EP0306801A2 - Use of an aquous suspension in air jet blasting - Google Patents

Use of an aquous suspension in air jet blasting Download PDF

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Publication number
EP0306801A2
EP0306801A2 EP88114106A EP88114106A EP0306801A2 EP 0306801 A2 EP0306801 A2 EP 0306801A2 EP 88114106 A EP88114106 A EP 88114106A EP 88114106 A EP88114106 A EP 88114106A EP 0306801 A2 EP0306801 A2 EP 0306801A2
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EP
European Patent Office
Prior art keywords
acid
diisocyanate
blasting
acrylate
groups
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EP88114106A
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German (de)
French (fr)
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EP0306801A3 (en
EP0306801B1 (en
Inventor
Jürgen Dr. Schwindt
Dieter Dipl.-Ing. Kuron
Manfred Schoenborn
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Bayer AG
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Bayer AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C11/00—Selection of abrasive materials or additives for abrasive blasts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C7/00—Equipment for feeding abrasive material; Controlling the flowability, constitution, or other physical characteristics of abrasive blasts

Definitions

  • the invention relates to the use of aqueous dispersions based on carboxyl group-containing binder, the carboxyl groups of which are at least partially neutralized, for compressed air blasting.
  • wet blasting This process, referred to as "wet blasting", has been improved by introducing the liquid in the form of a mist into the air flow so that the necessary amount of liquid could be reduced (“wet blasting", DE-OS 2 724 318).
  • the object of the invention was therefore to find additives for compressed air jets which should combine a good binding of the resulting dusts with good disposal options with a simultaneously highly effective provisional corrosion protection.
  • organic binders containing carboxyl groups the carboxyl groups of which have been at least partially neutralized with certain amines, solve the problem described.
  • the invention relates to the use of an aqueous dispersion based on organic binder, the carboxyl groups (before neutralization) correspond to an acid number of 40 to 70 and at least 60, preferably at least 70%, in particular at least 80% by a tertiary amine formula NR1R2R3 wherein R1, R2, R3 independently of one another C1-C6-alkyl, C6-C12-aryl, hydroxy-C2-C3-alkyl mean, are neutralized for compressed air blasting.
  • aqueous dispersions to be used in accordance with the invention allow, in addition to the primarily desired binding of the dust by the permanent dust binding, unproblematic disposal, offer surprisingly good temporary corrosion protection and are compatible with subsequent corrosion protection coatings.
  • Suitable organic binders for the dispersions to be used according to the invention are preferably (1) oil-free polyesters, (2) alkyd resins, (3) acrylate resins and (4) polyurethanes.
  • Oil-free polyesters (1) and alkyd resins (2) are understood to be polycondensates of the type produced from alcohols and carboxylic acids by polycondensation by known processes, of the type described, for example, in Römpp's Chemielexikon, Vol. 1, p. 202, Frankh'sche Verlagbuch Stuttgart, 1966 or described in DH Solomon, The Chemistry of Organic Filmformers, pp. 75-101, John Wiley & Sons Inc., New York, 1967.
  • alkyd resins are understood to mean fatty acid- or oil-modified polyesters.
  • Preferred acid components for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids, with 2 to 14, preferably 4 to 12 C- Atoms per molecule or their esterifiable derivatives (eg anhydrides or esters), eg phthalic anhydride, isophthalic acid, tetrahydro- and hexahydrophthalic anhydride, endomethylene tetrahydrophthalic acid, succinic acid, glutaric acid and trimellitic acidic acid, trimellitic acid, trimellitic acid. Phthalic anhydride is the most common acid component.
  • Preferred alcohols for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic and / or araliphatic alcohols with 1-15, preferably 2-6 C atoms, and 1-6, preferably 1-4, of non-aromatic C-bonded OH groups per molecule, e.g.
  • Glycols such as ethylene glycol, 1,2-propanediol and -1,3, 1,2-butanediol, 1,3 and -1,4, 1,3-2-ethylpropane, 1,3-2-ethylhexane, neopentyl glycol, 2,2-trimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1,4, 1,2- and 1,4-bis (hydroxymethyl) cyclohexane, adipic acid bis (ethylene glycol ester) ); Ether alcohols such as di- and triethylene glycol, dipropylene glycol; Dimethylolpropionic acid, oxalkylated bisphenols with 2 C2-C3-oxalkyl groups per molecule, perhydrogenated bisphenols; 1,2-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, trimethyl
  • Monocarboxylic acids preferred for the preparation of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 3-24 carbon atoms per molecule, such as benzoic acid, p-tert-butylbenzoic acid, tolylic acid, hexahydrobenzoic acid , Abietic acid and lactic acid.
  • the alkyd resins (2) or polyester (1) can also monohydric alcohols with 1 to 8 carbon atoms such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts up to 15 wt .-%, based on alkyd resin (2) or polyester (1), condensed in. It is also possible to replace up to 25% of the ester bonds with urethane bonds.
  • Polyisocyanates preferably diisocyanates, are suitable for introducing these urethane bonds.
  • Preferred diisocyanates for this purpose are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates, as described, for example, by W.
  • the length of the oil in the alkyd resins (2) is generally 5 to 50, preferably 20 to 40,% by weight.
  • the drying or non-drying fatty acids which generally contain 6 to 24 carbon atoms, can be used either as such or in the form of their glycerol esters (triglycerides).
  • Vegetable and animal oils, fats or fatty acids such as e.g. Coconut, peanut, castor, wood, olive, soybean, linseed, cottonseed oil, safflower oil or oil fatty acids, dehydrated castor oil or fatty acid, monounsaturated fatty acids, lard, tallow and tears, tall oil fatty acid and synthetic fatty acids, which can be made from natural unsaturated oils or fatty acids by conjugation or isomerization.
  • Preferred saturated fatty acids are e.g. Coconut oil fatty acids, 2-ethylhexanoic acid, isononanoic acid (3,4,4-trimethylhexanoic acid) as well as palmitic and stearic acid.
  • the number average molecular weight of the polyester (1) or alkyd resin (2) is 2000 - 10,000 (up to molecular weights of 5000 determined by vapor pressure osmometry in dioxane and acetone, whereby the lower value is considered correct if the values differ; for molecular weights over 5000 membrane osmometric determined in acetone).
  • Preferred acrylate resins (3) are copolymers with number-average molecular weights M n from 600 to 5000, where at least 2 of the following monomers can be selected as starting products: Acrylic acid and methacrylic acid; Acrylic acid and methacrylic acid alkyl esters with 1-18, preferably 1-8 C atoms in the alcohol component, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corresponding methacrylic acid esters; Acrylic and methacrylic acid cyclohexyl esters; Esters of acrylic acid and methacrylic acid with dihydric, saturated, aliphatic alcohols with 2-4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate
  • Starting materials for the production of component I are: (i) any organic polyisocyanates, preferably diisocyanates of the formula Q (NCO) 2 wherein Q represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms or an araliphatic hydrocarbon group having 7 to 15 carbon atoms.
  • Q represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms or an araliphatic hydrocarbon group having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ("isophorone diisocyanate"), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanate dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4- and 2,6-diisocyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-diphenylpropane - (2,2), p-xylylene diisocyanate and ⁇ , ⁇ ,
  • polyisocyanates known per se in polyurethane chemistry or else modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
  • polyisocyanates examples include tris (6-isocyanatohexyl) biuret, optionally in a mixture with its higher homologues, tris (6-isocyanatohexyl) isocyanurate, optionally in a mixture with its higher homologues, as described, for example, in DE-OS 28 39 133 is accessible by trimerizing hexamethylene diisocyanate, and further by trimerizing aliphatic and / or aromatic diisocyanates, such as.
  • "Isophorone diisocyanate" diisocyanatotoluene and hexamethylene diisocyanate available, isocyanurate group-containing polyisocyanates as they belong to the known prior art.
  • polyisocyanates are the polyisocyanates known per se, such as those obtained by reacting excess amounts of 2,4-diisocyanatotoluene or "isophorone diisocyanate" with simple polyhydric alcohols in the molecular weight range 62 to 300, in particular with trimethylolpropane, and subsequent distillatives Removal of the unreacted excess diisocyanate can be obtained.
  • polyether and / or polyester polyols of the type known per se in polyurethane chemistry preferably polyether and polyester diols with molecular weights of 300 to 2,000.
  • the polyether in question hydroxyl groups are z. B. by polyaddition of cyclic ethers such as preferably propylene oxide or butylene oxide, tetrahydrofuran, styrene oxide and / or epichlorohydrin with itself, for. B. in the presence of boron trifluoride, or by the addition of these compounds, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols and amines, for. B. water, ethylene glycol, propylene glycol (1,3) or - (1,2), bisphenol-A or aniline.
  • the hydroxyl-containing polyesters are z. B. Reaction products of preferably polyhydric, particularly preferably dihydric and optionally additionally trihydric alcohols with preferably polybasic, particularly preferably dibasic carboxylic acids. Instead of the free carboxylic acids, the corresponding carboxylic acid anhydrides or corresponding carboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
  • the alcohols to be used as the polyester construction component are e.g. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butanediol (1,4), hexanediol (1,6), neopentyl glycol, octanediol (1,8), 2-ethyl-hexanediol - (1,3), 1,4-bishydroxymethylcyclohexane, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerin and pentaerythritol.
  • B ethylene glycol, propylene glycol (1,2) and - (1,3)
  • butanediol (1,4) hexanediol (1,6), neopentyl glycol, octanediol (1,8), 2-ethyl-hexanediol - (1,3), 1,4-bishydroxymethylcycl
  • Carboxylic acids to be used as polyester components are e.g. B. adipic acid, succinic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, saturated and unsaturated fatty acids such as. B. stearic acid, oleic acid, ricinoleic acid, linoleic acid, ricinic acid, linolenic acid, elaostearic acid and from natural oils, such as. B. linseed oil, soybean oil, peanut oil, safflower oil, castor oil or wood oil, obtained fatty acid mixtures.
  • B. linseed oil soybean oil, peanut oil, safflower oil, castor oil or wood oil
  • low molecular weight polyols with molecular weights from 62 to 300.
  • polyols suitable according to the invention are ethanediol, propanediol- (1,2) and - (1,3), butanediol- (1,4) and - (1,3 ), Pentanediols, hexanediols, octanediols such as B. 2-ethylhexanediol- (1,3), trimethylolpropane, glycerol and pentaerythritol.
  • Representatives of the polyisocyanate and hydroxyl compounds to be used for the preparation of the binders (4) are, for. B. High Polymers, Vol. XVI, "Polyurethane Chemistry and Technology” by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pp. 32-42 and pp. 44-54 and Band II, 1964, pp. 5-6 and 198-199, as well as in the Kunststoff-Handbuch , Volume VII, edited by Vieweg-Höchtlen, Carl Hanser Verlag, Kunststoff, 1966, z. B. on pp. 54-71.
  • caprolactam oximes such as acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, CH-acidic compounds such as malonic acid esters, acetoacetic acid esters and acetylacetone, alcohols such as the simple monoalcohols with 1 to 4 carbon atoms, 2-ethylhexanol, ethylene glycol monoethyl ether and diethylene glycol and phenol monomethyl ether, phenols Xylenol and heterocyclic compounds such as triazoles, imidazolines, imidazoles and tetrahydropyridines.
  • oximes such as acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime
  • CH-acidic compounds such as malonic acid esters, acetoacetic acid esters and acetylacetone
  • alcohols such as the simple monoalcohols with 1 to 4 carbon atom
  • the blocking agents can be used alone or as mixtures.
  • Preferred blocking agents are ⁇ -caprolactam, butanone oxime and diethyl malonate.
  • polyurethane prepolymers (component I) suitable as polyisocyanates I can be prepared by customary methods be prepared in accordance with the prior art, for example by reacting polyisocyanates (i) with higher molecular weight polyols (ii) and low molecular weight polyols (iii), the molar ratio of the isocyanate groups of the polyisocyanate (i) to the hydroxyl groups of the polyols (ii) and ( iii) can be from 1.5 to 3.0.
  • the resulting polyurethane prepolymers with free isocyanate groups are then reversibly blocked with suitable monofunctional compounds (iv) to block the isocyanate groups.
  • the structure of polyurethane prepolymers (I) is described, for example, in German Pat. No. 1,644,813.
  • Component I comprises both reaction products of the polyisocyanates (I) and blocking agents (iv) and blocked polyisocyanate prepolymers based on the above-mentioned compounds (i) and (ii) and / or (iii).
  • the polymers containing H-atoms reactive with isocyanate groups are polyester or polyether polyols, polyhydric low molecular weight alcohols, polyamines, polyepoxypolyols, polyhydroxy acrylates or any mixtures of the products mentioned.
  • the polyester polyols and polyether polyols are compounds of the type known per se in polyurethane chemistry with number average molecular weights M n from 300 to 10,000, preferably 300 to 5,000. they are preferably formed from the structural components (ii) of the polyurethane prepolymers (I) described above.
  • the low molecular weight alcohols are polyalcohols of the known type with at least 2 hydroxyl groups per molecule and molecular weights between 62 and 300.
  • the polyamines in question are preferably di- or polyfunctional aliphatic or cycloaliphatic amines such as 1,2-diaminoethane, tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine, 1,4-diaminocyclohexane, 1,4-bis-aminomethyl-cyclohexane, "isophorone” diamine, 4,4'-diamino-dicyclohexylmethane, 2,2-bis (4-amino-cyclohexyl) propane or m- or p-xylylenediamine. 4,4'-Diamino-3,3'-dimethyl-dicyclohexylmethane is particularly preferred.
  • Components (I) and (II) are preferably used in amounts such that the molar ratio of blocked isocyanate groups to hydroxyl and / or amino groups is 0.5 to 2, preferably 0.8 to 1.5.
  • dimethylolpropionic acid is preferably used in the preparation of the polyurethanes (4).
  • the organic binders suitable for the aqueous dispersions to be used according to the invention are preferably selected so that they are at least temporarily sticky. In other words, you should Have the property of binding them to their surface under practical conditions when they collide with the abrasive used as "sand" and the particle blasted off the substrate.
  • a droplet of binder would be completely surrounded by dust particles.
  • Tertiary aines preferred for neutralizing the carboxyl groups of the organic binders include, for example, triethyl, tripropyl and tributylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, methyldipropanolamine, dimethylpropanolamine, tripropanolamine, N, N-dimethylaniline. Tripropylamine and dimethylethanolamine are particularly preferred amines.
  • the water content of the aqueous dispersions to be used according to the invention is 60 to 95, preferably 85 to 93,% by weight, based on the aqueous dispersion.
  • the dispersions to be used according to the invention are preferably introduced in countercurrent to the blasting material, so that an optimal distribution is ensured and they reach the surface to be blasted with the blasting material in the finest distribution.
  • Salt spray test Condensation test ⁇ 190 x 106 mm Salt dissolving station 330 x 165 mm.
  • 256 g of precondensate from 0.077 mol of soybean oil fatty acid, 0.43 mol of trimethylolpropane, 0.87 mol of 1,6-hexanediol, 0.5 mol of adipic acid and 0.5 mol of isophthalic acid are mixed with 21.7 g of dimethylolpropionic acid, 72 g of isophorone diisocyanate, 52.5 g N-methylpyrrolidone, 10.3 g dimethylethanolamine and water processed to an aqueous dispersion with a solids content of 7 wt .-%.
  • the resulting dust consisting of rust and old coating, was irreversibly bound together with the blasting slag.
  • the material could be swept up and removed with the broom without raising dust.
  • test panels were coated according to the following criteria:
  • the subsequent coatings were applied every 24 hours.
  • the paints were applied in such a way that the behavior of the coatings on one, two and three layers can be assessed.
  • the paints were processed by spray application.
  • Salt spray test As test criteria were Salt spray test, DIN 53 167 -Condensation test, DIN 50 017 / KK -Storage at the salt dissolving station fixed.
  • the salt dissolving station is part of the production plant for chlor-alkali electrolysis with a very aggressive atmosphere related to the corrosion of steel. The exposure of the plates in salty, humid air makes it possible to test the behavior of paints under harsher conditions in practice.
  • Cover coat B3 / 1-2 B1 / 1-2 B1 / 1-2 B3 / 1-2 Primer / 1. Deck coat. Cover coat Wd 3 Wd 4, B1 / 1-2 Wd 0 Wd 7 Surface rust in primer 5 4th 1 5 Condensation test after 42 days if Rust breakthroughs in the primer if Rust breakthroughs in the primer Primer if if if B1 / 1 Primer / 1. Cover coat if if if Ri 0.5 Primer / 1. Deck coat. Cover coat if if if B2 / 1 Salt dissolving station after 6 months (with cut according to DIN 53 167) Primer Wd 4 Wd 3 Wd 1 Wd 4 Primer / 1. Cover coat Wd 3 if if Wd 2 Primer / 1. Deck coat. Cover coat Wd 5 Wd 3 Wd 2 Wd 5 oB without finding
  • the table above shows that the invention leads to at least the same coating quality as the prior art (the advantage being the problem-free removal of rust, old coating and blasting agent).
  • a comparison of the last two columns in the table shows the corrosion protection surprisingly obtained by the binder used.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Sealing Material Composition (AREA)
  • Special Spraying Apparatus (AREA)
  • Toys (AREA)
  • Prevention Of Fouling (AREA)
  • Processing Of Solid Wastes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The addition of aqueous dispersions based on certain organic binders to the carrier air stream in air jet blasting leads to good binding of the resulting dusts, permits good disposal and provides simultaneously highly effective provisional corrosion protection.

Description

Die Erfindung betrifft die Verwendung von wäßrigen Dis­persionen auf Basis von Carboxlgruppen-haltigem Binde­mittel, dessen Carboxylgruppen mindestens teilweise neu­tralisiert sind, für das Druckluftstrahlen.The invention relates to the use of aqueous dispersions based on carboxyl group-containing binder, the carboxyl groups of which are at least partially neutralized, for compressed air blasting.

Beim Bautenschutz ist es regelmäßig notwendig, vor Auf­bringen eines Überzugs das Substrat - meist Stahl - von Rost oder den Resten eines alten Überzugs zu befreien. Eine bewährte Methode hierfür ist das als "Sandstrahlen" bekannte Druckluftstrahlen. Wegen der dabei auftre­tenden Staubentwicklung, die insbesondere aufgrund der Zusammensetzung der alten Überzüge (man denke bei­spielsweise an Mennige oder Zinkchromat) physiologisch nicht immer unbedenklich ist, hat man schon frühzeitig daran gedacht, in den das Strahlmittel enthaltenden Tragluftstrom eine Flüssigkeit einzubringen, die zu­sammen mit diesem gegen die zu behandelnde Oberfläche geblasen wird und so die Stäube mindestens temporär bindet (US-PS 2 405 854, 2 440 643).In building protection, it is regularly necessary to remove rust or the remains of an old coating from the substrate - usually steel - before applying a coating. A proven method for this is the compressed air blasting known as "sandblasting". Because of the dust development that occurs, which is not always physiologically harmless, particularly due to the composition of the old coatings (think, for example, red lead or zinc chromate), it was considered early on to introduce a liquid into the air stream containing the blasting agent, which together with this is blown against the surface to be treated and thus binds the dusts at least temporarily (US Pat. No. 2,405,854, 2,440,643).

Dieses als "Naßstrahlen" bezeichnete Verfahren hat man dadurch verbessert, daß die Flüssigkeit in Form eines Nebels in den Tragluftstrom eingebracht wird, so daß die notwendige Flüssigkeitsmenge reduziert werden konnte ("Feuchtstrahlen", DE-OS 2 724 318).This process, referred to as "wet blasting", has been improved by introducing the liquid in the form of a mist into the air flow so that the necessary amount of liquid could be reduced ("wet blasting", DE-OS 2 724 318).

Eine Weiterentwickung dieses Verfahrens besteht darin, daß man die Flüssigkeit als Schaum in den Tragluftstrom einbringt und damit die wirksame Oberfläche der einzu­bringenden Flüssigkeit stark vergrößert (DE-OS 3 415 174).A further development of this method is that the liquid is introduced as foam into the air flow and thus the effective surface of the liquid to be introduced is greatly increased (DE-OS 3 415 174).

Bei den geschilderten Verfahren hat man zum Teil auch bereits daran gedacht, Korrosionsschutzmittel, wie z.B. Zink oder Blei in Form von Metallstaub oder von che­mischen Verbindungen, in den Tragluftstrom einzubringen. Es hat jedoch bislang eine Methode gefehlt, die sämt­lichen Wünschen Rechnung tragen konnte.In the processes described, some have already considered corrosion protection agents such as Zinc or lead in the form of metal dust or chemical compounds to be introduced into the air flow. So far, however, there has been a lack of a method that could take all of the wishes into account.

Aufgabe der Erfindung war deshalb das Auffinden von Zusätzen zum Druckluftstrahlen, die eine gute Bindung der anfallenden Stäube bei guter Entsorgungsmöglichkeit mit einem gleichzeitig hochwirksamen vorläufigen Kor­rosionsschutz verbinden sollten.The object of the invention was therefore to find additives for compressed air jets which should combine a good binding of the resulting dusts with good disposal options with a simultaneously highly effective provisional corrosion protection.

Überraschenderweise wurde gefunden, daß Carboxylgruppen­haltige organische Bindemittel, deren Carboxylgruppen mindestens teilweise mit bestimmten Aminen neutralisiert worden sind, das geschilderte Problem lösen.Surprisingly, it has been found that organic binders containing carboxyl groups, the carboxyl groups of which have been at least partially neutralized with certain amines, solve the problem described.

Gegenstand der Erfindung ist die Verwendung einer wäßrigen Dispersion auf Basis von organischem Binde­mittel, dessen Carboxylgruppen (vor der Neutralisation) einer Säurezahl von 40 bis 70 entsprechen und zu min­destens 60, vorzugsweise zu mindestens 70 %, insbe­sondere zu mindestens 80 % durch ein tertiäres Amin der Formel

NR¹R²R³

worin
R¹, R², R³ unabhängig voneinander C₁-C₆-Alkyl, C₆-C₁₂-Aryl, Hydroxy-C₂-C₃-alkyl
bedeuten,
neutralisiert sind,
für das Druckluftstrahlen.The invention relates to the use of an aqueous dispersion based on organic binder, the carboxyl groups (before neutralization) correspond to an acid number of 40 to 70 and at least 60, preferably at least 70%, in particular at least 80% by a tertiary amine formula

NR¹R²R³

wherein
R¹, R², R³ independently of one another C₁-C₆-alkyl, C₆-C₁₂-aryl, hydroxy-C₂-C₃-alkyl
mean,
are neutralized
for compressed air blasting.

Die erfindungsgemäß zu verwenden wäßrigen Disper­sionen gestatten neben der in erster Linie erwünschten Bindung des Staubes durch die andauernde Staubbindung eine unproblematische Entsorgung, bieten einen über­raschend guten temporären Korrsionsschutz und sind mit nachfolgenden Korrosionsschutzbeschichtungen verträg­lich.The aqueous dispersions to be used in accordance with the invention allow, in addition to the primarily desired binding of the dust by the permanent dust binding, unproblematic disposal, offer surprisingly good temporary corrosion protection and are compatible with subsequent corrosion protection coatings.

Als organisches Bindemittel für die erfindungsgemäß zu verwendenden Dispersionen eignen sich vorzugsweise (1) ölfreie Polyester, (2) Alkydharze, (3) Acrylatharze und (4) Polyurethane.Suitable organic binders for the dispersions to be used according to the invention are preferably (1) oil-free polyesters, (2) alkyd resins, (3) acrylate resins and (4) polyurethanes.

Unter ölfreien Polyestern (1) und unter Alkydharzen (2) versteht man durch Polykondensation nach bekannten Verfahren aus Alkoholen und Carbonsäuren hergestellte Polykondensate der Art, wie sie z.B. in Römpp's Chemie­lexikon, Bd. 1, S. 202, Frankh'sche Verlagsbuchhandlung, Stuttgart, 1966 definiert oder bei D.H. Solomon, The Chemistry of Organic Filmformers, S. 75 - 101, John Wiley & Sons Inc., New York, 1967, beschrieben sind. Oil-free polyesters (1) and alkyd resins (2) are understood to be polycondensates of the type produced from alcohols and carboxylic acids by polycondensation by known processes, of the type described, for example, in Römpp's Chemielexikon, Vol. 1, p. 202, Frankh'sche Verlagbuchhandlung, Stuttgart, 1966 or described in DH Solomon, The Chemistry of Organic Filmformers, pp. 75-101, John Wiley & Sons Inc., New York, 1967.

Unter "Alkydharzen" werden in dieser Anmeldung fett­säure- bzw. ölmodifizierte Polyester verstanden.In this application, “alkyd resins” are understood to mean fatty acid- or oil-modified polyesters.

Für die Synthese der Polyester (1) bzw. Alkydharze (2) bevorzugte Säurekomponenten sind aliphatische, cyclo­aliphatische gesättigte oder ungesättigte und/oder aromatische mehrbasische Carbonsäuren, vorzugsweise Di-, Tri- und Tetracarbonsäuren, mit 2 bis 14, vorzugsweise 4 bis 12 C-Atomen pro Molekül oder deren vereste­rungsfähige Derivate (z.B. Anhydride oder Ester), z.B. Phthalsäureanhydrid, Isophthalsäure, Terephthalsäure, Tetrahydro- und Hexahydrophthalsäureanhydrid, Endo­methylentetrahydrophthalsäure, Bernsteinsäure, Glutar­säure, Sebacinsäure, Azelainsäure, Trimellithsäure und Trimellithsäureanhydrid und Pyromellithsäureanhydrid. Phthalsäureanhydrid ist die gebräuchlichste Säure­komponente.Preferred acid components for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated or unsaturated and / or aromatic polybasic carboxylic acids, preferably di-, tri- and tetracarboxylic acids, with 2 to 14, preferably 4 to 12 C- Atoms per molecule or their esterifiable derivatives (eg anhydrides or esters), eg phthalic anhydride, isophthalic acid, tetrahydro- and hexahydrophthalic anhydride, endomethylene tetrahydrophthalic acid, succinic acid, glutaric acid and trimellitic acidic acid, trimellitic acid, trimellitic acid. Phthalic anhydride is the most common acid component.

Für die Synthese der Polyester (1) bzw. Alkydharze (2) bevorzugte Alkohole sind aliphatische, cycloaliphatische und/oder araliphatische Alkohole mit 1-15, vorzugsweise 2-6 C-Atomen, und 1-6, vorzugsweise 1-4, an nicht­aromatische C-Atome gebundenen OH-Gruppen pro Molekül, z.B. Glykole wie Ethylenglykol, Propandiol-1,2 und -1,3, Butandiol-1,2, -1,3, und -1,4, 2-Ethylpropandiol-1,3, 2-Ethylhexandiol-1,3, Neopentylglykol, 2,2-Trimethyl­pentandiol-1,3, Hexandiol-1,6, Cyclohexandiol-1,2 und -1,4, 1,2- und 1,4-Bis-(hydroxymethyl)-cyclohexan, Adi­pinsäure-bis-(ethylenglykolester); Etheralkohole wie Di- und Triethylenglykol, Dipropylenglykol; Dimethylolpro­pionsäure, oxalkylierte Bisphenole mit 2 C₂-C₃-Oxalkyl­gruppen pro Molekül, perhydrierte Bisphenole; Butan­triol-1,2,4, Hexantriol-1,2,6, Trimethylolethan, Tri­methylolpropan, Trimethylolhexan, Glycerin, Pentaery­thrit, Dipentaerythrit, Mannit und Sorbit. Die gebräuch­lichsten Alkohole sind Glycerin, Trimethylolpropan, Neo­pentylglykol und Pentaerythrit.Preferred alcohols for the synthesis of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic and / or araliphatic alcohols with 1-15, preferably 2-6 C atoms, and 1-6, preferably 1-4, of non-aromatic C-bonded OH groups per molecule, e.g. Glycols such as ethylene glycol, 1,2-propanediol and -1,3, 1,2-butanediol, 1,3 and -1,4, 1,3-2-ethylpropane, 1,3-2-ethylhexane, neopentyl glycol, 2,2-trimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1,4, 1,2- and 1,4-bis (hydroxymethyl) cyclohexane, adipic acid bis (ethylene glycol ester) ); Ether alcohols such as di- and triethylene glycol, dipropylene glycol; Dimethylolpropionic acid, oxalkylated bisphenols with 2 C₂-C₃-oxalkyl groups per molecule, perhydrogenated bisphenols; 1,2-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, trimethylolhexane, glycerol, pentaerythritol, dipentaerythritol, mannitol and sorbitol. The most common alcohols are glycerin, trimethylolpropane, neopentyl glycol and pentaerythritol.

Für die Herstellung der Polyester (1) bzw. Alkydharze (2) bevorzugte Monocarbonsäuren sind aliphatische, cycloaliphatische gesättigte und ungesättigte und/oder aromatische Monocarbonsäuren mit 3-24 C-Atomen pro Molekül wie Benzoesäure, p-tert.-Butylbenzoesäure, Tolylsäure, Hexahydrobenzoesäure, Abietinsäure und Milchsäure.Monocarboxylic acids preferred for the preparation of the polyesters (1) or alkyd resins (2) are aliphatic, cycloaliphatic saturated and unsaturated and / or aromatic monocarboxylic acids with 3-24 carbon atoms per molecule, such as benzoic acid, p-tert-butylbenzoic acid, tolylic acid, hexahydrobenzoic acid , Abietic acid and lactic acid.

Die Alkydharze (2) bzw. Polyester (1) können auch ein­wertige Alkohole mit 1 bis 8 C-Atomen wie Methanol, Propanol, Cyclohexanol, 2-Ethylhexanol, Benzylalkohol in Mengen bis zu 15 Gew.-%, bezogen auf Alkydharz (2) bzw. Polyester (1), einkondensiert enthalten. Ebenso ist es möglich, bis zu 25 % der Esterbindungen durch Ure­thanbindungen zu ersetzen.The alkyd resins (2) or polyester (1) can also monohydric alcohols with 1 to 8 carbon atoms such as methanol, propanol, cyclohexanol, 2-ethylhexanol, benzyl alcohol in amounts up to 15 wt .-%, based on alkyd resin (2) or polyester (1), condensed in. It is also possible to replace up to 25% of the ester bonds with urethane bonds.

Zur Einführung dieser Urethanbindungen geeignet sind Polyisocyanate, vorzugsweise Diisocyanate. Für diesen Zweck bevorzugte Diisocyanate sind aliphatische, cyclo­aliphatische, araliphatische, aromatische und hetero­cyclische Diisocyanate, wie sie z.B. von W. Siefken in Justus Liebigs Annalen der Chemie 562, Seiten 75-136, beschrieben werden, beispielsweise Ethylen-diisocyanat, 1,4-Tetramethylendiisocyanat, 1,6-Hexamethylendiiso­cyanat, 1,12-Dodecandiisocyanat, Cyclobutan-1,3-di­isocyanat, Cyclohexan-1,3- und -1,4-diisocyanat sowie beliebige Gemische dieser Isomeren, 1-Isocyanato-3,3,5-­trimethyl-5-isocyanatomethyl-cyclohexan (DE-AS 1 202 785), 2,4- und 2,6-Hexahydrotoluylendiiso­cyanat sowie beliebige Gemische dieser Isomeren, Hexa­hydro-1,3- und/oder -1,4-phenylen-diisocyanat, Perhydro-­1,3′- und/oder -4,4′-diphenylmethan-diisocyanat, 1,3- und 1,4-Phenylendiisocyanat, 2,4- und 2,6-Toluylendiiso­cyanat sowie beliebige Gemischer dieser Isomeren, Di­phenylmethan-2,4′- und/oder -4,4′-diisocyanat, Naphthy­len-1,5-diisocyanat.Polyisocyanates, preferably diisocyanates, are suitable for introducing these urethane bonds. Preferred diisocyanates for this purpose are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates, as described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie 562 , pages 75-136, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate , 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5- trimethyl-5-isocyanatomethyl-cyclohexane (DE-AS 1 202 785), 2,4- and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, Perhydro-1,3'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixture of these isomers, diphenylmethane-2 , 4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate.

In den Alkydharzen (2) beträgt die Öllänge, berechnet als Triglycerid und bezogen auf das Alkydharz (2), in der Regel 5 bis 50, vorzugsweise 20 bis 40 Gew.-%. Die trocknenden oder nichttrocknenden Fettsäuren, die im allgemeinen 6 bis 24 C-Atome enthalten, können entweder als solche oder in Form ihrer Glycerinester (Triglyce­ride) eingesetzt werden.The length of the oil in the alkyd resins (2), calculated as triglyceride and based on the alkyd resin (2), is generally 5 to 50, preferably 20 to 40,% by weight. The drying or non-drying fatty acids, which generally contain 6 to 24 carbon atoms, can be used either as such or in the form of their glycerol esters (triglycerides).

Als bevorzugt sind pflanzliche und tierische Öle, Fette oder Fettsäuren zu nennen, wie z.B. Kokos-, Erdnuß-, Ricinus-, Holz-, Oliven-, Sojabohnen-, Lein-, Baumwoll­saatöl, Saffloröl oder -ölfettsäuren, dehydratisiertes Ricinusöl bzw. -fettsäure, einfach ungesättigte Fett­säuren, Schmalz, Talg und Trane, Tallölfettsäure sowie synthetische Fettsäuren, die durch Konjugierung oder Isomerisierung aus natürlichen ungesättigten Ölen oder Fettsäuren hergestellt sein können. Bevorzugte gesättig­te Fettsäuren sind z.B. Kokosölfettsäuren, 2-Ethylhexan­säure, Isononansäure (3,4,4-Trimethylhexansäure) sowie Palmitin- und Stearinsäure.Vegetable and animal oils, fats or fatty acids, such as e.g. Coconut, peanut, castor, wood, olive, soybean, linseed, cottonseed oil, safflower oil or oil fatty acids, dehydrated castor oil or fatty acid, monounsaturated fatty acids, lard, tallow and tears, tall oil fatty acid and synthetic fatty acids, which can be made from natural unsaturated oils or fatty acids by conjugation or isomerization. Preferred saturated fatty acids are e.g. Coconut oil fatty acids, 2-ethylhexanoic acid, isononanoic acid (3,4,4-trimethylhexanoic acid) as well as palmitic and stearic acid.

Das als Zahlenmittel bestimmte Molekulargewicht der Polyester (1) bzw. Alkydharze (2) beträgt 2000 - 10,000 (bis zu Molekulargewichten von 5000 dampfdruckosmo­metrisch bestimmt in Dioxan und Aceton, wobei bei differierenden Werten der niedrigere Wert als korrekt angesehen wird; bei Molekulargewichten über 5000 membranosmometrisch in Aceton bestimmt).The number average molecular weight of the polyester (1) or alkyd resin (2) is 2000 - 10,000 (up to molecular weights of 5000 determined by vapor pressure osmometry in dioxane and acetone, whereby the lower value is considered correct if the values differ; for molecular weights over 5000 membrane osmometric determined in acetone).

Bevorzugte Acrylatharze (3) sind Copolymerisate mit als Zahlenmittel bestimmten Molekulargewichten M n von 600 bis 5000, wobei mindestens 2 der folgenden Monomeren als Ausgangsprodukte gewählt werden können:
Acrylsäure und Methacrylsäure;
Acrylsäure- und Methacrylsäurealkylester mit 1-18, vor­zugsweise 1-8 C-Atomen in der Alkoholkomponente, wie z.B. Methylacrylat, Ethylacrylat, Propylacrylat, Iso­propylacrylat, n-Butylacrylat, tert.-Butylacrylat, 2-­Ethylhexylacrylat, Stearylacrylat und die entsprechenden Methacrylsäureester;
Acrylsäure- und Methacrylsäurecyclohexylester; Ester der Acrylsäure und Methacrylsäure mit zweiwer­tigen, gesättigten, aliphatischen Alkoholen mit 2-4 C-­Atomen, wie z.B. 2-Hydroxyethylacrylat, 2-Hydroxypro­pylacrylat, 4-Hydroxybutylacrylat und die entsprechenden Methacrylsäureester;
vernetzend wirkende Acryl- und Methacrylverbindungen, wie z.B. Acryl- und/oder Methacrylsäureallylester, Methylenbisacrylamid, Methylenbismethacrylamid, Tri­acryloyl-perhydro-s-triazin, Bisacrylate bzw. Bis­methacrylate von Glykolen bzw. Polyglykolen mit 2-20 C-­Atomen, wie Ethylenglykol-(meth-)acrylat, Propylen­glykoldi-(meth-)acrylat, Butylenglykol-1,4-di-(meth-) acrylat, Tetraethylenglykol-di-(meth-)-acrylat, Tris-­(meth-)acrylate des Triethanolamins und des Tri­methylolethans, -propans, -hexans und des Glycerins;
Acryl- und Methacrylsäurevinylester;
Acrylnitril und Methacrylnitril;
Acrylamid und Methacrylamid;
N-Methylolether des Acylsäure- und Methacrylsäureamids der Formel

Figure imgb0001
worin
R¹ für Wasserstoff oder Methyl,
R² für Wasserstoff, Alkyl,
R³ für Alkyl oder Cycloalkyl, wie Methyl, Ethyl, n-­Propyl, Isopropyl, n-Butyl, Isobutyl, Cyclohexyl stehen;
N,N-dialkylsubstiutierte Acryl- und Methacrylsäure­amide;
primäre, sekundäre und tertiäre Aminoalkylester der Acrylsäure und Methacrylsäure.Preferred acrylate resins (3) are copolymers with number-average molecular weights M n from 600 to 5000, where at least 2 of the following monomers can be selected as starting products:
Acrylic acid and methacrylic acid;
Acrylic acid and methacrylic acid alkyl esters with 1-18, preferably 1-8 C atoms in the alcohol component, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corresponding methacrylic acid esters;
Acrylic and methacrylic acid cyclohexyl esters; Esters of acrylic acid and methacrylic acid with dihydric, saturated, aliphatic alcohols with 2-4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and the corresponding methacrylic acid esters;
cross-linking acrylic and methacrylic compounds, such as, for example, acrylic and / or methacrylic acid allyl esters, methylenebisacrylamide, methylenebismethacrylamide, triacryloyl-perhydro-s-triazine, bisacrylates or bismethacrylates of glycols or polyglycols with 2-20 C atoms, such as ethylene glycol (meth -) acrylate, propylene glycol di (meth) acrylate, butylene glycol 1,4-di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tris (meth) acrylates of triethanolamine and trimethylolethane, propane, hexane and glycerol;
Acrylic and methacrylic acid vinyl esters;
Acrylonitrile and methacrylonitrile;
Acrylamide and methacrylamide;
N-methylol ether of acyl acid and methacrylic acid amide of the formula
Figure imgb0001
 wherein
R¹ is hydrogen or methyl,
R² for hydrogen, alkyl,
R³ is alkyl or cycloalkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl;
N, N-dialkyl-substituted acrylic and methacrylic acid amides;
primary, secondary and tertiary aminoalkyl esters of acrylic acid and methacrylic acid.

Bevorzugte Polyurethane (4) sind Reaktionsproudkte aus

  • I) Polyisocyanaten mit durchschnittlich mindestens 1,8, vorzugsweise mindestens zwei Isocyanatgruppen pro Molekül und
  • II) zur Reaktion mit Isocyanatgruppen befähigte H-Atome enthaltenden Polymeren.
Preferred polyurethanes (4) are reaction products
  • I) polyisocyanates with an average of at least 1.8, preferably at least two isocyanate groups per molecule and
  • II) polymers capable of reacting with isocyanate groups containing H atoms.

Ausgangsmaterialien zur Herstellung der Komponente I sind:
(i) beliebige organische Polyisocyanate, vorzugsweise Diisocyanate der Formel

Q(NCO)₂

wobei Q einen aliphatischen Kohlenwasserstoffrest mit 4 bis 12 Kohlenstoffatomen, einen cycloalipha­tischen Kohlenwasserstoffrest mit 6 bis 15 Kohlen­stoffatomen, einen aromatischen Kohlenwasserstoff­rest mit 6 bis 15 Kohlenstoffatomen oder einen ara­liphatischen Kohlenwasserstoffrest mit 7 bis 15 Kohlenstoffatomen bedeutet.Starting materials for the production of component I are:
(i) any organic polyisocyanates, preferably diisocyanates of the formula

Q (NCO) ₂

wherein Q represents an aliphatic hydrocarbon group having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms or an araliphatic hydrocarbon group having 7 to 15 carbon atoms.

Beispiele derartiger bevorzugter Diisocyanate sind Te­tramethylendiisocyanat, Hexamethylendiisocyanat, Dodeca­methylendiisocyanat, 1,4-Diisocyanatocyclohexan, 3-Iso­cyanatomethyl-3,5,5-trimethylcyclohexylisocyanat ("Iso­phorondiisocyanat"), 4,4′-Diisocyanato-dicyclohexylme­than, 4,4′-Diisocyanato-dicyclohexylpropan-(2,2), 1,4-­Diisocyanatobenzol, 2,4- und 2,6-Diisocyanatotoluol oder Gemische dieser Isomeren, 4,4′- oder 2,4′-Diisocyanato­diphenylmethan, 4,4′-Diisocyanato-diphenylpropan-(2,2), p-Xylylendiisocyanat und α,α,α′,α′-Tetramethyl-m- oder -p-xylylendiisocyanat sowie diese Verbindungen enthal­tende Gemische.Examples of such preferred diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ("isophorone diisocyanate"), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanate dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4- and 2,6-diisocyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-diphenylpropane - (2,2), p-xylylene diisocyanate and α, α, α ', α'-tetramethyl-m- or -p-xylylene diisocyanate and mixtures containing these compounds.

Es ist selbstverständlich auch möglich, die in der Poly­urethanchemie an sich bekannten höherfunktionellen Poly­isocyanate oder auch an sich bekannte modifizierte, bei­spielsweise Carbodiimidgruppen, Allophanatgruppen, Iso­cyanuratgruppen, Urethangruppen und/oder Biuretgruppen aufweisende Polyisocyanate (mit)zuverwenden. Beispiele derartiger höherfunktioneller Polyisocyanate sind Tris-­(6-isocyanatohexyl)-biuret, gegebenenfalls im Gemisch mit seinen höheren Homologen, Tris-(6-isocyanatohexyl-) isocyanurat, gegebenenfalls im Gemisch mit seinen höhe­ren Homologen, wie es beispielsweise gemäß DE-OS 28 39 133 durch Trimerisieren von Hexamethylendiisocy­anat zugänglich ist, sowie weitere durch Trimerisieren von aliphatischen und/oder aromatischen Diisocyanaten, wie z. B. "Isophorondiisocyanat", Diisocyanatotoluol und Hexamethylendiisocyanat erhältliche, Isocyanuratgruppen aufweisende Polyisocyanate, wie sie zum bekannten Stand der Technik gehören. Sehr gut einsetzbare Polyisocyanate sind auch die an sich bekannten Urethangruppen aufwei­senden Polyisocyanate, wie sie beispielsweise durch Um­setzung von überschüssigen Mengen an 2,4-Diisocyanato­toluol oder an "Isophorondiisocyanat" mit einfachen mehrwertigen Alkoholen im Molekulargewichtsbereich 62 bis 300, insbesondere mit Trimethylolpropan, und anschließende destillative Entfernung des nicht umgesetzten Diisocyanatüberschusses erhalten werden können.It is of course also possible to use the higher-functionality polyisocyanates known per se in polyurethane chemistry or else modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups. Examples of such higher-functionality polyisocyanates are tris (6-isocyanatohexyl) biuret, optionally in a mixture with its higher homologues, tris (6-isocyanatohexyl) isocyanurate, optionally in a mixture with its higher homologues, as described, for example, in DE-OS 28 39 133 is accessible by trimerizing hexamethylene diisocyanate, and further by trimerizing aliphatic and / or aromatic diisocyanates, such as. B. "Isophorone diisocyanate", diisocyanatotoluene and hexamethylene diisocyanate available, isocyanurate group-containing polyisocyanates as they belong to the known prior art. Also very useful polyisocyanates are the polyisocyanates known per se, such as those obtained by reacting excess amounts of 2,4-diisocyanatotoluene or "isophorone diisocyanate" with simple polyhydric alcohols in the molecular weight range 62 to 300, in particular with trimethylolpropane, and subsequent distillatives Removal of the unreacted excess diisocyanate can be obtained.

Bei der Mitverwendung von monofunktionellen Polyisocy­anaten ist ihre Menge vorzugsweise so zu bemessen, daß die unten angegebene minimale Funktionalität der resul­tierenden blockierten Polyurethan-Prepolymeren nicht unterschritten wird.If monofunctional polyisocyanates are used, their amount should preferably be such that the minimum functionality of the resulting blocked polyurethane prepolymers given below is not undershot.

(ii) Polyether- und/oder Polyesterpolyole der in der Polyurethanchemie an sich bekannten Art, vorzugs­weise Polyether- und Polyesterdiole mit Molekular­gewichten von 300 bis 2.000. Die in Frage kommenden Hydroxylgruppen aufweisenden Polyether werden z. B. durch Polyaddition von cyclischen Ethern wie vorzugsweise Propylenoxid oder auch Butylenoxid, Tetrahydrofuran, Styroloxid und/oder Epichlorhydrin mit sich selbst, z. B. in Gegenwart von Bortrifluo­rid, oder durch Anlagerung dieser Verbindungen, ge­gebenenfalls im Gemisch oder nacheinander, an Startkomponenten mit reaktionsfähigen Wasserstoff­atomen wie Alkohole und Amine, z. B. Wasser, Ethy­lenglykol, Propylenglykol-(1,3) oder -(1,2), Bis­phenol-A oder Anilin, hergestellt.(ii) Polyether and / or polyester polyols of the type known per se in polyurethane chemistry, preferably polyether and polyester diols with molecular weights of 300 to 2,000. The polyether in question hydroxyl groups are z. B. by polyaddition of cyclic ethers such as preferably propylene oxide or butylene oxide, tetrahydrofuran, styrene oxide and / or epichlorohydrin with itself, for. B. in the presence of boron trifluoride, or by the addition of these compounds, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols and amines, for. B. water, ethylene glycol, propylene glycol (1,3) or - (1,2), bisphenol-A or aniline.

Die in Frage kommenden Hydroxylgruppen aufweisenden Po­lyester sind z. B. Umsetzungsprodukte von vorzugsweise mehrwertigen, besonders bevorzugt zweiwertigen und gege­benenfalls zusätzlich dreiwertigen Alkoholen mit vor­zugsweise mehrbasischen, besonders bevorzugt zweibasi­schen Carbonsäuren. Anstelle der freien Carbonsäuren können auch die entsprechenden Carbonsäureanhydride oder entsprechende Carbonsäureester von niederen Alkoholen zur Herstellung der Polyester verwendet werden.The hydroxyl-containing polyesters are z. B. Reaction products of preferably polyhydric, particularly preferably dihydric and optionally additionally trihydric alcohols with preferably polybasic, particularly preferably dibasic carboxylic acids. Instead of the free carboxylic acids, the corresponding carboxylic acid anhydrides or corresponding carboxylic acid esters of lower alcohols can also be used to prepare the polyesters.

Die als Polyesteraufbaukomponente zu verwendenden Alko­hole sind z. B. Ethylenglykol, Propylenglykol-(1,2) und -(1,3), Butandiol-(1,4), Hexandiol-(1,6), Neopentylgly­kol, Octandiol-(1,8), 2-Ethyl-hexandiol-(1,3), 1,4-Bis­hydroxymethylcyclohexan, Diethylenglykol, Dipropylen­glykol, Trimethylolpropan, Glycerin und Pentaerythrit.The alcohols to be used as the polyester construction component are e.g. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butanediol (1,4), hexanediol (1,6), neopentyl glycol, octanediol (1,8), 2-ethyl-hexanediol - (1,3), 1,4-bishydroxymethylcyclohexane, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerin and pentaerythritol.

Als Polyesteraufbaukomponenten zu verwendende Carbonsäu­ren sind z. B. Adipinsäure, Bernsteinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Terephthalsäure, Tetrahydrophthalsäure, Hexahydrophthal­säure, Maleinsäure, Fumarsäure, gesättigte und ungesät­tigte Fettsäuren wie z. B. Stearinsäure, Ölsäure, Rici­nolsäure, Linolsäure, Ricinensäure, Linolensäure, Eläo­stearinsäure sowie aus natürlichen Ölen, wie z. B. Lein­öl, Sojaöl, Erdnußöl, Saffloröl, Rizinusöl oder Holzöl, gewonnene Fettsäuregemische.Carboxylic acids to be used as polyester components are e.g. B. adipic acid, succinic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, saturated and unsaturated fatty acids such as. B. stearic acid, oleic acid, ricinoleic acid, linoleic acid, ricinic acid, linolenic acid, elaostearic acid and from natural oils, such as. B. linseed oil, soybean oil, peanut oil, safflower oil, castor oil or wood oil, obtained fatty acid mixtures.

(iii) Gegebenenfalls niedermolekulare Polyole mit Mole­kulargewichten von 62 bis 300. Beispiele für solche erfindungsgemäß geeigneten Polyole sind Ethandiol, Propandiol-(1,2) und -(1,3), Butandiol-(1,4) und -(1,3), Pentandiole, Hexandiole, Octandiole wie z. B. 2-Ethylhexandiol-(1,3), Trimethylolpropan, Glycerin und Pentaerythrit.(iii) If appropriate, low molecular weight polyols with molecular weights from 62 to 300. Examples of such polyols suitable according to the invention are ethanediol, propanediol- (1,2) and - (1,3), butanediol- (1,4) and - (1,3 ), Pentanediols, hexanediols, octanediols such as B. 2-ethylhexanediol- (1,3), trimethylolpropane, glycerol and pentaerythritol.

Vertreter der genannten zur Herstellung der Bindemittel (4) zu verwendenden Polyisocyanat- und Hydroxyl-Ver­bindungen sind z. B. in High Polymers, Vol. XVI, "Polyurethane Chemistry and Technology", verfaßt von Saunders-Frisch, Interscience Publishers, New York, London, Band I, 1962, S. 32-42 und S. 44-54 und Band II, 1964, S. 5-6 und 198-199, sowie im Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg-Höchtlen, Carl Han­ser Verlag, München, 1966, z. B. auf S. 54-71 beschrie­ben.Representatives of the polyisocyanate and hydroxyl compounds to be used for the preparation of the binders (4) are, for. B. High Polymers, Vol. XVI, "Polyurethane Chemistry and Technology" by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pp. 32-42 and pp. 44-54 and Band II, 1964, pp. 5-6 and 198-199, as well as in the Kunststoff-Handbuch , Volume VII, edited by Vieweg-Höchtlen, Carl Hanser Verlag, Munich, 1966, z. B. on pp. 54-71.

(iv) Gegenüber Isocyanaten monofunktionelle Verbindun­gen, die sich zur reversiblen Blockierung von Iso­cyanatgruppen eignen und wie sie z. B. bei Z. W. Wicks, Progress in Organic Coatings 9, 3-28 (1981) beschrieben sind. Beispiele solcher zur Herstellung der Komponente (I) der Polyurethane (4) geeigneten Blockierungsmittel sind Lactame wie z. B. Capro­lactam, Oxime wie Acetonoxim, Methylethylketonoxim und Cyclohexanonoxim, C-H-acide Verbindungen wie Malonsäureester, Acetessigsäureester und Acetylace­ton, Alkohole wie die einfachen Monoalkohole mit 1 bis 4 C-Atomen, 2-Ethylhexanol, Ethylenglykol­monoethylether und Diethylenglykolmonomethylether, Phenole wie Phenol, Kresol und Xylenol sowie he­terocyclische Verbindungen wie Triazole, Imidazo­line, Imidazole und Tetrahydropyridine.(iv) Compared to isocyanates monofunctional compounds which are suitable for the reversible blocking of isocyanate groups and how they z. B. at ZW Wicks, Progress in Organic Coatings 9 , 3-28 (1981). Examples of such blocking agents suitable for the production of component (I) of the polyurethanes (4) are lactams such as, for. B. caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, CH-acidic compounds such as malonic acid esters, acetoacetic acid esters and acetylacetone, alcohols such as the simple monoalcohols with 1 to 4 carbon atoms, 2-ethylhexanol, ethylene glycol monoethyl ether and diethylene glycol and phenol monomethyl ether, phenols Xylenol and heterocyclic compounds such as triazoles, imidazolines, imidazoles and tetrahydropyridines.

Die Blockierungsmittel können allein oder als Gemische eingesetzt werden. Bevorzugte Blockierungsmittel sind ε-Caprolactam, Butanonoxim und Malonsäurediethylester.The blocking agents can be used alone or as mixtures. Preferred blocking agents are ε-caprolactam, butanone oxime and diethyl malonate.

Die als Polyisocyanate I geeigneten Polyurethan-Prepoly­meren (Komponente I) können nach üblichen Verfahren entsprechend dem Stand der Technik hergestellt werden, beispielsweise durch Umsetzung von Polyisocyanaten (i) mit höhermolekularen Polyolen (ii) und niedermolekularen Polyolen (iii), wobei das molare Verhältnis der Isocy­anatgruppen des Polyisocyanats (i) zu den Hydroxylgrup­pen der Polyole (ii) und (iii) von 1,5 bis 3,0 betragen kann. Die resultierenden Polyurethan-Prepolymeren mit freien Isocyanatgruppen werden anschließend zur Blockierung der Isocyanatgruppen mit den dazu geeigneten monofunktionellen Verbindungen (iv) reversibel blockiert Der Aufbau von Polyurethan-Prepolymeren (I) ist bei­spielsweise in der DE-PS 1 644 813 beschrieben.The polyurethane prepolymers (component I) suitable as polyisocyanates I can be prepared by customary methods be prepared in accordance with the prior art, for example by reacting polyisocyanates (i) with higher molecular weight polyols (ii) and low molecular weight polyols (iii), the molar ratio of the isocyanate groups of the polyisocyanate (i) to the hydroxyl groups of the polyols (ii) and ( iii) can be from 1.5 to 3.0. The resulting polyurethane prepolymers with free isocyanate groups are then reversibly blocked with suitable monofunctional compounds (iv) to block the isocyanate groups. The structure of polyurethane prepolymers (I) is described, for example, in German Pat. No. 1,644,813.

Die Komponente I umfaßt sowohl Umsetzungsprodukte aus den Polyisocyanaten (I) und Blockierungsmitteln (iv) als auch blockierte Polyisocyanat-Prepolymere auf Basis der oben genannten Verbindungen (i) und (ii) und/oder (iii).Component I comprises both reaction products of the polyisocyanates (I) and blocking agents (iv) and blocked polyisocyanate prepolymers based on the above-mentioned compounds (i) and (ii) and / or (iii).

Bei den mit Isocyanatgruppen reaktionsfähige H-Atome enthaltenden Polymeren (Komponente II) handelt es sich um Polyester- oder Polyether-Polyole, um mehrwertige niedermolekulare Alkohole, Polyamine, Polyepoxypolyole, Polyhydroxylacrylate oder um beliebige Mischungen der genannten Produkte.The polymers containing H-atoms reactive with isocyanate groups (component II) are polyester or polyether polyols, polyhydric low molecular weight alcohols, polyamines, polyepoxypolyols, polyhydroxy acrylates or any mixtures of the products mentioned.

Die Polyester-Polyole und Polyether-Polyole sind Verbin­dungen der in der Polyurethanchemie an sich bekannten Art mit als Zahlenmittel bestimmter Molekulargewichten M n von 300 bis 10.000, bevorzugt 300 bis 5.000. Sie werden vorzugsweise aus den oben beschriebenen Auf­baukomponenten (ii) der Polyurethan-Prepolymeren (I) gebildet. Die niedermolekularen Alkohole sind Poly­alkohole der bekannten Art mit mindestens 2 Hydroxyl­gruppen pro Molekül und Molekulargewichten zwischen 62 und 300.The polyester polyols and polyether polyols are compounds of the type known per se in polyurethane chemistry with number average molecular weights M n from 300 to 10,000, preferably 300 to 5,000. they are preferably formed from the structural components (ii) of the polyurethane prepolymers (I) described above. The low molecular weight alcohols are polyalcohols of the known type with at least 2 hydroxyl groups per molecule and molecular weights between 62 and 300.

Die in Frage kommenden Polyamine sind vorzugsweise di- oder mehrfunktionelle aliphatische oder cycloaliphati­sche Amine wie 1,2-Diaminoethan, Tetramethylendiamin, Hexamethylendiamin, Dodecamethylendiamin, 1,4-Diamino­cyclohexan, 1,4-Bis-aminomethyl-cyclohexan, "Isophoron"-­diamin, 4,4′-Diamino-dicyclohexylmethan, 2,2-Bis-(4-­amino-cyclohexyl)-propan oder m- oder p-Xylylendiamin. Besonders bevorzugt ist 4,4′-Diamino-3,3′-dimethyl-di­cyclohexylmethan.The polyamines in question are preferably di- or polyfunctional aliphatic or cycloaliphatic amines such as 1,2-diaminoethane, tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine, 1,4-diaminocyclohexane, 1,4-bis-aminomethyl-cyclohexane, "isophorone" diamine, 4,4'-diamino-dicyclohexylmethane, 2,2-bis (4-amino-cyclohexyl) propane or m- or p-xylylenediamine. 4,4'-Diamino-3,3'-dimethyl-dicyclohexylmethane is particularly preferred.

Die Komponenten (I) und (II) werden vorzugsweise in sol­chen Mengen eingesetzt, daß das molare Verhältnis von blockierten Isocyanatgruppen zu Hydroxyl- und/oder Ami­nogruppen 0,5 bis 2, bevorzugt 0,8 bis 1,5 beträgt.Components (I) and (II) are preferably used in amounts such that the molar ratio of blocked isocyanate groups to hydroxyl and / or amino groups is 0.5 to 2, preferably 0.8 to 1.5.

Um die gewünschten Carboxylgruppen zu erhalten, wird bei der Herstellung der Polyurethane (4) vorzugsweise Di­methylolpropionsäure mitverwendet.In order to obtain the desired carboxyl groups, dimethylolpropionic acid is preferably used in the preparation of the polyurethanes (4).

Die für die erfindungsgemäß zu verwendenden wäßrigen Dispersionen geeigneten organischen Bindemittel werden vorzugsweise so ausgesucht, daß sie mindestens vorüber­gehend klebrig sind. Mit anderen Worten: Sie sollen die Eigenschaft besitzen, unter Praxisbedingungen beim Zu­sammenstoß mit dem als "Sand" verwendeten Strahlmittel und dem vom Substrat abgesprengten Teilchen diese an ihre Oberfläche zu binden.The organic binders suitable for the aqueous dispersions to be used according to the invention are preferably selected so that they are at least temporarily sticky. In other words, you should Have the property of binding them to their surface under practical conditions when they collide with the abrasive used as "sand" and the particle blasted off the substrate.

Im Idealfall wäre dann ein Bindemitteltröpfchen voll­kommen von Staubpartikeln umgeben.Ideally, a droplet of binder would be completely surrounded by dust particles.

Im Prinzip ist dann unerheblich, ob das Bindemittel klebrig bleibt oder trocknet und dabei die Staubpatikel weiter festhält. Es ist natürlich zu berücksichtigen, daß die Dispersionströpfchen im Strahl während der Fluges zum Substrat wenigstens teilweise, unter Um­ständen aber auch völlig das Wasser verlieren und die erwünschte Klebrigkeit nicht etwa nur beim Einführen in den Strahl, sondern vielmehr beim Auftreffen auf das Substrat noch vorhanden sein soll. Üblicherweise werden gute Ergebnisse dann erhalten, wenn eine aus der wäß­rigen Dispersion auf eine Glasplatte aufgebrachte Schicht einer Naßfilmdicke von 100 µm bei Lagerung bei 25°C nach höchstens 2 Stunden bis unbegrenzt, vor­zugsweise nach 2 Stunden bis 1 Woche, sandtrocken im Sinne von DIN 53 150, T1 (=Teil 1) ist.In principle, it is then irrelevant whether the binder remains sticky or dries while still holding the dust particles. It is of course to be taken into account that the dispersion droplets in the jet lose at least part of the water during the flight to the substrate, but under certain circumstances also completely lose the water and the desired stickiness is not only present when it is introduced into the jet, but rather when it hits the substrate should. Good results are usually obtained when a layer of a wet film thickness of 100 μm applied from the aqueous dispersion to a glass plate when stored at 25 ° C. after a maximum of 2 hours to unlimited, preferably after 2 hours to 1 week, sand dry in the sense of DIN 53 150, T1 (= part 1).

Zur Neutralisation der Carboxylgruppen der organischen Bindemittel bevorzugte tertiäre Aine umfassen bei­spielsweise Triethyl-, Tripropyl- und Tributylamin, Methyldiethanolamin, Dimethylethanolamin, Triethanol­amin, Methyldipropanolamin, Dimethylpropanolamin, Tri­propanolamin, N,N-Dimethylanilin. Besonders bevorzugte Amine sind Tripropylamin und Dimethylethanolamin.Tertiary aines preferred for neutralizing the carboxyl groups of the organic binders include, for example, triethyl, tripropyl and tributylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, methyldipropanolamine, dimethylpropanolamine, tripropanolamine, N, N-dimethylaniline. Tripropylamine and dimethylethanolamine are particularly preferred amines.

Der Wassergehalt der erfindungsgemäß zu verwendenden wäßrigen Dispersionen beträgt 60 bis 95, vorzugsweise 85 bis 93, Gew.-%, bezogen auf wäßrige Dispersion.The water content of the aqueous dispersions to be used according to the invention is 60 to 95, preferably 85 to 93,% by weight, based on the aqueous dispersion.

Die erfindungsgemäß zu verwendenden Dispersionen werden vorzugsweise im Gegenstrom zum Strahlgut eingebracht, so daß eine optimale Verteilung gewährleistet ist und sie mit dem Strahlgut in feinster Verteilung die zu strahlende Fläche erreichen.The dispersions to be used according to the invention are preferably introduced in countercurrent to the blasting material, so that an optimal distribution is ensured and they reach the surface to be blasted with the blasting material in the finest distribution.

AnwendungsbeispielApplication example 1. Vorbereitung der Prüfplatten1. Preparation of the test plates

Im Stahlbau verwendete Stahlplatten, mit den Maßen 1000x1000x4 mm wurden unter Praxisbedingungen in senkrechter Stellung nach verschiedenen Verfahren metallisch blank - Reinheitsgrad Sa 2 1/2 nach DIN 55 928 - gereinigt.

  • 1. Sandstrahlen = Strahlen mit trockener Hochofenschlacke
  • 2. Feuchtstrahlen = Strahlen mit wasserbefeuch­teter Hochofenschlacke
  • 3. Dispersionsstrahlen = Strahlen mit Hochofen­schlacke, die mit einer 7 gew.-%-igen wäßrigen Dis­persion befeuchtet ist.
Steel plates used in steel construction, with the dimensions 1000x1000x4 mm, were cleaned under practical conditions in a vertical position using a variety of processes using a metallic blank - degree of purity Sa 2 1/2 according to DIN 55 928.
  • 1. Sandblasting = blasting with dry blast furnace slag
  • 2. Wet blasting = blasting with water-moistened blast furnace slag
  • 3. Dispersion blasting = blasting with blast furnace slag, which is moistened with a 7% by weight aqueous dispersion.

Anschließend wurden die Stahlplatten auf das für die jeweiligen Korrosionsschutzprüfungen erforderliche Maß zugeschnitten.
Salzsprühnebeltest }
Kondenswassertest }      190 x 106 mm
Salzlösestation      330 x 165 mm.The steel plates were then cut to the size required for the respective corrosion protection tests.
Salt spray test}
Condensation test} 190 x 106 mm
Salt dissolving station 330 x 165 mm.

2. Wäßrige Dispersion für das Dispersionsstrahlen2. Aqueous dispersion for dispersion blasting

256 g Vorkondensat aus 0,077 Mol Sojaölfettsäure, 0,43 Mol Trimethylolpropan, 0,87 Mol Hexandiol-1,6, 0,5 Mol Adipinsäure und 0,5 Mol Isophthalsäure werden mit 21,7 g Dimethylolpropionsäure, 72 g Isophorondiisocyanat, 52,5 g N-Methylpyrrolidon, 10,3 g Dimethylethanolamin und Wasser zu einer wäßrigen Dispersion mit einem Fest­körpergehalt von 7 Gew.-% verarbeitet.256 g of precondensate from 0.077 mol of soybean oil fatty acid, 0.43 mol of trimethylolpropane, 0.87 mol of 1,6-hexanediol, 0.5 mol of adipic acid and 0.5 mol of isophthalic acid are mixed with 21.7 g of dimethylolpropionic acid, 72 g of isophorone diisocyanate, 52.5 g N-methylpyrrolidone, 10.3 g dimethylethanolamine and water processed to an aqueous dispersion with a solids content of 7 wt .-%.

Beim Strahlvorgang wurden der anfallende Staub, beste­hend aus Rost und Altbeschichtung zusammen mit der Strahlschlacke irreversibel gebunden. Das Material konn­te ohne Staubaufwirbelung mit dem Besen zusammengekehrt und beseitigt werden.During the blasting process, the resulting dust, consisting of rust and old coating, was irreversibly bound together with the blasting slag. The material could be swept up and removed with the broom without raising dust.

3. Beschichtung der Prüfplatten mit Lack3. Coating the test panels with paint

Die Beschichtung der Prüfplatten erfolgte nach folgenden Kriterien:

Figure imgb0002
The test panels were coated according to the following criteria:
Figure imgb0002

Die Folgebeschichtungen sind jeweils im Abstand von 24 Stunden aufgebracht worden. Dabei wurden die Lacke so aufgetragen, daß das Verhalten der Anstriche bei einer, zwei und drei Schichten beurteilt werden kann. Die Ver­arbeitung der Lacke erfolgte durch Spritzapplikation.The subsequent coatings were applied every 24 hours. The paints were applied in such a way that the behavior of the coatings on one, two and three layers can be assessed. The paints were processed by spray application.

4. Anstrichsystem4. Painting system

Angewendet wurde ein praxisbewährter 3-schichtiger Auf­bau auf Polyurethanharz-Basis Anstrichaufbau Lacksystem Schichtdicke (µm) Primer 1K-PUR/Zink (RR 2742/1) ca. 80 1. Deckbeschichtung 1K-PUR/Eisenglimmer (RR 2760/28) ca.100 2. Deckbeschichtung 2K-PUR/unipigmentiert (RR 2383/A) ca. 70 A tried and tested 3-layer structure based on polyurethane resin was used Painting structure Paint system Layer thickness (µm) Primer 1K-PUR / zinc (RR 2742/1) about 80 1. Top coating 1K-PUR / iron mica (RR 2760/28) approx. 100 2. Top coating 2K-PUR / unipigmented (RR 2383 / A) about 70

5. Korrosionsschutzprüfung5. Corrosion protection test

Als Prüfkriterien wurden
-Salzsprühnebeltest, DIN 53 167
-Kondenswassertest, DIN 50 017/KK
-Lagerung an der Salzlösestation
festgelegt. Die Salzlösestation ist Betriebsteil der Produktionsanlage zur Chlor-Alkali-Elektrolyse mit, auf die Korrosion von Stahl bezogener, sehr aggressiver At­mosphäre. Die Exposition der Platten in salzhaltiger, feuchter Luft ermöglicht, das Verhalten von Anstrichen unter verschärften Bedingungen in der Praxis zu prüfen. Sandstrahlen Feuchtstrahlen Dispersionsstrahlen Dispersionsstrahlen + abwaschen Salzsprühnebeltest nach 42 Tagen Primer B5/1-2 B5/1-2 B5/1-2 B5/1-2 Primer/1. Deckbesch. B3/1-2 B1/1-2 B1/1-2 B3/1-2 Primer/1. Deckbesch./2. Deckbesch. Wd 3 Wd 4, B1/1-2 Wd 0 Wd 7 Flächenrost in Grundierung 5 4 1 5 Kondenswassertest nach 42 Tagen o.B. Rostdurchbrüche in Grundierung o.B. Rostdurchbrüche in Grundierung Primer o.B. o.B. o.B. B1/1 Primer/1. Deckbesch. o.B. o.B. o.B. Ri 0,5 Primer/1. Deckbesch./2. Deckbesch. o.B. o.B. o.B. B2/1 Salzlösestation nach 6 Monaten (mit Schnitt nach DIN 53 167) Primer Wd 4 Wd 3 Wd 1 Wd 4 Primer/1. Deckbesch. Wd 3 o.B. o.B. Wd 2 Primer/1. Deckbesch./2. Deckbesch. Wd 5 Wd 3 Wd 2 Wd 5 o.B. = ohne Befund As test criteria were
Salt spray test, DIN 53 167
-Condensation test, DIN 50 017 / KK
-Storage at the salt dissolving station
fixed. The salt dissolving station is part of the production plant for chlor-alkali electrolysis with a very aggressive atmosphere related to the corrosion of steel. The exposure of the plates in salty, humid air makes it possible to test the behavior of paints under harsher conditions in practice. Sandblasting Wet blasting Dispersion rays Dispersion rays + wash off Salt spray test after 42 days Primer B5 / 1-2 B5 / 1-2 B5 / 1-2 B5 / 1-2 Primer / 1. Cover coat B3 / 1-2 B1 / 1-2 B1 / 1-2 B3 / 1-2 Primer / 1. Deck coat. Cover coat Wd 3 Wd 4, B1 / 1-2 Wd 0 Wd 7 Surface rust in primer 5 4th 1 5 Condensation test after 42 days if Rust breakthroughs in the primer if Rust breakthroughs in the primer Primer if if if B1 / 1 Primer / 1. Cover coat if if if Ri 0.5 Primer / 1. Deck coat. Cover coat if if if B2 / 1 Salt dissolving station after 6 months (with cut according to DIN 53 167) Primer Wd 4 Wd 3 Wd 1 Wd 4 Primer / 1. Cover coat Wd 3 if if Wd 2 Primer / 1. Deck coat. Cover coat Wd 5 Wd 3 Wd 2 Wd 5 oB = without finding

Die Bezeichnung für die Blasenbildung ist zusammenge­setzt aus "B" für "Blasen, einer Ziffer als Maß für den Flächenanteil der Blasen (5 = 100 %, 3 = 60 %) und dem durchschnittlichen Blasendurchmesser in Millimetern.The designation for the formation of bubbles is composed of "B" for "bubbles", a number as a measure for the area fraction of the bubbles (5 = 100%, 3 = 60%) and the average bubble diameter in millimeters.

"Wd" gibt die Unterwanderung durch Rost in Millimetern an."Wd" indicates the infiltration by rust in millimeters.

Die obige Tabelle zeigt, daß die Erfindung zu mindestens gleicher Beschichtungsqualität wie der Stand der Technik führt (wobei der Vorteil in der problemlosen Beseitigung von Rost, Altbeschichtung und Strahlmittel liegt). Ein Vergleich der beiden letzten Spalten der Tabelle zeigt den überraschenderweise durch das verwendete Bindemittel erhaltenen Korrosionsschutz.The table above shows that the invention leads to at least the same coating quality as the prior art (the advantage being the problem-free removal of rust, old coating and blasting agent). A comparison of the last two columns in the table shows the corrosion protection surprisingly obtained by the binder used.

Claims (4)

1. Verwendung einer wäßrigen Dispersion auf Basis von organischem Bindemittel, dessen Carboxylgruppen (vor der Neutralisation) einer Säurezahl von 40 bis 70 entsprechen und zu mindestens 60 % durch ein tertiäres Amin der Formel

NR¹R²R³

worin
R¹, R², R³ unabhängig voneinander C₁-C₆-Alkyl, C₆-C₁₂-Aryl, Hydroxy-C₂-C₃-alkyl
bedeuten,
neutralisiert sind,
für das Druckluftstrahlen.1. Use of an aqueous dispersion based on organic binder, the carboxyl groups (before neutralization) correspond to an acid number of 40 to 70 and at least 60% by a tertiary amine of the formula

NR¹R²R³

wherein
R¹, R², R³ independently of one another C₁-C₆-alkyl, C₆-C₁₂-aryl, hydroxy-C₂-C₃-alkyl
mean,
are neutralized
for compressed air blasting. 2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Carboxylgruppen zu mindestens 70 % neutra­lisiert sind.2. Use according to claim 1, characterized in that the carboxyl groups are neutralized to at least 70%. 3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Carboxylgruppen zu mindestens 80 % neu­tralisiert sind.3. Use according to claim 1, characterized in that the carboxyl groups are neutralized to at least 80%. 4. Verwendung nach Ansprüchen 1-3, dadurch gekenn­zeichnet, daß das tertiäre Amin aus der Gruppe Tripropylamin und Dimethylethanolamin ausgewählt ist.4. Use according to claims 1-3, characterized in that the tertiary amine is selected from the group tripropylamine and dimethylethanolamine.
EP88114106A 1987-09-10 1988-08-30 Use of an aquous suspension in air jet blasting Expired - Lifetime EP0306801B1 (en)

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DE19873730320 DE3730320A1 (en) 1987-09-10 1987-09-10 USE OF WAITER DISPERSIONS FOR THE PRESSURE AIR RADIATION

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JPS57149161A (en) * 1981-06-12 1982-09-14 Matsushita Seinosuke Shot blast method
EP0069874A2 (en) * 1981-07-09 1983-01-19 Ernst Peiniger GmbH Unternehmen für Bautenschutz Abrasive blasting method using air under pressure
JPS58186365A (en) * 1982-04-21 1983-10-31 Shinko Electric Co Ltd Manufacture of pole group of linear pulse motor
DE3415174A1 (en) * 1984-04-21 1985-10-31 Ernst Peiniger GmbH Unternehmen für Bautenschutz, 4300 Essen Process for abrasive blasting using compressed air
EP0178164A1 (en) * 1984-10-10 1986-04-16 Brent Chemicals International Plc Method of cleaning surfaces

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460296A (en) * 1966-10-24 1969-08-12 Xerox Corp Metalworking
DE2724318A1 (en) * 1977-05-28 1978-11-30 Peiniger Ernst Gmbh Sand blasting equipment using additives - has tanks for blasting medium and additive with separate connections to blasting nozzle
JPS57149161A (en) * 1981-06-12 1982-09-14 Matsushita Seinosuke Shot blast method
EP0069874A2 (en) * 1981-07-09 1983-01-19 Ernst Peiniger GmbH Unternehmen für Bautenschutz Abrasive blasting method using air under pressure
JPS58186365A (en) * 1982-04-21 1983-10-31 Shinko Electric Co Ltd Manufacture of pole group of linear pulse motor
DE3415174A1 (en) * 1984-04-21 1985-10-31 Ernst Peiniger GmbH Unternehmen für Bautenschutz, 4300 Essen Process for abrasive blasting using compressed air
EP0178164A1 (en) * 1984-10-10 1986-04-16 Brent Chemicals International Plc Method of cleaning surfaces

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 6, Nr. 253 (M-178)[1131], 11. Dezember 1982; & JP-A-57 149 161 (SEINOSUKE MATSUSHITA) 14-09-1982 *
PATENT ABSTRACTS OF JAPAN, Band 8, Nr. 28 (M-274)[1465], 7. Februar 1984; & JP-A-58 186 365 (MITSUBISHI JUKOGYO K.K.) 31-10-1983 *

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DE3870554D1 (en) 1992-06-04
DE3730320A1 (en) 1989-03-30
ES2036637T3 (en) 1996-07-16
ATE75438T1 (en) 1992-05-15
EP0306801A3 (en) 1990-10-24
EP0306801B1 (en) 1992-04-29

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