EP0473622A1 - Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive. - Google Patents

Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive.

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Publication number
EP0473622A1
EP0473622A1 EP90906974A EP90906974A EP0473622A1 EP 0473622 A1 EP0473622 A1 EP 0473622A1 EP 90906974 A EP90906974 A EP 90906974A EP 90906974 A EP90906974 A EP 90906974A EP 0473622 A1 EP0473622 A1 EP 0473622A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
granular
less
grain size
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
EP90906974A
Other languages
German (de)
English (en)
Other versions
EP0473622B1 (fr
Inventor
Franz Hundgeburt
Dieter Jung
Fred Schambil
Guenther Vogt
Gerti Nienhaus
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Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0473622A1 publication Critical patent/EP0473622A1/fr
Application granted granted Critical
Publication of EP0473622B1 publication Critical patent/EP0473622B1/fr
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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a granular detergent additive consisting of two granular powder components of a defined composition, to which liquid, semi-solid or solid nonionic surfactants are adsorbed. Both powder components have a porous structure and can absorb up to 30% by weight, based on the additive, of such nonionic surfactants without the free-flowing properties suffering.
  • nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in low-temperature detergents.
  • their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since this would otherwise result in excessive smoke formation in the exhaust air from the spray towers and poor giant properties of the spray powder.
  • Methods have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
  • DE 24 18 294 discloses detergents which consist of a powder component obtained by hot spray drying and granular sodium perborate tetrahydrate, the latter being impregnated with a defined mixture of nonionic surfactants. Due to the selection of nonionic surfactants, the granulate is dust-free and free-flowing. According to EP-A 34 194, the perborate tetrahydrate is treated with nonionic surfactants which contain both ethylene glycol ether groups and propylene glycol ether groups. In addition to good flowability, the granules are particularly characterized by being odorless.
  • DE-B 25 07 926 contains examples of the preparation of premixes, powder mixtures of aluminosilicate (zeolite), perborate and optionally also a bleach activator being sprayed with non-ionic surfactants.
  • the resulting granules are then mixed with other powder components, in particular tower spray powder.
  • a certain stickiness of the granules disturbs, which can also be transferred to the overall mixture, especially if the admixed tower spray powder contains no phosphates.
  • the ignition range of the mixture is reduced to such an extent that, under unfavorable conditions, the mixtures can self-ignite even at room temperature.
  • EP-A 168 102 discloses a process for the production of high-density detergents in which nonionic surfactants are sprayed onto a powder mixture of sodium perborate monohydrate, zeolite and other builder salts. In this spray mixing process, granulation of the base powder occurs at the same time. Another part of the nonionic surfactants used overall is sprayed onto a second powder component which is free of sodium sulfate and consists of spray-dried granules which contain the usual surfactants, builder salts and other detergent components. Both the perborate-containing base powder and the spray-dried powder component contain considerable amounts of sodium tripolyphosphate in the agents according to the examples.
  • absorbent carrier particles consist of Here ⁇ ren ingredients and are made mostly by spray drying her ⁇ . Examples of these are the agents according to US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683).
  • these carrier grains developed especially for the adsorption of nonionic surfactants contain considerable amounts of phosphates, which limits their possible uses.
  • Phosphate-free carrier grains are known from DE-A 32 06265 (GB 20 97 419) and DE-A 32 06 379 (GB 20 95 274). They consist essentially of sodium carbonate or hydrogen carbonate, zeolite, sodium silicate, bentonite and polyacrylate. The high proportion of carbonates, however, favors the formation of calcium carbonate in hard water, while the sodium silicate in conjunction with zeolite considerably deteriorates the dispersibility of the grains in water.
  • EP-A 184794 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight zeolite, 0 , 1 to 8% by weight of sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight % contains nonionic surfactants and can be obtained by spray drying.
  • nonionic surfactants based on anhydrous substance
  • the object was therefore to develop a granular adsorption material which avoids the disadvantages listed, in particular the formation of highly flammable mixtures, and has a high adsorption capacity for nonionic surfactants and, together with them, has improved dissolving and flushing behavior .
  • the invention accordingly relates to a granular, free-flowing, phosphate-free detergent additive containing
  • the granular components (A) and (B) as well as the finished agent have one in the interest of good flowability an average grain size of 0.2 to 1.2 mm, preferably of 0.3 to 1 mm.
  • the proportion of particles in the composite with a grain size below 0.05 mm is less than 1% by weight, preferably less than 0.1% by weight, and the proportion with a grain size below 0.1 m less than 2% by weight, preferably less than 1% by weight, the fraction with a grain size of more than 2 mm less than -5% by weight, preferably less than 1% by weight and the fraction with a grain size over 1.2 mm less than 10% by weight, preferably less than 5% by weight.
  • Both components can have the same or a different grain size within the specified limits.
  • the joint mixing and treatment with nonionic surfactants can result in a slight agglomeration of the particles, in particular in the connection of finely divided constituents to larger grains, and thus overall a slight increase in the average grain size.
  • the proportion of sodium perborate monohydrate (component A) is 10 to 70% by weight, preferably 20 to 60% by weight and in particular 30 to 50% by weight.
  • the proportion of component (B) is 25 to 80% by weight, preferably 35 to 70% by weight and in particular 40 to 60% by weight.
  • the proportion of the nonionic component (C) is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 10 to 15% by weight.
  • the perborate monohydrate is preferably used as loose, expanded pellets with a liter weight of 450 to 650 g / 1, preferably 500 to 600 g / 1.
  • Such grains are characterized by a good adsorption capacity for liquid to lard-like nonionic surfactants. Loading the grains with the nonionic surfactants generally increases the bulk density another 50 to 200 units, which is in the interest of a higher total bulk weight and a saving in packaging and transport volume.
  • Component (B) likewise preferably consists of a granular, porous material, as can be obtained by spray drying aqueous slurries of water-insoluble or water-soluble salts or salt mixtures. It contains synthetic zeolite of the NaA type in proportions of 45 to 75, preferably 50 to 70% by weight and in particular 55 to 68% by weight (based on anhydrous substance). Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being below 30%, in particular below 20%. Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% of particles smaller than 10 ⁇ m.
  • Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 ⁇ m.
  • the zeolites can still contain excess alkali from their production.
  • Their water content of synthetic zeolites is usually 18 to 22% by weight.
  • component (B) Another advantageous component of component (B) is sodium sulfate, which is calculated as an anhydrous substance and is present in proportions of 0 to 30% by weight, preferably 1 to 25 and in particular 3 to 20% by weight.
  • the sodium sulfate contributes to a considerable improvement in the grain structure of component (B) and the washing-in behavior of the detergent additive and at the same time increases its bulk density, which results in the possibility of saving packaging and transport volume.
  • Another inorganic salt that can be combined with the zeolite is sodium carbonate, which can be present in proportions of up to 20% by weight, based on component (B). With regard to the flushing-in behavior, however, such mixtures are inferior to the mixtures of zeolite and sodium sulfate.
  • component (B) in inorganic salts including zeolite should be at least 75% by weight, preferably at least 85% by weight (based on component B).
  • component (B) contains organic salts which are particularly advantageous for the grain structure, the grain rod 1 and in particular for the washing-in behavior of the granules and their mixtures with other detergent constituents.
  • organic salts which are contained in component (B) include the sodium or potassium salts, preferably the sodium salts of homopolymeric and / or copolymeric carboxylic acids.
  • Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid, with polyacrylic acid being preferred.
  • 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.
  • the proportion thereof in the interest of sufficient water solubility is not more than 50 mole percent, preferably less than 30 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail, for example, in EP 25 551-B1, have proven particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Such copolymers are particularly preferred, in which 45 to 85 percent by weight acrylic acid and 55 to 15 percent by weight maleic acid are present.
  • the molecular weight of the homo- or copolymers are generally employed is from 2000 to 150,000, preferably 5000 to 100 000.
  • My An ⁇ part in the component attempts (B) is for example 1 to 12 wt .-% preferably 1.5 to r 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt.
  • the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.
  • An optional, advantageous component of component (B), which in particular significantly improves the washing-up behavior in the washing machine, consists of a water-soluble soap, preferably a sodium soap, which is derived from saturated fatty acids with 10 to 24, preferably 12 to 22 C. -Atoms and mixtures thereof with oleic acid, the proportion of saturated fatty acids should be at least 50 wt .-%, preferably at least 75 wt .-%. Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 0 to 6, preferably 1 to 5 and in particular 2 to 4% by weight, based on component (B).
  • a readily usable granular component (B) accordingly contains (calculated as anhydrous constituents) 45 to 75% by weight, preferably 50 to 70% by weight, zeolite,
  • the zeolite In cases where the zeolite is used in the production of the granular component (B) not in powdery or spray-dried form, but rather as a moist filter cake, it can contain dispersion stabilizers, as described in DE 25 27 388 in more detail are described. Suitable stabilizers are, in particular, nonionic surfactants with HLB values below 12, such as ethoxylated tallow alcohol with 3 to 8 E0.
  • the proportion of these additives in the powder component (B) can, depending on the zeolite content, be up to 4% by weight, usually 0.3 to 3% by weight. In the final balance, this portion of component (C) is added.
  • the difference of up to 100% by weight is due to water, which is present in a bound form and as moisture, the major amount being bound to the zeolite.
  • a proportion of the water which is approximately 8 to 18% by weight (based on the agent), can be removed at a drying temperature of 145 ° C.
  • a further fraction which is between 4 and 8% by weight depending on the zeolite fraction, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.
  • the average grain size of component (B) is 0.2 to 1.2 m, the proportion of the grains below 0.05 m less than 1% by weight, preferably less than 0.5% by weight and above 2 mm should not be more than 5% by weight.
  • At least 80% by weight, in particular at least 90% by weight, of the grains preferably have a size of 0.1 to 1.2 mm, the proportion of the grains being between 0.1 and 0.05 mm, preferably not more than 3% by weight, in particular less than 1% by weight, the proportion of the grains between 0.1 and 0.2 mm less than 20% by weight, in particular less than 10% by weight and the proportion the grain between 1.2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.
  • the bulk density of component (B) in the preferred embodiment is 400 to 680 g / 1, preferably 450 to 650 g / 1. Adsorption of the nonionic surfactants also increases it by 50 to 200 g / 1.
  • the nonionic surfactants adsorbed on the mixture of components (A) and (B) are those which are usually used in washing and cleaning agents.
  • Other suitable additives are organic solvents with which the cleaning ability of detergents and cleaning agents is improved, in particular in relation to greasy soiling, and which can be incorporated into a granular cleaning agent in this way without problems.
  • other substances such as fragrances, finishing agents, optical brighteners and anionic or cationic surfactants, can also be added to the mixture of components (A) and (after prior dissolving or dispersing in organic solvents or the liquid or molten nonionic surfactants). B) are added. These substances penetrate into the porous grains together with the solvent or dispersant and are thus protected against interactions with other powder components.
  • Preferred detergent ingredients which are bound to the granular mixture and together with it as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of polyglycol ethers, derived from alcohols with 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl branched in the 2-position (oxo radical).
  • EO ethylene oxide
  • PO propylene oxide
  • They reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. In the case of technical alkoxylates, the number of EO or PO groups corresponds to the statistical mean.
  • ethoxylated fatty alcohols examples include C 1-10 coco alcohols with 3 to 12 EO, Ci6_ ⁇ s-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures From the series of ethoxylated oxo alcohols, for example, those with the composition C12-15 + to 10 EO and C14-C15 + 3 to 12 EO are suitable.
  • Mixtures are characterized by low and high levels of detergency against greasy and mineral soiling highly ethoxylated alcohols, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or Ci3_ ⁇ s-0xoalkohol + 3 to 5 EO and Ci2-14-0x - alcohol + 8 to 12 EO.
  • Particularly good washing-in properties have agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation.
  • component (B) in the preferred embodiment is based on an aqueous batch containing a total of 40 to 55% by weight of water-free ingredients, which is sprayed into a falling space by means of nozzles and by means of drying gases which have an inlet temperature of 150 to 280 ° C and have an outlet temperature of 50 to 120 ° C, is dried to a removable moisture content of 145 ° C of 8 to 18 wt .-%.
  • the aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction.
  • the soap or the salts of the polymeric carboxylic acids instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately.
  • alkali hydroxide in particular NaOH
  • NaOH is also recommended in order to make the aqueous zeolite suspension or the slurry alkaline, i.e. adjust to a pH of at least 8 and provide a sufficient alkali excess so that the pH does not drop to less than 8 during the spray drying.
  • Such a lowering of the pH value which would lead to a loss of activity of the zeolite, can be caused by CO2 in the dry gas.
  • the addition of NaOH which ensures a sufficient alkali reserve, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient.
  • the content of water-free ingredients in the aqueous mixture is preferably 43 to 50% by weight. Its temperature is expediently 50 to 100 ° C and its viscosity 2,000 to 20,000 mPa-s, usually 8,000 to 14,000 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, is (ie immediately before entering the lower part of the tower) 150 to 280 ° C, preferably 170 to 250 ° C.
  • the exhaust gas which is laden with moisture and leaves the tower, has a temperature of 50 to 130 ° C, preferably 55 to 115 ° C.
  • the spray drying is conducted in such a way that the particle size of the spray product has the distribution given above.
  • Existing fine and coarse grains are screened before further processing. It has been shown that the flushing behavior of the adsorbent impregnated with nonionic surfactants deteriorates with increasing proportion of fine grain.
  • Both powder components are combined to form a homogeneous mixture and then treated with liquid or nonionic surfactants or surfactant mixtures liquefied by heating.
  • the nonionic surfactant is expediently sprayed onto the agitated mixture. Heating the nonionic surfactant to temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the adsorption process.
  • the abrasion resistance and constancy of shape of the grains is so high when the specified proportions or production conditions are met that the freshly prepared, but especially the cooled and, if necessary, reheated, ripened grains are treated with the liquid additives under the usual spray mixing conditions , can be mixed and conveyed without the formation of fine fractions or coarser agglomerates. There is also no risk of spontaneous combustion during processing and storage when using the mixtures according to the invention.
  • the mixing of the two granular components and the subsequent spraying with nonionic surfactants can be carried out in the usual way mechanical mixing devices, such as drum mixers, fluidized bed mixers or spray mixers, are carried out continuously or discontinuously.
  • the mixing and spraying process can also be carried out with continuous operation of a single mixing apparatus, the two powder components being combined in a first mixing section and the nonionic component being added in a final mixing section.
  • a particular advantage of the invention is that the adsorption of the liquid nonionic surfactants and their diffusion into the interior of the grain takes place comparatively quickly. Shortly after leaving the mixing apparatus, the grain mixtures have their full flow properties and can be processed further without intermediate storage or a time-consuming post-ripening process.
  • Suitable powdering agents have a grain size of 0.001 to a maximum of 0.1 mm, preferably less than 0.05 mm and can be in proportions of 0.03 to 3, preferably 0.05 to 2% by weight ⁇ applied to the adsorbent loaded with additive.
  • finely powdered zeolites for example, finely powdered zeolites, silica airgel (Aerosil ( R )), colorless or colored pigments, such as titanium dioxide, and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose.
  • a treatment is generally not necessary, especially since the washability is not improved thereby.
  • the granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, as can be obtained, for example, by spray drying or granulation, or with bleaches or with detergents containing bleach known composition can be mixed in any ratio.
  • their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided.
  • the powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.
  • the admixed spray powders and granules can also contain sodium sulfate, which is often advantageous for their grain properties, especially in the absence of phosphates. These admixed detergent components are therefore preferably also phosphate-free.
  • the absorbency of the granulate mixture according to the invention for nonionic surfactants is so high that an additional application of these surfactants to other mixture components is unnecessary.
  • the zeolite used had a calcium binding capacity of 165 mg CaO / g and an average particle size of 3 ⁇ m, with no proportions above 20 ⁇ m. It was used as an aqueous dispersion (filter cake) containing 48% by weight of anhydrous zeolite and the other additives mentioned under (a) and 50.2% by weight of water. A copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan W) in the form of the sodium salt was used as the polycarboxylic acid.
  • the aqueous slurry which had a temperature of 85 ° C. and a viscosity of 10 200 mPa * s, was sprayed with a pressure of 40 AT in a tower in which combustion gases at a temperature of 226 ° C. (measured in the ring channel) spray product were brought up to.
  • the outlet temperature of the Dry gas was 63 ° C.
  • the granular adsorbent leaving the spray tower contained e) 19.2 pbw of water.
  • the bulk weight was 563 g / 1.
  • the run-out time of the dry sand after opening the outflow opening was set at 100%.
  • the free-flowing properties of the products according to the invention are given in%, based on this 100% value. Values above 75% are considered very good.
  • washing-in behavior was investigated, conditions being simulated that of a washing-in device operated under critical conditions
  • a and B values are very good to satisfactory in practice.
  • C values indicate inadequate induction behavior.
  • test series were carried out, namely (I) with the detergent additive without the addition of a detergent and (II) a mixture of 25 parts of the detergent additive and 75 parts of a detergent, consisting of 50 parts of tower spray powder and 25 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators.
  • the tower spray powder had the following composition (in% by weight):
  • a base powder was used for comparison, consisting of (given in parts by weight):
  • the zeolite was in powder form and corresponded to the product HAB 40 according to the information in EP-A 168 102.
  • the above recipe differs from example 1 in that the tripolyphosphate (7 T) was replaced by zeolite.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Abstract

Cet additif comporte (A) entre 10 et 70 % en poids d'un sodium-perborate-monohydrate; (B) entre 25 et 80 % en poids d'un mélange granulaire de sels; et (C) entre 5 et 30 % en poids d'agents tensio-actifs non ioniques. Le constituant (B) est un granulé absorbant séché par pulvérisation, contenant entre 45 et 75 % en poids (poids à sec) d'une zéolite en fins cristaux; entre 0 et 30 % en poids de sulfate de sodium; entre 1 et 12 % en poids de sels d'acides carboxyliques (co)polymères, ainsi que de l'eau liée. Le constituant (C) peut en outre contenir des quantités minimes de savon soluble dans l'eau, la teneur totale en composés inorganiques de (C) étant d'au moins 75 % en poids.
EP90906974A 1989-05-22 1990-05-14 Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive Expired - Lifetime EP0473622B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3916629A DE3916629A1 (de) 1989-05-22 1989-05-22 Granulares, nichtionische tenside enthaltendes waschmitteladditiv
DE3916629 1989-05-22
PCT/EP1990/000776 WO1990014412A1 (fr) 1989-05-22 1990-05-14 Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive

Publications (2)

Publication Number Publication Date
EP0473622A1 true EP0473622A1 (fr) 1992-03-11
EP0473622B1 EP0473622B1 (fr) 1994-06-29

Family

ID=6381153

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90906974A Expired - Lifetime EP0473622B1 (fr) 1989-05-22 1990-05-14 Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive

Country Status (6)

Country Link
EP (1) EP0473622B1 (fr)
AT (1) ATE107957T1 (fr)
DE (2) DE3916629A1 (fr)
ES (1) ES2055910T3 (fr)
PT (1) PT94102A (fr)
WO (1) WO1990014412A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4209435A1 (de) * 1992-03-24 1993-09-30 Henkel Kgaa Granulares, nichtionische Tenside enthaltendes, phosphatfreies Additiv für Wasch- und Reinigungsmittel
DE4229660A1 (de) * 1992-09-04 1994-03-10 Henkel Kgaa Wasch- und Reinigungsmittel mit Buildersubstanzen
GB2343457A (en) * 1998-11-07 2000-05-10 Procter & Gamble Bleach containing detergent composition
US6551983B1 (en) 1998-11-07 2003-04-22 The Procter & Gamble Company Bleach-containing detergent composition
IT201700035338A1 (it) * 2017-03-30 2018-09-30 Bio On Spa Composizione cosmetica comprendente un poliestere biodegradabile e una fase oleosa.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8412537D0 (en) * 1984-05-17 1984-06-20 Unilever Plc Detergent powder compositions
DE3424987A1 (de) * 1984-07-06 1986-02-06 Unilever N.V., Rotterdam Verfahren zur herstellung eines pulverfoermigen waschmittels mit erhoehtem schuettgewicht
EP0296813A1 (fr) * 1987-06-24 1988-12-28 Imperial Chemical Industries Plc Compositions de poudre et compositions détergentes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9014412A1 *

Also Published As

Publication number Publication date
DE59006321D1 (de) 1994-08-04
ATE107957T1 (de) 1994-07-15
DE3916629A1 (de) 1990-11-29
EP0473622B1 (fr) 1994-06-29
WO1990014412A1 (fr) 1990-11-29
PT94102A (pt) 1991-01-08
ES2055910T3 (es) 1994-09-01

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