EP0139547B1 - Granulierte Reinigungsmittel mit geringem Phosphatgehalt und Verfahren zu deren Herstellung - Google Patents

Granulierte Reinigungsmittel mit geringem Phosphatgehalt und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0139547B1
EP0139547B1 EP84401588A EP84401588A EP0139547B1 EP 0139547 B1 EP0139547 B1 EP 0139547B1 EP 84401588 A EP84401588 A EP 84401588A EP 84401588 A EP84401588 A EP 84401588A EP 0139547 B1 EP0139547 B1 EP 0139547B1
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Prior art keywords
weight
sodium
surface active
ionic surface
sodium tripolyphosphate
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French (fr)
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EP0139547A1 (de
Inventor
Joaquim Barba
Josep M. Ros
Josep M. Vila
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Sa Camp
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Sa Camp
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    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying

Definitions

  • the present invention relates to a process for the manufacture of granular detergent compositions, the phosphate content of which is reduced, and which have excellent qualities with regard to the washing of textile fibers, as well as in their physical homogeneity characteristics, fluidity and density, without the need to use large quantities of phosphate-substituting additives.
  • an alternative consists in formulating detergent compositions with a low phosphate content, using a surfactant system which is rich in surfactants which are not sensitive to hard water, such as for example those of nonionic type, and in strengthening the composition using additives like those already mentioned.
  • This technique comes up against two fundamental problems. Firstly, nonionic surfactants of the type of alkoxylated alcohols having a low or medium degree of alkylation, if they are best indicated for the detergent action, do not however support the atomization conditions well, because of a on the other hand they undergo degradation due to oxidation and on the other hand they are evaporated and released into the atmosphere.
  • the present invention relates to a process for obtaining granular detergent compositions which solves the problems in question, since it makes it possible to obtain homogeneous and flowable granules; these compositions have a sodium tripolyphosphate content of less than approximately 25% by weight, are practically devoid of orthophosphate and of pyrophosphate and may contain up to approximately 10% by weight of nonionic surfactants.
  • the main object of the invention is therefore to find a process for obtaining granular detergent compositions with low tripolyphosphate content and high content of nonionic surfactant, which have good conditions of homogeneity, fluidity and density and excellent properties from the point of view of washing and bleaching textiles.
  • Another object of the invention is to find a method for obtaining detergent compositions having a low phosphate content which would require small amounts of additives to improve the capacity. city of sequestration of ions responsible for the hardness of water and additives inhibiting encrustation and redeposition. For this, another object of the invention is to find a process for obtaining detergent compositions with a low phosphate content at the lowest prices.
  • the process which is the subject of the invention consists essentially in the formation of a hot aqueous suspension with the thermostable components of the composition, said suspension being dried in an atomization tower and the atomized base being mixed in a suitable apparatus, sodium tripolyphosphate and other heat-sensitive components of the composition.
  • the granules After a certain period of maturation and when the nonionic surfactant has finished its absorption, the granules become fluid and do not show a tendency to agglutination.
  • tripolyphosphate does not pass through the hot aqueous suspension phase or that of atomization, prevents it from undergoing hydrolysis into orthophosphate and pyrophosphate, so that said products will only appear in the detergent composition finished only in very small quantities corresponding to those already contained in sodium tripolyphosphate available on the market as a raw material. Consequently, the tendency to form insoluble precipitates which, by inlaying, make the fabrics gray is considerably reduced in such a detergent composition.
  • This operation is carried out by means of a spraying of the nonionic surfactant on the atomized base mixture, of the tripolyphosphate and of the heat-sensitive components, in a suitable apparatus which may be that in which the mixing of the solids is carried out, for example a rotary drum or a “Lôdige” type mixer.
  • a suitable apparatus which may be that in which the mixing of the solids is carried out, for example a rotary drum or a “Lôdige” type mixer.
  • the temperature of the nonionic surfactant during the agglomeration process must be between 25 ° C and 80 ° C and preferably between 50 ° C and 70 ° C.
  • the product thus prepared is placed directly in the container and requires a time of maturation so that the process of absorption of the nonionic surfactant is completed, time during which the granules acquire the necessary fluidity.
  • This maturation time essentially depends on the characteristics of the atomized base, but is in no way greater than 24 hours.
  • Figures 1 and 2 attached allow to assess the characteristics of the granules obtained according to the method of the invention.
  • Figure 1 shows the photograph, taken with a scanning electron microscope, magnified 20 times, of a group of granules in which we observe their uniform appearance and size, and their rare tendency to clump together.
  • FIG. 2 shows the photograph, taken with a scanning type electron microscope, magnified 160 times, of an open granule, in which the agglomeration of the various components inside the granule and the good cohesion of the latter are observed. .
  • the granules according to the invention can also contain other types of components, such as the salts which enhance the detergent action, of organic or mineral type, soluble or insoluble in water, foam controllers of different types, bleach activators of the peroxide precursor type, those with sequestering action of the polycarboxylic or phosphonic acid type, polymers that inhibit encrustation and redeposition, optical whiteners, photoactivators, dyes, perfumes, and in general, any type of additives commonly used in detergents.
  • thermostable components mention may be made of anionic surfactants, including in this group both alkaline soaps and synthetic anionic surfactants.
  • anionic surfactants including in this group both alkaline soaps and synthetic anionic surfactants.
  • the soaps there may be mentioned the sodium, potassium, ammonium, alkanol-ammonium salts of fatty acids which contain from 8 to 24 carbon atoms, the preferred of which are the sodium and potassium salts mixed with fatty acids derived from coconut, tallow, fish and rapeseed oil.
  • anionic surfactants which can be used in the present invention, mention may be made of the soluble salts of alkylbenzene sulfonates, of alkyl sulfates, of alkylpolyethoxyether sulfonates, of ⁇ -olefin-sulfonates, of paraffin sulfonates, alkyl glyceryl ether sulfonates, ⁇ -sulfocarboxylates and their esters; sulfates and sulfonates of fatty acid monoglycerides, of alkylphenolpolyether sulfates, etc.
  • the preferred are the sodium and potassium alkylbenzene sulfonates, the alkyl chain of which is essentially linear and the number of carbon atoms of which is between 10 and 14.
  • thermostable components it is also possible to add, in proportions of less than 2%, nonionic surfactants of the type of polyoxyethylenated or polyoxypropylenated fatty alcohols which have a high degree of alkoxylation, that is to say, with a number of moles of alkylene oxides per mole of fatty alcohol greater than 10 and whose fatty alcohols have straight or partially branched chains whose carbon number varies between 8 and 22.
  • nonionic surfactants of the type of polyoxyethylenated or polyoxypropylenated fatty alcohols which have a high degree of alkoxylation, that is to say, with a number of moles of alkylene oxides per mole of fatty alcohol greater than 10 and whose fatty alcohols have straight or partially branched chains whose carbon number varies between 8 and 22.
  • nonionic surfactants of the type of polyoxyethylenated or polyoxypropylenated fatty alcohols which have a high degree of al
  • cationic surfactants of the type of quaternary ammonium salts, among which at least one or two of the alkyl radicals are C 8 -C 18 carbon chains, linear or partially branched.
  • amphoteric type surfactants which can also be used, there are water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical can be in a linear or branched chain, and among water-soluble derivatives one of their substituents contains 8 to 18 carbon atoms and the other consists of a hydrophilic anionic group such as for example the carboxy, sulfonate, phosphate or phosphonate groups.
  • surfactants of hybrid or zwitterionic ions such as the water-soluble derivatives of cationic aliphatic compounds of quaternary ammonium, phosphoric and sulphonic in which the radicals can be linear or branched and one of which of their aliphatic sibstituants contains 8 to 18 carbon atoms and the other contains an anionic group which dissolves in water.
  • the alkaline salts such as the borates, the carbonates of alkali metals and among the water-insoluble salts
  • the salts which enhance the detergent action of organic type by way of example, the water-soluble salts of glycolic acid, the water-soluble amino polyacetates among which sodium nitrilotriacetate is preferred, the polycarboxy- water-soluble lates, such as the salts of lactic acid, phytic acid and its derivatives of ether, citrates, maleates, carboxymethylsuccinates, etc.
  • Alkaline polyphosphonates such as the alkaline salts of methylene diphosphonic acids, ethylene diamine tetramethylene phosphonic and diethylene triamine pentamethylene phosphonic are also suitable.
  • the salts which enhance the detergent action organic and mineral, can be used together in appropriate proportions.
  • an alkali metal silicate can be added, in a proportion varying between 3 and 13%, which has a molar ratio Si0 2 / M 2 0 of between 1 and 4, and preferably between 1.5 and 2.5 (M denoting an alkali metal).
  • thermostable components are polymers which give a better appearance to the washed laundry. In fact, they have an inhibiting action on encrustation, that is to say that they prevent insoluble mineral salts from forming in the washing bath, and from being deposited on the tissues by producing gray stains.
  • These polymers are water-soluble salts of polycarboxylic homo- or co-polymers, the carboxylic radicals of which are separated from one another by at least one or two carbon atoms.
  • Products of this type are homo- or co-polymers having monomer units, such as, for example, maleic anhydride, maleic acid, methyl vinyl ether, acrylic acid, metacrylic acid, etc. These products are found on the market under the name of Sokalan °, Gantrez®, Primal®, etc.
  • foam controllers other than soaps or nonionic surfactants with a high degree of oxyethylenation such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones.
  • special silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silane silicas or else copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals are preferred.
  • These special silicones are sold by the Dow-Corning Company under the references Q2-3092, DC-100, DC-190, DC-193, DC-198.
  • silicones can be added as well in the atomization phase as in the mixing and agglomeration phase and they can be used as they appear by the supplier or else be protected by granulation and by the fact that they are coated. using inert materials to avoid their interaction with the alkaline components of the composition.
  • anionic fluorescent brightening agents which are also known as optical whiteners.
  • anionic fluorescent brightening agents which are also known as optical whiteners.
  • the most indicated are the water-soluble derivatives of stylbene-sulfonates and the water-soluble derivatives of distyrylbiphenylsulfonates.
  • Tinopal O BMS Tinopal ° DMS
  • Tinopal ° LMS-X Tinopai CBS-X.
  • Photoactivator type products are also useful and can be added in the atomization phase; these are products which, in contact with light, decompose producing oxygen which ensures better stain removal and improves the whiteness of the laundry. These products are the soluble sulfonated phthalocyamines which maintain a metal cation in the form of a complex, among which zinc and aluminum are preferred. As an example of this type of product, mention may be made of Tinolux @ sold by the company CIBA-GEIGY.
  • Sodium tripolyphosphate acts as a salt which strengthens the main detergent of the composition. It is added to the composition during the mixing phase, to avoid its partial hydrolysis into pyrophosphate and orthophosphate, in proportions of less than 25%.
  • any type of sodium tripolyphosphate available on the market can be used, with the sole condition that the total amount of orthophosphate and pyrophosphate remains less than about 7%, preferably 5%, of the total weight of tripolyphosphate. This constitutes a significant improvement compared to the prior art, for example illustrated by patent application EP-A-9 952, in the context of which it is essential to mix with the atomized base a tripolyphosphate endowed with particular particle size characteristics. and having undergone hydration before or after the mixing operation, which has the consequence of increasing the cost of both the raw material and the finished product and making the implementation of the process more complicated.
  • nonionic surfactants with medium and low degree of alkoxylation are very important, because among the nonionics, they are the most effective from the detergent point of view. They can be of the type of the reaction product of fatty alcohols of straight or partially branched chain with a number of carbon atoms between 8 and 22, with a number of moles of ethylene or propylene oxide between 3 and 10, and preferably between 5 and 8 per mole of alcohol, or alternatively alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, with a number of moles of ethylene oxide or propylene between 7 and 12 per mole of phenol.
  • enzymes can also be added which promote the action of the detergent, in the form of particles.
  • These enzymes can be proteases or amylases and are found on the market under the name of Alcalase @ , Maxatase °, etc.
  • whitening chemicals are also very suitable. These products are also heat-sensitive, which is why they must be added in the mixing phase, for example in proportions of between 1 and 30% by weight, and they can be chosen from peroxide salts such as sodium perborate mono and tetrahydrate.
  • peroxyacids also called bleach activators, can be added in the crystalline state or under form of granules with a protective cover to ensure their stability during storage.
  • fluidizers which have an anti-mass action
  • fluidizers which have an anti-mass action
  • constituents such as perfumes, dyes and color granules.
  • compositions of several granular detergents obtained according to the following process are indicated: in an mixer provided with stirring, an aqueous suspension of at least part of the components C 1 to C 18 is prepared.
  • the total amount of water must be between 20 and 40% of the total weight of the suspension and the temperature of the mixture must be between 55 ° C and 75 ° C.
  • the suspension is homogeneous, it is sprayed in an atomization tower, against the current, with an inlet temperature of hot air between 300 ° C and 370 ° C and an outlet temperature of the gases between 80 ° C and 110 ° C.
  • the resulting granules are cooled in a stream of cold air and passed through a sieve to remove the coarse ones.
  • the atomized base is introduced into a rotary drum and the addition is carried out, by means of a hopper, of the components C19, C21, C22 and C23.
  • the component C20 is brought to a temperature between 50 ° C and 60 ° C by means of an appropriate nozzle.
  • the granular composition is placed directly in the containers suitable for its consumption, and it is stored for 24 hours during which the product matures, that is to say at the total absorption of the nonionic surfactant and consequently to the fluidification of the granules.
  • the data appearing in the table are expressed as a percentage by weight of the final detergent composition.
  • composition is completed with water, perfume and dyes up to 100%.
  • the standard UNE 55-547-81 (Spain), which corresponds to International Standard ISO-4324-1977, was used as a criterion, in which the value formed in radians of the angle formed by the mound of granular material tested is determined, when it is poured through a funnel under the conditions described in the standard.

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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)
  • Detergent Compositions (AREA)

Claims (6)

1. Verfahren zur Herstellung von körnigen Detergens-Zusammensetzungen mit geringem Gehalt an Phosphaten, d.h. mit einem Gehalt an Natriumtripolyphosphat zwischen 10 und 25 Gew.-% und einem Gehalt an Natriumorthophosphat und an Natriumpyrophosphat von insgesamt weniger als etwa 2 Gew.-% und vorzugsweise weniger als etwa 1 Gew.-%, und mit einem Gehalt an nicht-ionischen oberflächenaktiven Agentien, der bis zu etwa 10% des Gesamtgewichtes der Zusammensetzung erreichen kann, bei dem im wesentlichen zusammen mit den wärmebeständigen Bestandteilen in der Wärme eine wässrige Suspension hergestellt wird, diese Suspension in einem Zerstäubungsturm getrocknet wird, die zerstäubte Basis mit dem Natriumtripolyphosphat und den anderen wärmeempfindlichen Bestandteilen gemischt wird und dann die festen Komponenten durch Pulverisierung mit Hilfe eines nicht-ionischen oberflächenaktiven Agens pulverisiert werden, bis im wesentlichen homogene Körnchen und mit einer geringen Neigung zur Agglutination erhalten werden, dadurch gekennzeichnet, dass die Gesamtmenge des Natriumtripolyphosphats nicht den wässrigen Wärmesuspensions- und Zerstäubungsphasen unterworfen wird und dass während der Agglomerationsphase die Temperatur des nicht-ionischen oberflächenaktiven Agens zwischen 25 und 80°C und vorzugsweise zwischen 50 und 70°C gehalten wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man ein hydratisiertes oder nichthydratisiertes Natriumtripolyphosphat verwenden kann, das eine beliebige Korngrössenverteilung aufweist.
3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das von den festen Bestandteilen absorbierte nicht-ionische oberflächenaktive Agens über seine Detergenswirkung hinaus als Agglomerationsmittel für diese wirkt.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das als Agglomerationsmittel verwendete nicht-ionische oberflächenaktive Agens zur Gruppe der Fettalkohole mit einer linearen oder teilweise verzweigten Cg-C22-Polyoxyethylen-Kette mit einer Anzahl der Ethylenoxidmoleküle pro Mol Alkohol zwischen 3 und 10 und vorzugsweise zwischen 5 und 8 gehört.
5. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das als Agglomerationsmittel verwendete nicht-ionische oberflächenaktive Agens zur Gruppe der Alkylphenole, deren Alkylrest 7 bis 11 Kohlenstoffatome enthält, mit einer Anzahl von Ethylenoxidmolen pro Mol Phenol zwischen 7 und 12 gehört.
6. Körnige Detergens-Zusammensetzung, hergestellt durch Durchführung des Verfahrens nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie im wesentlichen der folgenden Grundzusammensetzung entspricht:
- 1 bis 12 Gew.-% anionische oberflächenaktive Agentien,
- 2 bis 10 Gew.-% nicht-ionische oberflächenaktive Agentien,
- 15 bis 60 Gew.-% Aufbausalze,
- 5 bis 20 Gew.-% Alkalisalze,
- 10 bis 25 Gew.-% Natriumtripolyphosphat,
- 1 bis 30 Gew.-% Peroxid-Aufheller und
- 0 bis 2 Gew.-% Natriumorthophosphat und Natriumpyrophosphat.
EP84401588A 1983-09-27 1984-07-27 Granulierte Reinigungsmittel mit geringem Phosphatgehalt und Verfahren zu deren Herstellung Expired EP0139547B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84401588T ATE26300T1 (de) 1983-09-27 1984-07-27 Granulierte reinigungsmittel mit geringem phosphatgehalt und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8315306A FR2552446B1 (fr) 1983-09-27 1983-09-27 Detergents granulaires a faible teneur en phosphates, et leur procede de fabrication
FR8315306 1983-09-27

Publications (2)

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EP0139547A1 EP0139547A1 (de) 1985-05-02
EP0139547B1 true EP0139547B1 (de) 1987-04-01

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EP84401588A Expired EP0139547B1 (de) 1983-09-27 1984-07-27 Granulierte Reinigungsmittel mit geringem Phosphatgehalt und Verfahren zu deren Herstellung

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EP (1) EP0139547B1 (de)
AT (1) ATE26300T1 (de)
DE (2) DE3462923D1 (de)
ES (1) ES534997A0 (de)
FR (1) FR2552446B1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2617183B2 (fr) * 1983-09-27 1990-01-05 Camp Sa Perfectionnements au procede d'obtention de detergents granulaires a faible teneur en phosphates
CA1297376C (en) * 1985-11-01 1992-03-17 David Philip Jones Detergent compositions, components therefor, and processes for theirpreparation
US4762636A (en) * 1986-02-28 1988-08-09 Ciba-Geigy Corporation Process for the preparation of granules containing an active substance and to the use thereof as speckles for treating substrates
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1107870B (de) * 1959-01-22 1961-05-31 Budenheim Rud A Oetker Chemie Verfahren zur Herstellung von nicht staeubenden Wasch-, Reinigungs-, Spuel- und Entfettungsmitteln
US4006110A (en) * 1971-11-30 1977-02-01 Colgate-Palmolive Company Manufacture of free-flowing particulate heavy duty synthetic detergent composition
US3849327A (en) * 1971-11-30 1974-11-19 Colgate Palmolive Co Manufacture of free-flowing particulate heavy duty synthetic detergent composition containing nonionic detergent and anti-redeposition agent
US4136051A (en) * 1974-02-25 1979-01-23 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
NZ191691A (en) * 1978-10-03 1982-02-23 Unilever Ltd Preparation of particulate alkaline detergent compositions by spray drying
ATE3056T1 (de) * 1978-10-03 1983-04-15 Unilever Nv Reinigungsmittelzusammensetzungen.

Also Published As

Publication number Publication date
FR2552446A1 (fr) 1985-03-29
FR2552446B1 (fr) 1985-12-20
EP0139547A1 (de) 1985-05-02
ES8504921A1 (es) 1985-04-16
ES534997A0 (es) 1985-04-16
DE3462923D1 (en) 1987-05-07
ATE26300T1 (de) 1987-04-15
DE139547T1 (de) 1985-08-29

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NLR2 Nl: decision of opposition
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