EP0283912A2 - Process for the formation of metal sheets in the presence of cooling and lubricating agents - Google Patents
Process for the formation of metal sheets in the presence of cooling and lubricating agents Download PDFInfo
- Publication number
- EP0283912A2 EP0283912A2 EP88104151A EP88104151A EP0283912A2 EP 0283912 A2 EP0283912 A2 EP 0283912A2 EP 88104151 A EP88104151 A EP 88104151A EP 88104151 A EP88104151 A EP 88104151A EP 0283912 A2 EP0283912 A2 EP 0283912A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- aqueous emulsion
- binder
- resin
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C10N2040/241—Manufacturing joint-less pipes
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- C10N2040/243—Cold working
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/244—Metal working of specific metals
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
Definitions
- a process is described for forming sheet metal, in particular iron and aluminum sheet, in the presence of a coolant and lubricant.
- an aqueous emulsion or solution of a paint film-forming binder or binder mixture is used as the coolant and lubricant, the film on the formed product from the aqueous emulsion or solution being cured or dried immediately after the forming process.
- the method has the advantage that the coolant and lubricant emulsion remaining on the metal surface after the forming process does not have to be washed off, but rather can be cured, for example by heating in the heat, to form a lacquer film.
- a lubricant is used for a low degree of deformation, and a coolant and lubricant for a high degree of deformation, which has the task of minimizing tool wear and, in the case of extreme forming such as deep drawing and stripping, dissipating the forming heat and cold welding prevent between material and tool. If the parts shaped in this way are then intended for use in a corrosive environment, the surface of the moldings must be freed of lubricant and then painted. The higher the adhesion to the paint, the more important it is to clean or pretreat the metal surface.
- a sheet metal strip is greased with about 1 g / m2 of coolant and lubricant emulsion or solution (K + S emulsion or solution) before punching out and drawing the cup.
- K + S emulsion or solution coolant and lubricant emulsion or solution
- the K + S dripping-wet can is cut to the correct height and cleaned inside and outside in a washing machine with water and dried as quickly as possible.
- the can runs upside down between two conveyor belts in different flow zones. In it, cleaning liquid, rinsing liquid, passivation liquid and rinsing liquid are sprayed in succession with a powerful jet.
- the further processing is then carried out with external painting and internal painting by roller or spray application.
- Coolant and lubricant emulsions based on mineral oils and polyglycols are known (DE-PS 29 10 496, EP-A-158 306, DE-OS 34 06 427).
- the K + S emulsion is removed by saponification at 40 ° C to 80 ° C (EP-A-154 950).
- the procedural complexity of the cleaning agent is extremely high. If traces of the cleaning agent remain on the metal surface, there will be problems with the properties of the coatings applied later. When painting with water-borne paints, pinholes and craters can occur if the metal surface is contaminated with mineral oils or drawing greases.
- the object and invention is to provide a method and a means by which the problematic cleaning treatment of metal substrates following the forming treatment is avoided and an immediate coating of the formed products obtained is made possible. This object is achieved by the method described in the patent claims and the means for carrying out this method, which form the subject of the invention.
- this object can be achieved by using lacquer binders in the form of aqueous emulsions and / or solutions as coolants or lubricants in the shaping of the metal substrates, acid functions being contained in these binders, for example (e.g. 2 to 250 mg KOH per g solid resin).
- the binders can then be cured directly to a coating.
- the present invention thus creates a coolant and lubricant system which can remain on the metal surface after the shaping work and cutting work and cures during drying either alone or after overcoating with, for example, a water-dilutable paint to form a protective film.
- An advantage of the method according to the invention is that the metal surface intended for sheet metal forming comes into contact only with those reagents which can be cured to form an effective protective lacquer.
- the saponification of the oil-water emulsion or polyglycol-water emulsion previously used as a coolant and lubricant, with subsequent cleaning and drying, is no longer necessary.
- the procedure according to the invention has a particularly favorable effect on the ironing treatment of a sheet metal substrate in the production of cans. This is always a new one Metal surface formed, which is protected against corrosion by the use of a binder emulsion according to the invention in the "Statu nascendi" and provided with the curable coating.
- the binders used in the aqueous emulsions according to the invention are preferably those with an acid number of up to 250, measured as mgKOH per g of binder (solid resin).
- the acid number is at least 2, so that a range of 2 to 250 results according to the invention.
- the acid number is preferably 2 to 150 or 3 to 100 and particularly preferably 5 to 75.
- K + S emulsion according to the invention has good corrosion protection properties, this system can be used at an earlier stage in sheet metal strip treatment than before.
- chrome passivation and / or DOS pre-greasing can be dispensed with.
- Suitable base binders are, for example, epoxy, acrylate, polyester and alkyd resins with acid functions.
- the acid functions such as carboxyl groups, phosphoric acid or sulfonic acid residues can be introduced in a manner known per se.
- Examples of usable epoxy resin phosphoric acid esters are described in DE-OS 27 57 733.
- polyesters modified with phenolic resin as described, for example, in DE-OS 26 38 464 and EP-A-62 786.
- Further examples of resins which can be used are those in DE-OS 27 21 822 and DE-OS 27 21 823 and graft polymers of epoxy resins described in EP-A-17 911.
- Combinations of different binders can also be used, for example combinations of epoxy resin-acrylic acid graft polymers with epoxy resin-phosphoric acid esters, as described in EP-A-144 872 and EP 174 628. Further examples are graft polymers on epoxy resin phosphoric acid esters, as are described, for example, in EP-A-122 603 or EP 164 589.
- binders that can be used are as follows:
- a fatty acid-free, acidic phosphoric acid ester with an acid number of 10 to 40 made from an epoxy group-containing polyglycidyl ether and / or polyglycidyl (meth) acrylate resin with more than 1.3 epoxy groups per molecule by reaction with 0.2 to 1.0 mol of 70 to 90% orthophosphoric acid per epoxy group at 110 to 130 ° C if necessary in the pressure vessel in the presence of some water.
- a mixture of 40 to 80% by weight of a fatty acid-free, acidic epoxy resin-phosphoric acid ester with a low acid number of 10 to 30 and 20 to 60% by weight of a phenolic resin-modified, carboxyl group-containing, oil-free polyester with a higher acid number of 35 to 70 is preferred .
- reaction products of different molecular weights from dihydroxy-diphenylpropane (bisphenol A) or dihydroxy-diphenylmethane (disphenol F) and epichlorohydrin and / or methylepichlorohydrin. Products with higher molecular weights can also be produced by other processes, for example by reacting low polyepoxides with bisphenol A.
- These polyglycidyl ethers have an epoxy equivalent of 180 to 5000, especially 2000 to 4000. They can be partially or completely hydrogenated or in Mixtures with different epoxy equivalent or with different structure can be used.
- Polyglycidyl ethers of phenolic novolak resins are also suitable, as a result of which the functionality can be increased from 2 to about 6 glycidyl groups per molecule.
- the functionality of the resins can also be reduced by reaction with monofunctional (alkyl) phenols or monocarboxylic acids, preferably ⁇ -branched monocarboxylic acids.
- Examples are reaction products of epichlorohydrin with polypropylene glycol or polybutylene glycol of different molecular weights.
- the epoxy resins can be obtained by reacting longer-chain dicarboxylic acids such as isophthalic acid, cyclohexanedicarboxylic acid, adipic acid or sebacic acid with long-chain polyalcohols such as 1,6-hexanediol, glycerol, monoanhydropentaerythritol, polytetrahydrofuranediol, polycaprolactonediol, polycaprolactam diol Polybutadiene diol and NCO-terminated reaction products made from polyalcohols and polyisocyanates or semi-blocked diisocyanates can be modified or produced in stages.
- Resins containing epoxy groups can also be poly (meth) acrylate resins which, in addition to (meth) acrylic acid esters with C1 to C15 alcohol residues and / or optionally substituted vinylaromatics, contain copolymerized epoxy-containing unsaturated monomers. Suitable for this are glycidyl ethers of (meth) acrylic acid and maleic and / or fumaric acid, glycidyl ethers of unsaturated alcohols such as vinyl alcohol, allyl alcohol and / or hydroxyalkyl (meth) acrylate. Glycidyl compounds of (meth) acrylamide, maleic and / or fumaric acid diamide or maleimide. The resins are produced by radical solution polymerization at temperatures from 60 to 160 ° C.
- a fatty acid-free, acidic epoxy resin carboxylic acid ester with an acid number of 30 to 50 is prepared by reacting an epoxy group-containing resin with more than 1.3 epoxy groups per molecule and an epoxy equivalent of 180 to 2500 with mono (alkyl) phenols and / or excess multinuclear phenols and subsequent reaction of the epoxy group-free reaction product thus obtained with cyclic carboxylic anhydrides.
- the epoxy equivalent of the compound used is preferably 400 to 2000.
- These basic binders are not modified with linear saturated or unsaturated fatty acids.
- These are epoxy resins as described above and which have been reacted with saturated or unsaturated aliphatic, cycloaliphatic and / or aromatic polycarboxylic acids and / or their anhydrides, such as adipic acid, sebacic acid, isophthalic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, trimellitic anhydride.
- the reaction can also be carried out with hydroxycarboxylic acids such as dimethylolpropionic acid or hydroxybenzoic acid. Resins whose ester groups are difficult to saponify are particularly suitable.
- a common method is the reaction of the epoxy groups with monocarboxylic acids that form difficult-to-saponify esters, or with (C1 to C15 alkyl) phenols.
- the reaction takes place in the melt or by azeotropic condensation at temperatures from 100 to 220 ° C., preferably 130 to 180 ° C., optionally with the addition of suitable basic catalysts, such as triphenylphosphine, tetramethylammonium chloride or suitable metal salts, such as chromium-III-ethylhexanoate complex .
- suitable basic catalysts such as triphenylphosphine, tetramethylammonium chloride or suitable metal salts, such as chromium-III-ethylhexanoate complex .
- suitable basic catalysts such as triphenylphosphine, tetramethylammonium chloride or suitable metal salts, such as chromium-III-ethylhexanoate complex .
- Saponification-stable esters are prepared by reaction with acrylic monocarboxylic acid, such as benzoic acid or tert-butylbenzoic acid, or with linear ⁇ -branched C2 to C20-alkane monocarboxylic acids, such as Versatic acid®.
- acrylic monocarboxylic acid such as benzoic acid or tert-butylbenzoic acid
- linear ⁇ -branched C2 to C20-alkane monocarboxylic acids such as Versatic acid®.
- a prerequisite for the increased saponification stability of the resin is that all epoxy groups have been converted, if possible.
- cyclic anhydrides are attached to the secondary hydroxyl groups at reaction temperatures from 100 to 160 ° C. to form a relatively stable acidic half-ester.
- cyclic anhydrides are preferably used succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride or tricarboxylic acid anhydrides, the carboxyl group of which is esterified with a linear or branched C2 to C20 monoalcohol.
- Resins of this type are described in DE-A-23 54 607 (US-A-3,862,914) or DE-C-27 47 818.
- the acid number of the resins is 25 to 100. In order to achieve good sterilization strength, it should be as low as possible, preferably below 40, particularly preferably below 35.
- the polyester resins used must have an average molecular weight Mn have at least 1500 and each contain 0.3 to 3, preferably 0.8 to 2 hydroxyl and carboxyl equivalents per 1000 g of polyester.
- the polyester unsaturated fatty acids are not produced from polyalcohols such as 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, trimethylolpropane, glycerol and / or pentaerythritol, and polycarboxylic acids such as adipic acid, isophthalic acid, cyclohexane-1,4-dicarboxylic acid or trimellitic anhydride contain.
- polyesters are used in the absence of acidic catalysts or polynuclear phenols, especially alkylphenols and with aldehydes at 60 to 160 ° C, especially 100 to 130 ° C, implemented.
- Preferred phenols are monoalkylphenols, such as p-tert-butylphenol, p-cumylphenol, nonylphenol, phenylphenol or bisphenol A (1.1-bis-4-hydroxy-phenyl-propane), which are incorporated in amounts of 0.5 to 50% by weight .
- Particularly favorable results with regard to the resistance properties of the baked films against aggressive solvents are achieved with partial or complete replacement of the phenols mentioned by phenolcarboxylic acids.
- Suitable for this are, for example, 4,4-bis- (4-hydroxyphenyl) pentanoic acid, glycolic acid derivatives of diphenols, such as 2- (4-hydroxyphenyl) -2- (carbethoxyphenyl) propane, or salicylic acid.
- formaldehyde is preferably added as an aldehyde in an amount of 0.5 to 3 moles per mole of phenolic hydroxyl group.
- condensation products can be prepared by reacting an isolated resol made from mono- and / or polynuclear phenols with carboxyl-containing polyesters at 80 to 240 ° C, which have an average molecular weight Mn from 300 to 1500 and an acid number from 50 to 150 mg KOH / g solid resin.
- the phenolic resin-modified polyester preferably contains an acid number of 30 to 110, particularly preferably 40 to 90.
- Carboxyl-containing acrylate resins with an acid number from 20 to 120 and a hydroxyl number from 0 to 200 can be used as non-yellowing resins.
- a resin with a low acid number a high hydroxyl number is to be used and vice versa.
- a soluble product can be produced with an acid number of 25 and a hydroxyl number of 150.
- Such resins are known in the art Technique preferably by radical solution polymerization at temperatures from 60 to 160 ° C from ⁇ , ⁇ -unsaturated mono- and dicarboxylic acids and their esters with linear or branched aliphatic and cycloaliphatic mono- and polyalcohols, the polyalcohols being only esterified with one hydroxyl group and the remaining hydroxyl groups remain as potential crosslinking sites.
- monomers containing carboxyl groups are acrylic acid, methacrylic acid, crotonic acid, maleic acid (anhydride) or fumaric acid, or maleic or fumaric acid monoesters.
- the (meth) acrylic acid esters and / or maleic acid and / or fumaric acid dialkyl esters include, for example, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isopropyl methacrylate, stearyl methacrylate, cyclohexyl acrylate, benzyl acrylate and / or corresponding crotonic acid.
- Unsaturated ethers such as ethoxyethyl methacrylate or tetrahydrofury acrylate can also be used.
- the copolymerizable monomers also include vinyl esters of ⁇ -branched C2 to C20 alkane carboxylic acids, such as the vinyl ester of Versatic acid®.
- the monomers with hydroxyl groups include allyl alcohol, monovinyl ethers of polyols, such as monovinyl ethers of ethylene glycol and butanediol, and hydroxyl-containing allyl ethers or esters, such as 2,3-dihydroxyallyl ether, trimethylolpropane monoallyl ether or 2,3-dihydroxypropanoic acid allyl ester.
- (Meth) acrylic acid hydroxyalkyl esters such as ⁇ -hydroxypropyl methacrylate, hydroxyethyl acrylate, butanediol 1,4-monoacrylate, 2,3-dihydroxypropyl methacrylate, polypropylene glycol monoacrylate or fumaric acid di-hydroxyalkyl ester, are particularly suitable.
- Corresponding monomers can also be prepared via (meth) acrylamides, such as hydroxyethyl acrylamide or 2-hydroxypropyl methacrylamide. Particularly elastic properties are obtained when using a reaction product of hydroxyalkyl (meth) acrylate with ⁇ -caprolactone.
- the binders are neutralized with the neutralizing agents individually or in a mixture and, if appropriate, diluted with deionized or distilled water in the presence of solvents.
- volatile amines and / or amino alcohols can also be used if they have the ability to react firmly into the film dressing by means of suitable substituents, such as hydroxyl groups.
- amines are diethylamine, triethylamine, n-butylamine, morpholine, N-methylmorpholine, aminoethanol, diisopropanolamine, 2-dimethylamino-2-methylpropanol, 2-amino-2-methyl-1-propanol, tris- (hydroxymethyl) aminomethane, methyldiethanolamine , Triethanolamine.
- the pH of the K + S emulsions is preferably between 7.0 and 9.0.
- DMAMP dimethylaminomethylpropanol
- Aldehyde condensation resins can be chemically incorporated into the binders for the K + S emulsions and / or admixed before or after the emulsion preparation. Will the Once the K + S emulsion has been overpainted again after forming, it is often practical to use the K + S emulsion without a crosslinking agent and then apply a lacquer with a crosslinking agent over it.
- aldehyde condensation resins can serve as thermal crosslinking agents for the acid-functional binders. They are added to the base binders in an amount of, for example, 2 to 30% by weight, in particular 10 to 30% by weight, based on the base binder. The weight ratio of parent binder to crosslinking agent is preferably about 80:20.
- Aldehyde condensation resins are understood as thermal crosslinking agents: amine and phenol-formaldehyde condensation resins as they correspond to the prior art, but also copolymers which can react via built-in reactive monomers. These crosslinking agents are generally dispersible in the binders according to the invention. To improve solubility, they can optionally contain an acid number of up to about 80 mg KOH per g solid resin.
- Amine-formaldehyde condensation resins are formed by the reaction of aldehydes with urea, N-alkylurea, dicyandiamide, various triazines, such as melamine, benzoguanamine and acetoguanamine or their mixtures.
- Aldehydes can be monofunctional, but also polyfunctional. Examples include formaldehyde and its polymerization products, such as paraformaldehyde, polyoxymethylene, trioxane, or aliphatic and cyclic aldehydes, such as glyoxal, acetaldehyde, acrolein, propionaldehyde, butyraldehyde and furfural.
- the alcohol, preferably methylol, of the aldehyde condensation products are partially or preferably completely etherified with alcohols.
- Preferred amine-formaldehyde resins are those whose main amount of methylol groups has been reacted with monoalcohols or mixtures thereof.
- Methanol, ethanol, propanol, butanol, heptanol, benzyl alcohol and other aromatic alcohols, cyclic alcohols, such as cyclohexanol, or monoethers of ethylene glycols, such as ethoxyethanol or butoxyethanol, are particularly preferred.
- the methylol group is first etherified with a lower alcohol and then the higher alcohol is introduced by transetherification.
- the preferred alcohols are lower aliphatic monoalcohols, such as methanol and / or butanol.
- Melamine resins which are reacted with 3 to 6 moles of formaldehyde and then completely etherified with methanol are particularly preferred.
- the resins are manufactured according to the state of the art and offered by many companies as sales products.
- carboxyl group-containing melamine resin types are formed which are unsaturated when using hydroxyalkyl (meth) acrylates or allyl alcohol.
- the preferred phenolic resins are reaction products of phenol or substituted phenols with various aldehydes in molar excess in the presence of alkaline catalysts (resol type).
- phenolic compounds are phenol, cresol, xylenol, resorcinol and substituted phenols such as p-tert-butylphenol, p-tert-amyl phenol, p-phenylphenol, isothymol, cardanol or polynuclear phenols such as dihydroxy-diphenyl-propane (bisphenol A) or dihydroxy-diphenylmethane (bisphenol F).
- Phenolic novolak resins are also used as the starting material, which are optionally defunctionalized with monocarboxylic acids, preferably ⁇ -branched monocarboxylic acids, monophenols, which are particularly substituted with C2 to C18 alkyl groups or also monoepoxides such as ⁇ -monoepoxyalkanes, monoglyceride ethers or monoglyceride esters.
- monocarboxylic acids preferably ⁇ -branched monocarboxylic acids
- monophenols which are particularly substituted with C2 to C18 alkyl groups or also monoepoxides such as ⁇ -monoepoxyalkanes, monoglyceride ethers or monoglyceride esters.
- Formaldehyde and its polymerization products such as paraformaldehyde, trioxymethylene, polyformaldehyde or also hexamethylenetetramine are used as aldehydes.
- Acetaldehyde, paraldehyde and metaldehyde, butyraldehyde or furfural are particularly suitable.
- the methylol groups are partially or preferably completely etherified with methanol, ethanol, propanol and / or butanol.
- Resins are preferred which are reacted per phenolic OH group with excess formaldehyde, ie about 1.1 to 2.5 mol of formaldehyde in an alkaline medium.
- Resins based on bisphenol A which are reacted with about four formaldehyde molecules and are completely etherified with butanol, are particularly preferred. Both water-insoluble and carboxyl-containing phenolic resins of different molecular weights can be used.
- Suitable phenol carboxylic acids for this are, for example, 4,4-bis (4-hydroxyphenyl) pentanoic acid, glycolic acid derivatives of bisphenols, such as 2- (4-hydroxyphenyl) -2 (carbethoxyphenyl) propane, or salicylic acid.
- glycolic acid derivatives of bisphenols such as 2- (4-hydroxyphenyl) -2 (carbethoxyphenyl) propane, or salicylic acid.
- very low molecular weight, optionally unsaturated, methylolphenol ethers can also be used, such as trimethylol phenol allyl ether (Methylonharze ®).
- Reactive copolymers which can crosslink with carboxyl groups or hydroxyl groups of the binders are produced by copolymerization of N-methylol ethers of the (meth) acrylamides or methacrylamidoglycolate methyl esters.
- N-methylol ethers can also be incorporated by polymer-analogous reaction of polymerized (meth) acrylamide with formaldehyde and monoalcohols.
- the resins are generally prepared by solution polymerization with a solids content of 60 to 90% by weight with the addition of free radical initiators.
- aqueous emulsions of water-dilutable binders can take on the function of lubricant and coolant emulsions in the processing of metal substrates, such as metal sheets.
- Aqueous emulsions are used which, when neutralized with amines, are not tacky and can therefore perform the lubricant and coolant functions. It has been shown that this function is achieved in particular with the acid numbers defined above. Without wanting to make a binding statement, it can be assumed that the part of the emulsions that gets between the tool and the material creates a hydrodynamic lubricating film that prevents the so-called cold welding.
- the binder emulsions can contain customary additives, for example ionic or non-ionic emulsifiers, defoamers, leveling additives, waxes, lubricants and other customary liquid additives.
- customary additives for example ionic or non-ionic emulsifiers, defoamers, leveling additives, waxes, lubricants and other customary liquid additives.
- the emulsions according to the invention have solids concentrations of 1 to 10% by weight. These concentrations can vary depending on the application. When applied to the metal substrate, for example the sheet, before the shaping treatment, there are preferably solid concentrations of 0.2 to 20% by weight. During the cutting, pressing or deep-drawing processes, for example in the cup press or the ironing press, for example Kon concentrations of 5 to 20 wt .-% may be preferred.
- the solids concentration in the emulsions also depends on the desired coating obtained by hardening after the shaping process. Such a coating can serve, for example, as a primer or as a final top coating.
- the method according to the invention can be applied to all metal substrates which are subjected to a shaping treatment in which metal surfaces are released, such as pressing, deep drawing, drawing, cutting and / or punching. It can be applied particularly favorably to the treatment of metal sheets.
- a shaping treatment in which metal surfaces are released, such as pressing, deep drawing, drawing, cutting and / or punching. It can be applied particularly favorably to the treatment of metal sheets.
- Any type of sheet metal is suitable, for example steel sheet, tin-plated sheet, galvanized sheet, black sheet or aluminum sheet.
- the method according to the invention is particularly suitable for the production of two-part cans, the can body being produced by cup drawing and ironing treatment and the can lid being punched out of sheet metal.
- the method can also be used particularly advantageously for the production of those can lids in which pouring openings are to be produced according to the sealing plate principle.
- the emulsions used according to the invention serve as lubricants or paints for the cut surfaces.
- Binders, crosslinking agents and amines which comply with the health regulations of the individual countries (eg FDA and BGA) are used in the manufacture of cans which are intended to contain food and beverages, such as beer.
- FDA and BGA health regulations of the individual countries
- the coating obtained can serve as a final coat.
- the lacquer should contain a crosslinking agent in order to achieve the necessary resistance to the contents. Under certain circumstances, the crosslinking agent can also react with the K + S coating if it originally did not contain any crosslinking agent.
- Epoxy resin phosphoric acid ester
- the cooling, lubricating and painting emulsion is made by mixing: 21.3% epoxy resin phosphoric acid ester 60% 3.7% carboxy-functional melamine resin of the HMM type (hexamethoxymethylmelamine) with an acid number of about 30 (mg KOH per g solid resin) 0.9% dimethylaminomethylpropanol (80% in water) 0.1% polysiloxane as leveling agent and stirring with a dissolver for 30 minutes at 60 ° C. The concentrated material is carefully diluted with 74% deionized water after thorough stirring and filtered.
- the emulsion has a solids content of 15% by weight and a pH of 9.0.
- the 15% emulsion is used for the bowl drawing, and for the ironing, it is diluted to a solids content of 4.5% by weight with deionized water.
- the can surface has a trouble-free, optically perfect, smooth lacquer film with a dry film thickness of 1.8 g / m2.
- the K + S emulsion can be sprayed on conventionally.
- 10% butoxyethanol, 1.1% silicone-modified wetting agent are added to the binder mixture instead of the leveling agent and diluted to 33% solids with deionized water.
- the cooling, lubricating and painting emulsion is made by mixing: 29.5% polyester, modified with phenolic resin (acid number 70 to 90 mg KOH, solids 80% in butoxyethanol) 1.0% dimethylaminomethylpropanol (80% in water) 1.6% silicone modified wetting agent while stirring with a dissolver for 5 minutes at 30 ° C. Then 68.1% deionized water is slowly added with vigorous stirring and filtered.
- the K + S emulsion has a solids content of 15% by weight and a pH of 9.8.
- the procedure is then analogous to EXAMPLE 1.
- the K + S emulsion from Example 3 can be electrophoretically deposited on the sheet at 25 ° C., 80 volts and 5 seconds in a dipping process and Example 1 further processed. This mainly increases the paint weight in the non-deep-drawn sectors of the can, i.e. in the floor area.
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Abstract
Description
Beschrieben wird ein Verfahren zur Umformung von Blechen, insbesondere Eisen- und Aluminiumblechen, in Anwesenheit eines Kühl- und Schmiermittels. Bei diesem Verfahren wird als Kühl- und Schmiermittel eine wäßrige Emulsion oder Lösung eines lackfilmbildenden Bindemittels oder Bindemittelgemisches verwendet, wobei der auf dem umgeformten Produkt befindliche Film aus der wäßrigen Emulsion oder Lösung unmittelbar anschließend an den Umformungsvorgang gehärtet oder getrocknet wird. Das Verfahren hat den Vorteil, daß die nach dem Umformungsprozeß auf der Metalloberfläche verbleibende Kühl- und Schmiermittelemulsion nicht abgewaschen werden muß, sondern beispielsweise durch Erwärmen in der Hitze zu einem Lackfilm ausgehärtet werden kann.A process is described for forming sheet metal, in particular iron and aluminum sheet, in the presence of a coolant and lubricant. In this process, an aqueous emulsion or solution of a paint film-forming binder or binder mixture is used as the coolant and lubricant, the film on the formed product from the aqueous emulsion or solution being cured or dried immediately after the forming process. The method has the advantage that the coolant and lubricant emulsion remaining on the metal surface after the forming process does not have to be washed off, but rather can be cured, for example by heating in the heat, to form a lacquer film.
Beim Herstellen von metallischen Formteilen wird bei geringem Umformungsgrad ein Schmiermittel, bei hohem Umformungsgrad ein Kühl- und Schmiermittel eingesetzt, welches die Aufgabe hat, den Verschleiß der Werkzeuge zu minimieren und im Falle einer extremen Umformung wie Tiefziehen und Abstrecken die Umformwärme abzuführen, sowie die Kaltverschweißung zwischen Werkstoff und Werkzeug zu verhindern. Sind die so geformten Teile anschließend für den Gebrauch in einer korrosiven Umgebung bestimmt, so muß die Oberfläche der Formlinge von Schmiermittel befreit und sodann lackiert werden. Je höher die Haftungsbeanspruchung an die Lackierung ist, desto wichtiger ist die Reinigung bzw. Vorbehandlung der Metalloberfläche.In the production of metallic molded parts, a lubricant is used for a low degree of deformation, and a coolant and lubricant for a high degree of deformation, which has the task of minimizing tool wear and, in the case of extreme forming such as deep drawing and stripping, dissipating the forming heat and cold welding prevent between material and tool. If the parts shaped in this way are then intended for use in a corrosive environment, the surface of the moldings must be freed of lubricant and then painted. The higher the adhesion to the paint, the more important it is to clean or pretreat the metal surface.
Die wohl intensivste Reinigung der Metalloberfläche ist bei der Herstellung von Dosen für den Getränke- und Lebensmittelbereich erforderlich, insbesondere bei der Herstellung von tiefgezogenen/abgestreckten zweiteiligen Dosen.Probably the most intensive cleaning of the metal surface is necessary in the manufacture of cans for the beverage and food sector, in particular in the manufacture of deep-drawn / ironed two-part cans.
Die heutige Technik verläuft beispielsweise so:
Ein Blechband wird vor dem Ausstanzen und Napfziehen mit etwa 1 g/m² Kühl- und Schmiermittelemulsion bzw. Lösung (K + S-Emulsion bzw. Lösung) eingefettet. Beim Abstrecken des Napfes zu einer Dose wird die K+S-Emulsion zwecks Kühlung der Werkzeuge und Dosen im Überschuß eingesetzt (∼10 l/min.).Today's technology works like this:
A sheet metal strip is greased with about 1 g / m² of coolant and lubricant emulsion or solution (K + S emulsion or solution) before punching out and drawing the cup. When the bowl is stretched into a can, the K + S emulsion is used to cool the tools and cans in excess (∼10 l / min.).
Die K+S tropfnasse Dose wird auf die richtige Höhe geschnitten und in einer Waschmaschine innen und außen wäßrig gereinigt und so schnell wie möglich getrocknet. Die Dose läuft dabei zwischen zwei Durchlaufbändern auf dem Kopf stehend in verschiedene Durchlaufzonen. Darin werden nacheinander mit einem kräftigen Strahl Reinigungsflüssigkeit, Spülflüssigkeit, Passivierungsflüssigkeit und Nachspülflüssigkeit versprüht. Die Weiterverarbeitung erfolgt danach mit Außenlackierung und Innenlackierung durch Walz- oder Spritzauftrag. Es sind Kühl- und Schmiermittelemulsionen auf Basis von Mineralöen sowie Polyglykolen bekannt (DE-PS 29 10 496, EP-A-158 306, DE-OS 34 06 427). Die K+S-Emulsion wird durch Verseifung bei 40°C bis 80°C (EP-A-154 950) entfernt. Die verfahrenstechnische Aufwand des Reinigungsmittels ist extrem hoch. Verbleiben Spuren des Reinigungsmittels auf der Metalloberfläche zurück, so treten Störungen bei den Eigenschaften der später aufgebrachten Lackierungen auf. Bei der Lackierung mit wasserverdünnbaren Lacken können Nadelstiche und Krater auftreten, wenn die Metalloberfläche mit Mineralölen oder Ziehfetten verunreinigt ist.The K + S dripping-wet can is cut to the correct height and cleaned inside and outside in a washing machine with water and dried as quickly as possible. The can runs upside down between two conveyor belts in different flow zones. In it, cleaning liquid, rinsing liquid, passivation liquid and rinsing liquid are sprayed in succession with a powerful jet. The further processing is then carried out with external painting and internal painting by roller or spray application. Coolant and lubricant emulsions based on mineral oils and polyglycols are known (DE-PS 29 10 496, EP-A-158 306, DE-OS 34 06 427). The K + S emulsion is removed by saponification at 40 ° C to 80 ° C (EP-A-154 950). The procedural complexity of the cleaning agent is extremely high. If traces of the cleaning agent remain on the metal surface, there will be problems with the properties of the coatings applied later. When painting with water-borne paints, pinholes and craters can occur if the metal surface is contaminated with mineral oils or drawing greases.
Aufgabe und Erfindung ist die Bereitstellung eines Verfahrens sowie eines Mittels, durch die die problematische Reinigungsbehandlung von Metallsubstraten im Anschluß an die Umformungsbehandlung vermieden und eine unmittelbare Beschichtung der erhaltenen umgeformten Produkte ermöglicht wird. Diese Aufgabe wird durch das in den Patentansprüchen beschriebene Verfahren sowie die Mittel zur Durchführung dieses Verfahrens gelöst, die den Gegenstand der Erfindung bilden.The object and invention is to provide a method and a means by which the problematic cleaning treatment of metal substrates following the forming treatment is avoided and an immediate coating of the formed products obtained is made possible. This object is achieved by the method described in the patent claims and the means for carrying out this method, which form the subject of the invention.
Überraschenderweise hat sich im Rahmen der Erfindung gezeigt, daß diese Aufgabe gelöst werden kann durch Verwendung von Lack-Bindemitteln in Form von wäßrigen Emulsionen und/oder Lösungen als Kühl- bzw. Schmiermittel bei der Umformung der Metallsubstrate, wobei beispielsweise in diesen Bindemitteln Säurefunktionen enthalten sind (z.B. 2 bis 250 mg KOH pro g Festharz). Die Bindemittel können anschließend direkt zu einem Überzug gehärtet werden.Surprisingly, it has been shown in the context of the invention that this object can be achieved by using lacquer binders in the form of aqueous emulsions and / or solutions as coolants or lubricants in the shaping of the metal substrates, acid functions being contained in these binders, for example (e.g. 2 to 250 mg KOH per g solid resin). The binders can then be cured directly to a coating.
Durch die vorliegende Erfindung wird somit ein Kühl- und Schmiermittelsystem geschaffen, welches nach der Umformarbeit und Schneidarbeit auf der Metalloberfläche verbleiben kann und während des Trocknens entweder allein oder nach Überlackieren mit einem zum Beispiel wasserverdünnbaren Lack gemeinsam zu einem Schutzfilm aushärtet.The present invention thus creates a coolant and lubricant system which can remain on the metal surface after the shaping work and cutting work and cures during drying either alone or after overcoating with, for example, a water-dilutable paint to form a protective film.
Vorteil des erfindungsgemäßen Verfahrens ist, daß die für die Blechumformung bestimmte Metalloberfläche ausschließlich mit solchen Reagenzien in Kontakt kommt, die zu einem effektiven Schutzlack ausgehärtet werden können. Die Verseifung der bisher als Kühl- und Schmiermittel verwendeten Öl-Wasser-Emulsion bzw. Polyglykol-Wasser-Emulsion mit anschließender Reinigung und Trocknung entfällt. Die erfindungsgemäße Verfahrensweise wirkt sich besonders günstig auf die Abstreckbehandlung eines Blechsubstrates bei der Herstellung von Dosen aus. Hierbei wird ständig eine neue Metalloberfläche ausgebildet, die durch den erfindungsgemäßen Einsatz einer Bindemittel-Emulsion bereits im "Statu nascendi" korrosionsbeschützt und mit dem aushärtbaren Überzug versehen wird.An advantage of the method according to the invention is that the metal surface intended for sheet metal forming comes into contact only with those reagents which can be cured to form an effective protective lacquer. The saponification of the oil-water emulsion or polyglycol-water emulsion previously used as a coolant and lubricant, with subsequent cleaning and drying, is no longer necessary. The procedure according to the invention has a particularly favorable effect on the ironing treatment of a sheet metal substrate in the production of cans. This is always a new one Metal surface formed, which is protected against corrosion by the use of a binder emulsion according to the invention in the "Statu nascendi" and provided with the curable coating.
Bei den in den erfindungsgemäßen wäßrigen Emulsionen eingesetzten Bindemitteln handelt es sich bevorzugt um solche mit einer Säurezahl bis zu 250, gemessen als mgKOH pro g Bindemittel (Festharz). Die Säurezahl beträgt mindestens 2, so daß sich erfindungsgemäß ein Bereich von 2 bis 250 ergibt. Bevorzugt liegt die Säurezahl bei 2 bis 150 oder 3 bis 100 und besonders bevorzugt bei 5 bis 75.The binders used in the aqueous emulsions according to the invention are preferably those with an acid number of up to 250, measured as mgKOH per g of binder (solid resin). The acid number is at least 2, so that a range of 2 to 250 results according to the invention. The acid number is preferably 2 to 150 or 3 to 100 and particularly preferably 5 to 75.
Für die Behandlung von Dosen, die für Nahrungsmittel oder Getränke bestimmt sind, werden besonders aminneutralisierte Epoxidharz-Phosphorsäureester, Acrylatharze und/oder Polyester mit einer Säurezahl von 2 bis 150 verwendet, gegebenenfalls kombiniert mit Melamin- und/oder Phenolharzen, deren eingebrannte Filme physiologisch unbedenklich und geschmacksmeutral sind. Weil die erfindungsgemäße K+S Emulsion gute Korrosionsschutzeigenschaften besitzt , kann dieses System bereits in einem früheren Stadium der Blechbandbehandlung eingesetzt werden als bisher. So kann zum Beispiel im Falle von Weißblech auf die Chrompassivierung und/oder DOS Vorfettung verzichtet werden.For the treatment of cans intended for food or beverages, amine-neutralized epoxy resin-phosphoric acid esters, acrylate resins and / or polyesters with an acid number of 2 to 150 are used, optionally combined with melamine and / or phenolic resins, the baked films of which are physiologically harmless and are neutral in taste. Because the K + S emulsion according to the invention has good corrosion protection properties, this system can be used at an earlier stage in sheet metal strip treatment than before. In the case of tinplate, for example, chrome passivation and / or DOS pre-greasing can be dispensed with.
Als Basis-Bindemittel sind beispielsweise Epoxid-, Acrylat-, Polyester- und Alkydharze mit Säurefunktionen geeignet. Die Säurefunktionen wie Carboxylgruppen, Phosphorsäure oder Sulfonsäurereste können in an sich bekannter Weise eingeführt werden. Beispiele für verwenbare Epoxidharz-Phosphorsäureester werden in der DE-OS 27 57 733 beschrieben. Geeignet sind auch mit Phenolharz modifizierte Polyester, wie sie beispielsweise in der DE-OS 26 38 464 und EP-A-62 786 beschrieben werden. Weitere Beispiele für verwenbare Harze sind die in der DE-OS 27 21 822, der DE-OS 27 21 823 und in der EP-A-17 911 beschriebenen Pfropfpolymerisate von Epoxidharzen.Suitable base binders are, for example, epoxy, acrylate, polyester and alkyd resins with acid functions. The acid functions such as carboxyl groups, phosphoric acid or sulfonic acid residues can be introduced in a manner known per se. Examples of usable epoxy resin phosphoric acid esters are described in DE-OS 27 57 733. Also suitable are polyesters modified with phenolic resin, as described, for example, in DE-OS 26 38 464 and EP-A-62 786. Further examples of resins which can be used are those in DE-OS 27 21 822 and DE-OS 27 21 823 and graft polymers of epoxy resins described in EP-A-17 911.
Es können auch Kombinationen verschiedener Bindemittel eingesetzt werden, beispielsweise Kombinationen von Epoxidharz-Acrylsäure-Pfropfpolymerisaten mit Epoxidharz-Phosphorsäureester, wie in EP-A-144 872 und der EP 174 628 beschrieben. Weitere Beispiele sind Pfropfpolymerisate auf Epoxidharz-Phosphorsäureester, wie sie beispielsweise in der EP-A-122 603 oder EP 164 589 beschrieben werden.Combinations of different binders can also be used, for example combinations of epoxy resin-acrylic acid graft polymers with epoxy resin-phosphoric acid esters, as described in EP-A-144 872 and EP 174 628. Further examples are graft polymers on epoxy resin phosphoric acid esters, as are described, for example, in EP-A-122 603 or EP 164 589.
Spezielle Beispiele für verwendbare Bindemittel sind im folgenden:
Specific examples of binders that can be used are as follows:
1. Ein fettsäurefreier, saurer Phosphorsäureester mit einer Säurezahl von 10 bis 40, hergestellt aus einem epoxidgruppenhaltigen Polyglycidylether und/oder Polyglycidyl(meth)acrylatharz mit mehr als 1.3 Epoxidgruppen pro Molekül durch Umsetzung mit 0.2 bis 1.0 Mol 70 bis 90%iger Orthophosphorsäure pro Epoxidgruppe bei 110 bis 130°C gegebenenfalls im Druckgefäß in Anwesenheit von etwas Wasser.1. A fatty acid-free, acidic phosphoric acid ester with an acid number of 10 to 40, made from an epoxy group-containing polyglycidyl ether and / or polyglycidyl (meth) acrylate resin with more than 1.3 epoxy groups per molecule by reaction with 0.2 to 1.0 mol of 70 to 90% orthophosphoric acid per epoxy group at 110 to 130 ° C if necessary in the pressure vessel in the presence of some water.
Es ist naturgemäß möglich, Kombinationen von zwei oder mehr der genannten Verbindungen einzusetzen. Dabei ist es bevorzugt, Verbindungen mit einer relativ niedrigen Säurezahl, beispielsweise 15 bis 35, im Gemisch einzusetzen mit Verbindungen mit einer höheren Säurezahl, beispielsweise 35 bis 100. Verbindungen mit sehr niedriger Säurezahl sind unter Umständen in Wasser nicht gut löslich. Durch Vermischen mit Verbindungen mit hoher Säurezahl wird jedoch eine ausreichende Mischbarkeit erzielt. Eine ausreichende Mischbarkeit mit Wasser bei Verbindungen mit niedriger Säurezahl von zum Beispiel 20 bis 40 kann man auch dadurch erzielen, daß man diesen Komponenten eine relativ hohe OH-Zahl, zum Bei spiel 100 bis 200 verleiht. Bevorzugt wird ein Gemisch aus 40 bis 80 Gew.-% eines fettsäurefreien, sauren Epoxidharz-Phosphorsäureesters mit einer niedrigen Säurezahl von 10 bis 30 und 20 bis 60 Gew.-% eines phenolharzmodifizierten, carboxylgruppenhaltigen, ölfreien Polyesters mit einer höheren Säurezahl von 35 bis 70.It is naturally possible to use combinations of two or more of the compounds mentioned. It is preferred to use compounds with a relatively low acid number, for example 15 to 35, in a mixture with compounds with a higher acid number, for example 35 to 100. Under certain circumstances, compounds with a very low acid number are not readily soluble in water. However, sufficient miscibility is achieved by mixing with compounds with a high acid number. Sufficient miscibility with water in the case of compounds with a low acid number of, for example, 20 to 40 can also be achieved by adding a relatively high OH number to these components game gives 100 to 200. A mixture of 40 to 80% by weight of a fatty acid-free, acidic epoxy resin-phosphoric acid ester with a low acid number of 10 to 30 and 20 to 60% by weight of a phenolic resin-modified, carboxyl group-containing, oil-free polyester with a higher acid number of 35 to 70 is preferred .
Unter Polyglycidylether im Rahmen dieser Erfindung werden vorzugsweise Harze der allgemeinen idealisierten Formel
Rʹ = -CmH2m+1 und/oder bevorzugt -H,
R⁴ = -SO₂-, -O-, bevorzugt -CR³₂-,
R² = -(CR¹₂)m-, bevorzugt -CH₂-,
R³ = Halogen oder Rʹ
n = 0 bis 15, bevorzugt 6 bis 13, und
m = 1 bis 8, bevorzugt 1 ist.Polyglycidyl ether in the context of this invention preferably includes resins of the general idealized formula
Rʹ = -C m H 2m + 1 and / or preferably -H,
R⁴ = -SO₂-, -O-, preferably -CR³₂-,
R² = - (CR¹₂) m -, preferably -CH₂-,
R³ = halogen or Rʹ
n = 0 to 15, preferably 6 to 13, and
m = 1 to 8, preferably 1.
Beispiele sind Reaktionsprodukte verschiedenen Molekulargewichts aus Dihydroxy-diphenylpropan (Bisphenol A) oder Dihydroxy-diphenylmethan (Disphenol F) und Epichlorhydrin und/oder Methylepichlorhydrin. Produkte mit höheren Molekulargewichten können auch nach anderen Verfahren hergestellt werden, zum Beispiel durch Umsetzung von niedrigen Polyepoxiden mit Bisphenol A. Diese Polyglycidylether haben ein Epoxy-Äquivalent von 180 bis 5000, besonders von 2000 bis 4000. Sie können teilweise oder vollständig hydriert sein oder in Gemischen mit unterschiedlichem Epoxy-Äquivalent oder mit unterschiedlicher Struktur eingesetzt werden. Geeignet sind auch Polyglycidylether von phenolischen Novolakharzen,wodurch die Funktionalität von 2 bis auf etwa 6 Glycidylgruppen pro Molekül gesteigert werden kann. Die Funktionalität der Harze kann auch durch Reaktion mit monofunktionellen (Alkyl)phenolen oder Monocarbonsäuren, bevorzugt α-verzweigte Monocarbonsäuren herabgesetzt werden. Zum Elastifizieren kann ein Teil des beschriebenen Polyglycidylethers durch aliphatische Polyglycidylether der Formel
Als epoxidgruppenhaltige Harze können auch Poly(meth)acrylatharze eingesetzt werden, die neben (Meth)acrylsäureestern mit C₁ bis C₁₅-Alkoholresten und/oder gegebenenfalls substituierten Vinylaromaten epoxidgruppenhaltige, ungesättigte Monomere einpolymerisiert enthalten. Hierfür geeignet sind Glycidylether der (Meth)acrylsäure sowie der Malein- und/oder Fumarsäure, Glycidylether von ungesättigten Alkoholen wie Vinylalkohol, Allylalkohol und/oder Hydroxyalkyl(meth)acrylat. Glycidylverbindungen des (Meth)acrylamids, des Malein- und/oder Fumarsäurediamids oder des Maleinimids. Die Harze werden durch radikalische Lösungspolymerisation bei Temperaturen von 60 bis 160°C hergestellt.
Resins containing epoxy groups can also be poly (meth) acrylate resins which, in addition to (meth) acrylic acid esters with C₁ to C₁₅ alcohol residues and / or optionally substituted vinylaromatics, contain copolymerized epoxy-containing unsaturated monomers. Suitable for this are glycidyl ethers of (meth) acrylic acid and maleic and / or fumaric acid, glycidyl ethers of unsaturated alcohols such as vinyl alcohol, allyl alcohol and / or hydroxyalkyl (meth) acrylate. Glycidyl compounds of (meth) acrylamide, maleic and / or fumaric acid diamide or maleimide. The resins are produced by radical solution polymerization at temperatures from 60 to 160 ° C.
2. Ein fettsäurefreier, saurer Epoxidharz-Carbonsäureester mit einer Säurezahl von 30 bis 50 wird hergestellt durch Umsetzung von einem epoxidgruppenhaltigen Harz mit mehr als 1.3 Epoxidgruppen pro Molekül und einem Epoxy-Äquivalent von 180 bis 2500 mit Mono(alkyl)phenolen und/oder überschüssigen mehrkernigen Phenolen und anschließende Reaktion des so erhaltenen epoxidgruppenfreien Reaktionsproduktes mit cyclischen Carbonsäureanhydriden. Das Epoxy-Äquivalent der eingesetzten Verbindung ist bevorzugt 400 bis 2000.2. A fatty acid-free, acidic epoxy resin carboxylic acid ester with an acid number of 30 to 50 is prepared by reacting an epoxy group-containing resin with more than 1.3 epoxy groups per molecule and an epoxy equivalent of 180 to 2500 with mono (alkyl) phenols and / or excess multinuclear phenols and subsequent reaction of the epoxy group-free reaction product thus obtained with cyclic carboxylic anhydrides. The epoxy equivalent of the compound used is preferably 400 to 2000.
Diese Basisbindemittel sind nicht mit linearen gesättigten oder ungesättigten Fettsäuren modifiziert. Es handelt sich um Epoxidharze wie sie vorstehend beschrieben wurden und die umgesetzt wurden mit gesättigten oder ungesättigten aliphatischen, cycloaliphatischen und/oder aromatischen Polycarbonsäuren und/oder ihren Anhydriden, wie Adipinsäure, Sebacinsäure, Isophthalsäure, Cyclohexandicarbonsäure, Tetrahydrophthalsäureanhydrid, Trimellithsäureanhydrid. Die Umsetzung kann auch mit Hydroxycarbonsäuren wie Dimethylolpropionsäure oder Hydroxybenzoesäure erfolgen. Besonders geeignet sind solche Harze, deren Estergruppen schwer verseifbar sind.These basic binders are not modified with linear saturated or unsaturated fatty acids. These are epoxy resins as described above and which have been reacted with saturated or unsaturated aliphatic, cycloaliphatic and / or aromatic polycarboxylic acids and / or their anhydrides, such as adipic acid, sebacic acid, isophthalic acid, cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, trimellitic anhydride. The reaction can also be carried out with hydroxycarboxylic acids such as dimethylolpropionic acid or hydroxybenzoic acid. Resins whose ester groups are difficult to saponify are particularly suitable.
Ein übliches Verfahren ist die Reaktion der Epoxidgruppen mit Monocarbonsäuren, die schwer verseifbare Ester bilden, oder mit (C₁ bis C₁₅-Alkyl)-Phenolen. Die Umsetzung erfolgt in der Schmelze oder durch azeotrope Kondensation bei Temperaturen von 100 bis 220°C, bevorzugt 130 bis 180°C, gegebenenfalls unter Zusatz von geeigneten basischen Katalysatoren, wie Triphenylphosphin, Tetramethylammoniumchlorid oder geeigneten Metallsalzen, wie Chrom-III-ethylhexanoat-Komplex. Beispiele für Phenole sind substituierte Monophenole, wie tert.-Butylphenol, und Bisphenol A, das im Überschuß eingesetzt die Polymerkette abbricht. Verseifungsstabilere Ester werden durch Reaktion mit Acrylmonocarbonsäure, wie Benzoesäure oder tert.-Butylbenzoesäure, oder mit linearen α-verzweigten C₂ bis C₂₀-Alkanmonocarbonsäuren, wie Versaticsäure®, hergestellt. Voraussetzung für die erhöhte Verseifungsstabilität des Harzes ist, daß möglichst alle Epoxidgruppen umgesetzt sind. Durch Verknüpfen von zwei Molekülen dieses Vorproduktes mit bevorzugt C₄ bis C₁₈-Alkandicarbonsäuren wird eine hydrolysestabilere Elastifizierung erreicht.A common method is the reaction of the epoxy groups with monocarboxylic acids that form difficult-to-saponify esters, or with (C₁ to C₁₅ alkyl) phenols. The reaction takes place in the melt or by azeotropic condensation at temperatures from 100 to 220 ° C., preferably 130 to 180 ° C., optionally with the addition of suitable basic catalysts, such as triphenylphosphine, tetramethylammonium chloride or suitable metal salts, such as chromium-III-ethylhexanoate complex . Examples of phenols are substituted monophenols, such as tert-butylphenol, and bisphenol A, which, when used in excess, breaks off the polymer chain. Saponification-stable esters are prepared by reaction with acrylic monocarboxylic acid, such as benzoic acid or tert-butylbenzoic acid, or with linear α-branched C₂ to C₂₀-alkane monocarboxylic acids, such as Versatic acid®. A prerequisite for the increased saponification stability of the resin is that all epoxy groups have been converted, if possible. By linking two molecules of this intermediate with preferably C₄ to C₁₈ alkanedicarboxylic acids, a hydrolysis-stable elastification is achieved.
In einem zweiten Reaktionsschritt werden cyclische Anhydride an die sekundären Hydroxylgruppen bei Reaktionstemperaturen von 100 bis 160°C unter Bildung eines relativ stabilen sauren Halbesters angelagert. Als cyclische Anhydride werden bevorzugt verwendet Bernsteinsäureanhydrid, Tetrahydrophthalsäureanhydrid, Trimellithsäureanhydrid oder Tricarbonsäureanhydride, deren Carboxylgruppe mit einem linearen oder verzweigten C₂ bis C₂₀-Monoalkohol verestert ist. Harze dieser Art werden in der DE-A-23 54 607 (US-A-3,862,914) oder DE-C-27 47 818 beschrieben. Die Säurezahl der Harze beträgt 25 bis 100. Sie sollte, um eine gute Sterilisationsfestigkeit zu erzielen, möglichst niedrig liegen, bevorzugt unter 40, besonders bevorzugt unter 35.
In a second reaction step, cyclic anhydrides are attached to the secondary hydroxyl groups at reaction temperatures from 100 to 160 ° C. to form a relatively stable acidic half-ester. As cyclic anhydrides are preferably used succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride or tricarboxylic acid anhydrides, the carboxyl group of which is esterified with a linear or branched C₂ to C₂₀ monoalcohol. Resins of this type are described in DE-A-23 54 607 (US-A-3,862,914) or DE-C-27 47 818. The acid number of the resins is 25 to 100. In order to achieve good sterilization strength, it should be as low as possible, preferably below 40, particularly preferably below 35.
3. Ein phenolharzmodifizierter carboxylgruppenhaltiger, ölfreier Polyester mit einer Säurezahl von 35 bis 110 und einer OH-Zahl von 15 bis 175, hergestellt aus Polyolen oder hydroxylgruppenhaltigen Polyestern oder Polyethern mit vorzugsweise 2 bis 6 OH-Gruppen pro Molekül mit höhermolekularen hydroxylgruppenhaltigen Phenolethern bei 60 bis 160°C.3. A phenol resin-modified, carboxyl-containing, oil-free polyester with an acid number of 35 to 110 and an OH number of 15 to 175, made from polyols or hydroxyl-containing polyesters or polyethers with preferably 2 to 6 OH groups per molecule with higher molecular weight hydroxyl-containing phenol ethers at 60 to 160 ° C.
Um optimale Eigenschaften zu erreichen, müssen die eingesetzten Polyesterharze ein mittleres Molekulargewicht
In order to achieve optimal properties, the polyester resins used must have an average molecular weight
4. Als nicht vergilbende Harze können carboxylgruppenhaltige Acrylatharze verwendet werden mit einer Säurezahl von 20 bis 120 und einer Hydroxylzahl von 0 bis 200. Bei Einsatz eines Harzes mit niedriger Säurezahl ist eine hohe Hydroxylzahl anzuwenden und umgekehrt. So kann beispielsweise mit einer Säurezahl von 25 und einer Hydroxylzahl von 150 ein lösliches Produkt hergestellt werden. Solche Harze werden nach dem Stand der Technik vorzugsweise durch radikalische Lösungspolymerisation bei Temperaturen von 60 bis 160°C aus α,β-ungesättigten Mono- und Dicarbonsäuren und deren Estern mit linearen oder verzweigten aliphatischen und cycloaliphatischen Mono- und Polyalkoholen hergestellt, wobei die Polyalkohole nur mit einer Hydroxylgruppe verestert sind und die restlichen Hydroxylgruppen als potentielle Vernetzungsstellen erhalten bleiben. Als carboxylgruppenhaltige Monomere dienen beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure(anhydrid) oder Fumarsäure, bzw. Maleinsäure- oder Fumarsäure-Monoester. Zu den (Meth)acrylsäureestern und/oder Maleinsäure- und/oder Fumarsäuredialkylestern zählen beispielsweise n-Butylacrylat, tert-Butylacrylat, 2-Ethyl-hexylacrylat, Methylmethacrylat, Isopropylmethacrylat, Stearyl-methacrylat, Cyclohexylacrylat, Benzylacrylat und/oder auch entsprechende Crotonsäureester. Es können auch ungesättigte Ether wie Ethoxyethylmethacrylat oder Tetrahydrofurylacrylat eingesetzt werden. Zu den einpolymerisierbaren Monomeren gehören auch Vinylester von α-verzweigten C₂ bis C₂₀-Alkancarbonsäuren, wie der Vinylester der Versaticsäure®. Zu den Monomeren mit Hydroxylgruppen gehören Allylalkohol, Monovinylether von Polyolen, wie Monovinylether des Ethylenglykols und Butandiols, sowie hydroxylgruppenhaltige Allylether oder -ester, wie 2.3-Dihydroxyallylether, Trimethylolpropanmonoallylether oder 2.3-Dihydroxypropansäure-allylester. Besonders geeignet sind (Meth)acrylsäure-hydroxyalkylester, wie β-Hydroxypropylmethacrylat, Hydroxyethylacrylat, Butandiol-1.4-monoacrylat, 2.3-Dihydroxypropylmethacrylat, Polypropylenglykolmonoacrylat oder auch Fumarsäure-di-hydroxyalkylester.4. Carboxyl-containing acrylate resins with an acid number from 20 to 120 and a hydroxyl number from 0 to 200 can be used as non-yellowing resins. When using a resin with a low acid number, a high hydroxyl number is to be used and vice versa. For example, a soluble product can be produced with an acid number of 25 and a hydroxyl number of 150. Such resins are known in the art Technique preferably by radical solution polymerization at temperatures from 60 to 160 ° C from α, β-unsaturated mono- and dicarboxylic acids and their esters with linear or branched aliphatic and cycloaliphatic mono- and polyalcohols, the polyalcohols being only esterified with one hydroxyl group and the remaining hydroxyl groups remain as potential crosslinking sites. Examples of monomers containing carboxyl groups are acrylic acid, methacrylic acid, crotonic acid, maleic acid (anhydride) or fumaric acid, or maleic or fumaric acid monoesters. The (meth) acrylic acid esters and / or maleic acid and / or fumaric acid dialkyl esters include, for example, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isopropyl methacrylate, stearyl methacrylate, cyclohexyl acrylate, benzyl acrylate and / or corresponding crotonic acid. Unsaturated ethers such as ethoxyethyl methacrylate or tetrahydrofury acrylate can also be used. The copolymerizable monomers also include vinyl esters of α-branched C₂ to C₂₀ alkane carboxylic acids, such as the vinyl ester of Versatic acid®. The monomers with hydroxyl groups include allyl alcohol, monovinyl ethers of polyols, such as monovinyl ethers of ethylene glycol and butanediol, and hydroxyl-containing allyl ethers or esters, such as 2,3-dihydroxyallyl ether, trimethylolpropane monoallyl ether or 2,3-dihydroxypropanoic acid allyl ester. (Meth) acrylic acid hydroxyalkyl esters, such as β-hydroxypropyl methacrylate, hydroxyethyl acrylate, butanediol 1,4-monoacrylate, 2,3-dihydroxypropyl methacrylate, polypropylene glycol monoacrylate or fumaric acid di-hydroxyalkyl ester, are particularly suitable.
Entsprechende Monomeren können auch über (Meth)acrylamide hergestellt werden, wie Hydroxyethylacrylamid oder 2-Hydroxypropylmethacrylamid. Besonders elastische Eigenschaften werden beim Einsatz eines Reaktionsproduktes von Hydroxyalkyl(meth)acrylat mit ε-Caprolacton erhalten.
Corresponding monomers can also be prepared via (meth) acrylamides, such as hydroxyethyl acrylamide or 2-hydroxypropyl methacrylamide. Particularly elastic properties are obtained when using a reaction product of hydroxyalkyl (meth) acrylate with ε-caprolactone.
Die Bindemittel werden mit den Neutralisationsmitteln einzeln oder im Gemisch neutralisiert und gegebenenfalls in Gegenwart von Lösemitteln mit entionisiertem oder destilliertem Wasser verdünnt. Als Neutralisationsmittel dienen beispielsweise leicht flüchtige Amine, wie Ammoniak, niedere primäre, sekundäre oder tertiäre Alkylamine, die beim Einbrennen leicht aus dem Film herausgehen. Es können jedoch auch schwerflüchtige Amine und/oder Aminoalkohole eingesetzt werden, wenn sie die Fähigkeit haben, durch geeignete Substituenten, wie Hydroxylgruppen, in den Filmverband fest einzureagieren. Beispiele für Amine sind Diethylamin, Triethylamin, n-Butylamin, Morpholin, N-Methylmorpholin, Aminoethanol, Diisopropanolamin, 2-Dimethylamino-2-methylpropanol, 2-Amino-2-methyl-1-propanol, Tris-(hydroxymethyl)aminomethan, Methyldiethanolamin, Triethanolamin. Der pH-Wert der K+S-Emulsionen liegt bevorzugt zwischen 7.0 und 9.0.The binders are neutralized with the neutralizing agents individually or in a mixture and, if appropriate, diluted with deionized or distilled water in the presence of solvents. Easily volatile amines, such as ammonia, lower primary, secondary or tertiary alkylamines, which easily leave the film when baked, serve as neutralizing agents. However, volatile amines and / or amino alcohols can also be used if they have the ability to react firmly into the film dressing by means of suitable substituents, such as hydroxyl groups. Examples of amines are diethylamine, triethylamine, n-butylamine, morpholine, N-methylmorpholine, aminoethanol, diisopropanolamine, 2-dimethylamino-2-methylpropanol, 2-amino-2-methyl-1-propanol, tris- (hydroxymethyl) aminomethane, methyldiethanolamine , Triethanolamine. The pH of the K + S emulsions is preferably between 7.0 and 9.0.
In Systemen , die für die Beschichtung von Metallgegenständen, wie Dosen, verwendet werden, die für die Aufnahme von Nahrungsmitteln vorgesehen sind, werden Amine verwendet, die den gesundheitlichen Vorschriften, wie zum Beispiel der FDA der USA und der BGA der Bundesrepublik Deutschland entsprechen; ein Beispiel hierfür ist Dimethylaminomethylpropanol (DMAMP).Systems used for the coating of metal objects, such as cans, which are intended for the intake of food, use amines which comply with the health regulations, such as the FDA of the USA and the BGA of the Federal Republic of Germany; an example of this is dimethylaminomethylpropanol (DMAMP).
In die Bindemittel für die K+S-Emulsionen können Aldehyd-Kondensationsharze chemisch eingebaut und/oder vor bzw. nach der Emulsionsherstellung zugemischt werden. Wird die K+S-Emulsion nach der Umformung noch einmal überlackiert, so ist es oft praktisch, die K+S-Emulsion ohne Vernetzungsmittel zu verwenden und anschließend einen Lack mit Vernetzungsmittel darüber aufzutragen.Aldehyde condensation resins can be chemically incorporated into the binders for the K + S emulsions and / or admixed before or after the emulsion preparation. Will the Once the K + S emulsion has been overpainted again after forming, it is often practical to use the K + S emulsion without a crosslinking agent and then apply a lacquer with a crosslinking agent over it.
Als thermische Vernetzungsmittel für die säurefunktionellen Bindemittel können beispielsweise ein oder mehrere Aldehyd-Kondensationsharze dienen. Sie werden den Basisbindemitteln in einer Menge von beispielsweise 2 bis 30 Gew.-%, insbesondere 10 bis 30 Gew.-%, bezogen auf das Basisbindemittel, zugesetzt. Bevorzugt liegt das Gewichtsverhältnis von Stammbindemittel zu Vernetzungsmittel bei etwa 80:20. Unter Aldehyd-Kondensationsharzen als thermische Vernetzungsmittel werden verstanden: Amin- und Phenol-Formaldehyd-Kondensationsharze, wie sie dem Stande der Technik entsprechen, aber auch Copolymerisate, die über eingebaute reaktive Monomere reagieren können. Diese Vernetzungsmittel sind im allgemeinen in den erfindungsgemäßen Bindemitteln dispergierbar. Zum Verbessern der Löslichkeit können sie gegebenenfalls eine Säurezahl bis zu etwa 80 mg KOH pro g Festharz enthalten.One or more aldehyde condensation resins, for example, can serve as thermal crosslinking agents for the acid-functional binders. They are added to the base binders in an amount of, for example, 2 to 30% by weight, in particular 10 to 30% by weight, based on the base binder. The weight ratio of parent binder to crosslinking agent is preferably about 80:20. Aldehyde condensation resins are understood as thermal crosslinking agents: amine and phenol-formaldehyde condensation resins as they correspond to the prior art, but also copolymers which can react via built-in reactive monomers. These crosslinking agents are generally dispersible in the binders according to the invention. To improve solubility, they can optionally contain an acid number of up to about 80 mg KOH per g solid resin.
Amin-Formaldehyd-Kondensationsharze entstehen durch Reaktion von Aldehyden mit Harnstoff, N-Alkyl-Harnstoff, Dicyandiamid, verschiedenen Triazinen, wie Melamin, Benzoguanamin und Acetoguanamin oder ihren Mischungen. Aldehyde können dabei monofunktionell, aber auch polyfunktionell sein. Beispiele hierfür sind Formaldehyd und seine Polymerisationsprodukte, wie Paraformaldehyd, Polyoxymethylen, Trioxan, oder aliphatische und cyclische Aldehyde, wie Glyoxal, Acetaldehyd, Acrolein, Propionaldehyd, Butyraldehyd und Furfural. Je nach Reaktionsbedingungen und Methylolierungsgrad werden Harze mit verschiedenen Molekulargewichten und unterschiedlicher Reaktivität erhalten. Die Kondensation mit Formaldehyd , Furfural, Paraformaldehyd, Polyoxymethylen oder Trioxan wird im allgemeinen unter Zusatz von schwachen Säuren oder Basen als Katalysator ausgeführt. Starke Säuren werden verwendet bei Kodensation mit Acrolein, Glyoxal, Acetaldehyd, Propionaldehyd oder Butyraldehyd. Hierbei wird das primäre Reaktionsprodukt neutralisiert, dann Aldehyd zugesetzt und unter Zusatz von schwachen Säuren oder Basen weiter reagiert. Der bevorzugte Aldehyd ist Formaldehyd. Die Alkohol-, bevorzugt Methylolpruppen, der Aldehyd-Kondensationsprodukte werden teilweise oder bevorzugt vollständig mit Alkoholen verethert. Es werden solche Amin-Formaldehydharze bevorzugt, deren Hauptmen e an Methylolgruppen mit Monoalkoholen oder deren Gemischen umgesetzt ist. Besonders bevorzugt werden Methanol, Ethanol, Propanol, Butanol, Heptanol, Benzylalkohol und andere aromatische Alkohole, cyclische Alkohole, wie Cyclohexanol, oder Monoether von Ethylenglykolen wie Ethoxyethanol oder Butoxyethanol. Sollen Alkohole mit mehr als 4 C-Atomen eingebaut werden, so wird die Methylolgruppe erst mit einem niedrigeren Alkohol verethert und anschließend der höhere Alkohol durch Umetherung eingeführt. Die bevorzugten Alkohole sind niedere aliphatische Monoalkohole, wie Methanol und/oder Butanol. Besonders bevorzugt werden Melaminharze, die mit 3 bis 6 Molen Formaldehyd umgesetzt und anschliessend vollständig mit Methanol verethert sind. Die Harze werden nach dem Stand der Technik hergestellt und von vielen Firmen als Verkaufsprodukte angeboten. Bei Veretherung mit Hydroxycarbonsäuren wie Hydroxybenzoesäure, Salicylsäure oder Dimethylolpropionsäure entstehen carboxylgruppenhaltige, bei Verwendung von Hydroxyalkyl(meth)acrylaten oder Allylalkohol ungesättigte Melaminharztypen.Amine-formaldehyde condensation resins are formed by the reaction of aldehydes with urea, N-alkylurea, dicyandiamide, various triazines, such as melamine, benzoguanamine and acetoguanamine or their mixtures. Aldehydes can be monofunctional, but also polyfunctional. Examples include formaldehyde and its polymerization products, such as paraformaldehyde, polyoxymethylene, trioxane, or aliphatic and cyclic aldehydes, such as glyoxal, acetaldehyde, acrolein, propionaldehyde, butyraldehyde and furfural. Depending on the reaction conditions and degree of methylolation, resins with different molecular weights and different reactivity are obtained. The condensation with formaldehyde, furfural, paraformaldehyde, polyoxymethylene or trioxane is generally added of weak acids or bases as a catalyst. Strong acids are used for the codification with acrolein, glyoxal, acetaldehyde, propionaldehyde or butyraldehyde. The primary reaction product is neutralized, then aldehyde is added and further reaction is carried out with the addition of weak acids or bases. The preferred aldehyde is formaldehyde. The alcohol, preferably methylol, of the aldehyde condensation products are partially or preferably completely etherified with alcohols. Preferred amine-formaldehyde resins are those whose main amount of methylol groups has been reacted with monoalcohols or mixtures thereof. Methanol, ethanol, propanol, butanol, heptanol, benzyl alcohol and other aromatic alcohols, cyclic alcohols, such as cyclohexanol, or monoethers of ethylene glycols, such as ethoxyethanol or butoxyethanol, are particularly preferred. If alcohols with more than 4 carbon atoms are to be incorporated, the methylol group is first etherified with a lower alcohol and then the higher alcohol is introduced by transetherification. The preferred alcohols are lower aliphatic monoalcohols, such as methanol and / or butanol. Melamine resins which are reacted with 3 to 6 moles of formaldehyde and then completely etherified with methanol are particularly preferred. The resins are manufactured according to the state of the art and offered by many companies as sales products. When etherified with hydroxycarboxylic acids such as hydroxybenzoic acid, salicylic acid or dimethylolpropionic acid, carboxyl group-containing melamine resin types are formed which are unsaturated when using hydroxyalkyl (meth) acrylates or allyl alcohol.
Die bevorzugten Phenolharze sind Reaktionsprodukte von Phenol oder substituierten Phenolen mit verschiedenen Aldehyden im molaren Überschuß in Gegenwart alkalischer Katalysatoren (Resol-Typ). Beispiele für phenolische Verbindungen sind Phenol, Kresol, Xylenol, Resorcin und substituierte Phenole wie p-tert.-Butylphenol, p-tert.-Amyl phenol, p-Phenyl-phenol, Isothymol, Cardanol oder auch mehrkernige Phenole wie Dihydroxy-diphenyl-propan (Bisphenol A) oder Dihydroxy-diphenylmethan (Bisphenol F). Als Ausgangsmaterial dienen auch phenolische Novolakharze, die gegebenenfalls mit Monocarbonsäuren, bevorzugt α-verzweigten Monocarbonsäuren, Monophenolen, die besonders mit C₂ bis C₁₈-Alkylgruppen substituiert sind oder auch Monoepoxiden wie α-Monoepoxidalkane, Monoglyceridether oder Monoglyceridester, defunktionalisiert werden. Als Aldehyde finden Verwendung Formaldehyd und seine Polymerisationsprodukte wie Paraformaldehyd, Trioxymethylen, Polyformaldehyd oder auch Hexamethylentetramin. Gut geeignet sind Acetaldehyd, Paraldehyd und Metaldehyd, sowie Butyraldehyd oder Furfural. Die Methylolgruppen werden teilweise oder bevorzugt vollständig verethert mit Methanol, Ethanol, Propanol und/oder Butanol. Bevorzugt werden Harze, die pro phenolischer OH-Gruppe mit überschüssigem Formaldehyd, d.h. etwa 1.1 bis 2.5 Mol Formaldehyd in alkalischem Medium umgesetzt werden. Harze auf Basis Bisphenol A, die mit etwa vier Formaldehyd-Molekülen umgesetzt und vollständig mit Butanol verethert sind, werden besonders bevorzugt. Es können sowohl wasserunlösliche, wie auch carboxylgruppenhaltige Phenolharze verschiedenen Molekulargewichtes verwendet werden. Hierfür geeignete Phenolcarbonsäuren sind beispielsweise 4.4-Bis-(4-hydroxyphenyl)-pentansäure, Glykolsäurederivate von Bisphenolen, wie das 2-(4-Hydroxyphenyl)-2(carbethoxyphenyl)-propan , oder Salicylsäure. Gegebenenfalls können auch sehr niedrigmolekulare, gegebenenfalls ungesättigte, Methylolphenolether eingesetzt werden wie Trimethylol-phenolallylether (Methylonharze ®).The preferred phenolic resins are reaction products of phenol or substituted phenols with various aldehydes in molar excess in the presence of alkaline catalysts (resol type). Examples of phenolic compounds are phenol, cresol, xylenol, resorcinol and substituted phenols such as p-tert-butylphenol, p-tert-amyl phenol, p-phenylphenol, isothymol, cardanol or polynuclear phenols such as dihydroxy-diphenyl-propane (bisphenol A) or dihydroxy-diphenylmethane (bisphenol F). Phenolic novolak resins are also used as the starting material, which are optionally defunctionalized with monocarboxylic acids, preferably α-branched monocarboxylic acids, monophenols, which are particularly substituted with C₂ to C₁₈ alkyl groups or also monoepoxides such as α-monoepoxyalkanes, monoglyceride ethers or monoglyceride esters. Formaldehyde and its polymerization products such as paraformaldehyde, trioxymethylene, polyformaldehyde or also hexamethylenetetramine are used as aldehydes. Acetaldehyde, paraldehyde and metaldehyde, butyraldehyde or furfural are particularly suitable. The methylol groups are partially or preferably completely etherified with methanol, ethanol, propanol and / or butanol. Resins are preferred which are reacted per phenolic OH group with excess formaldehyde, ie about 1.1 to 2.5 mol of formaldehyde in an alkaline medium. Resins based on bisphenol A, which are reacted with about four formaldehyde molecules and are completely etherified with butanol, are particularly preferred. Both water-insoluble and carboxyl-containing phenolic resins of different molecular weights can be used. Suitable phenol carboxylic acids for this are, for example, 4,4-bis (4-hydroxyphenyl) pentanoic acid, glycolic acid derivatives of bisphenols, such as 2- (4-hydroxyphenyl) -2 (carbethoxyphenyl) propane, or salicylic acid. If necessary, very low molecular weight, optionally unsaturated, methylolphenol ethers can also be used, such as trimethylol phenol allyl ether (Methylonharze ®).
Reaktive Mischpolymere, die mit Carboxylgruppen oder Hydroxylgruppen der Bindemittel vernetzen können, werden durch Copolymerisation von N-Methylolethern der (Meth)acrylamide oder Methacrylamidoglykolat-methylester hergestellt. Neben diesen reaktiven Monomeren werden noch (Meth)acrylsäure ester, Hydroxylalkyl(meth)acrylate oder gegebenenfalls substituierte Vinylaromaten mit einpolymerisiert. Der Einbau von N-Methylolethern kann auch durch polymeranaloge Umsetzung von einpolymerisiertem (Meth)acrylamid mit Formaldehyd und Monoalkoholen erfolgen. Die Harze werden im allgemeinen durch Lösungspolymerisation bei einem Festkörper von 60 bis 90 Gew.-% unter Zusatz von radikalischen Initiatoren hergestellt.Reactive copolymers which can crosslink with carboxyl groups or hydroxyl groups of the binders are produced by copolymerization of N-methylol ethers of the (meth) acrylamides or methacrylamidoglycolate methyl esters. In addition to these reactive monomers, there are also (meth) acrylic acid esters, hydroxylalkyl (meth) acrylates or optionally substituted vinyl aromatics. N-methylol ethers can also be incorporated by polymer-analogous reaction of polymerized (meth) acrylamide with formaldehyde and monoalcohols. The resins are generally prepared by solution polymerization with a solids content of 60 to 90% by weight with the addition of free radical initiators.
Im Rahmen der Erfindung hat es sich überraschenderweise gezeigt, daß wäßrige Emulsionen wasserverdünnbarer Bindemittel die Funktion von Schmier- und Kühlmittelemulsionen bei Umformungsverarbeitungen von Metallsubstraten, wie Blechen, übernehmen können. Man verwendet wäßrige Emulsionen, die im mit Aminen neutralisierten Zustand nicht klebrig sind und daher die Schmiermittelfunktion und Kühlmittelfunktion übernehmen können. Es hat sich gezeigt, daß diese Funktions insbesondere bei den vorstehend definierten Säurezahlen erzielt wird. Ohne eine bindende Aussage machen zu wollen, kann vermutet werden, daß der Teil der Emulsionen, der zwischen Werkzeug und Werkstoff gerät, einen hydrodynamischen Schmierfilm erzeugt, der die sogenannte Kaltverschweißung verhindert.Within the scope of the invention it has surprisingly been found that aqueous emulsions of water-dilutable binders can take on the function of lubricant and coolant emulsions in the processing of metal substrates, such as metal sheets. Aqueous emulsions are used which, when neutralized with amines, are not tacky and can therefore perform the lubricant and coolant functions. It has been shown that this function is achieved in particular with the acid numbers defined above. Without wanting to make a binding statement, it can be assumed that the part of the emulsions that gets between the tool and the material creates a hydrodynamic lubricating film that prevents the so-called cold welding.
Die Bindemittelemulsionen können übliche Zusätze, beispielsweise ionische oder nicht-ionische Emulgatoren, Entschäumer, Verlaufsadditive, Wachse, Gleitmittel und weitere übliche flüssige Additive enthalten.The binder emulsions can contain customary additives, for example ionic or non-ionic emulsifiers, defoamers, leveling additives, waxes, lubricants and other customary liquid additives.
Die erfindungsgemäßen Emulsionen weisen Festkörperkonzentrationen von 1 bis 10 Gew.-% auf. Diese Konzentrationen können je nach Anwendungszweck variieren. Beim Auftrag auf das Metallsubstrat, beispielsweise das Blech, vor der Umformungsbehandlung liegen vorzugsweise Festkörperkonzentrationen von 0.2 bis 20 Gew.-% vor. Während der Schneid-, Preß- oder Tiefziehvorgänge, beispielsweise in der Napfpresse oder der Abstreckpresse können beispielsweise Kon zentrationen von 5 bis 20 Gew.-% bevorzugt sein. Die Festkörperkonzentration in den Emulsionen richtet sich dabei auch nach dem gewünschten im Anschluß an den Umformungsvorgang durch Härten erhaltenen Überzug. Ein derartiger Überzug kann beispielsweise als Grundierung oder als endgültiger Decküberzug dienen.The emulsions according to the invention have solids concentrations of 1 to 10% by weight. These concentrations can vary depending on the application. When applied to the metal substrate, for example the sheet, before the shaping treatment, there are preferably solid concentrations of 0.2 to 20% by weight. During the cutting, pressing or deep-drawing processes, for example in the cup press or the ironing press, for example Kon concentrations of 5 to 20 wt .-% may be preferred. The solids concentration in the emulsions also depends on the desired coating obtained by hardening after the shaping process. Such a coating can serve, for example, as a primer or as a final top coating.
Das erfindungsgemäße Verfahren läßt sich auf sämtliche Metallsubstrate anwenden, die einer Umformungsbehandlung unterworfen werden, bei der Metalloberflächen freigesetzt werden, wie Pressen, Tiefziehen, Abstrecken, Schneiden und/oder Stanzen. Es läßt sich besonders günstig auf die Behandlung von Metallblechen anwenden. Geeignet ist jede Art von Metallblech, beispielsweise Stahlblech, verzinnte Bleche, verzinkte Bleche, Schwarzblech oder Aluminiumblech.The method according to the invention can be applied to all metal substrates which are subjected to a shaping treatment in which metal surfaces are released, such as pressing, deep drawing, drawing, cutting and / or punching. It can be applied particularly favorably to the treatment of metal sheets. Any type of sheet metal is suitable, for example steel sheet, tin-plated sheet, galvanized sheet, black sheet or aluminum sheet.
Besonders geeignet ist das erfindungsgemäße Verfahren zur Herstellung von zweiteiligen Dosen, wobei der Dosenkörper durch Napfziehen und Abstreckbehandlung hergestellt wird und der Dosendeckel aus Tafelblechen gestanzt wird. Besonders günstig läßt sich das Verfahren dabei auch auf die Herstellung solcher Dosendeckel anwenden, bei denen Ausgußöffnungen nach dem Siegellaschenprinzip hergestellt werden sollen. In diesem Falle dienen die erfindungsgemäß eingesetzten Emulsionen als Schmier- bzw. Lackiermittel der Schnittflächen.The method according to the invention is particularly suitable for the production of two-part cans, the can body being produced by cup drawing and ironing treatment and the can lid being punched out of sheet metal. The method can also be used particularly advantageously for the production of those can lids in which pouring openings are to be produced according to the sealing plate principle. In this case, the emulsions used according to the invention serve as lubricants or paints for the cut surfaces.
Bei der Herstellung von Dosen, die für die Aufnahme von Nahrungsmitteln und Getränken, wie beispielsweise Bier, dienen sollen, werden solche Bindemittel, Vernetzungsmittel und Amine eingesetzt, die den Gesundheitsvorschriften der einzelnen Länder ( z.B. FDA und BGA) entsprechen. Von besonderem Interesse ist das erfindungsgemäße Verfahren zur Herstellung von Dosen aus Aluminium für die Aufnahme von Nahrungsmitteln und Getränken. Der dabei erhaltene Überzug kann als Endlackierung dienen.Binders, crosslinking agents and amines which comply with the health regulations of the individual countries (eg FDA and BGA) are used in the manufacture of cans which are intended to contain food and beverages, such as beer. Of particular interest is the process according to the invention for the production of cans from aluminum for the intake of food and beverages. The coating obtained can serve as a final coat.
Bei kritischen Füllgütern, insbesondere für den Einsatz in Stahldosen, kann eine innenseitige Nachlackierung bzw. Überlackierung erforderlich sein. Es kann dabei mit den gleichen Bindemittelsystemen überlackiert werden. Der Lack sollte jedoch ein Vernetzungsmittel enthalten, um die notwendige Beständigkeit gegen die Füllgüter zu erreichen. Das Vernetzungsmittel kann unter Umständen auch mit dem K+S-Überzug reagieren, falls dieser ursprünglich kein Vernetzungsmittel enthielt.In the case of critical filling goods, especially for use in steel cans, it may be necessary to repaint or overpaint the inside. It can be overpainted with the same binder systems. However, the lacquer should contain a crosslinking agent in order to achieve the necessary resistance to the contents. Under certain circumstances, the crosslinking agent can also react with the K + S coating if it originally did not contain any crosslinking agent.
914 g Polyglycidylether auf Basis Bisphenol A mit einem Epoxid-Äquivalentgewicht von 2250 werden unter Erwärmen auf 125°C in 440 g Butoxyethanol gelöst. 19.2 g 85%ige Orthophosphorsäure werden mit 100 g Butoxyethanol verdünnt und innerhalb von 30 Minuten unter kräftigem Rühren bei 125°C zugegeben. Diese Temperatur wird 2 Stunden bis zur vollständigen Umsetzung der Orthophosphorsäure gehalten und dann auf 115°C abgekühlt. In das druckfest verschlossene System werden vorsichtig 10 g Wasser unterhalb der Oberfläche zugegeben, wobei der Druck vorübergehend leicht ansteigt. Anschließend wird zum Vervollständigen der Hydrolyse 2 Stunden bei 115°C gehalten. Das erhaltene Produkt wird mit Butoxyethanol auf einen Festkörpergehalt von 60 Gew.-% verdünnt.
Säuregehalt: ca. 20 ( mg KOH pro g Festharz).914 g of polyglycidyl ether based on bisphenol A with an epoxy equivalent weight of 2250 are dissolved in 440 g of butoxyethanol while heating to 125 ° C. 19.2 g of 85% orthophosphoric acid are diluted with 100 g of butoxyethanol and added over 30 minutes with vigorous stirring at 125 ° C. This temperature is held for 2 hours until the orthophosphoric acid has reacted completely and then cooled to 115.degree. 10 g of water below the surface are carefully added to the flameproof system, the pressure temporarily increasing slightly. The mixture is then held at 115 ° C. for 2 hours to complete the hydrolysis. The product obtained is diluted with butoxyethanol to a solids content of 60% by weight.
Acidity: approx. 20 (mg KOH per g solid resin).
Die Kühl-, Schmier- und Lackieremulsion wird hergestellt durch Mischen von:
21.3 % Epoxidharz-Phosphorsäureester 60%
3.7 % Carboxyfunktionelles Melaminharz vom HMM-Typ (Hexamethoxymethylmelamin) mit einer Säurezahl von etwa 30 (mg KOH pro g Festharz)
0.9 % Dimethylaminomethylpropanol (80% in Wasser)
0.1 % Polysiloxan als Verlaufsmittel
und Rühren mit Dissolver für 30 Minuten bei 60°C. Das konzentrierte Material wird mit 74% vollentsalztem Wasser nach gutem Rühren vorsichtig verdünnt und filtriert.The cooling, lubricating and painting emulsion is made by mixing:
21.3% epoxy resin phosphoric acid ester 60%
3.7% carboxy-functional melamine resin of the HMM type (hexamethoxymethylmelamine) with an acid number of about 30 (mg KOH per g solid resin)
0.9% dimethylaminomethylpropanol (80% in water)
0.1% polysiloxane as leveling agent
and stirring with a dissolver for 30 minutes at 60 ° C. The concentrated material is carefully diluted with 74% deionized water after thorough stirring and filtered.
Die Emulsion hat einen Festkörpergehalt von 15 Gew.-% und einen pH-Wert von 9.0.The emulsion has a solids content of 15% by weight and a pH of 9.0.
Für das Napfziehen wird die 15%ige Emulsion eingesetzt, für das Abstreckziehen wird auf ein Festkörper von 4.5 Gew.-% mit vollentsalztem Wasser verdünnt. Die so mit kommerziell erhältlichen Werkzeugen und dem erfindungsgemäßen Kühl- und Schmiermittel hergestellte Dose wird 2 Minuten auf dem Kopf stehend von überschüssigem K+S befreit und sodann 3 Minuten bei 220°C eingebrannt.The 15% emulsion is used for the bowl drawing, and for the ironing, it is diluted to a solids content of 4.5% by weight with deionized water. The can thus produced using commercially available tools and the coolant and lubricant according to the invention is freed of excess K + S standing upside down for 2 minutes and then baked at 220 ° C. for 3 minutes.
Die Dosenoberfläche hat einen störungsfreien, optisch einwandfreien, glatten Lackfilm mit einer Trockenfilmdicke von 1,8 g/m².The can surface has a trouble-free, optically perfect, smooth lacquer film with a dry film thickness of 1.8 g / m².
Um das Lackgewicht an der Innenseite der Dose zu erhöhen, kann mit der K+S-Emulsion konventionell nachgespritzt werden. Hierzu werden dem Bindemittelgemisch 10% Butoxyethanol, 1.1% silikonmodifiziertes Netzmittel anstelle des Verlaufsmittels zugegeben und mit vollentsalztem Wasser auf 33% Festkörper verdünnt.To increase the weight of the paint on the inside of the can, the K + S emulsion can be sprayed on conventionally. For this purpose, 10% butoxyethanol, 1.1% silicone-modified wetting agent are added to the binder mixture instead of the leveling agent and diluted to 33% solids with deionized water.
Die Kühl-, Schmier- und Lackieremulsion wird hergestellt durch Mischen von:
29.5 % Polyester, modifiziert mit Phenolharz (Säurezahl 70 bis 90 mg KOH, Festkörper 80% in Butoxyethanol)
1.0 % Dimethylaminomethylpropanol (80% in Wasser)
1.6 % silikonmodifiziertes Netzmittel
unter Rühren mit Dissolver für 5 Minuten bei 30°C. Danach werden langsam unter kräftigem Rühren 68.1% vollentsalztes Wasser zugegeben und filtriert.The cooling, lubricating and painting emulsion is made by mixing:
29.5% polyester, modified with phenolic resin (acid number 70 to 90 mg KOH, solids 80% in butoxyethanol)
1.0% dimethylaminomethylpropanol (80% in water)
1.6% silicone modified wetting agent
while stirring with a dissolver for 5 minutes at 30 ° C. Then 68.1% deionized water is slowly added with vigorous stirring and filtered.
Die K+S-Emulsion hat einen Festkörpergehalt von 15 Gew.-% und einen pH-Wert von 9.8.
Es wird dann analog BEISPIEL 1 weiterverfahren.The K + S emulsion has a solids content of 15% by weight and a pH of 9.8.
The procedure is then analogous to EXAMPLE 1.
Durch Mischung der K+S-Emulsionen der Beispiele 1 und 2 im Verhältnis 1:5 wird eine K+S-Emulsion erhalten mit gleichem Ergebnis.Mixing the K + S emulsions of Examples 1 and 2 in a ratio of 1: 5 gives a K + S emulsion with the same result.
Zwecks Erhöhung der Trockenfilmstärke auf der fertigen Dose kann die K+S-Emulsion aus Beispiel 3 bei 25°C, 80 Volt und 5 Sekunden in einem Tauchvorgang elektrophoretisch auf das Blech abgeschieden und die Beispiel 1 verfahrenstechnisch weiterverarbeitet werden. Dadurch wird hauptsächlich das Lackgewicht in den nicht tiefgezogenen Sektoren der Dose erhöht, also im Bodenbereich.In order to increase the dry film thickness on the finished can, the K + S emulsion from Example 3 can be electrophoretically deposited on the sheet at 25 ° C., 80 volts and 5 seconds in a dipping process and Example 1 further processed. This mainly increases the paint weight in the non-deep-drawn sectors of the can, i.e. in the floor area.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19873709270 DE3709270A1 (en) | 1987-03-20 | 1987-03-20 | METHOD FOR FORMING SHEETS IN THE PRESENCE OF A COOLANT AND LUBRICANT |
DE3709270 | 1987-03-20 |
Publications (2)
Publication Number | Publication Date |
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EP0283912A2 true EP0283912A2 (en) | 1988-09-28 |
EP0283912A3 EP0283912A3 (en) | 1989-03-08 |
Family
ID=6323645
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88104151A Withdrawn EP0283912A3 (en) | 1987-03-20 | 1988-03-16 | Process for the formation of metal sheets in the presence of cooling and lubricating agents |
Country Status (2)
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EP (1) | EP0283912A3 (en) |
DE (1) | DE3709270A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2113538A1 (en) * | 2008-04-30 | 2009-11-04 | Emil Frei GmbH & Co. KG | Anodal dipping varnish system |
EP2826136B1 (en) * | 2012-03-14 | 2019-12-25 | Kienle + Spiess GmbH | Stack of laminations and method for the production thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3375193A (en) * | 1966-07-05 | 1968-03-26 | Chrysler Corp | Metalworking lubricant |
US3974674A (en) * | 1973-01-12 | 1976-08-17 | Man-Gill Chemical Company | Composition for and method for preparation of metal for subsequent cold working |
EP0144872A2 (en) * | 1983-11-28 | 1985-06-19 | THE GLIDDEN COMPANY (formerly known as ATKEMIX EIGHT INC.) | Aqueous polymeric blends |
EP0164589A2 (en) * | 1984-05-14 | 1985-12-18 | DeSOTO, INC. | Epoxy-maleate-phosphate copolymers |
EP0174628A2 (en) * | 1984-09-10 | 1986-03-19 | Ppg Industries, Inc. | Blends of phosphates epoxy and acidic resins and the use thereof in coating compositions |
EP0175547A2 (en) * | 1984-09-19 | 1986-03-26 | Nihon Kousakuyu Co. Ltd. | Cold working lubricants for metallic conduits |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2807501C2 (en) * | 1978-02-22 | 1985-08-22 | R.W. Moll & Co, Chemische Fabrik, 4330 Mülheim | Process for reducing the wear of the cutting tool during mechanical processing, in particular during punching and cutting, of metallic materials |
NZ191183A (en) * | 1979-03-01 | 1981-05-01 | American Can Co | Deep drawing lubricant containing lubricant silicone resin and solvent |
-
1987
- 1987-03-20 DE DE19873709270 patent/DE3709270A1/en not_active Ceased
-
1988
- 1988-03-16 EP EP88104151A patent/EP0283912A3/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3375193A (en) * | 1966-07-05 | 1968-03-26 | Chrysler Corp | Metalworking lubricant |
US3974674A (en) * | 1973-01-12 | 1976-08-17 | Man-Gill Chemical Company | Composition for and method for preparation of metal for subsequent cold working |
EP0144872A2 (en) * | 1983-11-28 | 1985-06-19 | THE GLIDDEN COMPANY (formerly known as ATKEMIX EIGHT INC.) | Aqueous polymeric blends |
EP0164589A2 (en) * | 1984-05-14 | 1985-12-18 | DeSOTO, INC. | Epoxy-maleate-phosphate copolymers |
EP0174628A2 (en) * | 1984-09-10 | 1986-03-19 | Ppg Industries, Inc. | Blends of phosphates epoxy and acidic resins and the use thereof in coating compositions |
EP0175547A2 (en) * | 1984-09-19 | 1986-03-26 | Nihon Kousakuyu Co. Ltd. | Cold working lubricants for metallic conduits |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2113538A1 (en) * | 2008-04-30 | 2009-11-04 | Emil Frei GmbH & Co. KG | Anodal dipping varnish system |
EP2826136B1 (en) * | 2012-03-14 | 2019-12-25 | Kienle + Spiess GmbH | Stack of laminations and method for the production thereof |
Also Published As
Publication number | Publication date |
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EP0283912A3 (en) | 1989-03-08 |
DE3709270A1 (en) | 1988-09-29 |
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