EP1163318A1 - Granulats de tensioactif anionique - Google Patents

Granulats de tensioactif anionique

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Publication number
EP1163318A1
EP1163318A1 EP00910787A EP00910787A EP1163318A1 EP 1163318 A1 EP1163318 A1 EP 1163318A1 EP 00910787 A EP00910787 A EP 00910787A EP 00910787 A EP00910787 A EP 00910787A EP 1163318 A1 EP1163318 A1 EP 1163318A1
Authority
EP
European Patent Office
Prior art keywords
granules
anionic surfactant
weight
acid
surfactants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00910787A
Other languages
German (de)
English (en)
Inventor
Wilfried Rähse
Günter KREIENFELD
Georg Assmann
Martina Kihn-Botulinski
Dieter Jung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1163318A1 publication Critical patent/EP1163318A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

  • the present application relates to anionic surfactant granules for use in detergents and cleaning agents.
  • Anionic surfactants based on alkyl sulfates especially alkali salts of alkyl sulfate, especially fatty alcohol sulfates (FAS), are of great importance in the construction of textile detergent formulations.
  • These anionic surfactants which are solid in the dried state, are, in combination with nonionic surfactant compounds, widely used basic components of textile detergents.
  • Anionic surfactants based on FAS are in particular the sodium salts of esters of sulfuric acid with fatty alcohols of natural and / or synthetic origin of suitable chain length.
  • the derivatives based on natural products, which are known for their straight-chain fatty alcohol residues - and the associated particular ecological compatibility - are particularly important .
  • Suitable FAS components with an anionic surfactant effect are, in particular, the corresponding fatty alcohol derivatives of a chain length of the fatty alcohol residues with 10 to 22 carbon atoms, in particular the C12-18 range.
  • the solubility of the FAS sodium salts decreases with increasing chain length, especially in the range of low washing temperatures - for example in the temperature range from approximately 20 to 40 ° C.
  • the washing properties of these anionic surfactants decrease on the other hand, with increasing C number of fatty alcohol residues.
  • the use of FAS components based on saturated fatty alcohols with 16/18 carbon atoms is particularly desirable from the point of view of washing technology and in particular from the point of view of the desired textile cleaning. In the implementation of this approach, because of the weightlessness of these components, considerable practical difficulties arise, particularly at the low wash liquor temperatures mentioned.
  • US Pat. No. 3,632,517 describes detergent compositions which, in addition to FAS, also contain methyl ⁇ -sulfo fatty acid (MES) and soap flakes and builders.
  • MES methyl ⁇ -sulfo fatty acid
  • the principle is used here that mixtures of surfactants can have a common Krafft point that is lower than the Krafft point of one of the surfactants.
  • ⁇ -sulfo fatty acid methyl ester is used to improve the solubility of alkyl (en) suifates.
  • This surfactant mixture has better washing properties than FAS alone and improves the dissolution behavior of FAS.
  • Mixtures of FAS with MES and soap flakes are particularly advantageous, in particular in the presence of disodium ⁇ -sulfo fatty acids.
  • the improvement in the dissolving properties can be measured by lowering the Krafft point from 46 ° C. in the case of pure FAS to 31 to 38 ° C. in the mixture.
  • alkyl sulfate granules show improved washing action and in particular an improved solubility in cold water if mixtures of the alkyl sulfates with certain other anionic surfactants are present in the granules in such a way that the granules behave like granules of only a single surfactant and accordingly only have a Krafft point.
  • a first subject of the invention are anionic surfactant granules which are suitable as additives in detergents and / or cleaning agents and contain alkyl sulfate, which are characterized in that they contain at least 45% by weight of anionic surfactant, at least 20% by weight of the anionic surfactant contained consists of alkyl sulfate and the granules contain at least two different anionic surfactants, but only have one Krafft point which is below 46 ° C.
  • the determination of the Krafft point is carried out according to DIN 53918 by means of a turbidity measurement.
  • Such granules have particular advantages in cold water solubility, i.e. the solubility below 40 ° C.
  • the improvement achieved is often significantly greater than would be assumed when looking at the Krafft points alone.
  • a second subject of the invention is accordingly anionic surfactant granules which are suitable as additives in detergents and / or cleaning agents and contain alkyl sulfate, characterized in that at least 45% by weight of anionic surfactant is present, at least 20% by weight of the content being contained
  • Anion surfactant consists of alkyl sulfate and the granules contain at least two different anionic surfactants, and the granules leave less than 5% by weight residue in the solubility test (L test at 30 ° C.).
  • the solubility test (L test) is carried out as follows: To determine the solubility behavior (L test), 8 g of the granules to be tested are stirred in a 2 l beaker (800 rpm with laboratory stirrer / propeller stirring head 1, Centered 5 cm from the beaker bottom) and 1.5 minutes at the measuring temperature (30 ° C or 20 ° C) stirred. The test is carried out with water with a hardness of 16 ° d.
  • the lye is then poured off through a sieve (80 ⁇ m).
  • the beaker is rinsed out with very little cold water over the sieve. There is a double determination.
  • the sieves are dried in a drying cabinet at 40 ° C ⁇ 2 ° C to constant weight and the residue is weighed out.
  • the granules according to the invention already leave less than 5% by weight of residue at 30 ° C., while pure alkyl sulfate granules are only very poorly soluble and typically leave more than 50% by weight of residue under the conditions specified here.
  • Granules preferred according to the invention even leave less than 3% by weight residue in the L test at 30 ° C., and particularly advantageous embodiments of the invention even less than 5% by weight residue even at 20 ° C.
  • the debris weight of the granules is typically in the range of 500 to 750 g / l. If special requirements are placed on the bulk density for the incorporation of the granules into washing or cleaning agents, then it can also be chosen higher or lower than the specified range.
  • the surfactants are homogeneously mixed in the granules. According to the current state of knowledge, it can only be ensured that the granules behave like a surfactant when dissolved and have only one Krafft point. According to the invention, this Krafft point is lower than the Krafft point of the pure alkyl sulfate used in the granules.
  • This homogeneous mixture is achieved by using a homogeneous mixture of at least two of the surfactants contained, one of which is the alkyl sulfate, for the granulation.
  • Alkyl sulfates for the purposes of this invention are understood to be C 8 -C 22 alk (en) yl sulfates.
  • the C 8 -C 22 alkyl sulfates are the alkali metal and, in particular, the sodium salts of the sulfuric acid semiesters of C 8 -C 22 fatty alcohols, such as lauryl -, My ⁇ styl-, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol, or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols this chain length.
  • alkyl sulfates of the chain length mentioned which are synthetic, based on petrochemicals straight-chain alkyl radical produced, which have a degradation behavior analogous to the adequate compounds based on oleochemical raw materials.
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • 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®, are also suitable alkyl sulfates.
  • the granules contain at least one further anionic surfactant, an anionic surfactant being selected here which is suitable for forming mixtures with alkyl sulfates which have only one Krafft point, the Krafft point of the mixture being lower than the Krafft point. Point of the alkyl sulfate used.
  • Surfactants of the sulfonate type are preferably used.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and disulfonates of the type obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates 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 (MES), in particular hydrogenated coconut, palm kernel or tallow fatty acids, which are derived from vegetable and / or animal fatty acids by ⁇ -sulfonation of the methyl esters of fatty acids Origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present.
  • ⁇ -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.
  • the methyl esters of ⁇ -sulfofatty acids (MES) are used with particular advantage.
  • the use of the so-called disalts of the ⁇ -sulfo-fatty acid methyl esters, ie the di-metal- ⁇ -sulfo-fatty acids, is not desirable according to the invention, since these compounds are comparatively difficult to dissolve and thus the requirement according to the invention to improve the solubility of anionic surfactant granules , do not match. Therefore, the metal pellets can contain only small amounts of di-metal- ⁇ -sulfo fatty acids.
  • a small proportion of ⁇ -sulfo fatty acid di-salt is understood to mean that disalts of ⁇ -sulfo fatty acid comprise less than 5% by weight of the granules, preferably even less than 3% by weight of the granules turn off.
  • Granules that contain methyl ⁇ -sulfo fatty acid have a Krafft point below 46 ° C. If the granules contain alkylbenzenesulfonate in addition to alkyl sulfate, they preferably have a Krafft point below 42 ° C.
  • Suitable anionic surfactants can be sulfonated fatty acid glycerol esters, which are mono- and ester esters and mixtures thereof, such as those used in the preparation by esterification by a monoglycene with 1 to 3 mols of fatty acid or in the transesterification of glycine derivatives with 0.3 to 2 mols of glycene be preserved.
  • anionic surfactants in particular sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxy-containing 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-d alcohols with an average of 3.5 moles of ethylene oxide (EO) or C , 2 -C 8 fatty alcohols with 1 to 4 EO and the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, are used.
  • anionic surfactants that can be used are fatty acid derivatives of amino acids, for example N-methyl taurine (tauride) and / or N-methyl glycine (sarcosides).
  • fatty acid derivatives of amino acids for example N-methyl taurine (tauride) and / or N-methyl glycine (sarcosides).
  • sarcosides are particularly preferred the sarcosides or the sarcosinates and here in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.
  • the anionic surfactants can be present in the form of their sodium, potassium, ammonium or magnesium salts and also 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, in particular in the form of Nat ⁇ umsaize before.
  • the granules contain anionic surfactants at least in amounts of 45% by weight, preferably in amounts above 50% by weight, and in particular even more than 60% by weight of anionic surfactant. At least 20% by weight of the anionic surfactant content of alkyl sulfates is mandatory. Alkyl sulfates are preferred contained in the granules in amounts of 15-40% by weight, based on the granules. It may also be preferred that the various anionic surfactants are contained in the granules in similar amounts.
  • the preferred ratio of alkyl sulfate to ⁇ -sulfo-fatty acid methyl ester is narrow for example in the range 2 1 to 1 5, in particular in the range 1, 5 1 to 1 3
  • Granules which are particularly preferred from a washing point of view contain alkyl sulfate, methyl ⁇ -sulfo fatty acid and alkyl benzene sulfonate in each case in amounts of 10 to 40% by weight, preferably in amounts of 15 to 30% by weight, with the fact that both the ratio of alkyl sulfate to ⁇ - Sulfo-fatty acid methyl ester as well as the ratio of alkyl sulfate to alkylbenzenesulfonate is in the range 1, 5 1 to 1 3.
  • the Krafft point of such a granulate is significantly reduced, it is below 42 ° C
  • nonionic surfactants may also be present in the granules.
  • Nonionic surfactants are preferably alkoxy, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol and alkyl glycosides general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G for a glycose unit with 5 or 6 C atoms, preferably for glucose, is used.
  • R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G for a glycose unit with 5 or 6 C atoms, preferably for glucose, is used.
  • 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 less than 2, in particular less than 1.5.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R 1 CO for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [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 group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xyiosis.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xyiosis.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-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 in the Containing granules they are contained in a maximum of 20% by weight, preferably in a maximum of 15% by weight.
  • the granules according to the invention preferably contain only medium to small amounts of water, since the free-flowing properties of the surfactant granules decrease significantly with increasing water content. According to the invention, preference is given to those granules which contain a maximum of 10% by weight of water, preferably less than 7% by weight of water and in particular if the surfactant content is above 70% by weight, preferably less than 4.5% by weight Water.
  • the anionic surfactant granules preferably also contain carrier substances.
  • carrier substances Compounds that can perform a builder or cobuilder function in washing or cleaning agents are particularly suitable here. These can be inorganic or organic compounds.
  • Suitable inorganic carrier components include in particular aluminosilicates, alkali sulfates and carbonates. Also preferred according to the invention is the joint use of various inorganic carriers, in particular the combination of aluminosilicate and soda as carrier, the weight ratio of aluminosilicate to soda being in the range from 1: 5 to 5: 1, particularly preferably in the range from 1: 2 to 2: 1, has been found to be advantageous in anionic surfactant granules.
  • crystalline aluminosilicates - the zeolites - are preferably used.
  • Zeolites A, P, X, Y and mixtures thereof are preferred zeolites as carriers.
  • the use of zeolite A as a carrier is known from numerous publications.
  • zeolite P and the faujasite-type zeolites have an increased oil absorption capacity compared to zeolite A and can therefore be preferred in granules.
  • at least part of the zeolite used preferably at least 20% by weight and preferably even the entire zeolite, is made of faujasite-type zeolite.
  • zeolite of the faujasite type denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite Y and faujasite as well as Mixtures of these compounds can be used according to the invention, pure zeolite X being preferred.
  • the zeolite A-LSX described in European patent application EP-A-816 291 which corresponds to a co-crystallizate of zeolite X and zeolite A and in its anhydrous form the formula ( ⁇ O + M ' 2 / n O) Al 2 O 3 zSiO 2 , where M and M' can be alkali or alkaline earth metals and z is a number between 2.1 and 2.6.
  • This product is commercially available under the brand name VEGOBOND AX from CONDEA Augusta SpA.
  • zeolite P it may be preferred to use a zeolite MAP as described in European patent EP-B-380 070.
  • the particle sizes of the zeolites used according to the invention are preferably in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and in particular between 1 and 30 ⁇ m, each measured using standard particle size determination methods
  • Organic builder components suitable as carriers are, in particular, polycarboxylates.
  • polycarboxylic acids which can be used in the form of their sodium salts are to be mentioned, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • citric acid adipic acid
  • succinic acid glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid, ammocarboxylic acid, nitlotriacetic acid (NTA)
  • NTA ammocarboxylic acid
  • Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these, in particular tin nitrate citrate.
  • polymeric polycarboxylates are also suitable as organic carrier materials. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molar masses specified for polymeric polycarboxylates are, in the context of this document, weight-average Molar masses M w of the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid 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. Against
  • Molar masses measured for polystyrene sulfonic acids are generally significantly higher than the molar masses specified in this document. Suitable polymers are in particular
  • Polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol.
  • the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven to be particularly suitable.
  • mixtures of organic and inorganic carriers can also be used. Regardless of whether mixtures of different carriers or only one carrier component are used, the carrier content in the granules is preferably between 5 and 55% by weight. From the point of view of providing anionic surfactant granules with the highest possible surfactant content, it is preferred, however, if the granules contain the carrier in amounts of less than 50% by weight, particularly preferably less than 40% by weight, carbonates in particular preferably only are contained in amounts of less than 30% by weight.
  • the granules are to have only low water contents, it is particularly preferred to use those compounds as carriers which can still absorb moisture in the granules and thus prevent the anionic surfactants from sticking together.
  • Particularly suitable carriers for this purpose are the zeolites of the faujasite type and zeolite P and additionally, for example, calcined soda.
  • the zeolite is used in an over-dried form, ie that it has a water content which can be removed at 800 ° C.
  • preferred granules are obtained by preparing a paste from at least two anionic surfactants and mixing them intimately, then adjusting this paste to a pH in the range from 6.0 to 8.5 and then subjecting it to a granulation step.
  • Another object of the invention is a process for the preparation of anionic surfactant granules which are suitable as additives in detergents and / or cleaning agents and have a Krafft point below 46 ° C, characterized in that a paste is prepared from at least two anionic surfactants and is mixed intimately, this paste is then adjusted to a pH from the range 6.0 to 8.5 and then subjected to a granulation step.
  • the surfactants already described above are used as surfactants, the anionic surfactants being used in the form of pastes, preferably aqueous pastes.
  • one of the anionic surfactants is an alkyl sulfate.
  • this production process can also be used advantageously for the production of alkyl sulfate-free anionic surfactant granules.
  • the pastes can be mixed in any liquid mixer that ensures thorough mixing.
  • Systems such as static mixers (from Suizer or Kenics), loop reactors and mixing vessels with an intensely mixing stirring element are suitable here, for example. It is only essential that the resulting paste has a homogeneous mixture of the anionic surfactants.
  • the pH is preferably adjusted using an acidic component.
  • All acidic components suitable for use in detergents and cleaning agents are preferably suitable for this purpose. These can be carboxylic acids as well as mineral acids or acidic salts of mineral acids. Under the carboxylic acids are particularly preferred those which are also suitable as cobuilders.
  • 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 objectionable for ecological reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • These acids can be used anhydrous or in the form of their hydrates.
  • mineral acids that can be used are, in particular, sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid, and their acid salts.
  • the viscosity of neutral anionic surfactant pastes is generally lower than the viscosity of alkaline anionic surfactant pastes. Accordingly, the processing of the pastes is facilitated and, in particular, economical spraying of the pastes is made possible by the pH adjustment. On the other hand, it can be preferred with regard to the use of the resulting granules if they have a neutral effect. Particularly noteworthy here is the use in agents that can come into contact with human skin when used. For example, in cosmetic products, but also in washing and cleaning agents, for example hand washing agents, it may be desirable to use neutral components.
  • the adjustment of the pH value has another essential function:
  • the hydrolysis of the methyl ester, which takes place in an alkaline state, in particular at elevated temperature, which leads to the undesired formation of the so-called disalt salt, in particular the disodium salt corresponding sulfo fatty acid leads is prevented.
  • the process described here is particularly suitable for the production of anionic surfactant granules which contain methyl ⁇ -sulfo-fatty acid ester, but which contain only a small proportion of ⁇ -sulfo-fatty acid disodium salt.
  • a small proportion of ⁇ -sulfo fatty acid disodium salt is understood to mean that disalts of ⁇ -sulfo fatty acids less than 5 wt .-% of the granules, preferably even less than
  • the subsequent granulation step can take place in any suitable plant. However, it is preferred if the paste, preferably using a carrier component, is granulated by spray agglomeration and preferably dried at the same time.
  • the granulation can take place in any mixer / granulator suitable for spray agglomeration; however, the granulation is preferably carried out in a batch or continuous fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed.
  • the liquid preparations are introduced into the fluidized bed via disposable or reusable nozzles or via several nozzles.
  • a surfactant preparation which has a non-surfactant liquid component and is in liquid to pasty form under normal pressure at 20-40 ° C. is granulated and dried at the same time.
  • Advantages of this process for the production of free-flowing granules of different types of surfactants is the avoidance of browning of the surfactants and gentle drying and the absence of dust particles in the granules.
  • the carrier materials used are the carriers already described above.
  • the carrier component, as well as any other solids present, are either dusted pneumatically via blow lines, the addition either taking place before the atomization of the liquid components or simultaneously with them, or as a solution or suspension in a mixture with the liquids.
  • the liquid components are mixed either before spraying or directly in the nozzle.
  • the arrangement of the nozzle or nozzles and the spray direction can be as long as an essentially uniform distribution of the liquid components in the fluidized bed is achieved.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m. In particular, fluidized bed apparatuses are preferred, the one
  • Base plate with a diameter between 0.4 and 5 m, for example 1, 2 m or
  • a base plate with a diameter larger than 5 m Have a base plate with a diameter larger than 5 m.
  • a perforated base plate or a Conidur plate (commercial product of the company) is preferably used as the base plate
  • the process according to the invention is preferably carried out at fluidized air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s.
  • the granules are discharged from the fluidized bed advantageously by means of a size classification of the granules.
  • This classification can take place, for example, with a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is composed of the heated or unheated filter air and the heated soil air.
  • the soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C.
  • the fluidized air cools down due to heat losses and the heat of vaporization of the constituents of the solvent.
  • the temperature of the vortex air is about 5 cm above the base plate 60 to 120 ° C, preferably 70 to 100 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C., in particular below 100 ° C.
  • the discharge from the fluidized bed takes place against a classifier air flow, as described in EP-B-0 603 207, dust-free granules are obtained by this classification, ie the particle sizes of the particles are above 0.2 mm.
  • Granules preferred according to the invention have ad 50 values between 0.4 and 2.0 mm.
  • the grain fraction that is greater than 2.0 mm is returned. This coarse grain fraction can either be added as a solid component after grinding the fluidized bed or it is dissolved again and sprayed into the fluidized bed.
  • the fluidized bed apparatus can be a device for generating a
  • Air rotation around the vertical axis of a fluidized bed apparatus as described, for example, in the earlier application DE 19850099.8, is included, which is designed in such a way that an air supply is attached above the horizontally running fluidized bed, which has at least two injection channels, which are in uniform
  • This device leads to a homogeneous in a round fluidized bed apparatus with increasing external flow
  • Apparatus and an air supply above the vortex floor generates a vortex flow about the vertical axis of the apparatus.
  • a powdering agent can be continuously introduced into the fluidized bed to maintain the fluidized bed granulation process.
  • Zeolites are preferably used as powdering agents, it being particularly preferred to also use the zeolites used as carriers according to the invention as powdering agents. These powdering agents additionally reduce the stickiness of the moist granules during the granulation and thus promote the swirling and drying to the desired product.
  • the particle size of the powdering agent is less than 100 ⁇ m and the granules thus obtained then contain between 1 and 4% by weight of the powdering agent. This variant can be advantageous for the production of granules by the process according to the invention, but it is not absolutely necessary for carrying out the invention.
  • the present invention furthermore relates to detergents or cleaning agents which, in addition to other constituents, contain at least one anionic surfactant granulate according to the invention or one anionic surfactant granulate which is the product of the process according to the invention.
  • the detergents and cleaning agents according to the invention which can be in the form of granules, powdered or tablet-shaped solids or other molded articles, can, besides the compounds mentioned contain in principle all known ingredients which are customary in such compositions.
  • the agents are manufactured according to methods known per se.
  • the anionic surfactant granules according to the invention are preferably mixed with other particulate ingredients. After mixing, further assembly processes can follow.
  • the compacting of the ingredients which preferably takes place in a press agglomeration process, should be mentioned here in particular.
  • the press agglomeration process to which the solid premix is subjected can be carried out in various apparatuses. Depending on the type of agglomerator used, there are different ones
  • press aggiomerization processes A distinction is made between press aggiomerization processes.
  • the four most common and preferred press agglomeration processes in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes in the context of the present invention are extrusion, roll compacting, pelletizing or Tableting processes are.
  • Anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants can be mentioned primarily as ingredients of the detergents according to the invention.
  • Suitable anionic surfactants are in particular the surfactants already mentioned above, which are preferably used in the form of the granules according to the invention. Soaps, for example in amounts of 0.2% by weight to 5% by weight, are particularly suitable as further anionic surfactants. 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and 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, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of 1% by weight to 35% by weight and in particular in amounts of 5% by weight to 30% by weight.
  • the nonionic surfactants which are preferably also mentioned above are also preferred
  • Surfactants used are alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and average
  • ethylene oxide 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is usually the case in
  • Residues from alcohols of native origin with 12 to 18 carbon atoms e.g. from coconut,
  • Palm, tallow or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -
  • Alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, too
  • Fatty alcohols with more than 12 EO can be used. Examples include (tallow)
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) "in which R is 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 a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of homogenization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as the quantity to be determined analytically, can also take fractional values - between 1 and 10; preferably lies
  • 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: R 2
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars
  • Polyhydroxy fatty acid amides also include compounds of the formula (II)
  • R 4 for a linear, branched or cyclic alkylene radical or an arylene radical with 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • N-alkoxy or N Aryloxy-substituted compounds can then, for example, according to the teaching of international patent application WO 95/07331, by reaction with fatty acid methyl esters in G an alkoxide can be converted into the desired polyhydroxy fatty acid amides as a catalyst
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxy-etherified fatty alcohols and / or alkyl glycosides, are alkoxy-ethereal, preferably ethoxy-ethereal or ethoxy-ethereal and propoxy-etherified 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 produced by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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 per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally 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 distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants.
  • Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061.
  • End group-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 stand out especially 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 as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.
  • the detergents according to the invention further contain a builder system consisting of organic and / or inorganic builders.
  • a builder system consisting of organic and / or inorganic builders.
  • Usable organic builders are, for example, those in the form of their
  • Sodium salts usable polycarboxylic acids where polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 acids and mixtures of these. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus, as for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. This substance class has already been described in detail above.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsuifonic acids, such as, for example, in EP-B-727448 allyloxybenzenesulfonic acid and methallylsuifonic acid, as monomers.
  • allylsuifonic acids such as, for example, in EP-B-727448 allyloxybenzenesulfonic acid and methallylsuifonic acid, as monomers.
  • 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 as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • other preferred builder substances include polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • Particularly preferred are 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 they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic 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 are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • 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 saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to the German patent application DE-A-196 00 018.
  • a product oxidized at C 6 of the Saccha ⁇ d ⁇ ngs can be particularly advantageous.
  • Ethylene diamine N, N ' -disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
  • glycine disuccinates and glycine succinates as described, for example, in US Pat. Nos.
  • organic cobuilders are, for example, acety ered hydroxycarboxylic acids or their salts, which may optionally 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.
  • Such cobuilders are described, for example, in international patent application WO 95/20029
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the dinate salt being neutral and the tetrasodium salt reacting alkaline (pH 9).
  • the preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate. EDTMP), diethylene pentamethylene phosphonate (DTPMP) and their higher homologs in question.
  • EDTMP hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred To use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • a preferred inorganic builder is finely crystalline, synthetic and bound water-containing zeolite, as has already been described as a carrier for the granules according to the invention.
  • Suitable partial substitutes for zeolites are layer silicates of natural and synthetic origin.
  • Layer silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not restricted to a special composition or structural formula, but smectites, in particular bentonites, are preferred here. Also crystalline, layered
  • Nat ⁇ umsi cate of the general formula NaMSLO ⁇ y ⁇ O where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are suitable for substitution of zeohthene or phosphates.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 2 or 3 - as well as ⁇ -sodium disihcate
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 0 S ⁇ 0 2 from 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 solution delayed and Having secondary washing properties
  • amorphous sodium silicates with a modulus Na 2 0 S ⁇ 0 2 from 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 solution delayed and Having secondary washing properties
  • the delay in dissolution compared to conventional amorphous sodium silicates can be achieved in various ways, for example by surface treatment, compounding,
  • the term "amorphous” is also understood to mean “x-ray amphi”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max.
  • X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred, the over-dried ones in particular Silicates preferably also occur as carriers in the granules according to the invention or are used as carriers in the method according to the invention
  • phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
  • bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H 2 0 2 supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelamino aa or diperdodecanedioic acid.
  • the bleaching agent content of the agents is 0 to 30% by weight and in particular 5 to 25% by weight, advantageously using perborate monohydrate or percarbonate
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H 2 0 2 , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyioxy) benzenesulfonate, in particular sodium isononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, furthermore caprolactam derivatives,
  • acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils
  • Carboxylic anhydrides such as phthalic anhydride and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239, and acetylated pentaerythritol.
  • 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.
  • bleach activators are NNN'.N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN) .
  • the bleach activator can be coated with Hulis substances in a known manner or, if necessary with the aid of auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded / pelleted and, if desired, contain further additives, for example dye.
  • Such granules preferably contain over 70% by weight, in particular from 90 to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under washing conditions.
  • Transition metal salts or transition metal complexes may be included as so-called bleaching catalysts.
  • the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from German patent application DE 195 29 905 and those from the German patent application DE 196 20 267 known N-analog compounds, which from the German
  • Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, described in German patent application DE 196 05 688 Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the manganese, copper described in German patent application DE 44 16 438 and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, the manganese, iron and cobalt known from European patent EP 0 392 592 - and copper complexes and / or those described in European patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • the enzymes optionally contained in agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ® , Optimase ® , Opticlean ® , Maxacal ® , Maxapem ® , Durazym ® , Purafect ® OxP, Esperase ® and / or Savinase ®, amylases such as Termamyl ®, amylase LT ®, Maxamyl ®, Duramyl ®, Purafect ® OxAm, cellulases as Celluzyme ®, Carezyme ®, KAC® and / or the international patent applications WO 96/34108 from and WO 96/34092 known cellulases and / or lipases such as Lipolase ® , Lipomax ® , Lumafast ® and / or Lipozym ®
  • the enzymes used can, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are preferably in amounts of up to 10% by weight, in particular of, in detergents and cleaning agents according to the invention 0.05% by weight to 5% by weight, with enzymes stabilized against oxidative degradation being particularly preferred, as described, for example, in international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94 / 23053 or WO 95/07350 are used.
  • Suitable stabilizers in particular for per-compounds and enzymes which are sensitive to heavy metal ions, are the salts of polyphosphonic acids, in particular 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediammetetramethylenephosphonic acid.
  • HEDP 1-hydroxyethane-1, 1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediammetetramethylenephosphonic acid ethylenediammetetramethylenephosphonic acid
  • the agents can also contain components which have a positive effect 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-free component.
  • 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, are among the preferred oil- and fat-free components on the nonionic cellulose ether, as well as 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 of these. Particularly preferred of these are those sulfonated derivatives of phthalic and terephthalic polymers.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -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 different 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, bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • 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, e.g. degraded starch, aldehyde starches etc.
  • polyvinylpyrrolidone in particular in the form of PVP granules, is preferred in the agents according to the invention.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyicellulose, methyl carboxymethyl cellulose and mixtures thereof are also preferred.
  • Graying inhibitors, such as PVP are usually used in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the agents can also contain other known additives which are usually used in detergents, dishwashing detergents or cleaning agents, for example small amounts of neutral filler salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • the bulk density of the advantageously granular agents is preferably at least about 600 g / l, in particular 650 to 1100 g / l.
  • agents can also be produced which have a lower bulk density. In particular, this can be preferred if the agents are composed of granular individual components in a kind of modular system. High bulk densities of above 750 g / l are preferably achieved when the compacting steps described above are used.
  • AGT 400, Glatt fluidized bed granulation system
  • EIES ⁇ -sulfo-fatty acid methyl ester of C 14/16 -fatty acids was used as the ⁇ -sulfo-fatty acid methyl ester in all examples according to the invention.
  • As FAS an alkyl sulfate of the C12-18 chain cut was used in E1 and E2 (Sulfopon 1218G®, trade name of Henkel); in E3, an oleyl cetyl alcohol sulfate (Sulfopon O 680®, trade name from Henkel) was used.
  • E2 and E3 alkylbenzenesulfonate was used in addition to the homogeneous MES-FAS paste.
  • FAS granules (Sulfopon 1218G®, trade name from Henkel) were produced as comparative example V.
  • Resistable granules with compositions according to Table 1 were obtained.
  • the particle size distribution was measured directly at the discharge from the fluidized bed, and there was no coarse particle sieving here.

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Abstract

Des sulfates d'alkyle à longue chaîne se dissolvent mal dans l'eau froide. On a maintenant trouvé que la solubilité dans l'eau froide de certains granulats de tensioactif anionique dans lesquels le sulfate d'alcool gras est intimement mélangé avec au moins un autre tensioactif anionique est améliorée. Un procédé de production de tels granulats de tensioactif anionique se caractérise en ce qu'une pâte constituée d'au moins deux tensioactifs anioniques est produite, les deux tensioactifs étant mélangés intimement, en ce que le pH de cette pâte est ensuite ajusté à une valeur comprise dans la plage 6,0-8,5 et en ce qu'ensuite ladite pâte est soumise à une étape de granulation.
EP00910787A 1999-03-16 2000-03-08 Granulats de tensioactif anionique Withdrawn EP1163318A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999111570 DE19911570A1 (de) 1999-03-16 1999-03-16 Aniontensid-Granulate
DE19911570 1999-03-16
PCT/EP2000/002015 WO2000055289A1 (fr) 1999-03-16 2000-03-08 Granulats de tensioactif anionique

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EP1163318A1 true EP1163318A1 (fr) 2001-12-19

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CA (1) CA2300786A1 (fr)
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WO2009050026A2 (fr) * 2007-10-17 2009-04-23 Unilever Nv Compositions de blanchisserie
CN116328737A (zh) * 2023-01-10 2023-06-27 湖南大学 一种Fe/Mn-MOFs复合材料及制备方法与应用

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WO1998001529A1 (fr) * 1996-07-04 1998-01-15 The Procter & Gamble Company Procede de conditionnement de pates tensioactives afin de former des agglomerats tensioactifs tres actifs

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WO1998001529A1 (fr) * 1996-07-04 1998-01-15 The Procter & Gamble Company Procede de conditionnement de pates tensioactives afin de former des agglomerats tensioactifs tres actifs

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WO2000055289A1 (fr) 2000-09-21
AU3287300A (en) 2000-10-04
CA2300786A1 (fr) 2000-09-16
DE19911570A1 (de) 2000-09-28

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