CN1203265A - 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 surface drying, reduce the static friction coefficient of treat surface, to be coated with thereon coating or the bounding force of lacquer have no adverse effect; (ii) promote water to discharge, do not cause " moisture film breakage ", promptly promote to be created in the discharge of the thin continuous film (rather than each water droplet (being called " moisture film breakage ") that is separated by dried relatively zone between the water droplet) of jar last water from the surface of having handled; (iii) these jars 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 jars representative largest application areas of the present invention.Yet, should know that by conspicuous 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 packaging vessel of variety of products.After it is made, wash therefrom to remove aluminium powder dirt and other dirt with acidic cleaner usually.Recently, consider that the resistates influence of staying after environment and acid are cleaned on the jar is packaged in the possibility of the smell of the beverage in the jar, causes people to remove the interest of these dust and dirt with alkaline cleaner.Yet, no matter be to handle aluminium pot with alkaline cleaner or acidic cleaner, generally all cause etch in various degree on jar outer and jar inner metal surface.For example, for the desired optimal conditions of jar internal surface that reaches no aluminium powder dirt causes the mobility problem of jar on handling equipment usually, reason has been to increase the roughness of jar outside surface.

The aluminium pot that outside surface does not have low static friction coefficient (following often abbreviate as " COF ") generally can not move and the conveying belt that passes through jar equipment reposefully one by one.The obstruction of removing because of evenly causing by failure raises for manual operation equipment inconvenience and owing to lost units makes cost.When jar during by the canned decorations apparatus processing of vast majority of conventional, the COF of internal surface also is important.The operating requirement jar of these machines slides on the axle of rotation, with this jar is carried cylinder by rotation then, these cylinders with the decorative ink seal to the outside surface of jar.Being difficult for the sliding jar of going up or skid off axle can not suitably be decorated and be caused the production fault to be referred to as " printing press tripping operation ".Except the mistake that directly causes this printing press tripping operation is carried the jar, before or after mistake is carried a jar, because the mechanical fault of printing press and delivery system is generally lost three to four jars.Along with streamline speed in recent years increases to the level of about 1200 to 1500 jars of quotidian per minute, stop up and printing press trips and more and more becomes two hang-ups of being paid close attention to.Therefore, in jar, especially aluminium pot production, need to improve COF on jar surfaces externally and internally more to improve its mobility.

In improving jar surface properties, a major issue that relates to is when jar by printing or when going up label workshop section, can to print jar performance counteract or disadvantageous effect.For example, after the cleaning jar, can print label on its outer surface, on internal surface, spray paint.To this, the bounding force of coating and lacquer is a most critical.Therefore the objective of the invention is to improve mobility and the bounding force of coating, decorative ink, lacquer or analogue is not had disadvantageous effect.

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

A kind of method that reduces oven temperature is to reduce a jar lip-deep surplus water behind water rinse.Therefore, it is favourable impelling rinse water to discharge from the surface of having handled.Yet, in the case, importantly prevent to form surface usually 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 of treat surface the uneven possibility for the critical nature of practicality.

Therefore; in order to increase output, reduce the production line obstruction, reduce stop time to greatest extent, to reduce the waste product jar, improve ink deposition or at least do not cause disadvantageous effect also can make washed jar oven temperature reduction, need provide a kind of mobility of improving aluminium pot by single-row production line and printing press to ink deposition.

In the most widely used industrial practice at present, 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 is operated.(before any step in table 1, also use sometimes with room temperature under the tap water contact procedure; When using, the step of this step for mark usually is called one " passage ".

Table 1
		Step	When step is carried out to the effect on surface
????1	Aqueous acids pre-washing
		????2	Aqueous acids and surfactant washing
????3	The tap water rinsing
		????4	Clean behind the weak acid, conversion coated, or the tap water rinsing
????5	The tap water rinsing
		????6	Deionization (" DI ") water rinse

Might produce the mobile jar of to be satisfied with at present, in step 4 or step 6, use suitable tensio-active agent to make printing ink and/or lacquer have enough bounding forces coating subsequently by above-mentioned.The preferably treatment 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 abbreviate as " P+A ") of Henkel company with trade(brand)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 pharmaceutical chemicals such as ME-40 in step 6 ^TMIn 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, 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 technology, 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 treatment processs that are used for above-mentioned steps 4, kept a little treatment processs and be disclosed in US5030323 and 5064500.In these materials some can be from P+A with trade(brand)name FIXODINE ^TM500 have bought.

Yet,,, often can be reduced to unacceptable level substantially for the reduction of the frictional coefficient that provides by the prior art treatment process in step 4 or the step 6 if the jar of handling additionally heats after finishing above-mentioned six step process.Even if whenever high-speed production lines parking several minutes, this jar of extra heating in baking oven always takes place, such situation is often run in actual production.In fact, the higher COF numerical value and the reduction of mobility interrelate, and the tensio-active agent that therefore adds the raising mobility in the batching of washing tank is still not enough.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 treat surface stable.

In addition, some beverage that is packaged in the aluminium pot will carry out pasteurize, unless the therefore composition of careful controlled temperature and the aqueous solution that contact with jar in pasteurization processes, otherwise the corrosion of frequent 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 frictional coefficient, and these compositions and method also can stop the top cover corrosion in the pasteurization processes.

Except in operation embodiment, or except other had explanation, this paper was used to represent the amount of component or all numerical value of reaction conditions, when describing wide region of the present invention, was interpreted as in all cases by the term " about " correction.Yet in the numerical range that provides, implement normally preferred.

In addition, unless opposite offering some clarification on arranged, describe below 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 counterions of the total composition of charge neutrality.Usually, these counterions should be chosen from the ionic state material as the present invention's part at first as far as possible; The counterion of required various remainders generally can freely be chosen, but should avoid selecting for use to the disadvantageous counterion of the object of the invention.

According to the present invention, be applied to the lubricant of aluminium pot and the mobility that surface conditioner has strengthened jar after having found to wash, and in preferred embodiments, moisture film discharge that has improved jar and evaporation characteristic be so that can make oven temperature reduce about 25 ℃ to about 38 ℃, and the label printing process is not caused any disadvantageous effect.This lubricant and surface conditioner have reduced the static friction coefficient on jar outside surface, can significantly increase the speed of production line, and have improved significantly that moisture film is discharged and vaporator rate makes because of reducing energy requirement and saves the cost while and also satisfied requirements for quality control.

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 aqueous 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, and the fluorochemical activity is for the influence of the characteristic of processing back jar.

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 membrane of aluminium pot outside surface coating, it finally provides improved mobility to jar, and has improved the speed of drying chamber and the post intensity pressure test by controlling quality.Find that also the improvement mobility of jar and the degree of drying rate depend on the thickness or the amount of organic membrane, and depend on the chemical property that is applied to the material on the jar.

According to the present invention, be used for aluminium pot lubricant and surface conditioner, for example can be selected from water soluble alkoxylated tensio-active agent 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, amides, 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 Unimac 5680 of the lubricant of aluminium pot and stearic acid that surface conditioner preferably includes saturated fatty acid such as ethoxylation or ethoxylation, or its an alkali metal salt such as ethylating stearate of polyoxy and the ethylating isostearate of polyoxy.In addition, be used for the lubricant of aluminium pot and surface conditioner and can comprise having at least about the water-soluble alcohol of 4 carbon atoms and can contain up to about 50 moles oxyethane.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 on the aluminium pot film forming organic substance of shape before the outside surface final drying after alkali or acid are cleaned and before conveying and comprise and be selected from phosphoric acid ester, alcohol, comprise one, two, three and the water soluble organic substance matter of the fatty acid of polyacid derivative of fatty acid (comprising salt, hydroxyl acids, amides, 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 film forming water soluble organic substance matter of shape on the aluminium pot, have static friction coefficient after the drying and be no more than 1.5 surface so that be provided at, this static friction coefficient is lower than the static friction coefficient that is not coated with this film and obtains on similar jar of 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 phosphoric acid ester, especially phosphoric acid and various alcohol contain free acid or neutral list and diester also be used for the present invention.Object lesson comprises Tryfac ^TM5573 phosphoric acid ester, 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 mineral acid comprises that per molecule contains 3 water-soluble cpdss to about 20 carbon atoms.Concrete example comprises that Sodium Lauryl Sulphate BP/USP is as the Duponol available from Witco company ^TMWAQ, Duponol ^TMQC, Duponol ^TMWA and Duponol ^TMC, and the alkyl sodium sulfonate of sale monopoly is as available from E.I.du Pont de Nemours﹠amp; Co. AlRanol ^TM189-S.

Suitable polyvalent alcohol comprises aliphatic series or the aralkyl polyvalent alcohol that contains two or more oh groups.Object lesson comprises glycerine, Sorbitol Powder, mannitol, synthesising biological polymeric gel, hexylene glycol, glyconic acid, glyconic acid salt, glucoheptonic acid salt, tetramethylolmethane 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 Viscotrol C triglyceride.

According to the present invention, we find to use alkoxylate, especially ethoxylated castor oil triglyceride to cause the further improvement of jar mobility as lubricant and surface conditioner, and particularly wherein a jar production line operation causes jar to be exposed to the improvement of the jar mobility of following long period of high temperature when being interrupted.Therefore, especially preferred material comprises Trylox ^TM5900, Trylox ^TM5902, Trylox ^TM5904, Trylox ^TM5906, Trylox ^TM5907, Trylox ^TM5909, Trylox ^TM5918 and hydrogenated castor oil derivative such as Trylox ^TM5921 and Try-lox ^TM5922, they all can be available from Henkel company.

Preferred lipid acid comprises butyric acid, valeric acid, caproic acid, sad, capric acid, n-nonanoic acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, oleic acid, stearic acid, linolic acid and ricinolic acid; Propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, toxilic acid, tartrate, glyconic acid and dimeracid; And any salt in these acid, the imino-diacetic propionate compound is as can be available from the Amphoteric 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, nitrilotriacetic acid(NTA) and 1,2, the 4-benzenetricarboxylic acid; Can be available from the Versenol of Dow Chemical ^TM120 HEEDTA, N-(hydroxyethyl) ethylenediamine triacetic acid ester.

Preferred acid amides generally comprises the 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 lauric acid/TETRADECONIC ACID alkanolamide, Alka-mide ^TMDS 280/S Stearic acid diethanolamine salt, Alkamide ^TMCD coconut diethanolamide, Alamide ^TMDIN 100 lauric acid/linolic acid diglycollic amide, Alkamide ^TMDIN295/S linolic acid diglycollic amide, Alkamide ^TMDL 203 lauric acid diethyl amides; Can be available from the Monamid of Mona industrial ^TM150-MW TETRADECONIC ACID glycollic amide, Mon-amid ^TM150-CW capric acid glycollic amide, Monamid ^TM150-IS Unimac 5680 glycollic amide and can be available from the Ethomid of AKZO chemical company ^TMHT/23 and Ethomid ^TMHT60 polyoxy ethylization hydrogenated tallow acid amides.

The preferred anionic surfactants organic derivative generally comprises the vitriol and the sulfonate derivatives of lipid acid, comprises the vitriol of natural and synthetic deutero-alcohols, acids and natural product and the derivative of sulfonate.Concrete example is: dodecylbenzene sulfonate is as can be available from the Dowfax of Dow Chemical ^TM2A1, Dowfax ^TM2AO, Dowfax ^TM3BO and Dowfax ^TM3B2; Can be available from the Lomar of Henkel company ^TMLS polycondensation naphthene sulfonic acid, sylvite; Sulfo-succinate derivative is as can be available from the Monamate of Mona industrial ^TMSulfo-Soduxin, 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-Soduxin; 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 (ricinolic 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 lipid 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 polymers.

Preferred lipid acid amine salt comprises fatty acid and all contains ammonium, quaternary ammonium, Phosphonium and an alkali metal salt up to the derivative of 50 moles of alkylidene group oxygen at positively charged ion or anionicsite or positively charged ion and anionicsite.Object lesson comprises can be available from the 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-disodium beclomethasone and Deriphat ^TM160 (N-lauryls-β imino-disodium beclomethasone).

The preferred amino acids class 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, sarkosine (sarcosine); The hydroxyethyl glycine; Can be available from W.R.Grace﹠amp; Co. Hamposyl ^TMTL-40 trolamine 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-hydroxyethyl) cocounut oil alkylamine, Aromox ^TMT/12 bis oxide-(2-hydroxyethyl) 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 hexadecyl alkylamine; With can be available from the Tomah of Exxon chemical company ^TMAO-14-2 and Tomah ^TMAO-728.

Preferred quaternary salt comprises the quaternary ammonium salt derivative that contains at least one substituent fatty amine, this substituting group contains the propylene oxide of 12 to 20 carbon atoms and 0 to 50 moles of ethylene oxide and/or 0 to 15 mole, and wherein counter ion are made up of halogen, sulfate radical, nitrate radical, 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 hexadecyl 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 acetate three (2-hydroxyethyl) 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 ^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, lauric acid, TETRADECONIC ACID, oleic acid, stearic acid or Unimac 5680 tetraethyl ammonium.

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

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

R wherein ¹Be 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 a straight chain; R ²And R ³Be the monovalence part respectively, be selected from (i) respectively 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 the aryl and the aralkyl moiety of preferred 6 to 8 carbon atoms; R ⁴Be to be selected from and R ²And R ³Identical group adds-O ^-The monovalence part; X ^-Be univalent anion or have the anionic monovalence part that valence state is higher than 1 valency, and if R ⁴And-O ^-, if a=0 then is R ⁴Be not-O ^-, a=1 then;

(B) compound fluorine anion component, the anionic plural components of wherein preferred fluotitanate, fluohafnate 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 radical; And it is nonessential;

(D) aluminate negatively charged ion comprises the fluoaluminate negatively charged ion; And it is nonessential;

(E) aluminium cations comprises clad aluminum fluorine positively charged ion, 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 in US 5116912,5068299,5063089,4944812,4517028,4457790,4433015 and 4376000;

(G) reduce foamy component (defoamer).

For component defined above (A), when the anti-top cover corrosion of needs, quaternary ammonium salt is better than amine oxide.R preferably ², R ³And R ⁴In the part at least two kinds, or more preferably all three kinds all be hydroxyalkyl group, preferred 2-hydroxyethyl groups.Planting all is 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, as Oleum Cocois, 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 fluorochemical (as if needing) in use easily also can be monitored from the fluorochemical sensitive electrode that Orion Instruments has bought by being disclosed among the US3431182." the fluorochemical activity " used as term measured with respect to the 120E ActivityStandard Solution (active standardized solution) available from P+A by being described in detail in the method among the P+A TechnicalProcess Bulletin No.88 herein.Orion fluoride ion electrode (Orion Fluoride Ion Electrode) and reference electrode that Orion Instrument is provided all immerse in the described standardized solution, 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 0 the identical temperature of standardized solution 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 abbreviate as " the mv ") survey meter from the instrument reads.Use this instrument, the lower higher fluorochemical activity of positive mV readings signify, the negative mV readings signify fluorochemical activity also higher, and the high active height of negative mV readings signify fluorochemical of absolute value than positive mV reading.

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 of whole this composition keep at least substantially.For the composition that comprises said components (A), (B) and this embodiment of the present invention (C), the free active mV reading of fluorochemical 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 negatively charged ion 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 phosphoric acid salt, because pH and the phosphate content of component (C) and the preferred value (will further consider below) of component (A) and ratio (B), need transfer to the pH value in the preferable range with some other acid except that phosphoric acid usually 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 obstruction realizes that other enough strong acid of the object of the invention 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 produce accumulation at this when generally under physical condition, being used to handle 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 part/1000,000 weight parts (following often abbreviate 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 steps 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 causes being lower than the required rust resistance of top cover usually, 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 the long-time course of processing, 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 dissolved aluminium in the composition use, 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 not phosphorous hydrochlorate as fruit component (C), then for this two component, ratio (B): (A) preferably fall into above-mentioned wherein in 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 mmole/liter (following often abbreviate 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 anionic stoichiometric calculation equivalent 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 blistered trend of composition 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 low more, and then the concentration of component (Cp) just should be high more, because for improving the top cover rust resistance, component (Cp) shows the synergy with component (A).When component (D) and/or concentration (E) were high relatively, in above-mentioned scope, higher component (B) concentration was preferred.

Under some operational 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 some material in other embodiment of the present invention, also do not contain some other material with various unfavorable character simultaneously.Particularly, for the following various possibility components of listing separately (increasing preferred property) with the order that provides, the composition based on amine oxide and/or quaternary ammonium salt that is used for above-mentioned steps 4 (or with behind itself or dilute with water) of the present invention preferably contains and is no more than 5,1.0,0.2,0.05,0.01,0.003,0.001 or any following material of 0.0005 weight % [except as must those materials or nonessential said components (A)-(G) of regulation]: (a) tensio-active agent is as (a.1) organophosphorus compounds, (a.2) alcohols, (a.3) fatty acid comprises one, two, three and polyacid and derivative (a.4) thereof as (a.4.1) salt, (a.4.2) hydroxyl acids, (a.4.3) amides, (a.4.4) ester class and (a.4.5) ethers; (b) oxyalkylated (but except describing) tensio-active agent as part (a) is middle; (c) oxyalkylated castor is sheltered oily triglyceride, (d) natural and synthetic deutero-alcohols.The vitriol of acids and/or natural product and sulfonate derivatives; (e) amino acids; (f) water-soluble homopolymer of oxyethane, propylene oxide, butylene oxide ring, vinylformic acid and derivative thereof, toxilic acid and derivative thereof and/or vinyl alcohol and/or heteropolymer; (g) contain the organic acid salt of at least two carboxyls and oh group altogether.

Preferred water-soluble fluidity polymkeric substance comprises the homopolymer and the heteropolymer of oxyethane, propylene oxide, butylene oxide ring, vinylformic acid and derivative thereof, toxilic 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 ^TM200, Carbowax ^TM600, Carbowax ^TM900, Carbowax ^TM1450, Carbowax ^TM3350, Carbowax ^TM8000 and Compound 20M ^TMCan be available from the Pluronic of BASFWyandotte company ^TML61, Pluronic ^TML81, Pluronic ^TM31R1, Pluronic ^TM25R2, Tetronic ^TM304, Tetronic ^TM701, Tetronic ^TM908, 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 toxilic acid/olefin copolymer, and Acusol ^TMThe sodium salt of 479N vinylformic acid/maleic acid; And the N-methylglucosamine adducts 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 materials 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 outside surface realizes further improving to produce one or more bonded films in one or more and the above-mentioned organic materials in these metals again.The film that produces has and is no more than 1.5 static friction coefficient and preferably is lower than static friction coefficient when not having this film, the mobility of improving thus in carrying at a high speed jar and do not hinder container japanning, other coating, printing or other similar decoration subsequently.

Add these inorganic materials, especially refer in detail to and add the method contain zirconia material and be disclosed among the US5030323 and the US5064500 on November 12nd, 1991 on July 9th, 1991, complete open (the clearly statement with this paper does not meet to a certain extent) of this 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 metallic substance.

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 have static friction coefficient and be no more than the tensio-active agent of 1.5 suitable thin baseization and the mixture of the organic materials of non-ethoxylatedization, in final drying with carry before and jar surperficial contact of cleaning in order on the jar surface, to produce after drying.Preferred surfactants comprises the sulfation or the sulfonated aliphatic alcohols of ethoxylation and non-ethoxylatedization, as lauryl alcohol and lauric alcohol.Each anionoid, nonionic, positively charged ion or amphoterics all are suitable.The alkylpolyglycosides class is as having the C of mean polymerisation degree between 1.2 and 2.0 ₈-C ₁₈The alkylpolyglycosides class also is suitable.Other is suitable for the blended various surfactants is nonyl and the octyl phenol that contains the ethoxylation of 1.5 to 100 moles of ethylene oxide, preferably with the nonylphenol of 6 to 50 moles of ethylene oxide condensations as can be available from the Igepal of Rh  ne-Poulenc ^TMCO-887; The alkyl polyethers is as Triton ^TMDF-16; Phosphoric acid ester is as the Triton available from Union Carbide Corporation ^TMProduct is 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 polyvinylization 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 as Neodol ^TM25-3S (shell chemical company); Sulfonated aryl derivatives is as Dyasulf ^TM9268-A, Dyasulf ^TMC-70, Lomar ^TMD (but all structure from Henkel company) and Dowfox ^TM2A1 (can available from Dow Chemical); And the multipolymer of oxyethane and propylene oxide, for example Pluronic ^TML-61, Pluronic ^TM81, Pluronic ^TM31R1, Tetronic ^TM701, 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 phosphoric acid ester or preferred ethoxylation.These phosphoric acid ester can trade(brand)name Rhodafac ^TMPE 510 is from Rh  ne-Poulenc company, Wayne, and NJ has bought.And with trade(brand)name Ethfac ^TM136 and Ethfac ^TM161 from Ethox chemical company, Greenville, SC trade(brand)name Ethfac ^TM136 and Ethfac ^TM161 from Ethox chemical company, Greenville, and SC has bought.Usually, these organophosphates can comprise the alkyl and the aryl phosphate ester of ethoxylation or non-ethoxylatedization.

The lubricant and the surface conditioner that are used for aluminium pot can be in its washing operation cycles, one of its processing 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 metallic cation) in its last water rinse periodic process, be applied on the jar.In addition, lubricant and surface conditioner can before promptly drying, or after the oven dry, be applied on the jar in the solution of water or another non-combustible volatile solvent by thin spraying coating method after it is at last with the water rinse operation.Found on the aluminium surface that lubricant and surface conditioner can be deposited on jar so that it has required characteristic.Lubricant and surface conditioner can by spraying coating and by chemistry or physical adsorption 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 duration of contact and the treating processes, 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 ") duration 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 jar, after jar cleaned, they generally were exposed to rinsing in the sour water.According to the present invention, available lubricant and the surface conditioner treatment tank that comprises anion surfactant such as phosphoric acid ester.The pH value of treatment compositions is important and should is tart usually that promptly the pH value is between about 1 to about 6.5, preferred about 2.% to about 5.If then need not lubricant of the present invention jar after the sour water rinsing and surface conditioner handle, then often jar is exposed to rinsing in the tap water, use rinsed with deionized water then.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 ethylating alcohols of above-mentioned polyoxy or the ethylating fatty acid of polyoxy, or the nonionogenic tenside of above-mentioned any other suitable substance, after this handled, jar can pass through oven drying in further first being processed.

Remaining in the lubricant on the treat 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 jar outside 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 abbreviate as " g/L ") to form lubricant and surface conditioner film on the jar surface of handling after the 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, be difficult for by adding heat collapse with this lubricant and surface conditioner surface treated frictional coefficient, these organic substances are: oxyalkylated or non-oxyalkylated Viscotrol C triglyceride and hydrogenated castor oil derivative oxyalkylatedly and non-oxyalkylatedly comprise one, two, three and the amine salt of the lipid acid of polyacid; Alkoxylate and non-oxyalkylated amino fatty acid; Alkoxylate and non-oxyalkylated aliphatics 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 843 135 the U.S. Patent application to the alkyl ester of 2-substituted alkoxy aliphatics 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-alkoxylate polymkeric substance.In addition, if before lubricant and the surface conditioner last surface drying before automatic transport, from the final aqueous composition that contacts with the surface, be not 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 jar by the required aluminium pot lubricant of the mobility of the guide rail of industry jar producing apparatus and printing workshop section and the amount of surface conditioner, and proof lubricant and surface conditioner have no adverse effect to the bounding force that is printed in the label on jar outside surface and is sprayed at the lacquer on jar internal surface.

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

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

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

After from binding power test solution, taking out the jar printed, each jar crossed hachure to expose the aluminum steel seen through coating or lacquer and jar is tested paint adhesion with sharp metal object.This test comprises Scotch ^TMScotch tape NO.610 is bonded on the cross hachure zone securely, by ripping action rapidly adhesive tape is drawn back facing to itself then, so adhesive tape is shut down from cross hachure zone.Test-results 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 jar or the vestige that comes off of lacquer detect by an unaided eye.

In addition, use laboratory stiction tester to measure the static friction coefficient of jar.The static friction coefficient that this device measuring is relevant with the aluminium pot surface property.Do this test by adopting through inclined-plane, coil and the hawser that is connected with free pendulum moved end, inclined-plane that 90 ° of arcs rise by constant velocity motors.With fixing the be separated by jar 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 inboardend on inclined-plane.The 3rd jar is placed on two jars, and the top cover of this jar is in the face of the free pendulum moved end on inclined-plane, and the limit of three jars is arranged in a straight line, and it is alignd mutually.

Along with the inclined-plane begins to move through arc, gauger is automatically opened when the inclined-plane arrives that wherein the 3rd jar is from 2 low jar of angles that are free to slide, and optoelectronic switch cuts out timing register.This time in second is commonly referred to " sliding time " just.When static friction coefficient equals jar 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 a sliding time.In some cases, with proof jar in 210 ℃ of following rebake 5 minutes and measure CO F again, this as a result following table be shown " COF-2 ".

The mean value of binding power test and static friction coefficient observed value are generally listed in the table 2.In brief, the aluminium pot that discovery was cleaned for coating, even lubricant and surface conditioner enriched material are when lower concentration very, also can provide improved mobility to jar, even use 20 to 100 times simultaneously to reducing jar concentration that the static friction coefficient requirement is used, label seal China ink or the interior lacquer of testing also had no adverse effect.

Embodiment group 2

These embodiment explanation when jar with 1260 jars/minute speed during by printing workshop section, the aluminium pot lubricant of embodiment 1 and the surface conditioner service condition in industry jar production unit.

With aluminium pot product acidic cleaner (Ridoline ^TM125 CO are available from P+A) washing, use Chrome-free convertible coating (Alodine then ^TM404, with the hurdle available from Parker+AmchemDivision, Henkel company, Madison Heights MI) handles.Then this aluminium pot product is carried out " slip " test, find the static friction coefficient about 1.63 that jar outside surface has.These jars by the printing workshop section course of processing in, jar can with 1150 to 1200 jars/minute speed do not have too much " tripping operation " by printing workshop section, the accident of promptly inappropriate load jar, in the case, jar loaded on inadequately the printing jar spool on.At every turn " tripping operation " all cause jar loss, these jars have to abandon, because they are not accepted by last procedure of processing.

Table 2

Bounding force is measured

Lubricant and table

The dense test static friction coefficient of face conditioning agent test number degree (%/volume) solution O SW ISW ID

Comparative group 1 (not handling)--------1.42 2 0.1 B, 10 10 10 0.94 3 0.25 A 10 10 10---4 0.5 B 9.5 ^*10 10 0.80 5 0.75 A, 10 10 10 0.63 6 1.0 B, 10 10 10 0.64 7 2.0 A, 10 10 10 0.56 8 5.0 B, 10 10 10 0.55 9 10.0 A 9.8 ^*10 10 0.56 ^*Be observed visually on outer side wall, mainly on behalf of outer side wall " ISW ", seldom come off " OSW " at contact lines place represent inner side-wall " ID " to represent internal head cover

About 1 milliliter/liter aluminium pot lubricant and surface conditioner are added in the deionization rinse water system of jar washing machine, it makes the static friction coefficient on jar outside surface reduce to 1.46, or reduce about 11% of its former static friction coefficient, after jar passed through printing press, the bounding force of rustproof lacquer was not influenced by lubricant and surface conditioner in finding.In addition, press speed can increase to 1250 to 1260 jars of its mechanical limit/minute and do not have new problem.

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

Embodiment and comparative example group 3

These embodiment illustrate and use the basal component of other material as 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, handle with three kinds of different lubricants that comprise various phosphoric acid ester solution and surface conditioner then.Phosphoric acid ester solution 1 comprises that concentration is that the phosphoric acid ester of 0.5 grams per liter is (with trade(brand)name Rhodafac ^TMPE 510 is available from Rhone-Poulenc, Wayne, NJ).Phosphoric acid ester solution 2 comprises that concentration is that the alkyl alcohol phosphoric acid ester of ethoxylation of 0.5 grams per liter is (with trade(brand)name Ethfac ^TM161, available from Ethox chemical company, Greenville, SC).Phosphoric acid ester solution 3 comprises that concentration is that the ethoxylated alkyl alcohol phosphoric acid ester of 1.5 grams per liters is (with trade(brand)name Eth-fac ^TM136 available from Ethox chemical company, Greenville, SC).

Measure the movability with the static friction coefficient measurement of jar, the results are shown in following table 3.

Table 3

Phosphoric acid ester pH value of solution static friction coefficient

1??????????3.6?????????0.47

2??????????3.3?????????0.63

3??????????2.6?????????0.77

Do not have---1.63

Above-mentioned phosphoric acid ester solution all can provide aluminium pot qualified mobility, but aluminium pot is covered fully by " moisture film breakage ".And what need is that aluminium pot does not have the moisture film breakage, promptly has thin continuous moisture film thereon, because otherwise they contain bigger water droplet, and moisture film is inhomogeneous and discontinuous simultaneously.Whether this moisture film breakage is printed with harm to jar in order to measure, and measures the bounding force of these jars.Here it is, this decorated jar cut and at the deionization that comprises 3: 1: the detergent solution (Joy of the liquid dishwashing of tap water ^TM) in boiled 10 minutes.Then with these jars rinsing and dry in deionized water.The same with embodiment group 1, on the coating of the interior outer side wall of jar and internal head cover, carve 8 cross hachures.This score line is pasted upward adhesive tape.Tear adhesive tape then off.These jars are carried out the bounding force classification.Its mean value is generally listed in the table 4, abbreviation wherein and the same meaning in the table 2.

The phosphoric acid ester solution bounding 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 phosphoric acid ester solution 1 on outer side wall, inner side-wall or the internal head cover of jar, observe on the jar outer side wall to exist hardly and come off, on the inner side-wall of jar, do not exist substantially to come off, and on the jar internal head cover complete failure.For phosphoric acid ester solution 2, observe on the outer side wall of jar to exist hardly and come off, on the inner side-wall of jar, do not exist to come off, on the jar internal head cover, do not exist to come off.For phosphoric acid ester solution 3, observe on jar outer side wall, inner side-wall or internal head cover, not exist and come off.

Embodiment group 4

Present embodiment illustrates the influence to the characteristic of the drainage water of the aluminium pot handled with its of lubricant of the present invention and surface conditioner.

Aluminium pot (is used Ridoline earlier with acidic cleaner ^TM125 CO then use Alodine ^TM404 handle, or only use Ridoline ^TM125 CO handle) 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 weight % and the rinsed with deionized water of surface conditioner.Jar draining after 30 seconds when making rinsing like this is determined at each jar and goes up the remaining water yield.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 jar more equably, simultaneously these jars not residual in a long time " moisture film breakage ".

Table 5

The gram number of the residuary water of each jar, use:

Drain the 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 to the influence of aluminium pot side wall strength.This test is the quality control applied voltage test of the piezometry jar post degree when measuring jar flat tin.The result who obtains generally lists in the table 6.

The value that the value that obtains when as can be seen from Table 6, the value that obtains in the post strength trial when oven temperature is 193 ℃ is 227 ℃ with oven temperature obtains when being 227 ℃ with oven temperature is compared increases by 1.38 * 10 ⁴Handkerchief (2psi).

Table 6

Oven temperature (℃) post intensity (handkerchief)

227?????????????5.94×10 ⁵

204?????????????6.05×10 ⁵

193?????????????6.08×10 ⁵

182?????????????6.15×10 ⁵

Higher post strength trial result preferably and usually needs, because final jar thin-walled must bear applied pressure in the jar after jar is full of the solution of carbonic anhydride.Otherwise the jar of sidewall matter difference 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 higher post intensity results thus.More specifically, for the jar of dry rinsing fully, make jar before entering baking oven, make its draining a little.Jar 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 the jar of thorough drying in the section between at this moment, general about 227 ℃ of oven temperature.Yet, in a series of tests (wherein rinse water contain the organic substance of the 0.3 weight % that has an appointment to form lubricant of the present invention and surface conditioner), find the drying chamber that when oven temperature is low to moderate 204 ℃, can be satisfied with, even when oven temperature is reduced to 188 ℃, still can obtain the exsiccant jar.

Embodiment group 6

To in embodiment type A, use Division from the unwashed aluminium pot of industry jar factory available from Parker+Amchem, Henkel company, Madison Heights, the alkaline cleaner of Michigan utilizes Ridoline ^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, with the lubricant and the surface conditioner processing that jar are used in the acitve organic matter matter (I) that comprises about 1 weight % in the deionized water of cleaning, 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 jar that cleaned is used the reactive lubricant and the surface conditioner processing of the inorganics (II) (listing in the table 7) of about 1% acitve organic matter (I) of being included in the deionized water and about 2 grams per liters (0.2 weight %).In another kind of embodiment, before drying after the initial rinsing and in the end, the jar that cleaned is used lubricant and the surface conditioner processing that is included in the acitve organic matter (I) of about 1% in the ionized water and the tensio-active agent (III) of about 0.5 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 jar 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% inorganics (II), about 0.5% tensio-active agent (III) (be listed in the table below 7 in) formation in the deionized water.For all situations in this group embodiment, the COF value of Chan Shenging is lower than 1.5 in its surface.

Embodiment and comparative example group 7

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

Test is most of jars in pilot scale belt washing machine, and this belt washing machine is single-rail seven step conveyor belt type washing machines (following usefulness " BW " expressions), and its top speed is 1.890 meters/minute (6.2 inch per minute clocks).In addition, use aforesaid CCW, this equipment is processed 14 jars in an order pilgrim-step under microcomputer control.Two types washing machine can be simulated order, pause and the emission performance that big examination scale washing machine is produced.

Measure free acidity and the fluorochemical activity that clean-out system is bathed by the method that is described in for Ridoline 124C among the P+A Technical Process Bulletin (NO.968).With dry in jar electric heating air oven that is described below that cleans and handled.The same with embodiment group 1, the mobility of test tank.

Table 7

The embodiment type	Acitve organic matter (I)		Inorganics (II)	Tensio-active agent (III)	??pH
						Trade(brand)name	Chemical name
	?A	?Emery?657						Sad	Al 2(SO 4) 3	IGEPAL?CO-887	?2.2
?B			?Emery?659	Capric acid	H 2ZrF 6	TRITON?X-101	?2.2
	?A	?Emery?651						Lauric acid	FeF 3	NEODOL?25-5-3	?2.3
?B			?Emery?655	TETRADECONIC ACID	SnCl 4	TERGITOL TMN-6	?2.3
	?A	?Emersol ?143						Palmitinic acid 91%	Ce(NO 3) 4	TRITON?DF-16	?2.6
?B			?Emersol ?153?NF	Stearic acid 92%	H 2TiF 6	TRYCOL?6720	?2.6
	?A	?Emersol ?871						Unimac 5680	H 2HfF 6	ANTAROX?LF- 330	?2.6
?B			?Emersol ?6313?NF	Oleic acid 75%	(NH 4) 2ZrF 6	TRITON?H-55	?2.6
	?A	?Empol ?1014						Dimeracid 95%	Fe 2(SO 4) 3	TRITON?H-66	?2.6
?B			?Emery ?1110	Nonane diacid	Al(NO 3) 3	TRITON?QS-44	?2.6
	?B	?Ethox?M15						The ethoxylation Unimac 5680	TiCl 4	TRYCOL?6720	?3.0
?A			?Emulphor ?VN?430	Polyoxy ethylization oleic acid	CeI 3	SURFONIC?LF- 17	?3.0
	?B	?Ethox ?MO5						Polyoxy ethylization oleic acid	FeF 3	LOMAR?D	?3.0
?A			?Monamide ?150?LW	The lauric acid alkanolamide	FeCl 3	DOWFAX?2A1	?2.0
	?B	?Monamide ?150?MW						The TETRADECONIC ACID alkanolamide	FeBr 3	DYASULF?9268- A	?3.0
?A			?Monamide ?150?IS	The Unimac 5680 alkanolamide	H 2ZrF 6	DYASULF?C-70	?4.0

* table continued on next page

The embodiment type	Acitve organic matter (I)		Inorganics (II)	Tensio-active agent (III)	?pH
						Trade(brand)name	Chemical name
	?B	?Monamide ?718						The stearic acid alkanolamide	H 2TiF 6	?IGEPAL?CO-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	?PLURONIC?L-61	?3.0
?A			?Rhodafac ?BL?750	Aromatic phosphate acid ester, sour form	TaF 5	?TETRONIC?701	?6.0
	?B	?Rhodafac ?PE510						Aromatic phosphate acid ester, sour form	NbF 5	?PLURONIC?31R1	?5.0
?A			?Ethfac ?142W	Aromatic phosphate acid ester	H 2ZrF 6	?PLURONIC ?150R1	?4.0
	?B	?Rhodafac ?RA?600						Aromatic phosphate acid ester acid form	(NH 4) 2MoO 4	?APG?300	?6.0
?A			?Armeen?Z	N-cocounut oil-B-aminobutyric acid	H 2TiF 6	?TRITON?CF-21	?6.0
	?B	?Hamposyl ?L						Lauroyl sarcosine	VF 4	?TRITON?DF-18	?5.0
?A			?Hamposyl ?C	The cocoyl sarkosine	FeF 3	?TRITON?GR-7M	?4.0
	?B	?Hamposyl ?O						Oleoylsarcosine	SnCl 4	?TRITON?H-55	?3.0
?A			?Hamposyl ?S	Stearyl sarcosine	Al 2(SO 4) 3	?TRITON?X-100	?2.0
	?B	?Acusol ?410N						Polyacrylic acid sodium salt	H 2ZrF 6	?TRITON?X-120	?4.0

* table continued on next page

The embodiment type	Acitve organic matter (I)		Inorganics (II)	Tensio-active agent (III)	??pH
						Trade(brand)name	Chemical name
	?B	?Triton?GR- ?5M						Dioctyl sulfo-sarkosine	Al(NO 3) 3	TRYCOL?5882	?6.0
?A			?Avanel?S ?70	The alkyl oxide sodium sulfonate	VOSO 4	TRYCOL?5887	?5.0
	?B	?Igepon ?TC-42						N-coconut and N-N-methyltaurine (taurate) sodium	VF 3	TRYCOL?5964	?4.0
?A			?Igepon ?TK-32	N-methyl-N-tall oil acid taurine (taurate) sodium	VF 3	IGEPAL?CO-887	?3.0
	?B	?Neodol?25- ?3A						The sulfonation linear alcohol, ammonium salt	(NH 4) 2WO 4	IGEPAL?CO-630	?3.0
?A			?Aromox ?C/12	Bis oxide (2-hydroxyl-ethyl) α-ample former times cocaine	(NH 4) 2ZrF 6	NEODOL?25-3	?3.0
	?B	?Aromox ?DMC						Cacodyl oxide base cocamine	FeF 3	NEODOL?25-35	?3.0
?A			?Ethoquad ?0/25	Chlorinated oil acyl group (POE (15)) ammonium	Fe 2(SO 4) 3	NEODOL?25-9	?2.0
	?B	?Ethoquad ?C/12						Chlorination cocounut oil methyl (POE (2)) ammonium	Al 2(SO 4) 3	NEODOL?91-25	?3.0
?A			?Ethoquad ?18/5	Chlorination octadecyl (POE (15)) ammonium	Sn(SO 4)	TRITON?QS-15	?3.0

* table continued on next page

The embodiment type	Acitve organic matter (I)		Inorganics (II)	Tensio-active agent (III)	???pH
						Trade(brand)name	Chemical name
	?B	?Propoquad ?T/12						Methylsulfuric acid tallow alkyl-methyl-two-(2-hydroxy-2-methyl ethyl) ammonium	?Ce 2(SO 4) 3	?TRITON?DF-12	??2.0
?A			?Ethfac?136	Phosphoric acid ester	?H 2ZrF 6	?IGEPAL?C0-887	??2.3
	?B	?Ethox ?2684						Phosphoric acid ester	?H 2ZrF 6	?IGEPAL?CO-887	??2.7
?A			?Trylox ?5922	The hydrogenated castor oil of ethoxylation	?H 2ZrF 6	?IGEPAL?CO-887	??2.3
	?B	?Trylox ?5921						?????″	?H 2TiF 6	?IGEPAL?CO-887	??2.7
?A			?Trylox ?5925	?????″	?H 2ZrF 6	?TRITON?H-66	??2.7

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

The damaged characteristic of handling jar with candidate's final rinsing mobility toughener (" FRME ' S) of moisture film, by each four main surfaces of range estimation classification jar: the method for the moisture film breakage of internal head cover and inner side-wall and outer top cover and outer side wall is estimated.In this hierarchy system, numerical value 2 expressions do not have the surface of moisture film breakage fully, the surface of the complete moisture film breakage of 0 expression, and intermediate value represents to be in moisture film breakage therebetween.Estimate four jars in this way and amount to the result to provide the number between 32 to 0, no moisture film breakage (WBF) divides progression.

7.2 clean-out system is bathed the influence of fluorochemical activity to COF and reflectivity.Use following CCW and last baking oven.

Step 1 tap water, 54.4 ℃, 30sec

Step 2 RIDOLINR ^TM124C, the 15ml free acid, total tensio-active agent is

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

60℃，60sec

Step 3 tap 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 following 5 minutes

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

Removing the effect of crude removal measures by using " brightness tester ".This equipment is made up of a power supply of stablizing high-intensity lamp and transmission light to jar fibre bundle on surface.Illumination from the jar reflection is mapped on the phototube, and its outward current is by International Microtronics company, and the Model350 amplifier amplifies and is converted into numeral to be read.Shown in digital recording be surface brightness.It is 440 that this instrument is calibrated to measurement of reflectivity with the plane mirror of backing silver.Once calibration, can measure the reflectivity and the calculating mean value of 14 jars.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 active increase of fluorochemical dull increasing.On the contrary, the COF value is equivalent to pact+10mv place in the fluorochemical activity and peak value and slowly increase or reduction herein certainly occur.In these experiments, COF is with the variation of fluorochemical 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 fluorochemical 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 decontamination 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 period of time between jar and the cleaning; from the jar that forms remove the oily resistates than breadboard experiment easily, in breadboard experiment, form one group of jar 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 fluorochemical 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 brightness high when jar, in these scopes is preferred than the high fluoride activity.7.3 screen various FRAM active substances.According to following scheme operation CCW, the rinsing time simulation that wherein prolongs step C3 is wherein used as the conventional steps 3,4 of rinse application and 5 production sequence:

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% Virahol 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 that preferred lubricant and surface conditioner form thing 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 more detailed below 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 chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 IFH PFH WBF comparison average StD average StD without-----1.168 .108 1.126 .071--32 without-----1.098 .129-----without-----1.141 .151----32 without-----1.331 .263----32 without-----1.362 .194----32 without-----1.295 .197----32Surfynol^TM420 acetylene series-EO TMDD (EO) 1.3-4 1.363 .201--59 50 32Surfynol ^TM440 acetylene series-EO TMDD (EO) 3.5-8 1.404 .276--56 51 32Surfynol ^TM465 acetylene series-EO TMDD (EO) 10-13 1.623 .549--70 53 31.8 dimethyl formamide acid amides--73.1-1.371 .181--56 50 32Monamine ^TMThe AD-100 acid amides----.457 .020 .645 .127 74 73 32M-Pyrol ^TMAcid amides----1.184 .172--53 51 32Macamine ^TMC-10 acid amides----1.645 .476--64 50 32 trolamine acid amides----1.134 .120--53 51 32Armox ^TMT/12 amine oxide C12 tallow N=O/2-hydroxyethyl 366-.548 .129 .672 .107--32Aromox ^TMC/12 amine oxide C12 coconut N=O/2-hydroxyethyl--.527 .090 1.005 .190 77 71 32Aromox ^TMDM-16 amine oxide C16---1.519 .202--54 54 32Macamine ^TMCAO amine oxide cocamine N=O--1.532 .468--70 64 32

Propyl group

                            (cocamidopropyl) Macamine ^TMCO amine oxide coconut oleoyl amine N=O--1.329 .222--51 50 32 Macamine^TMSO amine oxide stearmide N=O--1.180 .116--76 73 32 Triton^TM10---16 .802 .179 1.136 .132 69 61 32 Triton of RW-100 amine-(EO)^TM5---13 1.099 .096--69 66 32 Triton of RW-50 amine-(EO)^TM7.5---15 1.001 .130 1.496 .430 71 62 32 TEA Oleate amine-fat----1.214 .438 1.430 .315 52 50 32 Armeen of RW-75 amine-(EO)^TMThe C12 RCOOH/NH of Z both sexes--.660 .182 1.463 .299 71 64 32 APG^TM300 glycosides----1.146 .201--75,66 32 APG^TM325 glycosides----1.015 .251,1.211 .183 72 70 32 Hostacor^TMBF borate----1.211 .157--53 51 32 material standed fors or chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 IFH PFH WBF comparison average StD average StD Hostacor^TMBS borate---1.339 .231--58 54 32 OAE-1 C-18 EO/PO C-18/PO (1) (EO) 5--.315 .040 .343 .032--32 OAE-2 C16-18 EO C16-18 (EO) 5--.305 .030 .386 .066--28 OAE-3 C8-10 EO C8-10 (EO) 5--.602 .149 .687 .118--32 OAE-4 C8-18 EO C8-18 (EO) 5--.282 .017 .483 .071--16 Acrysol^TMLMW-45 carboxylic acid n/a RCOO (-) 4500-1.102 .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 Mirawet^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^TM 701       EO/PO          (PO)2.04           (EO)13.7     3600  1-7    .972  .244  2.129 .363 64   51   32 Henkel ^TM SF-7063     EO/PO/Me-esterC13/CH ₂-C(＝O)OCH ₃(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-10 LA/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 Ethal^TMCSA-10 fatty alcohol C16-18 (EO) 12--.748 .164 .761 .166 high-32 material standed for or chemical classification hydrophobe hydrophile molecular weight HLB COF COF-2 IFH PFH WBF comparison average StD average StD Ethal^TMCSA-17 aliphatic alcohol C16-18 (EO) 17--.726 .177 .677 .167--32 Ethal^TMDA-6 aliphatic alcohol C10 (EO) 6-12.4 .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-C10-12 LA/PO EO-11 .913 .107 .885 .105--32 Sandoxylate^TMSX-424 aliphatic alcohol i-C10-12 LA/PO EO-15 .688 .160 .676 .137--32 Sandoxylate^TMSX-602 aliphatic alcohol i-C10-12 LA/PO EO-8 .966 .132 1.145 .175--32 Triton^TMXL-80N aliphatic alcohol C8-10 EO/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^TM Methoxy PEG      PEG           O-CH3          (EO)44.7                 2000  -      .766  .222 .886  .199  -    -    32 Carbowax ^TM Methoxy PEG      PEG           O-CH3          (EO)7.3                  350   -      .955  .126 1.047 .113  -    -    32 Carbowax ^TM Methoxy PEG      PEG           O-CH3          (EO)112.8                5000  -      .739  .158 .839  .118  -    -    32 Carbowax ^TM Methoxy PEG      PEG           O-CH3          (EO)16.3                 750   -      .927  .236 .915  .190  -    -    32 Carbowax ^TM PEG 20M          PEG           -              (EO)n                    17500 -      .663  .149 .934  .155  -    -    32 Carbowax ^TM PEG-1450         PEG           -              (EO)32.5                 1450  -      .778  .158 .854  .229  -    -    32 Carbowax ^TM PEG-200          PEG           -              (EO)4.15                 200   -      1.122 .140 1.050 .114  -    -    32 Carbowax ^TM PEG-3350         PEG           -              (EO)75.7                 3350  -      .747  .105 .921  .149  -    -    32 Carbowax ^TM PEG-8000         PEG           -              (EO)181.2                8000  -      .778  .188 .840  .162  -    -    32 Carbowax ^TM PEG-900          PEG           -              (EO)19.5                 900   -      .819  .199 .865  .212  -    -    32 Dequest ^TM2000 phosphonate esters-N[CH2-P=O (OH)₂] ₃     299   -      1.506 .203 -     -     52   50   32 Dequest ^TM2006 phosphonate esters-Na, N[CH₂-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 Dequest^TM2016 phosphonate esters-[(C-CH₃OH)][P＝O(Na) ₂] ₂  294   -    1.271  .209 -     -    51   51   32 Dequest ^TM2054 phosphonates-HMDA[CH₂-P＝O(Na) ₂] ₄ 721   -    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^TM2001 polyhydric----1.335 .134--51 50 32 polyhydric 2-Me of hexylene glycol of 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----1.266 polyhydric----1.059 .139--52 51 32 SOMAT of .125--60 52 32 synthesising biological polymerization glue of polypropylene glycol^TMSpecial-purpose----.714 .161-----Tween^TM20 dehydration sorb (sugar) C12 EO--.601 .100 1.146 .498 59 68 32

The 20 Sodium dodecylbenzene sulfonate sulphonate C12-Ph SO3 (-) of alcohol ester-(EO)--.396 .029 .616 .182 100 82 8.5Dowfax ^TM2A1 sulphonate iso-C12-Ph (bis) [SO3 (-)] 2 576-.614 .112 .793 .109 71 68 0 heptanesulfonic acid salt sulphonate C6 C6-COOH--1.214 .436--52 50 32Nacconol ^TMThe 90F sulphonate----.387 .021 .462 .065 100 95 9

The note of table 8

Ben Biao and below table in " StD " be meant " standard deviation of average ", " WBF " refers to " not have

The damaged progression that divides of moisture film ".Multinomial " nothing " and EXthox ^TMMI-14 represents the jar with different amounts

Measure." OAE-" product has following chemical general formula: RO-(C ₃H 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

Hydrogenated castor oil derivative as the ethoxylation of the mobility toughener of last rinsing

And comparison

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

Mean value StD mean value StD

Do not have 0 1.231 .149----Trylox ^TM5,922 1.6 .479 .072 .503 .085,69 65Trylox ^TM5,922 0.4 .974 .161,1.055 .151,60 56Trylox ^TM5,922 0.8 1.007 .117,1.131 .132,70 60Trylox ^TM5,921 1.6 .511 .108 .548 .093,74 68Trylox ^TM5,921 0.4 1.072 .144,1.034 .201,63 59Trylox ^TM5,921 0.8 .883 .154 .958 .152,62 54Trylox ^TM5,925 3.2 .914 .140,1.139 .157,67 62Trylox ^TM5,925 6.4 1.020 .149,1.231 .122,74 67Trylox ^TM5,925 9.6 .965 .180,1.007 .122,73 63Ethox ^TMMI-14 1.6 .621 .118 1.059 .144 75 707.5 oxyethane are to the influence of the binary mixture of isostearoyl base FRME ' s and other tensio-active agent.By describe in 7.3 and table 10 shown in step 4 change CCW batching and operation CCW.Result in the table 10 points out only only to obtain very little froth breaking effect at most with these defoamers.Yet the composition that the preliminary ethoxylation Unimac 5680 lubricant of a small amount of 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

Ethoxylation in initial lubricant and surface conditioner (ethoxylation Unimac 5680)

Degree changes and the influence of the cosurfactant variation of defoamer adding on probation

COF ethoxylation defoamer IFH PFH

Unimac 5680 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^TM3,1R1 77 50.817 .155 0-1.60 Triton ^TMDF-16 79 55.659 .175 0-1.60 Trycol ^TMLF-1 50 50.499 .099 1.60 9 0-55 55.478 .072 1.20 9 .40 Pluronic ^TM3,1R1 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 ^TM3,1R1 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 ^TM3,1R1 67 64.628 .176 .40 9 1.20 Triton ^TMDF-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 ^TM3,1R1 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 ^TM3,1R1 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 ^TM3,1R1 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 ^TM3,1R1 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 ^TM3,1R1 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 ^TM3,1R1 82 79.615 .149 .40 14 1.20 Triton ^TMDF-16 81 78.538 .106 .40 14 1.20 Trycol ^TMThe mobility toughener of LF-1 80 767.6 last rinsings and the auxiliary agent of drainage 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, fluorochemical activity-10mV, 60 ℃

Step 3 tap 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

For the variation lubricant of last rinsing drainage water and line speed and additive and/or promote the life average StD mean value StD (mean value) that the additive of drainage water hydropexis COF COF-2 is set

------------70 28.29 .81 1.446 .071-are without 70 27.02 1.00-for nothing--without 40 23.34----Ethox without 70 28.40 without 100 30.44 to produce linear velocity without 100 31.72^TMMI-14 40 19.11----Neodol ^TM91-2.5 70 15.65 .37,1.356 .211-Pluronic ^TML-81 70 17.44 .14 1.124--Pluronic ^TML-61 70 17.71 .09 1.206--Neodol ^TM91-6 70 20.83 .27 1.201 .175-Ethox ^TMMI-14/ 70 21.02 .53 .728-.970 Pluronic ^TML-81 (1: 1) Ethox ^TMMI-14/ 70 21.63 .32 .725-.832 Pluronic ^TML-61 (1: 1) Ethal ^TMOA-23 70 21.64 .72 .919-1.141Ethox ^TMMI-14 70 21.68 .18---Ethox ^TMMI-14 70 21.69----Ethox ^TMMI-10.5 70 21.93 .38 .550-.727Neodol ^TM91-8 70 22.55 .30 1.009 .204-Ethox ^TMMI-14/ 70 24.07 1.00 .581-.707 Trylox ^TM5922 (1: 1) Trylox ^TM5,925 70 24.62 .92 1.090--Trylox ^TM5,922 70 25.21 .97 .581-.680Trylox ^TM5,921 70 25.88 .26 .546-.645Ethox ^TMMI-14 100 26.60----

The linear velocity of cleaning machine is controlled by variable rheostat, and output percentage ratio has following approximation relation with speed with rice/minute expression: set: 100% speed: 1.890 meters/minute (6.2 feet per minutes

Clock)

70 1.036 meters/minute (3.4 feet per minutes

Clock)

40 0.549 meters/minute (1.8 feet per minutes

Clock)

Handle and collect three groups of jars of every group of 14 jars with pliers in the cleaning machine end.These jars are deposited on the slim aluminium drip pan and with the pliers weighing, are careful in the operating process and reduce the loss of water as far as possible.Then with jar, pliers and dish dry 10 minutes and weighings once more under 210 ℃.The mean value of triplicate test is as the estimated value of whole jar of hydropexis amount.The 4th group of jar 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 drainage water than the good tensio-active agent of ethoxylation Unimac 5680 (they are more effective for lubricant and surface modulation agent film are provided).Yet, poorer than ethoxylation Unimac 5680 on reduction COF value for promoting the good especially tensio-active agent of drainage water.This two classes material mixing can be improved drainage, keep reaching performance 7.7 ammonium oxide of the COF value that is suitable for many-sided purposes and/or the combination of quaternary ammonium salt and fluorochemical simultaneously

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

The composition of step 4 or by the dilution enriched material or directly by the preparation of each component.In order to simulate situation about occurring in the operation of industrial cleaning of evaporator, with aluminium amount (i.e. Shang Mian component

Table 12

Time (second) temperature step spray quinoline pause blowdown ℃ composition

1 30 10 30 54.4 make moisture H ₂SO ₄PH=2

2 90 10 30 60.0 see the note below this table

3 30 10 30 22 ± 4 tap water

4 20 20 30 37.8 change; See for details following

5 30 00 22 ± 4 tap water rinsings

6 90 0 30 22 ± 4 DI water rinses

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, (if need) adds sulfuric acid in addition to make free acid value is 15 and fluorion activity readings and be-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 titrating solution milliliter number of lightpink terminal point.

Table 13

Change changing value

High, normal, basic H ₂ZrF ₆ ¹0.0099 0.0069 0.0040pH, 4.50 3.50 2.50H ₃PO ₄With H ₂ZrF ₆2.0 1.0 0.0 mol ratio AO ²With H ₂ZrF ₆1.0 0.75 0.5 mol ratio

Value shown in the note 1 of table 13 is mole number 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, pH value, fluorochemical activity and other component concentrations change with particular experiment.

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

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

With can opener top cover is removed from jar.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 as the reverse side contrast, is used Alodine based on the jar that only cleans (being untreated) ^404 jars of handling are estimated judgement as positive contrast.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 structure that following formula represents:

Cocoa-N (O) (CH ₂CH ₂OH) ₂Wherein " Cocoa " expression is by usefulness-CH ₂-part replace in the fatty acid mixt that obtains 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 frictional coefficient result of treatment tank test.

Table 14 experiment number is with the changing value in the experiment of this numerical value ¹COF-SB ²COF-DB ³

H ₂ZrF ₆?pH??[H ₃PO ₄]/??[AO]/

[H ₂ZrF ₆]?[H ₂ZrF ₆]???1??????0??????0??????0??????????0????????0.739????0.874???2?????-1?????+1?????+1?????????+1????????1.421??????-???3?????+1?????+1?????-1?????????+1????????0.728????0.712???4?????-1?????-1?????-1?????????+1????????1.065????1.189???5?????+1?????-1?????-1?????????+1????????0.565????0.638???6??????0??????0??????0??????????0????????0.582????0.578???7?????+1?????-1?????+1?????????-1????????1.366??????-???8?????-1?????-1?????+1?????????+1????????1.410??????-???9?????+1?????-1?????+1?????????+1????????0.605????0.581??10?????-1?????+1?????-1?????????+1????????0.781????0.885??11??????0??????0??????0??????????0????????1.046??????-??12?????-1?????-1?????+1?????????-1????????1.547??????-??13?????+1?????+1?????+1?????????+1????????1.459??????-??14?????-1?????-1?????-1?????????-1????????1.312??????-??15?????+1?????+1?????-1?????????+1????????0.609????0.588??16??????0??????0??????0??????????0????????0.606????0.647??17?????-1?????+1?????+1?????????-1????????1.410??????-??18?????+1?????+1?????+1?????????-1????????1.470??????-??19?????+1?????-1?????-1?????????-1????????0.550????0.593??20?????-1?????+1?????-1?????????-1????????1.400??????-??21??????0??????0??????0??????????0????????0.828????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

The trade name chemical structure

Anionic counter-ion

ETHOQUAD ^C-12?????

???Cl ^-

ETHOQUAD ^?C-12B???

??Cl ^-

ETHOQUAD ^?T-13/50?

???????-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 " Tal-

Low " refer to except Oleum Cocois is replaced by the animal tallow in the definition that provides with " Cocoa " mutually

With, " φ " represents phenyl moiety.In this group in steps 4 composition contain 9.6 the gram Al ₂(SO ₄) ₃15 1/2H ₂(it is equivalent to the A of 104ppm to O ^{+ 3}), 2.05 the gram H ₂ZrF 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 compositions ₃PO ₄Composition pH value all is 2.5.By the results are shown in the following table 16 of described processing.

Quat in table 16 composition F that dissociates ^-1COF-SB COF-DB DSETHOQUAD ^C-12-89.0 1.12 1.28 3ETHOQUAD ^C-12/PA-90.0 0.69 0.87 3ETHOQUAD ^C-12B-93.1 0.98 1.21 3ETHOQUAD ^C-12B/PA-89.9 0.90 0.94 3ETHOQUAD ^T-13/50-84.0 0.85 0.98 3ETHOQUAD ^T-13/50/PA-90.3 0.49 0.53 2

The note gauge outfit of table 16 is " free F ^-1" row provide composition reading with millivoltmeter; use Orion fluorochemical sensitive electrode and with above-mentioned 120E Activity Standard Solution calibrating instrument, gauge outfit is that the row of " DS " provide top cover rust resistance estimated value by following grade: 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 only ₂ZrF ₆As component (B).Except ETHOQUAD ^Outside the T-13/50, other variation of research is H ₂ZrF ₆Concentration, pH and 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 sodium aluminate and the mole number of 50ppm equals used H by Al concentration ₂ZrF ₆Phosphoric acid use together, the fluorochemical activity is transferred to reading-90mV on above-mentioned fluorochemical sensitive electrode.The aluminium of 50ppm is with (i) Tai-Ace S 150 (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 Tai-Ace S 150 (to this use mol ratio two kind sour adjust pHs suitable) adding simultaneously with its aluminium salt.Gained is the result describe in detail below.Four variablees of test and three values of each variable are shown in Table 17.The combination and the result of three variate-values are shown in table 18

Table 17

The value of variable and dispensing variable

High, normal, basic

0.009 0.00675 0.0045

X2＝pH????????????????????????3.1???????2.8????????2.5 ???100???????50??????????0

???????1.00??????0.75????????0.5

table 18 experiment number., X1, X2, X3, X4, COF-SB, COF-DB, DS, 1, 1,-1,-1,-1, 0.513, 0.531, 2, 2, 1, 1, 1, 1, 0.544, 0.700, 3, 3, 1, 1,-1,-1, 1.274, 1.406, 3, 4, 0, 0, 0, 0, 0.499, 0.629, 3, 5,-1,-1, 1,-1, 0.508, 0.517, 2, 6, 0, 0, 0, 0, 0.572, 0.731, 2, 7, 0, 0, 0,-1, 1.229, 1.257, 3, 8,-1, 1, 1,-1, 1.421, 1.397, 3, 9, 0, 0, 1, 0, 0.516, 0.700, 2, 10,-1, 1,-1,-1, 1.451, 1.458, 3, 11, 1, 1, 1,-1, 1.311, 1.412, 3, 12, 1, 1,-1, 1, 0.976, 1.149, 3, 13, 0, 0, 0, 1, 0.501, 0.549, 2, 14,-1, 1, 1, 1, 0.762, 1.049, 3, 15, 1,-1, 1,-1, 0.552, 0.553, 1, 16, 0,-1, 0, 0, 0.537, 0.553, 2, 17, 1,-1, 1, 1, 0.559, 0.592, 1, 18, 0, 1, 0, 0, 1.158, 1.346, 3, 19, 1,-1,-1, 1, 0.522, 0.561, 1, 20, 0, 0, 0, 0, 0.599, 0.813, 3, 21,-1, 0, 0, 0, 0.484, 0.518, 2, 22, 0, 0, 0, 0, 0.619, 0.732, 3, 23,-1, 1,-1, 1, 0.738, 0.998, 3, 24, 1, 0, 0, 0, 0.732, 0.913, 3, 25, 0, 0, 0, 0, 0.581, 0.875, 3, 26,-1,-1,-1, 1, 0.520, 0.546, 2, 27,-1,-1, 1, 1, 0.511, 0.518, 2, 28,-1,-1,-1,-1, 0.503, 0.532, 2, 29, 0, 0, 0, 0, 0.610, 0.673, 2

The note of table 18 is at gauge outfit " X ₁", " X ₂", " X ₃" and " X ₄" row in, the high value of regulation variable in "+1 " expression table 17; The intermediate value 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 Tai-Ace S 150 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 experiment pH concentration (mole/8 liters) mol ratio COF-SB COF-DB DS

H ₂ZrF ₆H ₃PO ₄T13 ²1, only clean, 1.155,-, 3.0, 2, 2.00, 9.00, 9.00, 4.50, 1: 1: 0.5, 0.543, 0.582, 3.0, 3, 2.20, 9.00, 9.00, 4.50, 1: 1: 0.5, 0.546, 0.551, 2.0, 4, 2.50, 9.00, 9.00, 4.50, 1: 1: 0.5, 0.505, 0.492, 2.0, 5, 2.50, 9.00, 0.00, 4.50, 1: 0: 0.5, 0.584, 0.576, 3.0, 6, 2.50, 9.00, 4.50, 2.25, 1: 0.5: 0.25, 0.512, 0.557, 3.0, 7, 2.50, 9.00, 4.50, 9.00, 1: 0.5: 1, 0.522, 0.545, 2.0, 8, 2.50, 9.00, 4.50, 18.00, 1: 0.5: 2, 0.479, 0.509, 2.0, 9, 2.50, 9.00, 18.00, 2.25, 1: 2: 0.25, 0.511, 0.531, 2.0, 10, 2.50, 9.00, 18.00, 9.00, 1: 2: 1, 0.514, 0.513, 2.0, 11, 2.50, 9.00, 18.00, 18.00, 1: 2: 2, 0.466, 0.491, 1.5, 12, 2.50, 4.50, 2.25, 1.13, 1: 0.5: 0.25, 0.481, 0.496, 2.5, 13, 2.50, 4.50, 2.25, 4.50, 1: 0.5: 1, 0.485, 0.528, 3.0, 14, 2.50, 4.50, 2.25, 9.00, 1: 0.5: 2, 0.468, 0.509, 3.0, 15, 2.50, 4.50, 9.00, 1.13, 1: 2: 0.25, 0.531, 0.577, 2.5, 16, 2.50, 4.50, 9.00, 4.50, 1: 2: 1, 0.475, 0.480, 2.0, 17, 2.50, 4.50, 9.00, 9.00, 1: 2: 2, 0.458, 0.503, 2.0, 18, 2.50, 13.50, 6.75, 3.38, 1: 0.5: 0.25, 0.515, 0.529, 2.0, 19, 2.50, 13.50, 6.75, 13.50, 1: 0.5: 1, 0.497, 0.544, 1.5, 20, 2.50, 13.50, 6.75, 27, 1: 0.5: 2, 0.470, 0.519, 1.5, 21, 2.50, 13.50, 27.00, 3.38, 1: 2: 0.25, 1.453, 1.338, 2.0, 22, 2.50, 13.50, 27.00, 13.50, 1: 2: 1, 0.535, 0.595, 2.0, 23, 2.50, 13.50, 27.00, 27, 1: 2: 2, 0.479, 0.514, 1.5, 24, 2.80, 9.00, 9.00, 4.50, 1: 1: 0.5, 0.568, 0.733, 2.0, 25, ALODINE^404 1.463-2.0

The ratio that preface provides: H be docile and obedient in the note 1 of table 19 ₂ZrF ₆: H ₃PO ₄: T13.2 " T13 " refers to ETHOQUAD ^T-13/50. each tabulation head " COF-SB ", the same meaning in " COF-DB " and " DS " and these row in every and the table 16

The enriched material of table 20 ethoxylated castor oil derivative and fluorine zirconic acid is to the H that influences of top cover rust resistance and frictional coefficient ₂ZrF ₆Tryol ^TM5921 COF pasteurize grams/liter grams/liter protection classification 00 1.16 failure 0 0.2 0.57 failure 0.14 0.2 0.52 failures 0.29 0.2 0.61 pass and 0.58 0.2 0.63 by 1.16 0.2 0.70, pass 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: every kilogram of enriched material group of component

The inorganic additional enriched material 45% fluorine zirconic acid aqueous solution 32.375% phosphate aqueous solution 9.1 moisture nitric acid of component gram number of compound, 42 ° of Baumes (Baume), 25.5 organic replenishing and strengthening agent enriched material ETHOQUAD ^T-13/50 70.0SURFYNOL ^The 104 23.8 inorganic additional enriched material 45% fluorine zirconic acid aqueous solution 44.475% phosphate aqueous solution 12.670% hydrofluoric acid aqueous solution 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 Productsand Chemicals company, and according to supplier's report, it is 2,4,7,9-tetramethyl--5-decine-4,7-glycol.

In preferable methods embodiment of the present invention, the effect composition is by adding above-mentioned each additional enriched material preparation of 1% in deionized water, (its pH value is 2.7 to 2.9 with the solution that obtains, fluorochemical activity with respect to Standard Solution 120E extremely-80mV) is used for step 4 for-60 ℃, by handling available from D﹠amp at 43 ℃ of following sprayed tank 25sec; The aluminium pot of I is so that the mobility enhancing.Special when the aluminium cation concentration in the treatment compositions is 100 to 300ppm, it is 0.5 to 0.6 that the jar 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 strengthening agent composition is as keeping COF and top cover rust resistance to need to add.

Bao Zhuan additional enriched material is the example (water that constitutes surplus is no longer listed) of preferred enriched material: every kilogram of enriched material group of component below if desired

The component gram number aqueous sulfuric acid of compound, the 66 ° of Baume 13.045% fluorine zirconic acid aqueous solution 41.475% phosphate aqueous solution 11.670% hydrofluoric acid aqueous solution 7.7ETHOQUAD ^RT-13/50 40.9

In using the preferred method embodiment of this enriched material, 50 milliliters of enriched materials dilutions are formed 8 liters of effect compositions, (if needs), its pH value was transferred to 2.4-2.6 and the fluorochemical activity of dissociating transfers to-85 to-95mV.In being followed the tracks of, the several experiment of the enriched material of storing for 13 weeks obtains to be lower than 0.6 COF value.

Embodiment and comparative example group 8

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

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

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 surfactivitys

Agent, fluorochemical 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, all pH value of solution values are transferred to 4.5 by adding required ammoniacal liquor or nitric acid.

By at first remove the method estimation top cover corrosion of top cover from the jar of handling with cap opener.Water-bath when top cover is put into 65.6 ℃ that contain 0.2 grams per liter borax 30 minutes, rinsing and dry in baking oven in deionized water then.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 shown in the table 20 all are ideal very for the rust resistance in COF and the pasteurization processes.

Table 21: use tin-coated steel D﹠amp; The average COF value of the additive hydropexis percentage ratio of the last rinsing of result of I jar

There are not 1.04 100% (qualifications)

Ethox ^TM???????????0.70???????????????83.6Pluronic ^TM/Plurafac ^TM??0.81???????????????77.3

Tergitol ^TM?????????0.82???????????????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 promotor that three class materials are configured for tin can: (i) Ethox ^TMMI-14; (ii) 1 weight part Pluron-ic ^TM31R1 and 4 weight part Plurafac ^TMThe mixture of D25; (iii) Tergitol ^TMMin-Foam ^TM1X.Wherein, Ethox ^TM, Tergitol ^TMAnd Plurafac ^TMProduct is ethoxylated fatty acid class or alcohols, some situation they poly-oxyethane) have poly-{ propylene oxide } block end-blocking on the end, and pluronic ^TMBe the segmented copolymer of ethene and propylene oxide, it has poly-{ propylene oxide } block end-blocking on polymkeric substance is not held.After the frequent rules preface washing of tin can, all substances are all used with deionized water with the concentration of 0.2 grams per liter in the last rinsing before dry.The water and the COF value that keep are measured with above-mentioned general fashion, the results are shown in the table 21.

Claims (6)

1. the liquid composition of a material, described material basically by water and:

(A) dissolved phosphorated surface active agent composition, this component are the mixture of the molecule of general molecular formula I:

Wherein M is the group that is selected from the 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 group 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 Sauerstoffatoms; R is the tetrahydroglyoxaline part of general molecular formula II:

R wherein ¹And R ²Except not all being the hydrogen, all can be selected from hydrogen, by from propionitrile-CH ₃Remove a hydrogen atom in the group and deutero-part and group with part of general formula III:

Wherein, Q be selected from-OM ,-NH ₂With-OR ⁴, wherein M and same meaning defined above, R ⁴Expression C _2-12Alkyl, alkaryl or alkyl cyclic aliphatic part; R ³Be selected from the aliphatic series with 2 to 22 carbon atoms and cyclic aliphatic and alkaryl part that not replacement or hydroxyl replace;

(B) be selected from and contain the component that comprises the ionic water-soluble salt that is selected from Zr, Ti, Sn, Al and Fe atom;

(C) metal etch component; With

(D) " free fluorine ion "; And one or more nonessential following components:

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

R wherein ⁶For having the saturated monovalence aliphatic hydrocrbon of straight chain, ring-type or the side chain part of 1 to 25 carbon atom; X is selected from hydrogen, halogen, phenyl and R ⁵S is 1 to 50 integer; R ⁵Be selected from hydrogen and the alkyl group that contains 1 to 4 carbon atom;

(F) be selected from the component of molecule general molecular formula V:

R wherein ⁷Be straight chain, ring-type or the side chain monovalence aliphatic hydrocrbon that contains 4 to 25 carbon atoms; (C ₆H ₄) be adjacent, or to penylene ring, R ⁵With s and the same meaning in general formula I V;

(G) be selected from the component of molecule general molecular formula VI:

R wherein ⁸Be the straight or branched with 1 to 25 carbon atom, saturated or undersaturated monovalence aliphatic hydrocrbon part; R ⁵Have and meaning identical in general formula I V with s;

(H) be selected from the chelator component that is used to contain component (2) metal ion (B); With

(J) disinfectant.

2. according to the composition of claim 1, wherein the amount of component (A) reaches every liter of composition provides 0.00060 to 5 mole phosphorus; The amount of component (B) reaches every liter of composition provides 0.00010 to 5 mole total Zr, Ti, Sn, Al and Fe; Component (A) is selected from general molecular formula I and " Y " group contains 2 to 4 carbon atoms but the molecule of anaerobic atomic time, R ¹And R ²Being selected from hydrogen and general formula III and Q=OM and M is hydrogen or alkali-metal part, and total at least R ³50 moles of % in composition, have 8 to 20 carbon atoms.

3. according to the composition of claim 2, 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 fluorion, difluoride salt and hydrofluoric acid of composition.

4. according to the composition of claim 3, wherein component (A) reaches every liter of composition provides 0.0010 to 0.40 mole phosphorus; Component (B) comprises dissolved fluorine zirconic acid, fluorine zirconate ion or fluorine zirconic acid and fluorine zirconate ion; The amount of component (B) reaches every liter of composition provides at least 0.0039 mole Zr.

5. according to the composition of claim 4, wherein component (A) is selected from general molecular formula I and Y is ethylidene group and total R ³Molecule when at least 76 moles of % of group have 10 to 14 carbon atoms and are not replacement or nonbranched alkyl group; The amount of component (A) reaches the degree that every liter of composition provides at least 0.02 mole phosphorus; The amount of component (B) reaches the degree that every liter of composition provides at least 0.0040 mole Zr; The amount of component (C) reaches every liter of degree that 0.21 to 11 mole fluorine atom is provided; The amount of component D is 0.10 to 2.2 weight %.

6. the composition of claim 5, wherein the property quality and quantity of component (B) reaches the degree that every liter of composition provides 0.057 to 0.103 mole Zr, and the amount of component (C) reaches every liter of degree that 0.9 to 2.4 mole fluorine atom is provided.

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