EP0605495A1 - Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants. - Google Patents

Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants.

Info

Publication number
EP0605495A1
EP0605495A1 EP92919454A EP92919454A EP0605495A1 EP 0605495 A1 EP0605495 A1 EP 0605495A1 EP 92919454 A EP92919454 A EP 92919454A EP 92919454 A EP92919454 A EP 92919454A EP 0605495 A1 EP0605495 A1 EP 0605495A1
Authority
EP
European Patent Office
Prior art keywords
fatty alcohol
alkali metal
immersion
cleaner according
builder
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.)
Granted
Application number
EP92919454A
Other languages
German (de)
English (en)
Other versions
EP0605495B1 (fr
Inventor
Hans-Christian Raths
Achim Richling
Yves Guinomet
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 EP0605495A1 publication Critical patent/EP0605495A1/fr
Application granted granted Critical
Publication of EP0605495B1 publication Critical patent/EP0605495B1/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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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 the use of fatty alcohol polyalkylene glycols with a narrow homolog distribution in low-foam immersion cleaners, in particular alkaline cleaners for industrial cleaning of metallic surfaces based on concentrated aqueous solutions of alkaline builder substances and mixtures.
  • a large number of agents are used for the industrial cleaning of hard surfaces with aqueous solutions.
  • the most important components of these substances are builder and surfactant systems alone and in combination with each other.
  • the properties of these base mixtures of builders and surfactants often have to be adapted to the respective application by adding further ingredients, such as complexing agents and corrosion inhibitors.
  • the aqueous, mildly alkaline solutions of the immersion cleaners usually have a pH of about 10 to 11.5. They are used in particular for difficult cleaning tasks, for example for removing thick oil and pigment contaminations in repair shops and for cleaning containers and systems. These alkaline immersion cleaners can also be used for fine cleaning of metallic surfaces, provided that clean metallic surfaces are required. This applies, for example, to cleaning before and after hardening processes, cleaning strip steel before annealing and coating, and pretreatment of workpieces in electroplating, phosphating, paint shops and Email! With the aqueous solutions of the alkaline immersion cleaners, a very high level of purity of the workpiece surfaces and, at the same time, good removal of dirt from the bath are expected.
  • Typical alkaline immersion cleaners are produced as a powder by mixing 80 to 100% alkaline builder substance and 0 to 20% different anionic and / or nonionic surfactants.
  • the most common inorganic builders are alkaline hydroxides, silicates, phosphates and carbonates of sodium and / or potassium.
  • gluconates, polyalkanols, polycarboxylic acids, polyoxycarboxylic acids and phosphonates are also used as complexing agents.
  • the surfactant mixtures usually consist of low and highly ethoxylated or propoxylated alkylphenols and / or fatty alcohols with different chain lengths.
  • Nonylphenol alkoxylates are distinguished by excellent technical properties and are universally applicable surfactants for a large number of detergents and cleaning agents, and also as emulsifiers for a large number of technical applications.
  • the degreasing properties of nonylphenol alkoxylates are particularly pronounced on both metallic surfaces and textile fabrics.
  • the ecological assessment is disadvantageous for this product group. It has been shown that alkylphenol ethoxylates form toxic metabolites during biodegradation.
  • fatty alcohol polyalkylene glycol ethers are of great importance as nonionic surfactants due to their excellent detergent properties and their high solubility in cold water for the production of washing, rinsing and Detergents.
  • alkoxylation which is usually carried out in the presence of readily soluble alkali metal hydroxides or alcohols, there is, however, no selective attachment of a discrete number of ethylene and / or propylene oxide units to one molecule of the alcohol; the reaction follows more or less statistical laws and leads to a mixture of homologous addition products whose degrees of alkoxylation encompass a broad spectrum.
  • Suitable processes for the preparation of fatty alcohol polyalkylene glycol ethers with a narrow homolog distribution are known, for example, from DE-A-38 43 713 and US-A-4 962 237. In both cases, the alkoxylation of fatty alcohols is carried out in the presence of inorganic layer compounds, for example calcined hydrotalcite.
  • the object of the present invention was to find substitution products for alkylphenol alkoxylates which have at least comparable application properties and, moreover, are ecologically harmless according to the current state of knowledge.
  • the solution to the aforementioned problem therefore consists in an alkaline immersion cleaner based on alkaline builder substances and surfactants, characterized in that they (a) 85 to 98% by weight of a builder or a builder mixture and
  • alkaline immersion cleaners according to the invention have greatly improved application properties compared to comparable cleaners based on alkylphenol alkoxylates. Compared to the nonionic fatty alcohol polyalkylene glycol ethers which have been customary in the prior art with a standard (ie: broad) homolog distribution, corresponding advantages in terms of application technology have been achieved.
  • the dip cleaners according to the invention preferably contain at least one alkali metal silicate and / or one alkali metal phosphate as a builder.
  • the usual industrial industrial cleaners are usually divided into silicate and phosphate cleaners.
  • Such cleaners can be dissolved at room temperature up to a maximum concentration of approx. 100 g / 1, provided the corresponding sodium salts and caustic soda are used.
  • solutions with a maximum concentration of 500 g / 1 result.
  • the alkaline immersion cleaners are characterized in that the In addition to an alkali metal silicate and / or an alkali metal phosphate, builderge ische also contain alkali metal hydroxides and / or alkali metal carbonates and / or alkali metal gluconates and / or alkanolamines.
  • the alkaline immersion cleaners according to the invention can thus contain the following builder substances: either alkali metal silicate and alkali metal phosphate, in each case alone or in a mixture.
  • builder substances either alkali metal silicate and alkali metal phosphate, in each case alone or in a mixture.
  • these builder substances there is the preferred possibility within the meaning of the invention of combining these builder substances with alkali metal hydroxides, alkali metal carbonates, alkali metal gluconates and alkanolins, such combinations being able to contain one or more of the additional builder substances.
  • sodium and / or potassium are preferably used as alkali metals.
  • Mixtures of corresponding sodium and potassium compounds are preferably used, the proportion of potassium ions exceeding that of sodium ions.
  • alkali metal phosphates is understood to mean alkali metal orthophosphates, pyrophosphates and triphosphates (also called tripolyphosphates). Of these, however, the triphosphates are preferred according to the invention, in particular the potassium triphosphate.
  • the proportion of silicate in the aqueous builder solutions should generally predominate; i.e. the proportion of phosphate is in the range from about 0.1 to 10% by weight, based on the aqueous builder solution.
  • alkanolamines mentioned are preferably 1- to 3-fold substituted amines by hydroxylalkyl groups - having 1 to 4 carbon atoms in the alkyl radical.
  • Di- and / or triethanolamines are preferably used for the purposes of the invention.
  • Suitable starting materials for the fatty alcohol polyalkylene glycol ethers are, in particular, fatty alcohols having 6 to 24 carbon atoms in the fatty alcohol radical and 0, 1, 2 or 3 double bonds.
  • fatty alcohols having 6 to 24 carbon atoms in the fatty alcohol radical and 0, 1, 2 or 3 double bonds are capronal alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, gadoleyl alcohol, behenyl alcohol or erucyl alcohol.
  • Saturated fatty alcohols having 8 to 18 carbon atoms in the fatty alcohol residue, in particular lauryl alcohol are preferably used.
  • these alcohols can also be present in the form of technical mixtures, such as are obtainable, for example, by high-pressure hydrogenation of fatty acid methyl ester cuts of vegetable or animal origin or by hydrogenation of technical aldehyde fractions from Roelen's oxosynthesis.
  • the fatty alcohol polyalkylene glycol ethers can be reacted with ethylene and / or propylene oxide in the presence of layered compounds.
  • layered compounds are to be understood as natural or synthetic, optionally chemically modified hydrotalcites.
  • the layer compounds which are insoluble in the reaction mixture are colloidally dispersed, which generally means that the removal of the catalyst required after the alkoxylation is associated with considerable difficulties, for example clogging of the filter pores, frequent filter changes etc. .
  • it is generally not necessary to separate these catalysts since the presence of the layer compounds in the immersion cleaners according to the invention does not constitute a disadvantage. This represents an essential cost factor in the manufacture of the immersion cleaners according to the invention.
  • the fatty alcohol polyalkylene glycol ethers to be used for the purposes of the present invention preferably contain an aliphatic hydrocarbon radical (fatty alcohol radical) having 6 to 24 carbon atoms and 0, 1, 2 or 3 olefinic double bonds with an average of 1 to 30 mol of ethylene and / or propylene oxide per mole of fatty alcohol.
  • Those fatty alcohol polyalkylene glycol ethers which contain an aliphatic hydrocarbon radical (fatty alcohol radical) having 8 to 18 carbon atoms and having an average of 6 to 20 moles of ethylene and / or propylene oxide per mole of fatty alcohol are particularly preferred according to the invention.
  • mixtures of two or more fatty alcohol polyalkylene glycol ethers which differ from fatty alcohol polyalkylene glycol ethers with a standard homolog distribution in that degrees of alkoxylation in the range from 0 to 3 and above are also used here 20 moles of alkylene glycol per mole of fatty alcohol practically do not occur if one assumes a fatty alcohol polyalkylene glycol with a narrow homolog distribution and a degree of alkoxylation of 10 and 12 moles of alkylene glycol per mole of fatty alcohol.
  • the present invention furthermore relates to the use of the immersion cleaners according to the invention in the cleaning of metal surfaces, in particular steel, non-ferrous metals, copper and zinc, before finishing processes such as phosphating, galvanizing, Enamelling and painting as well as during intermediate cleaning before processing, in particular before the annealing.
  • dip cleaners according to the invention can of course also be used in undiluted form, it is preferred for the purposes of the present invention, however, to use the dip cleaners in such a way that an aqueous solution containing 1 to 20% by weight dip cleaner is used for the cleaning process mentioned above. Accordingly, preferably used solutions of the dip cleaners contain 10 to 200 g / 1 of the cleaner concentrates according to the invention.
  • liquid, alkaline immersion cleaners according to the invention is, on the one hand, that they have a high active ingredient content in builders and at the same time contain surfactants in high concentration.
  • the combination of builder substances and fatty alcohol polyalkylene glycol ethers according to the invention within the immersion cleaners means that suitable products can be offered for all applications in industrial technical cleaning. Cleaners can be formulated for spraying, brushing, dipping and ultrasonic processes as well as for electrolytic cleaning. Using suitable combinations, predetermined cloud points can be set and high-temperature or low-temperature immersion cleaners can be prepared.
  • immersion cleaners according to the invention can of course also contain further constituents commonly used in alkaline cleaning agents, such as, for example, defoamers, corrosion inhibitors, complexing agents and / or the like.
  • defoamers such as, for example, benzyl alcohol, benzyl ether, benzyl ether, benzyl ether, benzyl ether sulfonate, benzyl ether sulfoamers, sulfoamers, sulfoamers, corrosion inhibitors, complexing agents and / or the like.
  • defoamers corrosion inhibitors, complexing agents and / or the like.
  • compounds which are particularly suitable in the context of the invention are: Defoamer:
  • Polycarboxylic acids e.g. Polyacrylates
  • Phosphonic acids such as hydroxyethane-l, l-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid) (ATMP), or their water-soluble salts
  • Aminopolycarboxylic acids e.g. Ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) or their water-soluble salts
  • Polyoxycarboxylic acids e.g. Citric acid or its salts; each in amounts of 0.1 to 10 wt .-%, based on the immersion cleaner.
  • the immersion cleaners according to the invention are generally prepared in the following manner: the aqueous builder solutions are first mixed with one another with stirring and at room temperature, for example a water glass solution with potassium hydroxide solution and, if appropriate, potassium triphosphate solution. The remaining constituents, ie the surfactants and optionally additives, are then likewise added to the concentrated aqueous builder solution with stirring. To prepare dilute application solutions, ie cleaning solutions, the immersion cleaners are generally metered directly into the cleaning bath with stirring.
  • Alkaline immersion cleaners containing an aqueous solution of 36.8 g / 1 builder and 3.2 g / 1 surfactant each were prepared by stirring the surfactant into the aqueous builder solution.
  • the builder each consisted of 3.7 g / 1 sodium pyrophosphate, 5.9 g / 1 sodium metasilicate and 9.9 g / 1 sodium carbonate.
  • the surfactant base can be found in each of the examples and comparative examples.
  • the immersion cleaner contained a 1: 1 mixture of a fatty alcohol ethoxylate with 12 to 18 C atoms in the fatty alcohol residue and an average degree of ethoxylation of 8 moles of fatty alcohol with a narrow homolog distribution and another fatty alcohol ethoxylate with 12 to 18 C atoms in the fatty alcohol residue and one average degree of ethoxylation of 16 moles per mole of fatty alcohol with narrow homolog distribution.
  • Tables 1 and 2 show the properties of such an immersion cleaner.
  • Example 2 a fatty alcohol ethoxylate with 12 to 18 carbon atoms and an average degree of ethoxylation of 12 moles per mole of fatty alcohol with a narrow homolog distribution was used.
  • Tables 1 and 2 below show the data obtained from this immersion cleaner.
  • the foam test for determining the primary foam was carried out at 60 ° C. according to DIN 53902, part 1. The primary foam and foam disintegration over 10 min were observed. To determine the cloud point, the solutions were slowly heated while observing the temperature. The cloud point of the surfactant mixtures should be above 60 ° C. To determine the cleaning effect, the immersion cleaners were greased with a corrosion protection oil "WD 40" at 60 ° C. in test plates and annealed at 75 ° C. for 24 hours.
  • Test sheets of ST 1203 were immersed at 60 ° C. for 5 minutes and the water wettability was then assessed optically and a combustion analysis was carried out at 400/600 ° C.
  • the data obtained are shown in column a) of Table 2.
  • Column b) shows the corresponding data obtained when the corrosion protection oil "WD 40" was replaced by a cutting oil "KS 212" from Shell Makron GmbH.
  • Column c) of Table 2 shows the data obtained when the sheets of ST 1203 were replaced by CuZn 37 sheets. While column d) shows the data when greased with the corrosion protection oil "WD 40", column e) contains the data when greased with the cutting oil "KS 212". Column e) shows the data which are obtained when the CuZn 37 sheets are immersed in immersion cleaning solutions after they have been previously greased with a cooling lubricant (P3-Multan R 86-7) containing non-ferrous metals.
  • a cooling lubricant P3-Multan R 86-7
  • the immersion cleaners were loaded with the corrosion protection oil "WD 40" to check the maximum oil load. Test plates were then immersed for 5 minutes and the water wettability after the sink was assessed optically.

Abstract

L'invention concerne l'utilisation de polyalkylèneglycoléthers d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion alcalins en association avec des adjuvants et/ou des mélanges d'adjuvants.
EP92919454A 1991-09-25 1992-09-16 Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants Expired - Lifetime EP0605495B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4131877 1991-09-25
DE4131877A DE4131877A1 (de) 1991-09-25 1991-09-25 Fettalkoholpolyalkylenglykole mit eingeengter homologenverteilung in schaumarmen tauchreinigern
PCT/EP1992/002128 WO1993006200A1 (fr) 1991-09-25 1992-09-16 Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants

Publications (2)

Publication Number Publication Date
EP0605495A1 true EP0605495A1 (fr) 1994-07-13
EP0605495B1 EP0605495B1 (fr) 1995-12-20

Family

ID=6441439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92919454A Expired - Lifetime EP0605495B1 (fr) 1991-09-25 1992-09-16 Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants

Country Status (3)

Country Link
EP (1) EP0605495B1 (fr)
DE (2) DE4131877A1 (fr)
WO (1) WO1993006200A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19515086A1 (de) * 1995-04-25 1996-10-31 Hoechst Ag Verfahren zur Entfernung von verunreinigenden Beschichtungen von Metalloberflächen
BR9611595A (pt) * 1995-11-17 1999-04-06 Unilever Nv Aditivo para uma formulação para lavagem de garrafas formulação para a lavagem alcalina de garrafas e processo para a lavagem de garrafas
DE19948413A1 (de) * 1999-10-07 2001-04-12 Unruh Stephan Reinigungslösung und Verfahren zur Reinigung von Werkstücken

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1445716A (en) * 1973-04-24 1976-08-11 Diversey Ltd Cleaning compositions
US3888783A (en) * 1973-10-10 1975-06-10 Amchem Prod Cleaner for tin plated ferrous metal surfaces, comprising phosphate, silicate and borax
US4048121A (en) * 1977-01-24 1977-09-13 Fremont Industries, Inc. Low temperature metal cleaning composition
DE3018173A1 (de) * 1980-05-12 1981-11-19 Henkel KGaA, 4000 Düsseldorf Schaumarme reinigungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9306200A1 *

Also Published As

Publication number Publication date
DE4131877A1 (de) 1993-04-01
EP0605495B1 (fr) 1995-12-20
DE59204782D1 (de) 1996-02-01
WO1993006200A1 (fr) 1993-04-01

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