MXPA96004750A - Composition and process for treating metal surface aluminife - Google Patents

Abstract

The present invention relates to an aqueous liquid composition for the surface treatment of aluminum metals, either as such or after dilution with additional water, said composition comprises water and: A) from 1 to 30 parts by weight of phosphate ions B) from 0.1 to 10 parts by weight of condensed phosphate ions, and C) from 0.1 to 20 parts by weight of water soluble polymer according to the general formula (I) where i) each of X1 and X2, is independently of each other and independently of a polymer unit, which is defined as a part of the polymer according to formula (I) except that the brackets and the subscript n are omitted, to another polymer unit, represents a hydrogen atom, a C1 to C5 alkyl group, or a C1 to C5 hydroxyalkyl group, ii) each of Y1 and Y2, independently of each other and independently of one polymer unit to another, represents a hydrogen atom or a "Z" portion in accordance with the f Ormula (II) or (III): where each of R1, R2, R3, R4 and R5, independently of each other and independently of one polymer unit to another, represents a C1 to C10 alkyl group, or a C1 hydroxyalkyl group to C10; iii) the Z-portion attached to a phenyl ring in the polymer molecule may be identical or may be different than the Z-portion bound to any other phenyl ring in the polymer molecule; iv) the average value of the number of substituted Z-portions in each phenyl ring in the polymer molecule is from 0.2 to 1.0, v) n is an integer with a value from 2 to 50, and vi) each polymer molecule contains at least a portion

Description

COMPOSITION AND PAPA PROCESS TREATING THE SURFACE OF ALU METAL METALS FIELD DF THE TECHNICAL FIELD The present invention relates to a novel composition and method for the treatment of the surface of metals at 1 um íní pi pi to provide this way to 1 is surfaces, before, and application of paint, an xc l nt resistance to corrosion and adhesion of pi ture. This invention can be applied eff ectively, inter alia, to the surface treatment of canned aluminum cans pressed with, in general, abbreviated "DI" '1. When applied to the aluminum ID 's manufactured by the drawing / ironing of aluminum sheet, the composition and method of surface treatment in accordance with the present invention are especially effective in providing the surface of cans with before application of paint or printing on s miomas, excellent resistance to corrosion and paint adhesion and also an e; high capacity of the required length for the transport of the can (abbreviated below simply as "slow sliding capacity"). BACKGROUND OF THE ART Liquid compositions are often referred to below as "baths" for short, although they may be employed by spraying or contact stabilization methods other than immersion, useful for surface treatment of metals a) umi ni ros, defined as aluminum and its alloys containing at least 45% by weight of aluminum, can be broadly classified into chromate-type baths and non-chromate-type deodorization baths; Surface treatments of the chromate type are typically divided in chromate acid chromate conversion baths / l, i baths > He treatment of onvergi < .- > In the case of chromium or phosphoric chromate, the chromate conversion treatment baths of 5c chromic were used by the first around 195 ° "and are still widely used today for the surface treatment of intercapping fins. heat, for example, and the like. Chromic chromate conversion treatment baths contain acid ,, chromic (Cr03) and hydrofluoric acid (HF) as its essential components may also contain a conversion accelerator. These baths form a revelation that contains small amounts of chromium he :; ava 1 ent. The phosphoric acid chromate conversion bath was invented in 1945 (see the non-American patent No. 2,418,877). This conversion treatment bath contains chromic acid (Cr03), phosphoric acid 5 (H3PG4), and - '• < > Hydrofluoric acid (HF1 mo ~ u = > essential components E3 main component) of the coating produced by this bath is hydrated chromium phosphate (CrP04 * 4H20) Since this conversion coating does not contain hexavalent chromium lens, e-jte bath is still widely used, for example, as an inner hand paint treatment for the lid and the body of cans for drink.The treatment bath presented in JCI Luci sol of open Japanese patent (1 ol ai oi aia inada) no.Sho 52-l3l ° 37 j < 131, 937/1 7"" t) - =, ipopi of the treatment baths for conversion of non-crust tioo. This treatment bath is a waterborne coating solution, acid fpH - approximately 1.0 to 4.), which contains phosphate, fluoride and zirconium or titanium or its compounds. The tratment of surface *; 3 to 3 mm with this bath and conversion treatment of the non-chromate type produces in it a conversion film whose main component is; gone zirconium and i nio. The absence of chrome he'raval is an advantage associated with baths non-chromate type conversion treatment; however, the conversion coatings oroducidos them, in many cases, have a resistance to corrosion and a paint adhesion that is lower than the revetments generated by type conversion treatment baths. chromate. In addition, both the conversion treatment d > - > ti or chromate as a non-chromatic type d or e contain fluorine, which conflicts with the current desire, due to environmental crossovers, of the i p} ements in the practice of surface baths without fluorine. The use of solute solids in water in bathrooms and supefici treatment and methods to provide aluminum metals with resistance to 1 i > Orrosion and paint adhesion is described, for example, in the Japanese open patent application O-ol-ai or n > ~. = • a nada) num "" os Sho 61-91369 '1, 309 / l ^ S?) And He i 1-172406 M 72, 406/1 ° 8 °, Hei 1-177379 f ly-71 9 / l S-9), H i 1 - 1.7738'- '' 17", Z 198. He i 2 - ?? 8 (or <8 • '1 C'C') and He i 2- Q '609 In these cases of surface brine baths method of the prior art, the metal surface is treated with a solution containing a derivative of a phenol compound pal ih tdpcü. , the formation of a revelation that contains acceptably stable resin on the surfaces of metals. - Luminifers are sometimes highly probical with these methods of the internal technique that do not always provide an acceptable performance (resistance to 1J corrosion), the invention described in the Japanese patent application opened fkol-a? O no e; -. Am? Nada) na Hei 4-66671 (66, 71 'i 99) constitutes an improvement to the methods of treatment that derives from < g > '- from polyhydric phenol, but even in this case, the problem of an unsatisfactory adherence arises sometimes. The surface-; of DI aluminum cans is currently mainly treated with the above-described phosphoric acid chromate surface treatment baths and zirconium-containing surface treatment non-chromate baths. The lower surface of the DI aluminum cans is not painted, but is subjected to sterilization at high temperatures. If the resistance to corrosion is not l '? high, the aluminum will oxidize at this point and there will be a discoloration ng-), a phenomenon generally known as "epnegrecimm ent" »To avoid enne reciento, the revetment produced by the surface treatment must itself , even if it is not piinta, present a high resistance to 1 the corrosion. Moving on to another topic, a high coefficient of friction for the external surface of the can will cause the surface of the can to have a low slip capacity during transport in conveyor belts that occurs in the 0 processes of manufacturing and finishing the can . This will cause the tag to turn over, which will obstruct the transport process. The. Carrying capacity of the can is a special concern in relation to transportation to the printer. Therefore, there is a requirement in the The industry of the manufacture of the cans oara a decrease of the coefficient of static friction of the The outer surface of the can, which, however, must be achieved without negatively affecting the adhesion of the paint or the ink that will coat the can. The invention presented in the Japanese open patent solution (K'ot-ai or examined) no. Sho 64-8 * 5292, 83, 292/19"") "?) Is an example of a method envisaged for the improvement of this sliding ability. This invention relates to a surface-active agent par- I fa, where said surface treatment agent contains substances soluble in water at 3 c levels between phosphate esters, alcohols, monovalent fatty acids and polyvalent es, fatty acid derivatives, - However, this method, to increase the sliding capacity of the aluminum plate, does not provide any improvement in terms of corrosion resistance or paint resistance. Japanese open patent application ílolsi or no: aduna a1 No. Hei 5- 0 239434 (239, 434/1 Q3) and another method focused on the improvement of the sliding capacity of aluminum cans This invention is characterized by the use of phosphate steres, this method provides a greater capacity for It does not provide any improvement in terms of resistance to corrosion or paint adhesion.

PRESENTATION OF THE INVENTION PROBLEMS TO BE RESOLVED THROUGH THE INVENTION The present invention focuses on the solution of the problems described above for the prior art. In 5 specific terms, the present invention introduces a composition and method for the treatment of the metal surface to luminiferous which can provide the surface of the metal with a high resistance to corrosion and an e *; good adhesion of paint. When ! > . ' Specially placed on aluminum cans DI, s, comoosici n -. method impa in such cans an excellent sliding ability in combination with an e? c lens and i t ncia to corrosion and adhesion of intura. DETAILS OF THE INVENTION, INCLUDING PREFERRED MODALITIES It has been found that the problems described above for prior art cans can be solved by the application of a specific type of surface trawl bath prepared by the use of a surface treatment composition containing specific phosphate ions. , phosphate or condensed ions, water soluble polymers with a specific structure. It was found that the api icac LÓ? of this super fi cial surface treatment bath on the surface of the luminous metal will form on said surface a reflection that contains ina-m? resistant to 1 .-? corrosion and with 'excellent paint adhesion. It was also found that the application of said bath to aluminum cans DI forms on said cans a coating containing resins that has an increased sliding capacity as well as an excellent resistance to corrosion and paint adhesion. The invention was achieved based on these discoveries. A composition according to the present invention tj piara the treatment of the metal surface 3 lu i nf fr characteristically comprises, preferably consists essentially, and with a greater degree of preference consists of water and, in parts by weight:?) from 1 to 30 parts of phosphate ions; 15 ÍB from 0.1 to 10 parts of condensed phosphate ions; and < C) from 0.1 to 20 parts of water soluble polymer according to the following general formula (I) where each of I and X2 independently between them and independently of a unit of the polymer, as represented by the formula (I) above with the brackets and the subscript n omitted, to another unit of the. The polymer represents a hydrogen atom, a C1 to C5 alkyl group, or a hydroxy group. i.a 1 qui Cl a C5; each of Y1 and Y2 independently of each other and independently for each unit of the polymer represents a hydrogen atom or bn a "Z" portion which conforms to one of the following formulas (II) v (l1): -CH 2 - (lll) where each of R1, R2, P3, P4 and P5 in the formulas (II) and (III) independently represents an alkyl group Cl to CI or a group h? or i alqu i. Cl a Ct 0; l Z portion bound to any phenyl ring. The single molecule in the polymer molecule may be identical or may be different from the Z-portion attached to any other ferrule ring in the polymer molecule; the average value for the number of Z-substituted portions in each phenyl ring in the phenyl molecule is from 0.2 to 1.0; n, which can be mentioned with inuación as "the average degree of pol i er i rae i ón", has a value of 2 to 50; and each polymer molecule (I) must contain at least one fepilo ring substituted with Z-portion. This average value for the number of Z-substituted portions in ferule ring in the polymer molecules of the total component (C) is known. Then the average value of the Compositions according to the present invention as described above can be either compositions of < "work, suitable for directing metallic substrates to luminaires, or they can be useful compo- sitions that are useful.; to prepare working compositions, usually by dilution of concentrated components with water, and optional solution of the pH of the resulting working composition. A method according to the present invention for the treatment of the surface of metals to minerals or minerals characteristically comprises the capsules ta in contact with the surface of the surface, with a surface treatment bath containing the treatment composition. surface described above in accordance with the present invention, followed by rinsing the surface treated with water, and subsequently drying the surface by heating. Independently, in a method of compliance with the invention, the bath preferably has a pH value of 6.5 or less, the method of contacting the metal to be treated is preferably from 5 to 60 seconds, and the temperature during contact with the treated alu metal preferably ranges from 30 degrees C to 65 degrees C. The reactivity of the bath may be insufficient below 30 degrees C, which prevents the formation of a good quality film.While a good quality film is formed at temperatures above 65 degrees C, the higher energy costs for the product make these temperatures economically desirable. This can be inadequate and can not produce a corrosion-resistant coating when the immersion time is less than 5 seconds, and long immersion times, greater than 60 seconds, do not generally produce any improvement in quant or performance and are not preferred due to the additional expenses they represent. The method, ie surface treatment according to the present invention, can be increased by immersion of the metal, pyreferenced for 5 to 60 seconds, in the surface treatment bath described above. The method of surface treatment according to the present invention could also be increased by spraying the treatment bath with sunscreen on the surface of the metal to the light, preferably at least 2 times, and on the surface. ** - Preference with a non-spray interval of 2 to 5 seconds between each continuous spray period and the next continuous period if there is one The occurrence of the pH increase in the vicinity of the interface: with the surface , which is required for a proper training of numbers, e =, less reliable when the spray treatment is carried out by continuous spraying of the bath, and in a few seconds,? Q is a film , L 'sati f to ia. This is the reason why the use of a thermistor spray is preferred. The total of the spray or i and non-spray interval is preferably from 5 to 60 seconds. The reaction of being inadequate can not produce a coating of alpha resistance to corrosion when the time t l,. | E contact is less than 5 seconds. Long total contact times greater than the seconds do not generally produce any additional improvement in terms of the desire and are expensive. A composition of the surface treatment in accordance The present invention is an aqueous solution whose essential ingredients are phosphate ion, condensed phosphate ion, and soluble hydrogen peroxide with the chemical structure specified above. You can? Mpl -; r 4 i • lo or for < H3PH4), sodium phosphate (Na3Fcii1 ', y -, i mi 1 u e, as it was and ion fo f - «s in the.

Composition and surface treatment in accordance with the present invention The content of the phosphate ion in the form described above is from 1 to 30 parts by weight, while the preferred range is from 1 to 5 parts. The reaction between the surface treatment bath and the metal surface will be insufficient, and the formation of phosphorus ions will often be inadequate. in the formulation ar > -? ba described er, less than one Da e in weight, While it is formed \,? a film of good quality with m = í.s de 3 < "< oari.es n es - > phosphate ions, the elevated one of the irritation bath repulíanle makes them liv e i lles are econotti i c 3 men l The condensed phosphate ions epioleados in the present invention correspond -. 1 ^ rmul general chemistry H (p + 1 - q) PpO (3o + 1) -, where p represents a positive integer child > bird s 2 or greater and q represents a positive integer that is 1 a (p + t, «, 'examples are pi or phosph ac ions, ti ions Lpnl i phosph 3 to, tef r ions p.> 1 i phosph ato, and the like. 2 the copolyzed phosphoric acid or its acidic acid or can be used as sources of condensate with the condensate composition for the surface treatment composition in accordance with the present invention. For example, e can mple-ar 4 i do? ¡> I for? > _o H4P207, J? i '~? ln i rof • > sf 'o' li - "^ dico 'a2H2P2ü ~ t /, triodic acid fNa3HP207), and tetrasodium pyrophosphate (Wa4P207), as a source of ions and rofosf to.The content of condensed phosphate ions in the formulation described above for the surface treatment composition according to the present invention, measured as its equivalent esbequiométpcs of fully ionized condensed phosphate anions according to the formula PpQ f p + 1) - f + 2), where p and q have the same meanings as above, is used from 0.1 to 50 parts by weight, while the preferred range is from 0.5 to 3.0 parts by weight Surface treatment baths prepared with less than 0.1 parts by weight of condensed phosphate ion. The above-described formulation generally has a chemical attack activity and provides inadequate film formation, on the other hand, with more than 10 parts by weight, the chemical attack activity generated by the treatment bath. The resulting surface area is too strong in such a way that the film formation reactions are inhibited. The polymer according to formula f) with n less than 2 provides only an insufficient improvement of the corrosion resistance of the resulting surface coating. The stability of the corresponding surface treatment composition and the surface treatment bath is sometimes inadequate and often clarifies practical problems in the case of the polymer f T) with n greater than 50. The presence of 6 or more carbons in the alkyl groups eh Idra; - the one that is repeated by X1 and X2 in the formula f?) causes the resulting polymer molecule to be bulky and produce an obstacle. This interferes generally with the formation of dense recesses, fine that have x l nt resistance to corrosion. The polymer will keep the Z portion as its i fu ent, and the average value for the Z-substitution for each fepyl ring in the limer molecule must lie within the range of 0, a.l.O. For example, in a mere 11 with n = H'i having 2 femlo rings, if only 1 of these 20 feni ring is substituted by a Z portion each, the average value of the Z-portion substitution for this polymer it is calculated as follows: fl K 10 <; 20 - 0.5. The polymer is usually insufficiently soluble in water when the average value for the Z-portion is less than 0.2; this results in a surface treatment concentrate and / or insufficiently stable surface treatment bath. When, on the other hand, the average value for substitution of l per Z ion exceeds 1.0 fsus of a phenyl ring for 2 or more Z * Zions, the pol rummer 1 becomes you It is soluble in water that \ h the formation of a suitably protectant surface film is prevented. The alkyl and hydroalkyl portions encompassed pior Rl, P.2, P3, R4 and R5, in the formulas (II) and III) must contain from 5 to 10 carbon atoms each. The polymer molecule becomes bulky when this carbon number exceeds 10; this results in a gross reversal and therefore in an improvement, insufficient of the retention to the charges. The content of polymer l) soluble in water in the formulation described above for the surface treatment composition according to the present invention is from 0.1 to 20 parts by weight, while the content is preferred. range 0.5 to 5 parts by weight. The formation A coating on the metal surface by the cohesive surface treatment bath often becomes quite problematic when the content of the water-soluble polymer in the formulation described above is less than 0.1 part by weight. Values greater than 20 0 p. By weight are economically undesirable due to the increased cost of the composition of surface treatment and the. surface treatment method. The pH of the composition of the surface treatment according to the present invention is not restricted, but it is generally preferred to adjust the pH to values not higher than 6.5, preferably not lower than 2.0. The method according to the present invention is implemented by means of preparing a surface treatment bath using the above-described surface treatment composition (generally by diluting a concentrate with water). The pH of the working surface treatment bath at this point is adjusted if necessary to values not higher than 6.5 and preferably between 2 and 6.5. The polymer according to formula (T) in the surface treatment bath has a remarkable tendency to be deposited or recirculated at a surface treatment bath pH above 6.5; This results in a stability and useful life and is is. treatment bath. When the pH is less than 2.0, the surface treatment bath can chemically attack the metal surface too importantly, which can affect the formation of. surface coating. The piH of the surface treatment bath can be adjusted using an acid, for example phosphoric acid, nitric acid, hydrochloric acid, and the like, or by the use of an alkaline, for example sodium hydroxide, sodium carbonate, ammonium hydroxide, and similar. Fluorhydric acid can be used to adjust the pH- when the wastewater treatment presents no problems. When the aluminum ions eluted from the aluminum metal treated in accordance with the present invention are mixed in the surface treatment bath, a precipitate may be produced in some cases, due to the formation of a complex between the polymer I) and the aluminum ions. In such cases, an aluminum scavenger is preferably added to the treatment bath. Suitable kidnappers are, for example, acid 111 I am non-reactant, Cy-DTA, troll anolamine, gluconic acid, hepatocellular hepto, sialic acid, tartaric acid, milicium and The organism is not critical, but the hydrofluoric acid can be used as a scavenger when there are no problems with the treatment of the wastewater, a process according to the present invention is carried out in accordance with the present invention. The effluent is obtained by contacting the surface of the aluminum metal with a surface treatment bath prepared in accordance with the above described at 30 ° C to 65 ° C for a total of 5 -10 seconds. Rinse with water of the film formed on the methyl surface and dry by ca. 1 enta.

Problems with the coating can occur due to foaming of the surface treatment bath when a spray treatment is employed. The generation of foam and the intensity of the foam depends to a large extent on the type of spray equipment and on the conditions of oil: side, and preferably a foam remover is added to the surface treatment when a foam problem can not be satisfactorily resolved by changes to the equipment and / or spray conditions, such as the ion and the norm. The supply of the film remover is not critical, provided they do not affect the adhesion of the paint on the resulting coating A preferred method for the preparation of a surface treatment composition in accordance with the present invention will now be briefly summarized. To prepare the surface treatment composition, the phosphate ions and the condensed phosphate ions are prepared, first, in the proportions described above and are dissolved with intense agitation in a required amount of water in accordance with the above specifications. of the resulting solution exceeds 7, is adjusted to be less than or equal to 7 using a suitable acid as described above. Water-soluble esine specified by the invention is then added to the stirring and = >; e dissolve completely, and the *? pH is adjusted to a level less than or equal to 6.5 as above /; described. The coating formed on the surface of the aluminum metal will now be briefly presented. The coating 5 formed by the surface treatment bath in accordance with the present invention is an organic-i composite coating. Narganic whose pyrite components are phosphate salt and polymer (T). The chemical attack of the metal surface by phosphate ions and condensed phosphate ions causes a local increase in pH at the interface; this results in him. deposit of phosphate salt on the metal surface. In addition, the chelation activity of the amine group in the polymer l can result in the formation of a coordination compound with the substrate surface. fresh exposed by that chemist. It is believed that the presence of condensed phosphate ions in the surface trituration bath promotes the formation of the polymer-metal coordination compound and consequently makes it possible to form stable phosphate. Inorganic organic compound coating on the surface in a wide pH range. An additional polymerization of the polymer present on the surface may be even by heating the surface coating after it has been removed. training. In specific cases, when high resistance is required to In the case of corrosion, the backing is preferably heated to produce a higher molecular weight for the polymer on the surface. Suitable heating conditions for this purpose are at least 200 ° C. Aluminum aluminiferous substrates which can be subjected to the method according to the present invention comprise, for example, sheet, bars, tube, cable and similar forms of aluminum and its alloys, for example, inorganic manganese alloys, luminium alloys -magne io, luminium-silicon alloys, and the like. There is absolutely no limitation regarding the dimensions or shape of the aluminum metal. The composition of polymers according to the present invention may contain a preservative or anti-mold agent. Said agent serves to inhibit putrefaction or mold growth when the surface treatment bath is employed or stored at low temperatures. Hydrogen peroxide is a specific example of this type of agents. Below is a brief discussion of additional details of a process for treating the surface of an aluminum metal using the surface treatment bath in accordance with the present invention. The steps of the process outlined below are a preferred example of application of the surface treatment bath in accordance with the present invention. fl > cleaning the surface: grinding m aa - a solvent-based grease remover can be used, or it can be used, lcali no. f 2 E11 p 3 ge c n u 5 (3) Film formation process f th method of translation sn r f? >; i to 3 in accordance with the present i pc i n ', f4 ^ Eu u-t e c water f5 * Enjn g with desi nad water 10 f * Sec a i i m m and go n 3 illustrated with mi and are = > of all s with 1 rv > I I An - trivé of lo - examples of work, ^ its benefits can be observed ad ic i o 1 in conjunction with the comparison examples. The "indirect surface treatment bath components and the surface treatment methods are respectively described in the examples of rab and jo 11. EXAMPLES Methods of e 1 uac in ft '' Resistance ai 3 corro in The corrosion resistance of the unpainted parts of the DI aluminum beams gummed the epnegrec i my 'by boiling water) e evaluates based on the discoloration rate (begin with ugly) after immersion of aluminum cans 5 I treated in water. d l tap hirvienie during ", C niinnl - ,.

The results of this test appear in the following script: +: blackout absence x: partial blackening blackening over the entire surface f2) Adherence of paint The adhesion of the paint of Id was tested Following way. The supe of the treated can was coated with a pei faith or n sensu a spesor of 5 to 7 micrometers with a piara l ta of epo'-iurea.This was followed by norneado duranre 4 minutes at? 15"CA cut of 5 ml was then cut, generally abbreviated "mm") '150 mm from the painted can and was hot-pressed by a pol-amide film to provide a test sample. The test sample prepared in this way was subjected to a 100 * peel test, during which the peel strength was measured. Higher values of peel strength in this test indicate better paint adhesion, and peel strength values equal to or greater than 4.0 1 1 achieve strength: a by 5 millimeters in width then generally abbreviated here as " i-gf / 5mm ") are generally considered to be excellent from the point of view of -tp 11 falls ions prác t ¡>; _ 3 r ». < 3 > r? t? , dice e esliza ient The capacity of de-s i .H-II? It was evaluated by measuring the static friction factor on the surface of the can. Lower values for the coefficient of static friction indicate a better capacity of 5 or, and, in general, are considered as excellent value "---) less than or equal to 1.O. EXAMPLE 1 L "" aluminum tables DT fahrj > . ad-s pior a cimcesa i ento DI of aluminum alloy sheet A3004 f je ron li pi das 1Í < I'm - first, emo, in., with sprinkling, sleeping, -, -,,,,,,,,,,,,,,,,, -, -, -, -,. 3 s > a PAL! I_ IN 'mr * 0 Diániíf "' i'urad by Nihon P - •> rl er izi ng Comoany, Limited then rinsed with 3? Jua.The cleaned surface was roe i: td- Subsequently with the Surface Treatment Unit t fia composition is given ^ continuation) ,} heated to 60 ° C. The spray treatment consisted of 3 roi-i-i s > ie 5 seqnndo:? each or separated by intervals of 5 seconds for a total of 35 seconds. This was followed in order for rinsing with water from yp fo, spraying 10 seconds with water > Ion with a minimum of 3, OOO, OOO ohm-cm), in a hot oven dried at B 'C for 2 minutes. Bath Tr ata i erd o Super ici l * Ac id '"" »aqueous phosphoric at 75" < H fH3P04): 10.0 g / L PQ ions 7.2 g / L) Sodium pyrophosphate (Na4P207.1 H20): 3.0 g / L <ls P207: 1.2g / L) Polymer 1 soluble in water; 2.0 g / L fsolids) H: 4.0 fairness with sodium hydroxides) P ia polymer 1 soluble in water, n-5, VI \ V2- hydrogen, 1 = -CH2 fCH3) 2 in the formula f I i, the average value '"Je la 1" < his "- • t i ', I.IG I n." le oor .- i ó n -. ", E TEMPLE 7 I read 1" .f.?:? of aluminum T were cleaned in accordance with the procedure described in Example 1, after being submerged for 20 seconds in the surface bath, surface 2, or position is presented with heating, and S0 ° C. This treatment was followed by engua e '? with drying and drying according to the procedure described in Example 1. TREATMENT BAPO SUPERE ¡"C TAL 2 70 Aqueous phosphoric acid at 75 fH3P04) j 10. g / L f ions; P 4 7.7 g / L , 'Sodium pyrophosphate (No. 4 P207, 10H20), 3.0 g., P207 1, 2 Q / L * - Polymer t soluble in US g / L f solids) 5 pH 3, with carbonate The aluminum polymer was the same as the one described in Example 1. The EMPLO 3 5 The DT aluminum cans were cleaned in accordance with the friction described in Example 1 and submerged afterwards. ^ seconds in the bathroom er 1 am »nto > upor f ic L to the 3 fli composition was ur jj ut ": i with inuaci) heated i" ~ r "&rt '' r 'This', r > iaielo was followed f; ot enuuaje! ('' with water and drying of con rmi ad with ^] CU? "- • the i ' > 1 -1 - '"r i I" > i in - - • j m 11 i 1, B? f * TO OF TREATMENT SUPERE! C JAI "" A. "gone phosph rich.-Cough •) 1" "%? 3P04) í 70.0, j, 'L (unes: P04 14.4 g / L) 1 P i ro fos f i to? d ico f Na '¡-P707, 10H20): ó. , L f i one-,: P207 2.4 g / L 't > ^, Polymer 1 soluble in water: 8.0 g / L / solids * cH: .0 (adjusted hydroxide, 'sodium' 1 Ba 1 an &: water 20 Water soluble polymer 1 was the same that the one described in Example 1 EXAMPLE 4 The aluminum strands Di were cleaned with the description described in the following example: ». The first step was to use the 1, 2, 1, 2, 1, 2, 1, 2, 1, 2, 3, and 1 spray treatment consisting of 3 sprays ( 6 seconds each) sepiaractos per interval ". of 2 seconds (total of 22 seconds). This treatment was followed by rinsing with water 5 and drying according to the procedure described in e j m l t. SURFACE TREATMENT BASE A Aqueous phosphopeous acid at "75% fH7P0a-), 1.5 g / l. Ion s P04 1.3 Q / L) U? Fosf" i! or sodium f Na-lR ^ n? «1 H20) i 5.0 y.'L í i ones P707" ". g / l * 'Polymer 1 soluble- »in a ua:. i g / L (solids) uH; 7.5 Just with the use of the liquid solution 15 The water-soluble polymer was the same as the one described - ^ EXAMPLE 5 The aluminum samples were 1-in-1 in accordance with the decomp. to in example 1 and after 2 '' 'submerged for 70 seconds in the surface treatment bath 5 (the feed composition) heated to O'C.This was followed by rinsing with water and drying in accordance with the procedure described in FIG. EXAMPLE 1. 35 SURFACE TREATMENT BAFFlO Aqueous phosphoric acid 3 l 7r5 * / «fH3P0'H): 30.0 g / t ions: P04 21.6 g / L) Tr ipol 1 sodium phosphate fNa5P3010): 1.2 g / L f ions: P3010 0.8 g / L) Water soluble polymer 1: 2.0 g / L fsolids) pH "3.5 (only with water; The water-soluble polymer is the same as the one described in chapter 1. E TEMP LO A, I-1 i il ilimimini DT was n 1 i mo 1 ad: J «> _onf? > ud-.d -on the procedure not described in example 1 - after POC • sdas with the barium! ¡l - inuen o -iijp f icía 1 • 1 j. compos¡ ci n n is given to cont unnc ion 'cale ta a ^ "C. The treatment of hero 1" do cons 1 st 1 ón de roe 1 -idos of 5 seconds c- to one separated by an interval of 5 seconds for a total of 1 * "• Second treatment This treatment was followed by rinsing with drying according to the procedure described BAFlO CE SUFEPFTCIAL TREATMENT 75% aqueous gaseous acid IH3P04 »J 10. og / l. (ions; P04 - , 7 g / L) Pyro Phosphate;, 5? Co (Na4P207.1 H20) 1 7.0 g <L; ions; PQ "7 í .2 g / L Poly m > 'i'n 2 so l nb 1 n a oI a; 2.0, I. 1 -,. > 11 s * pH: 5.0 (adjusted with sodium hydroxide) Balance: water For water-soluble polymer 2, in formula (I), n) 5, XI and X2 = C2H5, and Z- -CH2N (CH2CH20H) 2, and the average value 5 for substitution of Z ~ 1.0 portion. EXAMPLE 7 The DT aluminum cans were cleaned according to the procedure described in Example 1 and then __. submerged for 30 seconds in the surface treatment bath LI '(the composition is given below *' heated to or> 0 ° C. This treatment followed by rinsing with water and drying in accordance with the procedure described in FIG. example 1. SURFACE TREATMENT BARO 7 5 7% aqueous phosphoric acid (H3P04): 10.0 g / L dones: P04 7.2 g / L) Sodium pyrophosphate (Na4P207 * 10H20). 3.0 g / L f ions: P207 1.2 g / L) Polymer 3 soluble in water; 2.0 g / L (solids) 0 pH: 4.0 (adjusted with sodium hydroxide) Balance: water For water-soluble polymer 3, in formula (I), n = 2, XI and X2 --- C2H5 and Z = -CH2N (CH2CH2CH20H) 2, and the average value for substitution of porcia Z-O.6. E COMPARATIVE TEMPLE 1 The DI aluminum cans were cleaned according to the procedure described in example 1 and then sprayed with the. surface treatment bath 8 (the composition is presented below) heated to? OßC. The spray treatment consisted of 5 sprays of 4 seconds each separated by i tervalos of 5 seconds each, for a total of 40 seconds. This fi ne treatment followed by rinsing with water and drying in accordance with the procedure described in example 1. l BAflO DF SURFACE TREATMENT 8 75% aqueous phosphoric acid (H7P04); 10. g / l. f ions: P 4 7.2 g / l) Pol L ero 1. water soluble: 2.0 g / L (solids) pH: 3.0 (adjusted with sodium carbonate) 5 B lance: water Water-soluble polymer 1 was the same as that described in example 1. COMPARATIVE EXAMPLE 2 The DI aluminum cans were cleaned in accordance with 0 the procedure described in example 1 and then submerged for 30 seconds in surface treatment bath 9 (the composition is given below) ) heated to 60'C. This treatment was followed by rinsing with water and drying in accordance with procedure 5 decrement in Example 1.

SURFACE TREATMENT BATH 9"75% aqueous phosphoric acid fH3P04): 1.0 g / t <ions: P04 7.2 g / L) Water soluble polymer 1: 2.0 g / L (solids) pH: 7.0 (adjusted with hydroxide) sodium) bl nce: water The water-soluble polymer 1 was the same as that described in the jemp lt COMPARATIVE EXAMPLE 3 The DI aluminum cans were li ned in accordance with the procedure described in example 1 and then submerged for seconds in the surface treatment bath the composition is given below) heated to 60 ° C. This treatment was followed by water treatment and drying in accordance with the procedure described in Example B. BAFlD OF SURFACE TREATMENT Aqueous phosphoric at "^ 5% (H3P04): 10.0 g / L (ions: P04 7.7 g / L) Sodium pyrophosphate fNa4P207.10H20): 1.0 g / L dones: P207 0.4 g / L) Water-soluble t polymer: 0.05 g / L (solids) pH: 4.0 (adjusted with sodium carbonate) balance: water The soluble polymer (water) was the same as the water content. 1. COMPARATIVE EXAMPLE The DI aluminum cans were cleaned in accordance with the procedure described in Example 1 and then immersed for 7 seconds in the rinse bath. = > uper f i c i - < 1 11 (the beat?>: Ion was present below) heated to Ó? "C. This tria - tion was followed by rinsing,., With water and drying of conf r i ad with the p rocedi mi in I 1 '' e-, v_r? or? -n the example 1. 7AÑ0 OF SUPERFICIAL TREATMENT 11 Acido sul -'- úprc »acu to the 5% < W2 04d 2,, _, 'L do es: S04-7 1.9 g' L 'Pi rofos sodium fato iN ^ 4P20"r« 10H70); lO g / L don: P207 15 O, 4 g / L' Pol f water-soluble substance 1: 0.05 g / | _ (solids) i- * pH1; 3.5 (adjusted for sodium) Polymer 1 -soluble n was the same as that described in example 1 7 COMPARATIVE EXAMPLE 5 The diaphragms of the diaphragm were cleaned by the procedure described in Example 1 and then submerged for 70 seconds in the surface bath 12 (the first phase). continued '75 to n' a 'i or' C This ra tio n was 'e uj o mii ni jeo rt aguysera ri o e e,' nfo ini da >: icon the process described in example: TREATMENT SURFACE TREATMENT 12 75% aqueous phosphoric acid (H3P045, 1.0 g / L dones: P0 - 5 0.77 g / L) Sodium pyrophosphate (Na4P207, 1 H20): 1.0 g / L dones P207- 0 and / 1.) Polymer 3 soluble in agn-a, 3-0 g / L (solids; , pH; . < "'(adjusted with sodium), d Bal nce; au The p? g? iero 4 soluble in a ua, in fr? f T' < -. n-5 .Y] Y2- -C2H, and Z - -CH2S03H, and the average value for the II II tution -CH2S03H = .6 COMPARATIVE EXAMPLE 6 1 The DT aluminum were clean in accordance with the procedure described in example 1 and then submerged for 30 seconds in the bath of surface treatment 13 f composition is given below, heated to 6 ° C. F? i> "l- a timi e to was followed by rinsing with water and drying in accordance with the procedure described in the example. SUPERFICIAL TREATMENT BAFFO 13"Surface treatment described in the patent application for open or closed lid or not) No. Hei 4-or? Oo> 71) 25 Phosphoric acid .CHOCO at 75 % ÍH3P04), 1.0 n Lions: P04- g / L) Sodium pyrophosphate (Na4P207 d H20): 1.0 g / L dones: P 07 0.4 g / L) Water soluble polymer 5: 2.0 g / L ( solids) pH: 4.0 (adjusted with sodium hydride) Balance: water The polymer soluble in < -gua had the following formula COMPARATIVE ETEMPLO 7 DI aluminum cans were cleaned in accordance with 1 the procedure described in example 1 and then submerged for 30 seconds in the treatment bath Í * /. surface 14 gives composition is given below) heated to p 'C, This' treatment was followed by rinsing with water and drying in accordance with the proc 2 (Referred to in Example 1. SUPERFICIAL TREATMENT BANK 14 75% Aqueous Phosphoric Acid (H3P04): 1.0 g * 'L (ions: P04- P rofos f a to sod i co f Na 4P207, 1 H20 l ,? < g 'L i s: P707 0.4 g / L) Polymer 6 soluble in water: 2.0 g / L (solids) pH: 4.0 (adjusted with e3 hydrous sodium) Balance: water Polymer 6 soluble in water had the following formula (V) (resin described in the open Japanese patent application (dol ai or no eia inada) No. H i 2-60S); E COMPARATIVE EMP10 8 DT aluminum cans were cleaned according to the procedure with the DTNE (mr) 404 non-chromate surface treatment agent, manufactured by Nihon Partep Company, Lunited, heated to 40 ° C. This spray treatment consisted of 5 sprays of 5 seconds each separated by 5 second intervals for a total of 25 seconds. This treatment was followed by rinsing with dried water according to the procedure described in Example 1. The results of the evaluation for Examples 1 to 7 and the comparative examples to 0 are presented in Table 1. TABLE 1. RESULTS OF LS EVALUATIONS Example number res i / 'gum resistance coefficient or of o jemp lo al _f 1 comparative friction blacken uni in The two static head I-gf / 5mm Example 1 + 4.0 0.9 5 Example 2 a- 4.0 0.9 E jemp 1 or 7 t 4.0 0, Example A + 4.0 0. E emp l o 5 + t- .0"9 E j emp 1 or 6 + 4.. <; * E j emp 1 o ~ t t- -1"0 .9 i comparatio i / o 1 7. o 1," 'Example> "omp-t r« L i 2 1.5 1.5 Comparative example 7 7.0 1.5 Comp era tion 4 1.5 1.3 5 Coiparatiun example 5 1.5 '. & Does he compare it to 11 *? Ó -I- 2, or 1., t fr ~ Comparative Example 7 1.5 1.6 E .i mp 1 or co pa ra ti vo 3 + 4"i, o, As shown by the results of Is table 1, Examples 1 to 7 which employ surface treatment compositions and surface treatment methods in accordance with the present invention provided me 3 is surface treated with an e-> g. -ei resistance entity-to the ennegrei. I ient, energetic adherence, and e? le t capacity 5 of d -al j - ,. t? to In contrast, all these properties (corrosion resistance, paint adhesion, and sliding ability) could not be obtained in the case of surface treated metals with surface treatment baths. outside the scope of the present invention (comparative examples 1 to 8). BENEFITS OF THE INVENTION As can be clearly seen from the previous description, the The surface treatment composition and the surface slowing method in accordance with the present invention can produce some pitfalls with very high resistance to corrosion? n and high conversion of adhesion of paint on the surface of metals alu all before the ariliear the paint on them. Especially, the The application of the surface treatment composition according to the present invention for the treatment of DI aluminum cans results in the formation on the surface of the DI aluminum cans, prior to the application of paint or printing, of a very high resistance to corrosion and with high paint adhesion which also provides the excellent sliding ability required for a smooth transpiorte of the can in the conveyor belts. Since the surface treatment composition according to the present invention and the surface coating bath employed in the method of the invention do not contain chromium or fluorine, they have excellent advantages p = t. sewage treatment. i < ' fifteen 0

Claims (8)

1. '.9
2. PE IVI MDI CAC IONS t. An aqueous liquid composition for the treatment of the surface of metals in ununions, either as at or after dilution with additional water, said composition comprises water and (A) from 1 to 30 parts by weight of phosphate ions: (B * < from .3 to 30 parts by weight of condensed phosphate ions:
3. (C) 0.3 to 2 parts by weight of water-soluble lime in accordance with the formula in CT ' where (i) each of X3 and X2, is independently between or independently of a polymer unit, which is defined as a part of the polymer of con fi rmity to formula (I) except that the brackets and the subscript n is omitted in another one of the polymer, rep-sen a -'atomo and hydrogen, a C1 to C alkyl group, or a hi-h-o'- ia 1 aui lo 03 a C51 group ( ii * every no of "- 1 v Y7. independently between the] and », and between one unit of the polymer to another, represents a hydrogen lathe or a portion (III where each of Rl, P2, P3, PA and P5, independently, "tr elleis ei rulependly from one unit" of the polymer to another, contains the group IiIIIII C3 and IOC, or a group hydr ii i 13 qu i] n Cl a C3 «í iii * < the portion 7 attached to a d feni ring in the polymer molecule may be identical or may be different than the Z portion bound to any other ring of femlo in the polymer molecule; (? v) the average value of the number of portions 7. replaced
4. J in each phenyl ring in the polymer molecule is
5. C.? .2 to t.O; i > \ n is an integer with u 'slor of 2 a; and (vi) caita polymer molecule > _onf? at least one 2. A composition according to claim 1, comprising from 1 to 5 parts by weight of phosphate ions, from 0.5 x 3 parts by weight of the phosphate ions condense, and from 0.5 to 5 parts by weight of 5 eomormity water soluble polymer with the formula < T ^, 3 »A composition according to claim 2, having a pH value of 2.0 to 6.5, and comprising 1 to 30 g / L of phosphate ions, from 0.1 to 10 g / L. of condensed phosphate ions, and from 0.1 to 20 g / L of water-soluble polymer according to formula (I). 4. A composition in accordance with rei indication 1, which has a pH value not greater than 6.5 and which comprises of 30 g-1 L of phosphate ions, from 0.1 to 10 g / L of condensed phosphate ions, and from 0.1 to 20 g / L of water soluble polymer according to formula (I). 5. A process for the treatment of an aluminiferous metal surface, said process comprises the steps of; (I) setting the aluminum surface for 5 to 60 seconds at a temperature of 30 degrees C to 65 degrees C with a composition according to claim 3 or 4; after finishing step (I), separate the aluminum metal surface from the contact with a composition in accordance with claim 3 or 4 and rinse the surface with water, and (III) heat up the metal surface aluminum rinsed in step (II)
6. 6. A p in accordance with step 5, where step (I) is achieved by immersing the metal surface alu inf.fero in the composition.
7. 7. A process according to claim 5, wherein step (I) is achieved by spraying the composition on the surface of the lamp.
8. 8. A pirocess according to claim 7, wherein: the aluminum metal surface is sprayed at least 2 times; Spray contact periods are interrupted by non-spraying integers > Je 7 to 5 seconds; and the total mp between the end of the first spraying and the spraying of the sprayer is 5 seconds. RF5UMFN OF THE INVENTION A surface of aluminum metal comes into contact at a temperature comprised between 30 degrees C and 65 degrees C for 5 to 60 seconds with a surface treatment bath with a pH value of 2.0 to 6.5 containing phosphate ion , condensed phosphate ion, and a water-soluble pyrolimide in the siui is provided by weight; 3 - 30: .3 -10: 0.7 - 7. This is followed > ^ u nj agu with water and dry'.io par cal nt mnto. The water-soluble pallet has a n.; I. I n i i> "confrmity" on the label (I * 1: where (i) each of XI and X7 represents a hydrogen atom, a group alkylene Cl a C, or a group h idro: - i a lqij i la Cl a C5; f ??) each of Yt and Y2 represents a hydrogen atom or a "Z" portion in accordance with l f or rmu l (II) a (Til): -'i 4 .CH 2 - N (III) where each of Rt, P2, R7, R4 F »5 l e reseul - an alkyl group or Cl to C0b bi n a hydroxy alkyl group Cl a C3 '(; to?? -, I- i ti i i. | to i-n, -i-I)? r ,? What is the problem? > t > »L éon 1 -a 11 i 1 1 i -) i, j,. "-" _ _ _, l n first I n i I 1 II ll "l un--, f | l > - f I - «Jf'i I -. f 1