EP0954559A1 - Produit detergent et nettoyant a l'etat pateux - Google Patents

Produit detergent et nettoyant a l'etat pateux

Info

Publication number
EP0954559A1
EP0954559A1 EP98907965A EP98907965A EP0954559A1 EP 0954559 A1 EP0954559 A1 EP 0954559A1 EP 98907965 A EP98907965 A EP 98907965A EP 98907965 A EP98907965 A EP 98907965A EP 0954559 A1 EP0954559 A1 EP 0954559A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
agent
alkyl
general formula
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
EP98907965A
Other languages
German (de)
English (en)
Other versions
EP0954559B1 (fr
Inventor
Thomas Merz
Khalil Shamayeli
Edgar Köppelmann
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.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
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Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0954559A1 publication Critical patent/EP0954559A1/fr
Application granted granted Critical
Publication of EP0954559B1 publication Critical patent/EP0954559B1/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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D1/72—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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to pasty detergents and cleaning agents for use in commercial laundry and a method for producing such agents.
  • Detergents used in the household are tailored to the needs there; they are usually powdery or liquid enough to be poured out and dosed easily. Since liquid detergents of this type are also said to be stable in storage within relatively wide temperature ranges, additions of organic solvents and / or hydrotropes are frequently added, but these do not themselves contribute to the washing or cleaning result and are therefore undesirable. A possibility for circumventing possible dosing problems with insufficiently liquid agents is proposed in the European patent application EP 253 151 A2.
  • liquid, partly highly viscous detergents based on nonionic and anionic surfactants which contain polyethylene glycol as hydrotrope and which do not have to be dosed by the user in liquid form, but rather are packed in portions in bags made of water-soluble material, for example polyvinyl alcohol.
  • the paste-like detergent described in European patent EP 295 525 B1 consists of a liquid phase in the temperature range below 10 ° C., which is formed from nonionic surfactant, and a solid phase of a certain grain size dispersed therein, which is formed from washing alkalis, sequestering agents and optionally anionic surfactants .
  • surfactants or their mixtures are used, the pour point (solidification point) of which must be below 5 ° C in order to avoid solidification of the paste at low transport and storage temperatures.
  • This detergent paste is intended for commercial laundries and is so flowable that it can be conveyed via a suction line using a conventional feed pump.
  • Another paste-like detergent which, as a nonionic surfactant, comprises 40 to 70% by weight of ethoxylated fatty alcohol with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohol which is liquid at room temperature
  • ethoxylated fatty alcohol with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohol which is liquid at room temperature
  • This pasty detergent is so structurally viscous that it is not flowable at room temperature under the influence of gravity, but has a significantly lower viscosity when sheared and is then flowable under the influence of gravity.
  • the metering of this pasty detergent or cleaning agent is preferably carried out by subjecting the agent to lowering the viscosity to shear and then metering the flowable agent by means of feed pumps.
  • the present invention was therefore based on the object of providing a pasty detergent for use in commercial laundries which has a reduced tendency to foam in the washing and pressing area and leads to lower amounts of surfactant on the washed fabrics and good washing performance with good storage stability exhibits, although it at least largely dispenses with the synthetic anionic surfactants of the alkylbenzenesulfonate type normally required for this.
  • the present invention relates to a pasty detergent for use in commercial laundries, containing nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which is characterized in that it 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of an ethoxylated alcohol of the general formula I,
  • R 3 -OR 4 (III) in which R 3 is an alkyl or alkenyl radical having 6 to 22 C atoms, in particular 8 to 22 C atoms and R 4 is hydrogen or an alkyl radical having 1 to 6 C atoms, and contains up to 15% by weight, preferably not more than 10% by weight, in particular not more than 8% by weight and particularly preferably not more than 5% by weight, of organic builders of the polymeric polycarboxylate type.
  • polymeric polycarboxylates are to be understood as meaning polymerization products of unsaturated mono- and / or dicarboxylic acids which, apart from carboxyl groups, have no further functionalities.
  • An agent according to the invention preferably contains up to 20% by weight, in particular up to 10% by weight, of an alkoxylated alcohol of the general formula IV as a further surfactant component in addition to the nonionic surfactants mentioned above,
  • the liquid phase of the paste-like composition according to the invention is essentially formed by the nonionic surfactants of the formulas I and II, which have different carbon chain lengths and different degrees of alkoxylation, and the alcohols or ethers of the formula III and, if appropriate, the additional surfactants according to formula IV.
  • the viscosity of the agent according to the invention can be adjusted by combining ethoxylated alcohols with the formulas I and II.
  • the radicals R 1 , R 2 and R 5 may be linear or branched, for example methyl-branched in the 2-position, linear residues with primary etherified alcohol functions being preferred.
  • the nonionic surfactant according to formula I preferably has a carbon chain length of 8 to 14, in particular 12 to 14, carbon atoms and an average degree of ethoxylation m of 1 to 8, in particular 1 to 5.
  • the nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, in particular 12 to 18 and particularly preferably 16 to 18 carbon atoms and a higher average degree of ethoxylation n of 3 to 14, in particular 6 to 12.
  • the ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably in weight ratios of 2: 1 to 1: 1.8.
  • the agent according to the invention can contain further nonionic surfactants usually used in washing and cleaning agents, such as, for example, alkyl polyglycosides and / or fatty acid polyhydroxyamides.
  • the surfactant component is preferably free from exclusively propoxylated alcohols.
  • R 4 is preferably a methyl, ethyl, propyl or butyl group, hydrogen and the methyl group, in particular hydrogen, being particularly preferred.
  • the agents contain up to 15% by weight, preferably 2% by weight to 10% by weight, of substances of the general formula III.
  • the agent can contain up to 25% by weight, preferably up to 7.5% by weight and in particular 0.5% by weight to 3% by weight of synthetic anionic surfactants, in particular selected from the alkylbenzenesulfonates, alkyl as further surfactants - or alkenyl sulfates and / or ether sulfates.
  • synthetic anionic surfactants which can preferably be incorporated into the agent according to the invention in solid, finely divided, largely anhydrous form, include in particular those of the sulfonate or sulfate type, which are normally present as alkali salts, preferably as sodium salts.
  • the surfactants of the sulfonate type mentioned can also be used in the form of their free acids.
  • Suitable anionic surfactants of the sulfonate type are in addition to the C 9 .
  • I3- alkylbenzenesulfonates are linear alkanesulfonates with 11 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, salts of sulfofatty acids and their esters, which are derived, in particular, from the sulfonated saturated C 12 - bis position C 18 fatty acids and lower alcohols such as methanol, ethanol and propanol derived, and olefin sulfonates, such as, for example, by sulfonation of terminal I2 C - C to be formed 18 -Olef ⁇ ne and subsequent alkaline hydrolysis.
  • Suitable surfactants of the sulfate type are, in particular, the primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation.
  • the derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • alkyl sulfates contain a tallow alkyl radical, that is to say mixtures with essentially hexadecyl and octadecyl radicals.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • the sulfated alkoxylation products of such alcohols so-called ether sulfates, can be contained in the compositions.
  • Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • the agent is completely free of synthetic anionic surfactants, at least free of synthetic anionic surfactants of the alkylbenzenesulfonate type.
  • the naturally occurring anionic surfactants include, in particular, the soaps which are present in the agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.5% to 2% by weight can.
  • the alkali salts of saturated and / or unsaturated C 12 come as soaps. I8 fatty acids, for example coconut, palm kernel or tallow fatty acid, in question.
  • salts of a carboxylic acid mixture is made, in each case based on the total carboxylic acid mixture, 2 wt .-% to 8 wt .-% C, 4 - up to 1 wt% C, 5 - 18 wt .-% up to 24 wt% C I6 -, up to 3 wt% C 17 -, 20 wt% to 42 wt% C I8 - and 30 wt% to 44 wt% C 20 . 22 carboxylic acid.
  • the solid phase of the agent according to the invention is essentially formed by the alkalizing agents and builder substances, it being possible for further particulate auxiliaries to be present if appropriate.
  • the solid phase should be dispersed as homogeneously as possible in the liquid surfactant phase.
  • the constituents of the paste-like composition contained as a solid phase should be finely divided and have an average grain size in the range from 5 ⁇ m to 200 ⁇ m, with at most 15% of the particles having a grain size of more than 200 ⁇ m.
  • relatively coarse-grained solids for example those which contain 20% to 50% particles with particle sizes above 100 ⁇ m, without disadvantage into the paste-like compositions.
  • the mean grain size of the particles forming the solid phase is preferably 10 ⁇ m to 80 ⁇ m and in particular 10 ⁇ m to 60 ⁇ m, the maximum grain size being below 300 ⁇ m, in particular below 250 ⁇ m. 90% by weight of the solid powdery constituents are preferably less than 200 ⁇ m, in particular less than 150 ⁇ m.
  • the average grain size can be determined using known methods (for example by means of laser diffraction or a Coulter Counter).
  • the alkalizing agents contained as a further component are often also referred to as washing alkalis. They are mainly assigned to the fixed phase. Under the conditions of use of agents according to the invention, they ensure a pH in the alkaline range which is normally in the range from 9 to 13, in particular from 10 to 12 (in each case measured in a 1% strength by weight solution of the agent in ion-exchanged water).
  • the preferred alkalizing agent is amorphous alkali silicate, in particular sodium metasilicate of the composition Na 2 O: SiO 2 from 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form.
  • alkali silicate In addition to the alkali silicate, they are also anhydrous Alkali carbonate or alkali hydrogen carbonate is suitable, but this requires larger amounts of liquid phase due to absorption processes and is therefore less preferred.
  • the proportion of alkalizing agents in the agents is 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight and in particular 40% by weight to 60% by weight.
  • the alkalizing agent component of the agent according to the invention can consist solely of silicate.
  • Alkali carbonate or alkali hydrogen carbonate is preferably present in amounts not exceeding 40% by weight, in particular up to 25% by weight, and in a preferred embodiment of the invention in amounts below 10% by weight.
  • polymeric alkali phosphates such as sodium tripolyphosphate
  • Their proportion is preferably up to 70% by weight, in particular 15% by weight to 40% by weight, based on the total composition, the proportion of the other solids, for example the alkali silicate and / or optionally contained aluminosilicate, accordingly can be reduced.
  • Suitable organic builder substances are, in particular, monomeric polycarboxylic acids or hydroxycarboxylic acids such as citric acid or gluconic acid or their salts and, in addition, those from the class of the aminopolycarboxylic acids and polyphosphonic acids.
  • the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, preference being given to using N, N-bis (carboxymethyl) aspartic acid.
  • Suitable polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, amino-tri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylene tetramine tetra (methylenephosphonic acid).
  • the aforementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts.
  • the builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts also being particularly preferred here.
  • Carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have been proven, such as oxidized polysaccharides according to international patent application WO 93/08251, polyacrylates, polymethacrylates, polymaleinates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those from 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European Patent EP 022 551.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000.
  • Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and by polymerizing esters of glycolic acid, Introduction of stable terminal end groups and saponification to the sodium or potassium salts can be obtained.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • the proportion of organic, carboxyl group-containing builder materials in the paste-like compositions according to the invention can be up to 10% by weight, preferably 1% to 7.5% by weight and in particular 2% by weight to less than 5% by weight, the proportion of polymeric polycarboxylate being as small as possible and in a preferred embodiment of the invention being less than 5% by weight.
  • these substances mentioned are also used in anhydrous form.
  • the proportion of other organic polymers is likewise preferably as small as possible and is preferably in the range from 0.5% by weight to 1% by weight; In a further preferred embodiment of the invention, the proportion of the sum of polymeric polycarboxylate and other organic polymers is less than 5% by weight.
  • crystalline alkali silicates and finely divided alkali alumosilicates are suitable as inorganic builders for use in agents according to the invention.
  • Suitable zeolites normally have a calcium binding capacity in the range from 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837.
  • Their particle size is usually in the range from 1 ⁇ m to 10 ⁇ m. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case.
  • Such crystalline layered silicates are described, for example, in European patent application EP 164 514.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
  • Usable crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc).
  • the content of inorganic builder material in the paste can be up to 35% by weight, preferably up to 25% by weight and in particular 10% by weight to 25% by weight.
  • agents according to the invention 5% by weight to 25% by weight, in particular 10% by weight to 20% by weight, of builder substances are present, the amount of polymeric polycarboxylates not more than 10% by weight, in particular not more than 7% by weight, and the amount of phosphonates is not more than 2% by weight, in particular not more than 1% by weight.
  • a paste-like agent according to the invention can contain an oxygen-containing oxidizing agent and optionally a bleach activator.
  • Inorganic peroxygen compounds in particular are used as oxidizing agents, the sodium perborate tetrahydrate and the sodium perborate monohydrate being of particular importance in addition to sodium percarbonate.
  • Other suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used.
  • Oxidizing agents can be present in the agents according to the invention preferably in amounts of up to 25% by weight and in particular from 10% by weight to 20% by weight.
  • the oxidizing power of such oxidizing agents can be improved by using bleach activators which form peroxocarboxylic acids under perhydrolysis conditions.
  • bleach activators which form peroxocarboxylic acids under perhydrolysis conditions.
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions, with tetraacetylethylenediamine being particularly preferred.
  • Agents according to the invention preferably contain up to 10% by weight, in particular from 3% by weight to 8% by weight, of bleach activator.
  • transition metal salts and complexes as for example in European patent applications EP 0 392 592, EP 0443 651, EP 0458 397, EP 0 544490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 suggests that, as so-called bleaching catalysts, in addition to or instead of the conventional bleaching activators, there is an increase in the bleaching performance. Also particularly suitable are those known from German patent applications DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20411 and DE 196 20 267 as bleach activating catalysts
  • Transition metal complexes Bleach-activating transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are present in agents according to the invention in amounts of preferably not more than 1% by weight, in particular 0.0025% by weight contain up to 0.25% by weight.
  • an agent according to the invention can contain further washing aids, which can normally be present in amounts of up to about 15% by weight, based on the finished agent.
  • Enzymes, graying inhibitors, soil-release agents, color transfer inhibitors such as hopmo and / or copolymers of vinylpyrrolidone and / or vinylimidazole, optical brighteners, further foam regulators and / or colorants and fragrances can be used, for example, as washing auxiliaries of this type.
  • fragrances are contained, which are generally liquid, these go into the liquid Phase of inventive agents over. Because of their small amount, however, they have no significant influence on the flow behavior of the pastes.
  • the pasty detergents according to the invention are preferably essentially free of water.
  • “Substantially free of water” is understood to mean a state in which the content of free water, that is to say which is not in the form of water of hydration and constitutional water, is below 3% by weight, preferably below 2% by weight and in particular below 1 % By weight. Higher water contents are disadvantageous because they increase the viscosity of the agent disproportionately and in particular reduce its stability.
  • Organic solvents which include the low molecular weight and low-boiling alcohols and ether alcohols usually used in liquid concentrates, and hydrotropic compounds may be present in amounts of up to 6% by weight, but are preferably not present.
  • Enzymes which may be present in the agents according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or cellulase is particularly preferred.
  • the proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight.
  • the enzymes can be adsorbed onto carriers in a conventional manner and / or embedded in coating substances or incorporated into the pastes as concentrated liquid formulations which are as anhydrous as possible.
  • Proteases that can be used are, for example, from international patent applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94 / 25579, WO 94/25583, WO 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95 / 27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627.
  • Enzymes stabilized against oxidative damage are preferably used, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm.
  • Suitable graying inhibitors or soil-release active substances are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose.
  • Methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose are preferably used.
  • the soil release active ingredients commonly used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer made from polyoxyethylene glycol and polyethylene terephthalate.
  • German laid-open specification DT 22 53 063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
  • European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such soil release polymer.
  • European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units.
  • the proportion of graying inhibitors and / or soil release active substances in agents according to the invention is generally not more than 2% by weight and is preferably 0.5% to 1.5% by weight. In a preferred embodiment of the invention, the agent is free from such active ingredients.
  • the color transfer inhibitors that are suitable for use in agents according to the invention include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole, and mixtures thereof.
  • the proportion of color transfer inhibitors in agents according to the invention is preferably 0.1% by weight to 2% by weight, in particular 0.2% by weight to 1% by weight.
  • the agent is free from such active ingredients.
  • Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be present as optical brighteners for textiles made in particular from cellulose fibers (for example cotton).
  • cellulose fibers for example cotton
  • salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable Instead of the morpholine group, wear a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • Brighteners of the optionally substituted dibenzofuranylbiphenyl or optionally substituted 4,4'-distyryl-diphenyl type may also be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used.
  • Brighteners of the 1,3-diaryl-2-pyrazoline type for example l- (p-sulfoamoylphenyl) -3- (p-chloro-henyl) -2-pyrazoline, and compounds of the same structure are particularly suitable for polyamide fibers.
  • the content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight. In a preferred embodiment of the invention, the agent is free from such active ingredients.
  • the usual foam regulators which can be used in the compositions according to the invention in addition to the foam-regulating compounds of the general formula III include, for example, polysiloxane-silica mixtures, the fine-particle silica contained therein preferably being silanated.
  • the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
  • Other defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C., saturated fatty acids or soaps with in particular 20 to 22 C. Atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms.
  • sodium monoalkyl phosphate and / or dialkyl phosphate is preferred
  • the proportion of foam regulators can preferably be 0.2% by weight to 2% by weight. In many cases, the additional use of defoaming agents can be dispensed with entirely.
  • dehydrating agents can also be used, for example in the form of salts which bind water of crystallization, such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P 4 O 10 or Al 2 O 3 can be used.
  • Such dehydrating agents with which the water content of agents according to the invention can be reduced to particularly low values, are present in the agents in amounts of preferably 1% by weight to 10% by weight and in particular 2% by weight to 8% by weight of the invention.
  • the procedure is preferably such that the nonionic surfactants of the formulas I and II and, if appropriate, IV are initially introduced, the alcohol or ether of the formula III is admixed and, if appropriate, polymeric with a further foam regulator, soap or the underlying fatty acid Polycarboxylate or other organic polymer, synthetic anionic surfactant and optical brightener mixed to form a homogeneous premix.
  • a premix is largely stable in storage and flowable at temperatures in the range from room temperature to 40 ° C., even if the components of the premix are not always completely liquid or dissolved at these temperatures.
  • This premix preferably after heating to temperatures in the range from 40 ° C.
  • the resulting washing or cleaning agents according to the invention are flowable and pumpable immediately after manufacture by the acting shear forces and can thus be filled into conventional sales containers.
  • a paste-like agent according to the invention preferably has a viscosity at 25 ° C. in the range from 80,000 mPas to 250,000 mPas, in particular 100,000 mPas to 250,000 mPa s, measured with a Brookfield rotary viscometer (spindle No. 7) at 5 revolutions per minute on. Under otherwise identical conditions, the viscosity at 50 revolutions per minute is preferably 20,000 mPas to 80,000 mPa s. In order to take into account any thixotropy effect of the paste, these numerical values for viscosity refer to the reading after a measuring time of 3 minutes.
  • the paste-like detergent and cleaning agent preferably has a viscosity at room temperature such that it is not flowable under the influence of gravity. It is then preferably particularly pseudoplastic, that is to say it has a significantly lower viscosity when sheared and is flowable under the influence of gravity, it being particularly preferred to have a viscosity in the range from 3,000 mPas to 12,000 mPas at 25 ° C. and a shear rate of 0.01 s "1 , to be determined with a CS rheometer from Bohlin with a plate / plate measuring system, plate spacing 0.5 to 4 mm.
  • an agent according to the invention preferably has a viscosity which is substantially 100 to 1000 times lower.
  • the reduction in viscosity during shear is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring.
  • the viscosities mentioned do not affect measurements directly after manufacture relate to the paste, but to stored pastes, so to speak in equilibrium, since the shear forces acting in the course of the manufacturing process lead to a lower paste viscosity, which increases over time to the decisive final viscosity. Storage times of 1 month are usually completely sufficient for this.
  • An agent according to the invention normally has a density in the range from 1.3 kg / 1 to 1.6 kg / 1.
  • the agent according to the invention can be metered using conventional devices for metering pastes, as described, for example, in international patent application WO 95/29282, German patent application DE 196 05 906, German patent DE 44 30418 or European patent EP 0 295 525 EP 0 356 707 have been described.
  • a device which is particularly well suited for metering structurally viscous pasty detergents is known, for example, from international patent application WO 95/09263 and is preferably used for metering paste-viscous pastes according to the invention.
  • the detergents and cleaning agents according to the invention can, if appropriate, also be filled in portions, in particular in water-soluble films. Films of this type are described, for example, in European patent application EP 253 151.
  • Tables 1 and 2 below give some examples of the composition of detergents according to the invention.
  • the pasty detergents had very good storage stability and had excellent cleaning performance even in the absence of synthetic anionic surfactant.
  • Table 1 Composition of pasty detergents (% by weight)
  • I4 fatty alcohol + 4 EO + 5 PO (Dehypon® LS 54; manufacturer Henkel KGaA) f) C, 6/22 fatty acid Na salt (Edenor® HT 35; manufacturer Henkel KGaA) g) polyvinylpyrrolidone (Sokalan® HP 50 ; Manufacturer BASF AG) h) polymeric polycarboxylate (Sokalan® CP 5; manufacturer BASF AG) i) disodium hydroxyethane diphosphonate (Turpinal® 2 NZ; manufacturer Henkel KGaA) k) carboxymethyl cellulose-methyl cellulose mixture (2.5: 1)
  • Table 2 Composition of pasty detergents (% by weight)

Abstract

L'invention concerne un produit détergent et nettoyant, à l'état pâteux, contenant un agent tensioactif non ionique, un adjuvant organique et/ou inorganique, un agent alcalinisant et, éventuellement, un agent de blanchiment, une enzyme, un polymère inhibant du grisage et/ou d'autres constituants courants, caractérisé en ce qu'il renferme de 5 % à 30 % en poids d'un alcool éthoxylé de formule générale (I): R1-(OC2H4)m-OH, dans laquelle R1 représente un reste alkyle ou alkényle de 9 à 15 atomes de carbone, avec un indice d'éthoxylation moyen, m, de 1 à 8, de 1 % à 20 % en poids d'un alcool éthoxylé de formule générale (II): R2-(OC2H4)n-OH, dans laquelle R2 désigne un reste alkyle ou alkényle de 12 à 22 atomes de carbone, avec un indice d'éthoxylation moyen, n, de 3 à 14, sous réserve que n soit au moins de 1,0 supérieur à m, de 20 % à 80 % en poids d'agent d'alcalinisation, de 1 % à 20 % en poids, en particulier, de 3 % à 15 % en poids d'alcool ou d'alkyléther de chaîne moyenne à longue, de formule générale (III): R3-O-R4, dans laquelle R3 désigne un reste alkyle ou alkényle de 6 à 22 atomes de carbone, et R4 désigne un hydrogène ou un reste alkyle de 1 à 6 atomes de carbone, et jusqu'à 15 % en poids d'adjuvant organique du type polycarboxylate polymère.
EP98907965A 1997-01-30 1998-01-21 Produit detergent et nettoyant a l'etat pateux Expired - Lifetime EP0954559B1 (fr)

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DE19703364A DE19703364A1 (de) 1997-01-30 1997-01-30 Pastenförmiges Wasch- und Reinigungsmittel
DE19703364 1997-01-30
PCT/EP1998/000299 WO1998033881A1 (fr) 1997-01-30 1998-01-21 Produit detergent et nettoyant a l'etat pateux

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DE (2) DE19703364A1 (fr)
ES (1) ES2185149T3 (fr)
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Also Published As

Publication number Publication date
CA2278743C (fr) 2007-05-15
SK101799A3 (en) 2000-05-16
DE59806048D1 (de) 2002-11-28
ATE226627T1 (de) 2002-11-15
PL186322B1 (pl) 2003-12-31
HUP0001025A3 (en) 2003-02-28
HUP0001025A2 (hu) 2000-09-28
US6329333B1 (en) 2001-12-11
PL334944A1 (en) 2000-03-27
DE19703364A1 (de) 1998-08-06
CA2278743A1 (fr) 1998-08-06
ES2185149T3 (es) 2003-04-16
EP0954559B1 (fr) 2002-10-23
WO1998033881A1 (fr) 1998-08-06

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