SK281376B6 - Particulate detergent compositions, process for producing thereof - Google Patents

Abstract

A particulate high-density detergent composition having excellent flow properties comprises 15 to 50 wt% of a high-performance surfactant system - selected ethoxylated alcohol nonionic surfactant plus optionally a minor amount of primary alkyl sulphate - and from 20 to 60 wt% of zeolite. The ethoxylated nonionic surfactant preferably has a peaked ethoxylation distribution, and the zeolite may advantageously be maximum aluminium zeolite P. The composition is preferably prepared by an agglomeration process utilising a high-speed mixer/granulator.

Description

Technical field

The invention relates to free-flowing detergent compositions which combine exceptionally good cleaning performance with high bulk density and excellent powder properties. The formulations contain a high amount of high-performance organic surfactants - selected ethoxylated alcohols, optionally also with a small amount of alkyl sulfates and a zeolite-based detergent builder, and are preferably prepared by agglomeration using a high speed mixer / granulator.

BACKGROUND OF THE INVENTION

EP 265 203A (Unilever) discloses a mixture of surfactants capable of operating at temperatures in the range of from 20 to 80 ° C, containing from 20 to 80 wt. % of an ethoxylated nonionic surfactant and from 0 to 10 wt. water. The surfactant mixture may be sprayed onto an absorbent particulate solid, such as Burkeite with a modified spray-dried polymer, to provide a free-flowing detergent composition containing up to about 25 wt. surfactant.

In EP 436 240A (Unilever) a similar mobile surfactant mixture containing a fatty acid soap has been described. Spraying this mixture onto an absorbing solid provides a powder with improved flow and dispersion properties.

GB 1 462 134 (Procter and Gamble / Collins) discloses mixtures of linear or predominantly linear ethoxylated primary alcohols with narrowly defined chain lengths, chain length distribution, ethylene oxide content, ethoxylation distribution and free alcohol content. These substances perform better on oily contamination than commercially available preparations.

EP 133 715A (Union Carbide) discloses a mixture of alkoxylation products having, in particular, a sharp distribution of alkoxylated substances, in which the predominant alkoxylated substances comprise from 20 to 40% by weight of the composition. and the amount of substances substantially different from those prevailing is strictly limited.

EP 384 070A (Unilever) discloses the use of a zeolite P having a silicon to aluminum ratio not greater than 1.33 (zeolite MAP) as a detergent builder. It has been found that this zeolite binds calcium ions more efficiently and faster than the commonly used zeolite 4A.

In our application 92 305 590.9, filed June 18, 1992, claiming priority date June 25, 1991, published December 1992, discloses free-flowing zeolite MAP based detergent compositions containing a high proportion of liquid, viscous, oily or waxy ingredients (e.g., non-ionic surfactants). active substances) and yet have excellent flow parameters.

In Example K of the present application, a high bulk density powder consisting of 50 wt. % zeolite 4A, 23.4 wt. % sodium carbonate and 26.6 wt. nonionic surfactant Synperonic A4 (synthetic C ₁₂ alcohol with ₅ _i average degree of ethoxylation equal to 3); and in Example 7, a high bulk powder consisting of 56.6 wt. % zeolite MAP, 13.3 wt. % sodium carbonate and 30.1 wt. Syperonicu A3. These preparations are not expressly claimed in this application.

In our application British Patent Application No. No. 91 25035.7, filed November 26, 1991, of which this application claims priority, is claimed a process for preparing a granular detergent composition having a bulk density of at least 650 g / l, which comprises treating a particulate starting liquid surfactant containing alkyl sulfate (20-80%). %), an ethoxylated nonionic surfactant (80 to 20 wt.%) and water (0 to 20 wt.%).

Current efforts in the development of new free-flowing detergent compositions are directed to obtaining an increased bulk density, for example above 600 g / l. These high-weight or "thickened" powders are obtained by a variety of processes, some of which additionally include spray-drying the dried powder and others are based on dry mixing, agglomeration, or other totally tower-free processes.

Using higher bulk densities and hence less porous particles, it has become more difficult to incorporate higher proportions of mobile organic components without losing the powder flow parameters. On the other hand, it is obviously desirable to increase the laundry performance of the compositions by adding higher proportions of surfactants and by using substances with the greatest possible effect on oily and greasy soiling. One group of such substances is ethoxylated alcohols with a relatively low degree of ethoxylation, and these substances are generally mobile liquids at ordinary temperatures.

Given the need to take greater account of the state of the environment, it is also necessary to give preference to alkyl sulphates over alkylbenzene sulphonates which have hitherto been traditionally used in detergent compositions. Alkyl sulfates are readily biodegradable and can be obtained from renewable sources such as coconut and palm oil. However, it is usually much more difficult to process alkyl sulfates than alkyl benzene sulfonates for use in high quality compositions.

Nonionic surfactants, alkyl sulfates and mixtures thereof have been found to be highly effective detergents, but due to their mobility, it is difficult to incorporate them, even in small amounts, into free-flowing powders to be dispersed in the wash liquid. These difficulties can be expected to be much greater in cases where higher proportions of these surfactants are required to further increase surface activity and become even more difficult to overcome in the case of highly dense, dense powders that are so popular with customers, also in the cleaning industry.

However, the inventors have been able to propose free-flowing detergent compositions of high bulk density which combine excellent performance with good powder properties and dispersible properties, despite the fact that they contain a relatively high proportion of high-performance mobile surfactants. The powders according to the invention contain a relatively high proportion of zeolite-based filler and can be prepared by granulation in high speed mixers / granulators. Particularly good powder properties can be obtained if a new zeolite P is used as a filler; and in particular good surface activity can be obtained when selected nonionic surfactants are used.

SUMMARY OF THE INVENTION

The present invention provides a particulate detergent composition having a bulk density of at least 650 g / l, preferably at least 700 g / l, and most preferably at least 800 g / l, comprising:

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a) from 15 to 50 wt. a surfactant system consisting of:

i) from 60 to 100 wt. based on the total weight of the surfactant system of ethoxylated nonionic surfactant which is a primary C ₈ -C ₈ alcohol having an average degree etoxylácic not exceeding 6.5, and ii) up to 40% by weight. based on the total weight of the primary C ₈ -C ₁₈ alkyl sulfate surfactant system

b) from 20 to 60 wt. zeolite and

c) optionally, an additional detergent component up to 100% by weight, which is prepared by granulating the zeolite and surfactants in a high speed mixer / granulator in a non-tower manner.

The free-flowing detergent composition of the invention is characterized by a particularly high proportion of a high-performance organic surfactant system. At least 15 wt. The surfactant may be up to 50% by weight. The compositions may advantageously comprise at least 20% by weight, more preferably at least 25% by weight. surfactants.

The surfactant system consists essentially of an ethoxylated alcohol with a relatively low degree of ethoxylation, optionally with a minor proportion (not exceeding 40% by weight of the surfactant system) of the primary alkyl sulfate.

The proportion of primary alkyl sulfate preferably does not exceed 35 wt. % of the surfactant system and most preferably does not exceed 30 wt. surfactant system. Preferred proportions of alkyl sulfate in the surfactant system are from 0.1 to 35 wt%, more preferably from 5 to 35 wt%. % and most preferably from 10 to 30 wt.

Preferred are surface active systems in which the proportion of alkyl sulfate does not exceed 15% by weight, for example from 0.1 to 15% by weight, preferably from 0.1 to 10% by weight.

Nonionic surfactants based on ethoxylated alcohols

The nonionic surfactants based on ethoxylated alcohols used in the detergent compositions of the invention have a relatively low degree of ethoxylation, not exceeding 6.5.

In the absence of primary alkyl sulfates, the average degree of ethoxylation of the nonionic surfactant is preferably at least 4, but may be lower, for example from 3 to 4, if the primary alkyl sulfate is present. Accordingly, in the presence of a primary alkyl sulfate, ethoxylated alcohols have an average degree of ethoxylation preferably in the range of from 3 to 6.5.

Whether or not alkyl sulfate is present, the average degree of ethoxylation of the nonionic surfactant is preferably in the range of from 4 to 6.5, more preferably from 4 to 6, and most preferably from 4 to 5.5.

A mixture of different ethoxylated materials may be used provided that the total degree of ethoxylation meets the above requirements.

The value of the nonionic surfactant preferably does not exceed 11.0 and most preferably does not exceed 10.5. It is desirable that the HLB value be in the range of 9.5 to 10.5.

The chain lengths of the ethoxylated alcohols may generally be in the range of C ₈ to C ₁₈ , preferably in the range of C 12 to C ₁₆ ; Preferably, the average chain length of C 12 to C _18th Particularly preferred are ethoxylated alcohols consisting wholly or predominantly of C1-chain lengths ₂ to C ₁₄ .

Ethoxylated alcohols are preferably used primary, but in principle ethoxylated secondary alcohols may also be used. Alcohols having a total or predominantly straight chain are preferred. Suitable are alcohols of vegetable origin, for example coconut, which are the most preferred substances. Of the synthetic alcohols, Ziegler alcohols are more preferred than those of oxo compounds.

A preferred embodiment of the invention, while obtaining an exceptionally good anti-oily contamination, consists in using a mixture of ethoxylated alcohols (which are always in a mixture of substances with different numbers of ethylene oxide units), the so-called " "Narrow range". The distribution of ethoxylated substances in such compositions is much more concentrated around the predominant value than is the case with conventional commercial nonionic surfactants. Also, the content of non-ethoxylated substances is generally low and can be further reduced by so-called " "Stripping".

"Narrow range" alkoxylates are described and claimed, for example, in the aforementioned EP 133 715A (Union Carbide).

These mixtures are sharply concentrated with an average alkoxy number of 4 and at least one alkoxylated substance (the "predominant substance") constitutes from 20 to 40% by weight therein; the proportion of substances having 3 or more alkoxy units more than average is less than 12% by weight, and substances having 1 alkoxy unit more and 1 less than average are each present in a weight to weight ratio of 0.6: 1 to 1: 1. A preferred blend product comprises from 80 to 95% by weight of alkoxylated materials having an alkoxy number in the range of plus or minus 2 from the average.

However, the term "narrow range" used in this specification also includes substances that are not as focused as required by the Union Carbide claims, but are substantially more focused than, for example, the commercially available ethoxylated alcohols ICI "Synperonic" (Trade Mark).

This term is therefore defined herein to refer to each alcohol ethoxylation product in which the individual ethoxylated substance is 13% by weight. % and more, preferably 15 wt. and more product. Conventional ethoxylates contain no more than about 10 wt. each of the ethoxylated substances. The predominant substance preferably contains 4 or 5 ethoxylated units.

The "narrow range" ethoxylated alcohols preferably used in the compositions of the invention may have any or more of the following parameters:

at least 20 wt. ethoxylated alcohols may be a single ethoxylated alcohol;

at least one ethoxylated substance (hereinafter referred to as the predominant substance) may comprise from 20 to 40% by weight of ethoxylated alcohols, wherein the proportion of substances having 3 or more ethoxylate units, such as average, is less than 12% by weight. and of substances having 1 more ethoxylated unit and 1 less than average, each present in a weight to weight ratio of from 0.6: 1 to 1: 1,

from 80 to 95 wt. The ethoxylated alcohols may consist of an ethoxylated substance having an ethoxy number in the range of plus or minus 2 from the average.

The different defined narrow-range ethoxylates are also described in GB 1 462 132 (Procter and Gamble / Collins): these are substances having an average degree of ethoxylation of between 3.5 and

6.5, wherein the amount of substances having a degree of ethoxylation in the range of 2 to 7 EO is at least 63% by weight. and the amount of free alcohols does not exceed 5% by weight. These compounds are also suitable for use in the compositions of the invention.

The following table shows the "narrow range" ethoxylation of some commercially available coconut based ethoxylates (NRE7,

NRE5, etc.) as well as “wide-ranging” (E7, E3). The digits show the nominal average degree of ethoxylation in each case.

The invention also encompasses the use of a mixture of commercial substances, for example, (nominal) 3EO ethoxylate and (nominal) 7EO ethoxylate in an average ratio, in order to achieve preferred values of an average degree of ethoxylation of from 4 to 6.5.

However, it is particularly preferred to use a simple commercial substance, particularly preferred are those designated NRE5, NRE4.6 and NRE4, of which NRE4.2 is most preferred.

According to the invention, ethoxylated alcohols with wholly or predominantly straight chains, which also have a " narrow range "

It may also be advantageous to use "narrow range" ethoxylates having a narrower chain length distribution than conventional commercial nonionic surfactants. For example, the nonionic surfactants described in the aforementioned GB 1 462 134 (Procter and Gamble / Collins) are such that at least 65 wt. The substance has a chain length in the range of plus or minus carbon from the mean.

"Narrow range" ethoxylates are now commercially available in Europe and North America, for example from Vista, Union Carbide and Hoechst.

EO distribution of non-ionic coconut-derived surfactants

EO NRE7 NRE5 NRE4.6 NRE4.2 NRE3 E7 E3 0 1.70 1.95 2.55 3.80 8.40 4.15 15,05 1 uo 1.10 1.40 2.25 5.50 2.70 10.95 2 2.45 2.35 3.25 5.15 12,30 3.80 12.50 * 3 4.65 5.85 8.00 11.85 22.25 4.80 12.20 4 7.10 13.60 16.05 19.80 24.25 * 5.55 10.40 5 12,30 20.20 20.55 * 20.85 * 14.45 5.45 6.95 6 16,10 21.10 * 20.25 18.35 9.25 6.20 6.75 7 17.80 · 17.60 15.85 12.05 2.85 6.75 6.15 8 16,30 10.70 8.60 4,70 0.30 7.15 5.30 9 11.70 3.95 2.60 0.95 7.25 * 4.30 10 6.00 1.00 0.65 0.30 7.20 3.30 11 2.05 0.40 0.35 - 7.00 2.40 12 0.55 - - - 6.60 1.65 13-15 - - 15,00 2.10 16-23 - 10.25 - EO average (peak *) 7 6 5 5 3 9 2 EO diameter (mol) 5.96 5.20 4.86 4.27 3.01 6.87 2.99

Primary alkyl sulfates

Primary alkyl sulfates (PAS), which may optionally be up to 40% hmon. of the surfactant system, may have a chain length in the range of C ₈ to C ₁₈ , preferably C ₁₂ to C 16, with a mean value preferably in the range of C ₁₂ to C ₁₅ . Preferred PAS, only or mainly consisting of _{C] 2} to C ₁₄ compounds.

Mixtures of different chain lengths as described and claimed in EP 342 917A (Unilever) may also be used as desired.

As in the case of ethoxylated alcohols, substances with a predominantly or entirely straight chain are preferably used. Particularly preferred is PAS of plant origin and in particular cocoPAS. However, the invention also includes the use of branched PASs as described and claims in EP 439 316A (Unilever).

The PAS is present in the form of the sodium or potassium salt, generally preferably in the form of the sodium salt.

Zeolite detergent builder

The amount of zeolite filler in the compositions according to the invention may range from 20 to 60% by weight, usually from 25 to 55% by weight. and in the high performance detergent composition preferably from 25 to 49 wt.

Depending on the amount and composition of the surfactant system, the zeolite may be a commercially available zeolite 4A, now generally used in washing powder powders. For example, using zeolite 4A, it is possible to obtain powders with satisfactory flow parameters, provided that 17 wt. % surfactant consists of 30 wt. % PAS and 70 wt. nonionic surfactant.

However, as the total surfactant content or the proportion of nonionic surfactants increases, it is more difficult to obtain acceptable powder flow characteristics. According to an embodiment of the invention, preferably the zeolite filler incorporated into the compositions of the invention is zeolite MAP as described and claimed in EP 384 070A (Unilever Case T3047). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminum dimension not exceeding 1.33, preferably in the range of 0.90 to 1.33, and most preferably in the range of 0.90 to 1.20.

Particularly preferred is a zeolite MAP having a silicon to aluminum ratio not exceeding 1.07. The calcium binding capacity of zeolite MAP is usually at least 150 mg CaO / g anhydrous.

The use of zeolite MAP according to the invention has yet another advantage which does not depend at all on its higher filling capacity: it allows the use of higher total amounts of surfactants and higher proportions of non-ionic components without losing the powder flow parameters.

The zeolite MAP preferably used according to the invention is particularly finely divided and has a d ₅₀ (as defined below) in the range of from 0.1 to 5.0 µm, more preferably from 0.4 to 2.0 µm, and most preferably from 0.4 to 1 µm. , 0 pm. The quantity "d ₅ o" indicates that 50 wt. the particles have a diameter smaller than said value; there are corresponding quantities "d ₈ o", "dpo", etc. Particularly preferred substances have a d _{90 of} less than 3 µm and also a 90 _{5 (} ) of less than 1 µm.

Sodium carbonate

The compositions of the invention may contain sodium carbonate to enhance surface activity and facilitate processing. Sodium carbonate may generally be present in an amount ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. % and most preferably from 2 to 13 wt.

Optional powder structure stabilizers

The flow properties of the powder can be improved by the addition of a small amount of powder stabilizing agents, for example fatty acid (or fatty acid soaps), sugar, acrylic or acrylic / maleic polymer or sodium silicate.

A preferred powder structure stabilizer is a fatty acid soap, preferably present in an amount of from 1 to 5 wt%. This substance is preferably added as a free fatty acid and neutralized in situ, as will be explained in the production process.

Powder flow parameters

The compositions of the invention are distinguished by excellent flow properties despite a high content of mobile high-performance organic surfactants.

For the purposes of the invention, the powder flow rate is defined in terms of dynamic flow rate (in ml / s) and measured by the following procedure. The apparatus used is a cylindrical glass tube with an inner diameter of 35 mm and a length

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600 mm. The tube is firmly attached so that its longitudinal axis is vertical. From below, the tube is terminated with a cone of polyvinyl chloride having an internal angle of 15 ° and a lower outlet opening having a diameter of 225 mm. The first sensor transmitting the beams is placed 150 mm above the outlet and the second sensor transmitting the beams is placed 250 mm above the first sensor.

The dynamic flow rate of the powder sample is determined as follows: the outlet opening is closed, for example by covering the card with a piece of powder and pouring the funnel into the upper tube opening so that the powder level is 10 cm above the upper sensor. An insert placed between the funnel and the tube ensures homogeneity of the cartridge. The discharge port is then opened and the time t in seconds is measured electronically as the difference in powder levels from the upper second sensor to the lower first sensor. The measurement is usually repeated two or three times and the average value is taken. If V is the volume (ml) of the tribica between the first and second sensors, the dynamic flow rate DFR (ml / s) is given by the following equation:

IN

DFR = ---- [ml / sec] t

The averaging and calculation is performed electronically and the dynamic flow rate is obtained in a directly readable form. The detergent composition and components of the present invention generally have a dynamic flow rate of at least 90 ml / s, preferably at least 100 ml / s.

Other optional ingredients

The complete detergent industrial detergent composition of the present invention may further comprise any suitable additives commonly used, for example inorganic salts such as sodium silicate or sodium sulfate; organic salts such as sodium citrate; anti-builders such as cellulose derivatives and acrylates or acrylate / maleate polymers; fluorescent substances; bleaching agents, bleach precursors and bleach stabilizers; proteolytic and lipolytic enzymes; coloring agents; colored particles; perfumes; suds control preparations; fiber softening compounds.

Preparation of detergent compositions

The compositions of the invention may preferably be prepared by granulating the zeolite and surfactants in a high speed mixer / granulator. If the surfactant system comprises PAS, it may be added either in the form of a salt (generally as an aqueous paste) or as a free acid (to neutralize in situ).

A particularly preferred process comprises the following steps:

(i) preparing a surfactant system in the form of a homogeneous mobile liquid mixture; and (ii) agglomerating the mobile liquid surfactant mixture with zeolite and other solids present in a high speed mixer / granulator.

iii) agglomeration of this mobile liquid surfactant mixture with zeolite and other substances present in a high speed mixer / granulator.

If no PAS is to be present, the surfactant system is simply a mixture of ethoxylated alcohols, which is already in the form of a homogeneous mobile liquid mixture.

In the presence of PAS, a homogeneous mobile fluid mixture can be prepared by mixing the PAS paste with a nonionic surfactant system. Another way is to mix the nonionic surfactant during the neutralization of the free acid PAS with a base, for example, in a loop reactor as described and claimed in EP 507 402A (Unilever) registered March 31, 1992 and published October 7, 1992.

The high speed mixer / granulator, also referred to as a high speed mixer / thickener, can operate in a dosing mode as a Fukae (Trade Mark) FS or continuously as a Lodige (Trade Mark) Recycler CB30.

The procedure is described in more detail and claimed in our co-pending British Patent Application Night. 91 25035.7 (Unilever), filed November 26, 1991, of which this application claims priority.

The process makes it possible to incorporate high levels of surfactants without loss of powder flow parameters, especially when the zeolite component of the formulation is zeolite MAP or when soap is added as a stabilizer of the powder structure.

When soap is used as a powder structure stabilizer, it is preferably added in the mobile surfactant mixture, either by itself or in the form of the corresponding fatty acid (together with an appropriate amount of base) to neutralize in situ).

The other optional ingredients mentioned may be added at any suitable process step. In accordance with conventional detergent manufacturing practice, bleaching ingredients (bleaches, precursors and bleach stabilizers), proteolytic and lipolytic enzymes, color spots, perfumes and grains of foam control agents are preferably added (dosed) to the bulk thickened product after it has been processed in a high speed mixer / granulator.

The compositions of the invention may, of course, be prepared by other processes, including drying, spraying, or tower-less technology, or a combination of both.

The invention is further explained in the following non-limiting examples, in which the amounts are expressed in parts by weight and by weight unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

The abbreviations used in the examples refer to the following substances:

Coco PAS sulfate linear C _l2 .i ₄ primary alcohol (sodium salt of coconut oil (Philippine Refining Co.)

E7 (s) .For _C13 oxo alcohol 6EO, not "narrow range":

Synperonic A7 (ICI)

E3 (s) ₃ . ₁₅ 3EO oxo alcohol, not "narrow range":

Synperonic (Trade Mark) A3 (ICI) E7 coconut alcohol 7EO, not “narrow range”

E3 coconut alcohol 3EO, not “narrow range”

NRE7 (s) _C12 . ₁₄ Narrow Ziegler Linear Alcohol 7EO:

Alfonic (Trade Mark) 7 (Vi sta)

NRE3 (s) _C12 . ₁₄ Ziegler linear alcohol 3EO “narrow range”:

Alfonic (Trade Mark) 3

NRE7 coconut alcohol 7EO 'with narrow range

NRE5 'narrow range' coconut alcohol 5EO

NRE4.6 narrow-range coconut alcohol 4.6EO

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NRE4.2 Narrow-range coconut alcohol 4.2EO

NRE3 'narrow range' 3EO coconut alcohol

Zeolite 4A Wessalith (Trade Mark) P Powder (Degussa)

Zeolite MAP Zeolite MAP prepared by a method similar to that described in Examples 1-3 of EP 384 O70A (Unilever); the Si: Al ratio is 1.07

Polymer acrylic / melein copolymer:

Sokalan CP5 (BASF)

LAS linear alkylbenzenesulfonate, sodium salt

% Sodium perborate perborate, TAED tetraacetylethylenediamine monohydrate, as granules 83 wt.

EDTMP ethylenediaminetetramethylenephosphonic acid, calcium salt:

% Dequest (Trade Mark) 2041 or 2047, active 34 wt. (Monsanto) Defoamer granules according to EP 266 863B (Unilever)

Examples 1 to 10 - surface activity

Examples 1 to 4

The detergent compositions were prepared according to the following general formula:

parts % Surface active system 17 20,11 Zeolite 4A 32 37.86 polymer 4 4.73 carbonate 14.5 17.16 silicate 0.5 0.59 metaborate 16.5 19:53

84.50 100.00

The surfactant system was prepared as follows (data in% by weight):

Example COCOP E7 (s) E3 (a) NRE7 (s) NRE3 (s) 1 30 30 40 - - 2 30 - - 30 40 3 10 40 50 - - 4 10 - - 40 50

Both mixtures of 30 parts nonionic surfactant 7EO and 40 parts nonionic surfactant 3EO had an average EO of 4.7 and a hydrophilic / lipophilic balance value of HLB of 10.1.

The predominant ethoxylated (4EO) content of the NRE blend was determined to be 14% by weight.

Surface activities (removal of radiolabeled triolein contamination from polyester) were compared from a tergotometer at a product concentration of 5 g / l, a water hardness of 24 ° (French scale) and a wash temperature of 23 ° C. The following results were obtained:

Example % removal of triolein 1 42.2 2 47.4 3 59.8 4 61.6

Comparing the results of Comparative Example A, Example 1 and Example 3 shows how increasing the proportion of nonionic surfactants in the PAS account increases surface activity: while comparing the results of Examples 1 and 2 and Examples 3 and 4 shows an improvement in surface activity using ethoxylated alcohols. narrow range ". The excellent results of Example 4 show the benefit of combining both of these parameters.

Examples 5 to 7

Further comparison of surface activity was made with a test fabric carrying many different types of soiling. This experiment was performed in a Miele computer controlled automatic washing machine (Trade Mark); washing was carried out for 30 minutes at a temperature of 20 ° C and a product concentration of 5 g / l in a water-hard 26 ° French scale.

The compositions had the following general composition:

parts % Surface active system 17.0 19.50 Zeolite 4A 30.5 35.00 Sodium carbonate 12.77 14.65 Sodium silicate 0.5 0.57 Sodium perborate, monohydrate 16.25 18.65 TAED (83% granules) 7.25 8.32 EDTMP 0.37 0.42

87.14 100.00

The surfactant system was prepared as follows (data in% by weight):

Example COCOP E7 (s) E3 (a) NRE7 (s) NRE3 (s) 5 30 30 40 - - 6 30 - - 30 40 7 10 - - 40 50

They obtained for the following results, expressed as a change in reflectance at 460 nm:

Test fabric 1: kaolin and wool grease on polyester / cotton (WFK10C)

Reflectance change (delta R460) Example 5 10.9 Example 6 11.8 Example 7 12.4

Test fabric 2: kaolin and wool grease on polyester (WFK 30C)

Reflectance change (delta R460) Example 5 21.4 Example 6 24.5 Example 7 27.5

Test fabric 3: kaolin and sebum on cotton (WFK 10D)

Change of reflectance (delta R ^ o) Example 5 16.5 Example 6 17.4 Example 7 18.8

Test fabric 4: kaolin and sebum on polyester (WFK 30D)

Reflectance change (delta R ₄₆₀ ) Example 5 18.7 Example 6 21.5 Example 7 25.1

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Example 8

In the manner described in Examples 1-4, the surface activities of various surfactant mixtures containing different amounts of ethoxylated coconut alcohols were compared using a tergotometer.

In all cases, the composition of the composition of Example 1 and the surfactant system consisted of 30 wt. % cocoPAS and 70 wt. ethoxylated alcohol. The ethoxylated alcohols were prepared by:

(i) mixing E7 and E3 (wide range) in different ratios; or (ii) mixing NRE7 and NRE3 (narrow range) in different ratios; or (iii) using a single "narrow range" ethoxylate. The actual degrees of ethoxylation were previously listed in the table in this application.

The dependence of surface activities (removal of radiolabeled triolein from polyester) on the degree of ethoxylation and on the type of initial ethoxylated alcohol is shown in the following table:

EO (average) E7 + E3 NRE7 + NRE3 NRE itself 6.88 9.9 (E7) 5.96 14.1 (NRE7) 5.90 15.7 5.22 18.4 5.20 25.1 (NRE5) 5.17 21.0 4.94 21.2 4.86 30.7 (NRE4.6) 4,70 23.3 4.66 26.4 4.49 31.1 4.27 35.7 (NRE4.2) 3.96 27.3 3.75 35.5 3.01 36.4 (NRE3) 3.00 28.5 (E3)

These results show the advantage of an average degree of ethoxylation of 6 and below; the improvements obtained through the use of narrow-range ethoxylation and the particular benefits of using a single narrow-range substance, in particular NRE4.2.

Example 9

The procedure of Example 8 was repeated using a variety of nonionic enriched surfactant compositions: 10 wt. % cocoPAS and 90 wt. ethoxylated alcohols. The results are shown in the following table.

EO (average) E7 + E3 NRE7 + NRE3 NRE itself 6.88 22.6 (E7) 5.96 34.3 (NRE7) 5.20 44.1 45.5 (NRE5) 5.17 35.3 4.94 35.5 51.5 (NRE4.6) 4,70 36.1 4.66 44.5 4.49 43.0 4.31 43.1 4.27 53.5 (NRE4.2) 3.75 44.1 3.01 35.4 (NRE3) 3.00 37.2 (E3)

Again, the benefits of using narrow-range ethoxylates, in particular pure substances, are evident.

Example 10

The procedure of Examples 8 and 9 was repeated using a number of compositions in which the surfactant system consisted exclusively of ethoxylated nonionic surfactants.

The results are shown in the following table:

EO (average) E7 + E3 NRE7 + NRE3 NRE itself 6.88 33.1 (E7) 5.96 42.9 (NRE7) 5.90 43.5 5.33 45.7 5.22 49.6 5.20 53.9 (NRE5) 4.94 47.6 4.86 55.5 (NRE4.2) 4.55 44.5 4.49 55.3 4.27 59.4 (NRE4.2) 4.19 55.9 3.96 38.5 3.75 51.2 3.01 12.8 (NRE3) 3.00 12.5 (E3)

These results are similar to those of Examples 8 and 9 and further show a clear substantial reduction in surface activity in cases where the average degree of ethoxylation is less than 4 and no PAS is present.

Examples 11 to 32 - Powder Properties

Examples 11 and 12, Comparative Example A

High bulk density detergent powders consisting of a surfactant system, zeolite and (in some examples) sodium carbonate were prepared by agglomeration in a Fukae FS100 batch speed mixer / granulator. It is not intended to design these powders as fully formulated detergent compositions, but to be easily converted into them by admixing (supplying) other ingredients such as bleaching agents, enzymes, suds control powders and perfumes.

The surfactant system was as follows:

% wt. % cocoPAS wt. % E7 (s) wt. E3 (s)

The composition of the compositions in parts by weight and percentage is shown by:

A 11 12

Surfactants 17 (38.64) 17 (31.48) 17 (40.48)

Zeolite 4A 27 (61.36) 27 (50.00)

Zeolite MAP - - 25 (59.52)

Carbonate 10 (18.52) (100.00) 54 (100.00) 42 (100.00)

A homogeneous liquid surfactant mixture was prepared by neutralizing the free acid PAS with a sodium hydroxide solution in a loop reactor in the presence of nonionic surfactants. Zeolite and sodium carbonate (if used) were dispensed into a Fukae mixer, a liquid surfactant mixture was added and granulated. The loose product was then dried in a fluid bed.

In the case of Comparative Example A, it appeared impossible to obtain a bulk material; the mixture formed a solid.

The preparation of the bulk product was made possible by the addition of 10 parts of sodium carbonate (Example 11). When the zeolite MAP was used in a slightly lower amount, the same amount of surfactant (in parts - in fact a slightly higher percentage) could be used without the need to add sodium carbonate; and a free-flowing, free-flowing product was obtained.

Comparative Examples B to E

Further attempts to prepare zeolite-containing 4A powders which would differ in the amount of surfactants (same system as in Examples A, 11 and 12) and carbonate were unsuccessful:

Composition of means in weight parts:

B C D E Surfactants 13 15.3 17.2 18.2 Zeolite 4A 27 27 27 27 carbonate - 5 10 15 40 47.3 54.2 60.5

Percentage of funds:

B C D E Surfactants 32.50 32.35 31.73 30.58 Zeolite 4A 67.59 57.08 49.82 44.63 carbonate - 10.57 18.45 24.79

Formulation B formed a solid, while compositions C, D and E initially produced free-flowing powders that lost fluidity during drying.

Examples 12 to 15

Powders with good parameters, even with a significantly higher surfactant content, were obtained in an experiment similar to Comparative Examples B to E, but using zeolite MAP. The composition and powder properties are shown by:

Composition of means in weight parts:

The melting was carried out as in the previous examples and the products were finally dried in a fluidized bed.

Powders with excellent flow parameters were obtained:

17

parts % parts % Surfactants 17 25.95 17 29.18 Zeolite 4A 32 48,85 32 54,94 carbonate 14.5 22.14 7.25 12.45 Soap 2 3.5 2 3:43 65.5 100.00 58.25 100.00 Powder properties 16 17 Bulk density (g / l) 9.18 872 DFR (ml / sec) 122 143

These examples show, when compared with Comparative Examples C to F, that the addition of soap from fatty acids makes it possible to prepare good powders of high density even according to the regulations from which the powder has not been prepared without the addition of soap.

Examples 18 to 19

Similar compositions to Examples 16 and 17 were prepared by the same method, but zeolite MAP was used instead of zeolite 4A.

Composition of funds:

19

parts % parts % Surfactants 17 25.95 17 29.18 Zeolite 4A 32 48,85 32 54,94 carbonate 14.5 22.14 7.25 12.45 Soap 2 3.5 2 3:43 65.5 100.00 58.25 100.00

12 13 14 15 Surfactants 17 18.4 19.6 20.8 Zeolite MAP 25 25 25 25 carbonate 4.4 8.9 13.9 42 47.8 53.5 59.7

Percentage of funds:

12 13 14 15 Surfactants 40.48 38.49 36,64 34.84 Zeolite MAP 59.52 52.30 46.73 41,88 carbonate - 9.21 16.64 23.28

Powder properties

12 13 14 15 Bulk density (g / l) 794 817 829 867 DFR (ml / sec) 100 93 56 72

Examples 16 to 17

Compositions of a similar composition to those of Comparative Examples B to E were prepared, but this time with the addition of fatty acid soap.

The process for preparing these powders was slightly different from the methods used in the previous examples. By mixing PAS in the form of sodium salt (70 wt%), fatty acid, sodium hydroxide solution in an amount sufficient to neutralize the fatty acid, and surfactants, a homogeneous moving mixture was prepared. The ingredients were dosed into a Fukae mixer in the order of zeolite, carbonate, surfactant, granulation and thickeningPowder properties

18 19 Bulk density (g / l) 980 959 DFR (ml / sec) 131 143

A comparison of these examples with Examples 12-15 shows that the addition of soap improves the flow properties of the compositions, but the use of zeolite was not essential to obtain acceptable powders.

Examples 20 and 21, Comparative Examples F and G

Basic detergent powders were prepared generally as described in Examples 11, 12 and A using a different surfactant system: 10 wt. % cocoPAS wt. % E7 (s) wt. E3 (s)

The surfactant system was prepared as a homogeneous mobile mixture as described in Examples 11, 12 and A, and the other steps were carried out according to these examples.

Composition of means in weight parts:

F 20 G 21 Surfactants 17 17 17 17 Zeolite 4A 27 27 - - Zeolite MAP - - 25 25 carbonate 25 15 42 69 42 57

SK 281376-6

Percentage of funds:

F 20 G 21 Surfactants 17 17 17 17 Zeolite 4A 27 27 Zeolite MAP - - 25 25 carbonate - 25 - 15

It has proved impossible to obtain a free-flowing product in Examples F and G, both mixtures forming a solid mass. To the composition based on zeolite 4A (Example 20), 25 parts of sodium carbonate had to be added to obtain a free-flowing product. If zeolite MAP was present (Example 21), it was sufficient to add only 15 parts of sodium carbonate.

Examples 22 and 23, Comparative Example H

Compositions similar to those described in Examples 18 and 19 but with a higher zeolite content were prepared.

Composition of means in weight parts:

H 22 23 Surfactants 17 17 17 Zeolite 4A 32 32 - Zeolite MAP - - 32 carbonate - 10 - 49 59 49

Percentage of funds:

H 22 23 Surfactants 34.69 28.81 34.69 Zeolite 4A 65.31 54,24 - Zeolite MAP - - 65.31 carbonate - 16.95 -

According to Regulation H no bulk product was obtained; 10 parts of sodium carbonate had to be added for successful processing. Using the same amount of zeolite MAP, however, no sodium carbonate had to be added despite the high percentage of surfactants in the composition (Example 23).

Example 24, Comparative Examples J and K

Formulations with zeolite 4A, with and without soap, were prepared using the surfactant system of Examples 20 and 22. The fatty acid soap was added by mixing the fatty acid and the corresponding amount of sodium hydroxide solution into the surfactant mixture (prepared according to Example 11), before adding the mixture to a Fukae mixer.

Composition of means in weight parts:

J The 24 Surfactants 17 17 17 Zeolite 4A 32 32 32 carbonate 14.5 14.5 14.5 Soap - 2 4 63.5 65.5 67.5

Percentage of funds:

J The 24 Surfactants 26.77 25.95 25.19 Zeolite 4A 50.39 48,85 47,41 carbonate 22.83 22.14 21.48 Soap - 3.05 5.93

Formulation J formed a non-fluid product both before and after drying, while Form K formed an initially good product, but it lost free flowing after drying. After adding more soap (Example 24), an excellent powder was obtained with a bulk density of 920 g / l and a dynamic flow rate of 109 ml / s.

Examples 25 and 26

Compositions similar to those described in Examples 24 and J, but containing zeolite MAP and having a higher surfactant content, were prepared.

Composition of funds:

26

parts % parts % Surfactants 20.5 30.6 20.5 29.71 Zeolite MAP 32 47.76 32 46.37 carbonate 14.5 21.64 14.5 21.01 Soap - 2 2.90 67.0 69.0

Powder properties: 25 26 Bulk density (g / l) 928 898 DFR (ml / sec) 115 114

Example 27, Comparative Example L

Formulations similar to those described in Examples J and K were prepared, but using a different surfactant system: 40 wt. E7 (s) 60 wt. E3 (s)

Composition of funds:

L 27

parts % parts % Surfactants 17 26.77 17 25.95 Zeolite 4A 32 50.39 32 48,85 carbonate 14.5 22.83 14.5 22.14 Soap - - 2 3.5 63.5 65.5

Formulation L formed a good product initially, but it lost free flowing after drying. After the addition of soap (Example 27), an excellent powder with a bulk density of 801 g / l and a dynamic flow rate of 139 m / s was obtained.

Examples 28 and 29

Examples L and 27 were repeated using zeolite MAP instead of zeolite 4A.

Composition of funds:

29

parts % parts % Surfactants 17 26.77 17 25.95 Zeolite MAP 32 59.39 32 48,85 carbonate 14.5 22.83 14.5 22.14 Soap 2 3.5 63.5 65.5

Powder properties: 28 29 Bulk density (g / l) 850 810 DFR (ml / sec) 145 131

In the case of these compositions, there was no need to add soap to obtain good powder properties, on the contrary, no benefit was observed.

Example 30

A composition with a composition similar to that of Example 24 but containing a different nonionic NRE5 surfactant was prepared. The particle size of all solids was less than 200 µm.

The preparation process proceeded essentially as described in Example 11. The free-flowing detergent composition was left in

2816 batch speed mixer / granulator on average about 3 minutes.

Composition:

%

Surfactant: PAS 8.3 NRE5 19.5 Zeolite 4A 43.7 carbonate 16.2 Water 12.3 100.0

A free-flowing detergent composition having a bulk density of approximately 77% g / l and a dynamic flow rate of 101 ml / s was obtained.

Examples 31 and 32

Using a Lodige (Trade Mark) Recycler CB30 type speed mixer / granulator, free-flowing detergent compositions were prepared in a composition similar to Example 30.

The liquid surfactant mixture contained fatty acid in conjunction with a stoichiometric amount of sodium hydroxide which formed soap during mixing and compaction.

The rotational speed was 1600 rpm and the bulk mixture remained in the Recycler for approximately 10 seconds on average.

The composition of the bulk material at the exit of the Rccyclcr was as follows:

31 32 Surfactant: PAS 8.5 8.3 NRE5 19.4 18.8 Zeolite 4A 52.6 47.1 carbonate - 8.0 Soap 2.9 2.9 Water 16.4 14.9

100.0 100.0

The bulk weights were approximately 700 g / l, particle sizes 500-600 µm, and the powder parameters were good.

Examples 33-35, Comparative Example M

Fully designed detergent powders were prepared according to the above-mentioned regulations.

M 33 34 35 LAS base powders 7.85 COCOP - 5.20 5.20 1.70 E7 (s) 3.92 5.20 - - E3 (s) 5.23 6.60 - - NRE7 (s) - - 5.20 6.80 NRE3 (s) - - 6.60 8.50 Soap 2.00 2.00 2.00 2.00 Zeolite 4A 32.00 32.00 32.00 - Zeolite MAP - - - 32.0 carbonate 11.52 11.52 11.52 - fluorescers 0.81 0.81 0.81 0.81 SCMC 0.60 0.60 0.60 0.60 humidity 9.00 9.00 9.00 9.00 dosing of carbonate 11.52 silicate 0.45 0.45 0.45 0.45 Perborat mono 15.00. 15,00 15,00 15,00 TAED 7.75 7.75 7.75 7.75 EDTMP 0.37 0.37 0.37 0.37

enzymes 1.00 1.00 1.00 1.00 defoamer 2.50 2.50 2.50 2.50 PERFUME 0.60 0.60 0.60 0.60 100.0 100.0 100.0 100.0

Comparative Detergent M is a high performance compacted powder based on a different surfactant system (LAS with sneionic surfactants), similar to those used in premium powders sold in Europe.

Surfactant system (wt%).

M 33 34 35 LAS 46 - - COCOP - 30 30 30 E7 (s) 23 30 - - E3 (s) 31 40 - - NRE7 (s) - - 30 40 NRE3 (s) - - 40 50 100 100 100 100

The total amount (non-soap surfactants) in each prescription was 17% by weight.

All base powders were prepared in said Fukae FS100 batch speed mixer / granulator.

Formulation M was prepared by adding zeolite and carbonate (including the amount added to neutralize the LAS) into a Fukae mixer, adding LAS, a homogeneous surfactant mixture (nonionic surfactant), fatty acid, and an equivalent amount of hydroxide solution. solution. After the granules, the powder was dried in a fluid bed, then the remaining ingredients were added.

Formulations 33 and 34 were prepared by dosing zeolite and carbonate into a Fukae mixer, then a surfactant mixture was prepared by mixing PAS paste (70%), nonionic surfactant, fatty acid and equivalent amounts. sodium hydroxide solution. After the granules, the powder was dried in a fluid bed and then the remaining ingredients were added.

Formulation 35 was prepared similarly except that no carbonate was used during granulation.

Powder parameters:

M 33 34 35 Bulk density 861 826 841 841 DFR 89 111 120 128

The surface activity was measured in a Miele washing machine containing a contaminated load by using a product concentration of 5 g / l at a washing temperature of 30 ° C in water with a hardness of 26 ° (French scale). The measure of the surface activity is considered to be the change in reflectance of the test polyester fabric contaminated with kaolin and self (WFK 3 OD) measured at 460 nm.

Surface Activity Measurement Results: Delta R o 16.2 15.0 15.7 17.2

Examples 36 to 38

In addition, other detergent compositions containing zeolite MAP and non-ionic coconut surfactants are provided.

36 37 38 Base powders COCOP 5.20 1.70 - E7 5.20 6.80 7.50 E3 6.60 8.50 9.50

Soap 2.00 2.00 2.00 Zeolite MAP 32.00 32.00 32.00 fluorescers 0.81 0.81 0.81 SCMC 0.60 0.60 0.60 humidity 9.00 9.00 9.00 dosing of carbonate 11.52 11.52 11.52 silicate 0.45 0.45 0.45 Perborat mono 15,00 15,00 15,00 TAED 7.75 7.75 7.75 EDTMP 0.37 0.37 0.37 enzymes 1.00 1.00 1.00 defoamer 2.50 2.50 2.50 perfume 0.60 0.60 0.60 100.00 100.00 100.00

A composition of similar compositions comprising, instead of E7 and E3 with a wide range of nonionic surfactants NRE7 and NRE3 obtained from coconut in these proportions may be proposed. It is also possible to use one of the pure substances NRE5, NRE4.6 or NRE4.2

Claims (14)

A free-flowing detergent composition having a bulk density of at least 650 g / l, comprising: a) from 15 to 50 wt. a surfactant system consisting of; (i) 60 to 100% based on the total weight of the ethoxylated surfactant surfactant system, which is a primary C ₈ to C ₁₈ alcohol with an average degree of ethoxylation not exceeding 6.5; and ii) up to 40% by weight. primary C 8 to C ₁₈ alkyl sulphate, based on the total weight of the surfactant system; b) from 20 to 60 wt. zeolite and d) up to 100 wt. other optional detergent ingredients. A free-flowing detergent composition according to claim 1, wherein the surfactant system a) comprises from 0.1 to 35 wt. alkyl sulfate ii). The free-flowing detergent composition according to claim 1 or 2, wherein the surfactant system comprises an alkyl sulfate (ii) and the ethoxylated i) has an average degree of ethoxylation of from 3 to 6.5. A free-flowing detergent composition according to claim 1 or claim 2, wherein the surfactant system comprises an ethoxylated alcoholic nonionic surfactant (i) and the ethoxylated alcohol i) has an average degree of ethoxylation of from 4 to 6.5. A free-flowing detergent composition according to any preceding claim wherein the ethoxylated alcohol has an average degree of ethoxylation of from 4 to 5.5. A detergent composition according to any one of the preceding claims, characterized in that at least 13 wt. ethoxylated alcohol is a single ethoxylated alcohol. A free-flowing detergent composition according to claim 6 wherein the single ethoxylated substance comprises 4 or 5 ethoxy units per mole of alcohol. A free-flowing detergent composition according to claim 6 or 7, wherein the ethoxylated nonionic surfactant system consists of a single component having an average degree of ethoxylation ranging from 4 to 5. A detergent composition according to any one of the preceding claims, characterized in that it comprises at least 17 wt. of the surfactant system. A free flowing detergent composition according to any one of the preceding claims wherein the zeolite is zeolite P having a silicon to aluminum ratio not exceeding 1.33. A free-flowing detergent composition according to any one of the preceding claims, characterized in that it comprises from 1 to 5 wt. fatty acid soaps. A process for preparing a free-flowing detergent composition according to claim 1, comprising mixing and granulating the zeolite, ethoxylated alcohol and optionally a primary alkyl sulfate, in the form of an acid or salt, in a high speed mixer / granulator. A method according to claim 12, characterized in that it comprises the following steps: (i) preparing a surfactant system in the form of a homogeneous liquid mixture; and (ii) agglomerating the homogeneous liquid surfactant mixture with zeolite and other solids present in the high speed mixer / granulator. The process according to claim 12 and claim 13, wherein the homogeneous liquid surfactant mixture also comprises a fatty acid and a fatty acid base or soap.