EP0084657B1 - Agents de lavage granulaires très moussants séchés par pulvérisation avec une stabilité élevée des granulations et procédé pour sa fabrication - Google Patents

Agents de lavage granulaires très moussants séchés par pulvérisation avec une stabilité élevée des granulations et procédé pour sa fabrication Download PDF

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Publication number
EP0084657B1
EP0084657B1 EP82111827A EP82111827A EP0084657B1 EP 0084657 B1 EP0084657 B1 EP 0084657B1 EP 82111827 A EP82111827 A EP 82111827A EP 82111827 A EP82111827 A EP 82111827A EP 0084657 B1 EP0084657 B1 EP 0084657B1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
sodium
proportion
component
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
EP82111827A
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German (de)
English (en)
Other versions
EP0084657A1 (fr
Inventor
Herbert Dr. Reuter
Wolfgang Dr. Seiter
Ingo Wegener
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 AT82111827T priority Critical patent/ATE18070T1/de
Publication of EP0084657A1 publication Critical patent/EP0084657A1/fr
Application granted granted Critical
Publication of EP0084657B1 publication Critical patent/EP0084657B1/fr
Expired 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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

Definitions

  • the present invention relates to a detergent which has a high content of anionic surfactants and is characterized by a grain structure which is resistant to mechanical or unfavorable weather-related influences and is particularly suitable for washing by hand.
  • Such agents are particularly suitable for use in developing countries, where mostly still under relatively simple conditions, i.e. is washed in the tub and without additional heat.
  • Detergents are already known which consist of compact granules and detergent substances incorporated therein, e.g. DE-A-2 536 594 and DE-A-2 742 683 (US-A-4 269 722). These are so-called carrier grains, which are produced by spray drying or targeted shaping without the addition of detergents and are subsequently subjected to liquid or melted nonionic surfactants. Such a procedure requires several process steps and is comparatively complex. Such a procedure is out of the question for salt-like anionic surfactants. In addition, such powders have a very compact grain structure and a comparatively high bulk density of over 500 g / l, mostly from 600 to 800 g / l. Such dense, specifically heavy detergent granules, however, only dissolve very slowly in cold or moderately heated
  • granular detergents can also be produced by spray-drying, but in general the spray-drying of conventional detergent compositions produces relatively soft, loose powders with a hollow spherical structure. Their bulk density is generally well below 500 g / l and is generally 200 to 350 gii.
  • Such powders which are usually produced by spraying a water-containing detergent paste under high pressure by means of fixed nozzles, have an optimal solution behavior, but are relatively sensitive to mechanical stress. Older drying systems equipped with rotating spray elements deliver a firmer, but much finer grain with a high dust content. Such powders are very prone to clumping and have an unfavorable pouring behavior.
  • Another problem is the spray drying of detergents with high, i.e. more than 40% of the organic matter content at the high drying temperatures usually prevailing in the spray towers due to the risk of dust explosions and autoxidation processes, which can lead to browning of the powder.
  • Preferred agents are those in which the sum of components (A) and (B) is 40 to 48% by weight and the sum of components (C) to (G) is 52 to 60% by weight.
  • Component (A) consists of linear sodium alkylbenzenesulfonate with 10 to 14 carbon atoms in the alkyl chain.
  • a preferred example of this class of compounds is dodecylbenzenesulfonate.
  • Component (B) is sodium fatty alcohol sulfates, which are derived from saturated and / or monounsaturated primary fatty alcohols of natural or synthetic origin and preferably have 12 to 18 carbon atoms. Examples include coconut and tallow fatty alcohols, oleyl alcohol and synthetic alcohols obtainable by ethylene polymerization or oxosynthesis, the latter consisting of mixtures of linear and a-methyl-branched alcohols. Coconut fatty alcohol sulfates and similarly composed mixtures of saturated C 12 -C 18 fatty alcohol sulfates are particularly preferred.
  • the surfactants contained in the agents can consist exclusively of alkylbenzenesulfonates.
  • a surfactant mixture is preferably used in which the amount of fatty alcohol sulfates (component B) is measured so that the content of this component (B) in the detergents is up to 15% by weight, in particular 3-10% by weight.
  • the amount of alkylbenzenesulfonates should be reduced accordingly, so that the total proportion of surfactants does not exceed 50% by weight and the proportion of alkylbenzenesulfonate is, in particular, 35 to 45% by weight.
  • the proportion of sodium tripolyphosphate (component C), based on anhydrous salt, is 5 to 25% by weight, preferably 8 to 20% by weight and in particular 10 to 17% by weight.
  • the tripolyphosphate is usually in the form of a hexahydrate, with the water content attributable to component (G).
  • the tripolyphosphate is usually in a mixture with small amounts of its hydrolysis products formed in the aqueous batch or in the course of spray drying, i.e. Diphosphate and orthophosphate before, but their proportion is less than 20 wt .-%, preferably less than 15% of that used for spray drying. Tripolyphosphate.
  • Component (D) consists of fine-crystalline sodium aluminum silicates of the formula (1) given above which are capable of cation exchange.
  • aluminosilicates of the formula used Preferably aluminosilicates of the formula used.
  • the water bound in the aluminosilicates is also included in the water content of component (G).
  • the aluminosilicates have a particle size of less than 25 ⁇ m, with at least 80% by weight of the particles having a size of less than 10 ⁇ m.
  • the calcium binding capacity in mg CaO / g AS is calculated from the formula: (30 - x) ⁇ 10.
  • aluminosilicates The proportion of aluminosilicates is 5 to 25% by weight, preferably 8 to 18% by weight, based on the anhydrous active substance.
  • Particularly suitable aluminosilicates are synthetic, finely divided zeolites of the NaA type and NaX type and their mixtures.
  • the ratio is preferably 1: 2 to 1: 3.5.
  • the sodium silicate content of the agents is 5 to 20% by weight, preferably 8 to 18% by weight and in particular 12 to 16% by weight. This information relates to anhydrous silicate.
  • the agents can contain sodium sulfate and / or sodium carbonate in amounts of up to 15% by weight. preferably contain no more than 10%. If component (F) consists of sodium sulfate, its proportion is generally 0.2 to 5% by weight. While components (C) to (E) are integrating components, which are essential for both the grain properties and the cleaning effect, component (F) is ancillary and filler that does not significantly improve the product.
  • An essential component of the agent is the water content, which is a total of 8 to 15% by weight. Part of the water is comparatively firmly bound, for example as a component of the sodium aluminosilicate.
  • the proportion of water which can be removed at a drying temperature of 140 ° C. is preferably 4 to 8% by weight. This proportion is dimensioned so that on the one hand there are no oxidative changes and browning, in particular no dust explosions, during spray drying, but on the other hand the desired grain properties such as high strength, good flowability and low tendency to form lumps even under unfavorable conditions and a sufficiently high level Solution speed result. If these limits are clearly undershot, the oxidative changes increase; if they are significantly exceeded, the grain properties deteriorate in the sense of reduced strength and free-flowing properties.
  • organic complexing agents such as alkali metal salts of aminoalkane polyphosphonic acids or hydroxyalkane phosphonic acids for example, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and 1-hydroxyethane-1,1-diphosphonic acids of aminopolycarboxylic acids, such as nitrilotriacetic acid or ethylenediaminetetraacetic acid and the higher homologues of the polyacids mentioned.
  • Polymeric carboxylic acids which may optionally contain hydroxy ether and / or carbonyl groups, can also be used as complexing agents.
  • optical brighteners and anti-graying components which include in particular cellulose ethers, such as carboxylmethyl or methyl cellulose.
  • cellulose ethers such as carboxylmethyl or methyl cellulose.
  • the sum of all organic components including components (A) and (B) must be such that their proportion does not significantly exceed 50% by weight.
  • the invention further relates to a process for the preparation of the compositions, characterized in that the aqueous slurry of components (A) to (F) containing 30 to 45% by weight of water is atomized in a spray device, the process being carried out in the same or Countercurrent drying gases have an inlet temperature of 150 ° to 350 ° C and an outlet temperature of 65 ° to 95 ° C.
  • the optional components are also incorporated into the aqueous slurry and atomized.
  • Stabilized aluminosilicate suspensions of this type generally contain small amounts of stabilizing agents, for example nonionic surfactants or water-soluble polymers, which are incorporated into the end product in this way.
  • stabilizing agents for example nonionic surfactants or water-soluble polymers
  • the content of such suspension stabilizers in the agents according to the invention is generally considerably less than 1% by weight, usually less than 0.5% by weight.
  • the remaining components of the agent can be distributed without problems in the aqueous slurry, and they can also be used as a dry substance or - if the total water balance allows this - also as an aqueous paste.
  • the latter applies in many cases to the surfactants, in particular to the alkylbenzenesulfonate, which e.g. can be incorporated into the aqueous mixture as a sodium salt solution or as a free acid with the addition of the appropriate amount of sodium hydroxide.
  • Spraying is usually carried out under high pressure using nozzles.
  • Air and combustion gases which can be introduced directly into the tower, are the primary drying gases.
  • the dry gas can be conducted in cocurrent or countercurrent to the spray product; the countercurrent principle is preferably used and the drying gas is introduced tangentially into the drying tower, so that a cyclone-like flow is produced.
  • the spray product obtained has an average particle size of 0.4 to 0.8 mm, the proportion of particles with a particle size of less than 0.1 mm being less than 10% by weight, in particular less than 5% by weight and a grain size over 1.2 mm is less than 5% by weight, in particular not more than 2% by weight. Portions deviating from this grain spectrum are expediently sieved out and can be returned to the aqueous batch.
  • the bulk density is in the range from 250 to 450 g / l, preferably from 300 to 400 g / l.
  • the spray-dried agents have a porous grain structure, which differs from conventional spray-dried detergents or delicates by an increased grain strength, without the solution properties being adversely affected.
  • a porous grain structure which differs from conventional spray-dried detergents or delicates by an increased grain strength, without the solution properties being adversely affected.
  • explosive or combustible dusts do not form during normal processing. They are easy to pour and do not tend to form lumps.
  • the agents can be used as detergents without further additives. But it can also be done retrospectively, i.e. to the finished product, in addition to other common detergent ingredients such as anionic and / or nonionic synthetic surfactants, soap, skeletal salts, e.g. Phosphates, washing alkalis, e.g. Soda, as well as bleaching agents, such as per-compound or active chlorine carrier, are added in granular or powdery form or added in another form immediately before or during use.
  • other common detergent ingredients such as anionic and / or nonionic synthetic surfactants, soap, skeletal salts, e.g. Phosphates, washing alkalis, e.g. Soda
  • bleaching agents such as per-compound or active chlorine carrier
  • the ingredients listed below were mixed into a 50% by weight sodium ethoxalosilicate suspension stabilized by means of ethoxylated tallow alcohol (5 EO groups), the dodecylbenzenesulfonate being used as a 55% solution.
  • the aqueous slurry containing 56.3% by weight of solids was heated to 75 ° C. and sprayed under a pressure of 20 bar through nozzles in a drying tower.
  • the counter-current drying gas consisting of air and combustion gases, had an inlet temperature of 180 ° C and an outlet temperature of 87 ° C.
  • the spray product was composed as follows (% by weight):
  • the bulk density was 320 g / l.
  • packages made of cardboard are evenly filled with the product up to the standard fill level, closed with a lid that can be placed on top, and compressed in a machine-driven vibrator under defined conditions by directional jolts, which results in a reproducible compression of the contents.
  • the package is opened and fastened in a device that allows it to be poured out at defined tilting angles.
  • the packages can be shaken by means of a motorized impact device.
  • the amount of powder flowing out is collected in a measuring cylinder. The following ratings are given, with the given degrees indicating the position of the package:
  • the consumer registers grades 1 to 3 as very good to good, grade 4 as satisfactory and grades 5 and 6 as poor or unsatisfactory.
  • the determination of the powder gave the grade 4 immediately after the spray drying and the grade 3 after storage for 3 days.
  • test value was 30 g with freshly sprayed powder and 0 g after storage for 3 days.
  • last value is generally 10 to 60 g.
  • compositions of the following composition were produced (in the form of the Na salts):

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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)

Claims (11)

1. Agent de lavage fortement moussant, grenu, séché par pulvérisation, à plus grande stabilité de grain, contenant des tensioactifs anioniques, du tripolyphosphate de sodium, de l'alumosilicate de sodium et du silicate de sodium, caractérisé par une teneur de
A) 35 à 50% en poids d'alcoylbenzène-sulfonate de sodium linéaire ayant 10 à 14 atomes de carbo- dans la chaîne alcoyle,
B) 0 à 15% en poids de sulfate d'alcool gras et de sodium ayant 10 à 20 atomes de carbone dans le radical alcoyle ou alcényle,
la somme des composants (A) et (B) représentant 35 à 50% en poids,
C) 5 à 25% en poids de tripolyphosphate de sodium,
D) 5 à 25% en poids de silicate de sodium et d'aluminium finement cristallin de formule:
0,7 - 1,5 Na2O · Al2O3 · 1,3 - 4 SiO2

qui contient de l'eau liée, un pouvoir fixateur du calcium d'au moins 100 mg de CaO/g de substance active (AS) et présente une dimension de particule inférieure à 25 µm, au moins 80% en poids des particules possédant une dimension inférieure à 10 µm,
E) 5 à 20% en poids de silicate de sodium de composition NazO : Si02 = 1 : 1,5 - 1 : 3,6,
F) 0 à 10% en poids de sulfate de sodium et/ou de carbonate de sodium et
G) 8 à 15% en poids d'eau, en y comprenant l'eau de

cristallisation liée dans les composants (C) à (F), la somme des constituants (C) à (G) s'élevant à 50 à 65% en poids, le poids en vrac de l'agent à 250 à 450 g/litre et sa granulométrie moyenne à 0,4 à 0,8 mm, la fraction des particules ayant une dimension de grain inférieure à 0,1 mm s'élevant à moins de 10% en poids et celle ayant une dimension de grain supérieure à 1,2 s'élevant à moins de 5% en poids.
2. Agent selon la revendication 1, dans lequel la somme des composants (A) et (B) représente 40 à 48% en poids et la somme des composants (C) à (G) 52 - 60% en poids.
3. Agent selon les revendications 1 et 2, dans lequel la fraction de composant (A) s'élève à 35 à 45% en poids et la fraction du composant (B) à 3 à 10% en poids.
4. Agent selon les revendications 1 à 3, dans lequel la fraction du composant (C) s'élève à 8 à 20% en poids.
5. Agent selon les revendications 1 à 4, dans lequel la fraction du composant (D) s'élève à 8 à 18% en poids.
6. Agent selon les revendications 1 à 5, dans lequel la fraction de composant (E) s'élève à 8 à 18% en poids.
7. Agent selon la revendication 6, dans lequel le composant (E) présente la composition Na2O : SiO2 = 1 : 2 à 1 : 3,5.
8. Agent selon les revendications 1 à 7, dans lequel le composant (F) consiste en du sulfate de sodium dont la proportion s'élève à 0,2 à 5% en poids.
9. Agent selon les revendications 1 à 8, dans lequel la proportion d'eau éliminable à une température de séchage de 140°C s'élève à 4 à 8% en poids.
10. Agent selon les revendications 1 à 9, caractérisé par un poids en vrac de 300 à 400 g/litre.
11. Procédé de fabrication de l'agent selon les revendications 1 à 10, caractérisé en ce qu'on pulvérisé un mélange contenant 30 à 45% en poids d'eau des composants (A) à (F) dans un appareillage de pulvérisation, les gaz de séchage qui circulent en équi-ou en contre-courant présentant une température d'entrée de 150 à 350°C et une température de sortie de 65 à 95°C.
EP82111827A 1981-12-28 1982-12-20 Agents de lavage granulaires très moussants séchés par pulvérisation avec une stabilité élevée des granulations et procédé pour sa fabrication Expired EP0084657B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82111827T ATE18070T1 (de) 1981-12-28 1982-12-20 Starkschaeumendes, koerniges waschmittel mit erhoehter kornstabilitaet und verfahren zu dessen herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813151536 DE3151536A1 (de) 1981-12-28 1981-12-28 Starkschaeumendes, koerniges waschmittel mit erhoehter kornstabilitaet und verfahren zu dessen herstellung
DE3151536 1981-12-28

Publications (2)

Publication Number Publication Date
EP0084657A1 EP0084657A1 (fr) 1983-08-03
EP0084657B1 true EP0084657B1 (fr) 1986-02-19

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EP82111827A Expired EP0084657B1 (fr) 1981-12-28 1982-12-20 Agents de lavage granulaires très moussants séchés par pulvérisation avec une stabilité élevée des granulations et procédé pour sa fabrication

Country Status (4)

Country Link
US (1) US4524010A (fr)
EP (1) EP0084657B1 (fr)
AT (1) ATE18070T1 (fr)
DE (2) DE3151536A1 (fr)

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CA1275019A (fr) * 1985-10-09 1990-10-09 The Procter & Gamble Company Compositions detergentes granulees a solubilite accrue
AU597909B2 (en) * 1985-10-09 1990-06-14 Procter & Gamble Company, The Granular detergent compositions having improved solubility
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DE3742043A1 (de) * 1987-12-11 1989-06-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumschichtsilikaten
CA2027518A1 (fr) * 1990-10-03 1992-04-04 Richard L. Tadsen Methode de preparation de compositions detergentes a haute densite, contenant des particules tensio-actives sensibles au ph
AU2309892A (en) * 1991-07-15 1993-02-23 Procter & Gamble Company, The Process for producing a detergent composition containing alkyl sulfate particles and base granules
IL108500A (en) * 1994-01-31 1998-06-15 Zohar Detergent Factory Fatty alcohol sulphates in granular form and process for their preparation
GB9604022D0 (en) * 1996-02-26 1996-04-24 Unilever Plc Anionic detergent particles
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
DE69817811T2 (de) * 1997-05-30 2004-04-01 Unilever N.V. Rieselfähige körnige waschmittelzusammensetzungen
US8939388B1 (en) 2010-09-27 2015-01-27 ZoomEssence, Inc. Methods and apparatus for low heat spray drying
US9332776B1 (en) 2010-09-27 2016-05-10 ZoomEssence, Inc. Methods and apparatus for low heat spray drying
US10486173B2 (en) 2017-08-04 2019-11-26 ZoomEssence, Inc. Ultrahigh efficiency spray drying apparatus and process
US9861945B1 (en) 2017-08-04 2018-01-09 ZoomEssence, Inc. Ultrahigh efficiency spray drying apparatus and process
US9993787B1 (en) 2017-08-04 2018-06-12 ZoomEssence, Inc. Ultrahigh efficiency spray drying apparatus and process
US10155234B1 (en) 2017-08-04 2018-12-18 ZoomEssence, Inc. Ultrahigh efficiency spray drying apparatus and process
CA3071115C (fr) 2017-08-04 2022-06-21 ZoomEssence, Inc. Appareil et procede de sechage par pulverisation a tres haut rendement
US10569244B2 (en) 2018-04-28 2020-02-25 ZoomEssence, Inc. Low temperature spray drying of carrier-free compositions

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JPS5919597B2 (ja) * 1980-04-23 1984-05-07 ライオン株式会社 ゼオライト含有無燐粒状洗剤組成物
US4344871A (en) * 1981-03-23 1982-08-17 The Procter & Gamble Company Spray-dried aluminosilicate detergents containing silicate and metaborate

Also Published As

Publication number Publication date
DE3151536A1 (de) 1983-07-07
DE3269269D1 (en) 1986-03-27
EP0084657A1 (fr) 1983-08-03
US4524010A (en) 1985-06-18
ATE18070T1 (de) 1986-03-15

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