EP0647261A1 - Granule de lavage et de nettoyage. - Google Patents

Granule de lavage et de nettoyage.

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Publication number
EP0647261A1
EP0647261A1 EP93912982A EP93912982A EP0647261A1 EP 0647261 A1 EP0647261 A1 EP 0647261A1 EP 93912982 A EP93912982 A EP 93912982A EP 93912982 A EP93912982 A EP 93912982A EP 0647261 A1 EP0647261 A1 EP 0647261A1
Authority
EP
European Patent Office
Prior art keywords
weight
fatty acid
glycerol esters
acid glycerol
granules according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93912982A
Other languages
German (de)
English (en)
Other versions
EP0647261B1 (fr
Inventor
Frank Wangemann
Brigitte Giesen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
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Publication of EP0647261A1 publication Critical patent/EP0647261A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP93912982A 1992-06-22 1993-06-15 Granule de lavage et de nettoyage Expired - Lifetime EP0647261B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4220387 1992-06-22
DE4220387A DE4220387A1 (de) 1992-06-22 1992-06-22 Granulares Wasch- und Reinigungsmittel
PCT/EP1993/001515 WO1994000544A1 (fr) 1992-06-22 1993-06-15 Granule de lavage et de nettoyage

Publications (2)

Publication Number Publication Date
EP0647261A1 true EP0647261A1 (fr) 1995-04-12
EP0647261B1 EP0647261B1 (fr) 1996-07-24

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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745119B1 (fr) * 1994-02-18 1999-12-08 Henkel-Ecolab GmbH & Co. OHG Procede de preparation de granules sechees par pulverisation
US11767495B2 (en) 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules
US11499124B2 (en) 2020-03-13 2022-11-15 YFY Consumer Products, Co. Solid granules used for cleaning agents

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2243306A1 (de) * 1972-09-02 1974-03-21 Henkel & Cie Gmbh Schaumregulierte waschmittel, insbesondere fuer trommelwaschmaschinen
DE3941365A1 (de) * 1989-12-15 1991-06-20 Henkel Kgaa Verfahren zur herstellung von salzen sulfierter fettsaeureglycerinester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9400544A1 *

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Publication number Publication date
EP0647261B1 (fr) 1996-07-24
WO1994000544A1 (fr) 1994-01-06
JPH07508055A (ja) 1995-09-07
ES2091011T3 (es) 1996-10-16
DE59303332D1 (de) 1996-08-29
ATE140724T1 (de) 1996-08-15
DE4220387A1 (de) 1993-12-23

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