EP1817398B1 - Produit nettoyant pour metaux contenant un polyethylene imine - Google Patents

Produit nettoyant pour metaux contenant un polyethylene imine Download PDF

Info

Publication number
EP1817398B1
EP1817398B1 EP05792155A EP05792155A EP1817398B1 EP 1817398 B1 EP1817398 B1 EP 1817398B1 EP 05792155 A EP05792155 A EP 05792155A EP 05792155 A EP05792155 A EP 05792155A EP 1817398 B1 EP1817398 B1 EP 1817398B1
Authority
EP
European Patent Office
Prior art keywords
multan
weight
cleaning solution
range
alusol
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
EP05792155A
Other languages
German (de)
English (en)
Other versions
EP1817398A1 (fr
Inventor
Bernd Stedry
Andreas Heinze
Werner Opitz
Gerhard Rehm
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35462267&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1817398(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1817398A1 publication Critical patent/EP1817398A1/fr
Application granted granted Critical
Publication of EP1817398B1 publication Critical patent/EP1817398B1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D3/2068—Ethers
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
    • 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
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—Organic inhibitors
    • 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
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
    • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the cleaner Due to its special combination of nonionic surfactants or glycol ethers and polyethyleneimine, the cleaner is low in foaming in the process according to the invention and can therefore be preferred as a spray cleaner in the entire application temperature range of about 15 to about 80 ° C are used. Furthermore, the cleaner in the process according to the invention is demulsifying and therefore easy to work up.
  • Industrial cleaners are mainly used in the automotive industry and their supply industries for cleaning and passivation mainly in spray cleaning equipment. They are suitable for intermediate and final cleaning of non-cutting as well as machined parts in aggregate and assembly plants. Practically all relevant materials, such as iron and steel, aluminum, silumin, copper, brass, zinc and plastics, can be treated and the majority of all contaminations on an organic or inorganic basis, such as coolants, rust inhibiting oils, processing oils, drawing aids, pigments and light metal abrasion, can be removed. Such cleaning agents can also find application in conventional dipping, but their use in the spray process is usually preferred.
  • detergent formulations (obviously for laundering) containing surfactants, builders, enzymes and from 0.001 to 5 weight percent polyethyleneimine are known.
  • Polyethyleneimine is hereinafter abbreviated to PEI.
  • PEI Polyethyleneimine
  • Suitable surfactants are the entire range of surfactants from anionic surfactants, nonionic surfactants, zwitterionic surfactants, ampholytic surfactants, cationic surfactants and mixtures thereof.
  • WO 95/03389 describes a cleaning agent for technical applications, the particular advantage of which is that low-polarity plastic surfaces are well wetted. This is essentially determined by the use of certain Amino acids causes.
  • this agent contains nonionic surfactants, preferably selected from the group of ethoxylated and / or ethoxylated and propoxylated fatty alcohols.
  • the detergent solution have demulsifying properties. This means that oily impurities are very easily removed from the surfaces to be degreased, but that these impurities do not form a stable emulsion in the aqueous cleaner solution, but - at the working temperature or, if appropriate, after temperature adjustment and / or dilution - as oily phase on the aqueous Cleaner floating up. The oil phase can then be easily removed from the detergent solution, so that the service life of the detergent bath can be extended considerably. This property is particularly desired in the context of the present invention.
  • cleaning solutions according to the cited document WO 95/03389 may have this property if they contain cationic surfactants, betaines and / or cationically modified polymers in amounts between 0.01 and 3 wt .-%.
  • protonated PEI or methylated PEI are mentioned. These polymers should have relatively high molecular weights in the range of 50,000 to 50,000,000, preferably between 75,000 and 5,000,000.
  • EP-A-116 151 discloses a process for the regeneration of aqueous degreasing and cleaning solutions, in which one adds the cationic surfactants or cationically modified polymers for the emulsion splitting the used and oil-loaded cleaner solutions. These are intended to cause a breakdown of the emulsions present in the water.
  • the list of choices for cationic demulsifiers listed here includes protonated PEI. These should also have molecular weights, as indicated in the above-cited WO document. According to this teaching, therefore, the PEI is not present from the outset in the cleaning solution and thus during the actual cleaning process, but is added in a separate step to work up the used cleaning solution.
  • WO 98/55578 foam-free detergents for the technical cleaning of hard surfaces are known which contain glycol ethers of the general formula RO- (CH 2 -CH (CH 3 ) -O n -H instead of the usual anionic or nonionic surfactants, wherein R is an alkyl radical having 1 to 4 C atoms or a phenyl radical and n is a number in the range from 1 to 5 mean.
  • the detergent described herein contains cationic surfactants, with the weight ratio of the glycol ethers to the cationic surfactants being between 8: 1 and 100: 1. An addition of PEI is not mentioned here.
  • the present invention has as its object to provide an improved cleaning method for metallic surfaces, which are contaminated, for example, for corrosion protection or from previous processing steps such as a forming or a metal-cutting machining with oils and / or fats.
  • This detergent should be sufficiently low foaming in the application to be used in injection molding, and at the same time have the demulsifying properties described above. In this case, low foaming must be ensured even if adhere to the parts to be cleaned impurities containing foam-forming components. This is the case, for example, when the parts are contaminated with residues of coolant lubricant emulsions containing emulsifiers. Furthermore, the demulsifying properties must be maintained during cleaning despite the entrained emulsifiers.
  • the components of the cleaning agent should contain as few potentially corrosive ions (in particular chloride ions).
  • the cleaning solution can therefore contain either the stated glycol ethers or nonionic surfactants or a mixture thereof.
  • glycol ethers are to be used, the same glycol ethers are suitable for this purpose, which are described in the cited document WO 98/55578 are characterized in detail. Accordingly, glycol ethers are preferred in which n is a number in the range of 1 to 3. Examples of these are: tripropylene glycol monoethyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether. Tripropylene glycol monomethyl ether and tripropylene glycol n-butyl ether are preferred.
  • nonionic surfactants are used as component (b), preference is given to using ethoxylates, propoxylates and / or ethoxylates / propoxylates of fatty alcohols.
  • Fatty alcohols are alkyl alcohols having 6 to 22, in particular having 8 to 18 carbon atoms in the alkyl radical.
  • the alkyl radicals are preferably linear, but may also be branched. They can be saturated or mono- or polyunsaturated. It is possible to use fatty alcohol alkoxylates with only one alkyl radical or those having different alkyl radicals, such as are derived from the fatty acids in naturally occurring vegetable or animal fats and oils.
  • the degree of alkoxylation is generally in the range from about 1.5 to about 20.
  • propoxylates of fatty alcohols in which at least 50% of the alkyl radicals is a mono- or poly-unsaturated alkyl radical having 18 carbon atoms.
  • at least 50% of the alkyl radicals are oleyl radicals.
  • Particular preference is given to propoxylates of fatty alcohols in which at least 80% of the alkyl radicals are oleyl radicals.
  • the degree of propoxylation may be between about 1.5 and about 6, preferably between 1.5 and 3.
  • polyethylenimine The component c), polyethylenimine, is commercially available from different manufacturers under different brand names. An overview of brand names and sources of supply as well as a more detailed description of polyethyleneimine can be found in the cited document US 5,904,735 , Column 16, line 49 to column 18, line 19 are taken. This is explicitly referred to here. Accordingly, polyethyleneimines of very different molecular weights are known, which may be between about 100 and about 5,000,000. The molecular weights can be determined by gel permeation chromatography. As stated in the above passage, polyethylenimine may be linear or branched.
  • cationic surfactants d may improve the demulsifying effect of PEI.
  • cationic surfactant in a much smaller amount than the present amount of PEI
  • Suitable cationic surfactants are, for example, quaternary organic ammonium compounds which have at least one alkyl radical having at least 10 carbon atoms.
  • Suitable counterions are, for example, chloride ions or preferably carboxylate ions, for example propionations.
  • the positive charge on the nitrogen atom can be brought about not only by a quaternization with 4 alkyl radicals, but also by protonation of a tertiary amine.
  • cationic surfactant for example, lauryldimethylbenzylammonium chloride or N, N-didecyl-N-methyl-poly (oxyethyl) ammonium propionate is suitable.
  • PEI having a very low or very high molecular weight has a demulsifying effect compared with a lower number of introduced lubricating lubricants than PEI having a molecular weight in the range of between about 1200 and less than 50 000.
  • the polyethyleneimine c) has an average molecular weight which is greater than 2000 and which is less than 35,000. In particular, the molecular weight may be in the range of 5,000 to 25,000.
  • the PEI is not protonated, quaternized or alkoxylated at all in the form in which it is mixed with the other active ingredients of the detergent concentrate. For an alkoxylation, a deteriorated demulsifying effect would be expected. Protonation or quaternization, d. H. a conversion to a cationic state is not required for the demulsifying effect.
  • By dispensing with protonation or quaternization it is avoided that the corresponding anions then also enter the cleaning agent concentrate and thus the cleaning solution. As a result, an unnecessary salt contamination of the cleaning solution is avoided on the one hand. On the other hand, it reduces the corrosivity of the cleaning solution, which can be caused by the counterions of the cationically modified PEI.
  • the cleaning solution additionally contains corrosion inhibitors.
  • corrosion inhibitors for example, alkanolamines can be used. Monoethanolamine, monoisopropanolamine, triethanolamine, triisopropanolamine or mixtures thereof are preferably used here. Dialkanolamines would also be useful because of their excellent corrosion protection. For toxicological reasons (risk of nitrosamine formation), however, the use of dialkanolamines is nowadays avoided.
  • the corrosion inhibitors may be selected from branched or unbranched, saturated or unsaturated aliphatic carboxylic acids having 6 to 10 carbon atoms and / or from aromatic carboxylic acids having 7 to 10 carbon atoms.
  • the carboxylic acids are largely present as anions.
  • counter ions with which the acids can be neutralized, it is possible, for example, to use alkali metal ions, in particular sodium or potassium ions, but preferably the cations of the alkanolamines listed above.
  • carboxylic acids examples include caproic acid, caprylic acid, ethylhexanoic acid, heptanoic acid, isononanoic acid and benzoic acid or derivatives thereof, in particular 3-nitrobenzoic acid or 4-hydroxybenzoic acid.
  • the cleaning solution may contain builders such as, for example, alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates. Some of these builder substances also have complexing properties and thus have a water-softening effect. Instead of or in addition to this, stronger complexing agents such as, for example, 1-hydroxyethane-1,1-diphosphonic acid or 2-phosphonobutane-1,2,4-tricarboxylic acid can be used. Ethylenediaminetetraacetates and nitrilotriacetates may also be used but may lead to wastewater treatment problems. In order to protect the cleaning solutions against bacterial contamination, biocides may be added if desired.
  • the cleaning solution In principle, it would be possible to prepare the cleaning solution by dissolving the individual active components in water in the required concentration range. In the industrial sector concerned, however, it is customary for the manufacturer to supply concentrates which contain all the active ingredients in the required quantity ratio and from which the user can prepare the ready-to-use cleaning solution by simple dilution with water.
  • the concentrates are usually adjusted so that they are used as about 0.5 to about 5 wt .-% aqueous solution used, ie that they are diluted for use with water in the ratio of about 1: 200 to about 1: 20 (Df one dilutes 0.5 to 5 parts by weight of concentrate with 99.5 to 95 parts by weight of water).
  • cationic surfactants are present, they are preferably present in the concentration range from 0.00005 to 0.05% by weight, preferably in the range from 0.0002 to 0.025% by weight.
  • Optional corrosion inhibitors preferably have concentrations in the range of 0.025 to 2% by weight.
  • the surfaces are brought into contact with the aqueous cleaning solution by immersion or preferably by spraying.
  • the aqueous cleaning solution preferably has a temperature in the range of about 15 to about 80 ° C and in particular in the range of about 40 to about 70 ° C.
  • the process according to the invention is used for the degreasing of metal parts in spray systems, for which purpose a temperature in the range from about 15 to about 80 ° C. and in particular in the range from about 40 to about 70 ° C. is set.
  • oil or grease floats on the cleaning solution, especially when either the cleaning process is interrupted or when a calming zone with low turbulence is provided, in which oil or grease can separate from the aqueous cleaning solution.
  • the floating oil or grease is removed continuously or discontinuously so that the cleaning solution so treated can continue to be used for cleaning.
  • VE water means: demineralized water
  • EO ethylene oxide
  • PO propylene oxide
  • Part 1 Cleaning tests.
  • Detergent solution 1% by weight of the PEI types given in Table 1 were added to Cleaner 1 (concentrate) and the cleaner was added at a concentration of 20 g / l in water in order to obtain the detergent solution.
  • the demulsifying effect was checked by adding different commercial oil-containing cooling lubricant emulsions from different manufacturers to the cleaner solutions.
  • the coolants and the results are listed in Table 2.
  • PEI in cleaner cleavage 1 Alusol BA 370 without (comparison) 0 No 1 Alusol BA 370 800 2 Yes 1 Alusol BA 370 5000 1 Yes 1 Alusol BA 370 5000 2 Yes 1 Alusol BA 370 1300 2 Yes 1 Alusol BA 370 2000 2 Yes 1 Alusol BA 370 25000 1 Yes 1 Alusol BA 370 25000 2 Yes 1 Alusol BA 370 750000 1 Yes 1 Alusol BA 370 750000 2 Yes
  • the above example shows an easily fissile coolant, whose emulsion in the cleaner solution of all PEI types is split at a maximum of 2% in the cleaner concentrate.
  • both a nonionic surfactant and a cationic surfactant are added as indicated in the table, and a foaming test is carried out in a spray-washer.
  • a 2gew-% cleaning solution in tap water about 16 ° dH
  • 4 l of this solution were sprayed at 50 ° C. in a single-jet spray system with a starting injection pressure of 10 bar for a period of 10 minutes.
  • the pressure as well as the foam height was measured, which is defined as the height of the foam above the liquid level in the initial state.
  • Cationic surfactants cause the spray pressure to drop during operation, and the foam development is significantly lower. This is all the more remarkable, since cationic surfactants foaming strongly on their own.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (8)

  1. Procédé pour le nettoyage de surfaces métalliques souillées par des huiles et/ou des graisses, caractérisé en ce qu'on met les surfaces en contact avec une solution aqueuse de nettoyage qui contient
    b) des glycoléthers de formule générale

            R-O-(CH2-CH(CH3)-O)n-H,

    R signifiant un radical alkyle comprenant 1 à 4 atomes de carbone ou un radical phényle et n signifiant un nombre dans la plage de 1 à 5 et/ou des agents tensioactifs non ioniques et
    c) une polyéthylène-imine,
    la polyéthylène-imine n'étant ni protonisée, ni quaternisée, ni alcoxylée et présentant une masse molaire moyenne qui est supérieure à 1200 et inférieure à 50 000.
  2. Procédé selon la revendication 1, caractérisé en ce que la solution aqueuse de nettoyage contient en outre des agents tensioactifs cationiques et/ou des inhibiteurs de corrosion.
  3. Procédé selon l'une des revendications ou les deux revendications 1 et 2, caractérisé en ce que la polyéthylène-imine c) présente une masse molaire moyenne qui est supérieure à 2000, et inférieure à 35 000.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que la solution aqueuse de nettoyage contient des agents tensioactifs non ioniques b) en une concentration dans la plage de 0,002 à 0,25% en poids.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que la solution aqueuse de nettoyage contient des glycoléthers b) en une concentration dans la plage de 0,002 à 4% en poids.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que la solution aqueuse de nettoyage contient la polyéthylène-imine c) en une concentration dans la plage de 0,0005 à 0,25% en poids, de préférence dans la plage de 0,001 à 0,1% en poids.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6, caractérisé en ce que la solution aqueuse de nettoyage contient des agents tensioactifs cationiques d) en une concentration dans la plage de 0,00005 à 0,05% en poids, de préférence dans la plage de 0,0002 à 0,025% en poids.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on élimine en continu ou de manière discontinue l'huile ou la graisse flottant sur la solution de nettoyage.
EP05792155A 2004-11-29 2005-09-10 Produit nettoyant pour metaux contenant un polyethylene imine Expired - Lifetime EP1817398B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004057623A DE102004057623A1 (de) 2004-11-29 2004-11-29 Metallreiniger mit Polyethylenimin
PCT/EP2005/009768 WO2006058570A1 (fr) 2004-11-29 2005-09-10 Produit nettoyant pour metaux contenant un polyethylene imine

Publications (2)

Publication Number Publication Date
EP1817398A1 EP1817398A1 (fr) 2007-08-15
EP1817398B1 true EP1817398B1 (fr) 2012-02-01

Family

ID=35462267

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05792155A Expired - Lifetime EP1817398B1 (fr) 2004-11-29 2005-09-10 Produit nettoyant pour metaux contenant un polyethylene imine

Country Status (5)

Country Link
US (1) US20070270323A1 (fr)
EP (1) EP1817398B1 (fr)
AT (1) ATE543895T1 (fr)
DE (1) DE102004057623A1 (fr)
WO (1) WO2006058570A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006018216B4 (de) 2006-04-18 2008-09-25 Chemetall Gmbh Verfahren zum demulgierenden Reinigen von metallischen Oberflächen
US20080274929A1 (en) * 2007-05-01 2008-11-06 Whitekettle Wilson K Method for removing microbes from surfaces
DE102007000501A1 (de) * 2007-10-15 2009-04-16 Chemetall Gmbh Reinigerzusammensetzung für metallische Oberflächen
WO2014086577A1 (fr) * 2012-12-04 2014-06-12 Unilever N.V. Composition de nettoyage de surface dure
DE102015211020A1 (de) * 2014-06-17 2015-12-17 Chemetall Gmbh Reinigungsmittel zur schonenden Entfernung von Tinten und Marker
CN104178772B (zh) * 2014-08-11 2016-05-11 浙江久晟油茶科技股份有限公司 一种茶皂素水基金属清洗剂及使用方法
CA2975435A1 (fr) 2015-02-25 2016-09-01 Basf Se Procede de nettoyage de surfaces metalliques souillees et des substances utiles pour un tel procede
EA201792172A1 (ru) * 2015-04-10 2018-05-31 Басф Се Способ ингибирования коррозии металлических поверхностей
CN109267074B (zh) * 2018-11-29 2020-12-22 苏州市神顺新晨科技有限公司 一种金属零件清洗剂
CN111321419A (zh) * 2020-04-13 2020-06-23 宿迁盾嘉生物科技有限公司 一种用于马口铁工艺中的脱脂剂及使用方法
CN115821276A (zh) * 2022-07-07 2023-03-21 中山市浩科化工科技有限公司 一种新能源金属用的强力清洗剂及其制备方法
WO2024047074A1 (fr) * 2022-08-31 2024-03-07 Chemetall Gmbh Procédé de prétraitement de substrats métalliques

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627687A (en) * 1968-02-09 1971-12-14 Dow Chemical Co Cleaning of ferrous metal surfaces
DE2414924A1 (de) 1974-03-28 1975-10-16 Keller & Bohacek Rostschutzges Mineralsaure reinigungsloesung
DE3247431A1 (de) 1982-12-22 1984-06-28 Henkel KGaA, 4000 Düsseldorf Verfahren zur regenerierung bzw. zum recycling von waessrigen entfettungs- und reinigungsloesungen
DE4014859A1 (de) * 1990-05-09 1991-11-14 Henkel Kgaa Verwendung einer kombination ionischer und nichtionischer tenside
DE4136442A1 (de) * 1991-11-06 1993-05-13 Henkel Kgaa Verfahren zum entfetten und reinigen metallischer oberflaechen und vorrichtung zu dessen durchfuehrung
US5372741A (en) * 1991-11-27 1994-12-13 Ethone-Omi, Inc. Aqueous degreasing composition and process
US5328518A (en) * 1991-12-06 1994-07-12 Golden Technologies Company, Inc. Method for separating components of liquids in industrial process
DE4324396A1 (de) 1993-07-21 1995-01-26 Henkel Kgaa Reinigungsmittel mit hohem Benetzungsvermögen
US5614027A (en) * 1994-09-23 1997-03-25 Church & Dwight Co., Inc. Metal cleaner with novel anti-corrosion system
CA2200747A1 (fr) * 1994-09-23 1996-03-28 Alfredo Vinci Agent de nettoyage aqueux pour surfaces metalliques
DE19515086A1 (de) * 1995-04-25 1996-10-31 Hoechst Ag Verfahren zur Entfernung von verunreinigenden Beschichtungen von Metalloberflächen
DE19723990A1 (de) 1997-06-06 1998-12-10 Henkel Kgaa Schaumarmes Reinigungsmittel
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
DE10027634A1 (de) * 2000-06-06 2001-12-13 Basf Ag Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül- oder Pflegemitteln für Textilien und als Zusatz zu Waschmitteln
DE10027638A1 (de) * 2000-06-06 2001-12-13 Basf Ag Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül-, Reinigungs- und Imprägniermitteln für harte Oberflächen
CN1193410C (zh) 2000-09-01 2005-03-16 株式会社德山 残渣洗涤液
WO2003018732A1 (fr) * 2001-08-24 2003-03-06 The Clorox Company Composition nettoyante amelioree
US6719421B2 (en) * 2002-06-18 2004-04-13 Hewlett-Packard Development Company, L.P. Modification of inks during printing to reduce color intensity
US7255750B2 (en) * 2003-03-24 2007-08-14 The Clorox Company Cleaner with soil flocculant

Also Published As

Publication number Publication date
DE102004057623A1 (de) 2006-06-01
EP1817398A1 (fr) 2007-08-15
WO2006058570A1 (fr) 2006-06-08
ATE543895T1 (de) 2012-02-15
US20070270323A1 (en) 2007-11-22

Similar Documents

Publication Publication Date Title
EP0986631B1 (fr) Detergent faiblement moussant
EP0527824B1 (fr) Utilisation d'une combinaison de tensio-actifs ioniques et non ioniques
EP1817398B1 (fr) Produit nettoyant pour metaux contenant un polyethylene imine
EP0710274B1 (fr) Nettoyants a haut pouvoir mouillant
EP1670972A1 (fr) Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
EP3158049B1 (fr) Agent de nettoyage pour une élimination douce d'encres et de marqueurs
EP2205711A1 (fr) Composition nettoyante pour surfaces métalliques
EP0511253B1 (fr) Produits de nettoyage desemulsifiants et application
EP2010696A1 (fr) Procédé de nettoyage désémulsifiant de surfaces métalliques
EP3835399A1 (fr) Agent de nettoyage pour surfaces dures
EP0506751B1 (fr) Utilisation d'une combinaison de tensio-actifs non ioniques
DE69614029T2 (de) Von Ketonen stammendes Tensid und Verfahren zum Behandeln von Abwässern aus Industrie, Handel oder öffentlichen Körperschaften
EP1137748A1 (fr) Procede d'usinage et de nettoyage de metal
DE69425378T2 (de) Tenside
DE69216525T2 (de) Reinigungsverfahren
EP1468065B1 (fr) Nettoyants pour surfaces exterieures de moyens de transport
EP1108073B1 (fr) Agents et procedes pour l'usinage et le nettoyage des metaux ou leur traitement anticorrosion
EP1655362A1 (fr) Composition de nettoyage pour enlever la suie
DE4102709C1 (en) Degreasing metal surfaces using aq. prepn. - contg. biologically degradable adducts of lower alkylene oxide(s), fatty alcohol(s) and cationic surfactants
WO2021043772A1 (fr) Robot de nettoyage comprenant un chiffon de nettoyage et un agent de nettoyage
WO1993006200A1 (fr) Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants
DE2442844B2 (de) Korrosionshemmende wäßrige Lösung für spanabhebend bearbeitete Werkstücke aus Metallen und Kunststoffen

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: 20070307

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

17Q First examination report despatched

Effective date: 20091019

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C23G 1/18 20060101ALI20110811BHEP

Ipc: C11D 1/62 20060101AFI20110811BHEP

Ipc: C23G 1/06 20060101ALI20110811BHEP

Ipc: C11D 3/37 20060101ALI20110811BHEP

Ipc: C23G 1/26 20060101ALI20110811BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 543895

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502005012416

Country of ref document: DE

Effective date: 20120329

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120201

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120201

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120601

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120601

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120502

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20121026

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502005012416

Country of ref document: DE

Effective date: 20121026

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120512

Ref country code: MC

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

Effective date: 20120930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120910

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20130531

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

Ref country code: GB

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

Effective date: 20120910

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120501

Ref country code: LI

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

Effective date: 20120930

Ref country code: CH

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

Effective date: 20120930

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: 20121001

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 543895

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120910

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: 20120910

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20121026

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120201

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

Ref country code: LU

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

Effective date: 20120910

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502005012416

Country of ref document: DE

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050910

PLAG Information modified related to despatch of communication that opposition is rejected

Free format text: ORIGINAL CODE: EPIDOSCREJ1

PLAO Information deleted related to despatch of communication that opposition is rejected

Free format text: ORIGINAL CODE: EPIDOSDREJ1

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

PLAE Information related to rejection of opposition modified

Free format text: ORIGINAL CODE: 0009299REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

R27O Information related to the rejection of opposition modified: opposition rejected

Effective date: 20140712

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502005012416

Country of ref document: DE

Effective date: 20140712

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230705

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

Ref country code: DE

Payment date: 20240918

Year of fee payment: 20

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

Ref country code: BE

Payment date: 20240918

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 502005012416

Country of ref document: DE

REG Reference to a national code

Ref country code: BE

Ref legal event code: MK

Effective date: 20250910