ES2157223T5 - HIGH DENSITY GRANULAR DETERGENT COMPOSITION. - Google Patents

Abstract

A process in which the bulk density of a particulate detergent material is increased starting from an initial bulk density of at least 600 g/l, by spraying a liquid onto the particles and dusting with a fine powder in one or more rotating drum(s) or mixer(s), characterised in that the particulate detergent material initially has a mean particle size greater than 400 micrometers, and that the increase in the mean particle size during the process is not greater than 60 %. The invention also discloses a detergent composition having excellent dispensing and dissolving properties.

Description

High granular detergent composition density.

Background of the invention

There is a trend among detergents commercially available granules towards bulk densities more  high. This provides advantages both for the convenience of the user as for the reduction of packaging materials.

Many of the prior art attempts to move in this direction they have encountered problems of the few solubility properties that arise from a low dissolution speed or gel formation. A consequence of this in a typical washing procedure can be a scarce supply of the product, either from the drawer of supply of a washing machine or from a device dispenser placed with the wash load inside the machine. This poor supply is often caused by gelation. of particles that have high levels of surfactant after contact with water. The gel prevents a proportion of the powder from detergent is solubilized in the wash water, which reduces the dust efficiency Another adverse consequence arises even if the powder is well supplied and dispersed in the wash water, if It does not dissolve quickly. The wash cycle has a duration limited, during which the detergent can act on the load washing If the cleaning action is delayed because the dust is slowly dissolves this, too, will limit the effectiveness of powder.

The engineer and the formulator of the procedure have frequently found that the need for a good supply  and the need for a good dissolution rate have raised conflicting demands between them. The solution has been generally find a compromise that provides a supply adequate and an adequate dissolution rate. For example, him poor supply of granular detergents of apparent density  elevated is often associated with particles with high content of surfactants having a high specific surface area, due to the high porosity or the small particle size (especially "fine"). However, the decrease in porosity and / or the increase in the average particle size cause decrease the rate of decrease.

Various methods to increase density Apparently they have been described in the prior art, in many cases using procedures that densify dried powders by aspersion.

The document EP-A-184-794 published on June 18, 1986 (Henkel) describes a procedure to introduce an adsorbent vehicle with non-ionic surfactant in a Loedige mixer that increases the bulk density. He Vehicle is typically prepared by spray drying.

The document EP-A-327,963 published on 16 August 1989 (Henkel) describes a densification procedure of basic rear tower in which the component dried by spray is sprayed before re-agglomerating in one stage of granulation.

The document EP-A-0.367.339 published on 19 May 1990 describes an agglomeration procedure in two stages

The document EP-A-0.342.043 published on 15 November 1989 describes laundry detergent compositions granular that can be successfully released from the Supply compartment of an automatic washing machine.

Procedures have also been developed in which has been completely eliminated a drying stage by aspersion. This has been achieved by preparing particles that they comprise surfactants and detergency builders, for example, by extrusion or agglomeration of viscous pastes.

The document US-A-4,666,740 issued on 19 May 1977 and the document US-A-4,411,809 granted on 25 October 1983 describe both laundry detergents that have a high apparent density that are prepared by a agglomeration procedure with a surfactant normally liquid or pasty and coated with zeolite powder. The surfactant used for agglomeration, as well as to provide a sticky surface on which the zeolite adheres, is predominantly a non-ionic detergent.

However, all the procedures of the prior art suffer from the presence of very small particles  (fine) that tend to gel and cause few properties of supply, or the presence of large particles of low porosity that overcome the supply problem, but which are slow to dissolve in the washing procedure.

It is the objective of the present invention provide a detergent composition that has three properties keys:

i) high bulk density

ii) good supply properties

iii) and dissolve quickly.

This can be done by mixing dry first place most (or all) of the components of the detergent composition finished in a granular form and, subsequently, increase the bulk density by spraying on a liquid in one or more drums or rotary mixers.

These initial particles must be granular, (not powdery) and have not passed through a stage of spray. This is crucial to get the advantages of supply properties.

It is also an essential feature of the present invention that the average particle size of the granular particles of the finished product should not be so large so that the dissolution rate is low.

Summary of the invention

The invention provides a composition. specific detergent that has excellent delivery properties  and of dissolution, namely a detergent composition as defined in claim 1.

Detailed description of the invention

The required properties are achieved mixing most (or all) of the components detergents in the form of granular powders, in order to provide a mixed particulate material that has a defined average particle size and bulk density. Next, the apparent density is further increased. spraying a liquid and sprinkling with a flow aid in shape of fine particles in one or more drums or mixers rotary in order to "round" the particles by filling pores and superficial irregularities.

It is an essential feature of the procedure of preparation of the product of the present invention that the powder to the entrance of the rotating drums / mixers is in a form granular (with few or no fines) and not pulverized in the form of a powdery material. This feature provides the Supply advantages (because the absence of fine dust / material Powdery prevents the formation of gels after contact with the Water).

Preparation of the mixture of granular components

The granular components used herein invention are prepared from a wide range of ingredients useful for their detergency that are chosen according to the requirements of the product formulator Suitable ingredients are described at continuation.

Surfactants

The composition of the invention comprises from 5 to 20% of an organic surfactant comprising mixed systems of anionic surfactants having a Krafft temperature lower than 40 ° C, anionic surfactant systems comprise sulfate salts and / or sulfonate.

The surfactants are selected from the group consisting of anionic, hybrid, ampholytic and cationic ionic surfactants, and mixtures thereof. Anionic surfactants are preferred. Surfactants useful herein are cited in US Pat. No. 3,664,961, of Norris, issued May 23, 1972 and in US Pat. 3,919,678, of Laughlin et al ., Issued December 30, 1975. Useful cationic surfactants also include those described in US Pat. 4,222,905, of Cockrell, issued on September 16, 1980 and in US Pat. 4,239,659, of Murphy, granted on December 16, 1980. However, cationic surfactants are generally less compatible with the aluminosilicate materials therein and, therefore, are preferably used at low levels, if used, in the present compositions. The following are representative examples of surfactants useful in the present compositions.

Water soluble salts of fatty acids superior, that is, "soaps" are anionic surfactants useful in the compositions herein. These include alkali metal soaps such as salts of sodium, potassium, ammonium and alkyl ammonium acids higher fats containing about 8 to about 24 carbon atoms and preferably of about 12 to about 18 carbon atoms. The Soaps can be prepared by direct fat saponification and oils or by using free fatty acids. They are particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, that is, soap of sodium or potassium tallow and coconut.

Useful anionic surfactants include also water soluble salts, preferably salts of alkali metals, ammonium and alkyl ammonium of organic sulfuric reaction products that have in their molecular structure an alkyl group containing from 10 to 20 atoms of carbon and an ester group of sulfonic acid or acid sulfuric. (Included in the term "alkyl" is the part alkyl of acyl groups). Examples of this group of synthetic surfactants are alkyl sulfates of sodium and potassium, especially those obtained by sulfation of higher alcohols (C 8 -C 18 atoms of carbon) such as those produced by reducing glycerides of tallow or coconut oil; and the sodium alkyl benzene sulphonates and potassium in which the alkyl group contains 9 to 15 atoms of carbon, in linear or branched chain configuration, by example, those of the type described in US Pat. nº 2,220,099 and 2,477,383.

Other anionic surfactants herein descriptive memory are the alkyl glyceryl ether sulfonates of sodium, especially ethers of higher alcohols derived from tallow and coconut oil, sulphonates and sulfates of monoglycerides from fatty acids of sodium coconut oil; sodium or potassium salts alkyl phenol oxide ethylene ether sulfates containing 1 to 10 units of ethylene oxide per molecule and in which the groups alkyl contain from 8 to 12 carbon atoms; and sodium salts and potassium alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and in which the alkyl group contains from 10 to 20 atoms of carbon.

Other anionic surfactants useful in the Present specification include water soluble salts of esters of alpha-sulphonated fatty acids that they contain 6 to 20 carbon atoms in the fatty acid group and from 1 to 20 carbon atoms in the ester group; soluble salts in acid water 2-acyloxy-alkane-1-sulfonic  containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing 10 to 20 atoms of carbon in the alkyl group and 1 to 30 moles of oxide of ethylene; water soluble salts of olefin sulphonates containing 12 to 24 atoms carbon; Y beta-alkyloxy-alkane sulfonates  containing 1 to 3 carbon atoms in the alkyl group and 8 at 20 carbon atoms in the alkane moiety.

Sulfonation products are also useful of fatty acid methyl esters containing a group alkyl with 10 to 20 carbon atoms. Sulfonates are preferred of C 16-18 methyl esters (MONTH).

Water-soluble nonionic surfactants they are also useful as a secondary surfactant in Compositions of the invention. Such nonionic materials include compounds produced by condensation of oxide groups alkylene (hydrophilic in nature) with a hydrophobic compound organic, which can be aliphatic in nature or alkyl aromatic. The length of the group of polyoxyalkylene which is condensed with any hydrophobic group particular can be easily adjusted to produce a compound water soluble that has the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the condensates of poly (ethylene oxide) of alkyl phenols, for example, the products of condensation of alkylphenols having an alkyl group that contains 6 to 16 carbon atoms, in a configuration of linear chain or branched chain, with 4 to 25 moles of oxide ethylene per mole of alkyl phenol.

Preferred non-ionic components are those water soluble condensation products of aliphatic alcohols containing 8 to 22 carbon atoms, in a configuration of linear or branched chain, with 4 to 25 moles of ethylene oxide per mole of alcohol. Particularly preferred products are condensation of alcohols having an alkyl group containing from 9 to 15 carbon atoms with 4 to 25 moles of ethylene oxide per mole of alcohol; and the condensation products of propylene glycol with ethylene oxide.

Other useful nonionic surfactants are based on natural renewable sources such as glucose. The alkyl polyglycosides (APG), preferably those containing 10 at 20 carbon atoms and an average of 1 to 4 glucose groups. Also useful are nonionic surfactants based on amides of glucose containing an alkyl group with 10 to 20 atoms of carbon for example N-methyl glucamine.

Polyhydroxy fatty acid amides can be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine. The preferred amine for use in the present invention is N- (R1) -CH2 (CH2)
OH) 4 -CH 2 -OH, and the preferred ester is a C 12 -C 20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl-glucamine with C 12 -C 20 fatty acid methyl ester.

The methods for making acid amides polyhydroxy fatty acids have been described in the document WO-A-92-6073, published on April 16, 1992. This application describes the preparation of polyhydroxy fatty acid amides in presence of solvents. In a highly preferred embodiment of the invention is reacted N-methyl glucamine with an ester C 12 -C 20 methyl. It also states that the granular detergent compositions formulator can find convenient to carry out the amidation reaction in the presence of solvents comprising alcohols of C 12 -C 14 alkoxylated, especially ethoxylates (EO 3-8) (page 15, lines 22-27). This directly produces systems nonionic surfactants that are preferred herein invention, such as those comprising N-methyl glucamide and alcohols of C_ {12} -C_ {14} with an average of 3 groups ethoxylate per molecule.

Semi-polar nonionic surfactants include water soluble amine oxides containing a residue alkyl of 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups that they contain 1 to 3 carbon atoms; oxides of soluble phosphines in water containing an alkyl moiety of 10 to 18 carbon atoms and 2 remains selected from the group consisting of groups alkyl and hydroxyalkyl groups containing 1 to 3 atoms of carbon and water-soluble sulfoxides that contain a residue alkyl of 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of 1 to 3 carbon atoms

Ampholytic surfactants include derivatives of aliphatic compounds or aliphatic derivatives of amines secondary and tertiary heterocyclics in which the rest aliphatic can be straight or branched chain and in which one of the aliphatic substituents contains 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic group water solubilizer

Hybrid ion surfactants include derivatives of aliphatic quaternary ammonium compounds, phosphonium and sulfonium in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.

Particularly preferred surfactants in This specification includes tallow alkyl sulfates; alkyl glyceryl ether sulfonates of coconut; alkyl ether sulfates in which the rest alkyl contains from 14 to 18 carbon atoms and in which the degree ethoxylation medium is 1 to 4; olefin sulphonates or paraffins containing 14 to 16 carbon atoms; oxides of alkyldimethylamines in which the alkyl group contains from 11 to 16 carbon atoms; propane sulfonates from alkyldimethylammonium e hydroxy propane sulfonates of alkyldimethylammonium in which the alkyl group contains from 14 to 18 carbon atoms; soaps of higher fatty acids that they contain from 12 to 18 carbon atoms; condensation products of C 9 -C 15 alcohols with 3 to 8 moles of ethylene oxide and mixtures thereof.

Useful cationic surfactants include water soluble quaternary ammonium compounds of formula
R 4 R 5 R 6 R 7 N + X -, wherein R 4 is an alkyl group having from 10 to 20, preferably 12-18 atoms carbon and R 5, R 6 and R 7 are each C 1 to C 7 alkyl, preferably methyl; X <-> is an anion, for example, chloride. Examples of such trimethyl ammonium compounds include C 12-14 alkyltrimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.

Preferred specific surfactants for to be used herein include: alpha-olefin sulfonates; rent C 11 -C 13 -benzene sulfonate of triethanolammonium; alkyl sulfates (tallow, coconut, palm, of synthetic origins, for example, of C_ {45}, etc.); sodium alkyl sulfates; ester sulphonate methyl; coco-alkyl glyceryl ether sulfonate  of sodium; the sodium salt of a sulfated condensation product of a tallow alcohol with about 4 moles of oxide ethylene; the condensation product of a coconut fatty alcohol with 6 moles of ethylene oxide; the alcohol condensation product tallow fat with 11 moles of ethylene oxide; the condensation of a fatty alcohol containing 14 to 15 carbon atoms with 7 moles of ethylene oxide; the condensation product of a C 12 -C 13 fatty alcohol with 3 moles of ethylene oxide; 3- (N, N-dimethyl-N-cocoalkylammonium) -2-hydroxypropane-1-sulfonate; 3- (N, N-dimethyl-N-cocoalkylammonium) -1-propane-1-sulfonate; 6- (N-dodecylbenzyl-N, N-dimethylammonium) hexanoate;  dodecyldimethylamine oxide; cocoalkyl dimethylamine oxide and water-soluble sodium and potassium salts of coconut fatty acids and tallow

Detergency builders

The compositions of the invention comprise 5 to 20% sodium aluminosilicate.

Any compatible detergency builder or combination of detergency builders or powder can be used in the compositions of the present invention.

The detergent compositions herein Descriptive memory may contain an exchange material crystalline aluminosilicate ionic formula

Na_ {z} [(AlO_2) {z} \ cdot (SiO 2) y] x H2O

in which z and y are at least 6, the mole ratio of z a y is 1.0 to 0.4 and z is 10 to 264. The amorphous hydrated aluminosilicate materials useful in the present specification have the formula empirical

M_ {z} (zAlO_ {2} \ cdot and SiO_ {2})

in which M is sodium, potassium, ammonium or substituted ammonium, z is 0.5 to 2 e and is 1, having said material a magnesium ion exchange capacity of al minus 50 milligrams equivalent of CaCO 3 hardness per gram of anhydrous aluminosilicate. Sodium Zeolite A hydrated with a particle size from 1 to 10 micrometers is preferred.

The detergency builder materials of ion exchange of aluminosilicates herein descriptive are in hydrated form and contain 10% to 28% of water by weight if it is crystalline and potentially quantities even superior water if it is amorphous. The materials of ion exchange of highly crystalline aluminosilicates Preferred contain 18% to 22% water in their crystal matrix. The ion exchange materials of aluminosilicates crystals are further characterized by an average diameter of 0.1 micrometer to 10 micrometer particles. The materials Amorphous are often smaller, for example, up to less than 0.01 micrometer. Preferred ion exchange materials have a particle size diameter of 0.2 micrometers to 4 micrometers The expression "particle size diameter" in the present specification represents in diameter of the average particle size by weight of an exchange material ionic ion as determined by analytical techniques conventional such as, for example, microscopic determination using a scanning electron microscope. The materials of ion exchange of crystalline aluminosilicates of the present descriptive report are usually additionally characterized for its ability to exchange calcium ions, which is at least of 200 mg equivalent water hardness in CaCO 3 / g of aluminosilicate, calculated on an anhydrous basis, and that It is generally in the range of 300 mg eq / g to 352 mg eq / g. The aluminosilicate ion exchange materials of the present descriptive report are further characterized by their calcium ion exchange rate that is at least 129.68 x 10-3 g / l / min / g / l aluminosilicate (anhydrous base) and it is generally in the range of 129.68 x 10-3 to 389.04 x 10-3 g / l / min / g / l, based on the ion hardness of calcium. The optimum aluminosilicate for improver purposes of detergency exhibits an ion exchange rate of calcium of 259.36 x 10-3 g / l / min / g / l.

The ion exchange materials of amorphous aluminosilicates usually have an exchange of Mg ++ of at least 50 Mg eq CaCO3 / g (12 mg of Mg ++ / g) and a Mg ++ exchange rate of at least 64.87 g / l / min / g / l. Amorphous materials do not exhibit a model of diffraction observable when examined by Cu radiation (1.54 Angstrom units).

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. The aluminosilicates useful in this invention can be of crystalline or amorphous structure and can be aluminosilicates that occur naturally or synthetically derived. A method of producing aluminosilicate ion exchange materials is described in US Pat. No. 3,985,669 to Krummel et al ., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolita A, Zeolita B and Zeolita X. In one Especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula

Na 12 [(AlO 2) 12 (SiO 2) 12] \ cdot x H2O

in which x is from 20 to 30, especially 27 and has a generally smaller particle size that 5 micrometers

The granular detergents of the present invention may contain neutral or alkaline salts that have a pH in solution of seven or greater, and may be organic in nature or inorganic The detergent builder salt helps provide the desired density and bulkiness to the granules of detergents of the present specification. Although some of the salts are inert, many of them also function as detergency builder materials in the solution of laundry.

Examples of water soluble neutral salts include chlorides, fluorides and alkali metal sulfates, ammonium or substituted ammonium. Metal salts are preferred alkaline and, especially, sodium. Sodium Sulfate is used typically in detergent granules and is a salt particularly preferred Citric acid and, in general, any other organic or inorganic acid can be incorporated into the granular detergents of the present invention to the extent that that are chemically compatible with the rest of the composition agglomerated

Other useful water soluble salts include the compounds commonly known as improver materials detergency Detergency builders are selected generally among the various phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates and alkali metal, ammonium or ammonium polyhydroxysulfonates Water soluble substituted. Metal salts are preferred alkaline, especially sodium, of the above.

Specific examples of improvers detergency of inorganic phosphates are tripolyphosphate, pyrophosphate,  polymer metaphosphate having a polymerization degree of 6 to 21 and sodium and potassium orthophosphate. Examples of improvers Polyphosphate detergency are sodium and potassium acid salts ethylene diphosphonic, sodium and potassium salts of acid ethane-1-hydroxy-1,1-diphosphonic and the sodium and potassium salts of ethane-1,1,2-triphosphonic. Others phosphorus builder compounds are described in the US patents . 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176 and 3,400,148.

Examples of detergency builders non-phosphoric inorganic are carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate and sodium silicate and potassium having a mole ratio of SiO2 to oxide of alkali metal 0.5 to 4.0, preferably 1.0 to 2.4. The Layered silicates of the type manufactured by Hoechst AG, Frankfurt, Germany, and marketed under the registered trademark SKS-6 are also useful herein. invention.

As mentioned earlier, the ingredients chemicals normally used in detergents, such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, percarbonate, etc. and process adjuvants such as the Starch can be used in the preferred embodiments of the present invention

Polymers

Various organic polymers are also useful, some of which can also act as breeders for Improve detergency. Included among such polymers can be mention carboxy-alkyl lower-sodium celluloses, alkyl lower-sodium celluloses and hydroxy lower alkyl celluloses sodium, such as carboxymethyl cellulose of sodium, sodium methyl cellulose e sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some poly (vinyl acetate)), polyacrylamides, polyacrylates and various copolymers, such as acids Maleic and acrylic. Molecular weights for such polymers they vary widely, but most are within the range of 2,000 to 100,000.

Polymer detergency builders from Polycarboxylates are disclosed in US Pat. 3,308,067 of Diehl, granted on March 7, 1967. Such materials include water soluble salts and homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, acid itaconic, mesaconic acid, fumaric acid, aconitic acid, acid citraconic and methyleneomalonic acid.

Optional ingredients

Other ingredients commonly used in detergent compositions can be included in the compositions of the present invention. These include flow aids, coloring particles, bleaching agents and activators of bleaching, foaming enhancers or suppressants foam, antiwear and anticorrosive agents, suspending agents of dirt, soil release agents, clays softeners, dyes, fillers, brighteners optical, germicidal, pH adjusting agents, sources of alkalinity non-detergency builders hydrotropes, enzymes, enzyme stabilizing agents, chelating agents and perfumes.

The optical brighteners can be incorporated directly into one (or more) of the components granular, or a solution or suspension of optical brightener can be sprayed on the drum or rotary mixer during the Process of the compositions of the present invention.

Suppressors can also be incorporated foam in the form of particles in the finished composition by mixing according to the present invention. Preferably, the foam suppression activity of these particles is based in fatty acids or silicones.

Mixing

Granular components can be prepared and mixed by any conventional means. Typically, the mixing procedure can be carried out continuously measuring each component by weight on a moving belt, and mixing them in a drum or rotary mixer. The average size of particles of mixed granular components must be larger than 400 micrometers, and the apparent density must be greater than 600 g / l

In order to achieve these characteristics physical mixture of granular components and in order to maintain the supply advantages of the present invention, it prefers individual granular components to be prepared by methods other than spray drying such such as agglomeration, compaction, encapsulation, etc. A particularly preferred method of agglomerating pastes of highly active surfactants with detergency builders and other powders described in the European application in process of Applicants No. EPA 510746 published on October 28, 1992.

None of the granular components are prepared by spray drying the suspensions comprising organic surfactants Such spray dried components they generally require a spray stage in order to Prepare a high bulk density component.

The drum / mixer procedure

The composition of the invention is prepared by a procedure that is carried out in one or more drum (s) or mixer (s) in which the density apparent product is increased without loss of the advantages of good supply properties and high speed of dissolution.

Although theoretical links are not desired, the granular particles are crushed in the drum / mixture.
clador in the "wet" state causing them to become a more rounded and increasingly regular shape and size of particles (ie, more spherical). This results in a finished composition with a density of at least 750 g / l, preferably greater than 800 g / l.

Proper installation includes various rotary drums or mixers with a rotation axis, such as  belt mixers or low shear mixers supplied by Lödige Machinenbau GmbH, Paderborn, Germany (especially mixers supplied under the brand Registered Löedige KM). Such low shear mixer It includes mixing tools, often of the type "grid of plow "arranged on the axis of rotation. If a low shear mixer, shaft rotation speed It must be less than 250 rpm.

It is preferred that the liquid sprayed on the mixture of granular components comprise a non-surfactant ionic. Useful nonionic surfactants have been described with anteriority. Particularly preferred products are condensation of alcohols having an alkyl group containing from 9 to 15 carbon atoms with 4 to 25 moles of ethylene oxide per mole of alcohol; and propylene glycol condensation products with ethylene oxide.

Others can also be sprayed liquid ingredients on the mixture of granular components of separately or previously mixed form. Typically, you can spray perfumes and suspensions of optical brighteners. Although any optical brightener can be added in this way, it has been found that the index fluorescent brightener color number 351 (as published by the "Society of Dyers and Colorfulists and the American Association of Textile Chemists and Colourists ") provides particular stability advantages of color

Speed cutters or choppers elevated can be advantageously used in order to prevent large balls of product form when wet, but must avoid powder spraying (which could occur when they are dry). Speed cutters or choppers raised can be mounted on a shaft that is radially oriented with respect to the mixer wall and, preferably, the shaft rotates at a speed greater than 1,000 rpm.

The procedure must be differentiated from a more conventional agglomeration procedure. This can be clearly check by observing the increase in the average size of particles from the beginning to the end of the procedure. In the present invention, the average particle size does not increase by more than about 60% of the initial average particle size. Preferably, it does not increase by more than 40% and, more preferably, does not increase by more than 20% of the initial average particle size.

The expression "average particle size", as defined herein, it is calculated sifting a sample of the composition in a certain number of fractions (typically 5 fractions) in a series of sieves Tyler The fractions obtained by weight are represented graphically against the size of the sieve opening. The size particle medium is considered to be the opening size theoretical through which 50% by weight of the sample will pass.

The finely divided flow adjuvant (such as zeolites, carbonates, silicates or silicas) is added to the mixture of granular components, preferably towards the end of process. These agents of powder materials are the only components that are added in the form of a material pulverulent. Therefore, it is particularly important that Selected flow aids do not gel on contact with the water (as some forms of silicates would do finely divided). This careful selection of a flow adjuvant finely divided makes the apparent density increase additionally without losing the advantages of good properties of supply.

Finished compositions

The present invention provides compositions detergents with very high apparent densities, which have also the characteristics of excellent properties of supply and high dissolution rate. The method for preparing the composition is very flexible with respect to formulations that can be treated. In fact any product chemical can be incorporated in the form of a granular particle in a composition of high apparent density by the procedure described above.

The compositions of the present invention they comprise mixed anionic surfactant systems that have a Krafft temperature of less than 40 ° C, the systems comprising anionic surfactants salts sulfate and / or sulphonate, in order to achieve a good dissolution rate at an average size of 550-750 micrometer particles.

In addition, the most preferred compositions they are alkyl benzene sulfonate no phosphate and nonlinear (nil-LAS) for reasons environmental.

Examples Example I

A mixture of raw materials is prepared granular according to the following composition:

% in weight Agglomerate of surfactant anionic 30.0 Compacted granule silicate in layers 17.7 Percarbonate 24.7 Agglomerate from TAED 9.2 Chipboard suppressor of foams 2.2 Encapsulated of fragrance 0.2 Granular polymer detachment of dirt 0.6 Sodium carbonate dense and granular 8.6 Copolymer acrylic-maleic granular 3.2 Enzymes 3.6 \ overline {100.0}

The anionic surfactant agglomerate is prepared by agglomeration of an active C45AS / C35A3 S paste in 78% and a phosphonate solution (35%) in a mixture of powders that Contains zeolite / carbonate / MgSO4 / CMC at ratios of 17/13/1/1 in a high shear mixer.

44 parts of the paste / phosphonate are mixed with 66 parts of the powder mixture.

The wet chipboard is dried in a dryer fluidized bed to a relative humidity in equilibrium of approximately 12% at 20 ° C. The final agglomerate contains 30% of anionic surfactant and 2% phosphonate and has an average size of particles of approximately 500 mm with less than 4% across Tyler 65. The bulk density of the agglomerates is 750 g / l

The mixture of granular components has an apparent density of 780 g / l and a size distribution of particles as follows:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 2 twenty 850 13 35 425 68 65 212 97 100 150 99

The average particle size of the mixture of Granular ingredients is approximately 525 micrometers.

The mixture of granular ingredients described above is placed inside a drum 600 l rotary operating at 15 rpm. A mix of nonionic surfactant (C25E3) and a 20% aqueous solution of optical brightener (registered trademark Pinopal CBS-X, supplied by the company Ciba-Geigy) at 14: 1 ratios is pulverized on the granular mixture while operating the drum at a 7% level. Spray time is about 7 minutes

Immediately afterwards, perfume is sprayed to 0.5% level while rotating the drum. Then without stopping the rotation of the drum, zeolite is slowly added to the mixer up to a level of approximately 8%, taking approximately 2 minutes Once the addition of the zeolite, the mixer is allowed to rotate for approximately 30 seconds and then stop. The product is removed by opening the door and rotating the drum further during approximately 10 seconds

The product has a density after 2 days of aging of 910 g / l. The size distribution of particles is:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 5 twenty 850 2. 3 35 425 87 65 212 99 100 150 99.5

The average particle size of the product is approximately 640 micrometers This represents an increase in average particle size of 22%.

The delivery results of this invention according to the method described in Section B is

Supply waste (%) 2 l / min 24 3 l / min 2

The dissolution profile of the surfactant anionic measured according to the method also described in Section B shows that the time for dissolution of 50% of the surfactant Anionic is 1.8 minutes.

Example II

A mixture of raw materials is prepared granular according to the following composition:

% in weight Agglomerate of surfactant anionic 53.3 Silicate granular 3.2 Sodium carbonate dense and granular 11.0 Citrate of granular sodium 18.1 Copolymer acrylic-maleic granular 7.9 Chipboard suppressor of foams 2.0 Enzymes 4,5 \ overline {100.0}

       \ vskip1.000000 \ baselineskip
    

The anionic surfactant agglomerate is prepared by agglomerating a paste of LAS / TAS / C35E_ {S} S  74: 24: 2 activates 78% on a powder mixture containing zeolite / carbonate / CMC at 10/20/1 ratios in a mixer high shear. The wet chipboard is dried in a dryer fluidized bed to a relative equilibrium humidity of approximately 12% at 20 ° C. The final agglomerate contains 35% of anionic surfactant, has an average particle size of 600 micrometers with 8% particles smaller than 212 micrometers and an apparent density of 740 g / l.

The mixture of granular components has an apparent density of 740 g / l and the following distribution of particle size:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 5 twenty 850 17 35 425 66 65 212 97 100 150 99

       \ vskip1.000000 \ baselineskip
    

The average particle size of the mixture of Granular ingredients is approximately 525 micrometers.

The previous mixture (50 kg) is placed in a Lödige FM 130 D device. The shaft rotates at approximately 160 rpm and the speed of the chopper is 3000 rpm. A mix of non-ionic surfactant (C45E7) and a 20% aqueous solution of a optical brightener at a ratio of 14: 1 is sprayed on the mixture of powders while operating both the shaft and the chopper A total of 5.2 kg of liquid mixture is added in a interval of about a minute and a half. Immediately then 0.3 kg of perfume is also sprayed. Then it add 5 kg of finely divided zeolite to the mixer. The time of Addition is approximately 2 minutes and after the addition, the unit is operated without the chopper during other means minute. The product is discharged through the opening in the bottom of the mixer.

The density of the product after 2 days is 897 g / l. The particle size distribution is:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 17 twenty 850 41 35 425 78 65 212 94 100 150 98

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The average particle size of the product is approximately 740 micrometers This represents an increase in average particle size of approximately 40%.

The results of supply of this product according to the method described in Section B are

Supply waste (%) 2 l / min 14 3 l / min 0

The dissolution profile of the surfactant anionic measured according to the method also described in Section B shows that the time for dissolution of 50% of the surfactant Anionic is 1.0 minute.

Comparative example III

A mixture of raw materials is prepared granular according to the following composition:

% in weight Agglomerate of surfactant anionic 12.0 Powder swollen 49.2 Silicate 3.2 Carbonate dense sodium and granular 11.0 Sodium citrate granular 18.1 Chipboard suppressor of foams 2.0 Enzymes 4,5 \ overline {100.0}

The anionic surfactant agglomerate is prepared by dry neutralization of LAS acid on a powder mixture containing zeolite / carbonate at a ratio of 1/1 in a high shear mixer. Chipboard Contains 30% anionic surfactant, has an average size of 500 micrometer particles with 16% smaller particles than 212 micrometers and an apparent density of 740 g / l.

The swollen powder is prepared by drying by sprinkling a mixture containing:

% in weight Pasta of surfactant anionic 40.0 Zeolite 44.0 Copolymer acrylic-maleic 16.0

in which the surfactant paste Anionic is 50% surfactant and contains LAS and TAS at ratios from 2.4: 1.

The mixture of raw material components It has an apparent density of 670 g / l and the following distribution particle size:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 4 twenty 850 eleven 35 425 33 65 212 64 100 150 86

The average particle size of the mixture of Ingredients is about 370 micrometers.

The previous mixture (50 kg) is placed in a Lödige FM 130 D device. The shaft rotates at approximately 160 rpm and the speed of the chopper is 3000 rpm. A mix of non-ionic surfactant (C45E7) and a 20% aqueous solution of a optical brightener at a ratio of 14: 1 is sprayed on the mixture of powders while operating both the shaft and the chopper

A total of 5.2 kg of liquid mixture is added in an interval of about a minute and a half. Immediately then, 0.3 kg of perfume is also sprayed. Then it add 5 kg of finely divided zeolite to the mixer. Time of addition is about 2 minutes and after the addition the unit is operated with the chopper for another 3 minutes The product is discharged through the opening in the bottom of the mixer.

The density of the product after 2 days is 847 g / l. The particle size distribution is:

Tyler sieve no micrometers % in weight of product in sieve 14 1180 7 twenty 850 13 35 425 47 65 212 75 100 150 88

The average particle size of the product is approximately 400 micrometers

The results of supply of this product according to the method described in Section B is

Supply waste (%) 2 l / min 102 3 l / min 84

The dissolution profile of the surfactant anionic measured according to the method also described in Section B shows that the time for dissolution of 50% of the surfactant Anionic is 0.8 minutes.

Section B

Test methods

Surfactant dissolution rate anionic under stress conditions (Sotax method)

Installation

1) Sotax container (1 l)

2) Distilled water

3) Electric agitator motor with speed variable (IKA-Werk RW 20 DZM)

4) Stirrer with stainless steel propeller (Sotax No. 3990-2)

5) 6 units of disposable filter type with one pore size of 0.22 micrometers (25 mm diameter, Millex No. SLGSO25NB Millipore)

6) Plastic syringes (2 ml) and needles disposable (21 x 1½)

7) Sample collectors (15 glass tubes ml)

8) Set of Tyler sieves and installation of sieving (Rotap)

9) Bathroom with thermostat

Sample Preparation

A representative sample of 10 g of the detergent composition

Experimental procedure

1) The container containing 1 l of water (or desired solution) in the bath at the desired temperature. Be It allows the temperature of the water to reach that of the bath.

2) The propellant is placed in the vessel at 33 mm from the bottom.

3) Prepare 5 syringes with a unit of Filter and a needle. A needle syringe is prepared without the filter.

4) Mixer speed is set to 200 rpm

5) Quickly add 10 g of the product that It will be rehearsed. The stopwatch starts.

6) It is removed, at precise intervals of 10 seconds, 30 seconds, 1 minute, 2.5 minutes and 5 minutes, samples about 2 ml with the syringes. For a proper take of samples, the needle has to be ± 4 cm below the liquid surface.

7) After taking the sample at 5 minutes, the speed of the propellant is increased to 300 rpm.

8) After 10 minutes, another sample is taken at through the filter

9) A sample of the liquid is taken with the syringe without filter. The difference between the result of this and the above is an indication of the solubility that can be expected at this temperature Care must be taken that during this period the system does not increase its temperature due to the action of the vigorous agitation.

10) Analytical determination is carried out of the active ingredient content (AtsSO3 analysis or Similary). When using a turbidimetric endpoint indication for the degree, care must be taken that there is no interference in the unfiltered sample due to the presence of insoluble matters.

11) The percentage dissolved in each sample using the unfiltered sample as 100% (by analysis CatSO 3, even the undissolved surfactant will be titrated).

12) The percentage is plotted dissolved against time for the first period of time (up to 5 minutes) The percentage of solubility in the conditions is calculated experimental from the filtered sample at 10 minutes

Supply under tension conditions (Method of Zanussi®).

Installation

1) Supply of drawer type supplier from Zanussi. The main wash compartment will be used.

2) Municipal running water.

3) Water temperature 20 ± 1 ° C.

4) Water flow 2 ± 0.05 l per 60 ± 1 seconds. The test is performed for 2 minutes. The water flow using a similar measuring or receiver cylinder.

5) Sample mass 105 ± 0.5 g of the product of testing.

Experimental procedure

1) The installation is calibrated for previous operating conditions. It ensures that the complete experimental instrument is horizontal and that none of The nozzles of the supply device are blocked.

2) Weigh the required quantity of product that It will be tested in a container. Make sure the sample is representative of the complete product (avoiding segregation when the container is filled).

3) The supply box is weighed after to ensure that it is properly dry.

4) A placement classifier is placed vertical in the main washing section of the device supply so as to block the width of the drawer at a distance of 12.5 cm from the end of the drawer farthest from the water outlet. The product is poured into the device supply between the vertical placement classifier and the end of the drawer farthest from the water outlet. Dust must be poured so that the dust surface is maintained as level as possible. The classifier is removed.

5) The supply box is placed gently in its groove, ensuring that it fits completely.

6) Water is opened at the calibrated flow rate. Be ensures that water flows completely into the compartment main wash.

7) Water flow is closed after 2 minutes and wait until the drawer drain stops completely.

8) The drawer is removed from the slot and Purge any excess water by lightly shaking the drawer. It ensures that no product falls from the drawer. Should not there is water in no other compartment of the drawer. Whether find some water, the system needs to be again checked to ensure all water flow goes to main wash compartment.

9) The supply box is weighed with the total waste

10) The determination is repeated at least 5 times.

11) The average waste is found wet The result is expressed in% by weight of the initial amount  of dry product.

Accuracy and assessment

Significant differences can be assessed. between products when the average percentage of waste differs by 10% or more. A product is considered to show a good profile of supply if under this test under voltage is below a 30% of waste at 2 l / minute (and / or below 10% of waste at 3 l / minute)

Claims (1)

1. A granular detergent composition that has an average particle size greater than 400 µm and having a bulk density of at least 750 g / l, preferably at least 800 g / l, comprising: a) 5% to 20% of an organic surfactant that it comprises mixed anionic surfactant systems that have a Krafft temperature less than 40 ° C, comprising the systems anionic surfactants salts sulfate and / or sulphonate; b) 5% to 20% sodium aluminosilicate in which components are not present granules that are prepared by spray drying and comprises  an organic surfactant; the supply residue being less than 30% when a sample of 150 g of the detergent composition is poured in a drawer of a shower-type supply device Zanussi®, and 4 liters of water are passed at a temperature of 20 ° C through said drawer from the nozzles of the delivery device at a speed of 2 liters / minute, after which the part of the detergent composition that remains in said supply box is heavy and the weight resulting is expressed as a percentage of the initial sample of 150 g and the average of at least 5 repetitions of the test is found, the resulting percentage being the supply residue; and the dissolution rate being at least 50% of the detergent composition of sulfate / sulphonate salts which they pass in solution form in less than 3 minutes when a sample 10 g is dissolved in 1 liter of distilled water at a temperature of 20ºC in a 1 liter Sotax container, and with a propellant of Sotax agitation No. 3990-2 rotating at 200 rpm around a vertical axis, the lower part of said stirring propeller 33 mm above the bottom of the container.