SK349592A3 - Detergent compositions - Google Patents

Abstract

A particulate detergent composition having a bulk density of at least 650 g/l, characterized in that it comprises: from 15 to 50 wt.% of a surfactant system consisting essentially of ethoxylated nonionic surfactant which is a primary C8-C18 alcohol having an average degree of ethoxylation not exceeding 6.5 (from 60 to 100 wt.% of the surfactant system), and primary C8-C18 alkyl sulphate (from 0 to 40 wt.% of the surfactant system); from 20 to 60 wt.% of zeolite, optionally other detergent ingredients to 100 wt.%. The composition is preferably prepared by an agglomeration process utilizing a high-speed mixer/granulator.

Description

DETERGENTS

TECHNICAL FIELD

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

**

INTRODUCTION TO THE PROBLEM

Current efforts in the development of new free-flowing detergents 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 include the post-thickening of the spray-dried powder and others are based on dry mixing, agglomeration, or other totally unweighted processes.

PoužitíΠ the use of higher bulk weights, and hence less porous particles, has become more difficult to incorporate higher proportions of movable loss of flow-through organic components without causing powder parameters. On the other hand, it is obviously desirable to increase the washing efficiency by adding higher 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 at ordinary temperatures.

Due to the need to take greater account of the state of the environment, it is also necessary to give preference to alkyl sulfates over alkyl benzene sulfonates which have been traditionally used in laundry detergents. The alkyl sulfates are readily biodegradable and can be obtained from renewable sources such as coconut and palm oil. However, it is usually more difficult to process alkylbutates than alkylbenzenesulfonates for use in high quality laundry detergents.

Nonionic surfactants, alkyl sulfates and mixtures thereof have been found to be highly effective detergents, but because of their mobility, it is difficult to incorporate them, even in small amounts, into free-flowing powders to be dispersed in the wash liquor. 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 and the cleaning industry.

However, the inventors have succeeded in designing free-flowing bulk detergent compositions having high bulk densities which combine excellent performance with good dust properties and dispersibility, despite the fact that they contain a relatively high proportion of highly effective mobile surfactants. The powders of the invention contain a relatively high proportion of zeolite-based fillers and can be prepared by granulation in high-speed mixers / granulators. Particularly good dust properties can be obtained when a new zeolite P is used as a filler; and especially good surface activity can be obtained when selected nonionic surfactants are used.

BACKGROUND OF THE INVENTION

In EP 265 203A (Unilever), a mixture of surfactants having a temperature range of 20 to 80 ° C containing 20 to 80 wt. X ethoxylated nonionic surfactants and from 0 to 10 wt. X water. The surfactant mixture may be sprayed onto an absorbent particulate solid, for example Burkeite with a spray-dried modified polymer, to provide a free-flowing detergent composition containing up to nearly 25 wt. X surfactants.

In EP 436 240A (Unilever) a similar moving surfactant mixture containing a fatty acid soap was disclosed. Powdering with improved flow and scattering properties is obtained by spraying this mixture onto an absorbing solid.

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

EP 133 715A (Union Carbide) discloses a mixture of an alkoxylation product having a particularly sharp distribution of alkoxylated substances in which the individual predominant alkoxylated substances comprise from 20 to 40 masses. and the amounts of substances substantially different from those prevailing are strictly limited.

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

In our European Patent Application no. 92 305 590.9, registered June 18, 1992, claiming priority date June 25, 1991, published December, 1992, disclose free-flowing zeolite MAP based detergent powders containing a high proportion of liquid, viscous, oily or waxy components (e.g., non-ionic surfactants), and the furnaces have excellent flow characteristics.

In Example K of the present application, a high bulk density powder of 50% by weight is disclosed. % zeolite 4A, 23.4 wt. % sodium carbonate and 26.6 wt. % non-ingenic Synperonic A3 surfactant (synthetic C 12-18 alcohol with an average degree of ethoxylation of 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. % Of Synperonic A3. These preparations are not expressly claimed in this application.

In our British Patent Application no. 91 25035.7, filed Nov. 26, 1991, from which this application claims priority, is claimed a process for preparing a granular detergent having a bulk density of at least 650 g / l, which comprises processing the bulk starting material in a high-speed mixer / granulator in the presence of a liquid surfactant containing alkyl sulfates (20-80 wt.%), ethoxylated nonionic surfactant (80-20 wt. 9S) and water (0-20 wt.%).

SUMMARY OF THE INVENTION

The present invention provides a free-flowing detergent having a bulk density of at least 650 g / l, preferably at least 700 g / l, and preferably at least 800 g / l, containing;

(a) from 15 to 50 wt. % of surface active system consisting essentially of:

(i) an ethoxylated surfactant which is a primary C 6 -C 18 alcohol with an average degree of ethoxylation not exceeding 6.5 (from 60 to 100 wt.% of the surface active system); and (ii) a primary C 8 -C 18 alkyl sulfate (from 0 to 40). mass (SS surface active system);

(b) from 20 to 60 wt. % of the zeolite; (c) optionally other component up to 100 wt. %.

DETAILED DESCRIPTION OF THE INVENTION

The free-flowing detergent composition according to the invention is characterized by a particularly high proportion of a highly effective organic surface active system. At least 15 masses. % of the formulation is surfactant; their content can be up to 50 masses. %. The compositions may preferably contain at least 20% by weight. %, more preferably at least 25 wt. % surfactants.

Surfactant System Advantages essential from an ethoxylated alcohol with a relatively low degree of ethoxylation, optionally with a minor proportion (not exceeding 40 wt.% Of the surfactant system) of the primary alkyl sulfate.

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

Preference is also given to surface active systems in which the proportion of alkyl sulphate does not exceed 15% by weight. for example from 0.1 to 15 wt. %, preferably from 0.1 to 10 wt. %.

Non-ionic surfactants based on ethoxylated alpha -olfolf

The nonionic surfactants based on ethoxylated alcohols which are 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 4 to 4, if the primary alkyl sulfate is present. Accordingly, in the presence of a primary alkylcellulose, the ethoxylated alcohols have an average degree of ethoxylation preferably in the range of 3 to 6.5.

Whether or not the 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 6 to 6 and most preferably from 4 to 5.5.

Mixtures of various ethoxylated materials may be used provided that the total degree of ethoxylation meets the above requirements.

The HLB of the nonionic surfactant preferably does not exceed 11.0 and more 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 Cg to C18, preferably in the range of C12 to C18; average length is preferred. chain C 1 - C 18. Especially preferred are ethoxylated alcohols consisting wholly or predominantly of C12 chain lengths

The ethoxylated alcohols are preferably used in the primary, but in principle also ethoxylated secondary alcohols may be used. Preference is given to alcohols having a fully or predominantly straight chain. Suitable are alcohols of vegetable origin, for example coconut, which are the most preferred. Of the synthetic alcohols, Ziegler alcohols are preferable to those of oxo compounds.

around the prevailing conventional commercial

A preferred embodiment of the invention, which provides exceptionally good anti-oily contamination performance, consists in the use of a mixture of ethoxylated alcohols (which are always mixtures of substances with different numbers of ethylene oxide units), so-called " The distribution of ethoxylated substances in such mixtures is much more concentrated than in the case of nonionic surfactants. Also, the content of non-ethoxylated substances is generally low and can be further reduced by so-called " striping.

Narrow range alkoxylates are described and claimed e.g. on the day amended by EP 133 715A (Union Carbide).

These mixtures are special concentrates having an average alkoxy number of 4 and at least one alkoxylated substance (the predominant substance) comprises from 20 to 40% by weight. 35; the proportion of substances having 3 or more alkoxy units more than diameter is less than 12 wt. and of substances having 1 alkoxy unit more and 1 less than the average, each is present in a weight to predominant ratio of from 0.6 to 1: 1. A preferred blend product comprises from 80 to 95 wt. % of alkoxylated substances having an alkoxy number in the range of plus or minus g

from the average.

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

The term is herein defined to refer to each alcohol ethoxylation product in which a single ethoxylated substance is 13 wt. % and more, preferably 15 wt. % or more of the product. Do not contain common ethoxy lei! more than about 10 masses. % of each ethoxylated substance. The predominant substance preferably contains 4 or 5 ethoxy 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 masses. % of 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 wt. % of ethoxylated alcohols, wherein the proportion of the substances having 3 or more ethoxylate units than the diameter is less than 12 wt. X and of substances having 1 ethoxy unit more and 1 less than the average, each present in a ratio of weight to predominant of from 0.6: 1 to 1: 1;

from 80 to 95 wt. % of ethoxylated alcohols may be formed by 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 S, Gamble / Collins): these are substances having an average degree of ethoxylation of between 3.5 and 6.5, the amount of substances having a degree of ethoxylation in the range 2-7 The EO is at least 63 masses. % and the amount of free alcohols does not exceed 5 wt. %. They are also suitable for use in the compositions of the invention.

The following table shows the ethoxylation distribution of some commercially available coconut based ethoxylates based on both the narrow range (NRE7, NRE5, etc.) and the wide range (E7, E3). The digits show the nominal average degree of ethoxylation in each case.

The invention also encompasses the use of a commercially available mixture of, for example, (nominal) 3E0 ethoxylate and (nominal) 7E0 ethoxylate in a proportional ratio in order to obtain an advantageous average degree of ethoxylation of from 4 to 6.5.

However, it is particularly advantageous to use a simple commercial substance; Particularly preferred are NRE5, NRE4.6 and NEE4.2, of which NRE4.2 is most preferred.

According to the invention, ethoxylated alcohols with wholly or predominantly straight chains having also a narrow range are also particularly preferred.

It may also be desirable to use narrow-range ethoxylates having a narrower chain length distribution than ml wl.

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The commercial nonionic surfactants are commercially available. For example, the nonionic surfactants described in the aforementioned GB 1 462 134 (Procter & Gamble / Collins) are such that at least 65 wt. % of the substance has a chain length in the range of plus or minus one carbon atom from the mean value.

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

Primary alkyl sulfates

Primary alkyl sulfates (PAS), which may optionally be up to 40 wt. % of the surface active system, the lengths of the chains may be in the range of C 6 -C 18, preferably C 2 -C 18, with a mean value preferably in the range of C 2 -C 18. Particularly preferred are PASs consisting wholly or predominantly of C 2 -C 14 substances.

Alternatively, mixtures with different chain lengths may be used as described and claimed in EP 342 917A (Unilever).

As in the case of ethoxylated alcohols, it is preferable to use substances which are predominantly or completely stringent. Particularly preferred is PAS of vegetable origin and especially coconut-oak PAS (cocoPAS). However, the invention also includes the use of branched PASs as described and claimed in EP 439 316A (Unilever).

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

Zeolite detergent filler

The amount of zeolite builder in the compositions of the invention may range from 20 to 60 wt. %, usually from 25 to 55 wt. % and in a high performance detergent suitable from 25 to 48% by weight. %.

Depending on the amount and composition of the surfactant system, the zeolite may be a commercially available zeolite 4A, now generally used in laundry detergent powders. For example, using zeolite 4A, powders with satisfactory flow characteristics can be obtained if 17 masses. % 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 ratio not exceeding 1.33, preferably in the range of 0.90 to 1.33, and more 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 typically at least 150 mg CaO / g anhydrous.

The use of zeolite MAP according to the invention has yet another advantage which does not depend entirely 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 (according to the distribution given below) in the range from 0.1 to 5.0 micrometers, more preferably from 0.4 to 2.0 micrometers, and most preferably from 0.1 to 5.0 micrometers. 4 to 1.0 microns. The dso value shows 50 masses. % of the particles have a diameter less than said value; there are corresponding quantities "dgo", d ^ o, etc. Particularly preferred substances have a ds &gt; of less than 3 microns and also a ds of less than 1 microns.

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 amounts ranging from 1 to 60 wt%. SS, preferably from 2 to 40 wt. SS and more preferably from 2 to 13 masses. %.

Optional powder structure stabilizers

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

A preferred fatty soap is 1 to 5 wt.

The powder stabilizing agent is an acid, preferably present in an amount from. This material is preferably added as a free fatty acid and neutralized in situ, as will be explained by the interpretation of the manufacturing process.

Flow parameter in powder

The compositions according to the invention are characterized by excellent flow properties, despite the high content of mobile highly effective organic surfactants.

For the purposes of the invention, powder flow is defined in terms of dynamic flow rates (in ml / s) and measured by the following procedure. The apparatus used consists of a cylindrical glass tube with an inner diameter of 35 mm and a length of 600 mm. The tube is firmly fixed so that its longitudinal axis is vertical. At the bottom, the tube is terminated with a smooth cone of polyvinyl chloride having an internal angle of 15 ° and a lower outlet opening having a diameter of 225 mm. The first beam sensor is positioned 150 mm above the outlet and the second beam sensor is positioned 250 mm above the first sensor.

The dynamic flow rate of the powder sample is determined as follows: The discharge opening is closed, for example by covering it with a piece of card, and the powder is poured into the lower opening of the tube with a funnel so that the powder level is 10 cm above the upper sensor. Insert placed between funnel and tube

Preparation of detergents

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

The process with particular advantage comprises the following steps:

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

If PAS is not to be present, the surface active system is simply a mixture of ethoxylated alcohols, which already has the form of a homogeneous mobile liquid mixture.

In the presence of PAS, a homogeneous moving fluid mixture can be prepared by mixing the PAS paste with a non-ionic surface active system. Another method is to admix the non-ionic surfactant during 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 on March 31, 1992 and published October 7, 1992.

- 18 Fast mixer / granulator, also referred to as fast mixer / thickener, can operate in batch mode as Fukae (Trade Mark) FS or continuously as Lodige (Trade Mark) Recycler CB30.

The process is described and claimed in detail in our co-pending British patent application no. 91 25035.7 (Unilever), filed Nov. 26, 1991, of which this application claims priority.

The process allows to incorporate high levels of surfactants without loss of powder flow parameters, especially when the zeolite composition of the formulation is zeolite MAP

or when structure. with was added soap like Stabilizing powder when with apply soap like Stabilizing powder structure with preferably with adds in a moving mix

surfactants, either as such or in the form of a corresponding fatty acid (together with an appropriate amount of base) for neutralization in situ.

The other optional ingredients mentioned above may be added at any suitable step in the process. In accordance with the common practice of detergent production, bleaching agents (bleaches, precursors and bleach stabilizers), proteolytic and lipolytic enzymes, color spots, perfumes and grains of liver regulators, it is best to add (supply) to the bulk concentrated product after it has been processed. in a high-speed mixer / granulator.

The compositions of the invention may, of course, be prepared by other methods, including spray drying or weightless technology, or a combination of both.

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

EXAMPLES OF EMBODIMENTS OF THE INVENTION

Abbreviations used in the Examples refer to the following substances;

CocoPAS Sulfate of linear C 14 ~ 14 primary alcohol (sodium salt) derived from coconut oil (Philippine Reining Co.)

E7 (s) Ci a-5 oxoalcohol 7E0, range: Synperonic (Trade Mark) not A7 with narrow E3 (a) C 13-15 oxoalcohol 3E0, range: Synperonic (Trade Mark) not A3 with narrow E7 7E0 Coconut Alcohol, range not with narrow E3 Coconut alcohol 3E0, not with narrow

range

NRE7 (s)

NRE3 (s)

NRE7

Ci2-i4 Zieg-ler linear alcohol 7E0 narrow range:

Alionic (Trade Mark) 7 (Vista)

Ciz-i4 Ziegler linear alcohol 3E0 narrow range:

Alionic (Trade Mark) 3 (Vista)

Coconut alcohol 7E0, narrow range

NRE5 Coconut alcohol 5E0, narrow range NRE4.6 Coconut alcohol 4.6E0, narrow winters ΝΕΕ4.2 Coconut alcohol 4.2E0, narrow winters NRE3 Coconut alcohol 3E0, narrow range Zeolite 4A WeBsalith (Trade Mark) P Pow (Degussa) Zeolite MAP MAP zeolite prepared by a similar method described in Examples 1 to 3 of EP 384 070 (Unilever); the Si: AL ratio is 1.07 polymer Acrylic / maleic copolymer: Sokalan CP5 (BASF) LAS Linear alkyl benzenesulfonate, sodium salt Perborat mono Sodium perborate, monohydrate TAED Tetraacetylethylenediamine, such as granules 83 masses. % EDTMP Ethylenediaminetetramethylenose- Ionic, calcium salt: Dequest (Trade Mark) 2041 or 2047, active 34 masses,% (Monsanto)

Odpértovač

Defoamer granules according to EP 266 863B (Unilever)

EXAMPLES 1 TO 10 - SURFACE ACTIVITY

Examples 1 to 4

Detergents were prepared according to the following general formula:

%:%

Surface active system

(see below) 17 20,11 2eolit 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 surface active system was prepared as follows (data are in% by weight):

PMCocoPAS E7 (s) E3 (s) NRE7 (s) NRE3 (s)

Both mixtures of 30 parts nonionic surfactant 7E0 and 40 parts nonionic surfactant 3EO had an average EO number of 4.7 and an HLB value of 10.1.

The predominant ethoxylated (4E0) content of the NRE was determined to be 14 wt. %.

Surface activities (removal of radiolabeled triolein contamination from polyester) were compared in 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

42.2

47.4

59.8

61.6

Comparison of 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 improved surface activity using narrow range ethoxylated alcohols. . The excellent results of Example 4 show the benefits of combining both of these parameters.

Examples 5 to 7

Further comparison of surface activity was performed using a test fabric carrying many different types of soiling. This experiment was carried out in a computer-controlled Miele 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 ° Irish scale.

Means having the following general composition:

Surface active system dfly .: % (see below) 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 SS Granules) 7.25 8.32 EDTMP 0, 37 0.42 foam suppressor 2, 50 2.87 87.14 100.00

The surface active system was prepared as follows (data are in mass X):

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

The following results were obtained, expressed as change in dilution at 460 nm:

Test fabric 1: kaolin and wool grease on polyester / / cotton (WFK 10C)

Changes in Relativity (delta Rieo)

Example 5 10.9

Example 6

Example 7

11.8

12.4

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

Delta Changes (Delta FUeo)

Example 5 21.4

Example 6 24.5

Example 7 27.5

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

Deltaance changes (delta lUeo)

Example 5 16.5

Example 6 17.4

Example 7 18.8

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

Relativity changes (delta R «i« o)

Example 5 18.7

Example 6 21.5

Example 7 25.1

27 Example 8

Using the method 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 was as in Example 1 and the surface active system consisted of 30 wt. 5 cocoPAS and 70 masses. % ethoxy lovsine alcohol. 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 reported in the Table in this work.

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

EO (average): (I) E7 + E3: (Ii) (Iii) SamotnV NRE NRE7 + NRE3: 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 (Ε3)

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

Example 9

The procedure of Example 8 was repeated using a series of compositions with a surface active system more enriched with non-ionic substances: 10 wt. % cocoPAS and 90 wt. % of ethoxylated alcohols. The results are shown in the following table.

EO (average): (I) E7 + E3: (Ii) NRE7 (Iii) + NRE 3 : 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) benefits resulting from application narrow-range ethoxylates especially Pure substances are i opét obvious. Example 10 Approach share PMhere 8 a 9 was repeated using rows of resources, in which the surface the active system was forms exclusive ethoxylated non-ionic surface

active substances.

The results are shown in the following table.

(I) (Ii) (Iii) 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 (NRE4.6) 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 - DUST PROPERTIES

Examples 11 and 12. Comparative Example A

The bases consisting of (in some washing powders with high bulk density, surface active system, zeolite and cases) of sodium carbonate were prepared by aggregation in a batch mixer / / granulator of the Fukae FS100 type. It is not intended to design these powders as fully formulated laundry detergents, but to be easily converted into them by admixing (supplying) other ingredients such as bleaching agents, enzymes, powders regulating dyes and perfumes.

The surface active system was as follows:

30 materials. % cocoPAS 30 materials. % E7 (with) 40 materials. % E3 (with)

The composition of the formulations in these is shown below.

A:

parts by weight and percentages

Surfactants

Zeolite 4A

Zeolite MAP

Carbonate (38,64) (61,36) (100,00)

W (31.48) (50.00) (18.52) (100.00) =

(40.48) (59.52)

4.2 (100.00)

A homogeneous liquid surfactant mixture was prepared by neutralizing PAS in the free acid 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 free-flowing product; the mixture formed a solid mass. 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 the free-flowing, free-flowing product was kissed.

Comparative Examples B to E

Further attempts to prepare zeolite 4A containing 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: Surfacing active substances 13 15.3 17.2 18.2 Zeolite 4A 27 27 27 27 carbonate - 5 10 15 40 47.3 54.2 60, 5 Composition of means in percent B: L>: &: Surfacing active substances 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 Device B create 1 solid mass while for

The means C, D and E initially produced free flowing powders but lost fluidity during drying.

Examples 12 to 15

Powders with good flow characteristics, even with a substantially higher surfactant content, were obtained in an experiment similar to that in Comparative Examples B to E, but using zeolite MAP. The composition and dust properties are shown below:

12: 13: 14 =

Composition of compositions in weighing parts

Surfactants

Zeolite MAP

carbonate

18.4

25

4.4

47.8

% Composition of the compositions

Surfactants

Zeolite MAP

carbonate

40.48 38.49

52.30

9.21

59.52

19,6 20,8

25

8.9 13.9

53.5 59.7

36.64 34.84

46.73 41.88

16.64 23,28

Dust properties

Bulk density (g / l) 794 817 829 867

DFR (ml / sec) 100 93 56 72

Examples 16 to 17

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

The method for preparing these powders was slightly different from the methods used in the previous Examples. By mixing PAS in sodium 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 fed into a Fukae mixer in the order of zeolite, carbonate, surface active mixture, granulation and concentration were carried out as in the previous Examples, and the products were finally dried in a fluidized bed.

Powders with excellent flow characteristics were obtained.

Composition of means

16: 17:

Surfacing djí_ly .: dí ly: active substances 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 3.05 2 3.43 65.5 100.00 58.25 100.00

Dust properties

16: ÍZ- Bulk density (g / l) 918 872 DFR (ml / sec) 122 143

These Examples show, when compared to Comparative Examples C to F, that the addition of soap from fatty acids makes it possible to prepare good high-density powders even according to 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 devices

18 .:

% · parts.

19:

parts:%.

Surfactants

25,95 17

29.18

Zeolite 4A

48,85

54,94

carbonate

14.5

22.14

7.25 12.45

Soap

3.05

3.43

65.5 100.00 58.25 100.00

Dust properties

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 MAP was not essential to obtain acceptable powders.

Examples 20 and 21, Comparative Examples F and G

The base laundry powders were prepared generally as described in Examples 11, 12 and A using a different surfactant system:

10 materials. % cocoPAS 40 materials. % E7 (s) 50 materials. % E3 (a)

The surface active system was prepared as a homogeneous moving mixture by the method described in Examples 11, 12 and A, and also the other steps of the procedure were carried out according to these Examples.

Composition of devices in weight parts

F:

21:

Surfactants

Zeolite 4A

Zeolite MAP

carbonate

Percentage of composition

Surfactants

Zeolite 4A

Zeolite MAP

carbonate

F: 20:

38.64 24.64

61.36 39.13

36.23

G: 21:

40.48 29.82

59.52 43.86

26,32

It has proved impossible to obtain a free-flowing product in Examples F and G; both mixtures formed a solid mass. To the zeolite-based formulation 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:

Surfactants

Zeolite 4A

Zeolite MAP

carbonate

Percent composition of the compositions

22:

23:

Surfactants

34.69

28.81

34.69

Zeolite 4A

65.31

54,24

Zeolite MAP

carbonate

16.95

65.31

Under H, no bulk product was obtained: 10 parts of sodium carbonate had to be added for successful processing. However, using the same amount of zeolite MAP, no sodium carbonate had to be added despite the high percentage of surfactants in the formulation (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 appropriate amount of sodium hydroxide solution into the surfactant mixture.

(ready to share) mixer type Fukae. Example 11) before ends by the addition mixture J: K = 24 = Composition of preparations in weight parts Surface active substances 17 17 17 Zeolite 4A 32 32 32 carbonate 14.5 14.5 14.5 Soap - 2 4 63.5 65, 5 67.5 Composition of preparations in percent Surface active 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 Formulation K formed a good original product, but it lost free flowing after drying. After the addition of more soap (Example 24), an excellent powder having a bulk density of 920 g / l and a dynamic flow rate of 109 ml / e was obtained.

PMKladv 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 devices

Surfacing parts: %: parts: %: active substances 20.5 30.60 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

69.0

67.0

Dust properties

25: 26:

Bulk density (g / l) 928 898

DFR (ml / sec) 115

114

Example 27. Comparative Example L

Preparations similar to those described in Example 1 were prepared.

positives J and K, but using a different system surface active ingredients: 40 masses. % E7 (s) 60 masses. % E3 (s)

S1ožení means

Surfacing parts: L: 35: parts: 27: 3i: active substances 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 3.05

63.5

65, 5 good product, but adding soap (Example of bulk density 801 139 ml / s.

AFTER

27) g / l

Initially, L formed drying and lost flowability. Excellent powder and dynamic flow rates were obtained

Examples 28 and 29

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

Composition of the compositions

28: 29:

Surfacing honored. active substances 17 Zeolite MAP 32 carbonate 14.5 Soap

*: parts:%:

26.77 17 25.95

50.39 32 48.85

22.83 14.5 22.14

3.05

63.5

65.5

Dust properties

28;

Bulk density (g / l)

850

810

DFR (ml / sec)

145

131

In the case of these preparations, it was not necessary to add soap to obtain good dust properties; on the contrary, no benefit was observed.

Example 30

A composition similar to Example 24, but containing a different non-ionic surfactant, NRE5, was prepared. The particle size of all solids was less than 200 microns.

The preparation process proceeded substantially as described in Example 11. The free-flowing detergent was left in the batch fast mixer / granulator for approximately 3 minutes on average.

Composition:%

Surfactant: PAS 8.3

NRE5 19,5

Zeolite 4A 43.7

Carbonate 16.2

Water 12.3

100.0

A free-flowing detergent having a bulk density of about 770 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 rapid mixer / granulator, bulk detergent compositions similar to Example 30 were prepared.

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.

- 47 The composition of the bulk material at the exit of the Recycler was as follows:

Surfactant:

Zeolite 4A

carbonate

Soap

Water

3i: £ 3: PAS 8.5 8.3 NRE5 19.4 18.8

52.6 47.1 - 8, 0 2.9 2.9 16.4 14.9 100.0 100, 0

The bulk densities were 500-600 microns.

around 700 and dust g / l, size parameters were

Examples 33-35. Comparative Example M

The fully designed detergent powders were prepared according to the regulations below.

Basic powders ÍS ^: 33: 34: 35: LAS 7.85 COCOP - 5.20 5.20 1.70 E7 (s) 3.92 5.20 - - E3 (a) 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

Podávkováno

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 Odpértovač 2.50 2.50 2.50 2.50 mullets 0.60 0.60 0.60 0.60 100.0 100.00 100.00 100.00

Comparative Detergent M is a highly effective dense powder based on a different surfactant system (LAS with non-ionic surfactants), similar to the ones used! in premium powders sold in Europe.

Surface active systems (mass%)

S: 33: 34: 25: LAS 46 - - - COCOP - 30 30 30 E7 (s) 23 30 - - E3 (a) 31 40 - - NRE7 (s) - - 30 40 NRE3 (s) - - 40 50 - - - -r 100 100 100 100 Overall number (Non-soap) surface active The substances in each recipe were 17 masses. %. all primary pills were ready in the past a batch type high-speed mixer / granulator type Fukae FS100. M was ready. that zeolite and carbon- tan (including number added for neutralization of LAS) were dosed into the blender type Fukae and she joined

LAS acid, a homogeneous mixture of surfactants (nonionic surfactant), fatty acid, and an equivalent amount of sodium hydroxide solution. After granulation, the powder was dried on a fluid bed, after which the remaining ingredients were added.

Formulations 33 and 34 were prepared by dosing zeolite and carbonate into a Fukae mixer, followed by the addition of a surfactant mixture prepared by mixing PAS paste (7035), nonionic surfactant, fatty acid, and an equivalent amount of solution. sodium hydroxide. After granulation, the powder was dried on a fluid bed, after which the remaining ingredients were added.

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

Dust parameters

S: 33: 34 = 25: Bulk density 861 826 841 841 DFR 89 111 120 128 Surface activity was measured in automatic washing machine

Miele containing a contaminated load using a product concentration of 5 g / l at a washing temperature of 30 ° C in water of 26 ° hardness (Irish scale). A measure of the surface activity is considered to be the variation in the re-reflectance of a test fabric coated with kaolin and self-polluted (WFK 30D) measured at 460 nm.

Results of surface activity measurements

Delta IUso 16.2 15.0 15.7 17.2

Examples 36 to 38

Further, there are further teachings of laundry detergents containing zeolite MAP and non-ionic coconut surfactants.

£ 3: 2Z = 3FI: Basic 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 Skimmer 2.50 2.50 2.50 mullets 0.60 0.60 0.60 100.00 100.00 100.00 Can be designed composition similar means containing instead of substances E7 a E3 with wide range

non-ionic surfactants NRE7 and NRE3 obtained from coconut in the same proportions. One of the pure substances NRE5, NRE4.6 or NRE4.2 may also be used.

ww? 5 - <? 2nd

Claims (14)

PATENT CLAIMS A free-flowing detergent having an alesport bulk density of 650 g / l, comprising: (a) from 15 to 50 wt. % surface active system consisting essentially of: (i) an ethoxylated surfactant which is a primary C 6 -C 16 alcohol with an average degree of ethoxylation not exceeding 6.5 (from 60 to 100 wt.% of the surface active system); and (ii) a primary C 6 -C 16 alkylsulfate (from 0 to 40 wt. % surface active system); (b) from 20 to 60 wt. X of zeolite, (c) optionally other component up to 100 wt. %. _r . ^ _ A detergent composition according to claim 1, characterized in that the surfactant system (a) comprises from 0.1 to 35% by weight. % alkylsulphate (ii). A detergent composition according to any one of the preceding claims wherein the surfactant system comprises an alkyl sulfate (ii) and the ethoxylated alcohol (i) has an average degree of ethoxylation of from 3 to 6.5. A detergent composition according to claim 1 or claim 2, wherein the surfactant system comprises no alkyl sulphate (ii) and the ethoxylated alcohol (i) has an average degree of ethoxylation of from 4 to 6.5. A free-flowing detergent according to any one of the preceding claims, characterized in that ... that. 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 masses are used. % of ethoxylated alcohol is a single ethoxylated alcohol. 7. The detergent composition according to claim 6, wherein the single ethoxylated substance contains 4 or 5 ethoxy units per mole of alcohol. A detergent composition according to claim 6 or claim 7, characterized in that the system of ethoxylated nonionic surfactants consists of a single component having an average degree of ethoxylation in the range of 4 to 5. A detergent composition according to any one of the preceding claims, characterized in that it comprises at least 17 masses. SS surfactant system. and A free-flowing detergent composition according to any of the preceding claims wherein the zeolite is zeolite P having a silicon to aluminum ratio not exceeding 1.33. A detergent composition according to any one of the preceding claims, characterized in that it contains from 1 to 5% by weight. % fatty acid soap. 12. A process for the preparation of a free-flowing detergent composition according to claim 1, comprising mixing and granulating zeolite, ethoxylated alcohol, a primary alkyl sulfate (if present) in an acid or salt, and optionally selecting another ingredient, in a high-speed mixer / granulator. . 13. A process according to claim 12 comprising as step (i) the preparation of a surfactant system in an extremely homogeneous liquid mixture; and I 56 (ii) agglomerating said homogeneous liquid surfactant mixture with zeolite and other solids present in the high-speed mixer / granulator. 14. A process according to claim 12 or claim 13 wherein the homogeneous liquid surfactant mixture also comprises a fatty acid and a base, or a fatty acid soap.