WO2000037596A2 - Procede permettant d'empecher les depots - Google Patents

Procede permettant d'empecher les depots Download PDF

Info

Publication number
WO2000037596A2
WO2000037596A2 PCT/EP1999/009731 EP9909731W WO0037596A2 WO 2000037596 A2 WO2000037596 A2 WO 2000037596A2 EP 9909731 W EP9909731 W EP 9909731W WO 0037596 A2 WO0037596 A2 WO 0037596A2
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
mol
polyacrylate
polymeric
Prior art date
Application number
PCT/EP1999/009731
Other languages
German (de)
English (en)
Other versions
WO2000037596A3 (fr
Inventor
Ulrich Pegelow
Maria Liphard
Beatrix Kottwitz
Katrin Schnepp-Hentrich
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2000037596A2 publication Critical patent/WO2000037596A2/fr
Publication of WO2000037596A3 publication Critical patent/WO2000037596A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a method for preventing deposits on heating elements during the machine washing of textiles, and to an agent which prevents such deposits.
  • Deposits on heating elements primarily consist of calcium and magnesium compounds, and if certain detergents containing silicate or zeolite are used in smaller quantities, they also consist of silicate and aluminosiiicatic deposits. The deposits arise in particular due to the hardness of the water used.
  • water hardness The most important components of water hardness are salts of calcium and magnesium, especially the chlorides, sulfates and hydrogen carbonates, which are referred to as the so-called hard formers. Since the bicarbonates are converted to carbonates in the heat, some of the calcium salts precipitate as poorly soluble CaCO 3 when washed at elevated temperatures. Basic magnesium carbonates also precipitate at high magnesium concentrations. If the detergents used themselves contain carbonate, for example in the form of alkali carbonates or precursors that release carbonate during the washing process, such as percarbonates, this carbonate content also requires the formation of insoluble calcium and magnesium carbonate residues on the heating elements. Especially in areas with high water hardness, ie water hardness of more than 140 mg calcium oxide per liter (14 ° d), such deposits on heating elements are a major problem.
  • copolymers of acrylic and maleic acid are also used to disperse calcium carbonate in the wash liquor.
  • a water softener in tablet form is proposed in European patent EP-B-628627, which is to be used in addition to a washing or cleaning agent.
  • This water softener consists of 60 to 98% by weight of a combination of citrate / citric acid and a water-softening polymer as well as polyethylene glycol and other auxiliary substances.
  • the polymer is either a biodegradable polymer based on peptides or a maleic acid-acrylic acid copolyme, for example Sokalan CP5
  • German published patent application DE 2240309 describes an agent which contains 5 to 40% by weight of surfactant, 30 to 70% by weight of alkali carbonate, 1 to 30% by weight of complexing agents, preferably citrate, and 0.05 to 15% by weight of a deposit preventing agent Cal ⁇ um carbonate contains this
  • Depositor is either a phosphate, a phosphonic acid or a polymeric carboxylate
  • EP-A-869169 a detergent is described which contains 5 to 80% by weight of soda, 5 to 24% by weight of surfactant and 0.5 to 25% by weight of a maleate copolymer, the copolymer having a molecular weight between 500 and 7000 g / mol, consists of at least 50% by weight of maleate units which are neutralized to at least 70 mol% and contains 10 to 50 mol% of acrylate units, as well as 1 to 10 mol% of nonionic comonomers To improve the washing performance and on the other hand to prevent the deposition of hard formers on the wash.
  • the document does not contain any references to its influence on heating rod deposits
  • the detergent compositions according to European patent EP-B-572288 contain 10 to 30% by weight of alkali carbonate, 2 to 10% by weight of an amorphous aluminosilicate and 3 to 15% by weight of a growth inhibitor for calcium carbonate crystals which is can be polyaspartic acid, a phosphonic acid, a copolymeric polycarboxylate with a molecular weight between 50,000 and 70,000 g / mol or a polyacrylate with a molecular weight between 2 and 10,000 g / mol, citrate or other carboxylic acids.
  • the function of the amorphous aluminosilicate as a host lattice for calcium-containing precipitates is essential for the action of this agent.
  • European patent application EP-A-130640 describes a detergent composition which, in addition to surfactants and phosphate-free builder substances, contains 0.3 to 5% by weight of such a polyacrylate polymer with a molecular weight between 2000 and 10000 g / mol.
  • This agent has particular advantages in removing clay-based soiling from the laundry.
  • the agents contain 5 to 80% by weight of builder substances, which can be selected from a wide range of organic and inorganic compounds. Zeolites, carboxylates, carbonates and alkali metal silicates are mentioned in particular here. The document does not contain any indication that the polymers prevent the formation of deposits on heating elements.
  • DE 3715051 describes a detergent builder which has advantages, among other things, in the inhibition of deposits on heating elements. It contains a silicate that binds calcium ions and a mixture of two different acrylic acid polymers with different viscosity numbers. This can be a mixture of two homopolymers, one homopolymer and a copolymer of acrylic acid (at least 50 mol%) with monomers of other ethylenically unsaturated dicarboxylic acids (C ⁇ ), for example methacrylic acid, itaconic acid or maleic acid, or two copolymers. The copolymers can contain up to 20 mol% of carboxyl-free ethylenically unsaturated monomers. It has now been found that polymeric polyacrylates are suitable for reducing the formation of residues on heating rods when used together with crystalline aluminosilicate and alkali carbonate as builders.
  • a first object of this invention is a method for preventing deposits on heating rods during the machine washing of textiles, using water of any water hardness and a builder system containing crystalline aluminosilicate and alkali carbonate as the main inorganic constituents, characterized in that an incrustation inhibitor polymeric polyacrylate with a molecular weight less than 10,000 g / mol is used.
  • the polymeric polyacrylates are preferably homopolymers, for example the sodium salts of polyacrylic acid.
  • polyacrylates which preferably have a molecular weight of 3000 to 8000 and particularly preferably 4000 to 5000 g / mol, have proven to be particularly suitable according to the invention.
  • the molar masses given in this document for polymeric polycarboxylates are weight-average molar masses M w , which were basically determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylate standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene sulfonic acids are generally higher than the molar masses specified in this document.
  • the method according to the invention can be used when using water of any hardness.
  • the most important components of water hardness are salts of calcium and magnesium, especially chlorides, sulfates and the like. Bicarbonates. Since the bicarbonates are converted to carbonates in the heat, some of the calcium salts precipitate as poorly soluble CaCO 3 when the water is heated. At very high magnesium concentrations, basic magnesium carbonates can also be used fail.
  • the hardness or total hardness of the water means the content of alkaline earth metal ions.
  • degree of hardness was introduced to identify water and its hardness (° d, previously also ° dH): 1 ° d corresponds to (in liters) 10.00 mg CaO or 7J9 mg MgO.
  • the specification millimoles per liter (mmol / l) is common. A distinction is made between the following hardness ranges:
  • the method according to the invention is preferably applied to hard or very hard water, i.e. Water with a hardness of at least 14 ° d; however, the advantages of the method can already be seen in soft and medium-hard water.
  • a detergent is preferably also used. It can be preferred if the polymeric polyacrylate and the builder system are present in the detergent, the polymer preferably in amounts of 0.1 to 15% by weight, in particular 0.5 to 10 and particularly preferably 2 to 5% by weight .-%, is used, and no other separate agent for water softening is used.
  • the polymeric polyacrylate is contained in a separately added water softener, which preferably also contains the inorganic softening constituents used in the process, and is preferably metered in such a way that the polyacrylate, based on the detergent additionally used, in amounts of 0.1 up to 15% by weight, in particular from 0.5 to 10 and particularly preferably from 2 to 5% by weight, is used.
  • the polymer can be added simultaneously with the addition of the detergent. Alternatively, however, the polymer can also be added before the detergent is added, so that a water pretreated with the polymer is then mixed with the detergent. It is also conceivable to add the polymers to the wash liquor after the detergent has been added, but this replenishment takes place before the wash liquor is heated.
  • inorganic constituents are used for water softening in the process. These are in particular crystalline aluminosilicates and alkali carbonates.
  • Preferred crystalline aluminosilicates are the zeolites A, P, X and Y. However, mixtures of A, X, Y and / or P are also suitable. Zeolite P®, for example, is particularly preferred as zeolite MAP® (commercial product from Crosfield). Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 10 to 22% by weight, in particular 15 to 22% by weight, of bound water.
  • detergents are used which contain at least part of the crystalline aluminosilicate in the form of zeolite A.
  • at least part of the zeolite used preferably at least 20% by weight, consists of faujasite-type zeolite.
  • zeolite of the faujasite type denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • the pure zeolite X is preferred.
  • the alkali carbonates are preferably sodium and / or potassium carbonate, the use of sodium carbonate being particularly preferred.
  • Alkali carbonate does not necessarily have to be used directly, but rather can also from precursors which only form alkali carbonate during the process Will be provided. Particularly noteworthy is alkali percarbonate, which releases alkali carbonate under the influence of moisture.
  • the use of zeolite and sodium carbonate is preferred, the weight ratio in which the crystalline aluminosilicate and the alkali carbonate are used being in the range from 1: 5 to 5 1, particularly preferably in the range from 1.2 to 2: 1 be preferred if the agents contain alkali carbonate at least in the same amount as crystalline aluminosilicates, since experience has shown that such compositions have a higher bulk density and additionally also have a larger alkali reserve
  • another object of the invention is a water softener which a) 0.1 to 30 wt .-% polymeric polyacrylate with a molecular weight ⁇ 10000 g / mol and b) 1 to 60% zeolite and c) 1 to Contains 60% by weight of alkali carbonate, the sum of components a, b and c making up at least 90% by weight of the total water softener.
  • This water softener is suitable for use in the process described above, where it is used in addition to an additional detergent.
  • the components a, b and c contained have already been described in detail above.
  • Preferred water softeners contain component a) in amounts of 0.5 to 15% by weight, particularly preferably in amounts of 2 to 10% by weight, and component b) in amounts of 10 to 50% by weight, particularly preferably in amounts of 15 to 45% by weight, and component c) in amounts of 10 to 50% by weight, preferably in amounts of 15 to 45% by weight.
  • the water softener can contain small amounts of other builder substances
  • detergents and water softeners used in the process can contain further builder substances.
  • the copolymeric polycarboxylates usually used as cobuilders in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, can also be found to be particularly suitable as copolymers of acrylic acid with maleic acid, 50 to 90 % By weight of acrylic acid and 50 to 10 % By weight of maleic acid.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the polymers can also contain allylsulfonic acids, such as, for example, in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as, for example, in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • both these copolymers and the polyacrylates essential to the invention are used in the process, the ratio of the polyacrylate to the acrylic acid-maleic acid copolymer being in the range from 2: 1 to 1:20, preferably 1: 1 to 1:15 , lies.
  • the total polymer content of the agents used in the process is preferably 0.5 to 20% by weight, in particular 2 to 10% by weight.
  • the invention further relates to a detergent or cleaning agent comprising inorganic builders and organic cobuilders, which is characterized in that it contains at least 2 different polymeric polycarboxylates as organic cobuilders.
  • the first polymeric polycarboxylate contains a copolymer of acrylic acid, in particular a copolymer with methacrylic acid with a molecular weight in the range from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol.
  • a further polymeric polycarboxylate is preferably a homopolymer of acrylic acid, in particular a homopolymer with a molecular weight of less than 10,000 g / mol contain.
  • a homopolymer and a copolymer are used as polymeric polycarboxylates in the composition, the weight ratio of copolymer to homopolymers being in the range from 20: 1 to 1: 2, preferably 15 : 1 to 1 year.
  • Suitable inorganic builders are preferably crystalline aluminosilicate and alkali carbonate, the ratio in which the crystalline aluminosilicate and alkali carbonate are used preferably in the range from 1: 5 to 5: 1, particularly preferably in the range 1: 2 to 2 : 1 lies.
  • these agents according to the invention are not only suitable for preventing incrustations on heating rods, but also show improved secondary washing behavior compared to conventional agents which contain only a polymeric polycarboxylate.
  • the agents show advantages in the overall incrustation, the textile ash and in the wet tear behavior.
  • the agents used in the process according to the invention or the agents according to the invention, in particular the detergent can contain further ingredients.
  • other builder substances which, however, are preferably only present in smaller amounts than the inorganic builder zeolites and alkali metal carbonates already mentioned.
  • M sodium or hydrogen
  • x is a number from 1.6 to 4
  • y is a number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3.
  • Na 2 Si2 ⁇ 5-yH 2 O preferred.
  • Such compounds are commercially available, for example, under the name SKS® (Clant).
  • SKS-6® is primarily a ⁇ -sodium disilicate with the formula Na 2 Si 2 O 5 yH 2 O
  • SKS-7® is predominantly ß-nathum disilicate.
  • acids e.g. citric acid or carbonic acid
  • Kanemit NaHSi 2 O 5 yH 2 O commercially available under the names SKS-9® or SKS-10® (Clariant).
  • SKS-9® or SKS-10® commercially available under the names SKS-9® or SKS-10® (Clariant).
  • SKS-9® or SKS-10® commercially available under the names SKS-9® or SKS-10® (Clariant).
  • the crystal modification can be changed by doping, or the alkalinity can be suitably adapted by reaction products.
  • Compounds made of the crystalline layered silicates with other ingredients of washing or cleaning agents
  • amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution and have secondary washing properties, are used as builders.
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • the X-ray diffraction experiments do not give the silicates the sharp X-ray reflections that are typical of crystalline substances, but at most one or more maxima of the scattered X-rays that have a width of several degree units of the diffraction angle.
  • the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delayed release compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.
  • phosphates can also be used as builder substances, provided that such use is not ecological Reasons should be avoided
  • the sodium salts of orthophosphates, pyrophosphates and especially polyphosphates are particularly suitable
  • Usable organic scent substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these
  • the acids themselves can also be used.
  • the acids typically also have the property of an acid component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid are used here and to name any mixtures of these
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • polyaspartic acids or their salts and derivatives of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, it also has a have a stabilizing effect
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccha ring to the carboxylic acid function.
  • An oxidized oligosaccha d according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous
  • Ethylenediamine N, N '-d ⁇ succinat (EDDS) whose synthesis is described for example in US 3,158,615, preferably in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycine trisuccinates are also preferred in this connection.
  • Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1 J-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the dmatnum salt neutral and the tetrasodium salt reacts alkaline (pH 9)
  • the preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylphosphonate (DTPMP) and their higher homologs - and Octa-Natnumsalz der DTPMP, used.
  • the builder from the phosphonate class is preferably HEDP.
  • the aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, bevo be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned
  • surfactants especially anionic surfactants.
  • anionic surfactants include, in particular, sulfonates and sulfates, but also soaps
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered Also suitable are alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are obtained by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -Atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, and also sulfonation products of unsaturated fatty acids, for example oleic acid may be present in small amounts, preferably in amounts not above about 2 to 3% by weight.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters
  • MES ⁇ -sulfofatty acids
  • abe r also used their saponified salts
  • Suitable anionic surfactants are sulfonated fatty acid glycine nests, which are mono-, di- and ⁇ d tri-esters and mixtures thereof, such as those used in the production by esterification by a monoglycene with 1 to 3 moles of fatty acid or in the transesterification of methylglycerides with 0.3 to 2 moles of glycine be preserved
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, my ⁇ styl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the appropriate compounds based on oleochemical raw materials, which are of interest in washing technology
  • 2,3-Alkyl sulfates which can be obtained, for example, from Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. coconut, palm kernel or taig fatty acids, derived
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri-ethanol amine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts
  • anionic surfactants are contained or used in the agents according to the invention or in the method according to the invention preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 to 25% by weight
  • nonionic surfactants are particularly preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably 2-branched methyl or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm tallow or oleyl alcohol and average 2 to 8 EO per mole of alcohol
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C ⁇ r alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO , 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 1 8 -Alcohol with 7 EO
  • the degrees of ethoxylation given represent statistical mean values which, for a specific product, can be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow-range ethoxylates NRE).
  • nonionic surfactants as described above - Fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO 16 EO, 20 EO, 25 EO, 30 EO or 40 EO
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • C 12 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred as nonionic surfactants, while, as described above, higher ethoxylated fatty acid methyl esters are particularly advantageous as binders, in particular C 12 -C 18 fatty acid methyl esters 10 to 12 EO can be used both as surfactants and as binders
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylammoxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called “spacer”. This spacer is usually a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group-blocked dimer and trimeric mixed ethers According to German patent application DE-A-195 13 391, they are particularly characterized by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents, bleach activators, optical brighteners, Enzymes, fabric softening agents, dyes and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts
  • Acidic salts or slightly alkaline salts can also be used to lower the pH of detergents or cleaning agents.
  • Bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances, are preferred as the acid component. Use is particularly preferred of citric acid
  • the sodium numperborate tetrahydrate, the sodium piperborate monohydrate and the sodium numpercarbonate are of particular importance.
  • Other bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, and peroxophthalates , Phthaloiminopersaure or Diperdodecandisaure
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give a phatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are O- and / or Carrying N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used.
  • Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0J to 5% by weight, preferably OJ to about 2% by weight.
  • the agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0J to 5% by weight, based on the composition, are preferably used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholione-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilmo group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • detergents which contain 15% by weight of a 3: 1 mixture of sodium alkylbenzenesulfonate and fatty alcohol sulfate, 4% by weight fatty alcohol ethoxylate, 1% by weight soap, 12% by weight % Sodium perborate monohydrate, 7% by weight TAED, enzyme granules and other auxiliaries contained.
  • the detergent builder according to Table 1 and contained 100% by weight of water, salts and other detergent ingredients used in small quantities (e.g. defoamers, dyes).
  • Sokalan CP5 ® acrylic acid-maleic acid copolymer; Sodium salt;
  • M 35000 g / mol
  • Commercial product from BASF Norasol LMW 45N ® polyacrylic acid, sodium salt
  • M 4500 g / mol
  • a 101 stainless steel vessel with a mounted heating rod was used to examine the heating rod deposits.
  • the temperature / temperature was raised from room temperature to 90 ° C. in the course of 45 minutes and this temperature was maintained for 30 minutes.
  • the liquor was then drained off and loosely adhering deposits were rinsed off with tap water.
  • the deposits on the heating elements were cleaned with citric acid Solution or alkaline EDTA solution completely detached and examined for the constituents CaO, MgO, SiO 2 , AL 2 O 3 by means of ICP (JY70 Plus; Fa. Instruments SA).
  • detergents which contain 16% by weight of a 3: 1 mixture of sodium alkylbenzenesulfonate and fatty alcohol sulfate, 5% by weight fatty alcohol ethoxylate, 0.7% by weight soap, 25% by weight zeolite NaA, 3 % By weight of soda, 17% by weight of sodium percarbonate, 3% by weight of citrate, 7% by weight of TAED, 2.0% by weight of enzyme granules and other auxiliaries.
  • the resulting detergents contained organic cobuilders according to Table 3 and contained 100% by weight of water, salts and other detergent ingredients used in small amounts (e.g. defoamers, dyes).
  • a 10l stainless steel vessel with a heating element attached was again used to examine the heating rod deposits.
  • the temperature and temperature were raised from room temperature to 90 ° C. within 60 minutes held this temperature for 30 minutes.
  • the liquor was then drained off and loosely adhering deposits were rinsed off with tap water.
  • the deposits on the heating elements were removed with citric acid or alkaline EDTA solution and examined using ICP (JY70 Plus; from Instruments SA) (Table 4).
  • detergents which contain 16% by weight of a 3: 1 mixture of sodium alkylbenzenesulfonate and fatty alcohol sulfate, 5% by weight fatty alcohol ethoxylate, 0.7% by weight soap, 25% by weight zeolite NaA, 3 % By weight of soda, 17% by weight of sodium percarbonate, 3% by weight of citrate, 7% by weight of TAED and other auxiliaries.
  • the resulting detergents contained organic cobuilders according to Table 5 and contained 100% by weight of water, salts and other detergent ingredients used in small amounts (e.g. defoamers, dyes).
  • the detergents were tested under practical conditions in household washing machines.
  • the machines were loaded with 3.0 kg of clean laundry and 0.5 kg of test fabric
  • the test fabric for the investigation of the primary washing behavior was partially impregnated with conventional test soiling and for testing the secondary washing ability consisted of white fabric.
  • Strips of standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.
  • strands with 3 g dust / skin fat on cotton yarn (15 g) were added in the last 5 washes.
  • the total incrustation was therefore also checked (1st weighing of the untreated fabric, 2 weighing of the fabric after 25 washing cycles, 3rd weighing) of the tissue after extraction with EDTA, 4. Determination of the so-called "soluble ash” from the difference between the weighings 2. and 3., 5. Ashing of the extracted tissue to determine the residual ash, 6. Determination of the total incrustation (sum of soluble ash and residual ash )). The loss of wet tear strength was determined according to DIN 53857.
  • Ash content of the textile samples (given in percent based on the weight of the test fabric before ashing), the total incrustation (given in percent based on the weight of the test fabric before determination), the loss of wet tensile strength (in% of the initial value) and the graying inhibition ( expressed in degree of remission; for comparison: the original degree of remission of the untreated tissue (mean over all test tissues) was 87).
  • the examples according to the invention - containing polymer mixtures - show clear advantages in the residues (ash and total incrustation) and (with the exception of E7) in the loss of wet tensile strength.
  • the graying-inhibiting effect is comparable to the comparative example.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Procédé permettant d'empêcher les dépôts sur les thermoplongeurs lors du lavage des textiles en machine, qui peut être utilisé avec de l'eau de n'importe quelle dureté et avec un adoucisseur d'eau contenant comme principaux composants inorganiques du silicate d'aluminium cristallin et un carbonate alcalin. Un polyacrylate polymère ayant une masse moléculaire inférieure à 10000 g/mol est utilisé comme inhibiteur d'incrustation.
PCT/EP1999/009731 1998-12-19 1999-12-10 Procede permettant d'empecher les depots WO2000037596A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19858888.7 1998-12-19
DE1998158888 DE19858888A1 (de) 1998-12-19 1998-12-19 Verhinderung von Ablagerungen

Publications (2)

Publication Number Publication Date
WO2000037596A2 true WO2000037596A2 (fr) 2000-06-29
WO2000037596A3 WO2000037596A3 (fr) 2000-11-23

Family

ID=7891858

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/009731 WO2000037596A2 (fr) 1998-12-19 1999-12-10 Procede permettant d'empecher les depots

Country Status (2)

Country Link
DE (1) DE19858888A1 (fr)
WO (1) WO2000037596A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193610B2 (en) 2011-08-10 2015-11-24 Ecolab USA, Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19938640A1 (de) * 1999-08-14 2001-02-15 Henkel Kgaa Verhinderung von Ablagerungen

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2097419A (en) * 1981-02-26 1982-11-03 Colgate Palmolive Co Base beads for manufacture of detergent compositions
EP0130640A1 (fr) * 1983-06-30 1985-01-09 THE PROCTER & GAMBLE COMPANY Détergents contenant du polymère de polyacrylate
US5076957A (en) * 1987-05-06 1991-12-31 Degussa Aktiengesellschaft Phosphate-free detergent builders
DE4128826A1 (de) * 1991-08-30 1993-03-04 Henkel Kgaa Wasch- und/oder reinigungsverfahren
EP0572288A1 (fr) * 1992-05-26 1993-12-01 Rhone-Poulenc Chimie Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320A1 (de) * 1993-02-05 1994-08-11 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
EP0628627A1 (fr) * 1993-06-07 1994-12-14 JOH. A. BENCKISER GmbH Agent builder hydrosoluble, adoucisseur d'eau
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
US5646103A (en) * 1993-02-05 1997-07-08 Henkel Kommanditgesellschaft Auf Aktien Builder for detergents or cleaning compositions
EP0727448B1 (fr) * 1995-02-17 1998-06-17 National Starch and Chemical Investment Holding Corporation Polymère solubles dans l'eau contenant des monomères d'acide allyloxy benzène sulfonique et des monomères d'acide methallyl sulfonique
EP0869169A1 (fr) * 1993-01-26 1998-10-07 National Starch And Chemical Investment Holding Corporation Composition détergente
US5830956A (en) * 1993-01-14 1998-11-03 Chemische Fabrik Stockhausen Gmbh Biodegradable copolymers, methods of producing them and their use

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2097419A (en) * 1981-02-26 1982-11-03 Colgate Palmolive Co Base beads for manufacture of detergent compositions
EP0130640A1 (fr) * 1983-06-30 1985-01-09 THE PROCTER & GAMBLE COMPANY Détergents contenant du polymère de polyacrylate
US5076957A (en) * 1987-05-06 1991-12-31 Degussa Aktiengesellschaft Phosphate-free detergent builders
DE4128826A1 (de) * 1991-08-30 1993-03-04 Henkel Kgaa Wasch- und/oder reinigungsverfahren
EP0572288A1 (fr) * 1992-05-26 1993-12-01 Rhone-Poulenc Chimie Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
US5830956A (en) * 1993-01-14 1998-11-03 Chemische Fabrik Stockhausen Gmbh Biodegradable copolymers, methods of producing them and their use
EP0869169A1 (fr) * 1993-01-26 1998-10-07 National Starch And Chemical Investment Holding Corporation Composition détergente
DE4303320A1 (de) * 1993-02-05 1994-08-11 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
US5646103A (en) * 1993-02-05 1997-07-08 Henkel Kommanditgesellschaft Auf Aktien Builder for detergents or cleaning compositions
EP0628627A1 (fr) * 1993-06-07 1994-12-14 JOH. A. BENCKISER GmbH Agent builder hydrosoluble, adoucisseur d'eau
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
EP0727448B1 (fr) * 1995-02-17 1998-06-17 National Starch and Chemical Investment Holding Corporation Polymère solubles dans l'eau contenant des monomères d'acide allyloxy benzène sulfonique et des monomères d'acide methallyl sulfonique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193610B2 (en) 2011-08-10 2015-11-24 Ecolab USA, Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide
US9896364B2 (en) 2011-08-10 2018-02-20 Ecolab Usa Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide

Also Published As

Publication number Publication date
WO2000037596A3 (fr) 2000-11-23
DE19858888A1 (de) 2000-06-21

Similar Documents

Publication Publication Date Title
EP0757094B1 (fr) Composition détergente contenant des disuccinates d'imine
EP0746599B1 (fr) Produit de lavage a adjuvants au silicate amorphes
DE10021726A1 (de) Verwendung von nanoskaligen Teilchen zur Verbesserung der Schmutzablösung
DE19936613B4 (de) Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
EP0682692B1 (fr) Adjuvant pour detergents ou nettoyants
EP0986629B1 (fr) Detergent granule
DE10044496A1 (de) Waschmitteltabletten
WO2000037596A2 (fr) Procede permettant d'empecher les depots
EP0793708B1 (fr) Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles
EP0696313A1 (fr) Poudre detergente comportant un adjuvant silicatique, une combinaison tensioactive particuliere et une lipase
DE19936614B4 (de) Verfahren zur Herstellung eines Waschmittels
EP0682693B1 (fr) Adjuvant pour detergents ou nettoyants
EP0769045B1 (fr) Detergent contenant de la cellulase
WO2000039261A1 (fr) Adjuvant de lavage soluble et de faible dosage
WO2001012770A2 (fr) Inhibition de la formation de depots
EP0853655B1 (fr) Combinaisons d'adjuvants de lavage renfermant des copolymeres d'acroleine et d'acetate de vinyle, produits de lavage et de nettoyage contenant lesdites combinaisons et leur production
EP1416039A1 (fr) Utilisation d'agents builders hydrosolubles de granulométries spécifiques dans des compositions détergentes sans agent de blanchiment
EP1004658A2 (fr) Agent de lavage comprenant de l'acide citrique
DE19846439A1 (de) Waschmittel mit kationischen Alkyl- und/oder Alkenylpolyglykosiden
DE19946342A1 (de) Formkörper mit verbesserter Wasserlöslichkeit
WO1997009404A1 (fr) Systeme inhibiteur de grisage a base d'enzyme
DE10002008A1 (de) Verfahren zur Herstellung von Tablettensprengmitteln
DE19916698A1 (de) Alkalischer Überschuß bei Zubereitung des Slurrys von Waschmitteln zur Vermeidung von Waschmittelrückständen auf Textilien
DE19728588A1 (de) Schweres Waschmittelgranulat mit hoher Löslichkeit und verbessertem Fettauswaschvermögen
DE19948669A1 (de) Waschmitteltabletten

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): CZ HU JP PL SK

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): CZ HU JP PL SK

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

122 Ep: pct application non-entry in european phase