EP0877789B1 - Detergent contenant des silicates alcalins amorphes et des agents de blanchiment peroxyde - Google Patents

Detergent contenant des silicates alcalins amorphes et des agents de blanchiment peroxyde Download PDF

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EP0877789B1
EP0877789B1 EP96937318A EP96937318A EP0877789B1 EP 0877789 B1 EP0877789 B1 EP 0877789B1 EP 96937318 A EP96937318 A EP 96937318A EP 96937318 A EP96937318 A EP 96937318A EP 0877789 B1 EP0877789 B1 EP 0877789B1
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weight
alkali metal
percarbonate
silicates
quantities
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EP0877789A1 (fr
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Beatrix Kottwitz
Jörg Poethkow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a detergent which water-soluble silicate builders and contains percarbonate as peroxy bleach.
  • Modern, compacted detergents generally have the disadvantage that they are due to their compact structure show poorer dissolving behavior in aqueous liquor than for example, lighter spray-dried detergents of the prior art.
  • detergents tend to have a poorer dissolving rate in water, the higher their degree of compaction.
  • Zeolites commonly found in laundry detergents as builders can be included due to their water insolubility in addition to the worsened dissolving behavior.
  • a water-soluble alternative for the zeolite are amorphous alkali silicates with secondary washing ability
  • spray or roller drying water glass solutions it is known to obtain hydrated water-soluble silicates in powder form, which still contain about 20% by weight of water (cf. Ullmann's Encyclopedia of Technical Chemistry, 4th edition 1982, volume 21, page 412).
  • Such products are for different Purposes in trade.
  • Such powders have spray drying a very loose structure; their bulk densities are generally well below 700 g / l.
  • Alkali silicates in granular form with higher bulk densities can be used according to the teaching of European patent application EP-A-0 526 978 can be obtained, where one Alkali silicate solution with a solids content between 30 and 53 wt .-% in a heated Introduces drum in the longitudinal axis of a shaft with a variety of near rotated arms reaching to the inner surface of the drum, the drum wall a Has temperature between 150 and 200 ° C and the drying process by an in the drum fed gas at a temperature between 175 and about 250 ° C. is supported. This process gives a product whose average particle size is in the range between 0.2 and 2 mm. A preferred drying gas is heated air.
  • European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air.
  • a cylindrical dryer with a heated wall 160 to 200 ° C.
  • a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).
  • the older, unpublished application P 4419 745.4 also describes a water-soluble, amorphous and granular alkali silicate, which in a similar way as is described in EP-A-0 526 978 but contains silicic acid.
  • amorphous means "X-ray amorphous”. This means that the alkali silicates do not provide sharp reflections in X-ray diffraction, but at most one or several broad maxima, the width of which is several degree units of the diffraction angle is. However, this does not rule out the fact that in electron diffraction experiments Areas are found that provide sharp electron diffraction reflections. This is to be interpreted as meaning that the substance has microcrystalline areas of an order of magnitude up to approx. 20 nm (max. 50 nm).
  • Granular amorphous sodium silicates which by spray drying aqueous water glass solutions, subsequent grinding and subsequent compaction and rounding under additional dehydration of the regrind can be obtained, are contents of the American one US 3,912,649, US 3,956,467, US 3,838,193 and US 3,879,527.
  • the water content of the products obtained is approximately 18 to 20% by weight at bulk densities well above 500 g / l.
  • EP-A-0 561 656 and EP-A-0 488 868 are known. It deals are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • a number of amorphous silicates with secondary washability and carbonate and silicate-containing compounds are available as commercial products. Reference is made here, for example, to the commercial products Britesil (R) from Akzo -PQ, Nabion 15 (R) from Rhône-Poulenc, Gransil (R) from Colin Stewart or Dizzil (R) G from Eka Nobel.
  • Preferred carbonate-alkali silicate compounds are those which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.
  • These commercially available alkali silicates or compounds can be granulated, for example, with aqueous solutions of anionic surfactants or with anionic surfactant acids.
  • the European patent application EP-A-0 639 639 describes a granular Detergent containing 2 to 50% by weight of percarbonate and 0.7 to 20% by weight of a powder Contains silicate, wherein at least 0.7 wt .-% silicate particles with a particle size are less than 425 ⁇ m.
  • Corresponding amorphous silicates are, for example commercially available (Hoechst AG, Akzo). The silicates can be retrofitted be added dry.
  • EP-A-634479 describes detergents which contain alkyl sulfate, percarbonate, Contain zeolite, clay and silicate.
  • M sodium or hydrogen
  • x is a number
  • Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium.
  • the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K 2 O, of up to 5% by weight.
  • Preferred alkali silicates are present as a compound with alkali carbonate, preferably sodium and / or potassium carbonate.
  • the water content of these preferred amorphous alkali silicate compounds is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 18% by weight can be particularly preferred.
  • silicates can have been produced by spray drying, granulation and / or compacting, for example by roller compacting.
  • Compounds containing carbonate and silicate can also be produced by spray drying, granulation and / or compaction, for example by roller compaction.
  • Some of these silicates and carbonate and silicate-containing compounds are available as commercial products. Reference is made here, for example, to the commercial products Britesil (R) from Akzo-PQ, Nabion 15 (R) from Rhône-Poulenc, Gransil (R) from Colin Stewart or Dizzil (R) G from Eka Nobel.
  • Preferred carbonate-alkali silicate compounds are those which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.
  • These commercially available alkali silicates or compounds can be granulated, for example, with aqueous solutions of anionic surfactants or with anionic surfactant acids.
  • amorphous silicates which according to the above-mentioned US patents Spray drying or in granulators of the type of the turbo dryer, for example the Vomm, Italy, are suitable silicates.
  • the agents according to the invention advantageously contain amorphous alkali silicates or Compounds containing alkali carbonate and alkali silicate with secondary washing power in Amounts from 10 to 45% by weight, preferably in amounts from 15 to 40% by weight and especially in amounts of 20 to 35 wt .-%.
  • Sodium percarbonate (2 Na 2 CO 3 ⁇ 3 H 2 O 2 ) is particularly suitable as the percarbonate, in particular in granular form. It is advantageous if these granules essentially contain sodium percarbonate and otherwise only those ingredients which are required for the chemical stabilization of the sodium percarbonate or which are used for the mechanical stabilization of the granule granules. These granules preferably contain at least 75% by weight and in particular at least 85% by weight of sodium percarbonate.
  • These granules containing sodium percarbonate preferably have a bulk density from at least 500 g / l up to about 1400 g / l, with even higher bulk densities are not exempt.
  • This granulate can be produced using a process known as fluidized bed spray granulation is referred to and in which a hydrogen peroxide and a sodium carbonate solution in a fluidized bed apparatus on sodium percarbonate seeds be sprayed and water is evaporated at the same time.
  • a hydrogen peroxide and a sodium carbonate solution in a fluidized bed apparatus on sodium percarbonate seeds be sprayed and water is evaporated at the same time.
  • One or both of these Solutions can continue to be additives for crystal formation, fillers or in particular Contain stabilizers for the sodium percarbonate granules that form.
  • a particularly preferred embodiment for the production of sodium percarbonate is the method described in international patent application WO-A-95/06615, in which an aqueous hydrogen peroxide solution and an aqueous sodium carbonate solution be sprayed into the fluidized bed using a single nozzle, wherein water in the range of 40 to 95 ° C is evaporated at the same time.
  • the agents preferably contain percarbonate or an essentially percarbonate-containing one Granules in amounts of 10 to 30% by weight, in particular in amounts of 15 up to 25% by weight.
  • amorphous alkali silicates or the alkali carbonate and compounds containing alkali silicate with secondary washing power in weight ratios to percarbonate from 1.1: 1 to 2.5: 1 and especially in weight ratios of 1.2: 1 to a maximum of 2: 1.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be prepared as a spray-dried powder or as an undried one still moist, stabilized suspension are used.
  • 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 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the agents either contain no zeolite or zeolite only in amounts up to a maximum of 5% by weight (based on anhydrous active substance). This amount can be used, for example, to powder or subsequently coat one or more components which are constituents of the composition with zeolite A and / or P.
  • crystalline sheet silicates of the formula given above, in which x is preferably 2, 3 or 4, in particular crystalline layered sodium disilicates, are preferably contained in the compositions in amounts well below 10% by weight.
  • agents according to the invention are even free of these crystalline, layered ones Silicates.
  • Phosphates in particular sodium tripolyphosphate, come as further inorganic builder substances into consideration. Mainly for ecological reasons, but also because they do not make a significant contribution to increasing the performance of the agents according to the invention, their content should also generally not exceed 10% by weight. In particular the agents are free of phosphates.
  • Usable organic builders are, for example, the preferred ones in the form of their Sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not permitted for ecological reasons is objectionable, 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 acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers have proven particularly suitable of acrylic acid with maleic acid, 50 to 90 wt .-% acrylic acid and Contain 50 to 10 wt .-% maleic acid.
  • Their relative molecular mass, based on free Acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Biodegradable are also particularly preferred Terpolymers, for example those described in DE-A-43 00 772 as monomers Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Other preferred copolymers are those described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 1 to 10 % By weight and in particular 2 to 8% by weight.
  • Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as, for example are described in international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described.
  • Also known as other preferred builder substances are the known polyaspartic acids or to name their salts and derivatives.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • bleach activators can be incorporated into the detergents.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0 525 239.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • the agents can also be customary perborates such as sodium perborate monohydrate or sodium perborate tetrahydrate, especially sodium perborate monohydrate, contain.
  • the weight ratio of sodium percarbonate to sodium perborate is at least 1: 1.
  • the detergents according to the invention can contain all other known ingredients of detergents, but especially surfactants, so-called soil repellent active ingredients, other solubility improvers, enzymes and enzyme stabilizers, Foam inhibitors, graying inhibitors, inorganic (for example alkali sulfates and / or alkali chlorides) and organic salts (for example phosphonates), fabric softening agents Fabrics and dyes and fragrances.
  • the detergents according to the invention contain sulfonate and Sulfate surfactants.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also 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.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of von-sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved.
  • the sulfonation products are a complex mixture that contains mono-, di- and triglyceride sulfonates with ⁇ and / or internal sulfonic acid groups.
  • sulfonated fatty acid salts glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • 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, myristyl, 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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the 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 C 9 -C 11 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.
  • Additional anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially 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.
  • additional anionic surfactants include, in particular, soaps, preferably in quantities from 0.1 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 tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • the anionic surfactant content of the agents is preferably 2 to 30% by weight and in particular 5 to 25% by weight.
  • 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 linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 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 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, 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 is the symbol which stands for a 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 any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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.
  • Particularly preferred is a C 12 -C 18 fatty acid methyl ester with an average of 10 to 15 EO, preferably with an average of 12 EO.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the nonionic surfactants in the agents according to the invention are preferably in Amounts of 1 to 15 wt .-%, especially in amounts of 2 to 12 wt .-% included.
  • the agents can also contain components that make oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component is washed becomes.
  • the preferred oil and fat dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or known from the prior art terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether
  • the agents can also contain components that increase the solubility of the densified Improve granules.
  • Such components and the introduction of such components are described, for example, in international patent application WO-A-93/02176 and described in German patent application DE 42 03 031.5.
  • To the preferred ingredients include in particular fatty alcohols with 20 to 80 Moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and Tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO and polyethylene glycols with a molecular weight between 200 and 2000.
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question. Especially from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic Active ingredients. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially mixtures containing protease and / or lipase or mixtures with lipolytically active enzymes of particular interest.
  • cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have proven to be suitable in some cases.
  • the enzymes can be adsorbed on carrier substances and / or embedded in coating substances, to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the salts come as stabilizers, in particular for per-compounds and enzymes polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid into consideration.
  • polyphosphonic acids in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid into consideration.
  • Graying inhibitors have the task of removing the dirt detached from the fiber to keep the fleet suspended and thus prevent the dirt from re-opening.
  • 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 suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used use, e.g. degraded starch, aldehyde starches, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and also polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the composition.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • 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.
  • the bulk density of the preferred granular agents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l.
  • the agents according to the invention can be prepared by any of the known processes such as mixing, spray drying, granulating and extruding.
  • Suitable surface modifiers are included known from the prior art.
  • Zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example Calcium stearate, but especially mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.
  • detergents W1 and W2 according to the invention with the composition given below were tested for their primary and secondary washing ability.
  • comparative detergents V1 and V2 detergents with the same composition as W1 and W2 were used, but which instead of sodium percarbonate contained sodium perborate monohydrate in such amounts that the active oxygen content in W1, W2, V1 and V2 was identical.
  • composition in% by weight Alkyl benzene sulfonate 10.0 Tallow fatty alcohol sulfate 5.0 C 12 -C 18 sodium fatty acid soap 1.0 C 12 -C 18 fatty alcohol with 5 EO 4.0 silicate builder substance 27.0 polymeric polycarboxylate (Sokalan CP5 (R) , commercial product from BASF, Germany) 5 Sodium percarbonate (commercial product from Degussa) 19.0 Tetraacetylethylenediamine 6.0 Protease granules 1.0 optical brightener 0.3 Carboxymethyl cellulose / methyl cellulose (weight ratio 1: 1) 0.4 Water and salts from solutions rest
  • W1 and V1 a granular sodium carbonate / sodium disilicate compound (Nabion 15 (R) , commercial product from Rhönen-Poulenc, France) was used as the silicate builder substance, whereas in W2 and V2 an amorphous sodium disilicate (Britesil H20 plus (R) , commercial product of Akzo-PQ) used.
  • R granular sodium carbonate / sodium disilicate compound
  • the application test was carried out under practical conditions in household washing machines.
  • the machines were filled with 3.0 kg of clean laundry and 0.5 kg of test fabric, the test fabric being used to test the primary washability was impregnated with usual test soiling and for testing the graying inhibition and the ash determination consisted of white tissue.
  • Strips of standardized cotton fabric were used as the white test fabric (Krefeld laundry research institute, WFK), nettle (BN), knitwear (cotton jersey; B) and terry cloth (FT) used.
  • Washing conditions for graying inhibition and ash determination tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 80 g, washing temperature 90 ° C, liquor ratio (kg washing: liters of washing solution in the main wash cycle) 1: 5.7, 3 times rinsing with tap water, spinning and drying, number of washes: 25.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Claims (6)

  1. Détergent renfermant des tensioactifs anioniques à base de sulfonate et de sulfate, des silicates de métaux alcalins amorphes et du percarbonate comme agent de blanchiment peroxydique, caractérisé en ce que le produit contient a) au moins 5 % en poids de silicates de métaux alcalins ou de compounds de silicates de métaux alcalins amorphes possédant un pouvoir lavant secondaire et présentant un rapport molaire M2O:SiO2 (M = métal alcalin) compris entre 1:1,5 et 1:3,3, b) jusqu'à 30 % en poids de percarbonate; le silicate de métal alcalin ou le compound de silicate de métal alcalin et le percarbonate étant entre eux dans un rapport pondéral d'au moins 1:1, et c) 0 à 10 % en poids de zéolithe (par rapport à la substance active anhydre) et/ou de silicates lamellaires cristallins de la formule NaMSixO2x+1·yH2O, dans laquelle M représente le sodium ou l'hydrogène, x correspond à un nombre de 1,9 à 4 et y est un nombre de 0 à 20, les silicates lamellaires cristallins n'étant présents qu'en proportions inférieures à 10 % en poids.
  2. Produit selon la revendication 1, caractérisé en ce qu'il renferme des silicates de métaux alcalins amorphes ou des compounds à base de carbonate et de silicate de métal alcalin à pouvoir lavant secondaire dans des proportions de 10 à 45 % en poids, de préférence de 15 à 40 % en poids et en particulier, de 20 à 35 % en poids.
  3. Produit selon la revendication 1 ou 2, caractérisé en ce qu'il renferme du percarbonate ou un granulé essentiellement à base de percarbonate, dans des proportions de 10 à 30 % en poids, en particulier en concentrations de 15 à 25 % en poids.
  4. Produit selon une des revendications 1 à 3, caractérisé en ce qu'il renferme les silicates de métaux alcalins amorphes ou les compounds à base de carbonate et de silicate de métal alcalin à pouvoir lavant secondaire dans un rapport pondéral, au percarbonate, de 1,1:1 à 2,5:1 et en particulier, dans un rapport pondéral de 1,2:1 à 2:1 au maximum.
  5. Produit selon une des revendications 1 à 4, caractérisé en ce qu'il ne renferme pas de zéolithe du tout ou de la zéolithe en proportions s'élevant à 5 % en poids au maximum (par rapport à la substance active anhydre).
  6. Produit selon une des revendications 1 à 5, caractérisé en ce qu'il renferme, en plus, du perborate de sodium, le percarbonate de sodium et le perborate de sodium étant entre eux dans un rapport pondéral de préférence d'au moins 1:1.
EP96937318A 1995-11-09 1996-10-31 Detergent contenant des silicates alcalins amorphes et des agents de blanchiment peroxyde Expired - Lifetime EP0877789B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19541755 1995-11-09
DE19541755A DE19541755A1 (de) 1995-11-09 1995-11-09 Waschmittel, enthaltend amorphe Alkalisilikate und Peroxybleichmittel
PCT/EP1996/004743 WO1997017421A1 (fr) 1995-11-09 1996-10-31 Detergent contenant des silicates alcalins amorphes et des agents de blanchiment peroxyde

Publications (2)

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EP0877789A1 EP0877789A1 (fr) 1998-11-18
EP0877789B1 true EP0877789B1 (fr) 2001-03-21

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EP (1) EP0877789B1 (fr)
AT (1) ATE199932T1 (fr)
DE (2) DE19541755A1 (fr)
ES (1) ES2156298T3 (fr)
WO (1) WO1997017421A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19700775A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger wasch- und reinigungsaktiver Tensidgranulate
EP1752527A3 (fr) * 1998-09-25 2010-05-05 The Procter & Gamble Company Compositions detergents solides
JP2002525422A (ja) * 1998-09-25 2002-08-13 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0639639A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8321923D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Machine-dishwashing compositions
US5279756A (en) * 1992-08-27 1994-01-18 Church & Dwight Co., Inc. Non-phosphate machine dishwashing detergents
JPH09500171A (ja) * 1993-07-14 1997-01-07 ザ、プロクター、エンド、ギャンブル、カンパニー 部分水和結晶性アルミノシリケート流動助剤で被覆されたペルカーボネート漂白剤粒子
EP0634479B1 (fr) * 1993-07-14 1999-12-15 The Procter & Gamble Company Compositions détergentes stables contenant des agents de blanchiment
ATE185838T1 (de) * 1993-07-14 1999-11-15 Procter & Gamble Stabilisierte reinigungsmittelzusammensetzungen
FR2720074B1 (fr) * 1994-05-20 1996-08-09 Rhone Poulenc Chimie Composition détergente en poudre à base de percarbonate stabilisée par ajout de cogranulés silicate/carbonate.
GB2294268A (en) * 1994-07-07 1996-04-24 Procter & Gamble Bleaching composition for dishwasher use
DE19501645A1 (de) * 1995-01-20 1996-07-25 Henkel Kgaa Silberkorrosionsschutzmittel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0639639A1 (fr) * 1993-08-17 1995-02-22 The Procter & Gamble Company Compositions détergentes contenant des percarbonates comme agents de blanchiment

Also Published As

Publication number Publication date
ES2156298T3 (es) 2001-06-16
EP0877789A1 (fr) 1998-11-18
DE59606648D1 (de) 2001-04-26
WO1997017421A1 (fr) 1997-05-15
DE19541755A1 (de) 1997-05-15
ATE199932T1 (de) 2001-04-15

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