EP1294834B1 - Method for treating or pretreating containers - Google Patents

Description

The invention relates to a method for the treatment or pretreatment of containers made of aluminum, aluminum-containing alloys, magnesium-containing alloys, iron materials such as steel, coated iron materials such as galvanized steel, galvanized or coated with aluminum or aluminum alloys metallic materials, tinplate, brass or bronze , These containers may include pouches, bags and similar packages, bottles, cans, canisters, barrels, pods, e.g. Be screwed.

Usually containers are prepared in a continuous pre-treatment plants for painting. Such containers, in particular cans, are produced in mass production using foils, sheets or moldings of aluminum, aluminum alloys or tinplate and after cleaning, pretreatment, painting and drying with drinks, food or other products filled and closed or closed. Cans are pretreated in most can pretreaters at a rate in the range of 500 to 5000 cans per minute. Therefore, high demands are placed on the speed of all processes and on the secure mastery of all process steps. In addition, high demands are placed on the sliding properties of the container in the continuous pretreatment plant including printer or paint shop and on the adhesion for paint or other subsequent coatings and corrosion resistance.

EP-A-0 293 820 . EP-A-0 413 328 and EP-A-0 542 378 describe methods of coating aluminum cans with a lubricant consisting essentially of ethoxylated compounds, especially surfactants.

Out WO 98/29580 For example, a method of coating self-assembling molecules for the pretreatment of metallic surfaces is known. These With regard to the compositions, process parameters and method steps mentioned therein, publication is expressly included in this application. This publication does not suggest which sliding properties have the coatings described therein and whether this method is also suitable for coating containers, in particular at very high speed and correspondingly short processing times. Because the coating conditions on individual parts or sheets, especially in slow coating or in the laboratory, deviate greatly from the conditions of extremely fast tape processing.

US-A-5,061,389 teaches a treatment agent based on polyethylene glycol ester and optionally a fluoride.

EP-A-0 612 833 describes a treatment agent for metal cans containing an ester based on polyglycerol and fatty acid.

D. Klamann et al .: Lubricants and Related Products, Verlag Chemie 1984 describes the properties

The object of the invention is to overcome the disadvantages of the prior art and in particular to propose a simpler and more cost-effective method for the treatment or pretreatment of containers that at the very high speeds of mass production safe pretreatment or treatment and high corrosion protection, a good paint adhesion and excellent lubricity of coated and dried containers offers.

The object is achieved by the use specified in claim 1. The further claims further shape the use.

The treatment or pretreatment agent is preferably in the form of an aqueous solution and / or dissolved in an organic solvent. However, it may also be a dispersion. The agent for the treatment or pretreatment contains - in the case of a mixture - or / and is not only well suited according to the invention with regard to paint adhesion and corrosion protection, but at the same time a good one Lubricant, so that hereby (pre) treated, in particular sprayed, outer parts better when contact similar container with each other or with the guides of the system.

In the method according to the invention, the treatment or pretreatment with solutions according to the invention can also be carried out on already treated or pretreated container surfaces, especially if the paint adhesion and / or the corrosion protection of the preceding treatment or pretreatment is not yet good enough and a combination of particularly high quality Properties should be achieved.

Hereinafter, for linguistic simplification in the pretreatment agent which simultaneously contains or is a lubricant, it is referred to only as the treatment agent, though in some cases it additionally or solely serves the pre-treatment.

The lubricant can develop its effect only after application of the coating according to the invention. Therefore, the term "lubricant contained in the treating agent or as a treating agent is also a lubricant" means an agent whose effect can be detected only after coating and after drying of this coating. The coating may consist of at least one chemical compound, which is possibly formed only in contact with a solvent or / and the substances contained in the solution or dispersion and / or drying, heating or / and polymerizing and only in the coating as Lubricant acts.

The use according to the invention relates to the treatment or pretreatment of containers made of aluminum, aluminum-containing alloys, magnesium-containing alloys, iron materials such as steel, coated iron materials such as galvanized steel, galvanized or coated with aluminum or aluminum alloys metallic materials, tinplate, brass or bronze, in which the steps of the treatment or pretreatment coincide with the application of the lubricant, the pretreatment or treatment agent which also contains or contains a lubricant not being essentially titanium or / and zirconium with fluoride and polymer ,

The use according to the invention is used in particular for the treatment or pretreatment of containers of aluminum, aluminum-containing alloys, magnesium-containing alloys, steel or tinplate, in particular of bags, bags, bottles, cans, cans or barrels, this being for the treatment or pretreatment applied agent is also a lubricant at the same time. In particular, pouches and bags may be made of metallic foils and / or laminates.

The preferred containers to be coated include pouches, bags, bottles, cans, canisters, barrels and pods; The sleeves include, in particular, single-part or multi-part sleeves, cartridge cases, tablet sleeves, closure sleeves, such as e.g. Screw caps and cigar tubes.

The metallic materials to be coated include in particular galvanized metallic substrates, which may have been galvanized in different ways, as well as other zinc-containing coatings such as Galfan ^Ⓡ , Galvalume ^Ⓡ and Galvanneal ^Ⓡ and tinned steel. On the other hand, it is also possible to use silicon-containing alloys which may contain, for example, aluminum, magnesium or / and silicon contents and in which the contents of these elements may be contained in different forms, for example as an element or as an intermetallic compound and in which the contents Of aluminum, magnesium or / and silicon are often only in the order of about 0.3 to 3%.

Preferably, in the use according to the invention with the means for pretreatment or treatment (= treatment agent) on the metallic substrate, a conversion coating of the first or / and second type is produced. At the Generating the conversion coating of the first type, atoms are dissolved out of the metallic surface, which if appropriate react as ions with atoms or ions from the treatment agent and produce a conversion layer on the surface. In producing the second type conversion coating, atoms or ions of the treating agent having atoms of the surface of the substrate remaining in the surface form a chemical bond to form a conversion layer. The latter type of conversion coating occurs in particular for compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *.

The treating agent may be an aqueous solution or an aqueous dispersion. The term dispersion here also includes emulsions and suspensions.

The treatment agent used for the inventive use is preferably free or substantially free of fluoride or of a combination of fluoride and polymer. In some cases, however, a small content of complex fluoride may be advantageous.

Most preferably, it is free or substantially free of phosphate, wherein the phosphate content is calculated in each case as PO ₄ .

The treatment agent is advantageously free or substantially free of chromium. The term "substantially free of chromium" refers to no intentional addition of a chromium compound during treatment or pretreatment. However, it can not be excluded that traces of chromium are dissolved out of the substrate, that traces of chromium are contained in the compounds used of the treatment agent and / or are introduced by one of the previous baths.

The treatment agent is preferably free or substantially free of iron, manganese, nickel, cobalt, copper, other steel refiners or / and zinc, in particular free or substantially free of heavy metals of all kinds. It is advantageous if it especially free or substantially free of nickel, cobalt, copper and / or other transition metals. The term "largely free of ..." has a similar meaning as before with the chromium content. In the case of a possibly occurring staining effect, however, the elements which are located in the pickled metallic surface are usually also incorporated in the bath, ie usually the elements of the metal or the alloy of the metallic surface.

The treatment agent may consist essentially of compounds based on compounds of the type X * Y * Z * or / and X * Y * Z * Y * X * or in particular of phosphonate. In addition, it may in particular in each case at least one biocide, a demulsifier, a fragrance, an emulsifier, a defoamer, a solubilizer, a surfactant, a pH adjusting agent, a means for adjusting the electrical conductivity and / or at least one other Excipient included. The other auxiliaries required for such solutions or dispersions are generally known to the person skilled in the art.

The treatment agent of the invention may be free or substantially free of ethoxylated compounds, preferably free or substantially free of all types of surfactants.

In a particularly preferred variant of the method according to the invention, the treatment or pretreatment agent, which is possibly a lubricant, contains at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * .
where Y is an unbranched alkyl group having 10 to 20 carbon atoms,
where X is an OH, SH, NH ₂ , NHR ', CN, CH = CH ₂ , OCN, CONHOH, COOR',
Acrylic acid amide, epoxy, CH ₂ = CR "-COO-, COOH-, HSO ₃ -, HSO ₄ -, (OH) ₂ PO-, (OH) ₂ PO ₂ -, (OH) (OR ') PO- , (OH) (OR ') PO ₂ -, -SiH ₃ - or / and an Si (OH) ₃ group,
where Z is an (OH) ₂ PO, (OH) ₂ PO ₂ , (OH) (OR ') PO or an (OH) (OR') PO ₂ group is
where R 'is an alkyl group having 1 to 4 C atoms,
wherein R "is an H atom or an alkyl group having 1 to 4 C atoms and wherein the groups X and Z are each bonded to the group Y in its end position,
where Y * is an unbranched alkyl group having 10 to 20 C atoms,
where X * is OH, SH, NH ₂ , NHR ', CN, CH = CH ₂ , OCN, CONHOH, COOR', acrylic acid amide, epoxy, CH ₂ = CR "-COO -, COOH-, HSO ₃ -, HSO ₄ -, (OH) ₂ PO-, (OH) ₂ PO ₂ -, (OH) (OR ') PO-, (OH) (OR') PO ₂ -, SiH ₃ -, Si (OH) ₃ ,> N-CH ₂ -PO (OH) 2- or a -N- [CH ₂ -PO (OH) ₂ ] ₂ - group,
where Z * is an (OH) ₂ PO-, (OH) ₂ PO ₂ -, (OH) (OR ') PO-, (OH) (OR') PO ₂ -,> N-CH ₂ -PO (OH) ₂ - or a -N- [CH ₂ -PO (OH) _{2] 2} group,
wherein R 'is an alkyl group having 1 to 4 carbon atoms and
wherein R "is an H atom or an alkyl group having 1 to 4 carbon atoms.

In this case, the means for the treatment or pretreatment, which is possibly a lubricant, contain at least one compound of the type XYZ,
where X is a COOH, HSO ₃ , HSO ₄ , (OH) ₂ PO, (OH) ₂ PO ₂ , (OH) (OR ') PO or (OH) (OR') PO ₂ group is
where Y is an unbranched alkyl group R containing 10 to 20 C atoms, of which at least 60% of these C atoms are present as CH ₂ groups,
wherein Z is an (OH) ₂ PO, (OH) ₂ PO ₂ , (OH) (OR ') PO or (OH) (OR') PO ₂ group, wherein R 'is an alkyl group of 1 to 4 C atoms is
and wherein R "is an H atom or an alkyl group having 1 to 4 C atoms.

Preferably, the groups X * and Z * of the compound of the type X * Y * Z * or / and X * Y * Z * Y * X * are each bonded to the group Y * in their end position.

In this case, the compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * may be suitable for forming self-assembling molecules ("SAMs"), which themselves form a layer In particular, here Y or Y * can be a linear unbranched group, in particular a monomolecular layer.

Due to the often rapid coating, the coating can be incomplete - amazingly almost without any effect on the properties of the coating becoming apparent. The coating may be partly in a regular arrangement and partially irregular, with the regularly arranged lots often being monomolecular. Despite this very low coverage, this coating has excellent properties, in particular excellent sliding properties, paint adhesion and corrosion resistance. It is therefore extremely economical to use and also environmentally friendly.

Preferably, Y or Y * is a linear, unbranched or branched chain, optionally with at least one functional group, in particular a chain with at least one alkyl group or / and an aromatic group.

In the process according to the invention, the more effective compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * often have a group Y or Y * which has an even number of C atoms. At least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * can hereby be present in an aqueous solution as salt and / or as acid. There is preferably at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * in the solution as a salt. The group Y or Y * of the more effective compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * may be an unbranched straight-chain alkyl group having 10 to 20 carbon atoms.

The treating agent may also contain at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * wherein Y or Y * is an unbranched alkyl group of 10 to 18 carbon atoms.

It may also contain at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, where X or X * is an (OH) ₂ PO ₂ - or (OH) ( OR ') is PO ₂ group.

• 1-Phosphonsäure-12-mercaptododecan,
• 1-Phosphonsäure-12-(N-ethylamino)dodecan,
• 1-Phosphonsäure-12-dodecen,
• 1,10-Decandiphosphonsäure,
• 1,12-bodecandiphosphonsäure,
• 1,14-Tetradecandiphosphonsäure,
• 1-Phosphorsäure-12-hydroxydodecan,
• 1-Phosphorsäure-12-(N-ethylamino)dodecan,
• 1-Phosphorsäure-12-dodecen,
• 1-Phosphorsäure-12-mercaptododecan,
• 1,10-decandiphosphorsäure,
• 1,12-Dodecandiphosphorsäure,
• 1,14-Tetradecandiphosphorsäure,
• 1-Phosphorsäure-12-Acryloyldodecan.

In the method according to the invention, the treatment or pretreatment agent contains at least one of the following compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * or / and at least one of the corresponding derivatives, in particular salts:

• 1-phosphonic acid-12-mercaptododecan,
• 1-phosphonic acid-12- (N-ethylamino) dodecane,
• 1-phosphonic acid-12-dodecene,
• 1,10-Decandiphosphonsäure,
• 1,12-bodecandiphosphonsäure,
• 1,14-Tetradecandiphosphonsäure,
• 1-phosphoric acid-12-hydroxydodecane,
• 1-phosphoric acid-12- (N-ethylamino) dodecane,
• 1-phosphoric acid-12-dodecene,
• 1-phosphoric acid-12-mercaptododecan,
• 1,10-decandiphosphorsäure,
• 1,12-Dodecandiphosphorsäure,
• 1,14-Tetradecandiphosphorsäure,
• 1-phosphoric acid-12-Acryloyldodecan.

Advantageously, the treatment agent or pretreatment with at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * is contained in an aqueous solution, wherein in particular 0.01 to 50% the water by at least one organic solvent such as may be replaced by an alcohol having 1 to 8 carbon atoms, by acetone, by dioxane or / and by tetrahydrofuran. Preferably, 0.1 to 50% of the water, more preferably 0.5 to 30% of the water is replaced by an organic solvent, which is in particular at least one alcohol having 1 to 4 carbon atoms.

The pretreatment agent may contain at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * which is in the range of the critical micelle concentration or below, in particular one Concentration of 0.05 to 10 g / L. Preferably, the concentration is 0.1 to 3 g / L, more preferably 50 to 1000 mg / L, most preferably 100 to 600 mg / L.

In addition, it may be advantageous if in addition to the compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * also low levels of other organic compounds are included, such. Esters, in particular based on phosphon, which are able to positively influence the solubility of the compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * in water.

It may in particular be contained in a content of 0.01 to 15 g / L in water or in a water-solvent mixture, preferably in a content of 0.02 to 2 g / L, in particular from 0.05 to 0.3 g / L.

When using at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * in an aqueous solution, contacting the metallic surface in the range of 0.5 seconds to 10 minutes may be sufficient , This is often carried out with a pH in the range of 1 to 10, preferably in the range of 2 to 4; in the coating of containers - especially cans - a mineral acid, e.g. Sulfuric acid is added so that the pH of this aqueous solution is then preferably in the range of 0.5 to 3. It is recommended to use demineralized water, which preferably has an electrical conductivity of ≦ 120 μS / cm, particularly preferably ≦ 5 20 μS / cm.

The coating of the surface with at least one of the compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * may be incomplete. The molecules of this compound (s) need not be aligned as usual in self-organizing molecules perpendicular to the surface and parallel to each other - yet an unexpectedly high efficiency of this coating is guaranteed. The longer the surface is coated with the agent according to the invention, the higher Usually the proportion of the surface coated with this compound (s) and often their molecules are oriented perpendicular to the surface and parallel to each other.

The pretreatment agent may only be composed of or substantially composed of compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X with respect to the compounds which form a conversion layer and serve as lubricants * consist.

In the method according to the invention, a treatment agent with at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * can also be used for improving corrosion resistance or / and paint adhesion.

The pH of the aqueous solution containing at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * may range from 1 to 12, depending on whether is worked with the acids and / or their salts, wherein the best working range can also vary depending on the selected compound. In many cases, the pH can be in the range of 1.5 to 6, preferably in the range of 2 to 4. Aluminum and aluminum alloys have proved to be particularly suitable metallic substrates for these treatment agents.

The most diverse treatment agents, ie not just those containing at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, may preferably also contain at least one defoamer and / or a solubilizer in particular in an amount of in each case 0.0005 to 5 wt .-%, preferably in an amount of in each case optionally 0.005 to 4 wt .-%, in particular in an amount of in each case optionally 0.1 to 3 wt. %.

The treatment agent may in addition to water or a water-solvent mixture of at least one compound of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * and optionally consist of biocide, demulsifier, fragrance, emulsifier, defoamer, solubilizer, surfactant, pH adjuster, electrical conductivity adjuster and / or other excipients, and optionally a proportion of an organic solvent.

The respective treatment agent can be applied by dipping or rolling, but preferably by spraying, spraying or atomizing, on the containers inside or / and outside, possibly only over a part of the outer and / or inner surface, in particular over a time per container in Range of 0.5 to 120 seconds, preferably in the range of 1 to 80 s, more preferably in the range of 1.5 to 40 s, most preferably in the range of 2 to 20 s. However, especially for large containers, the coating can last longer than 2 minutes, also because alone z. B. the times of immersion and extension from the bath and draining are significantly longer. The coating times are also dependent on the chosen system technology.

Advantageously, at least one rinse is carried out after the application of the treatment agent, in particular with deionized water.

The treatment agent may be applied to a cleaned, rinsed or / and pickled surface or to a pre-annealed surface.

The surface of the container can be neutral, acid or alkaline cleaned prior to application of the agent for treatment or pretreatment, optionally rinsed, optionally pickled alkaline or acidic and optionally rinsed again, being used as solvent water or / and organic Solvent can be used. In addition, a thin activation layer can be applied before the conversion coating, for. B. based on titanium - phosphate.

Before the treatment agent is applied, a different treatment or pretreatment agent may be used in a separate treatment step be applied, in particular an agent containing ions selected from the group of Ti, Zr, Hf, Cu, Fe, Mn, Ni, Zn, PO ₄ and F. The ions are preferably contained in aqueous solution.

Preferably, the (pre) treated container after application of the agent for treatment or pretreatment, which also improves the sliding, rinsed, if necessary rinsed with a rinsing solution, optionally rinsed again and dried, with water as the solvent and / or organic solvents can be used.

The process according to the invention can also be modified so that after the application of the treatment agent, which also serves as a lubricant at the same time, it is no longer rinsed. This may in particular apply to beverage cans with compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, especially those with self-organizing molecules.

Method according to at least one of the preceding claims, characterized in that the treatment agent is applied in a belt plant, in particular in pretreatment and painting installations for containers such as e.g. Cans or bags.

The treatment agent according to the invention can be applied to the belt for a time in the range of 0.1 to 120 s, preferably for a time in the range of 0.5 to 20 s, while it is preferably applied at a slower application over a time in the range of 1 to 120 s is applied, in particular over a time in the range of 5 to 60 s. In many cases, however, an application over z. B. not more than 10 minutes.

In the method according to the invention, the treatment agent can be applied to metallic surfaces of containers which have a temperature in Range from 10 to 120 ° C. The treatment agent may have a temperature in the range of 10 to 95 ° C when applied to the container.

After drying, the layer of the treatment agent may have a thickness in the range from 0.01 to 3 μm, preferably in the range from 0.1 to 1 μm, or from one or a few molecule layers, in particular from 1 to 20 molecule layers, in the case of Compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, in which case a coating can be present in particular in the range from 0.1 to 30 nm.

Preferably, the treated or pretreated containers are dried at a temperature of the furnace of at least 180 ° C in series production, in particular at temperatures ≥ 200 ° C, more preferably at temperatures ≥ 220 ° C, most preferably at temperatures ≥ 250 ° C. Especially in the case of a belt standstill during pretreatment and painting, e.g. Cans can reach elevated temperatures in the drying area. The band stoppage can in some cases, e.g. last half an hour or even longer. Such temperatures are particularly advantageous at very high belt speed.

On the other hand, the treated or pretreated containers can be mass-dried at a temperature of at most 150 ° C, which is a great advantage for energy saving. Preferably, the drying temperature is in the range ≤ 120 ° C, more preferably at temperatures ≤ 100 ° C, most preferably at temperatures ≤ 80 ° C, especially at temperatures ≤ 50 ° C, in particular in the range of room temperature to 90 ° C. In this case, the excess pretreatment liquid can be blown off in particular in the form of drops on the container surfaces, wherein the drying temperature depends above all on the particular system and the selected treatment speed. In this case, in particular the envelope of hydrophilic to hydrophobic properties of the coated surfaces is used, of which the excess liquid can be particularly easily blow off and Therefore, let's set very low drying temperatures: This process can be made much cheaper due to significantly reduced drying costs.

The method according to the invention can furthermore be varied advantageously by pretreating or treating different types of containers for different purposes, in particular different types of cans, on the same system with similar settings and / or in similar baths. The different types of baths may have, for example, the same composition but different concentrations. Here, different container shapes, in particular different container sizes, e.g. for various filling media such as e.g. Beer, mineral water, juice or rice pudding are suitable, since different filling media are often filled in differently shaped containers.

After drying of the treatment agent, at least one lacquer - in particular an electrodeposition lacquer, powder lacquer, coil coating lacquer, wet lacquer, low-solvent high-solid lacquer or / and a water-diluted lacquer, at least one different organic coating such as e.g. a primer with contents of inorganic constituents, at least one adhesive layer, at least one film, at least one paper layer and / or at least one printing ink are applied.

Surprisingly, it has been found that by coating with compounds according to the invention, in particular of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, in addition to excellent sliding properties, it is also possible to achieve particularly hydrophobic surface properties which Removing liquid residues of the treatment agent from the film produced simplify the treatment layer.

For a good sliding of the (pre-) treated container together and on the transport device, it is necessary to allow a minimum value of sliding, possibly under the respective coating and drying conditions. As a measure of the sliding quality, a sliding test of cans is used in which three cans are stacked in pyramidal fashion and the base surface on which the lower two cans rest can be raised by an angle change. It determines the angle of the inclined plane, in which the uppermost can, which rests in the same direction on the two lower cans, begins to slide on the lower cans. As a sufficient slip value, an angle is called, compared to the acidic cleaned, rinsed in deionized water, (pre) treated and completely dried in a convection oven doses to only acidic cleaned, rinsed in deionized water and completely dried in a convection oven doses of the same type otherwise results in at least 5 ° lower slip angle. This condition makes it possible to subject cans of very different design and size to this test. For aluminum alloy cans having a length of 11.5 cm and 6.5 cm diameter and a weight of 10.4 g, the cleaned, not yet treated with the treating agent doses slip angle in the range of 34 to 38 °, in particular of about 35.5 °; while the cleaned and according to the invention (pre) treated doses show a slip angle in the range of about 17 to 26 ° and thus about 9.5 to 18.5 ° lower sliding angle than the only cleaned cans. The smaller the slip angles, the better the slipperiness and the better these results.

In addition, it has surprisingly been found that in particular in coatings with compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * at different speeds of the coating or in the event of interruptions of the band (before) treatment by a disturbance of the process sequence with belt stop, which can affect a few seconds to eg 60 minutes, a nearly identical layer thickness and a nearly similar quality of the film of the treatment layer is set. The containers stretching through the belt stop Stay longer in the treatment / pre-treatment zone, thereby not too coated with the treatment agent and therefore not provided with expensive, unnecessarily thick coatings. As a result, less treatment agent is lost in the process than in conventional processes.

On the other hand, in particular coatings with compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X * are particularly advantageous because the films produced herewith at very different temperatures in the range of room temperature to over 200 ° C. can be dried over a very short or long time, without causing a significant change in the coating quality. As a result, belt stops do not adversely affect the containers in the dryer.

As a result, the treatment or pretreatment of the containers in a conveyor system can be made much more robust than before and be driven with a significantly lower failure rate of incorrectly coated containers. A belt stop on a can coater, e.g. is driven at 5000 cans per minute, therefore, with only three-minute tape stop over the entire length of the belt system does not lead to a loss of e.g. 1000 to 20,000 cans.

Tests on cans which have been coated in a variety of conditions in the laboratory or in a belt installation did not result in any problems in the boiling test, in which a discoloration of the dome (bottom vault, e.g. For 20 minutes in water at 75 ° C, or in the retort test, which is carried out in an autoclave at e.g. 120 ° C is sterilized. There were also no problems printing or varnishing.

It is also possible, slightly different coatings, as for example for a variety of container shapes, container sizes, container volumes or filling media such as alcoholic, caffeine-containing drinks, soft drinks, dairy products, mineral water, fish, vegetables, fruit or soup canned be adjusted by varying various parameters such as concentration, temperature or / and how the proportion of a compound in a treatment mixture.

In addition, the treatment agents according to the invention are particularly environmentally friendly, because hereby the formation of a sludge can be largely or completely avoided because the solution or dispersion can be used either alone with water or with a solvent-poor water-solvent mixture, because they are free of heavy metals may because they are possibly even free or largely free of metals and because the compounds of the treatment means are usually particularly environmentally friendly. Compounds of the type XYZ, X * Y * Z * or / and X * Y * Z * Y * X *, which are in the wastewater, can easily be chemically bound and / or degraded.

Examples:

In the following, individual embodiments will be exemplified.

Examples 1 to 3: Treatment agents containing self-organizing molecules based on phosphonate

Aluminum alloy AIMg1 sheets were degreased alkaline, rinsed with city water, acid pickled, flushed with city water and then deionized water. Subsequently, a bath with an aqueous solution / dispersion was used as the treatment agent in the dipping process, containing:

Example 1:

• about 0.22 g / L of diphosphonic acids or their salts formed therefrom with a chain Y of about 8 to 14 C atoms,
• about 0.15 g / L of other organic compounds for improvement the solubility of the phosphonic compounds, including esters,
• in deionized water, adjusting to the desired pH on its own.

Example 2:

• about 0.12 g / L of diphosphonic acids or their salts formed therefrom with a chain Y of about 8 to 14 C atoms,
• about 0.1 g / L of other organic compounds to improve the solubility of the phosphonic compounds, i.a. esters,
• in deionized water and
• at least 50 mg / L sulfuric acid to adjust the pH to a range of about 2.5.

Example 3:

• about 0.07 g / L of diphosphonic acids or their salts formed therefrom with a chain Y of about 8 to 14 carbon atoms,
• about 0.05 g / L of other organic compounds to improve the solubility of the phosphonic compounds, i.a. esters,
• in deionized water, adjusting to the desired pH on its own.

The coating with the treatment agent was carried out at about 50 ° C for 10 seconds at a pH of about 3. It layer weights in the range of 1 to 10 mg / m ^{2 were} achieved.

The (pre-) treated sheets were dried without rinsing at 80 ° C for 10 minutes and optionally then coated with a varnish. Analogously, aluminum cans were coated. The results are shown in Table 1. Table 1: Results of slip tests and other specific can tests on phosphonate (pre-) treated as well as the corrosion and paint adhesion tests on (pre) treated and painted sheets - Examples 1 to 3: Sliding test on similarly coated cans: Slip angle Cook on cans Retort test on cans pretreated, unpainted a) 14.5 - 18.5 ° less than cleaned no start within 2h no tarnishing b) for standard can * 17 - 21 ° CASS salt spray test according to DIN 50021 over 1008 h ESS test over 4032 h Cross-cut test after 240 h KK add. Polyester powder coating Scratch 1 mm Scratch <1 mm Gt 0 add. Polyester coil coating paint Ritz and edge <1 mm Score <1 mm, edge 0 mm Gt 0 * The standard aluminum alloy can weighed 10.4 g, was 11.5 cm long and had a diameter of 6.5 cm.

The slip angles were determined at room temperature on a self-constructed laboratory apparatus as the average value of several measurements. The sliding test on standard doses pretreated with phosphonates according to the invention gave, after a temperature treatment at about 180 ° C., a sliding angle of only about 28 °. In comparison, the standard can, which after the separate conversion coating was treated with a standard lubricant based on ethoxylated compounds that did not give a second conversion coating, showed a slip angle of 21-22 ° on average after low temperature drying but after about 180 ° C. of heat treatment a sliding angle of on average even about 32 °. The purified and according to the invention (before) treated doses show here in particular by at least 5 °, preferably at least 8 °, more preferably at least 12 ° lower slip angle than the similar, but only purified doses.

In addition, filiform tests were performed to determine the infiltration of the paint on a scribe after 3024 hours. Here, values of infiltration of less than 1 mm each resulted.

The results on polyester-powder-coated chromium-free phosphonate-pretreated sheets corresponded to the results on high-quality chromated sheets of this aluminum alloy with regard to the anticorrosion and paint adhesion results. However, the results of the ESS tests have yielded somewhat better results than the chromating.

Claims (43)

1. Use of an agent, as a lubricant, for the treatment or pretreatment of containers made of aluminium, aluminium-containing alloys, magnesium-containing alloys, iron-containing materials such as steel, coated iron-containing materials such as galvanised steel, galvanised metallic materials or metallic materials coated with aluminium or aluminium alloys, tinplate, brass or bronze, in particular the treatment or pretreatment of bags, tubs, bottles, cans, canisters, casks or tubes, wherein the agent employed for this essentially comprises at least one compound of the type XYZ, X*Y*Z* and/or X*Y*Z*Y*X*,
   wherein Y is an unbranched alkyl group having 10 to 20 C atoms,
   wherein X is an OH, SH, NH₂, NHR', CN, CH=CH₂, OCN, CONHOH, COOR', acrylic acid amide, epoxy, CH₂=CR"-COO, COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO, (OH) (OR')PO₂, SiH₃ or an Si(OH)₃ group,
   wherein Z is an (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO or an (OH) (OR')PO₂ group,
   wherein R' is an alkyl group having 1 to 4 C atoms, wherein R" is an H atom or an alkyl group having 1 to 4 C atoms and wherein the groups X and Z are in each case bonded to the group Y in its terminal position, wherein Y* is an unbranched alkyl group having 10 to 20 C atoms,
   wherein X** is an OH, SH, NH₂, NHR', CN, CH=CH₂, OCN, CONHOH, COOR', acrylic acid amide, epoxy, CH₂=CR"-COO, COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO, (OH)(OR')PO₂, SiH₃, Si(OH)₃, >N-CH₂-PO(OH)₂ or an -N-[CH₂-PO(OH)₂]₂ group,
   wherein Z* is an (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO, (OH) (OR')PO₂, >N-CH₂-PO(OH)₂ or an -N- [CH₂-PO(OH)₂]₂ group wherein R' is an alkyl group having 1 to 4 C atoms and wherein R" is an H atom or an alkyl group having 1 to 4 C atoms.
2. Use according to claim 1, characterised in that a conversion coating of the first and/or second type is produced on the metallic substrate with the agent used for the pretreatment or treatment (= treatment agent).
3. Use according to claim 1 or 2, characterised in that the lubricant is formed first in the agent for the pretreatment and/or treatment or/and during the formation of the coating produced therefrom.
4. Use according to at least one of the preceding claims, characterised in that the treatment agent is an aqueous solution or an aqueous dispersion.
5. Use according to at least one of the preceding claims, characterised in that the treatment agent is free or largely free of fluoride.
6. Use according to at least one of the preceding claims, characterised in that the treatment agent is free or largely free of phosphate, calculated as PO₄.
7. Use according to at least one of the preceding claims, characterised in that the treatment agent is free or largely free of chromium.
8. Use according to at least one of the preceding claims, characterised in that the treatment agent is free or largely free of iron, manganese, nickel, cobalt, copper, other steel additives/improvers or/and zinc, and in particular is free or largely free of heavy metals of all types.
9. Use according to at least one of the preceding claims, characterised in that the treatment agent is free or largely free of ethoxylated compounds, and is preferably free or largely free of all types of surfactants.
10. Use according to at least one of the preceding claims, characterised in that silicon-containing alloys are treated or pretreated.
11. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment, which is optionally a lubricant, comprises at least one compound of the type XYZ, wherein X is a COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO or (OH)(OR')PO₂ group,
    wherein Y is an unbranched alkyl group R that contains 10 to 20 C atoms, of which at least 60 % of these C atoms are present as CH₂ groups,
    wherein Z is an (OH)₂PO, (OH)₂PO₂, (OH)(OR')PO or (OH)(OR')PO₂ group,
    wherein R' is an alkyl group having 1 to 4 C atoms and wherein R" is an H atom or an alkyl group having 1 to 4 C atoms.
12. Use according to at least one of claims 1 to 11, characterised in that the groups X* and Z* of the compound of the type X*Y*Z* or/and X*Y*Z*Y*X* are in each case bonded to the group Y* in its terminal position.
13. Use according to at least one of the preceding claims, characterised in that the compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X** is suitable for forming self-assembling molecules that can form a layer of the said self-assembling molecules on the metallic surface, in particular a monomolecular layer.
14. Use according to at least one of the preceding claims, characterised in that Y or Y* is a linear unbranched chain.
15. Use according to at least one of the preceding claims, characterised in that the more effective compounds of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* have a group Y or Y* that has an even number of C atoms.
16. Use according to at least one of the preceding claims, characterised in that at least one compound of the type XYZ, X*Y*Z* and/or X*Y*Z*Y*X* is present as a salt or/and acid in an aqueous solution.
17. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X*, in which Y or Y* is an unbranched alkyl group having 10 to 18 C atoms.
18. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X*, in which X or X* is an (OH)₂PO₂ or (OH) (OR')PO₂ group.
19. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises at least one of the following compounds of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* or/and at least one of the corresponding derivatives, in particular salts:

    1-phosphonic acid-12-mercaptododecane,

    1-phosphonic acid-12-(N-ethylamino)dodecane,

    1-phosphonic acid-12-dodecene,

    1,10-decanediphosphonic acid,

    1,12-dodecanediphosphonic acid,

    1,14-tetradecanediphosphonic acid,

    1-phosphoric acid-12-hydroxydodecane,

    1-phosphoric acid-12-(N-ethylamino)dodecane,

    1-phosphoric acid-12-dodecene,

    1-phosphoric acid-12-mercaptododecane,

    1,10-decanediphosphoric acid,

    1,12-dodecanediphosphoric acid,

    1,14-tetradecanediphosphoric acid,

    1-phosphoric acid-12-acryloyldodecane.
20. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment is contained together with at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* in an aqueous solution, wherein in particular 0.01 to 50 % of the water may be replaced by at least one organic solvent, such as e.g. an alcohol having 1 to 8 C atoms, by acetone, by dioxane or/and by tetrahydrofuran.
21. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* that is present in the region of the critical micelle concentration or below it, in particular in a concentration of 0.05 to 10 g/l.
22. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises at least one compound of the type XYZ, X*Y*Z* and/or X*Y*Z*Y*X* that is present as a salt in the solution.
23. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises, as regards the compounds that produce a conversion layer and serve as a lubricant, only compounds of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X*.
24. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment is, as regards the compounds that produce a conversion layer and serve as a lubricant, contained in a content of 0.01 to 15 g/l in water or in a water-solvent mixture.
25. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment comprises, in addition to water or a water-solvent mixture, at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* as well as optionally a biocide, demulsifier, fragrance, emulsifier, defoaming agent, solubility promoter, surfactant, agent for adjusting the pH value, agent for adjusting the electrical conductivity or/and other auxiliary substances and optionally an amount of at least one organic solvent.
26. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment also comprises a defoaming agent and/or a solubility promoter, in particular in an amount of in each case 0.0005 to 5 wt.%.
27. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment is applied internally or/and externally to the containers by dipping or rolling, preferably by sprinkling, spraying or atomisation, in particular over a time per container in the range from 0.1 to 120 seconds.
28. Use according to at least one of the preceding claims, characterised in that optionally at least one rinsing is carried out after the application of the agent for the treatment and/or pretreatment, which at the same time also is or comprises a lubricant.
29. Use according to at least one of the preceding claims, characterised in that the agent for the treatment and/or pretreatment is applied to a cleaned, rinsed or/and pickled surface or to a pre-annealed surface.
30. Use according to at least one of the preceding claims, characterised in that before the application of the agent for the treatment and/or pre-treatment, the surface of the container is cleaned to a neutral, acid or alkaline pH, is optionally rinsed, optionally pickled to an alkaline or acid pH and optionally rerinsed, in which connection water or/and an organic solvent may be employed as a solvent.
31. Use according to at least one of the preceding claims, characterised in that before the application of the agent for the treatment and/or pretreatment, another type of agent for the treatment and/or pretreatment is applied, in particular an agent that comprises ions from the group of Ti, Zr, Hf, Cu, Fe, Mn, Ni, Zn, PO₄ and F.
32. Use according to at least one of the preceding claims, characterised in that after the application of the agent for the treatment and/or pretreatment, the surface of the container is optionally rinsed, optionally post-rinsed with a post-rinsing solution, optionally rerinsed and dried, in which connection water or/and an organic solvent may be employed as a solvent.
33. Use according to at least one of claims 1 to 32, characterised in that after the application of the agent for the treatment and/or pretreatment, rinsing is no longer performed.
34. Use according to at least one of the preceding claims, characterised in that at least one compound of the type XYZ, X*Y*Z* or/and X*Y*Z*Y*X* is employed to improve the corrosion resistance or/and the lacquer adhesion.
35. Use according to at least one of the preceding claims, characterised in that the treatment agent is applied in a conveyor belt unit, preferably by sprinkling.
36. Use according to at least one of the preceding claims, characterised in that the treatment agent is applied for a time in the range from 0.1 to 120 seconds.
37. Use according to at least one of the preceding claims, characterised in that the treatment agent is applied to metallic surfaces of containers that have a temperature in the range from 10 to 100°C.
38. Use according to at least one of the preceding claims, characterised in that the treatment agent during application to the containers has a temperature in the range from 10 to 90°C.
39. Use according to at least one of the preceding claims, characterised in that the coating formed with the treatment agent has after drying a thickness of one or a few molecular layers.
40. Use according to at least one of the preceding claims, characterised in that the treated and/or pretreated containers are dried under mass production conditions at a temperature of at least 180°C.
41. Use according to at least one of the preceding claims, characterised in that the treated and/or pretreated containers are dried under mass production conditions at a temperature of at most 150°C.
42. Use according to at least one of the preceding claims, characterised in that different types of containers for various intended uses, in particular different types of cans, are pretreated or treated in the same unit with similar operational settings and/or in similar baths.
43. Use according to at least one of the preceding claims, characterised in that after drying of the agent for the treatment and/or pretreatment, there is applied at least one lacquer - in particular an electrodeposition lacquer, powder lacquer, coil coating lacquer, wet lacquer, low-solvent high-solids lacquer or a lacquer diluted with water - at least one other type of organic coating, at least one adhesive layer, at least one foil, at least one paper layer or/and at least one printing ink.