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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/48—N-containing polycondensation products
• • 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
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

• the present invention relates to a phosphate-reduced, granular, builder-containing detergent with improved plasticizer properties through the use of a combination of natural phyllosilicates and fatty acid condensation products which are produced by reacting triglycerides with hydroxyalkyl polyamines.
• Phosphate-reduced detergents which contain layered silicates as textile softeners or cobuilders are known.
• EP-A-26 529 describes a detergent which, in addition to layered silicates, contains anionic surfactants and cationic salts of primary, secondary or tertiary alkylamines or water-soluble, quaternary ammonium compounds.
• anionic surfactants and cationic salts of primary, secondary or tertiary alkylamines or water-soluble, quaternary ammonium compounds are used in detergent formulations.
• the use of such surfactant mixtures in detergent formulations can worsen the washing result, since the cationic and anionic surfactants react with one another in an undesired manner.
• DE-OS 23 34 899 describes granular, builder-containing detergent compositions which contain, inter alia, layered silicates. It is known to the person skilled in the art that layered silicates only have a sufficient softening effect in the high temperature range at 60 to 95 ° C. At low temperatures, such as in hand washing or when using mild detergents at 40 to 60 ° C, phyllosilicates show a significantly deteriorated softening effect.
• DE-PS-19 22 046 describes detergents and washing aids which, in addition to a conventional surfactant base, contain fatty acid condensation products as textile softeners, which are prepared by reacting triglycerides from higher fatty acids with a hydroxylalkyl polyamine.
• Such fabric softeners have a sufficient fabric softening effect, especially at low temperatures, such as in hand washing.
• the present invention has set itself the task of providing granular, phosphate-reduced, builder-containing detergent compositions which have an excellent textile-softening effect both at low washing temperatures and at high washing temperatures.
• reduced phosphate means that detergents according to the invention contain at most 30% by weight tripolyphosphate, but can also be completely phosphate-free.
• the above-mentioned object is achieved by granular, phosphate-reduced, builder-containing detergent compositions which contain a combination of natural phyllosilicates and fatty acid condensation products.
• the advantage of the combination according to the invention is in particular that the textile-softening effect can be observed both at low temperatures, such as in hand washing, or at high temperatures.
• granular, phosphate-reduced, builder-containing detergent compositions are characterized in that they preferably contain 5 to 15% by weight of natural layered silicates.
• DE-PS 23 34 899 describes in column 4 under the heading "clay compounds" natural sheet silicates which are the basis of the combinations of the detergent compositions according to the invention.
• This list of phyllosilicates is also expressly referred to, as is the list of bentonites (smectites) of EP-A-26 529.
• Natural phyllosilicates which are composed of montmorillonites, volchonskoites, neutronites, hectorites are also particularly preferred for the purposes of the present invention , Smectite and Sauconite group are selected.
• a preferred embodiment of the present invention is directed to the combination preferably containing 1 to 6% by weight of fatty acid condensation products.
• Such a content of fatty acid condensation products is particularly suitable for the use of the detergent compositions according to the invention in mild detergents in the temperature range from 40 to 60 ° C.
• laundry is preferred that the combination contains up to 10% by weight of the fatty acid condensation products.
• granular, phosphate-reduced, builder-containing detergent compositions are characterized in that the weight ratio of the combination of natural phyllosilicates to fatty acid condensation products is set in the range from 5: 1 to 1: 2.
• the weight ratio according to the invention an excellent textile-softening effect of the detergent compositions according to the invention is achieved both at low and at high temperature.
• the fatty acid condensation products used in the detergent compositions according to the invention usually contain fatty acid triglycerides, since the fatty acid condensation products are produced by reacting triglycerides from fatty acids with hydroxyalkyl polyamine.
• the fatty acid condensation products are usually prepared by reacting triglycerides from higher fatty acids with 8 to 24 carbon atoms and at least 50% from those with 16 to 24 carbon atoms per fatty acid residue with hydroxyalkyl polyamines which have at least two hydrogen atoms bound to nitrogen, with the proviso that during the reaction, based on 1 mol of hydroxyalkyl polyamine, 1/3 mol of fatty acid triglyceride is reacted for each primary and secondary amino group and each hydroxyl group present therein.
• the production of such fatty acid condensation products and the Contents of fatty acid triglyceride can be found in DE-PS 19 22 046, which is therefore part of this description.
• Granular, phosphate-reduced, builder-containing detergent compositions are preferably characterized in the sense of the present invention in that the fatty acid condensation product is produced by the reaction of one mole of hardened tallow and one mole of hydroxyethylethylenediamine.
• Detergent compositions according to the invention preferably contain less than 20% by weight of phosphates. Since, as a result of environmental protection efforts, the greatest possible reduction in the phosphate content in detergent compositions is sought, a preferred embodiment of the present invention is directed to granular, phosphate-reduced, builders-containing detergent compositions being phosphate-free.
• the combination of natural sheet silicates and fatty acid condensation products according to the invention can be incorporated using conventional techniques for producing detergents, for example by hot atomization together with other detergent components, by granulation together with solid and / or liquid detergent constituents or by subsequent application to solid detergent parts (for example spray powder, Granules, zeolite, layered silicate).
• a particularly preferred process variant is the production of the combination of natural sheet silicates and fatty acid condensation products by spraying the fatty acid condensation product onto the natural sheet silicates.
• These can then known detergents can be added as detergent additive.
• the invention therefore furthermore relates to a detergent additive composed of a) natural sheet silicates and b) fatty acid condensation product, in a weight ratio of 5: 1 to 1: 2.
• the use of the combination according to the invention as detergent additive in mild detergents and / or is preferred for the purposes of the present invention Neutral detergents.
• detergent compositions according to the invention can contain further builder substances, builder substances, surfactants, soaps, non-surfactant-like foam inhibitors and dirt carriers.
• Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline-reacting salts, in particular alkali salts, which are able to precipitate or bind calcium ions in a complex manner.
• alkali salts which are able to precipitate or bind calcium ions in a complex manner.
• the water-soluble alkali metal or alkali polyphosphates in particular pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, are of particular importance. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
• Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids such as methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid.
• the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions which also include polymers containing carboxyl groups, are of particular importance.
• citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid are suitable.
• Polycarboxylic acids containing ether groups are also suitable, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, for example biscarboxymethylethylene glycol, carboxymethyloxysuccinic acid, carboxymethyltartronic acid and carboxymethylated or oxidized polysaccharides.
• Polymeric carboxylic acids with a molecular weight between 350 and about 1,500,000 in the form of water-soluble salts are also suitable.
• Particularly preferred polymeric polycarboxylates have a molecular weight in the range from up to 175,000 and in particular in the range from 10,000 to 100,000.
• These compounds include, for example, polyacrylic acid, poly-hydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds like vinyl methyl ether.
• the water-soluble salts of polyglyoxylic acid are also suitable.
• Suitable water-insoluble inorganic builders are the finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A type described in DE-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents.
• the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, that is to say that they have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
• Your calcium binding capacity which is determined according to the details of DE-OS 24 12 837, is in the range of 100 to 200 mg CaO / g.
• Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
• Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates - also referred to as "washing alkalis".
• alkali silicates the sodium silicates in which the Na2O: SiO2 ratio is between 1: 1 and 1: 3.5 are particularly preferred.
• builder substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids Sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid. Acetamide and ureas are also suitable as solubilizers.
• Surfactants which may be present as further components in detergents and cleaning agents, have at least one hydrophobic organic radical in the molecule and a water-solubilizing anionic, zwitterionic or nonionic group.
• the hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 carbon atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16, aliphatic carbon atoms.
• anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can be used.
• Suitable synthetic anionic surfactants are those of the sulfate, sulfonate and synthetic carboxylate type.
• the surfactants of the sulfonate type are alkylbenzenesulfonates (C 9-15- alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
• alkylbenzenesulfonates C 9-15- alkyl
• olefin sulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates
• alkanesulfonates which are obtainable from C 12-18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfofatty acids, for example the -sulfonated methyl or ethyl esters of the hydrogenated Coconut, palm kernel or tallow fatty acids.
• Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10-20 oxo alcohols, and those secondary Alcohols of this chain length.
• the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
• Sulfated fatty acid alcoholamides and sulfated fatty acid monoglycerides are also suitable.
• anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.
• the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and fatty acids can be used as nonionic surfactants.
• non-fully or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
• non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-polypropylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical.
• Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N, n-dihydroxyethylamine oxide.
• N-alkoxylated fatty acid amides are not to be understood as nonionic surfactants.
• the optionally used zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C8-C18 radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group.
• Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfo nat; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate.
• a reduced foaming power which is desirable when working in machines, can be achieved, for example, by using soaps.
• soaps foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated and unsaturated C 12-24 fatty acids are therefore particularly suitable as foam suppressants.
• the non-surfactant-like foam inhibitors are generally water-insoluble, mostly aliphatic C8-C22-carbon-containing compounds.
• Suitable non-surfactant foam inhibitors are e.g. the N-alkylaminotriazines, i.e. Reaction products of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical.
• Propoxylated and / or butoxylated aminotriazines e.g. the reaction products of 1 mole of melamine with 5 to 10 moles of propylene oxide and additionally 10 to 50 moles of butylene oxide and the aliphatic C18-C40 ketones, e.g.
• the detergents according to the invention can additionally contain bleaching agents and bleach activators.
• bleaching agents which supply H2O2 in water, are sodium perborate tetrahydrate (NaBO2. H2O2. 3H2O) and monohydrate (NaBO2. H2O2). But there are also other H2O2 supplying borates, for example the perborax Na2B4O7. 4H2O2.
• These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H2O2 or melamine / H2O2 compounds, and by H2O2-delivering peracid salts such as, for example, caroates (KHSO5), perbenzoates or peroxyphthalates.
• active oxygen carriers in particular by peroxypyrophosphates, citrate perhydrates, urea / H2O2 or melamine / H2O2 compounds, and by H2O2-delivering peracid salts such as, for example, caroates (KHSO5), perbenzoates or peroxyphthalates.
• bleaching components containing activator are preferably incorporated into the detergents.
• Certain organic peracid-forming N-acrylic or O-acyl compounds serve as activators for per compounds which supply H2O2 in water.
• Useful compounds include N-diacylated and N, N ⁇ -tetraacylated amines, e.g. N, N, N ⁇ , N ⁇ -tetraacetyl-methylenediamine or -ethylenediamine or the tetraacetylglycoluril.
• the washing and cleaning agents can contain dirt carriers, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
• water-soluble colloids mostly of an organic nature, are suitable, such as, 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, such as degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used.
• a copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000 (Sokalan CP 5®, BASF) in the form of the sodium salt was used as the polycarboxylic acid.
• the fatty acid condensation product was prepared according to DE-PS 19 22 046, column 17, line 67 ff from hardened beef tallow and n-hydroxyethyl-ethylenediamine.
• the fatty acid condensation product accordingly has the composition mentioned in DE-PS 19 22 046.
• Test textiles made of molton / terry cloth or polyester fibers artificially soiled with dust / skin fat were washed at 40 ° C and 60 ° C and wool at 30 ° C in an automatic household drum washing machine (type Miele W 433) with the programs "Delicates” or " Wool "washed together with normally soiled household laundry.
• the washing performance was determined by measuring the reflectance, the softness of the washed and dried textiles was checked by sensory evaluation of 5 people trained in this evaluation.
• the fatty acid condensation product used was that prepared according to Example 1.
• the fatty acid condensation product used was that prepared according to Example 1.
• the washing tests carried out showed that a formulation based on layered silicate and a formulation based on fatty acid condensation product are not able to achieve a softness performance corresponding to that achieved by the detergent compositions according to the invention.
• the softness performances achieved with the detergent compositions according to the invention lie above the additive values when the softness performances of the two comparative examples are added up.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6319999

Family Applications (1)

Country Status (4)

Cited By (2)

Families Citing this family (6)

Citations (4)

Family Cites Families (3)

• 1987
  • 1987-02-02 DE DE19873702968 patent/DE3702968A1/de not_active Withdrawn
• 1988
  • 1988-01-25 EP EP88101001A patent/EP0277571A3/fr not_active Withdrawn
  • 1988-02-02 US US07/151,388 patent/US4839075A/en not_active Expired - Fee Related
  • 1988-02-02 JP JP63024854A patent/JPS63193997A/ja active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events