EP0034194B1 - Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques - Google Patents

Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques Download PDF

Info

Publication number
EP0034194B1
EP0034194B1 EP80100803A EP80100803A EP0034194B1 EP 0034194 B1 EP0034194 B1 EP 0034194B1 EP 80100803 A EP80100803 A EP 80100803A EP 80100803 A EP80100803 A EP 80100803A EP 0034194 B1 EP0034194 B1 EP 0034194B1
Authority
EP
European Patent Office
Prior art keywords
powder
washing
ionic surfactant
formula
acid
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.)
Expired
Application number
EP80100803A
Other languages
German (de)
English (en)
Other versions
EP0034194A1 (fr
Inventor
Hans Peter Dr. Kubersky
Franz Hundgeburt
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
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
Priority to AT80100803T priority Critical patent/ATE4125T1/de
Priority to EP80100803A priority patent/EP0034194B1/fr
Publication of EP0034194A1 publication Critical patent/EP0034194A1/fr
Application granted granted Critical
Publication of EP0034194B1 publication Critical patent/EP0034194B1/fr
Expired legal-status Critical Current

Links

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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • nonionic surfactants commonly used in detergents solidify at temperatures below 25-30 ° C, however, considerable difficulties can arise in the mixing and granulating process if the powder to be charged has a temperature of less than 20 ° C, for example from 0 to 10 ° C. This is usually the case in the cold season when the powder is taken from a usually unheated wagon or silo.
  • the nonionic surfactant then solidifies into solid, fat-like agglomerates and can no longer be distributed homogeneously in the powder.
  • the invention relates to a process for the production of a pourable, nonionic surfactant from the class of detergent and cleaning agent granules containing polyalkylene glycol ether derivatives by admixing the nonionic surfactant to a powdery to granular component of the detergent and cleaning agent and then combining the premix obtained in this way with the other constituents of the detergent and cleaning agent, characterized in that a compound of the general formula I is used as the nonionic surfactant in which R is an aliphatic hydrocarbon radical having 8 to 20 carbon atoms, m is a number from 0.5 to 8 and n is a number from 2 to 20, with the proviso that n is equal to or greater than m.
  • R is a primary alkyl or alkenyl radical having 12 to 18 carbon atoms and in which m is a number from 1 to 5 and n is a number from 3 to 15 with the proviso that that n is 2 to 10 times m.
  • Nonionic surfactants of the formula (I) are known and are obtained, for example, according to US Pat. No. 2,174,761 by reacting alcohols with propylene oxide and then with ethylene oxide.
  • the process can be carried out by powdering any mixture. shaped detergent ingredients, optionally after prior granulation or spray drying, mixed with the nonionic surfactants of the formula (I) and granulated at the same time, uniform mixing being facilitated by spraying the surfactant in the form of a fine spray.
  • a certain powder constituent of the detergent is preferably treated in the manner according to the invention and this surfactant-containing premix is then combined with the other powder constituents.
  • the so-called builder salts are suitable, which include the condensed phosphates, alkali silicates, alkali carbonates, alkali borates and alkali sulfates.
  • Silica-containing agents or colloidal clays such as surface-active silica (aerosil), magnesium silicate, bentonites and smectite clays, are also suitable, but such substances are less interesting from a washing point of view since, in contrast to the builder salts, they only act as adsorbents and make no contribution to Perform washing and cleaning effects. Mixtures of various powdery or granular materials can also be used for the purpose mentioned.
  • the nonionic surfactant In the mixing or granulation process, stable agglomerates are formed between the nonionic surfactant and the powder particles, or the surfactant forms a more or less closed coating on the particles.
  • sodium perborate as the powder base
  • the amount of the nonionic agent should be 5 to 20 percent by weight, preferably 7 to 15 percent by weight of the premix. If builder salts are used as the base powder, the amount of the nonionic surfactant to be applied can be within the same limits.
  • the proportion of nonionic surfactant can be increased to 35 percent by weight, based on the premix containing surfactant.
  • the agglomerates or the coatings can be produced in such a way that the melted nonionic surfactant, heated to temperatures above 30 ° C., preferably 50 ° to 70 ° C., is intimately mixed with the base powder to be charged.
  • the base powder to be used can have a temperature of 0 ° to 30 ° C. Additional heating of the powder before or during the mixing process is not necessary. Rather, even when using a relatively cold powder, a homogeneous distribution without dust formation is guaranteed.
  • Mixing can be carried out continuously or in batches using conventional mixing, granulating or spraying devices. Suitable are e.g. Drum, cascade, plow shovel or other mixers working according to the compulsory mixing method as well as arrangements in which the liquid melt is continuously sprayed onto a free-falling powder or a thin layer spread on a conveyor belt. After spraying, granulation may follow.
  • conventional mixing, granulating or spraying devices Suitable are e.g. Drum, cascade, plow shovel or other mixers working according to the compulsory mixing method as well as arrangements in which the liquid melt is continuously sprayed onto a free-falling powder or a thin layer spread on a conveyor belt. After spraying, granulation may follow.
  • the grain size and liter weight of the base powder used can vary within wide limits. However, the proportion of coarse-grained particles with a grain size of more than 2 mm should expediently be less than 10 percent by weight and preferably less than 2 percent by weight.
  • the fine fraction with a grain size of less than 0.1 mm is preferably less than 25% by weight and in particular less than 10% by weight.
  • the average grain size is advantageously 0.1 to 0.8 mm.
  • the treatment with the liquid surfactant generally leads to an increase in grain size, the fine particles with a grain size of less than 0.2 mm being largely or completely cemented into larger particles.
  • the proportion of particles with a grain size of 1 to 3 mm increases only slightly. If necessary, coarser particles can be sieved out, crushed and then reused.
  • the average grain size of the perborate or builder salt treated with nonionic surfactant is 0.4 to 1.0 mm and is thus of the order of magnitude of a detergent and cleaning agent powder obtained by spray drying or granulation. This is a particular advantage, since it counteracts undesired segregation processes during the transport or storage of the detergents.
  • additives such as dyes, pigments or fragrances
  • further additives such as dyes, pigments or fragrances
  • dyes, pigments or fragrances can be applied to the base powder together with the nonionic compound.
  • colored additives enables the powder mixture to be spotted in a visually appealing and marking manner.
  • the powder charged with the nonionic surfactant of the formula (I) is mixed with the other, preferably spray-dried powder components using customary mixing devices, the weight ratio of the powder applied to the other powder components being 1:10 to 1: 3 and the content of the composite washing and detergent on the surfactant of formula (I) is 1 and 10 percent by weight.
  • this second component contains at least one anionic, nonionic or zwitterionic surfactant as well as at least one framework substance which has a complexing action or binds the lime hardness of the water and optionally further washing aids.
  • Suitable anionic surfactants are those of the sulfonate or sulfate type, in particular alkylbenzenesulfonates, olefin sulfonates, alkyl sulfonates and ⁇ -sulfofatty acid esters, primary alkyl sulfates and the sulfates of ethoxylated, 2 to 3 glycol ether groups having higher molecular weight alcohols.
  • alkali soaps of fatty acids of natural or synthetic origin for example the sodium soaps of coconut, Paimkern- or tallow fatty acids and, if foam suppression is desired, also those of hydrogenated rapeseed or fish oil fatty acids.
  • Alkyl betaines and especially alkyl sulfobetaines are suitable as zwitterionic surfactants.
  • the anionic surfactants are preferably in the form of the sodium salts. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22, preferably 12 to 18, carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain 6 to 16, in particular 10 to 14, carbon atoms.
  • the spray-dried detergents contain at least one nonionic surfactant which differs from the compound of the formula I.
  • nonionic surfactant which differs from the compound of the formula I.
  • these are ethoxylated alcohols, vicinal diols and alkylphenols of the structure indicated with an average of 3 to 20, preferably 5 to 15, glycol ether groups.
  • the quantitative ratio of the two parts can preferably be 4: 1 to 1: 4.
  • the surfactant of the formula applied to the perborate or builder salt does not contain more than 6-8 ethylene glycol ether groups at a content of 1 to 4 propylene glycol groups, water-soluble, higher ethoxyated C 14 -C 18 alcohols with 10 to 16 ethylene glycol ether groups are preferably used in the spray powder.
  • the weight ratio of the low-ethoxylated surfactants of the formula I applied to the perborate or builder salt to the higher-ethoxylated surfactants contained in the spray powder is advantageously 3: 1 to 1: 4, preferably 1: 1 to 1: 3.
  • nonionic surfactants are those which are derived from the abovementioned compounds and have both ethylene glycol and propylene glycol ether groups, for example alcohols with 10 to 30 ethylene glycol ether groups and 3 to 30 propylene glycol ether groups; also ethoxylation products of mercaptans, fatty acid amides and fatty acids.
  • the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain can also be used.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
  • Suitable builders are the polymer phosphates, carbonates and silicates of potassium and in particular sodium, the latter having a ratio of Si0 2 to Na 2 0 of 1: 1 to 3.5: 1.
  • the pentasodium triphosphate is suitable as the polymer phosphate, which may be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
  • the polymer phosphates can also be completely or partially replaced by organic, complexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriamineopentaacetic acid and the higher homologues of the aminopolycarboxylic acids mentioned are also suitable. These homologs can be prepared, for example, by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by reacting polyethylenimine with chloroacetic acid or bromoacetic acid salts in an alkaline medium.
  • aminopolycarboxylic acids are poly (N-succinic acid) ethylene imine, poly (N-tricarballylic acid) ethylene imine and poly (N-butane-2,3,4-tricarboxylic acid) ethylene imine, which are obtainable analogously to the N-acetic acid derivatives .
  • complexing polyphosphonic acid salts may be present, e.g. the alkali salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.
  • polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups.
  • Citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid are suitable.
  • Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxydisuccinic acid and polyhydric alcohols partially or completely etherified with glycolic acid or hydroxycarboxylic acids, for example triscarboxymethylglycerol, biscarboxymethylglyceric acid and carboxymethylated or oxidized polysaccharides.
  • polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts such as polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylene unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
  • Water-insoluble complexing agents can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of a woven fabric, non-woven fabric or powder. Furthermore, there are spatially crosslinked and thereby water-insoluble copolymers of acrylic, methacrylic, crotonic and maleic acids and others polymerizable polycarboxylic acids, if appropriate with other ethylenically unsaturated compounds in the form of the sodium or potassium salts, are suitable as sequestering agents. These insoluble copolymers can be in the form of nonwovens, sponges or in the form of finely ground, specifically light foams with an open-cell structure.
  • Inorganic water-insoluble cation exchangers for example zeolites and in particular water-containing aluminum silicates of the formula (Na20), can also be used.
  • Neutral salts in particular sodium sulfate, and magnesium silicate, which acts as a stabilizer for per compounds, can be considered as further constituents.
  • Further washing aids which may be present in the spray-dried powder component are graying inhibitors and optical brighteners and additives which improve the powder structure. e.g. Alkali salts of toluene, cumene or xylene sulfonic acid.
  • Suitable graying inhibitors are in particular carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betain groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinyl amide pyrrolidones which are soluble in water in a colloidal manner and acrylonitrile.
  • Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group or a .beta.-methoxyethylamino group instead of the morpholino group.
  • a 2- pyrazoline and compounds of the same structure which carry a carboxymethyl or acetylamino group instead of the sulfonamido group It is also possible to use substituted aminocoumarins, for example 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can be used.
  • the brighteners for polyester and polyamide fibers are the compounds 2 , 5-di- (2-benzoxaz olyl) thiophene, 2- (2-benzoxazolyl) naphtho [2,3-b] thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ethylene are suitable.
  • Brighteners of the substituted diphenylstyrile type may also be present. Mixtures of the aforementioned brighteners can also be used.
  • powder components that are not suitable for joint processing with the perborate and not for hot spray drying.
  • these include bleach activators, especially tetraacetylglycoluril or tetraacetylethylenediamine.
  • the powder particles consisting of the bleach activators can be coated with coating substances, in particular mixtures of water-soluble polymers and fatty acids or fatty alcohols, in order to avoid an interaction between the per compound and the activator during storage.
  • Other additives that are added to the powder separately are enzymes from the class of proteases, lipases and amylases or mixtures thereof.
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • the enzymes can be embedded in coating substances or subsequently granulated onto the spray-dried powder component.
  • Fragrances and certain fat-like foam suppressants, such as trialkyl melamines or paraffin hydrocarbons, are also preferably sprayed onto the spray-dried powder subsequently.
  • the granules produced by the process according to the invention are free of dust and lumps, homogeneous and free-flowing and free-flowing, these advantageous properties also being achieved when the base powder used has temperatures of less than 10 ° C. due to appropriate storage conditions.
  • the base powder used has temperatures of less than 10 ° C. due to appropriate storage conditions.
  • such granules which are produced using low-melting coconut fatty alcohol ethoxylates with a low degree of ethoxylation, they are characterized by a substantial lack of odor, which is welcomed by the consumer.
  • nonionic surfactants to be used according to the invention tend to form little undesirable foam compared to low-ethoxylated coconut fatty alcohols, which is why the process products can advantageously be used in automatic washing machines and dishwashers. When used, they are characterized by a high cleaning and fat dissolving power.
  • the dust test was carried out as follows. A round polyethylene film (diameter 45 cm) is spread out on a clean foam rubber mat (dimensions 50 x 50 cm, thickness approx. 1 cm). A cylindrical receptacle with a diameter of 18 cm and a height of 10 cm is placed in the middle of the film. A sheet metal cylinder of 40 cm in diameter and 70 cm in height which is closed on one side is placed with the opening facing downwards in such a way that the distance between the cylinder wall and the edge of the collecting vessel is the same everywhere. This cylinder has a round hole of approx.3.5 cm in diameter in the middle of the closed side, into which a funnel with a 19 cm long tube of 2.5 cm inside diameter is inserted.
  • 100 g of the product to be examined is trickled into the funnel or the cylinder via a shaking channel.
  • the product falls into the container on the bottom of the film.
  • the dust content of the product is released from the product flow in the free fall and is swirled in the air inside the large cylinder.
  • the dust is deposited on the film on the floor.
  • the cylinder and the receptacle are then carefully removed and the film is carefully folded up and the amount of dust deposited on it is determined by weighing. According to this method, the laterally deposited, i.e. the amount of dust not remaining in the product is recorded. It corresponds approximately to the loss of dust.
  • Detergent samples were filled into 200 g folding boxes and subjected to a shaking test for 2 hours. The detergent and perborate grains did not separate.
  • Example 1 450 kg of sodium perborate, which had been taken from an unheated silo and had a temperature of 4 ° C., were mixed in the mixer with 50 kg of a nonionic surfactant heated to 70 ° C. and 5 kg of perfume oil.
  • the nonionic surfactant was prepared by reacting a coconut tallow fatty alcohol mixture (chain length C 12 ⁇ C 18 , average chain length C 15 , 5 ) with 1.5 moles of propylene oxide and 5 moles of ethylene oxide.
  • the mixing process was finished after 3 minutes.
  • the premix was mixed in a continuously operating free-fall mixer with a spray-dried hollow-sphere powder in a weight ratio of 1: 4.
  • the two powder components were fed to the mixer via belt scales.
  • the mixed powder had the following composition (in percent by weight):
  • the powder mixture was homogeneous and had a liter weight of 460 g.
  • the sieve numbers were
  • the powder was free-flowing and free-flowing, free of unpleasant smells and did not tend to separate.

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)
  • Detergent Compositions (AREA)

Claims (6)

1. Procédé de préparation d'un produit de lavage et de nettoyage granuleux qui s'écoule bien, contenant des agents tensio-actifs non ioniques de la classe des dérivés d'éthers de polyalkylène- glycols, par mélange de l'agent tensio-actif non ionique avec un constituant pulvérulent à granuleux du produit de lavage et de nettoyage et combinaison subséquente du mélange préalable ainsi obtenu avec les autres constituants du produit de lavage et de nettoyage, caractérisé en ce que l'on utilise en tant qu'agent tensio-actif non ionique un composé de formule générale 1
Figure imgb0010
dans laquelle R représente un reste hydrocarboné aliphatique en C8―C20, m un nombre de 0,5 à 8 et n un nombre 2 à 20, étant spécifié que n est égal ou supérieur à m.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise un agent tensio-actif non ionique de formule dans laquelle R représente un groupe alkyle ou alcényle primaire en C12-C18.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on utilise un agent tensio-actif non ionique de formule dans laquelle m est un nombre de 1 à 5 et n un nombre de 3 à 15, n ayant 2 à 10 fois la valeur de m.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on applique l'agent tensio-actif non ionique de formule I en mélange sur le perborate de sodium tétrahydratépulvérulent à granuleux en quantité telle que la teneur du mélange préalable en l'agent tensio-actif non ionique soit de 5 à 20% en poids après quoi on combine ce mélange préalable avec les autres constituants de la poudre.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'on applique l'agent tensio-actif non ionique de formule 1 en mélange sur le perborate de sodium tétrahydraté pulvérulent à granuleux en quantité telle que la teneur du mélange préalable en l'agent tensio-actif non ionique soit de 7 à 15% en poids, après quoi on combine le mélange préalable avec les autres constituants de la poudre.
6. Procédé selon les revendications 1 à 5, caractérisé en ce que l'on utilise l'agent tensio-actif non ionique de formule 1 en quantité telle que sa proportion dans le produit de lavage et de nettoyage soit au total de 1 à 10% en poids.
EP80100803A 1980-02-18 1980-02-18 Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques Expired EP0034194B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AT80100803T ATE4125T1 (de) 1980-02-18 1980-02-18 Verfahren zur herstellung eines schuettfaehigen, nichtionische tenside enthaltenden wasch- und reinigungsmittelgranulates.
EP80100803A EP0034194B1 (fr) 1980-02-18 1980-02-18 Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP80100803A EP0034194B1 (fr) 1980-02-18 1980-02-18 Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques

Publications (2)

Publication Number Publication Date
EP0034194A1 EP0034194A1 (fr) 1981-08-26
EP0034194B1 true EP0034194B1 (fr) 1983-07-13

Family

ID=8186600

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100803A Expired EP0034194B1 (fr) 1980-02-18 1980-02-18 Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques

Country Status (2)

Country Link
EP (1) EP0034194B1 (fr)
AT (1) ATE4125T1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7160397B2 (en) 2002-07-04 2007-01-09 Akzo Nobel N.V. Alkoxylate mixture and its use as a cleaning agent for hard surfaces

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2145726A (en) * 1983-08-26 1985-04-03 Diversey Corp Surface active agents
US4668423A (en) * 1985-04-19 1987-05-26 Sherex Chemical Company Liquid biodegradable surfactant and use thereof
EP0229671B1 (fr) * 1986-01-17 1991-03-13 Kao Corporation Composition détergente granulaire de densité élevée
MY102879A (en) * 1986-08-28 1993-03-31 Colgate Palmolive Co Nonaqueous liquid nonionic laundry detergent composition and method of use.
GB9322806D0 (en) * 1993-11-05 1993-12-22 Dow Europ Sa Aqueous alkaline composition
CN101578130A (zh) 2007-01-11 2009-11-11 陶氏环球技术公司 烷氧基化物混合物表面活性剂
GB0917740D0 (en) * 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
ITMI20130757A1 (it) * 2013-05-09 2014-11-10 Unicalce S P A Composizione granulare a ridotta segregabilita', suo procedimento di preparazione e relativi usi

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1692017A1 (de) * 1968-01-12 1971-07-22 Henkel & Cie Gmbh Waschmittel
FR2281979A1 (fr) * 1974-08-12 1976-03-12 Sifrance Ste Silicates Speciau Nouvelle composition detergente sous forme pulverulente et procede d'obtention
DE2519655B2 (de) * 1975-05-02 1978-08-31 Henkel Kgaa, 4000 Duesseldorf Verfahren und Vorrichtung zur Herstellung sprühgetrockneter, nichtionische Tenside enthaltender Waschmittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7160397B2 (en) 2002-07-04 2007-01-09 Akzo Nobel N.V. Alkoxylate mixture and its use as a cleaning agent for hard surfaces

Also Published As

Publication number Publication date
ATE4125T1 (de) 1983-07-15
EP0034194A1 (fr) 1981-08-26

Similar Documents

Publication Publication Date Title
EP0184794B1 (fr) Produit adsorbant granulé
DE2820990C2 (fr)
EP0642576B1 (fr) Procede de fabrication continue d'un detergent et/ou d'un nettoyant granulaire
EP0344629B1 (fr) Composition adsorbente granulaire avec une capacité de dégagement ameliorée
EP0663946B1 (fr) Produits d'interet et melanges de produits d'interet pour agents mouillants, detergents et/ou nettoyants sous une nouvelle forme de preparation
DE69425534T2 (de) Mischverfahren zur Formulierung von Detergentien
DE3311568A1 (de) Teilchenfoermiges und weichmachendes grobwaschmittel fuer textilien
EP0034194B1 (fr) Procédé pour la fabrication de détergents granulés dispersifs pour le lavage et le nettoyage, contenant des agents tensio-actifs non-ioniques
DE3838086A1 (de) Verfahren zur herstellung zeolithhaltiger granulate hoher dichte
DE2753680C2 (de) Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften
AT394379B (de) Teilchenfoermiges waschmittelprodukt
EP0425804B1 (fr) Additif granulaire contenant un agent tensioactif pour détergent et agent de nettoyage avec des propriétés de rinçage améliorées
DE2837504C2 (de) Verfahren zur Herstellung eines schüttfähigen, nichtionische Tenside enthaltenden Wasch- und Reinigungsmittelgranulates
DE2431529A1 (de) Verfahren zur herstellung spruehgetrockneter, nichtionische tenside enthaltender waschmittel
EP0560802B2 (fr) Procede de fabrication de granulats de zeolite
DE3516548A1 (de) Teilchenfoermiges waschmittelprodukt mit einem gehalt an builder und nichtionischem tensid
DE2418294A1 (de) Pulverfoermiges bis koerniges, nichtionische waschaktivsubstanzen enthaltendes waschmittel
WO1994014946A1 (fr) Produits granules de lavage et/ou de nettoyage
EP0473622B1 (fr) Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive
EP0022998B1 (fr) Procédé de préparation d'un produit de lavage à faible pouvoir moussant
DE3236375A1 (de) Verfahren zur herstellung koerniger waschmittel mit einem gehalt an fettsaeurealkanolamiden
DE2431581A1 (de) Schaumgedaempftes waschmittel und verfahren zu seiner herstellung
DE2547203C2 (de) Pulverförmige, nichtionische Tenside und Seife enthaltende Wasch- und Reinigungsmittel, sowie Verfahren zu deren Herstellung
EP1235896B1 (fr) Procede de production de particules comprimees
DE3517458A1 (de) Teilchenfoermiges waschmittelprodukt

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19810418

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT NL SE

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT NL SE

REF Corresponds to:

Ref document number: 4125

Country of ref document: AT

Date of ref document: 19830715

Kind code of ref document: T

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EN Fr: translation not filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911223

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920122

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19920129

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920210

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920214

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920229

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920403

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930218

Ref country code: AT

Effective date: 19930218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19930228

Ref country code: BE

Effective date: 19930228

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19930228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930901

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930218

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931029

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 80100803.8

Effective date: 19930912