EP0642575B1 - Concentres de nettoyants alcalins susceptibles d'etre pompes - Google Patents

Concentres de nettoyants alcalins susceptibles d'etre pompes Download PDF

Info

Publication number
EP0642575B1
EP0642575B1 EP93909939A EP93909939A EP0642575B1 EP 0642575 B1 EP0642575 B1 EP 0642575B1 EP 93909939 A EP93909939 A EP 93909939A EP 93909939 A EP93909939 A EP 93909939A EP 0642575 B1 EP0642575 B1 EP 0642575B1
Authority
EP
European Patent Office
Prior art keywords
weight
alkali metal
cleaning concentrates
cleaning
contain
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.)
Expired - Lifetime
Application number
EP93909939A
Other languages
German (de)
English (en)
Other versions
EP0642575A1 (fr
Inventor
Christian Block
Petra Uhl
Yves Guinomet
Armin Friesendorf
Jürgen FALKOWSKI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0642575A1 publication Critical patent/EP0642575A1/fr
Application granted granted Critical
Publication of EP0642575B1 publication Critical patent/EP0642575B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions

Definitions

  • the invention relates to storage-stable, pumpable, alkaline cleaner concentrates, in particular for the industrial cleaning of metallic surfaces based on concentrated aqueous dispersions of alkaline builder substances, nonionic and / or anionic surfactants and stabilizers in alkali metal hydroxide solutions.
  • the aqueous solutions of the alkaline cleaning agents have a pH of approx. 11-14. They are particularly suitable for difficult cleaning tasks, e.g. for removing thick oil and pigment soiling in repair shops and for cleaning containers and systems. Furthermore, this type of product is used in particular for the fine cleaning of metallic surfaces, where metallic clean surfaces are required. This applies, for example, to cleaning before and after hardening processes the cleaning of strip steel before annealing and coating as well as the pretreatment of workpieces in electroplating, phosphating, paint shops and enamelling companies. With these cleaning solutions, a very high level of cleanliness of the workpiece surface is achieved with a good dirt-carrying capacity of the bathroom.
  • Typical alkaline cleaning agents are usually produced as a powder by mixing 80 to 100% by weight of alkaline builder substances and 0 to 20% by weight of various anionic and / or nonionic surfactants.
  • the most common inorganic builders are alkaline silicates, phosphates and carbonates of sodium and / or potassium.
  • gluconates, alkanolamines, polycarboxylic acids, polyoxycarboxylic acids and phosphonates are also used as complexing agents.
  • the surfactant mixtures consist of low and highly ethoxylated and propoxylated alkylphenols and / or fatty alcohols with different chain lengths and / or fatty amines with different chain lengths and / or fatty acids or sulfonic acids. These ingredients are present in the alkaline cleaning agents in various combinations and relative concentrations. The composition of an optimal product can usually only be found empirically through a special sample processing.
  • Powdery cleaning agents have a strong tendency to dust and can therefore cause annoyance or even endanger the user when dispensing.
  • nonionic surfactants cannot be dissolved at all, and anionic surfactants only offer the possibility of dissolving compounds which have a very short, less hydrophobic C chain of the order of six or fewer C atoms.
  • Nonylphenol ethoxylates, fatty alcohol ethoxylates, fatty acids and alkylbenzenesulfonates are then unsuitable for cleaning agents of this type.
  • Ch. Roßmann gives an overview of two-component cleaners that contain sodium hydroxide in a separate solution in "Rational pretreatment by continuous operation of degreasing baths", Metall Chemistry, Vol. 39 (1985), pages 41 to 44.
  • the usual industrial industrial cleaners are usually divided into silicate and phosphate cleaners.
  • the powdered silicate cleaners based on sodium metasilicate and caustic soda are generally characterized by the SiO 2 / Na 2 O weight or molar ratio that occurs when the products are dissolved in water.
  • Such cleaners can be dissolved in water at ambient temperature up to a maximum concentration of approx. 100 g / l if the corresponding sodium salts and caustic soda are used.
  • solutions with a maximum concentration of approx. 500 g / l result.
  • US Pat. No. 4,147,650 also describes an alkaline slurry which is to be used for automatic dishwashing detergents.
  • This aqueous slurry contains alkali metal hydroxides and / or silicates as alkaline builders, sodium hypochlorite as a chlorine source and sodium tripolyphosphate or sodium pyrophosphate or other condensed phosphates as well as sodium polyacrylate or sodium polymethacrylate as a water conditioning agent.
  • US-A-4 521 332 relates to cleaner dispersions for cleaning rolled steel strip before it is processed further.
  • These storage-stable, highly alkaline, aqueous dispersions contain sodium hydroxide, sodium carbonate as adjusting agents, alkali metal phosphates as builders and also chelating agents, nonionic surfactants and polyacrylic acid as dispersants.
  • DE-A-37 08 330 also discloses liquid, alkaline cleaner concentrates for cleaning metal surfaces before finishing or processing processes, which have the following components: a) 80 to 99.7% by weight of an aqueous solution of a builder or builder mixture , containing 50 to 60 wt .-% water and at least one alkali metal silicate and / or phosphate and b) 0.3 to 22 wt .-% of a surfactant combination consisting of anionic surfactants, nonionic surfactants and alkyl glucosides.
  • a surfactant combination consisting of anionic surfactants, nonionic surfactants and alkyl glucosides.
  • the object of the present invention was to provide pumpable alkaline cleaner concentrates based on aqueous dispersions of alkaline builders, alkali metal hydroxides and nonionic and / or anionic surfactants with high storage stability.
  • the dispersion often destabilizes after only a few days, which occurs in a phase separation, i.e. the removal of solid components.
  • Another object of the present invention is to stably incorporate nonionic and / or anionic surfactants into highly concentrated builder dispersions.
  • Another object of the present invention is to provide a pumpable cleaner concentrate for cleaning metal surfaces, in particular steel, non-ferrous metal, copper, aluminum and zinc, which are then to be subjected to finishing processes such as phosphating, electroplating, enamelling, painting, etc. .
  • the cleaner concentrates according to the invention are also intended to be used for intermediate cleaning before processing, for example before the annealing.
  • storage-stable, pumpable, alkaline cleaner concentrates consist of a concentrated aqueous dispersion of a builder substance or builder mixture and nonionic and / or anionic surfactants in alkali metal hydroxide solutions.
  • sodium and / or potassium are preferably used as alkali metals. Mixtures of appropriate sodium and potassium compounds are also used. However, the use of sodium as the alkali metal is particularly preferred.
  • the cleaner concentrates according to the invention are based on aqueous solutions of alkali metal hydroxides which contain the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and, if appropriate, the ingredients to be added in dispersed form.
  • alkali metal hydroxides which contain the alkaline builder substances, the nonionic and / or anionic surfactants, the stabilizers and, if appropriate, the ingredients to be added in dispersed form.
  • the cleaner concentrates according to the invention contain such sodium silicates in an amount of 5 to 80% by weight, based on the aqueous sodium hydroxide solution.
  • the molar ratio SiO 2 / Na 2 O of this combination shifts to lower values.
  • the resulting SiO 2 / Na 2 O molar ratio, based on the combination of sodium silicate and sodium hydroxide is preferably in the range from 0.1: 1 to 0.5: 1.
  • the cleaner concentrates according to the invention can contain alkali metal phosphates as alkaline builder substances, which are either present together with the alkali metal silicates or dispersed in place of the same in the sodium hydroxide solution.
  • alkali metal phosphates sodium triphosphate (also called tripolyphosphate) and / or sodium pyrophosphate are preferably used as alkali metal phosphates, sodium pyrophosphate being preferred is.
  • the cleaner concentrates according to the invention contain such sodium phosphates in an amount of 5 to 50% by weight, preferably in an amount of 10 to 50% by weight, based in each case on the aqueous sodium hydroxide solution.
  • nonionic surfactants to be used in the context of the invention are: ethoxylated or propoxylated alcohols, phenols and amines.
  • fatty alcohols with a chain length of 12 to 18 carbon atoms oxo alcohols with a chain length of 9 to 15 carbon atoms
  • nonylphenol and fatty amines with a chain length of 12 to 18 carbon atoms each with 1 to 14 mol ethylene oxide (E0 ) or propylene oxide (PO).
  • Examples include: C 12-18 fatty alcohols ethoxylated with 4, 9 or 14 moles of EO; Oleyl alcohol ethoxylated with 2 or 10 moles of EO; C 9-12 oxo alcohol ethoxylated with 6 EO; C 11-15 oxo alcohols, ethoxylated with 7 or 9 moles of EO; Nonylphenol, ethoxylated with 6 or 12 moles of EO; C 12-18 fatty amines (coconut amine), ethoxylated with 12 moles of EO; C 14-18 fatty amines (tallow amine), ethoxylated with 12 mol EO.
  • the corresponding propoxylated compounds can also be used.
  • anionic surfactants to be used in the context of the invention are: straight-chain or branched, saturated or unsaturated carboxylic acids having 10 to 18 carbon atoms and their alkali metal salts, preferably sodium salts, in particular corresponding fatty acid soaps; Alkylbenzenesulfonates with 8 to 18 carbon atoms in the alkyl radical; Alkanesulfonates with 12 to 18 carbon atoms in the alkane radical; ⁇ -olefin sulfonates with 12 to 18 carbon atoms in the olefin radical; ⁇ -sulfo fatty acid esters of C 12 to C 18 fatty acid methyl ester; Fatty alcohol sulfates with 8 to 18 carbon atoms in the fatty alcohol residue and Fatty alcohol ether sulfates with 12 to 16 carbon atoms in the fatty alcohol residue and 2 to 4 moles of ethylene oxide.
  • the cleaner concentrates according to the invention contain such nonionic and / or anionic surfactants in an amount of 0.1 to 10% by weight, preferably in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates.
  • the nonionic surfactants can be used for cleaning, emulsifying and defoaming as required.
  • nonionic surfactants can also be used to meet various cleaning solution requirements. The same applies to mixtures of anionic surfactants and to mixtures of nonionic and anionic surfactants. In general, the use of nonionic surfactants is preferred.
  • the cleaner concentrates polyacrylic acid and / or alkali metal polyacrylates in an amount of 0.5 to 10% by weight, in particular in an amount of 2 to 6% by weight, based in each case on the solid dispersed in the dispersion, contain.
  • polyacrylic acid is more advantageous than the neutralized sodium form with the same molecular mass in terms of the dispersion stability achieved.
  • the polyacrylic acids to be used are already known from US Pat. No. 4,521,332.
  • the use of polyacrylic acids is preferred over the salts because, in contrast to the salts, the free acids are significantly more soluble in water and are therefore very good in a first production step, also in combination with the nonionic and / or anionic surfactants used dispersing solids can be applied.
  • the particularly preferred molecular weight of the polyacrylic acids is in the range from 500 to 12,000, preferably below 10,000; best results were obtained using a 63% by weight solution of a polyacrylic acid with a molecular weight of 2,100.
  • Glycerol and / or polyglycerol are also part of the stabilizer combination according to the invention. These are present in the cleaner concentrates according to the invention in a preferred amount of 0.5 to 10% by weight, in particular in an amount of 1 to 3% by weight, in each case based on the total composition of the cleaner concentrates.
  • Polyglycerols in the sense of the present invention are known, for example, from Ullmanns Encyklopadie der industrial chemistry, 4th edition 1976, volume 12, page 374.
  • the polyglycerols have relative molecular weights of 166 (6 C atoms) to 2238 (90 C atoms) and 4 up to 32 hydroxyl groups.
  • the cleaner concentrates according to the invention can also contain further constituents which are commonly used in alkaline cleaning agents.
  • additional alkaline builders such as mono-, di- or triethanolamine
  • alkali metal carbonates such as sodium carbonate, alkali metal gluconates, in particular sodium or potassium gluconate, and further alkali metal hydroxides, ie in particular sodium hydroxide.
  • the cleaner concentrates according to the invention contain these additional alkaline builder substances in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, in each case based on the total composition of the cleaner concentrates.
  • Complexing agents polycarboxylic acids, phosphonic acids, such as hydroxyethane-1,1-diphosphonic acid (HEDP), aminotris (methylenephosphonic acid) (ATMP), aminopolycarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), polyoxycarboxylic acids, for example citric acid, and the like, water-soluble salic acid , preferably the sodium salts.
  • HEDP hydroxyethane-1,1-diphosphonic acid
  • ATMP aminotris (methylenephosphonic acid)
  • EDTA ethylenediaminetetraacetic acid
  • NDA nitrilotriacetic acid
  • polyoxycarboxylic acids for example citric acid, and
  • the cleaner concentrates according to the invention can contain such complexing agents in an amount of 0.5 to 5% by weight, preferably 2 to 4% by weight, in each case based on the total composition of the cleaner concentrates.
  • Defoamer C 12/18 fatty alcohol (coconut alcohol) polyethylene glycol butyl ether, ethylenediamine + 30E0 + 60P0; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates.
  • Corrosion inhibitors (for non-ferrous metals) benzotriazole, tolyltriazole; in each case in amounts of 0.1 to 5% by weight, based on the total composition of the cleaner concentrates.
  • the pumpable alkaline cleaner concentrates according to the invention are generally prepared in the following manner:
  • the builder substances are firstly treated as solids with the wetting agents used in the cleaner, i.e. the nonionic and / or anionic surfactants, and the stabilizers, i.e. mixed with polyacrylic acid and glycerin / polyglycerin, as well as any other ingredients to be used.
  • this mixture is dispersed in technical 40 to 50% by weight aqueous sodium hydroxide solution. It is of course also possible to individually disperse the builders, surfactants, stabilizers and any other ingredients to be used in any order in the aqueous sodium hydroxide solution.
  • ROTOR-STATOR systems Commercially available brands, e.g. from Janke & Kunkel GmbH & Co. (Ultra-Turrax®), from Silverson, from Fryma (Zahnkolloidmühle®), from Cavitron (Cavitron®) or from Krupp (Supratron®).
  • the ROTOR-STATOR systems can be designed as chamber, hole or cone tools.
  • the cleaning concentrates according to the invention can be produced at room temperature. However, it is preferred that this dispersion takes place at elevated temperature, ie at temperatures up to 220 ° C; a temperature range of 50 to 60 ° C. is particularly preferred here. Of course, the cleaning concentrates can be produced both batchwise and continuously.
  • the present invention furthermore relates to the use of the cleaner concentrates according to the invention in the cleaning of metal surfaces, in particular steel, non-ferrous metals, copper, aluminum and zinc before finishing processes such as phosphating, electroplating, enamelling and painting and in the intermediate cleaning before processing processes, in particular before the annealing.
  • cleaning solutions preferably used contain 10 to 200 g / l of the cleaning concentrates according to the invention.
  • the cleaning concentrates are usually dosed directly into the cleaning bath with stirring.
  • the advantage of the pumpable, alkaline cleaner concentrates according to the invention is, on the one hand, that they have a high active substance content of builder substances and at the same time have an extraordinary storage stability, and, on the other hand, that they allow simple dosing.
  • Suitable products can therefore be offered for all applications in industrial technical cleaning, for example for spraying, brushing, immersion and ultrasonic processes as well as for electrolytic cleaning.
  • predetermined cloud points can be set and high-temperature or low-temperature cleaners can be prepared.
  • the nonionic surfactants in each case were melted together with the polyacrylic acid solution and the glycerol and this mixture was then mixed with the builder substances in a laboratory mixer, i.e. especially sodium metasilicate and / or sodium pyrophosphate, mixed. This mixture was then stirred into a commercially available 50% by weight sodium hydroxide solution, heated to 60 ° C. and then dispersed using a high-performance disperser.
  • the dispersions according to the invention are stable to settling for several weeks at room temperature and show no change in the flow behavior, whereas in the case of dispersions not according to the invention a phase separation could be observed after a relatively short time, making the corresponding products unsuitable for industrial use.
  • the cleaner concentrate also contained 1.7% by weight of polyacrylic acid (Good-Rite K 752® (63%)) with a molecular weight of 2100 and a sodium content of 0.8% with a pH in the range from 2.2 to 3 .
  • the mixture of the two surfactants is contained in the cleaning concentrate in an amount of 2% by weight.
  • the cleaning concentrate also contains 3% by weight of glycerin.
  • Example 2 Analogously to Example 2, but using 0.6% by weight of polyacrylic acid, 9.7% by weight of sodium pyrophosphate and 75.1% by weight of 50% sodium hydroxide solution instead of the formulation constituents correspondingly mentioned in Example 2, it was also possible to use for 8 weeks stable cleaner concentrate can be obtained.
  • a cleaner concentrate was prepared using 53.9% by weight of the 50% sodium hydroxide solution, 41.0% by weight of the above sodium metasilicate, 2% by weight of the above surfactant base and 3.1% by weight of glycerin. in which, however, a phase separation already occurred after one day.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (19)

  1. Concentrés de produit de nettoyage alcalins aptes au pompage, stables au stockage, qui consistent en des dispersions aqueuses à base d'hydroxydes de métal alcalin et qui renferment en dispersion des silicates de métal alcalin, et/ou des phosphates de métal alcalin en tant que adjuvants alcalines ainsi que des agents tensioactifs non ioniques et/ou anioniques et le cas échéant d'autres adjuvants et/ou des agents complexants et/ou d'autres principes actifs ou adjuvants connus en soi,
    caractérisés en ce qu'
    ils possèdent comme agents stabilisants une combinaison de,
    a) acide polyacrylique et/ou de polyacrylate de métal alcalin, et
    b) du glycérol et/ou du polyglycérol.
  2. Concentrés de produit de nettoyage selon la revendication 1,
    caractérisés en ce qu'
    ils renferment comme métal alcalin du sodium et/ou du potassium, en particulier du sodium.
  3. Concentrés de produit de nettoyage selon la revendication 1 ou la revendication 2,
    caractérisés en ce qu'
    ils renferment comme hydroxyde de métal alcalin une solution aqueuse de 40 à 50 % en poids d'hydroxyde de sodium.
  4. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 3,
    caractérisés en ce qu'
    ils renferment comme silicates de métal alcalin des silicates de sodium ayant un rapport molaire SiO2/Na2O dans la zone de 1:1 à 3,5:1, de préférence de 1:1.
  5. Concentrés de produit de nettoyage selon la revendication 4,
    caractérisés en ce qu'
    ils renferment des silicates de sodium en quantités allant de 5 à 80 % en poids rapporté solution aqueuse d'hydroxyde de sodium, à cause de quoi le rapport molaire résultant SiO2/Na2O rapporté au silicate de sodium et à l'hydroxyde de sodium, se situe de préférence dans la zone de 0, 1:1 à 0,5:1.
  6. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 3,
    caractérisés en ce qu'
    ils renferment en tant que phosphates de métal alcalin du triphosphate de sodium et/ou du pyrophosphate de sodium, de préférence du pyrophosphate de sodium.
  7. Concentrés de produit de nettoyage selon la revendication 6,
    caractérisés en ce qu'
    ils renferment les phosphates de sodium en une quantité allant de 5 à 50 % en poids de préférence de 10 à 50 % en poids à chaque fois rapporté à la solution aqueuse d'hydroxyde de sodium.
  8. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 7,
    caractérisés en ce que
    les agents tensioactifs non ioniques sont choisis dans le groupe des produits d'addition de respectivement 1 à 14 mol d'oxyde d'éthylène ou d'oxyde de propylène sur des alcools gras ayant de 12 à 18 atomes de carbone, des oxo alcools ayant de 9 à 15 atomes de carbone, des amines grasses ayant de 12 à 18 atomes de carbone et du nonylphénol ou leurs mélanges.
  9. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 7,
    caractérisés en ce que
    les agents tensioactifs anioniques sont choisis parmi les acides carboxyliques saturés ou non saturés, en chaîne droite ou ramifiés, ayant de 10 à 18 atomes de carbone et leurs sels alcalins, les alkylbenzènesulfonates ayant 8 à 18 atomes de carbone dans le radical alkyle, des alkane sulfonates ayant de 12 à 18 atomes de carbone dans le radical alkane, des α-oléfine sulfonates ayant de 12 à 18 atomes de carbone dans le radical oléfinique, des esters d'acide gras α-sulfonés à partir d'esters méthylique d'acide gras en C12 à C18, des sulfates d'alcools gras avec de 8 à 18 atomes de carbone dans le radical d'alcool gras et des sulfates d'éther d'alcool gras ayant de 12 à 16 atomes de carbone dans le radical d'alcools gras et de 2 à 4 mol d'oxyde d'éthylène ou leurs mélanges.
  10. Concentrés de produit de nettoyage selon la revendication 8 ou la revendication 9,
    caractérisés en ce qu'
    ils renferment des agents tensioactifs non ioniques et/ou anioniques en une quantité allant de 0,1 à 10 % en poids, de préférence de 1 à 3 % en poids à chaque fois rapporté à la composition totale du concentré de produit de nettoyage.
  11. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 10,
    caractérisés en ce qu'
    ils renferment de l'acide polyacrylique et/ou des polyacrylates de métal alcalin, de préférence de l'acide polyacrylique en une quantité allant de 0,5 à 10 % en poids, de préférence de 2 à 6 % en poids, à chaque fois rapporté à la matière solide dispersé dans la dispersion.
  12. Concentrés de produit de nettoyage selon la revendication 11,
    caractérisés en ce que
    le poids moléculaire des acides polyacryliques se situe dans le domaine de 500 à 12 000.
  13. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 10,
    caractérisés en ce qu'
    ils renferment du glycérol et/ou du polyglycérol en une quantité allant de 0,5 à 10 % en poids, de préférence de 1 à 3 % en poids, à chaque fois rapporté à la composition totale des concentrés de produit de nettoyage.
  14. Concentrés de produit de nettoyage selon la revendication 13,
    caractérisés en ce que
    les polyglycérols possèdent des poids moléculaires relatifs dans la zone de 166 à 2 238 et possèdent de 4 à 32 groupes hydroxyle.
  15. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 14,
    caractérisés en ce qu'
    ils renferment des adjuvants alcalines supplémentaires, de préférence choisies parmi les alcanolamines, les carbonates de métal alcalins, les gluconates de métal alcalin et d'autres hydroxydes de métal alcalin, en quantité allant de 1 à 15 % en poids, de préférence de 3 à 10 % en poids à chaque fois rapporté à la composition totale des concentrés de produit de nettoyage.
  16. Concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 14,
    caractérisés en ce qu'
    ils renferment des agents complexants de préférence choisis parmi les acides polycarboxyliques, les acides polyoxycarboxyliques, les acides aminopolycarboxyliques, les acides phosphoniques et les sels solubles dans l'eau de ces acides, en une quantité allant de 0,5 à 5 % en poids, de préférence de 2 à 4 % en poids à chaque fois rapporté à la composition totale des concentrés de produit de nettoyage.
  17. Procédé de production de concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 16,
    caractérisé en ce qu'
    on met en dispersion les substances de structuration alcalines, les agents tensioactifs non ioniques et/ou anioniques, les agents stabilisants, ainsi que d'autres ingrédients à mettre en oeuvre éventuellement soit isolément dans n'importe quelle séquence soit conjointement en tant que mélange dans la solution aqueuse des hydroxydes de métal alcalin, de préférence sous l'action de forces élevées de cisaillement, de poussée et de frottement.
  18. Utilisation des concentrés de produit de nettoyage selon l'une ou plusieurs des revendications 1 à 16, pour le nettoyage de surfaces métalliques en particulier de l'acier, des métaux colorés non ferreux, du cuivre, de l'aluminium et du zinc, avant les processus de modification de ceux-ci, de préférence avant la phosphatation, la galvanisation, l'émaillage, et le laquage ainsi que dans la purification intermédiaire de ceux-ci avant les processus de façonnage en particulier avant la calcination portée au rouge.
  19. Utilisation selon la revendication 18,
    caractérisée en ce que
    l'on met en oeuvre les concentrés de produit de nettoyage sous forme d'une solution aqueuse de 1 à 20 % en poids.
EP93909939A 1992-05-18 1993-05-11 Concentres de nettoyants alcalins susceptibles d'etre pompes Expired - Lifetime EP0642575B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4216405A DE4216405A1 (de) 1992-05-18 1992-05-18 Pumpfähige alkalische Reinigerkonzentrate
DE4216405 1992-05-18
PCT/EP1993/001147 WO1993023522A1 (fr) 1992-05-18 1993-05-11 Concentres de nettoyants alcalins susceptibles d'etre pompes

Publications (2)

Publication Number Publication Date
EP0642575A1 EP0642575A1 (fr) 1995-03-15
EP0642575B1 true EP0642575B1 (fr) 1997-04-09

Family

ID=6459163

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93909939A Expired - Lifetime EP0642575B1 (fr) 1992-05-18 1993-05-11 Concentres de nettoyants alcalins susceptibles d'etre pompes

Country Status (10)

Country Link
US (1) US5520841A (fr)
EP (1) EP0642575B1 (fr)
JP (1) JPH07506608A (fr)
KR (1) KR950701680A (fr)
AT (1) ATE151457T1 (fr)
AU (1) AU660546B2 (fr)
CA (1) CA2136172A1 (fr)
DE (2) DE4216405A1 (fr)
ES (1) ES2100533T3 (fr)
WO (1) WO1993023522A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (fr) 2015-10-16 2018-06-06 Hans Georg Hagleitner Concentré de nettoyage liquide

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1021507B1 (fr) * 1995-11-17 2003-10-15 JohnsonDiversey, Inc. Utilisation des formulations de nettoyage et procede de nettoyage de bouteilles
US5770555A (en) * 1995-11-20 1998-06-23 Rohm And Haas Company High alkali-containing cleaning concentrates
FR2744132B1 (fr) * 1996-01-31 1998-04-24 Rhone Poulenc Chimie Systeme de base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin, sous forme d'une dispersion ou de granules et son utilisation en detergence
DE19741874A1 (de) * 1997-09-23 1999-04-01 Henkel Ecolab Gmbh & Co Ohg Alkoholathaltiger Reiniger
JP2003522818A (ja) * 1997-11-04 2003-07-29 日本パーカライジング株式会社 発泡を防止して表面から中間長カルボン酸金属塩を除去するクリ−ニング方法
AU1278799A (en) * 1997-11-06 1999-05-31 Henkel Corporation Cleaning metal salts of intermediate length carboxylic acids from surfaces
CN1198910C (zh) 1997-12-18 2005-04-27 宇野酱油株式会社 含有烷基苯磺酸盐阴离子表面活性剂和硅酸钠的透明液体洗涤剂
JP3262523B2 (ja) 1997-12-18 2002-03-04 宇野醤油株式会社 ケイ酸ナトリウムを含有する透明液体洗浄剤
US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
WO2000008124A1 (fr) * 1998-08-07 2000-02-17 Unilever N.V. Detergent fortement alcalin pour le lavage de la vaisselle et son procede de fabrication
JP2001021687A (ja) * 1999-07-02 2001-01-26 Ebara Kogyo Senjo Kk 放射性汚染物の処理方法およびこれに用いる装置
US6727214B1 (en) 1999-10-14 2004-04-27 Henkel Corporation Cleaning metal salts of intermediate length carboxylic acids from surfaces
DE10002710A1 (de) * 2000-01-22 2001-08-02 Henkel Ecolab Gmbh & Co Ohg Herstellung cremeförmiger komplexbildnerhaltiger alkalisch-wäßriger Reinigungsmittel
KR100420980B1 (ko) * 2000-12-16 2004-03-02 (주)아이티엠 코퍼레이션 건축사사무소 알루미늄 건자재 표면 세정제 및 그 시공법
US6818604B2 (en) * 2001-10-04 2004-11-16 Speedfam-Ipec Corporation System and method for cleaning workpieces
ITBS20030015A1 (it) * 2003-02-20 2004-08-21 Bettari Detergenti S R L Metodo per la preparazione di un agglomerato detergente di aspetto solido e prodotto risultante.
US20040180806A1 (en) * 2003-03-06 2004-09-16 Hilbert Esselbrugge Stabilized foam control compositions, their preparation, and use
DE102005050556B8 (de) * 2005-10-17 2007-07-26 Mack Gmbh Verfahren zur Reinigung von metallhaltigen Oberflächen und Verwendung einer Reinigungslösung
DE102005055768A1 (de) * 2005-11-21 2007-05-24 Ralf Waldmann Verfahren und Mittel zur elektrolytischen Reinigung und Entzunderung eines metallischen Werkstücks
EP2024190B9 (fr) * 2006-06-06 2012-09-05 Hydro Aluminium Rolled Products GmbH Procédé de conditionnement de la surface d'une pellicule de lithographie
CN101265583A (zh) * 2007-03-16 2008-09-17 深圳富泰宏精密工业有限公司 清洗药品及使用该清洗药品清洗金属表面的方法
US20120115766A1 (en) * 2009-06-01 2012-05-10 Yuken Industry Co., Ltd. Degreasing composition and production method thereof
BR102012010852A2 (pt) * 2012-05-08 2015-04-14 Oxiprana Ind Quimica Ltda Processo de galvanizacao livre de chumbo para materiais metalicos
MX2015008489A (es) * 2013-01-03 2015-10-05 Basf Corp Composicion detergente homogenea.
ES2700548T3 (es) * 2013-05-24 2019-02-18 Macdermid Enthone Inc Composición de decapado acuosa para la eliminación de selladores de superficie poliméricos sobre superficies metálicas
JP6533030B2 (ja) * 2013-12-17 2019-06-19 第一工業製薬株式会社 シリコンウエハ用洗浄剤組成物
ZA201508374B (en) * 2014-11-12 2016-12-21 Orangeimpact (Pty) Ltd A method and apparatus for removing an outer layer from an leongate body of metal
JP6430232B2 (ja) * 2014-12-18 2018-11-28 花王株式会社 鋼板用アルカリ洗浄剤組成物の製造方法
CN121006536A (zh) * 2017-08-31 2025-11-25 凯密特尔有限责任公司 用于无镍磷化金属表面的改进方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA666119A (en) * 1960-02-02 1963-07-02 A. Wright William Liquid detergent composition
US3691107A (en) * 1970-08-28 1972-09-12 Stauffer Chemical Co Novel detergent compositions
GB1370377A (en) * 1971-11-15 1974-10-16 Procter & Gamble Ltd Composition and method for cleaning hard surfaces
US3829387A (en) * 1972-06-22 1974-08-13 American Home Prod Caustic cleaner composition
US4157921A (en) * 1978-02-13 1979-06-12 American Home Products Corporation Oven cleaning method and composition
US4521332A (en) * 1981-03-23 1985-06-04 Pennwalt Corporation Highly alkaline cleaning dispersion
US4396525A (en) * 1981-09-14 1983-08-02 Lever Brothers Company Phosphate free liquid scouring composition
DE3246080A1 (de) * 1982-12-13 1984-06-14 Henkel KGaA, 4000 Düsseldorf Reinigungsverfahren
GB8307036D0 (en) * 1983-03-15 1983-04-20 Interox Chemicals Ltd Peroxygen compounds
US4601845A (en) * 1985-04-02 1986-07-22 Lever Brothers Company Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials
DE3601798A1 (de) * 1985-04-18 1986-10-23 Henkel KGaA, 40589 Düsseldorf Mehrzweckreinigungsmittel fuer harte oberflaechen
US4784788A (en) * 1985-12-14 1988-11-15 Colgate-Palmolive Co. Cleaning paste with soluble abrasive
CA1323280C (fr) * 1987-07-31 1993-10-19 Mario Bulfari Detergents liquides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3156475B1 (fr) 2015-10-16 2018-06-06 Hans Georg Hagleitner Concentré de nettoyage liquide

Also Published As

Publication number Publication date
AU660546B2 (en) 1995-06-29
DE59306127D1 (de) 1997-05-15
WO1993023522A1 (fr) 1993-11-25
US5520841A (en) 1996-05-28
DE4216405A1 (de) 1993-11-25
KR950701680A (ko) 1995-04-28
AU4066393A (en) 1993-12-13
JPH07506608A (ja) 1995-07-20
EP0642575A1 (fr) 1995-03-15
CA2136172A1 (fr) 1993-11-25
ATE151457T1 (de) 1997-04-15
ES2100533T3 (es) 1997-06-16

Similar Documents

Publication Publication Date Title
EP0642575B1 (fr) Concentres de nettoyants alcalins susceptibles d'etre pompes
DE3708330A1 (de) Fluessige, alkalische reinigerkonzentrate
DE69734427T2 (de) Hydrotrop enthaltende reiniger für harte oberflächen mit verminderter rückstandsbildung
DE68924189T2 (de) Ein unpolares Lösungsmittel enthaltende flüssige Reinigungszusammensetzung.
DE69709093T2 (de) Verdickte saure zusammensetzung
EP0282921A1 (fr) Composition de dégraissage liquide monophasé pour surfaces en aluminium ne contenant pas de phosphate
DE2001813B2 (de) Fluessiges wasch- und reinigungsmittel
DE2844399A1 (de) Fluessiger allzweckreiniger
DE4436151A1 (de) Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
EP0511253B1 (fr) Produits de nettoyage desemulsifiants et application
DE3728047A1 (de) Zusammensetzung zum behandeln und reinigen von textilien, diese enthaltendes vollwaschmittel und anwendung
DE69202681T2 (de) Flüssige Reinigungsmittel.
DE1243313B (de) Fluessiges Reinigungsmittelkonzentrat
DE69203430T2 (de) Entfettungslösung und deren Verfahren.
WO1991009925A2 (fr) Utilisation d'une combinaison de tensio-actifs non ioniques
DE2257642A1 (de) Biologisch abbaubare wasch- und reinigungsmittel
EP0111284B1 (fr) Procédé de nettoyage
DE2125965C3 (de) Reinigungsmittel, insbesondere für Metall, Glas und feuerfeste Stoffe
DE2328763C2 (de) Wässriges alkalisches borathaltiges Reinigungsmittel und Verfahren zu seiner Herstellung
EP0132792A1 (fr) Agent de nettoyage sous forme de poudre soluble dans l'eau pour surfaces dures
EP0755428B1 (fr) Utilisation d'ethoxylates d'amines grasses dans des nettoyants aqueux pour surfaces dures
EP0243907A2 (fr) Utilisation d'alkylaminopolyglycoléthers comme additifs antimousse dans des détergents peu moussants
EP0605495B1 (fr) Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants
DE19828578A1 (de) Verfahren zur Herstellung von cremeförmigen alkalisch-wäßrigen Reinigungsmitteln
DE3905671C2 (de) Zur Herstellung wäßriger Konzentrate geeignetes Waschmittelgranulat

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19941109

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR NL

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19960514

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR NL

REF Corresponds to:

Ref document number: 151457

Country of ref document: AT

Date of ref document: 19970415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59306127

Country of ref document: DE

Date of ref document: 19970515

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2100533

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19990512

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000508

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000510

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000511

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000531

Year of fee payment: 8

Ref country code: ES

Payment date: 20000531

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000717

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010512

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010531

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 20010531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20011201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020301

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030303