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EP1987119B1 - Agent de lavage ou de nettoyage - Google Patents

Agent de lavage ou de nettoyage Download PDF

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Publication number
EP1987119B1
EP1987119B1 EP07703005A EP07703005A EP1987119B1 EP 1987119 B1 EP1987119 B1 EP 1987119B1 EP 07703005 A EP07703005 A EP 07703005A EP 07703005 A EP07703005 A EP 07703005A EP 1987119 B1 EP1987119 B1 EP 1987119B1
Authority
EP
European Patent Office
Prior art keywords
acid
washing
cleaning agent
agent according
previous
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.)
Not-in-force
Application number
EP07703005A
Other languages
German (de)
English (en)
Other versions
EP1987119A1 (fr
Inventor
Arnd Kessler
Claudia Schattling
Katja Peveling
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
Priority to PL07703005T priority Critical patent/PL1987119T3/pl
Publication of EP1987119A1 publication Critical patent/EP1987119A1/fr
Application granted granted Critical
Publication of EP1987119B1 publication Critical patent/EP1987119B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • 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
    • C11D1/721—End blocked 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/75—Amino oxides

Definitions

  • the invention relates to a washing or cleaning agent, in particular a hard surface cleaner, which in comparison to known agents has an increased emulsifying ability for fats and oils and the use of this agent for cleaning and care of hard surfaces such as the interiors of washing machines and dishwashers ,
  • Cleaning or care products usually contain surfactants and have a wide range of uses and depending on a very different composition. After the pH, alkaline, neutral and acid cleaning or care products, according to the offer form liquid and solid cleaning or care products are distinguished. Especially from liquid cleaning or care products, the consumer expects that he can use the agents both in the undiluted and in - dilute aqueous state and in each case receives a satisfactory cleaning or care result.
  • the surfactants and / or alkali carriers which can be replaced by acids depending on the application, optionally also solvents such as glycol ethers and lower alcohols.
  • the formulations also contain builders, depending on the type, also bleaching agents, enzymes, as well as perfume oils and dyes. The cleaning success depends to a great extent on the - also geographically very different - type of dirt and the properties of the surfaces to be cleaned.
  • cleaning or care products are used as general-purpose or special agents (car care products, oven cleaners, descaling agents, window cleaners, stain removers, floor care products, glass ceramic hob cleaners, stoves, leather care products, metal cleaning agents, furniture care products, pipe cleaners, sanitary cleaners, abrasives, carpet care products or toilet cleaners) assembled.
  • Technical cleaning or care products are mainly used in the beverage, food, cosmetic and pharmaceutical industries, but also in the metal industry for metal degreasing.
  • the product group also includes cleaning or care products for car washes, tank truck and aircraft cleaning or care products.
  • the group of cleaning or care products includes, for example, the dishwashing detergents and agents for cleaning or care of washing machine or dishwasher interior.
  • Contaminations such as fats and oils, food leftovers, lime deposits, soap scum or metal deposits as well as the corrosion protection of metal and glass in the foreground. Also in the industry, for example, the removal of fats and oils of interest.
  • cleaning agent sprays for removing lime deposits on bathroom tiles or for degreasing metal objects such as extractor hoods.
  • Means that provide good cleaning or care results without significant mechanical treatment offer in addition to the convenience for the user also the ability to clean surfaces whose mechanical treatment with the means is not or only to a small extent possible.
  • mechanically poorly cleaned surfaces are corners and angled surfaces, the inner surface of pipes and funnels, sharp-edged or intertwined surfaces, meshes, hose connections, but also surfaces which, due to their nature, must not be subjected to mechanical stress.
  • appliances such as washing machines or dishwashers, coffee machines or kettles are incomplete from the inside and only with great effort by mechanical action, for example To clean by a rag or a brush, so that cleaning or care products that perform well without significant mechanical treatment, even for these applications are desired.
  • the effect of the cleaning or care products should be so great that not only the large surfaces of the The inside of the machine, which is exposed to the direct and intensive operating pressure of the cleaning fleet and thus experiences a mechanical load, but also angled areas, hose connections, door seals and all low-flow zones are optimally cleaned and / or maintained in these machines.
  • the effect can be observed that takes place during the rest periods of the liquor, that is, in the periods in which no circulation of the liquor takes place, a separation of the liquor into aqueous and oily phase.
  • the result is a fat edge in the lower machine interior, which does not dissolve or insufficiently in the further cleaning or care process and leads to an overall poor cleaning or care result.
  • the effect may arise that, during cleaning with the agents described in the prior art, fat soils accumulate intensively in the areas which are exposed to only a small flow of water and there persistent incrustations and / or Oily streaks form, while on the large surfaces inside the machine interior quite a cleaning effect can be observed.
  • the object of the present invention was to provide a washing or cleaning agent which overcomes the above-mentioned problems.
  • this agent should have an increased emulsifying ability for fats and oils and thus improved performance in the area of fat removal.
  • Inventive cleaning or care products show over conventional means a significantly increased emulsifying ability for fats and oils.
  • the cleaning or care agent according to the invention is preferably used in the treatment of hard surfaces and is particularly suitable for the cleaning or care of washing machines or dishwashers, especially for dishwashers.
  • compositions of the invention contain as a first ingredient 0.1 to 4 wt .-% of a nonionic surfactant (A) of the general formula R 1 O [CH 2 CH (R 2 ) O] x R 3 , in which R 1 and R 3 independently of one another for H or a linear or branched, saturated or on or polyunsaturated, functionalized or non-functionalized hydrocarbon radical having 2 to 26 carbon atoms, wherein at least one of R 1 and R 3 is not H; R 2 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical and x stands for values between 1 and 140, where each R 2 can be different.
  • A nonionic surfactant of the general formula R 1 O [CH 2 CH (R 2 ) O] x R 3 , in which R 1 and R 3 independently of one another for H or a linear or branched, saturated or on or polyun
  • the detergents or cleaners contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactant selected from C 6-20 monohydroxyalkanols or C 5-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • nonionic surfactants (A) which have a melting point above room temperature.
  • Suitable nonionic surfactants (A) which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula R 1 O [CH 2 CH 2 O] w [CH 2 CH (R 2 ) O] x [CH 2 CH 2 O] y [CH 2 CH (R 3 ) O] z H in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each group R 2 or R 3 is independently selected from CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • nonionic surfactants of the general formula R 1 O [CH 2 CH 2 O] w [CH 2 CH (CH 3 ) O] x H are preferred, in which R 1 is a straight-chain or branched, saturated or mono- or polysubstituted unsaturated C 6-24 alkyl or alkenyl radical, preferably represents a C 12 -C 14 alkyl radical and the indices w and x independently of one another are integers from 1 to 12, preferably from 1 to 7 and in particular from 2 to 5 ,
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • the group of these preferred surfactants (A) include, for example, surfactants of the general formula R 1 -CH (OH) CH 2 O- (AO) w (A'O) x - (A "O) y - (A"'O) z R 2 in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical; A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 24 carbon atoms, where x is between 1 and 24 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched one Hydrocarbon radical having 2 to 24 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is a value of at least 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • the proportion by weight of the nonionic surfactant (A) is preferably between 0.1 and 3 wt .-%, preferably between 0.2 and 2.5 wt .-% and in particular between 0.4 and 2.0 wt.%.
  • Preferred agents according to the invention contain only one nonionic surfactant (A).
  • the weight fraction of the nonionic surfactant (B) is between 0.02 and 2% by weight and in particular between 0.05 and 1% by weight.
  • the two nonionic surfactants (A) and (B) in any proportion in the compositions according to the invention, such agents have proved to be particularly advantageous in terms of emulsifiability and cleaning performance in which the weight ratio of the surfactants (A) and ( B) is between 30: 1 and 1: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • compositions according to the invention may contain further nonionic surfactants, it being possible for the proportion by weight of the further nonionic surfactants to vary within wide ranges.
  • the proportion of additionally used nonionic surfactants is preferably below 6% by weight, more preferably below 4% by weight, preferably below 3% by weight, more preferably below 2% by weight and especially below 1% by weight.
  • compositions according to the invention in which the weight fraction of nonionic surfactants (A) and (B), based on the total weight of all nonionic surfactants present in the composition, is at least 60% by weight, preferably at least 80% by weight, preferably at least 90 Wt .-%, most preferably at least 95 wt .-% and in particular at least 98 wt .-% is.
  • agents according to the invention whose nonionic surfactants can be assigned exclusively to the nonionic surfactants of groups (A) and (B).
  • the sum of the weight fractions of all nonionic surfactants present in the composition is preferably between 0.2 and 10% by weight, more preferably between 0.2 and 8% by weight, very particularly preferably between 0.2 and 6% by weight in compositions according to the invention. -% and in particular between 0.2 and 4 wt .-%.
  • the alkyl glycosides have proved to be detrimental to the inventive effect of the claimed detergents or cleaners.
  • Preferred washing or cleaning agents therefore contain less than 1% by weight, preferably less than 0.5% by weight and in particular no alkyl glycosides.
  • polyhydroxy fatty acid amides of the formula wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C 1 - 4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • compositions according to the invention also contain a natural or fully synthetic organic thickener.
  • the field of application of thickeners, also called thickeners, is generally to increase the viscosity of liquids.
  • the effect of the thickener is based on various effects such as swelling, gelation, association of micelles, solvation, formation of network structures and / or hydrogen bonds and their interaction.
  • the molecular structure and relative molecular weight of the hydrocolloids determine the degree of thickening.
  • the combination of the nonionic surfactants (A) and (B) and a natural or fully synthetic organic thickener in a cleansing or care agent significantly increases the fat emulsifiability of this agent. It is possible to use in the compositions according to the invention all natural or fully synthetic organic thickeners known to the person skilled in the art, it also being possible to use a combination of several thickeners.
  • the agents according to the invention contain low molecular weight organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or else polyamides.
  • organic thickeners such as metal soaps, hydrogenated castor oil, modified fatty derivatives or else polyamides.
  • Polyvinyl alcohols, polyacrylic and polymethacrylic acids and their salts, polyacrylamides, polyvinylpyrrolidone, polyethylene glycols, styrene-maleic anhydride copolymers and salts thereof are used in particular from the large group of organic fully synthetic thickeners. Particular preference is given to the copolymers and terpolymers of acrylic and methacrylic acid.
  • Preferred thickening agents come from the groups of organic natural thickening agents such as starch, gelatin and casein and the modified natural substances, in particular the polysaccharides.
  • Important representatives of the latter group are (hydroxy) ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, ethylhydroxyethylcellulose, succinoglycan, xanthan gum, guar gum, locust bean gum, tragacanth, as well as derivatives and mixtures of these thickeners.
  • the thickener contained in the agents of the invention is selected from polysaccharides, preferably from cellulose compounds, xanthan gum and guar gum, and from acrylate thickeners, urethane thickeners and clays.
  • xanthan gum and derivatives thereof are available under the names Keltrol® RD (CP Kelco), Kelzan® S (CP Kelco), Kelzan® T (CP Kelco), Rhodopol® T (Rhodia) and Rhodigel® X747 (Rhone Poulenc).
  • Keltrol® RD CP Kelco
  • Kelzan® S CP Kelco
  • Kelzan® T CP Kelco
  • Rhodopol® T Rhodia
  • Rhodigel® X747 Rhone Poulenc
  • the xanthan gum content preferably makes at least 20% by weight, preferably at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, especially 99% by weight. of the total thickener contained in the agent.
  • Natural or fully synthetic organic thickeners are in the detergent or cleaning agent in an amount of 0.05 to 1 wt .-%, preferably 0.1 to 0.9 wt.%, Particularly preferably 0.15 to 0.8 wt. %, preferably 0.2 to 0.7 wt .-%, more preferably 0.25 to 0.6 wt.%, Very particularly preferably 0.3 to 0.5 wt .-% and in particular 0.3 to 0, 4 wt .-% included.
  • the weight ratio of surfactant (A) to thickener is preferably between 50: 1 and 1:10. This ratio is preferably between 22: 1 and 1: 2, preferably between 18: 1 and 1: 1.5, more preferably between 14: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1, and in particular between 6: 1 and 2: 1.
  • the weight ratio between surfactant (B) and thickener is preferably between 40: 1 and 1:30. This ratio is preferably between 10: 1 and 1: 8, preferably between 7.5: 1 and 1: 6, more preferably between 5: 1 and 1: 4 and in particular between 2.5: 1 and 1: 2.
  • Inventive detergents or cleaning agents are further characterized in that they are between 10 and 90 wt .-%, preferably between 13 and 70 wt .-%, particularly preferably between 16 and 50 wt.%, Very particularly preferably between 19 and 40 wt. % and in particular between 22 and 30 wt .-% of one or more inorganic or organic acid (s).
  • the resulting acidic detergents or cleaners according to the invention are also suitable, in addition to the removal of greasy or oily contaminants, also for the removal of limescale and calcareous soils.
  • Preferred detergents or cleaners are characterized in that a 1% strength by weight solution of the composition in water (20 ° C.) has a pH of less than 6.0, preferably less than 5.0, more preferably less than 4.5, very particularly preferably less than 4.0 and in particular less than 3.5.
  • the undiluted liquid composition preferably has a pH of less than 6, preferably less than 5, more preferably less than 4, more preferably less than 3 and in particular less than 2.5.
  • Suitable acids are organic mono- or polybasic, optionally substituted by hydroxyl groups, optionally unsaturated carboxylic acids having 2 to 6 carbon atoms in the molecule.
  • the acid has a dissociation constant less than 10 -6 .
  • Preferred aliphatic acids are formic, acetic, adipic, succinic, tartaric, malic, glutaric, sorbic, maleic, malonic, lactic, glycolic, propionic, oxalic and especially citric acid.
  • Salicylic acid or benzoic acid is preferably used from the group of aromatic carboxylic acids.
  • lactobionic acid and gluconic acid are also suitable.
  • Preferred inorganic acids are boric acid, sulfamic acid, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid. Also suitable is cyanuric acid.
  • the inventive agents may simultaneously contain one, two, three, four or more organic and / or inorganic acids (acid mixtures).
  • the detergents or cleaners contain one or two acids.
  • Preferred washing or cleaning agents are characterized in that they contain citric acid and at least one further acid, wherein the weight fraction of citric acid in the acid mixture of two or more acids at least 50 wt .-%, preferably at least 60 wt .-%, preferably at least 70 Wt.%, Particularly preferably at least 80 wt .-%, more preferably at least 90 wt .-% and in particular at least 95 wt .-%, based on the acids contained, is.
  • this acid is preferably citric acid or acetic acid.
  • the content of the agent in this one acid is then preferably between 15 and 60% by weight, particularly preferably between 18 and 50% by weight, very particularly preferably between 21 and 40% by weight and in particular between 24 and 30% by weight.
  • inventive cleaning or care agents additionally contain at least one surfactant from the group of anionic, cationic and amphoteric surfactants.
  • inventive agent may be in solid form such as powders, pellets, tablets, capsules, pearls, as well as in liquid form. If the agent is solid at room temperature, it is preferably completely or partially flowable / liquid at temperatures below 90 ° C., preferably below 80 ° C., preferably below 70 ° C., more preferably below 60 ° C. and in particular below 55 ° C.
  • Liquid thus refers to any state which is characterized at 20 ° C by a fluid (flowable) state of matter.
  • the agent is in the liquid state and has a viscosity above 50 mPas, preferably between 100 and 700 mPas, preferably between 200 and 600 mPas and in particular between 300 and 500 mPas.
  • Suitable carriers of liquid agents are water, nonaqueous solvents and mixtures of these.
  • Suitable organic carriers are alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers ), Ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichlorome
  • Such a solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for dry-cleaning, preferably containing more than 60% by weight, more preferably more than 80% by weight and in particular more than 90% by weight, of C12 to C14 hydrocarbons, in each case on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.
  • the proportion by weight of the organic solvents in the total weight of compositions according to the invention is preferably between 0.1 and 7% by weight, preferably between 0.1 and 5% by weight and in particular between 0.1 and 3% by weight.
  • Preferred washing or cleaning agents are characterized in that they contain, based on the total weight of the washing or cleaning agent, between 10 and 95% by weight, preferably between 20 and 80% by weight, preferably between 30 and 80% by weight. and in particular between 40 and 70% by weight of a liquid carrier, this carrier preferably being selected from the group which, in addition to water, furthermore comprises the alcohols, a water / alcohol mixture and in particular a water / glycerol mixture being particularly preferred.
  • the ratio between alcohol and water in the carrier is preferably between 10: 1 and 1: 100, preferably between 1: 1 and 1:90, particularly preferably between 1: 5 and 1:80, very particularly preferably between 1:10 and 1: 60 and especially between 1:15 and 1:40.
  • composition according to the invention may contain abrasive, undissolved and / or dispersed constituents, be cloudy or translucent or clear.
  • agents according to the invention described above preferably comprise further cleaning-active and / or care-active substances, preferably from the group of builders, polymers, bleaches, bleach activators, enzymes, corrosion inhibitors, disintegration aids, fragrances and perfume carriers.
  • Nonionic surfactant 0.1 to 4.0
  • Nonionic surfactant 0.01 to 2.0 Org. Acid 15 to 30 thickener 0.05 to 1.0
  • Solvent 0.1 to 7.0 fragrances 0 to 0.5
  • Other ingredients 0 to 10 water rest
  • Nonionic surfactant 0.1 to 4.0
  • Nonionic surfactant 0.01 to 2.0 citric acid 15 to 30 thickener 0.05 to 1.0 glycerin 0.1 to 7.0 fragrances 0 to 0.5
  • Other ingredients 0 to 10 water rest
  • a liquor containing the inventive agent, a standardized oily component and water in fixed amounts in a pump simulation test within 1 minute shows a phase separation of less than 15%, preferably less than 10%, more preferably less than 5%. , more preferably less than 2.5%, more preferably less than 1.0% and especially less than 0.2%, or less than 40%, preferably less than 30%, more preferably within 5 minutes less than 20%, more preferably less than 10%, more preferably less than 5%, and most preferably less than 2.5%.
  • Another object of the present application is therefore the use of a washing or cleaning agent according to the invention for the removal of greasy or oily stains.
  • An additional subject of the present invention is the use of the agent according to the invention for cleaning and care of hard surfaces, preferably of washing machines or dishwashers, in particular for cleaning the interior of dishwashers.
  • the agent is preferably introduced into the cutlery basket or directly into one of the baskets or the machine interior (interior floor).
  • the compositions according to the invention are used either by introduction into the dosing drawer or into the washing drum.
  • the consumer applies the agent directly from a storage bottle or a storage package on the surface to be cleaned.
  • the consumer introduce the agent into the machine in a prefabricated dosing unit, such as a tablet, a pouch with a solid or liquid filling or a small bottle, without risking it to be exposed to skin contact with the agent.
  • This dosing unit comprises, especially when using liquid agents for cleaning the interiors of washing machines or dishwashers between 100 to 400 ml, preferably between 200 to 300 ml.
  • the inventive agent is released at the beginning of the consumer started washing or cleaning program of the washing machine or dishwasher in the machine interior.
  • This can be achieved by completely or partially dissolving or dispersing the packaging or by melting individual or all packaging parts at temperatures of preferably less than 60 ° C., more preferably less than 50 ° C. and in particular less than 40 ° C.
  • the consumer can remove the closure part, for example, from a dosing unit such as a bottle filled with a solidified melt, a wax or a gel, and then introduce the dosing unit with the opening downwards into the machine interior.
  • a dosing unit such as a bottle filled with a solidified melt, a wax or a gel
  • the viscosity of the agent is reduced by the warm wash liquor and thus allows a rapid release of the liquid agent by flowing out of the package.
  • At least 80% by weight, preferably at least 90% by weight and in particular at least 95% by weight of the agent used in a package are preferred within 15, preferably within 12, preferably within 9, more preferably within 6 and in particular released within 5 minutes after reaching the maximum liquor temperature in the washing machine or dishwasher interior.
  • the agent has such a low viscosity that it flows out immediately after removal of the closure with a suitable inclination of the container and thus is available during the entire cleaning or care process.
  • the maximum liquor temperature is preferably greater than 30 ° C, preferably greater than 35 ° C, more preferably greater than 40 ° C, more preferably greater than 45 ° C, most preferably greater than 50 ° C and in particular 60 ° C to 70 ° C.
  • This test is used to simulate the short-term energy input through a circulation pump in a household dishwasher.
  • the energy for making the emulsion is introduced into the system at 800 rpm using a four-blade 30 mm diameter stirrer (IKA RW 20).
  • IKA RW 20 a four-blade 30 mm diameter stirrer
  • the stirrer is switched on for 30 seconds.
  • the sample is transferred to a 100 mL graduated cylinder.
  • a phase separation takes place in which settles an aqueous phase at the bottom of the cylinder.
  • the volume of this newly forming phase is measured in milliliters as a function of time.
  • Phase separation after Recipe 1 Recipe 2 Recipe 3 1 minute 1 mL 0.5 mL 0.5 mL 3 minutes 5mL 1.5 2mL 5 minutes 8 mL
  • the formulations 2 and 3 according to the invention have a significantly improved emulsifying ability compared to the comparative example, despite the small total amounts of nonionic surfactants. At the same time, these formulations also significantly improve performance when removing soiling containing grease or oil. This is especially true for the cleaning of hard surfaces.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (15)

  1. Agent de lavage ou de nettoyage contenant
    a) de 0,1 à 4 % en poids d'un agent tensioactif non ionique (A) répondant à la formule générale R1O[CH2CH(R2)O]xR3 dans laquelle
    - R1 et R3 représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un résidu d'hydrocarbure linéaire ou ramifié, saturé ou bien une fois, respectivement plusieurs fois insaturé, fonctionnalisé ou non fonctionnalisé, contenant de 2 à 26 atomes de carbone, au moins un des résidus R1 et R3 ne représentant pas un atome d'hydrogène ;
    - R2 représente un atome d'hydrogène ou un groupe méthyle, un groupe éthyle, un groupe n-propyle, un groupe isopropyle, un groupe n-butyle, un groupe 2-butyle ou un groupe 2-méthyl-2-butyle ;
    - x représente des valeurs entre 1 et 140, chaque radical R2 pouvant être différent ;
    b) de 0,02 à 2 % en poids d'un agent tensioactif non ionique (B) choisi parmi le groupe des aminoxydes en C8-C22 ;
    c) de 0,05 à 1 % en poids d'épaississants organiques naturels ou complètement synthétiques ;
    d) de 10 à 90 % en poids d'un ou de plusieurs acides inorganiques ou organiques.
  2. Agent de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que la fraction pondérale de l'agent tensioactif non ionique (A) se situe entre 0,1 et 3 % en poids, de préférence entre 0,2 et 2,5 % en poids, et en particulier entre 0,4 et 2,0 % en poids.
  3. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent tensioactif non ionique (A) comprend un agent tensioactif répondant à la formule générale R1O[CH2CH(R2)O]xH dans laquelle
    - R1 représente un résidu d'hydrocarbure aliphatique linéaire ou ramifié, contenant de 4 à 20 atomes de carbone, de préférence de 12 à 20 atomes de carbone et en particulier de 12 à 18 atomes de carbone ;
    - R2 représente un atome d'hydrogène ou un groupe méthyle, un groupe éthyle, un groupe n-propyle, un groupe isopropyle, un groupe n-butyle, un groupe 2-butyle ou un groupe 2-méthyl-2-butyle, en particulier un atome d'hydrogène ou un groupe méthyle, chaque radical R2 pouvant être différent ; et
    - x représente des valeurs entre 1 et 140, de préférence entre 1 et 120, et en particulier entre 1 et 90.
  4. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent tensioactif non ionique (A) représente un agent tensioactif répondant à la formule générale R1O[CH2CH(R2)O]xCH2CH(OH)R3 dans laquelle
    - R1 et R3 représentent, indépendamment l'un de l'autre, un résidu d'hydrocarbure linéaire ou ramifié, saturé ou bien une fois, respectivement plusieurs fois insaturé, fonctionnalisé ou non fonctionnalisé, contenant de 2 à 24 atomes de carbone ;
    - R2 représente un atome d'hydrogène ou un groupe méthyle, un groupe éthyle, un groupe n-propyle, un groupe isopropyle, un groupe n-butyle, un groupe 2-butyle ou un groupe 2-méthyl-2-butyle ;
    - x représente des valeurs entre 1 et 140, chaque radical R2 pouvant être différent.
  5. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce que la fraction pondérale de l'agent tensioactif non ionique (B) se situe entre 0,05 et 1 % en poids.
  6. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent tensioactif non ionique (B) représente un agent tensioactif répondant à la formule générale R1R2R3N-O dans laquelle :
    - R1 et R2 représentent, indépendamment l'un de l'autre, un groupe méthyle, un groupe éthyle ou un groupe propyle ; et
    - R3 représente un résidu de carbone linéaire ou ramifié contenant de 10 à 22, de préférence de 12 à 18 atomes de carbone.
  7. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce que le rapport pondéral des agents tensioactifs (A) et (B) se situe entre 30:1 et 1:1, de préférence entre 20:1 et 2:1, et en particulier entre 15:1 et 4:1.
  8. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient entre 13 et 70 % en poids, de manière particulièrement préférée entre 16 et 50 % en poids, de manière tout particulièrement préférée entre 19 et 40 % en poids et en particulier entre 22 et 30 % en poids, d'un ou de plusieurs acides inorganiques ou organiques.
  9. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs acides organiques ou inorganiques choisis parmi les acides suivants : l'acide formique, l'acide acétique, l'acide adipique, l'acide succinique, l'acide tartrique, l'acide malique, l'acide glutarique, l'acide sorbique, l'acide maléique, l'acide malonique, l'acide lactique, l'acide glycolique, l'acide propionique, l'acide oxalique, l'acide citrique, l'acide salicylique, l'acide benzoïque, l'acide lactobionique, l'acide gluconique, l'acide borique, l'acide sulfamique, l'acide phosphorique, l'acide sulfurique, l'acide chlorhydrique, l'acide nitrique, l'acide cyanurique.
  10. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient de l'acide citrique et au moins un autre acide, la fraction pondérale de l'acide citrique dans le mélange d'acides constitué par deux acides ou plus, s'élève à au moins 50 % en poids, de préférence à au moins 60 % en poids, de manière préférentielle à au moins 70 % en poids, de manière particulièrement préférée à au moins 80 % en poids, de manière encore plus préférée à au moins 90 % en poids, et en particulier à au moins 95 % en poids, rapportés aux acides qu'il contient.
  11. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'une solution à 1 % en poids de l'agent dans de l'eau (à 20 °C) présente une valeur de pH inférieure à 6, de préférence entre 3 et 6.
  12. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient un agent tensioactif anionique choisi parmi le groupe des disulfonates d'alkylphénoxybenzènes, des alkylbenzènesulfonates linéaires ou ramifiés, des alkylnaphtalènesulfonates linéaires ou ramifiés, des alkylsulfonates, des sulfonates d'oléfines, des sulfonates de paraffine, des alkylarylsulfonates, des savons, des alkylsulfates, des alkyléthersulfates, des alkylamidoéthersulfates, des alkylarylpolyéthersulfates, des sulfates de monoglycérol, de préférence des alkylbenzènesulfonates.
  13. Agent de lavage ou de nettoyage selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il présente, rapportés au poids total de l'agent de lavage ou de nettoyage, entre 10 et 95 % en poids, de préférence entre 20 et 80 % en poids, de manière préférentielle entre 30 et 80 % en poids et en particulier entre 40 et 70 % en poids d'un support liquide, ce support étant choisi de préférence parmi le groupe qui comprend, outre l'eau, également des alcools, un mélange eau/alcool et en particulier un mélange eau/glycérol étant particulièrement préféré.
  14. Utilisation d'un agent de lavage de nettoyage selon l'une quelconque des revendications précédentes pour lutter contre les salissures grasses ou huileuses.
  15. Utilisation d'un agent de lavage de nettoyage selon l'une quelconque des revendications précédentes pour le nettoyage et l'entretien de surfaces dures, de préférence de lave-linge ou de lave-vaisselle, en particulier pour le nettoyage de l'intérieur des lave-vaisselle.
EP07703005A 2006-02-24 2007-01-25 Agent de lavage ou de nettoyage Not-in-force EP1987119B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07703005T PL1987119T3 (pl) 2006-02-24 2007-01-25 Środek piorący lub czyszczący

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006009138A DE102006009138A1 (de) 2006-02-24 2006-02-24 Wasch- oder Reingiungsmittel
PCT/EP2007/000603 WO2007098831A1 (fr) 2006-02-24 2007-01-25 Agent de lavage ou de nettoyage

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EP1987119A1 EP1987119A1 (fr) 2008-11-05
EP1987119B1 true EP1987119B1 (fr) 2012-04-11

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EP (1) EP1987119B1 (fr)
AT (1) ATE553175T1 (fr)
DE (1) DE102006009138A1 (fr)
ES (1) ES2382213T3 (fr)
PL (1) PL1987119T3 (fr)
WO (1) WO2007098831A1 (fr)

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US10030216B2 (en) 2015-06-12 2018-07-24 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
US9404069B1 (en) 2015-06-12 2016-08-02 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
WO2022241180A1 (fr) * 2021-05-14 2022-11-17 Ecolab Usa Inc. Retraitement d'instrument par neutralisation

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WO1996019559A1 (fr) * 1994-12-21 1996-06-27 Solvay Interox Limited Compositions de peracide epaissies

Also Published As

Publication number Publication date
EP1987119A1 (fr) 2008-11-05
PL1987119T3 (pl) 2012-09-28
ATE553175T1 (de) 2012-04-15
WO2007098831A1 (fr) 2007-09-07
DE102006009138A1 (de) 2007-08-30
ES2382213T3 (es) 2012-06-06

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