EP0228011B1 - Phospahtreduziertes, granulares Waschmittel - Google Patents

Phospahtreduziertes, granulares Waschmittel Download PDF

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Publication number
EP0228011B1
EP0228011B1 EP86117410A EP86117410A EP0228011B1 EP 0228011 B1 EP0228011 B1 EP 0228011B1 EP 86117410 A EP86117410 A EP 86117410A EP 86117410 A EP86117410 A EP 86117410A EP 0228011 B1 EP0228011 B1 EP 0228011B1
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EP
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Prior art keywords
weight
component
powder
detergent
sodium
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German (de)
English (en)
French (fr)
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EP0228011A3 (en
EP0228011A2 (de
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Wolfgang Dr. Seiter
Otto Dr. Koch
Herbert Dr. Reuter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • 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
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • 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
    • 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
    • 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 present invention relates to a reduced-phosphate detergent composed of a plurality of granular powder components, the essential constituents of which are fine-crystalline zeolites, nonionic surfactants from the class of polyglycol ether derivatives, anionic surfactants and homopolymeric or copolymeric carboxylic acids and, if appropriate, sodium tripolyphosphate and sodium silicate in a specific powder distribution.
  • a phosphate-reduced is understood to mean a detergent which contains less than 5% by weight of P in the form of phosphates.
  • Fine-particle zeolites of the NaA and NaX type have repeatedly been proposed as phosphate substitutes.
  • the synthetic zeolites are usually used in a form that is particularly suitable for further processing as a filter-moist, stabilized suspension containing approx. 50% water.
  • Such spray batches usually contain 30 to at most 45 percent by weight of water, of which between 8 and 15 percent by weight remain in the product after the spray drying.
  • nonionic surfactants These compounds, which are distinguished by a very high cleaning ability, undesirably increase its viscosity when incorporated into the slurry in the presence of anionic surfactants. They also cause aerosol formation in the tower exhaust air (technically referred to as "pluming").
  • pluming aerosol formation in the tower exhaust air
  • DE-22 04 842-A 1 it was proposed to apply the nonionic surfactants to a carrier powder which contains, inter alia, bentonite and, as a particularly effective binder, microfine silicon dioxide. This premix can then be mixed into a spray-dried detergent powder.
  • silicon dioxide is an active ingredient in washing, which means that it only causes additional costs and does not contribute to washing performance.
  • the premix is prepared by granulating the powdered carriers with the aid of the liquid or melted nonionic surfactant.
  • the production of uniform granules with a defined grain spectrum and bulk density encounters considerable difficulties with this process. Mixtures of these granules with specifically light spray drying powders therefore also have a more or less inconsistent particle size spectrum and tend to separate.
  • DE-25 07 926-B 2 teaches the use of finely crystalline aluminosilicates as carrier material for the nonionic surfactants, the composition of which comprises the zeolites of the NaA or NaX type. In this case too, a powdery zeolite is assumed.
  • DE 27 53 680 A2 discloses a detergent composed of three powdered or granular powder components.
  • the first powder component consists of a spray-dried powder and contains anionic and / or nonionic surfactants, skeletal salts including phosphates, zeolites, alkali metal silicates and carbonates.
  • the second component consists of skeletal salts, which serve as carrier material, and silicone defoamers adsorbed on them.
  • the third component consists of granules which are produced from perborate or another per compound or one or more builder substances, preferably phosphates, using nonionic surfactants as binders.
  • the cited application does not contain any teaching of the content of how the aluminosilicates, polycarboxylates and surfactants to be used, if any, are to be distributed over the individual powder components in order to achieve optimum washing power with phosphate-reduced agents.
  • the granular adsorbent has an average grain size of 0.4 to 0.8 mm, the proportion with a grain size of less than 0.1 mm and with a grain size of more than 1.6 mm in each case not more than 1 percent by weight.
  • the bulk density is between 400 and 700 g / l, preferably 450 to 650 g / l.
  • the component (A 1) consists of synthetic, bound water-containing sodium aluminosilicate, preferably of the zeolite A type. Mixtures of zeolite NaX and an excess of zeolite NaA can also be used.
  • the suitable zeolites have a calcium binding capacity which is determined according to DE 24 12 837 and which is in the range from 100 to 200 mg CaO / g. They are used as undried, stabilized suspensions that are still moist from their manufacture.
  • the component (A 2) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred.
  • Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as are characterized, for example, in EP 25 551-B 1, have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent by weight of acrylic acid or methacrylic acid and 60 to 10 percent by weight of maleic acid. Those copolymers in which 50 to 85 percent by weight acrylic acid and 50 to 15 percent by weight maleic acid are present are particularly preferred.
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups, and saponifying to give the sodium or potassium salts.
  • polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.
  • the molecular weight of the homopolymers or copolymers is generally 1,000 to 120,000, preferably 1,500 to 100,000.
  • Their proportion of the adsorbent is 0.5 to 7.5 parts by weight and preferably 1 to 5 parts by weight.
  • the resistance of the grains to abrasion increases with an increasing proportion of polyacid and its salts. Mixtures with 2 to 3 parts by weight of polyacid or its salts have optimal abrasion properties (in each case based on the granulate described above).
  • the moisture content which can be removed at a drying temperature of 145 ° C. is 3 to 6 parts by weight, preferably 3.5 to 5 parts by weight. Other amounts of water bound by the zeolite that are released at higher temperatures are not included in this amount.
  • the adsorbent can contain nonionic surfactants in proportions of up to 2 parts by weight, preferably 0.2 to 1.5 parts by weight.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 15, preferably 4 to 6, ethylene glycol ether groups.
  • ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups.
  • Alkylphenol polyglycol ethers having 5 to 12 carbon atoms in the alkyl radical and 3 to 15, preferably 4 to 10, ethylene glycol ether groups can also be used.
  • block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics @ are also suitable.
  • the nonionic surfactants are usually present when aqueous zeolite dispersions in which the surfactants function as dispersion stabilizers are used as the starting point for the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE 25 27 388.
  • component (A) can contain optical brighteners to improve the whiteness. The proportion of brighteners in component (B) can then be reduced accordingly.
  • NTA sodium nitrilotriacetate
  • component (A) Another optional component of component (A) is sodium nitrilotriacetate (NTA), which can be present in proportions of up to 10 parts by weight, preferably 0.5 to 6 parts by weight. It is known that NTA often increases the hygroscopicity of washing powder. It was surprisingly found that this disadvantage can be avoided if all or most of the NTA is incorporated into component (A).
  • component (A) should be free from alkali metal silicates, in particular sodium silicate, since these interact with the zeolite to impair its dispersibility in the wash liquor.
  • the production of the granular adsorbent by spray drying an aqueous, generally 50 to 65 wt .-% water containing batch of ingredients by means of nozzles into a drop zone, drying gases are introduced into the counter-current or direct current, which has an input temperature of 150 to 280 ° C and have an outlet temperature of 50 to 120 ° C.
  • the dried grains should have a moisture content of 8 to 18 parts by weight that can be removed at 145 ° C.
  • the water content of the aqueous batch is preferably 55 to 62% by weight. Its temperature is advantageously 50 to 100 ° C and its viscosity 5,000 to 20,000 mPa.s.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (ie immediately before entering the lower part of the tower), is 150 to 280 ° C, preferably 180 to 250 ° C and in particular 190 to 230 ° C.
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 120 ° C., preferably 55 to 105 ° C.
  • the granular adsorbent essentially consists of rounded grains which have a very good flow behavior. This very good flow behavior is also given when the grains are impregnated with large proportions of nonionic surfactants, which can be up to 40% by weight, based on the adsorbate. With regard to these properties, it is superior to the carrier materials which have been disclosed hitherto and have been proposed as useful for detergents and cleaning agents.
  • the granular adsorbent is then impregnated with nonionic surfactants. These can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled down or which has been warmed up again after cooling.
  • nonionic surfactants These can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled down or which has been warmed up again after cooling.
  • the abrasion resistance and constancy of shape of the grains are so high if the specified proportions or manufacturing conditions are observed that even the freshly prepared, but especially the cooled and, if necessary, reheated, matured grains can be treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions without the formation of fine fractions or coarser agglomerates.
  • the nonionic surfactants applied to the granular adsorbent can be of the same type as those used to stabilize the zeolite dispersion.
  • Preferred nonionic surfactants are derived from primary fatty alcohols of natural or synthetic origin, which can be saturated, monounsaturated, linear or methyl-branched in the 2-position (oxo radical) and have 10 to 18 carbon atoms.
  • Suitable fatty alcohols are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and their mixtures, such as those present in coconut oil alcohol or tallow oil alcohol.
  • the average number of glycol ether groups is 3 to 16.
  • nonionic surfactants are ethoxylated alkylphenols which have 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms in the alkyl group and 3 to 15, preferably 4 to 12, ethylene glycol ether groups. They can also be present in a mixture with the ethoxylated fatty alcohols mentioned above.
  • the granular adsorbent is also suitable for taking up surface active compounds containing amino groups or amide groups, which may optionally be ethoxylated and are insoluble or only slightly soluble in water, but are dispersible. They often have an effect that strengthens the primary washing power or are characterized by a high fat washing capacity.
  • examples of such compounds, which are also assigned to the nonionic surfactants are fatty acid amides which are derived from ethanolamine, diethanolamine, propanolamine and isopropanolamine and from alkylated diamines.
  • diamines examples include N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N-methyl-N-ethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dimethylpropylenediamine, N-methyl-N'- ethyl-propylenediamine and mixtures of such alkylated alkylenediamines.
  • the fatty acid residues contained in the amides are derived from saturated or monounsaturated fatty acids having 10 to 18, preferably 12 to 18, carbon atoms, with particular preference being given to those fatty acids whose acyl residues are more than 50% by weight, in particular more than 65 wt .-% consist of those with 12 to 14 carbon atoms. Mixtures obtained from coconut fatty acids are particularly suitable, from which the fraction with 10 and fewer carbon atoms has been largely separated.
  • nonionic agents which are assigned to this class are ethoxylated N-alkylamines which contain on average 1 to 3 ethylene glycol ether groups and alkyl groups with 10 to 18, in particular 12 to 14, carbon atoms, as are contained, for example, in coconut alkyl or oxo radicals .
  • the grain size distribution is not significantly influenced by the impregnation of the granular adsorbent. Any small fine particles (grain size less than 0.1 mm) will be used but generally bound and cemented with the remaining grains, so that their share tends towards zero. However, the bulk density increases with the amount of nonionic surfactant applied. A further increase in the bulk density can be achieved by finally powdering the adsorbate. Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be used in proportions of 0.03 to 5% by weight, preferably 0.05 to 2% by weight, based on the loaded adsorbent. For example, B.
  • the powder component (A) can have a bulk density between 450 and 800 g / l.
  • the granular powder component (B) contains anionic surfactants (component b). These contain at least one hydrophobic hydrocarbon residue and a water-solubilizing sulfonate or sulfate group in the molecule.
  • the hydrophobic radical is a linear or 2-position methyl branched aliphatic hydrocarbon radical with 10 to 20, preferably 12 to 18 C atoms or an alkyl aromatic radical with 8 to 14, preferably 10 to 12 aliphatic C atoms.
  • Preferred surfactants of the sulfonate type are linear alkylbenzenesulfonates (C 9-13 -alkyl), furthermore alpha-olefin sulfonates, which are known to consist of mixtures of alkene and hydroxyalkanesulfonates and disulfonates and of monoolefins with a terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline ones or acidic hydrolysis of the sulfonation products are available. Also suitable are alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.
  • esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulfated reaction products of 1 to 3 moles of ethylene oxide with primary or secondary fatty alcohols are also suitable.
  • Soaps can also be used as anionic surfactants.
  • the sodium salts of saturated fatty acids with 12 to 18 carbon atoms, such as lauric, myristic, palmitic and stearic acid, and oleic acid and mixtures thereof, are particularly suitable as such.
  • Suitable mixtures are e.g. B. soaps obtained from tallow, coconut oil or palm kernel fatty acids. If soap is also used, it must be taken into account that it increases the swelling of the sprayed particles in the spray strand. The result of this is that soap-rich spray-drying batches lead to particularly loose and therefore specifically light powders.
  • Nonionic surfactants whose constitution corresponds to the ethoxylates present in component (A) can also be used. However, only those nonionic surfactants are preferably processed in component (B) which have a degree of ethoxylation of at least 5 or whose hydrophobic residue has at least 16 C atoms or which are characterized by both features. Such nonionic surfactants have no tendency to "piuming" or only to a very small extent.
  • the liter weight of the spray powder (B) can be increased by adding nonionic surfactants to the spray mixture, ie these surfactants have the opposite effect as soap.
  • the addition of paraffins or silicone oils works in the same sense.
  • this component (B) it is possible to vary the liter weight of this component (B) within certain limits, for example in a range between 300 and 550 g / l, in particular 320 to 500 g / l.
  • the proportion of nonionic surfactants in batch (B) should not be chosen too high, since - as already mentioned - this leads to an increase in viscosity in the slurry and a deteriorated flowability of the spray powder leads.
  • the powder component (B) can also contain polymeric carboxylic acids (components d) of the type described above (cf. component A3 of the granular adsorbent). This additive can improve the grain strength of the spray product. However, it is advantageous if this component is completely or largely contained in the powder component (A), since in this component the grain-strengthening property is particularly pronounced and is relevant for processability.
  • the content of the total agent is preferably 0 to 18.5% by weight, in particular 0 to 10% by weight.
  • its proportion in component (B) can be 0 to 50% by weight, preferably 0 to 40% by weight and particularly preferably 10 to 30% by weight. These numbers refer to anhydrous phosphate. If tripolyphosphate is also used, it has been shown that the relatively high concentration of the tripolyphosphate in component (B) means that the losses due to hydrolysis to undesired orthophosphate and pyrophosphate are comparatively low.
  • the detergent auxiliaries summarized under component (f), which are stable under the conditions of spray drying or do not lose their activity, comprise washing alkalis, sequestering agents, perborate stabilizers, neutral salts, graying inhibitors, optical brighteners and agents which reduce the slurry viscosity or influence the bulk density of the spray product.
  • the above quantities refer to arithmetically on a sodium silicate with the composition 1: 2.5.
  • Another suitable washing alkali is sodium carbonate.
  • sodium bicarbonate and sodium borate can also be present.
  • Sodium silicate increases the washing ability, has an anti-corrosive effect and in particular improves the grain strength of the spray product, but without impairing its dissolving power, especially since component (B) is essentially free of zeolite.
  • component (B) should be free of zeolite.
  • Sodium carbonate present in component (B) improves the storage stability of the granular detergent mixture, especially in the case of increased atmospheric humidity.
  • high levels of sodium carbonate agents, e.g. B. those above 15 to 20 wt .-%, especially when larger proportions of component (A) are added to promote the incrustation of the washed textiles it is advisable to complete this optional component as completely as possible, ie to 75 to 100% to incorporate into the powder component (B).
  • Group (f) also includes the sequestering agents from the class of aminopolycarboxylic acids and polyphosphonic acids, which are usually present in comparatively small quantities and act as so-called co-builders, stabilizers, precipitation inhibitors (threshold substances).
  • the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues.
  • Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as.
  • the aforementioned polycarboxylic acids or polyphosphonic acids are usually used in the form of the sodium or potassium salts.
  • Suitable anti-graying agents are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers are also suitable, in particular mixtures of carboxymethyl cellulose and methyl cellulose.
  • Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 '"- amino) -stiiben-2,2'-disuifonic acid or compounds of the same structure which, instead of the morpholino group, carry other substituents containing amino groups, for example a diethanolamino group, or brighteners of the substituted diphenylstyryl type, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl , 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl-4 '- (2-sulfostyryl) diphenyl.
  • a further constituent of the powder component (B) are neutral salts, in particular sodium sulfate in proportions of 0 to 25% by weight, preferably 1 to 10% by weight, and textile-softening sheet silicates or smectite clays in proportions of 0 to 22% by weight. , preferably 0 to 15% by weight.
  • Other washing aids are additives that improve the powder structure, e.g. B. alkali salts or toluene, cumene or xylene sulfonic acid.
  • component (B) can be carried out under conditions as described above in the production of the granular adsorbent.
  • compositions can contain further powder components as a mixture component.
  • these further powder components contain substances which are unstable under the conditions of spray drying or which lose their specific effect in whole or in part.
  • active ingredients are e.g. B. enzymes, bleaches, bleach activators, foam inhibitors and fragrances.
  • Enzymes from the class of proteases, lipases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. They are preferably also in the form of granules with a comparable particle spectrum in order to prevent segregation.
  • the perhydrates and per-compounds usually used in washing and bleaching agents are suitable as bleaching components.
  • the perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or also as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea.
  • sodium perborate tetrahydrate or monohydrate is preferably also used.
  • the bleach activators represent another optional powder component.
  • the bleach activators include, in particular, N-acyl compounds and 0-acetylene compounds.
  • suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril.
  • Na-cyanamide N-alkyl-N-sulfonyl-carbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines.
  • carboxylic acid anhydrides such as phthalic anhydride and esters, such as Na (iso) nonanoyl phenol sulfonate
  • acylated sugars such as glucose pentaacetate
  • Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate.
  • the bleach activators can also be granulated and coated with coating substances in order to avoid interactions with the per compounds.
  • foam inhibitors (with the exception of high molecular weight fatty acid soaps) often lose all or part of their effectiveness when incorporated into the detergent slurry, they are also advantageously mixed into the detergent as a separate powder component.
  • Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors, e.g. B. from silicones and paraffins are useful.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance and, in this form, have a particle size spectrum which corresponds to that of components (A) and (B).
  • fragrances are used, they can be applied to one of the powder components.
  • one or more of the powder components can be colored or coated with pigments, for example in order to cover up the intrinsic colors of active ingredients or to give the powder mixture a colored, mottled appearance.
  • the average grain size or the proportion of the individual sieve fractions of the granular powder components (A) and (B) should not differ from one another by more than 50%.
  • the mixing ratio of the two components (A) and (B) is in the range from 1: 5 to 3: 1, preferably from 1: 4 to 2: 1 and should be chosen so that the distribution ratio of the components (a), ( c) and (d) moved within the scope of the definition of the invention.
  • the proportion of optional powder components can fluctuate within larger limits.
  • Bleach activators can be present in amounts of 0.2 to 5% by weight. As already explained, both additives are preferably used in granular form.
  • Enzymes and foam inhibitors are usually used in proportions of 0.01 to at most 2% by weight, preferably 0.05 to 1% by weight, based on the active ingredient.
  • the proportion of carrier substance, extender and coating material predominates by far and is in many cases more than 90%. Accordingly, the proportion of these granular powder constituents in the total mixture is generally 0.3 to 5% by weight.
  • the dosing and subsequent mixing of components (A) and (B) and the additional powder component can be carried out in individual stages or simultaneously. It is expedient to work continuously, with automatic belt scales in combination with free-fall mixers having proven particularly useful. Additional mechanically operated mixing devices are generally not required. If they are used, careful treatment of the powder mixture is recommended in order to avoid destruction of the hollow spherical structure of the spray powder and an undesirable increase in the proportion of fine particles and dust.
  • the agents according to the invention are distinguished by a high washing capacity, in particular by an excellent cleaning power against stubborn greasy soiling. Despite their comparatively high content of liquid non-ionic surfactants, they are extremely pourable and free-flowing and do not tend to grease cardboard packaging.
  • the zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns.
  • a copolymer of acrylic acid and maleic acid (molar ratio 7: 3) with an average molecular weight of 70,000 in the form of the sodium salt was used as the polycarboxylic acid.
  • EO ethylene oxide
  • composition of the agent and other agents produced in the same way are listed in Table 1 (in% by weight).
  • the powder component (A) was additionally powdered with 3% by weight (based on this component) with zeolite NaA powder after the application of the nonionic surfactant.

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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)
  • Glanulating (AREA)
EP86117410A 1985-12-23 1986-12-15 Phospahtreduziertes, granulares Waschmittel Expired - Lifetime EP0228011B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86117410T ATE51891T1 (de) 1985-12-23 1986-12-15 Phospahtreduziertes, granulares waschmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853545947 DE3545947A1 (de) 1985-12-23 1985-12-23 Phosphatfreies, granulares waschmittel
DE3545947 1985-12-23

Publications (3)

Publication Number Publication Date
EP0228011A2 EP0228011A2 (de) 1987-07-08
EP0228011A3 EP0228011A3 (en) 1987-08-26
EP0228011B1 true EP0228011B1 (de) 1990-04-11

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EP86117410A Expired - Lifetime EP0228011B1 (de) 1985-12-23 1986-12-15 Phospahtreduziertes, granulares Waschmittel

Country Status (7)

Country Link
US (1) US4849125A (tr)
EP (1) EP0228011B1 (tr)
JP (1) JPS62158800A (tr)
AT (1) ATE51891T1 (tr)
DE (2) DE3545947A1 (tr)
ES (1) ES2014411B3 (tr)
TR (1) TR26001A (tr)

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Also Published As

Publication number Publication date
TR26001A (tr) 1993-10-08
ES2014411B3 (es) 1990-07-16
ATE51891T1 (de) 1990-04-15
EP0228011A3 (en) 1987-08-26
US4849125A (en) 1989-07-18
DE3670306D1 (de) 1990-05-17
DE3545947A1 (de) 1987-07-02
JPS62158800A (ja) 1987-07-14
EP0228011A2 (de) 1987-07-08

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