WO1994000544A1 - Washing and cleaning granules - Google Patents

Washing and cleaning granules Download PDF

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Publication number
WO1994000544A1
WO1994000544A1 PCT/EP1993/001515 EP9301515W WO9400544A1 WO 1994000544 A1 WO1994000544 A1 WO 1994000544A1 EP 9301515 W EP9301515 W EP 9301515W WO 9400544 A1 WO9400544 A1 WO 9400544A1
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WO
WIPO (PCT)
Prior art keywords
weight
fatty acid
glycerol esters
acid glycerol
granules according
Prior art date
Application number
PCT/EP1993/001515
Other languages
German (de)
French (fr)
Inventor
Frank Wangemann
Brigitte Giesen
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59303332T priority Critical patent/DE59303332D1/en
Priority to JP6502002A priority patent/JPH07508055A/en
Priority to EP93912982A priority patent/EP0647261B1/en
Publication of WO1994000544A1 publication Critical patent/WO1994000544A1/en

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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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a granular washing and cleaning agent which contains anionic surfactants which are obtained entirely or at least to a large extent from renewable raw materials.
  • oleochemical surfactant compounds which are obtained from renewable vegetable and / or animal raw materials and which have a high ecological compatibility, is of great and rapidly increasing importance.
  • oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which in particular by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts the corresponding alkali salts, and the known ⁇ -sulfofatty acid alkyl esters (ester sulfonates), which are obtained by o-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono Salts, in particular the corresponding alkali salts, and their disalts obtainable by hydrolysis.
  • oleochemical surfactant compounds are sulfonated fatty acid glycerol esters, for example sulfonated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.
  • the anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates.
  • a disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.
  • the object was therefore to create a washing and cleaning agent which contains anionic surfactants which either completely or at least form one high proportion consist of native, i.e. renewable, fat chemical raw materials. These anionic surfactants are said to be able to replace alkylbenzene sulfonates completely or at least partially in washing detergent formulations which are otherwise customary, without any loss in washing performance.
  • the invention accordingly relates to a granular washing and cleaning agent containing anionic or anionic and nonionic surfactants, the surfactant content of the agents being from 5 to 45% by weight and the agents containing at least one anionic surfactant consisting of sulfated fatty acid glycerol esters consists.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, their fatty acid component usually builds up partly from saturated and partly from unsaturated fatty acids.
  • Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, pork lard or oleic acid-rape oil.
  • the sulfonation can take place in accordance with international patent application WO 91/6532.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one again starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, that is to say to iodine numbers less than 5, advantageously Harden less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or Lard. Because of their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases as described in of international patent application WO 91/9009.
  • the sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. 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, depending on the procedure, be up to about 60% by weight.
  • sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active constituents, but without aqueous components.
  • the total surfactant content of the granular washing and cleaning agents is preferably 5 to 40% by weight.
  • the granular agents preferably contain 2 to 25% by weight and in particular 5 to 20% by weight of sulfated fatty acid glycerol esters, sulfated fatty acid glycerol esters with iodine numbers less than 5, in particular less than 2, or mixtures of sulfated fatty acid glycerol esters with iodine numbers less than 5 and sulfonated Unsaturated fatty acid glycerol esters in a weight ratio of 10: 1 to 1: 1, in particular from 5: 1 to 2: 1, are preferred.
  • Granular compositions which contain 0.1 to 5% by weight of sulfated unsaturated fatty acid glycerol esters have a lower foam volume in use than conventional granular compositions with conventional surfactants.
  • surfactants of the sulfonate type are Cg-C ⁇ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and Hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 ⁇ Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • mixtures of sulfated fatty acid glycerol esters and the sulfonates mentioned which consist of 10 to 80% by weight, in particular 10 to 50% by weight, based in each case on the anionic surfactant mixtures, of sulfated fatty acid glycerol esters, where the washing ability compared to the pure sulfonate-containing anionic surfactant mixtures is not significantly impaired.
  • esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfofatty acids come from ⁇ -sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in consideration.
  • These are preferably the oc-sulfonated esters of hydrogenated coconut, 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. , may 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.
  • Other suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • Suitable surfactants of the sulfate type are the natural SchwefelTexcher of primary alcohols and of synthetic origin, more particularly from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or lkoholen the C ⁇ o-C20 _ ° a 0x , u ( - those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol, with mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight % on C12, 18 to 30% by weight on C14, 5 to 15% by weight on CI ⁇ , less than 3% by weight on C10 and less than 10% by weight on CQ of fatty alkyl sulfates in the granular compositions is preferably 2 to 20% by weight and in particular 5 to 15% by weight.
  • 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 in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Ciss 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with restricted homolog distribution are particularly preferred.
  • Preferred granular detergents and cleaning agents contain, in addition to the sulfonated fatty acid glycerol esters, alkylbenzene sulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the weight ratio of sulfated fatty acid glycerol esters, in particular sulfated fatty acid glycerol esters with iodine numbers less than 5, to alkyl and / or benzene sulfonates Alkyl sulfate is 1: 9 to 4: 1 and in particular 2: 5 to 2: 1.
  • granular agents are preferred which did not sulfate alkylbenzenesulfonate but rather as anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned.
  • anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned.
  • granular detergents and cleaning agents which contain sulfonated fatty acid glycerol esters with iodine numbers of less than 5 instead of alkylbenzenesulfonate achieve equal to better washing performance values than an agent which contains alkylbenzenesulfonate.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Ci8 ⁇ fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts.
  • the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight and in particular in amounts of 2 to 12% by weight.
  • the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or ethyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues from alcohols of native origin with 12 to 18 carbon atoms are preferred, such as from coconut, tallow or oleyl alcohol.
  • C ⁇ 2-Ci4 alcohols with 3 E0 or 4 E0 Cg-Cn alcohol with 7 E0
  • 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 restricted homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • anionic surfactant sulfonated fatty acid glycerol esters especially the sulfonated fatty acid glycerol esters with iodine numbers less than 5, which essentially contain fatty acids with 8 to 22 carbon atoms, can not only at least partially replace other conventional anionic surfactants such as alkylbenzenesulfonate, without the washing performance of the detergents being reduced , but that this effect also occurs when in agents with conventional anionic surfactants such as alkylbenzenesulfonate and / or fatty alkyl sulfate, which contain conventional ethoxylated C8-Ci8 ⁇ alcohols as nonionic surfactants, the latter at least partially, for example by 10 to 50% by weight, based on the amount of nonionic surfactants to be replaced by sulfated fatty acid glycerol esters.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes 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.
  • the content of the granular washing and cleaning agents in alkyl glycosides and in particular in alkyl glucosides is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.
  • the granular washing and cleaning agents according to the invention preferably contain builder substances as further constituents, in particular in quantities of 10 to 65% by weight.
  • Preferred inorganic builder substances are zeolites, crystalline layered silicates and phosphates, provided that the use of phosphates is not objectionable for ecological reasons.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-cis fatty alcohols with 2 to 5 ethylene oxide groups . Suitable zeolites have an average particle size of less than 10 ⁇ (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the granular agents is preferably 15 to 40% by weight and in particular 20 to 35% by weight (in each case based on anhydrous active substance).
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula Na Si x ⁇ 2 ⁇ + i * yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline layered silicates of the formula are those in which M is sodium and x is 2 or 3.
  • 'sodium disilicates a2Si2 ⁇ 5 * yH2 ⁇ are both .beta.- and ⁇ preferred, with beta-sodium disilicate being obtainable for example by the method / described in the intermetallic national patent application W091 08,171th
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, 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.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid and mixtures of these.
  • the granular detergents and cleaning agents according to the invention preferably contain the polycarboxylates mentioned in amounts of 0.5 to 25% by weight, in particular in amounts of 1 to 20% by weight and with particular advantages in amounts of 5 to 15% by weight ,
  • the zeolite content of the agents preferably being about 20 to 35% by weight and in particular about 20 to 32% by weight (in each case based on anhydrous active substance).
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, 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 contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, 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.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 1 to 8% by weight.
  • 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 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 ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline silicates or mixtures of these;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.
  • the other constituents of the granular agents include bleaching agents and bleach activators, graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening substances, colorants and fragrances, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, and neutral chloride salts such as sulfates in the form of their sodium or potassium salts.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate onohydrate.
  • bleach activators can be incorporated into the preparations.
  • Examples include N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing agents is 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'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • 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 can also be used.
  • carboxymethyl cellulose sodium salt
  • methyl cellulose methyl cellulose
  • hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose
  • polyvinylpyrrolidone for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps or, as indicated, by using sulfated unsaturated fatty acid glycerol esters.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt.
  • 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. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof.
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight.
  • the enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per compounds and enzymes.
  • the salts of the polyphosphonic acids are usually used in amounts of 0.1 to 2.5% by weight, preferably up to 1.5% by weight.
  • the agents can contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3 f 5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure instead the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. -, also small amounts, for example 10 "6 to 10" 3 wt .-%, preferably around 10 ⁇ 5 wt .-%, of a blue dye. A particularly preferred dye is Tinolu® (R) (commercial product from Ciba-Geigy).
  • the granular detergents and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / 1.
  • Granules are preferred which have a bulk density between 600 and 1100 g / l.
  • the granular detergents and cleaning agents can be produced by any of the known processes.
  • the granules can be produced by spray drying an aqueous slurry and, if appropriate, then adding temperature-sensitive components.
  • the granular washing and cleaning agents can be produced by one of the known granulating or extruding processes.
  • the granules are produced by an extrusion process which is described in international patent application WO 91/2047.
  • the granular detergents and cleaning agents are prepared by using the sulfated fatty acid glycerol esters in the form of a spray-dried or granulated compound as an additive component to other granular constituents of detergents and cleaning agents.
  • the sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head.
  • the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes.
  • the acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.
  • Table 1 Average composition of the fatty acid glycerol esters used after curing, in% by weight
  • HK hardened coconut oil
  • HPK hardened palm kernel oil
  • Washing program colored washing program (without prewash) at 30 ° C, 40 ° C or
  • the stains were:
  • compositions of the basic agents W1 and W2 were (data in% by weight):
  • the agents consisted of spray-dried granules, which were sprayed with ethoxylated Ci2-C] .8 fatty alcohol and to which the temperature-sensitive components were subsequently mixed.
  • the bulk density was 650 g / 1 or 670 g / 1.
  • Wl / 3 mixture of sulfated HK and tallow fatty alcohol sulfate in a weight ratio of 1: 1
  • Wl / 4 mixture of sulfated HPK and tallow fatty alcohol sulfate in a weight ratio of 1: 1
  • Example 1 Testing Wl, dosage 80 g
  • Example 2 Testing of Wl, dosage 120 g. The tests were repeated as in Example 1.

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Abstract

Washing and cleaning granules which contain anionic or anionic and non-ionic surfactants in amounts comprised between 5 and 45 % by weight and at least one anionic surfactant consisting of sulphurized fatty acid glycerin ester, suffer no losses in washing power, on the contrary of washing and cleaning granules which contain usual surfactants. The alkylbenzolsulphonates can be totally or at least partially substituted, and even ethoxylated fatty alcohols can be at least partially substituted, for example by 10 to 50 % by weight with respect to the amount of non-ionic surfactants, by the anionic surface-active sulphurized fatty acid glycerin esters. Preferred agents contain as further anionic surfactants alkyl sulphate, mixtures of alkyl sulphate and alkylbenzolsulphonate or are free from alkylbenzolsulphonates.

Description

"Granuläres Wasch- und Reinigungsmittel" "Granular detergent and cleaning agent"
Die Erfindung betrifft ein granuläres Wasch- und Reinigungsmittel, das Aniontenside enthält, die ganz oder zumindest zu einem hohen Anteil aus nachwachsenden Rohstoffen erhalten werden.The invention relates to a granular washing and cleaning agent which contains anionic surfactants which are obtained entirely or at least to a large extent from renewable raw materials.
Dem Einsatz fettchemischer Tensidverbindungen, die aus nachwachsenden pflanzlichen und/oder tierischen Rohstoffen gewonnen werden und die eine hohe ökologische Verträglichkeit aufweisen, kommt große und dabei stark zunehmende Bedeutung zu. Beispiele für derartige fettchemische Tensidver¬ bindungen mit hoher UmweltVerträglichkeit sind die bekannten Fettalkohol¬ sulfate, die durch Sulfatierung von Fettalkoholen pflanzlichen und/oder tierischen Ursprungs mit überwiegend 10 bis 20 C-Atomen im Fettalkoholmo¬ lekül und nachfolgende Neutralisation zu wasserlöslichen Salzen, insbe¬ sondere den entsprechenden Alkalisalzen, hergestellt werden, sowie die bekannten α-Sulfofettsäurealkylester (Estersulfonate), die durch oc-Sulfo- nierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit überwiegend 10 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen, insbesondere den entsprechenden Alkalisalzen, hergestellt werden, und deren durch Hy¬ drolyse erhältlichen Disalze.The use of oleochemical surfactant compounds, which are obtained from renewable vegetable and / or animal raw materials and which have a high ecological compatibility, is of great and rapidly increasing importance. Examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which in particular by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts the corresponding alkali salts, and the known α-sulfofatty acid alkyl esters (ester sulfonates), which are obtained by o-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono Salts, in particular the corresponding alkali salts, and their disalts obtainable by hydrolysis.
Beispiele für weitere fettchemische Tensidverbindungen sind sulfierte Fettsäureglycerinester, beispielsweise sulfierte ungesättigte Fettsäure- glycerinester, wie sie in der internationalen Patentanmeldung WO 91/6532 beschrieben sind, oder Sulfierprodukte gesättigter Fettsäureglycerinester, wie sie in der internationalen Patentanmeldung WO 91/9009 beschrieben sind.Examples of other oleochemical surfactant compounds are sulfonated fatty acid glycerol esters, for example sulfonated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.
Das in heutiger Zeit immer noch wirtschaftlich bedeutendste Aniontensid gehört der Tensidklasse der Alkylbenzolsulfonate an. Ein Nachteil dieser Alkylbenzolsulfonate besteht darin, daß sie aus petrochemisehen Grund¬ stoffen gewonnen werden.The anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates. A disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.
Es bestand daher die Aufgabe, ein Wasch- und Reinigungsmittel zu schaffen, das Aniontenside enthält, die entweder vollständig oder doch zu einem hohen Anteil aus nativen, also nachwachsenden fettchemischen Grundstoffen bestehen. Diese Aniontenside sollen in ansonsten üblichen Wasch- und Rei¬ nigungsmittelformulierungen Alkylbenzolsulfonate ohne Einbußen in der Waschleistung vollständig oder zumindest teilweise ersetzen können.The object was therefore to create a washing and cleaning agent which contains anionic surfactants which either completely or at least form one high proportion consist of native, i.e. renewable, fat chemical raw materials. These anionic surfactants are said to be able to replace alkylbenzene sulfonates completely or at least partially in washing detergent formulations which are otherwise customary, without any loss in washing performance.
Gegenstand der Erfindung ist dementsprechend ein granuläres Wasch- und Reinigungsmittel, enthaltend anionische oder anionische und nichtionische Tenside, wobei der Gehalt der Mittel an Tensiden 5 bis 45 Gew.-% beträgt und die Mittel mindestens ein anionisches Tensid enthalten, das aus sul¬ fierten Fettsäureglycerinestern besteht.The invention accordingly relates to a granular washing and cleaning agent containing anionic or anionic and nonionic surfactants, the surfactant content of the agents being from 5 to 45% by weight and the agents containing at least one anionic surfactant consisting of sulfated fatty acid glycerol esters consists.
Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Geht man von Fetten und Ölen, also natürlichen Gemischen unterschiedlicher Fettsäure¬ glycerinester aus, so baut sich deren Fettsäurekomponente üblicherweise teilweise aus gesättigten und teilweise aus ungesättigten Fettsäuren auf. Geeignete sulfierte Fettsäureglycerinester sind beispielsweise die Sulfierprodukte der ungesättigten Fettsäureglycerinester, die auf Basis von Korianderöl, Sonnenblumenöl, Baumwollsaatöl, Olivenöl, Erdnußöl, Leinöl, Fischöl, Schweineschmalz oder ölsäurereiehern Rüböl gewonnen wer¬ den. Die Sulfierung kann gemäß der internationalen Patentanmeldung WO 91/6532 erfolgen.Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, their fatty acid component usually builds up partly from saturated and partly from unsaturated fatty acids. Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, pork lard or oleic acid-rape oil. The sulfonation can take place in accordance with international patent application WO 91/6532.
Bevorzugte sulfierte Fettsäureglycerinester sind jedoch die Sulfierpro¬ dukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, bei¬ spielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure. Geht man dabei wiederum von Fetten und Ölen, also natürlichen Gemischen unterschiedlicher Fettsäureglycerinester aus, so ist es in diesem Fall erforderlich, die Einsatzprodukte vor der Sulfierung in an sich bekannter Weise mit Wasser¬ stoff weitgehend abzusättigen, d.h. auf Iodzahlen kleiner 5, vorteilhaf¬ terweise kleiner 2 zu härten. Typische Beispiele geeigneter Einsatzstoffe sind Palmöl, Palmkernöl, Palmstearin, Olivenöl, Rüböl, Korianderöl, Son¬ nenblumenöl, Baumwollsaatöl, Erdnußöl, Leinöl, Lardöl oder Schweineschmalz. Aufgrund ihres hohen natürlichen Anteils an gesättigten Fettsäuren hat es sich jedoch als besonders vorteilhaft erwiesen, von Ko¬ kosöl, Palmkernöl oder Rindertalg auszugehen. Die Sulfierung der gesät¬ tigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen oder der Mischungen aus Fettsäureglycerinestern mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoffatomen enthalten, erfolgt vorzugsweise durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließender Neutralisierung mit wä߬ rigen Basen, wie sie in der internationalen Patentanmeldung WO 91/9009 angegeben ist.However, preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one again starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, that is to say to iodine numbers less than 5, advantageously Harden less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or Lard. Because of their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases as described in of international patent application WO 91/9009.
Die Sulfierprodukte stellen ein komplexes Gemisch dar, das Mono-, Di- und Triglyceridsulfonate mit α-ständiger und/oder innenständiger Sulfonsäure- gruppierung enthält. Als Nebenprodukte bilden sich sulfonierte Fettsäure¬ salze, Glyceridsulfate, Glycerinsulfate, Glycerin und Seifen. Geht man bei der Sulfierung von gesättigten Fettsäuren oder gehärteten Fettsäure- glycerinestergemischen aus, so kann der Anteil der α-sulfonierten Fettsäure-Disalze je nach Verfahrensführung durchaus bis etwa 60 Gew.-% betragen. Im Rahmen dieser Erfindung wird unter sulfierten Fettsäureglycerinestern jeweils dieses komplexe Reaktionsgemisch, ein¬ schließlich der unsulfierten und nicht waschaktiven Bestandteile, jedoch ohne wäßrige Anteile verstanden.The sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid / glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight. In the context of this invention, sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active constituents, but without aqueous components.
Der Gehalt der granulären Wasch- und Reinigungsmittel an Tensiden insge¬ samt beträgt vorzugsweise 5 bis 40 Gew.-%. Die granulären Mittel enthalten dabei vorzugsweise 2 bis 25 Gew.-% und insbesondere 5 bis 20 Gew.-% sulfierte Fettsäureglycerinester, wobei sulfierte Fettsäureglycerinester mit Iodzahlen kleiner 5, insbesondere kleiner 2, oder Mischungen aus sul¬ fierten Fettsäureglycerinestern mit Iodzahlen kleiner 5 und sulfierten ungesättigten Fettsäureglycerinestern im Gewichtsverhältnis 10 : 1 bis 1 : 1, insbesondere von 5 : 1 bis 2 : 1, bevorzugt sind. Dabei weisen granu¬ läre Mittel, die 0,1 bis 5 Gew.-% sulfierte ungesättigte Fettsäureglycerinester enthalten, in der Anwendung ein geringeres Schaum¬ volumen auf als herkömmliche granuläre Mittel mit üblichen Tensiden.The total surfactant content of the granular washing and cleaning agents is preferably 5 to 40% by weight. The granular agents preferably contain 2 to 25% by weight and in particular 5 to 20% by weight of sulfated fatty acid glycerol esters, sulfated fatty acid glycerol esters with iodine numbers less than 5, in particular less than 2, or mixtures of sulfated fatty acid glycerol esters with iodine numbers less than 5 and sulfonated Unsaturated fatty acid glycerol esters in a weight ratio of 10: 1 to 1: 1, in particular from 5: 1 to 2: 1, are preferred. Granular compositions which contain 0.1 to 5% by weight of sulfated unsaturated fatty acid glycerol esters have a lower foam volume in use than conventional granular compositions with conventional surfactants.
Als Tenside vom Sulfonat-Typ kommen beispielsweise Cg-C^-Alkylbenzolsul- fonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Ci2~Ci8-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Ge¬ eignet sind auch Alkansulfonate, die aus Ci2-Ci8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden.Examples of surfactants of the sulfonate type are Cg-C ^ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and Hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 ~ Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
Im Rahmen dieser Erfindung sind dabei Mischungen aus sulfierten Fettsäureglycerinestern und den genannten Sulfonaten bevorzugt, welche zu 10 bis 80 Gew.-%, insbesondere zu 10 bis 50 Gew.-%, jeweils bezogen auf die Aniontensidmischungen, aus sulfierten Fettsäureglycerinestern beste¬ hen, wobei das Waschvermögen gegenüber den rein sulfonathaltigen Aniontensidmischungen nicht signifikant beeinträchtigt wird.In the context of this invention, preference is given to mixtures of sulfated fatty acid glycerol esters and the sulfonates mentioned, which consist of 10 to 80% by weight, in particular 10 to 50% by weight, based in each case on the anionic surfactant mixtures, of sulfated fatty acid glycerol esters, where the washing ability compared to the pure sulfonate-containing anionic surfactant mixtures is not significantly impaired.
Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate). Ins¬ besondere kommen hierbei Ester von α-Sulfofettsäuren, die durch α-Sul- fonierung der Alkylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neu¬ tralisation zu wasserlöslichen Mono-Salzen hergestellt werden, in Be¬ tracht. Vorzugsweise handelt es sich hierbei um die oc-sulfonierten Ester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren, wobei auch Sul¬ fonierungsprodukte von ungesättigten Fettsäuren, beispielsweise Ölsäure, in geringen Mengen, vorzugsweise in Mengen nicht oberhalb etwa 2 bis 3 Gew.-%, vorhanden sein können. Insbesondere sind α-Sulfofettsäurealkyl- ester bevorzugt, die eine Alkylkette mit nicht mehr als 4 C-Atomen in der Estergruppe aufweisen, beispielsweise Methylester, Ethylester, Propylester und Butylester. Mit besonderem Vorteil werden die Methylester der α- Sulfofettsäuren (MES) eingesetzt. Weitere geeignete Aniontenside sind die durch Esterspaltung der α-Sulfofettsäurealkylester erhältlichen α- Sulfofettsäuren bzw. ihre Di-Salze. Die Mono-Salze der α-Sulfofettsäure- alkylester fallen schon bei ihrer großtechnischen Herstellung als wäßrige Mischung mit begrenzten Mengen an Di-Salzen an. Auch Mischungen von Mono¬ Salzen und Di-Salzen mit weiteren Tensiden, beispielsweise mit Alkylben- zolsulfonat, sind bevorzugt. Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus pri¬ mären Alkoholen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalkoholen, z.B. aus Taigfettalkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den Cιo-C20_0x°alkoholen, u (- diejenigen sekundärer Alkohole dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2-Methyl-ver- zweigte Cg-Cn-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid, sind ge¬ eignet. Bevorzugte Fettalkylsulfate leiten sich von aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemischen, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. an Oleylalkohol, enthalten können, ab. Eine bevorzugte Verwendung finden dabei Gemische, in denen der Anteil der Alkylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf CIÖ, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C Q verteilt sind. Der Anteil an Fettalkylsulfaten in den granulären Mitteln beträgt vorzugsweise 2 bis 20 Gew.-% und insbesondere 5 bis 15 Gew.-%.The esters of α-sulfofatty acids (ester sulfonates) are also suitable. In particular, esters of α-sulfofatty acids come from α-sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in consideration. These are preferably the oc-sulfonated esters of hydrogenated coconut, 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. , may be present. In particular, α-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 α-sulfofatty acids (MES) are used with particular advantage. Other suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred. Suitable surfactants of the sulfate type are the natural Schwefelsäuremonoester of primary alcohols and of synthetic origin, more particularly from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or lkoholen the Cιo-C20 _ ° a 0x , u ( - those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol, with mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight % on C12, 18 to 30% by weight on C14, 5 to 15% by weight on CIÖ, less than 3% by weight on C10 and less than 10% by weight on CQ of fatty alkyl sulfates in the granular compositions is preferably 2 to 20% by weight and in particular 5 to 15% by weight.
Ebenso bevorzugte Aniontenside sind die Salze der Alkylsulfobernstein- säure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester be¬ zeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten CQ- bis Ciß-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit einge¬ schränkter HomologenVerteilung ableiten, besonders bevorzugt.Likewise preferred 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain CQ to Ciss 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). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with restricted homolog distribution are particularly preferred.
Bevorzugte granuläre Wasch- und Reinigungsmittel enthalten zusätzlich zu den sulfierten Fettsäureglycerinestern als weitere anionische Tenside Al¬ kylbenzolsulfonate und/oder Alkylsulfat, vorzugsweise Fettalkylsulfat, wobei das Gewichtsverhältnis sulfierte Fettsäureglycerinester, insbeson¬ dere sulfierte Fettsäureglycerinester mit Iodzahlen kleiner 5, zu Al- kylbenzolsulfonat und/oder Alkylsulfat 1 : 9 bis 4 : 1 und insbesondere 2 : 5 bis 2 : 1 beträgt. Insbesondere sind granuläre Mittel bevorzugt, die kein Alkylbenzolsulfonat, sondern als anionische Tenside sulfierte Fettsäureglycerinester allein oder in Mischung mit den genannten weiteren Aniontensiden enthalten. In Abhängigkeit von der Rezeptur ist es sogar möglich, daß granuläre Wasch- und Reinigungsmittel, welche sulfierte Fettsäureglycerinester mit Iodzahlen kleiner 5 anstelle von Alkylbenzolsulfonat enthalten, gleiche bis bessere Werte bezüglich des Waschvermögens erreichen als ein Mittel, das Alkylbenzolsulfonat enthält.Preferred granular detergents and cleaning agents contain, in addition to the sulfonated fatty acid glycerol esters, alkylbenzene sulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the weight ratio of sulfated fatty acid glycerol esters, in particular sulfated fatty acid glycerol esters with iodine numbers less than 5, to alkyl and / or benzene sulfonates Alkyl sulfate is 1: 9 to 4: 1 and in particular 2: 5 to 2: 1. In particular, granular agents are preferred which did not sulfate alkylbenzenesulfonate but rather as anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned. Depending on the recipe, it is even possible that granular detergents and cleaning agents which contain sulfonated fatty acid glycerol esters with iodine numbers of less than 5 instead of alkylbenzenesulfonate achieve equal to better washing performance values than an agent which contains alkylbenzenesulfonate.
Als weitere anionische Tenside kommen insbesondere Seifen, vorzugsweise in Mengen von 0,2 bis 8 und insbesondere von 0,5 bis 5 Gew.-% , in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abge¬ leitete Seifengemische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten Ci2-Ci8~Fettsäureseifen und zu 0 bis 50 Gew.-% aus Ölsäureseife zusammengesetzt sind.Other suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Ci8 ~ fatty acid soaps and 0 to 50% by weight of oleic acid soap.
Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammo¬ niumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze vor.The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts.
In einer weiteren bevorzugten Ausführungsform enthalten die granulären Wasch- und Reinigungsmittel zusätzlich zu den anionischen Tensiden auch nichtionische Tenside, vorzugsweise in Mengen von 1 bis 15 Gew.- und insbesondere in Mengen von 2 bis 12 Gew.-%.In a further preferred embodiment, the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight and in particular in amounts of 2 to 12% by weight.
Als nichtionische Tenside dienen vorzugsweise flüssige ethoxylierte und/oder propoxylierte Alkohole, die sich von primären Alkoholen mit vor¬ zugsweise 8 bis 18 Kohlenstoffatomen und durchschnittlich 1 bis 12 Mol Alkylenoxid ableiten, in denen der Alkoholrest linear oder in 2-Stellung ethylverzweigt sein kann, beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch lineare Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 Kohlenstoffatomen bevorzugt, wie z.B. aus Kokos-, Taigfett- oder Oleylalkohol. Insbesondere werden Cχ2-Ci4-Alkohole mit 3 E0 oder 4 E0, Cg-Cn-Alkohol mit 7 E0, Ci3-Ci5-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-Ci8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12- Ci4-Alkohol mit 3 EO und Ci2-Ci8-Alkohol mit 5 EO eingesetzt.The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or ethyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues from alcohols of native origin with 12 to 18 carbon atoms are preferred, such as from coconut, tallow or oleyl alcohol. In particular, Cχ2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Ci4 alcohol with 3 EO and Ci2 -Ci8 alcohol used with 5 EO.
Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeschränkte Homolo¬ genverteilung auf (narrow ränge ethoxylates, NRE). Insbesondere sind Alkoholethoxylate bevorzugt, die durchschnittlich 2 bis 8 Ethylenoxid- gruppen aufweisen.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 restricted homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
Dabei war es überraschend, daß die aniontensidischen sulfierten Fettsäureglycerinester, insbesondere die sulfierten Fettsäureglycerinester mit Iodzahlen kleiner 5, welche im wesentlichen Fettsäuren mit 8 bis 22 Kohlenstoffatomen enthalten, nicht nur andere herkömmliche Aniontenside wie Alkylbenzolsulfonat mindestens teilweise ersetzen können, ohne daß die Waschleistung der Mittel absinkt, sondern daß dieser Effekt auch auftritt, wenn in Mitteln mit herkömmlichen Aniontensiden wie Alkylbenzolsulfonat und/oder Fettalkylsulfat, welche als nichtionische Tenside herkömmliche ethoxylierte C8-Ci8~Alkohole enthalten, letztere mindestens teilweise, beispielsweise um 10 bis 50 Gew.-%, bezogen auf die Niotensidmenge, durch sulfierte Fettsäureglycerinester ersetzt werden.It was surprising that the anionic surfactant sulfonated fatty acid glycerol esters, especially the sulfonated fatty acid glycerol esters with iodine numbers less than 5, which essentially contain fatty acids with 8 to 22 carbon atoms, can not only at least partially replace other conventional anionic surfactants such as alkylbenzenesulfonate, without the washing performance of the detergents being reduced , but that this effect also occurs when in agents with conventional anionic surfactants such as alkylbenzenesulfonate and / or fatty alkyl sulfate, which contain conventional ethoxylated C8-Ci8 ~ alcohols as nonionic surfactants, the latter at least partially, for example by 10 to 50% by weight, based on the amount of nonionic surfactants to be replaced by sulfated fatty acid glycerol esters.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen primären geradkettigen oder in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Mono- glykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Der Gehalt der granulären Wasch- und Reinigungsmittel an Alkylglykosiden und insbesondere an Alkylglucosiden beträgt dabei vorzugsweise 0,5 bis 8 Gew.-% und insbeson¬ dere 1 bis 5 Gew.-%. Die erfindungsgemäßen granulären Wasch- und Reinigungsmittel enthalten als weitere Bestandteile vorzugsweise Buildersubstanzen, insbesondere in Men¬ gen von 10 bis 65 Gew.-%.In addition, alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes 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. The content of the granular washing and cleaning agents in alkyl glycosides and in particular in alkyl glucosides is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight. The granular washing and cleaning agents according to the invention preferably contain builder substances as further constituents, in particular in quantities of 10 to 65% by weight.
Bevorzugte anorganische Buildersubstanzen sind Zeolithe, kristalline Schichtsilikate und Phosphate, sofern der Einsatz von Phosphaten aus öko¬ logischen Gründen nicht zu beanstanden ist.Preferred inorganic builder substances are zeolites, crystalline layered silicates and phosphates, provided that the use of phosphates is not objectionable for ecological reasons.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser ent¬ haltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Er kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese ge¬ ringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12- Cis-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen. Geeignete Zeolithe wei¬ sen eine mittlere Teilchengröße von weniger als 10 μ (VolumenVerte lung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 20 bis 22 Gew.-% an gebundenem Wasser. Der Gehalt der granulären Mittel an Zeolith beträgt vorzugsweise 15 bis 40 Gew.-% und insbesondere 20 bis 35 Gew.-%, (jeweils bezogen auf wasserfreie Aktivsubstanz).The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-cis fatty alcohols with 2 to 5 ethylene oxide groups . Suitable zeolites have an average particle size of less than 10 μ (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the granular agents is preferably 15 to 40% by weight and in particular 20 to 35% by weight (in each case based on anhydrous active substance).
Geeignete Substitute bzw. Te lsubstitute für Phosphate und Zeolithe sind kristalline, schichtförmige Natriumsilikate der allgemeinen Formel Na Sixθ2χ+i*yH2θ, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispiels¬ weise in der europäischen Patentanmeldung 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ'-Natriumdisilikate a2Si2θ5*yH2θ bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der inter¬ nationalen Patentanmeldung W091/08171 beschrieben ist.Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula Na Si x θ2χ + i * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline layered silicates of the formula are those in which M is sodium and x is 2 or 3. In particular, 'sodium disilicates a2Si2θ5 * yH2θ are both .beta.- and δ preferred, with beta-sodium disilicate being obtainable for example by the method / described in the intermetallic national patent application W091 08,171th
Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuk- kersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein der¬ artiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure und Mischungen aus diesen. Die erfindungsgemäßen granulären Wasch- und Reinigungsmittel enthalten die genannten Polycarboxylate vorzugsweise in Mengen von 0,5 bis 25 Gew.-%, insbesondere in Mengen von 1 bis 20 Gew.-% und mit besonderen Vorteilen in Mengen von 5 bis 15 Gew.-%, wobei der Gehalt der Mittel an Zeolith vorzugsweise bei etwa 20 bis 35 Gew.-% und insbesondere bei etwa 20 bis 32 Gew.-% (jeweils bezogen auf wasserfreie Aktivsubstanz) liegt.Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, 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. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid and mixtures of these. The granular detergents and cleaning agents according to the invention preferably contain the polycarboxylates mentioned in amounts of 0.5 to 25% by weight, in particular in amounts of 1 to 20% by weight and with particular advantages in amounts of 5 to 15% by weight , The zeolite content of the agents preferably being about 20 to 35% by weight and in particular about 20 to 32% by weight (in each case based on anhydrous active substance).
Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Ge¬ eignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Malein¬ säure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säu¬ ren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000.Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, 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 contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, 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.
Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugs¬ weise 1 bis 8 Gew.-%.The content of (co) polymeric polycarboxylates in the compositions is preferably 1 to 8% by weight.
Weitere geeignete Bu ldersubstanzen sind Polyacetale, welche durch Umset¬ zung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der euro¬ päischen Patentanmeldung 280 223 beschrieben erhalten werden können. Be¬ vorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten. Weitere geeignete Inhaltsstoffe der granulären Mittel sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe oder kristalline Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2θ : Siθ2 von 1 : 1 bis 1 : 4,5, vorzugsweise von 1 : 2 bis 1 : 3,5, eingesetzt. Der Gehalt der Mittel an Natriumcarbonat beträgt dabei vor¬ zugsweise bis zu 20 Gew.-%, vorteilhafterweise zwischen 2 und 15 Gew.-%. Der Gehalt der Mittel an Natriumsilikat beträgt im allgemeinen bis zu 10 Gew.-%, vorzugsweise zwischen 2 und 8 Gew.-% und insbesondere 2 bis 5 Gew.-%.Further suitable powder substances are 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 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. Other suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline silicates or mixtures of these; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.
Zu den sonstigen Bestandteilen der granulären Mittel zählen Bleichmittel und Bleichaktivatoren, Vergrauungsinhibitoren (Schmutzträger), Schaumin¬ hibitoren, optische Aufheller, Enzyme, textilweichmachende Stoffe, Farb- und Duftstoffe, Löslichkeitsverbesserer wie herkömmliche Hydrotrope oder Polyalkylenglykole, beispielsweise Polyethylenglykole, sowie Neutralsalze wie Sulfate und Chloride in Form ihrer Natrium- oder Kaliumsalze.The other constituents of the granular agents include bleaching agents and bleach activators, graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening substances, colorants and fragrances, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, and neutral chloride salts such as sulfates in the form of their sodium or potassium salts.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbin¬ dungen haben das Natriumperborattetrahydrat und das Natriumperboratmono- hydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind bei¬ spielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate so¬ wie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure oder Diperdodecandisäure. Der Gehalt der Mittel an Bleichmitteln beträgt vorzugsweise 5 bis 25 Gew.-% und ins¬ besondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perborat onohydrat eingesetzt wird.Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate onohydrate.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit H2O2 organische Persäuren bildende N-Acyl- bzw. 0-Acyl-Verbindungen, vorzugsweise N,N'-tetraacy- lierte Diamine, ferner Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Der Gehalt der bleichmittelhaltigen Mittel an Bleich¬ aktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%. Besonders bevorzugte Bleichaktivatoren sind N,N,N' ,N'-Tetraacetylethylendiamin und 1,5- Diacetyl-2,4-dioxo-hexahydro-l,3,5-triazin.In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples include N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleach activator content of the bleach-containing agents is 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'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser, abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu ver¬ hindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur ge¬ eignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren SchwefelSäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxy- ethylcellulose, und deren Gemische sowie Polyvinylpyrrolidon, beispiels¬ weise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. 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 can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.
Das Schäumvermögen der Tenside läßt sich durch Kombination geeigneter Tensidtypen steigern oder verringern; eine Verringerung läßt sich eben¬ falls durch Zusätze nichttensidartiger Substanzen erreichen. Ein verrin¬ gertes Schäumvermögen, das beim Arbeiten in Maschinen erwünscht ist, er¬ reicht man vielfach durch Kombination verschiedener Tensidtypen, z.B. von Sulfaten und/oder Sulfonaten mit nichtionischen Tensiden und/oder mit Seifen bzw. wie angegeben durch den Einsatz sulfierter ungesättigter Fettsäureglycerinester. Bei Seifen steigt die schaumdämpfende Wirkung mit dem Sättigungsgrad und der C-Zahl des Fettsäuresalzes an. Als schaum¬ inhibierende Seifen eignen sich daher solche Seifen natürlicher oder syn¬ thetischer Herkunft, die einen hohen Anteil an Ci8-C24-Fettsäuren aufwei¬ sen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, ggf. silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure. Mit Vorteil werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z.B. solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren an eine granuläre, in Wasser lösliche bzw. dispergierbare Trägersubstanz gebunden. Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheni- for is und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vor¬ zugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsor¬ biert und/oder in Hü11Substanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps or, as indicated, by using sulfated unsaturated fatty acid glycerol esters. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin which have a high proportion of Ci8-C24 fatty acids are therefore suitable as foam-inhibiting soaps. 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. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition.
Als Stabilisatoren insbesondere für Perverbindungen und Enzyme kommen die Salze von Polyphosphonsäuren, insbesondere l-Hydroxyethan-l,l-diphos- phonsäure (HEDP) in Betracht. Die Salze der Polyphosphonsäuren werden da¬ bei üblicherweise in Mengen von 0,1 bis 2,5 Gew.-%, vorzugsweise bis 1,5 Gew.-%, eingesetzt.The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per compounds and enzymes. The salts of the polyphosphonic acids are usually used in amounts of 0.1 to 2.5% by weight, preferably up to 1.5% by weight.
Zusätzlich können die Mittel weitere Enzymstabilisatoren enthalten. Bei¬ spielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciu - salzen und einem Calciumgehalt von vorzugsweise etwa l,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).In addition, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
Die Mittel können als optische Aufheller Derivate der Diaminostilbendi- sulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B.. Salze der 4,4'-Bis(2-anilino-4-morpholino-l,3f5-triazin-6-yl-amino)stil- ben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die an¬ stelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methyla ino- gruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-di- phenyls anwesend sein, z.B. die Verbindung 4,4'-Bis(4-chlor-3-sulfo- styryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwen¬ det werden. Es wurde außerdem gefunden, daß einheitlich weiße Granulate erhalten wer¬ den, wenn die Mittel außer den üblichen Aufhellern in üblichen Mengen, beispielsweise zwischen 0,1 und 0,5 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.- , auch geringe Mengen, beispielsweise 10"6 bis 10"3 Gew.-%, vorzugsweise um 10~5 Gew.-%, eines blauen Farbstoffs enthält. Ein beson¬ ders bevorzugter Farbstoff ist Tinoluχ(R) (Handelsprodukt der Ciba-Geigy).As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3 f 5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure instead the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has also been found that uniform white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. -, also small amounts, for example 10 "6 to 10" 3 wt .-%, preferably around 10 ~ 5 wt .-%, of a blue dye. A particularly preferred dye is Tinolu® (R) (commercial product from Ciba-Geigy).
Die erfindungsgemäßen granulären Wasch- und Reinigungsmittel können ein Schüttgewicht zwischen etwa 300 und 1100 g/1 aufweisen. Dabei werden Gra¬ nulate bevorzugt, die ein Schüttgewicht zwischen 600 und 1100 g/1 aufwei¬ sen.The granular detergents and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / 1. Granules are preferred which have a bulk density between 600 and 1100 g / l.
Die granulären Wasch- und Reinigungsmittel können nach jedem der bekannten Verfahren hergestellt werden. So ist es zum Beispiel möglich, daß die Granulate durch Sprühtrocknung einer wäßrigen Aufschlämmung und gegebe¬ nenfalls anschließende Zumischung von temperaturempfindlichen Komponenten hergestellt werden. Ebenso ist es möglich, daß die granulären Wasch- und Reinigungsmittel nach einem der bekannten Granulier- oder Extrudierver- fahren hergestellt werden. In einer besonders bevorzugten Ausführungsform der Erfindung werden die Granulate nach einem Extrudierverfahren herge¬ stellt, das in der internationalen Patentanmeldung WO 91/2047 beschrieben wird.The granular detergents and cleaning agents can be produced by any of the known processes. For example, it is possible for the granules to be produced by spray drying an aqueous slurry and, if appropriate, then adding temperature-sensitive components. It is also possible for the granular washing and cleaning agents to be produced by one of the known granulating or extruding processes. In a particularly preferred embodiment of the invention, the granules are produced by an extrusion process which is described in international patent application WO 91/2047.
In einer weiteren Ausführungsform der Erfindung werden die granulären Wasch- und Reinigungsmittel dadurch hergestellt, daß die sulfierten Fett¬ säureglycerinester in Form eines sprühgetrockneten oder granulierten Compounds als Zumischkomponente zu anderen granulären Bestandteilen von Wasch- und Reinigungsmitteln eingesetzt werden. B e i s p i e l eIn a further embodiment of the invention, the granular detergents and cleaning agents are prepared by using the sulfated fatty acid glycerol esters in the form of a spray-dried or granulated compound as an additive component to other granular constituents of detergents and cleaning agents. Examples
Herstellung von sulfierten gesättigten Fettsäureglycerinestern mit Iodzahlen kleiner 5.Production of sulfated saturated fatty acid glycerol esters with iodine numbers less than 5.
In einem kontinuierlich arbeitenden Fallfilmreaktor (Länge 120 cm, Quer¬ schnitt 1 cm, Eduktdurchsatz 600 g/h) mit Mantelkühlung und seitlicher S03-Begasung wurden etwa 5 Mol eines Fettsäureglycerinesters mit einer Iodzahl kleiner 5 (siehe Tabelle 1) bei 80 °C mit etwa 15 Mol gasförmigem Schwefeltrioxid zur Reaktion gebracht. Der Fettsäureglycerinester wurde dabei über eine Düse mit einer Öffnung von 0,2 cm derartig in den Reaktor gesprüht, daß das Edukt entlang der Rohrwandung einen kontinuierlichen feinen Film mit einer Schichtdicke von weniger als 0,1 cm bildete. Das Schwefeltrioxid wurde durch Erhitzen aus einer entsprechenden Menge 65 Gew.-%igen Oleums ausgetrieben, mit Stickstoff auf eine Konzentration von 2 Vol.-% verdünnt und am Reaktorkopf seitlich eingeblasen. Das rohe Sulfierprodukt wurde nach Verlassen des Sulfierreaktors über 30 Minuten einer Nachreaktion bei 80 °C unterworfen. Anschließend wurde das saure Sulfierprodukt kontinuierlich mit wäßriger, 25 Gew.-%iger Natronlauge auf pH 6,5 bis 7,5 neutralisiert. In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO3 gassing, about 5 moles of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C. reacted about 15 moles of gaseous sulfur trioxide. The fatty acid glycerol ester was sprayed into the reactor through a nozzle with an opening of 0.2 cm in such a way that the starting material formed a continuous fine film with a layer thickness of less than 0.1 cm along the tube wall. The sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head. After leaving the sulfonation reactor, the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes. The acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.
Tabelle 1: Durchschnittliche Zusammensetzung der eingesetzten Fettsäureglycerinester nach Härtung Angaben in Gew.-%Table 1: Average composition of the fatty acid glycerol esters used after curing, in% by weight
Figure imgf000017_0001
Figure imgf000017_0001
Legende: HK = Gehärtetes KokosölLegend: HK = hardened coconut oil
HPK = Gehärtetes PalmkernölHPK = hardened palm kernel oil
Die nachfolgenden Beispiele beschreiben die zur Prüfung des Waschvermögens der erfindungsgemäßen Waschmittel in einer Haushaltswaschmaschine (Typ: Miele W 717) unter folgenden Bedingungen durchgeführten Versuche:The following examples describe the tests carried out to test the washing power of the detergents according to the invention in a household washing machine (type: Miele W 717) under the following conditions:
Waschprogramm: Buntwaschprogramm (ohne Vorwäsche) bei 30 °C, 40 °C oderWashing program: colored washing program (without prewash) at 30 ° C, 40 ° C or
60 °C60 ° C
Dosierung: 80 g, 100 g oder 120 g pro Maschine Wasserhärte: 16 °d Textilproben: 3,5 kg saubere Füllwäsche (normale Haushaltswäsche) Bestimmungen: 3fach Meßtechnische Bedingungen: künstliche Anschmutzungen: RFC 3/24 (465 nm, Ausblendung des Aufheller- Effektes) natürliche Anschmutzungen: Länge-Gerät (Y-Filter) Remissionsunterschiede von 2 % und mehr sind als signifikant anzusehen.Dosage: 80 g, 100 g or 120 g per machine Water hardness: 16 ° d Textile samples: 3.5 kg clean filling laundry (normal household laundry) Determinations: 3 times Measurement conditions: artificial soiling: RFC 3/24 (465 nm, suppression of the brightener effect) natural soiling: length device (Y-filter) reflectance differences of 2% and more are to be regarded as significant.
Die Anschmutzungen waren:The stains were:
SW-B Staub-Wollfett auf Baumwolle SH-B Staub-Hautfett auf Baumwolle SH-BV Staub-Hautfett auf veredelter Baumwolle SH-P Staub-Hautfett auf PolyesterSW-B Dust-wool grease on cotton SH-B Dust-skin fat on cotton SH-BV Dust-skin fat on finished cotton SH-P Dust-skin fat on polyester
SH-PBV Staub-Hautfett auf einem Gemisch aus Polyester und veredelter BaumwolleSH-PBV Dust-skin fat on a mixture of polyester and refined cotton
R-BV Rotwein auf veredelter Baumwolle T-BV Tee auf veredelter BaumwolleR-BV red wine on processed cotton T-BV tea on processed cotton
MU-PBV Make-up auf einem Gemisch aus Polyester und veredelter BaumwolleMU-PBV make-up on a mixture of polyester and refined cotton
Die Zusammensetzungen der Grundmittel Wl und W2 lauteten (Angaben jeweils in Gew.-%):The compositions of the basic agents W1 and W2 were (data in% by weight):
Figure imgf000018_0001
Handelsprodukt der BASF) 3,5 Natriumsulfat
Figure imgf000018_0001
Commercial product from BASF) 3.5 sodium sulfate
0,5 l-Hydroxyethan-l,l-diphosphonat — Rest Wasser, Enzym (Protease), optischer Rest Aufheller, Färb- und Duftstoffe, Schauminhibitor, Salze aus Roh¬ stoffen0.5 l-hydroxyethane-l, l-diphosphonate - rest of water, enzyme (protease), optical rest of brightener, colorants and fragrances, foam inhibitor, salts from raw materials
Die Mittel bestanden aus sprühgetrockneten Granulaten, die mit ethoxyliertem Ci2-C].8-Fettalkohol besprüht und denen die temperaturempfindlichen Bestandteile nachträglich zugemischt waren. Das Schüttgewicht betrug 650 g/1 bzw. 670 g/1.The agents consisted of spray-dried granules, which were sprayed with ethoxylated Ci2-C] .8 fatty alcohol and to which the temperature-sensitive components were subsequently mixed. The bulk density was 650 g / 1 or 670 g / 1.
Als "Aniontenside" wurden eingesetzt:The following were used as "anionic surfactants":
Wl/V , W2/V C9-Ci3-Alkylbenzolsulfonat, NatriumsalzWl / V, W2 / V C9-Ci3-alkylbenzenesulfonate, sodium salt
Wl/1 , W2/1 sulfiertes HKWl / 1, W2 / 1 sulfated HK
Wl/2 , W2/2 sulfiertes HPKWl / 2, W2 / 2 sulfated HPK
Wl/3 Mischung aus sulfiertem HK und Talgfettalkohol- sulfat in einem GewichtsVerhältnis von 1 : 1 Wl/4 Mischung aus sulfiertem HPK und Talgfettalkohol- sulfat in einem Gewichtsverhältnis von 1 : 1Wl / 3 mixture of sulfated HK and tallow fatty alcohol sulfate in a weight ratio of 1: 1 Wl / 4 mixture of sulfated HPK and tallow fatty alcohol sulfate in a weight ratio of 1: 1
Beispiel 1: Prüfung von Wl, Dosierung 80 gExample 1: Testing Wl, dosage 80 g
Die Versuche wurden bei 30 °C (Tabelle 2), 40 °C (Tabelle 3), und 60 °CThe experiments were carried out at 30 ° C (Table 2), 40 ° C (Table 3), and 60 ° C
(Tabelle 4) durchgeführt.(Table 4) performed.
Tabelle 2: T = 30 °CTable 2: T = 30 ° C
Mittel % Remission bei AnschmutzungenMedium% remission for soiling
SW-B T-BV MU-BVSW-B T-BV MU-BV
Figure imgf000019_0001
Tabel le 3: T = 40 °C
Figure imgf000019_0001
Table 3: T = 40 ° C
Mittel % Remission bei AnschmutzungenMedium% remission for soiling
SW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBVSW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBV
Figure imgf000020_0001
Figure imgf000020_0001
Tabelle 4: T = 60 °CTable 4: T = 60 ° C
Mittel % Remission bei AnschmutzungenMedium% remission for soiling
SW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBVSW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBV
Figure imgf000020_0002
Figure imgf000020_0002
Wl/4 76,1 79,3 72,7 64,9 71,3 74,8Wl / 4 76.1 79.3 72.7 64.9 71.3 74.8
Beispiel 2: Prüfung von Wl, Dosierung 120 g Die Versuche wurden gemäß Beispiel 1 wiederholt.Example 2: Testing of Wl, dosage 120 g. The tests were repeated as in Example 1.
Tabelle 5: T = 30 °CTable 5: T = 30 ° C
Mittel % Remission bei AnschmutzungMedium% remission when soiled
SH-PBVSH-PBV
Wl/V 69,8Wl / V 69.8
Wl/1 69,2Wl / 1 69.2
Wl/3 68,9
Figure imgf000021_0001
Wl / 3 68.9
Figure imgf000021_0001
Mittel Remission bei Anschmutzung SW-B SH-BV SH-PBV SH-P MU-PBVMedium remission when soiled SW-B SH-BV SH-PBV SH-P MU-PBV
Figure imgf000021_0002
Figure imgf000021_0002
Beispiel 3: Prüfung von W2Example 3: Testing W2
Die Ergebnisse der Versuche bei 40 °C und einer Dosierung von 100 g sind in der Tabelle 8 zusammengefaßt.The results of the tests at 40 ° C and a dosage of 100 g are summarized in Table 8.
Tabelle 8:Table 8:
Mittel Remission bei Anschmutzung SW-B SH-B SH-PBV SH-P R-BV T-BV MU-PBVMedium remission when soiled SW-B SH-B SH-PBV SH-P R-BV T-BV MU-PBV
Figure imgf000021_0003
Figure imgf000021_0003

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Granuläres Wasch- und Reinigungsmittel, enthaltend anionische oder anionische und nichtionische Tenside, dadurch gekennzeichnet, daß der Gehalt der Mittel an Tensiden 5 bis 45 Gew.-% beträgt, wobei die Mit¬ tel mindestens ein anionisches Tensid enthalten, das aus sulfierten Fettsäureglycerinestern besteht.1. Granular washing and cleaning agent containing anionic or anionic and nonionic surfactants, characterized in that the surfactant content of the agent is 5 to 45% by weight, the agents containing at least one anionic surfactant which consists of sulfonated fatty acid glycerol esters consists.
2. Granulat nach Anspruch 1, dadurch gekennzeichnet, daß es sulfierte Fettsäureglycerinester enthält, die aus Fettsäureglycerinestern mit Iodzahlen kleiner 5, vorzugsweise aus Mono-, Di- und Triglyceriden oder deren Mischungen mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoffatomen enthalten, durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließender Neutralisierung mit wäßrigen Basen erhalten werden.2. Granules according to claim 1, characterized in that it contains sulfonated fatty acid glycerol esters consisting of fatty acid glycerol esters with iodine numbers less than 5, preferably from mono-, di- and triglycerides or mixtures thereof with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, can be obtained by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases.
3. Granulat nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Ge¬ halt der Mittel an Tensiden 5 bis 40 Gew.-% und der Gehalt an Buildersubstanzen 10 bis 65 Gew.-% beträgt, wobei die Mittel 2 bis 25 Gew.-% sulfierte Fettsäureglycerinester, 1 bis 15 Gew.-% Niotenside und als Buildersubstanz Zeolith enthalten.3. Granules according to claim 1 or 2, characterized in that the Ge content of the detergents is 5 to 40% by weight and the content of builder substances is 10 to 65% by weight, the detergents being 2 to 25% by weight. -% sulfated fatty acid glycerol esters, 1 to 15 wt .-% nonionic surfactants and as a builder contain zeolite.
4. Granulat nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als nichtionische Tenside ethoxylierte Fettalkohole und/oder Alkyl- glykoside eingesetzt werden, wobei der Gehalt der Mittel an sulfierten Fettsäureglycerinestern vorzugsweise 5 bis 20 Gew.-% und an nichtio¬ nischen Tensiden vorzugsweise 2 bis 12 Gew.-% beträgt.4. Granules according to one of claims 1 to 3, characterized in that ethoxylated fatty alcohols and / or alkyl glycosides are used as nonionic surfactants, the content of the agent in sulfated fatty acid glycerol esters preferably 5 to 20% by weight and in nonionic African Surfactants is preferably 2 to 12 wt .-%.
5. Granulat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es weitere anionische Tenside aus der Gruppe der Sulfonate, Sulfate und Seifen enthält. 5. Granules according to one of claims 1 to 4, characterized in that it contains further anionic surfactants from the group of sulfonates, sulfates and soaps.
6. Granulat nach Anspruch 5, dadurch gekennzeichnet, daß es als weitere anionische Tenside Alkylbenzolsulfonat und/oder Alkylsulfat, vorzugs¬ weise Fettalkylsulfat, enthält, wobei das Gewichtsverhältnis sulfierte Fettsäureglycerinester zu Alkylbenzolsulfonat und/oder Alkylsulfat 1 : 9 bis 4 : 1 und insbesondere 2 : 5 bis 2 : 1 beträgt.6. Granules according to claim 5, characterized in that it contains alkylbenzenesulfonate and / or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the weight ratio of sulfated fatty acid glycerol esters to alkylbenzenesulfonate and / or alkyl sulfate 1: 9 to 4: 1 and in particular 2 : 5 to 2: 1.
7. Granulat nach einem der Ansprüche 1 oder 6, dadurch gekennzeichnet, daß es frei von Alkylbenzolsulfonaten ist.7. Granules according to one of claims 1 or 6, characterized in that it is free of alkylbenzenesulfonates.
8. Granulat nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es einen Gehalt an Zeolith von 15 bis 40 Gew.-% (bezogen auf wasser¬ freie Aktivsubstanz) enthält.8. Granules according to one of claims 1 to 7, characterized in that it contains a zeolite content of 15 to 40 wt .-% (based on water-free active substance).
9. Granulat nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es als organische Buildersubstanzen Polycarboxylate, vorzugsweise Citrat, Succinat, Tartrat, Glutarat, Adipat oder Mischungen aus diesen in Mengen von 0,5 bis 25 Gew.-%, vorzugsweise von 1 bis 20 Gew.-% und insbesondere von 5 bis 15 Gew.-% enthält.9. Granules according to one of claims 1 to 8, characterized in that they are organic builders polycarboxylates, preferably citrate, succinate, tartrate, glutarate, adipate or mixtures thereof in amounts of 0.5 to 25 wt .-%, preferably of Contains 1 to 20 wt .-% and in particular from 5 to 15 wt .-%.
10. Granulat nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es eine Mischung aus sulfierten Fettsäureglycerinestern mit Iodzahlen kleiner 5 und sulfierten ungesättigten Fettsäureglycerinestern im Ge¬ wichtsverhältnis 10 : 1 bis 1 : 1, vorzugsweise von 5 : 1 bis 2 : 1, enthält.10. Granules according to one of claims 1 to 9, characterized in that it is a mixture of sulfated fatty acid glycerol esters with iodine numbers less than 5 and sulfated unsaturated fatty acid glycerol esters in a weight ratio of 10: 1 to 1: 1, preferably from 5: 1 to 2: 1 , contains.
11. Granulat nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß es ein Schüttgewicht zwischen 600 und 1100 g/1 aufweist.11. Granules according to one of claims 1 to 10, characterized in that it has a bulk density between 600 and 1100 g / 1.
12. Verfahren zur Herstellung eines granulären Wasch- und Reinigungsmit¬ tels gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Granulat durch Sprühtrocknung hergestellt wird.12. A method for producing a granular detergent and cleaning agent according to one of claims 1 to 11, characterized in that the granulate is produced by spray drying.
13. Verfahren zur Herstellung eines granulären Wasch- und Reinigungsmit¬ tels gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Granulat durch ein Granulier- oder Extrudierverfahren hergestellt wird. 13. A method for producing a granular washing and cleaning agent according to one of claims 1 to 11, characterized in that the granulate is produced by a granulating or extruding process.
14. Verfahren zur Herstellung eines granulären Wasch- und Reingungsmittels gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die sulfierten Fettsäureglycerinester in Form eines sprühgetrockneten oder granulierten Compounds als Zumischkomponente zu anderen granulären Bestandteilen von Wasch- und Reinigungsmitteln eingesetzt werden. 14. A method for producing a granular detergent and cleaning agent according to one of claims 1 to 11, characterized in that the sulfonated fatty acid glycerol esters are used in the form of a spray-dried or granulated compound as an admixture component to other granular constituents of detergents and cleaning agents.
PCT/EP1993/001515 1992-06-22 1993-06-15 Washing and cleaning granules WO1994000544A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59303332T DE59303332D1 (en) 1992-06-22 1993-06-15 GRANULAR DETERGENT AND CLEANING AGENT
JP6502002A JPH07508055A (en) 1992-06-22 1993-06-15 Cleaning and cleaning granules
EP93912982A EP0647261B1 (en) 1992-06-22 1993-06-15 Washing and cleaning granules

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4220387.2 1992-06-22
DE4220387A DE4220387A1 (en) 1992-06-22 1992-06-22 Granular detergent and cleaner

Publications (1)

Publication Number Publication Date
WO1994000544A1 true WO1994000544A1 (en) 1994-01-06

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PCT/EP1993/001515 WO1994000544A1 (en) 1992-06-22 1993-06-15 Washing and cleaning granules

Country Status (6)

Country Link
EP (1) EP0647261B1 (en)
JP (1) JPH07508055A (en)
AT (1) ATE140724T1 (en)
DE (2) DE4220387A1 (en)
ES (1) ES2091011T3 (en)
WO (1) WO1994000544A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022596A1 (en) * 1994-02-18 1995-08-24 Henkel-Ecolab Gmbh & Co. Ohg Spray-dried granulate with high apparent density
US11499124B2 (en) 2020-03-13 2022-11-15 YFY Consumer Products, Co. Solid granules used for cleaning agents
US11767495B2 (en) 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197974A1 (en) * 1972-09-02 1974-03-29 Henkel & Cie Gmbh
WO1991009009A1 (en) * 1989-12-15 1991-06-27 Henkel Kommanditgesellschaft Auf Aktien Process for making salts of sulphonated fatty acid glycerine esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197974A1 (en) * 1972-09-02 1974-03-29 Henkel & Cie Gmbh
WO1991009009A1 (en) * 1989-12-15 1991-06-27 Henkel Kommanditgesellschaft Auf Aktien Process for making salts of sulphonated fatty acid glycerine esters

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995022596A1 (en) * 1994-02-18 1995-08-24 Henkel-Ecolab Gmbh & Co. Ohg Spray-dried granulate with high apparent density
US11499124B2 (en) 2020-03-13 2022-11-15 YFY Consumer Products, Co. Solid granules used for cleaning agents
US11767495B2 (en) 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules

Also Published As

Publication number Publication date
DE4220387A1 (en) 1993-12-23
JPH07508055A (en) 1995-09-07
EP0647261A1 (en) 1995-04-12
ES2091011T3 (en) 1996-10-16
EP0647261B1 (en) 1996-07-24
ATE140724T1 (en) 1996-08-15
DE59303332D1 (en) 1996-08-29

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