter; use Orion fluoride sensitive electrode and with above-mentioned 120E Activity Standard Solulion calibrating instrument; gauge outfit is that the row of " DS " are pressed following grade, provides top cover rust resistance estimated value: 1=ratio ALODINE^_404 good (corrosion is few); 2=and use ALODINE^_The time corrosion that equates; Erosion 3=and the corrosion when additive-free in the 4th step are as many (than using ALODINE^_404 is poor). " COF-SB "=through the coefficient of friction of baking once, " COF-DB "=through the coefficient of friction of twice baking

Embodiment and comparative example group 7.7.3

In this group, ETHOQUAD only^_T-13/50 is as component (A), and the while is H only₂ZrF ₆As component (B). Except ETHOQUAD^_Outside the T-13/50, other variation of research is H₂ZrF ₆Concentration, pH and the nitrate in solution and sulfate anion. In order to adjust pH and free F^-, having found to use sodium aluminate is favourable as the part aluminum feedstock. In all compositions of this group, will be that the sodium aluminate of 50ppm and molal quantity equal used H by Al concentration₂ZrF ₆Phosphoric acid use together, the fluoride activity is transferred to reading-90mV at above-mentioned fluoride sensitive electrode. The aluminium of 50ppm is with (ⅰ) aluminum sulfate (using the sulfuric acid adjust pH to this) in addition, (ⅱ) aluminum nitrate (this is used the nitric acid adjust pH); Or (ⅲ) aluminum nitrate and simultaneously (to this use mol ratio two kind sour adjust pHs suitable with its aluminium salt) adding of aluminum sulfate. Acquired results describes in detail below. Four variablees of test and three values of each variable are shown in Table 17. Combination and the result of three variate-values are shown in table 18

Table 18
								Experiment numbers 123456789 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29	X1     1     1     1     0     -1     0     0     -1     0     -1     1     1     0     -1     1     0     1     0     1     0     -1     0     -1     1     0     -1     -1     -1     0	X2     -1     1     1     0     -1     0     0     1     0     1     1     1     0     1     -1     -1     -1     1     -1     0     0     0     1     0     0     -1     -1     -1     0	X3     -1     1     -1     0     1     0     0     1     1     -1     1     -1     0     1     1     0     1     0     -1     0     0     0     -1     0     0     -1     1     -1     0	X4     -1     1     -1     0     -1     0     -1     -1     0     -1     -1     1     1     1     -1     0     1     0     1     0     0     0     1     0     0     1     1     -1     0	COF-8B     0.513     0.544     1.274     0.499     0.508     0.572     1.229     1.421     0.516     1.451     1.311     0.976     0.501     0.762     0.552     0.537     0.559     1.15B     0.522     0.599     0.484     0.619     0.738     0.732     0.581     0.520     0.511     0.503     0.610	COF-DB     0.531     0.700     1.406     0.629     0.517     0.731     1.257     1.397     0.700     1.458     1.412     1.149     0.549     1.049     0.553     0.553     0.592     1.346     0.561     0.813     0.518     0.732     0.998     0.913     0.875     0.546     0.518     0.532     0.673	DB     2     3     3     3     2     2     3     3     2     3     3     3     2     3     1     2     1     3     1     3     2     3     3     3     3     2     2     2     2

The note of table 18 is at gauge outfit " X₁”、“X ₂”、“X ₃" and " X₄" row in, the high value of regulation variable in "+1 " expression table 17; The median of regulation variable in " 0 " expression 17; The low value of regulation variable in " 1 " expression table 17. All the other tabulation heads are identical with table 16 with connotation

Embodiment and comparative example group 7.7.4

In this group, under all situations, all use aluminum sulfate and sulfuric acid without aluminum nitrate and the nitric acid, the general condition of use is identical with group 7.7.3 with material, but some value of variable is different. Various combinations and the result who obtains are shown in table 19.

Table 19
									The experiment number	pH	Concentration (mole/8 liters)			Mol ratio	COF-SB	COF-DB	DS
H 2ZrF 4	H 3PO 4	T13 2
			1     2     3     4     5     6     7     8     9     10     11     12     13     14     15     16     17     18     19     20     21     22     23     24	Only clean 2.00 2.20 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.50 2.80	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	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     1.13     4.50     9.00     3.38     13.50     27     3.38     13.50     27     4.50	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∶0.25  1∶0.5∶1  1∶0.5∶2  1∶2∶0.25  1∶2∶1  1∶2∶2  1∶1∶0.5			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	-  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	3.0  3.0  2.0  2.0  3.0  3.0  2.0  2.0  2.0  2.0  1.5  2.5  3.0  3.0  2.5  2.0  2.0  2.0  1.5  1.5  2.0  2.0  1.5  2.0
25	AL0DINE_404								1.463	-				2.0
						The ratio that the note 1 of table 19 provides in order: H2ZrF 6∶H 3PO 4: T13. 2 " T13 " refers to each tabulation head " COF-SB " of EIHOQUAD_T-13/50., " CORDB ", and " DS ", and meaning every and in the table 16 is identical in these row

The concentrate of table 20 ethoxylated castor oil derivative and fluorine zirconic acid is on the impact of top cover rust resistance and coefficient of friction
				H 2ZrF 6Grams/liter	Tryol TM5921 grams/liter	COF	Pasteurize protection classification
0     0     0.14     0.29     0.58     1.16	0     0.2     0.2     0.2     0.2     0.2	1.16     0.57     0.52     0.61     0.63     0.70	Failed WP is passed through

The concentrate composition of this embodiment preferred group has following composition (water of following each composition surplus of unlisted formation) according to the present invention: the inorganic additional concentrate 45% fluorine zirconic acid aqueous solution 32.3 75% phosphate aqueous solutions 9.1 moisture nitric acid of the component grams of every kilogram of concentrate composition of component, 42 ° of Baumes (Baume), 25.5 organic replenishing and reinforcing agent concentrate ETHOQUAD^_ T-13/50           70.0 SURFYNOL ^_The 104 23.8 inorganic additional concentrate 45% fluorine zirconic acid aqueous solution 44.4 75% phosphate aqueous solutions 12.6 70% hydrofluoric acid aqueous solutions 4.6 moisture nitric acid, 42 ° of Baumes 38.7

Add above-mentioned SURFYNOL^_104, play the effect of froth breaking; It is the commercially available prod of Air Products and Chemicals company, and according to supplier's report, it is 2,4,7,9-tetramethyl-5-decine-4, the 7-glycol.

In the preferred method embodiment of the present invention, the effect composition is by adding above-mentioned each additional concentrate preparation of 1% in deionized water, (its pH value is 2.7 to 2.9 with the solution that obtains, with respect to the fluoride activity of Standard Solution 120E be-60 ℃ to-80mV) be used for step 4, by processing at 43 ℃ of lower sprayed tank 25sec available from the aluminium pot of D ﹠ I so that mobility strengthens. Special when the aluminium cation concentration in the treatment compositions is 100 to 300ppm, it is 0.5 to 0.6 that the tank that obtains has the COF-SB value, its top cover rust resistance and use ALODINE^_Equating of 404 acquisitions. For using treatment compositions, above-mentioned reinforcing agent composition is as keeping COF and top cover rust resistance to need to add.

If need the additional concentrate of packing, the below is the example (water that consists of surplus is no longer listed) of preferred concentrate: the component grams aqueous sulfuric acid of every kilogram of concentrate composition of component, the 66 ° of Baume 13.0 45% fluorine zirconic acid aqueous solution 41.4 75% phosphate aqueous solutions 11.6 70% hydrofluoric acid aqueous solutions 7.7 ETHOQUAD^RT-13/50          40.9

In using the preferred method embodiment of this concentrate, 50 milliliters of concentrates dilutions are formed 8 liters of effect compositions, (if needs) transfers to 2.4-2.6 and free fluorine compound activity with its pH value and transfers to-85 to-95mV. In to the several follow-up experiment of the concentrate of storing for 13 weeks, obtain to be lower than 0.6 COF value.

Embodiment and comparative example group 8

The combination of the ethoxylated castor oil derivative shown in the discovery table 8 and fluorine zirconic acid has unexpected attendant advantages, will further specify in this group.

Found with the FRME of suitable concn in conjunction with fluorine zirconic acid and rilanit special derivative, anti-top cover corrosion is provided in pasteurization processes and most of purposes are suitably reduced COF.

The cleaning of evaporator scheme of this group embodiment is:

Step 1 sulfuric acid, pH2.0,30sec, 54.4 ℃

Step 2 RIDOLINE^TM124C, 15ml free acid, 3.4 grams per liter surface-actives

Agent, fluoride activity-10mV, 90sec, 54.4 ℃

Step 3 deionized water, 150sec (about 17.7L)

Step 4 is as in the table 7 and as described in following, 20Sec, and spray+20sec pause,

29.4 ℃ temperature.

Step 5 need not

Step 6 need not

Except listed component in the table 7, by adding required ammoniacal liquor or nitric acid all pHs are transferred to 4.5.

By at first remove the method estimation top cover corrosion of top cover from the tank of processing with cap opener. Water-bath when top cover is put into 65.6 ℃ that contain 0.2 grams per liter borax 30 minutes, then rinsing and dry in baking oven in deionized water. Rust resistance is by comparing with known satisfaction and dissatisfied standard and surveying and estimate. The result is as shown in Table 20. Last two kinds of situations all are very desirable for the rust resistance in COF and the pasteurization processes shown in the table 20.

Table 21: with the result of tin-coated steel D﹠1 tank
			The additive of last rinsing is without EthoxTM  Pluronic TM/PlurafacTM  Tergitol TM	Average COF value 1.04 0.70 0.81 0.82	Hydropexis percentage 100% (restriction) 83.6 77.3 78.6

Embodiment and comparative example group 9

This group illustrates with tin can. Repay and try out lubricant and surface conditioner and the water discharge promoter that three class materials are configured for tin can: (ⅰ) Ethox^TMMI-14; (ⅱ) 1 weight portion Pluron-ic^TM31R1 and 4 weight portion Plurafac^TMThe mixture of D25; (ⅲ) Tergitol^TM Min- Foam ^TM1X. Wherein, Ethox^TM、Tergitol ^TMAnd Plurafac^TMProduct is ethoxylated fatty acid class or alcohols, some situation they poly-oxirane) end has poly-{ expoxy propane } block end-blocking, and pluronic^TMBe the block copolymer of ethene and expoxy propane, it has poly-{ expoxy propane } block end-blocking in the polymer end. After the conventional program washing, all substances are all used with deionized water with the concentration of 0.2 grams per liter in the last rinsing before dry at tin can. The water and the COF value that keep are measured with above-mentioned general fashion, the results are shown in the table 21.

Claims (14)

1. aqueous lubricant and surface conditioner fluid composition that is used for formed metal surfaces is characterized in that described composition is become to be grouped into following by water basically:

(A) the phosphorous surface active agent composition of dissolving, this component is the mixture that meets the molecule of general formula I:

Wherein M is the group that is selected from monovalence part and the ammonium of H, alkali metal cation, alkaline earth metal cation and replaces the monovalence part of ammonium cation; X=1 or 2 and y=3-x; Y is alkylidene or alkylene ether group, it can be with the key that stretches out on its carbon atom branching or nonbranched and have 2 to 12 carbon atoms and up to 3 oxygen atoms; R is the imidazoline part that meets the general formula II:

R wherein¹And R²Except not being the hydrogen simultaneously, all can be selected from hydrogen, by from propionitrile-CH₃The part of removing a hydrogen atom in the group and deriving and the group with part of general formula III:

Wherein, Q be selected from-OM ,-NH₂With-OR⁴, wherein M is identical with meaning defined above, R⁴Expression C_2-12Alkyl, alkaryl or alkyl cyclic aliphatic part; R³Be selected from the aliphatic series with 2 to 22 carbon atoms and cyclic aliphatic and alkaryl part that not replacement or hydroxyl replace,

Wherein the amount of component (A) reaches every liter of composition provides 0.00060 to 5 mole phosphorus;

(B) be selected from the component that contains the water soluble salt that comprises the ion that is selected from Zr, Ti, Sn, Al and Fe atom,

Wherein the amount of component (B) reaches every liter of composition provides 0.00010 to 5 mole total Zr, Ti, Sn, Al and Fe;

(C) metal etch component, wherein the amount of component (C) reaches every liter of degree that 0.21 to 11 mole fluorine atom is provided; With

(D) " free fluorine ion ", the amount of component (D) are 0.10 to 2.2 % by weight.

2. the composition of claim 1 also comprises component (E) and (F), and wherein component (E) is selected from the component that molecule meets following general formula IV:

R wherein⁶For having the saturated monovalence aliphatic hydrocarbon of straight chain, ring-type or the side chain part of 1 to 25 carbon atom; X is selected from hydrogen, halogen, phenyl and R⁵ S is 1 to 50 integer; R⁵Be selected from hydrogen and the alkyl group that contains 1 to 4 carbon atom;

Component (F) is selected from the component that molecule meets the general formula V:

R wherein⁷Be straight chain, ring-type or the side chain monovalence aliphatic hydrocarbon that contains 4 to 25 carbon atoms; (C₆H ₄) be adjacent, or to penylene ring, R⁵Identical with meaning in the general formula IV with s;

Wherein component (E) and component (F) weight ratio are 1.7: 1.00 to 1.00: 1.4, and component (E) and (F) weight ratio of total amount and component (A) be 3.3: 1.00 to 1.00: 2.0.

3. claim 1 or 2 composition also comprise the component (G) of surface-active effective dose, and component (G) is selected from the component that molecule meets the general formula VI:

R wherein⁸Be the straight or branched with 1 to 25 carbon atom, saturated or undersaturated monovalence aliphatic hydrocarbon part; R⁵Have and meaning identical in the general formula IV with s.

4. claim 1 or 2 composition also comprise the chelator component (H) of chelating effective dose, and component (H) is selected from the chelator component be used to the metal ion that contains component (B).

5. the composition of claim 3 also comprises the chelator component (H) of chelating effective dose, and component (H) is selected from the chelator component for the metal ion of component (B).

6. claim 1 or 2 composition also comprise the bactericidal agent of sterilization effective dose.

7. the composition of claim 3 also comprises the bactericidal agent of sterilization effective dose.

8. the composition of claim 4 also comprises the bactericidal agent of sterilization effective dose.

9. the composition of claim 5 also comprises the bactericidal agent of sterilization effective dose.

10. according to claim 1 composition, component (A) are selected from and meet the general formula I and " Y " group contains 2 to 4 carbon atoms but the molecule of anaerobic atomic time, R¹And R²Being selected from hydrogen and general formula III and Q=OM and M is hydrogen or alkali-metal part, and total at least R³50 % by mole in composition, have 8 to 20 carbon atoms.

11. composition according to claim 10, wherein the amount of component (A) reaches every liter of composition provides at least 0.0010 mole of phosphorus; The amount of component (B) reaches every liter of composition provides at least 0.0017 mole total Zr, Ti, Sn, Al and Fe; Fluorine atom concentration is lacked 0.0020 mole fluorine atom for whenever rising in the component that is selected from fluorine ion, difluoride salt and hydrofluoric acid of composition.

12. composition according to claim 11, wherein component (A) reaches every liter of composition provides 0.0010 to 0.40 mole phosphorus; Component (B) comprises fluorine zirconic acid, fluorine zirconate ion or fluorine zirconic acid and the fluorine zirconate ion of dissolving; The amount of component (B) reaches every liter of composition provides at least 0.0039 mole Zr.

13. composition according to claim 12, wherein component (A) is selected from and meets the general formula I and Y is ethylidene group and total R³At least 76 % by mole of group have 10 to 14 carbon atoms and for not replacing or molecule during nonbranched alkyl group; The amount of component (A) reaches every liter of composition provides at least 0.02 mole phosphorus; The amount of component (B) reaches every liter of composition provides at least 0.0040 mole Zr.

14. the composition of claim 13, wherein every liter of composition provides 0.057 to 0.103 mole Zr and 0.9 to 2.4 mole fluorine atom.

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