SK280568B6 - Particulate detergent compositions - Google Patents

Abstract

A particulate detergent composition having a bulk density of at least 600 g/l comprises a surfactant system comprising a nonionic surfactant, at least one detergency builder and optionally other detergent ingredients, wherein the nonionic surfactant comprises a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C12 and an average degree of ethoxylation not exceeding 8, and the surfactant system is free of ethoxylated nonionic surfactants having an average chain length of C12 or above and an average degree of ethoxylation below 7. The use of short-chain nonionic surfactant improves delivery of the composition to the wash in an automatic washing machine, and also gives detergency benefits.

Description

Technical field

The invention relates to particulate detergent compositions comprising nonionic surfactants. In particular, the invention relates to particulate detergent compositions having a high bulk density, in particular to compositions containing a high sodium aluminosilicate detergent component.

BACKGROUND OF THE INVENTION

Nonionic surfactants preferably have cleaning characteristics when incorporated into detergent compositions, are particularly effective in eliminating hydrophobic contamination, such as hydrocarbon oils, complex fats and other long chain unsaturated and saturated glycerides.

However, when particulate detergent compositions containing non-ionic surfactants come into contact with aqueous solutions, the non-ionic surfactants tend to form viscous phases that interfere with dispensing from the dispenser dispenser or dispenser and give poor dispersions and dissolve poorly in the wash liquid. .

In powders with a high bulk density, this problem is exacerbated because the capillary diameter of the powder layer is smaller than for powders with a lower density of material and thus water penetration is slower. Dosing problems also appear particularly acute with powders containing water-insoluble detergent ingredients, such as alkali metal aluminosilicates.

It has been found that the difficulty of forming a detergent powder containing ethoxylated alcoholic nonionic surfactants having good dosing and dissolution characteristics, without the need for any manufacturing adjustments, can be overcome by using short chain nonionic surfactants with tightly controlled alkyl chain length and elimination. certain other ethoxylated nonionic surfactants, especially long chain materials with a low degree of ethoxylation. Surprisingly, this gain is achieved without loss of detergency efficiency, and efficiency can even be improved.

Particulate detergent compositions containing nonionic short chain surfactants are described in GB 1 566 326, GB 1 462 133, GB 1 462 134, GB 1 485 316 and GB 1 566 326 (Procter &Gamble); GB 1,519,433 and FR2,303,850A (Rhone-Poulenc); EP 200 953A and WO 91 10718A (Henkel). However, the use of short-chain nonionic surfactants to improve the dosing characteristics of high bulk density detergent compositions is not described.

SUMMARY OF THE INVENTION

The present invention provides a particulate detergent composition having a bulk density of at least 600 g / L and comprising a surfactant system comprising a nonionic surfactant, at least one detergent builder, and optionally other detergent ingredients, the composition comprising a nonionic surfactant comprising an aliphatic ethylene oxide condensation product. an alcohol having an average alkyl chain length of less than C and a nonionic surfactant whose mean chain length is less than C 1; ₂ , has an average degree of ethoxylation not exceeding 8, and the surfactant system is free of an ethoxylated nonionic surfactant having an average alkyl chain length of C or more and an average degree of ethoxylation of less than 7.

The invention further provides the use of a nonionic surfactant which is a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C and an intermediate degree of ethoxylate of not more than 8 to improve the dosing of the particulate detergent composition at least 600 g / l.

SUMMARY OF THE INVENTION

Short-chain surfactant.

The detergent compositions of the present invention are characterized by a surfactant system comprising, as an essential component, a nonionic surfactant having an average alkyl chain length of less than C and an average degree of ethoxylation not exceeding 8. This component will hereinafter be referred to as a short chain surfactant.

Commercial nonionic surfactants are generally compositions comprising a wide range of chain lengths of the average value. The surfactant system is free of non-ionic surfactants, which are commercial materials with a medium chain length of C and above and 12 with a mean degree of ethoxylation below 7.

In addition, ethoxylated nonionic surfactants other than the specifically excluded class will be present within the scope of the invention. However, preferred compositions of the invention are substantially free of all ethoxylated nonionic surfactants (commercial compositions) of any degree of ethoxylation with an average C chain length or greater.

Preferably, the short-chain surfactant is obtained from an alcohol of which at least 25% by weight, more preferably at least 50% by weight and most preferably at least 75% by weight has an alkyl chain length of less than C. Preferably, the surfactant system may be substantially free of any non-ionic surfactant material having a chain length of C or more.

Despite the absence of long chain (C or more) nonionic surfactants with low ethoxylation (less than 7EO), known for their oil-based detergency, the compositions of the invention have excellent detergency performance over a wide range of soils and also have better dispersing characteristics.

Preferred are nonionic surfactants having an average alkyl chain length in the range of C to C; more specifically, those having an average alkyl chain length in the range of C to C and C to C

11 11.5

Either primary or secondary alcohols are used, if ethoxylates of primary alcohols are generally preferred.

The average number of ethylene oxide groups per mole of alcohol in the leionic condensation product is 8 or less, preferably from 2.5 to 8. It may preferably be 6.5 or less, and more preferably from 2.5 to 6.5.

Nonionic surfactants obtained from alcohols with some chain branching may provide certain benefits in both detergent and improved powder dosing and dissolution.

It is preferred that the level of free alcohol in the nonionic surfactant is less than 5% by weight, more preferably less than 1% by weight.

Details of some nonionic alcohol ethoxylate surfactants are (* denotes trademark). Mixtures of these substances may also be used to achieve the intermediate ethoxylation step.

Dobanol * 91 series ex Shell

Ethoxylates: Dobanol 91-2.5

Dobanol 91-5

Dobanol 91-6

Dobanol 91 4-6

2,5 EO

5EO

6EO

4-6 EO

Nominal description: C alcohol with 20 to 25% branching (C -C).

^{K 1} 4 '

Medium chain length: 10.14

String Length Distribution:

C linear 0.7 0.7 C 9 linear 17.5 19.0 C _with 2-methyl 1.0 C _? 2-ethyl 1 0.3 C ₆ 2-propyl 0.2 C 10 linear 40.7 45.8 C _{g of} 2-methyl- 2.9 C 2 -ethyl 1.0 otherwise branched 1.2 c _u linear 25.5 33.3 C 2 -methyl 2.4 C ₉ 2-ethyl 1.0 otherwise branched 4.4 C 12 linear 0 1.6 branched 1.6

Lialet * 111 series ex Enichem

Ethoxylates: Lialet 111-4

Lialet 111-5

Lialet 111-6

Lialet 1114-6

Lialet 111 6.9

4EO

5EO

6EO

4-6 EO

6.9 EO

Nominal description: C alcohol with 50 to 60% branching (C -C).

^{1 4} .

Medium chain length: 11.0

String Length Distribution:

linear 49.2 C 2 -methyl 10 ^J 17.3 C _; 2-ethyl 9.3 C _with 2-propyl 9.7 C ₇ 2-butyl a 2-pentyl 10.6

Vista * (Alfonic *) ex Vista Series Chemicals________________

Ethoxylates: Vista 1012-62 6.25 EO

Vista 1012-52 4.3 EO

Vista Novel II 1012-52 4.5 EO (narrow range)

Nominal description: _{C] 2} linear alcohol

Medium chain length: 10.2

String Length Distribution:

C linear 90.0

C linear 10.0

Other non - ionic short - chain surfactants

The following materials are also suitable for use in the present invention:

Acropol * 91 4-6 ex Exxon

C chain, 35% branching (C), 4-6EO

9-11 ⁱⁿ 1-4 '

Dobanol * 1 cx Shell series:

98.5% C chain with traces of C and C ^r 10 12

Synperonic * 91-4-6 ex ICI:

C chain, 60% branching (C), 4-6 EO

9-11 ^V 1 '

Lialet * 91 ex Enichem:

C chain, 60% branching (C), 4-6EO

9-11 '1-4'

Inbentin * C E ex Kolb:

4

C linear chain, 4 EO

Nonionic surfactants excluded from the present invention

Long chain nonionic surfactants with an average degree of ethoxylation below 7 are excluded from the invention. They include the following materials:

Coconut based materials such as Lordac * series ex DAC Chemicals:

C -C, mean chain length 12.75

Low-ethoxylated nonionic Synperonic * cx ICI surfactants such as Synperonic A3 (3EO):

Medium string length: 13.65 C 13 linear 44.0 67.2 C 2 -methyl 11.9 C 2 -ethyl 3.8 C ₎ 2-propyl C2-butyl and 9 3.1 C _{g of} 2-pentyl 4.4 C 1: . linear 20,9 35,1 C 2 -methyl 2.4 C ₃ 2-ethyl 1.0 C, 2-propyl 0.8 C2-butyl, and pentyl C-2 and C _{g of} 2-hexyl 2.4 Low ethoxylated Dobanol * 23 ex Shell materials (C with 18.1% branching): C 38.4 12 ’ C 58.9 13 ’ C 14 1.2

Low ethoxylated Dobanol * 25 ex Shell materials (C with 22.9% branching):

^C 12

C 31.2

C'29,4

C19,1

Low ethoxylated Dobanol * 45 ex Shell materials (C with 14.8% branching):

C60,3

C73,5

Other ethoxylated non - ionic surfactants

As indicated, any other ethoxylated nonionic long chain surfactants present should not have a mean degree of ethoxylation of less than 7. However, materials with a medium chain length of C or more and a mean degree of ethoxylation of 7 or more may be present.

Thus, materials corresponding to said materials as excluded from this invention, such as coconut Synperonic and Dobanol 23 alcohol ethoxylates but with higher degrees of ethoxylation, may be present in the compositions of the invention, in addition to the low ethoxylated short chain nonionic surfactants which are essential. For example, short chain material can be used in combination with 7EO coconut alcohol.

Most preferably, however, ethoxylated nonionic surfactants of any degree of medium chain length C or more are not present.

The total amount of all nonionic detergent active agents present in the composition of the invention is suitably in the range of from 2 to 50% by weight, preferably from 5 to 30% by weight.

Other detergent active substances

If the nonionic surfactants of the class specifically excluded are absent, other detergent active materials may be present in the compositions of the invention.

Detergent active materials other than nonionic surfactants may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric, or any combination thereof.

The anionic detergent active may be present in an amount of from 0 to 40% by weight, preferably from 0 to 20% by weight. Preferably, the ratio of the nonionic surfactant to the anionic surfactant is in the range of 2: 8 to 9: 1.

Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkyl benzene sulfonates with alkyl chain lengths _{C8-C] 5;} primary and secondary alkyl sulphates, especially sodium C-primary sodium alcohol sulphate, olefin sulphonates; alkanesulfonates; dialkylsulfosuccinates and sulfonates of fatty acid esters.

It may also be desirable to include one or more fatty acid soaps. These are preferably sodium soaps obtained from naturally occurring fatty acids, for example fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil. Amount of surfactant system

The total amount of detergent-active material (surfactant) in the compositions of the invention is suitably from 5 to 50% by weight. Of particular interest are highly effective compositions containing relatively high levels of surfactant, preferably from 15 to 50% by weight.

The compositions may preferably contain at least 20% by weight of the surfactant system, more preferably at least 25% by weight.

Preferred surface active systems

Particularly preferred compositions in accordance with the present invention have a top active system consisting mainly of ethoxylated short chain nonionic surfactants as defined, either in combination with primary alcohol sulfate (PAS) or alone.

The primary alcohol sulphate (PAS), which may optionally be present, preferably constitutes up to 40% by weight of the surfactant system, may have a chain length in the range of C-C, preferably C-C, with a mean value of < _p . Particularly preferred is a PAS consisting wholly or predominantly of C material.

^{r J} 12-14

If desired, mixtures of different chain lengths as described and claimed in EP 342 917A (Unilever) can be used.

Generally, the predominant or totally straight chain PAS is preferred; PAS of plant origin, and more specifically coconut oil PAS (cocoPAS), is particularly preferred. However, it is also within the scope of the invention to use a branched PAS as described and claimed in EP 439 316A.

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

The surfactant system of particular interest consists mainly of

i) from 60 to 100% by weight, preferably from 65 to 100 wt% of ethoxylated nonionic surfactant ii) from 0 to 40% by weight, preferably 0-35% wt primary alcohol sulphate _Cg-C.

Particulate high density bulk detergent compositions containing such surfactant systems are disclosed and claimed in EP 544 492A (Unilever).

According to a first embodiment of the invention, the surfactant system consists essentially of 65 to 80% by weight, preferably 65 to 75% by weight, of ethoxylated nonionic surfactant i) and 20 to 35% by weight, preferably 25 to 35% by weight of primary alcohol sulphate ii). It has been found that in this system the following ethoxylated nonionic surfactants have a particularly good detergency:

(a) the average length of the C ₉ -C alkyl chain and the mean degree of ethoxylation from 2,5 to 4; or

b) an average C 1 -C 6 alkyl chain length and an average degree of ethoxylation of from 4 to 5.

According to a second embodiment of the invention, the surfactant system consists essentially of 80 to 95% by weight, preferably 85 to 95% by weight, of ethoxylated nonionic surfactant i) and 5 to 20% by weight, preferably 5 to 15% by weight, of sulfate at alcohol. The following ethoxylated nonionic surfactants have been found to have particularly good detergency in this system:

(a) an average C - chain alkyl chain length and an average ethoxylation degree of from 3.5 to 4.5; or

(b) an average C-chain alkyl chain length and an average ethoxylation degree of from 4 to 6.5.

According to a third embodiment of the invention, the surfactant system consists essentially of an ethoxylated nonionic surfactant (i) itself. The following ethoxylated nonionic surfactants have been found to provide particularly good detergency in this system:

(a) an average C - alkyl chain length and an average degree of ethoxylation of between 4,5 and 5,5; or

b) the mean length of the C -C alkyl chain and the mean

11.5 ¹ degree of ethoxylation from 4 to 6.5.

However, in all three embodiments of the invention, the use of a short chain nonionic surfactant of up _to 2.5 to 6.5 aethoxylation is preferred.

Detergent components

The detergent powders of the invention comprise one or more detergent ingredients, suitably in an amount of from 5 to 80% by weight, preferably from 20 to 60% by weight.

The invention is particularly applicable to compositions containing alkali metal aluminosilicates as detergent ingredients.

Alkali metal aluminosilicates (preferably sodium) may generally be incorporated in an amount of from 5 to 60% by weight (anhydrous basis) of the composition, preferably from 25 to 55% by weight, and suitably from 25 to 48% by weight in high performance detergent compositions.

The alkali metal aluminosilicates may be either crystalline or amorphous, or mixtures thereof, having the general formula:

0.8-1.5 Na O.A1 O .0.8-6SiO.

2 3 2

These materials contain bound water and have a calcium exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5 to 3.5 SiO units (in the above formula). Both amorphous and crystalline material can be prepared readily by reaction between sodium silicate and sodium aluminate, as is amply described in the literature.

Suitable crystalline sodium aluminosilicates as ion exchange detergent ingredients are described, for example, in GB 1 429 143 (Procter & Gamble). Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X and mixtures thereof.

The zeolite may be a commercially available zeolite 4A, at the same time widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminum zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type with 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 generally at least 150 mg CaO per gram of anhydrous material.

In the compositions of the present invention, the use of zeolite MAP has two particular advantages: it is a more efficient builder than zeolite A, and quite independently, allows the incorporation of higher overall surfactant levels, and surfactant systems richer in nonionic surfactants without losing powder flow.

The use of zeolite MAP as a carrier for liquid detergent ingredients is described and claimed in EP 521 635A (Unilever).

Preferred zeolite MAP for use in the present invention is especially finely divided and has a d _o (as defined) in the range from 0.1 to 5.0 T m, more preferably from 0.4 to 2.0 T m, and most preferably 0, 4 to 2.0 Tm. A value of d indicates that 50% by weight of the particles have a diameter smaller than that indicated and corresponding values of d _go , d ^, etc. exist. Particularly preferred materials have d d below 3 Tm as well as d d below 1 Tm.

Compositions in accordance with the present invention may contain an alkali metal carbonate, preferably sodium, to enhance detergency and facilitate processing. Sodium carbonate may generally be present in an amount ranging from 1 to 60% by weight, preferably from 2 to 40% by weight, and most preferably from 2 to 13% by weight. However, mixtures without alkali metal carbonate are also within the scope of this invention.

Other detergent builders may also be in the compositions of the present invention if desired or desired.

Particularly preferred additional detergent ingredients are polycarboxylate polymers. More particularly, polyacrylates and acrylate / maleate copolymers suitably used in an amount of from 0.5 to 15% by weight, especially from 1 to 10% by weight; and monomeric polycarboxylates, more particularly citric acid and salts thereof, suitably used in amounts of from 3 to 35% by weight, more preferably from 5 to 30% by weight.

Preferred compositions of the invention preferably contain no more than 5% by weight of inorganic phosphate detergent builders and are required to be substantially free of phosphate builders.

Other ingredients

Fully assembled laundry detergent compositions in accordance with the present invention may additionally contain any suitable ingredients normally incorporated in such compositions, for example inorganic salts such as sodium silicate or sodium sulfate; organic salts such as sodium citrate; anti-redeposition agents such as cellulose derivatives and acrylate or acrylate / maleate polymers; fluorescent substances; bleach; bleach precursors and bleach stabilizers; proteolytic and lipolytic enzymes; coloring agents; colored grains; perfumes; suds control agents; fabric softening agents.

Powder processing and properties

The particulate detergent compositions of the invention may in principle be prepared by any available tower (spray-drying), non-tower (granulation) or a combined process.

Of particular importance are compositions with a bulk density of at least 600 g / l, preferably at least 700 g / l, and most preferably 800 g / l, which can be prepared by granulation and / or compaction in a high speed mixer / granulator.

The high-speed mixer / granulator, also known as a high-speed mixer / compactor, can be a metering machine, such as a Fukae (trademark) FS, or a continuous machine, such as the Lodige (trademark) Recycler CB30. Suitable methods are described, for example, in EP 340 013A, EP 367 339A, EP 390 251A, EP 420 417A and EP 506 184A (Unilever).

One suitable method comprises spray-drying a slurry of compatible thermally insensitive ingredients, comprising zeolite and other detergent ingredients, and at least a portion of the detergent active agents; concentrating the resulting base powder in a batch or continuous high speed mixer / granulator; and then spraying or dispensing those ingredients that are unsuitable for slurry processing, such as bleaches and enzymes.

SK 280567 Bt

In another method, the spray-drying step can be omitted completely, the high-density base powder is prepared directly from its raw ingredients by mixing and granulating in a high-speed mixer / granulator and then post-dosing the bleach and other ingredients as in the spray-drying / post- tower thickening.

Generally, inorganic detergent ingredients and other inorganic materials (e.g., zeolite, sodium carbonate) are granulated with surfactants which act as binders and granulating and agglomerating agents. If an anionic surfactant such as PAS is present, mobile surfactant compositions may be suitably used as described in EP 265 203A (Unilever). Any optional components as mentioned above may be incorporated at any suitable stage of the process. In accordance with normal practice in the manufacture of detergent powders, bleach components (bleach, bleach precursor, bleach stabilizer), proteolytic and lipolytic enzymes; coloring agents; colored grains; perfumes; The suds control granules are most preferably admixed (post-dosed) to the densified granule product after leaving the high speed mixer / granulator.

The low-ethoxylated short-chain nonionic surfactants to which this invention pertains will not normally be incorporated in the base powder, but will be admixed, e.g., sprayed, to the finished base powder. Nonionic surfactants with higher ethoxylation can be incorporated in the base powder, post-dosed, or both. Preferably, at least a portion of the highly ethoxylated nonionic surfactant is incorporated in the base powder while either the low ethoxylated surfactant itself or the mixture of high and low ethoxylated nonionic surfactants is post-dosed.

DETAILED DESCRIPTION OF THE INVENTION

The following non-limiting examples illustrate the invention. Examples indicated by numbers are embodiments of the invention, examples given by letters are comparative. Parts and percentages are by weight unless otherwise indicated.

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

cocoPAS

Zeolite 4A

Zeolite MAP

Carbonate Silicate Metaborate Polymer

Perborate mono linear sulphate of primary alcohol C (sodium salt) obtained from coconut oil, ex Philippine Refining Co

Wessalith (Trade Mark) P powder ex Degussa

MAP zeolite prepared by a method similar to that described in Examples 1-3 of EP 384 070A (Unilever); Si: Al ratio is 1.0 to 1.07 sodium carbonate basic sodium silicate sodium borate acrylate / maleate copolymer: Sokalan (trademark) CO5 ex Basf sodium perborate monohydrate

TAED tetraacetylethylenediamine as 83% by weight of the granules

EDTMP ethylenediaminetetramethylenephosphonic acid, calcium salt; Dequest 2041 ex Monsanto (34% active ingredient)

Antifoam antifoam granules according to EP 266 863 (Unilever)

Examples 1 to 6, Comparative Example A

A detergent composition with a surfactant system consisting of 30 parts cocoPAS and 70 parts nonionic surfactant was formulated into the following general formulation:

%

cocoPAS 5.1 6.71 no ionic PAL 11.9 15.66 zc> lit 4A 32.0 42,11 carbonate 10,0 13.16 silicate 0.5 0.66 metaborate 16.5 21.70

76.0 100.00 (P AL - surfactant)

Detergences (removal of radiolabeled triolein contamination from polyester) were compared in a tergotometer using a product concentration of 5 g / l, 24 (French) hard water and a wash temperature of 20 ° C.

The results in Table 1 show that coconut 7EO / 3EO detergency can be comparable or exceeded with short chain material if the ethoxylation graft is appropriately selected. In the PAS / nonionic surfactant system, Dobanol 91-2.5, Dobanol 91-3.75, Lialet 111-4 and Lialet 111-5 gave excellent results.

Table 1

Exp. Non-ion PAL Length of re- String (Medium) EO detergency Dobanol 91-2.5 10.14 2.5 30.0 Dobanol 91-2.5 10.14 3.75 29.4 (35 ep.) Dobanol 91-5 (35 ep.) Dobanol 91-5 10,14 5.0 12.4 Lialet 111-4 11.0 4.0 27.1 Lialet 111-5 11.0 5.0 27.1 Lialet 111-6 11.0 6.0 9.5 coco 7EO (30 die- hunting) coco 3EO (40 die- 12.75 4,5-5 23.3

hunting)

Examples 7 to 12, Comparative Example B

The procedure of Examples 1 to 6 and A was repeated using mixtures whose surfactant systems consisted of 10 parts cocoPAS and 90 parts ethoxylated nonionic surfactant. The results are shown in Table 2. In this PAS / nonionic surfactant system, the best nonionic surfactants were Dobanol 91 3.75, Lialet 111-4 and Lialet 111-5. Dobanol 91-5 and Lialet 111-6 also had acceptable results.

%

cocoPAS 1.70 2.24 Neiónová PAL) 15,30 20.13 Zeolite 4A 32.0 42,11 carbonate 10,0 13.16 silicate 0.5 0.66 metaborate 16.5 21.70 76.0 100.00

Table 2

Exp. Neónová PAL Chain Length (Medium) EO detergency 1 Dobanol 91-2,5 10.14 2.5 11.0 2 Dobanol 91-2,5 10.14 3.75 42.0 3 (45 ep.) Dobanol 91-5 (45 ep.) Dobanol 91-5 10.14 5.0 33.5 4 Lialet 111-4 11.0 4.0 41.7 5 Lialet 111-5 11.0 5.0 37.8 6 Lialet 111-6 11.0 6.0 34.2 B coco 7EO (40 ep.) coco 3EO 12.75 4,5-5 36.1

(50 ep.)

Examples 13 to 18, Comparative Example C

The procedures of Examples 1 to 6 and A were repeated using mixtures with an ethoxylated nonionic surfactant alone. The results are shown in Table 3.

In this totally nonionic surfactant system, the best results were found with Dobanol 91-5 and all three Lialet 111 -y.

Table 3

Exp. Neónová PAL Chain Length (Medium) EO detergency 1 Dobanol 91-2,5 10.14 2.5 1.5 2 Dobanol 91-2,5 10.14 3.75 18.5 3 (50 parts) Dobanol 91-5 (50 ep.) Dobanol 91-5 10.14 5.0 53.3 4 Lialet 111-4 11.0 4.0 51.4 5 Lialet 111-5 11.0 5.0 49.9 6 Lialet 111-6 11.0 6.0 50.8 C coco 7EO (50 pieces) coco 3EO (50 pieces) 12.75 4,5-5 47.6

Example 19, Comparative Example D

The procedure of the previous examples was repeated with compositions comprising a surfactant system consisting of 30 parts cocoPAS and 70 parts ethoxylated nonionic surfactant composed of varying portions of coco 7EO and Dobanol 91-2.5 (providing variable mean EO values) as described in Table 4. Table 4

EO (middle- Detergency)

D

Dobanol 91-2.5 / coco coco 3EO / coco 7EO 7EO

2.5 31.0 - 2.99 - 28.5 3.37 30.4 - 3.96 - 27.3 4.25 25.0 - 4.70 - 23.3 5.12 19.2 - 5.17 - 21.0

5.90 15.7 6.00 12.2 - 6.87 9.2 - 6.88 - 9.9

These results show how Dobanol 91-2.5 can be used to replace coco 3EO in this PAS / nonionic surfactant system.

Example 20, Comparative Example E

The procedure of Examples 19 and D was repeated with compositions comprising a surfactant system consisting of 10 parts cocoPAS and 90 parts ethoxylated nonionic surfactant composed of varying portions of coco 7EO and Dobanol 91-2.5 (providing variable mean EO values) such as listed in Table 5.

Table 5

EO (middle- Detergence No) 209 Dobanol 91-2.5 / coco 7EO E coco 3EO / coco 7EO 2.5 9.6 - 2.99 - 37.2 3.37 36.6 - 4.25 40.5 - 4.70 - 36.1 5.12 38.2 - 5.17 - 35.3 6.87 26.4 - 6.88 - 22.6

These results show how Dobanol 91-2.5 can be used to replace coco3EO in this PAS / nonionic surfactant system.

Examples 21 and 22, Comparative Example F

These examples show how the use of the short chain nonionic surfactant of the present invention improves the dissolution of the particulate detergent composition in the wash liquid.

A basic detergent powder having a bulk density of about 800 g / liter was prepared having the following general composition:

parts by weight

zeolite 51.2 31.8 Sodium citrate 5.3 8.5 Water 9.2 14.8 Neónová PAL 15.8 25.5 62.1 100.0

Powders were prepared by spray-drying a slurry of all ingredients except the nonionic surfactant, which was then blended into the powder, and the fluidized bed was stirred for 10 minutes at 70 ° C; the powders were allowed to stand.

The following nonionic surfactants were used:

SK 280568-6

Exp. NeiónováPAL Chain Length (Medium) EO F Synperonic A7 13.65 7.0 G coco 6.5 EO (Kolb) 12.75 6.5 21 Dobanol 91-6 (Shell) 10.14 6.0 22 Vista 1012-62 (Vista) 10.2 6.25

Taauľka 7

Time (minutes) Quantity of dissolved powder (%) 0.5 1.0 2.0 3.0 H 33.5 61.2 88.1 96.3 23 43.4 73,4 94.3 98.0 24 38.0 65.5 93.6 98.6 25 41.6 69.8 92.5 97.1

Dissolution of the powders was studied in an Miele front loading machine W756. 15 g of powder was placed in the drum of the machine, which was programmed for economical main wash with filling of cold water (10.5 liters of demineralized water, isothermally at 11 ° C).

The percentage of dissolved powder was calculated using the standard conductivity method. This includes measuring the conductivity of the wash liquid at a given time and comparing the values with the values for a liquid containing the same mass of completely dissolved powder of identical composition. The results are shown in Table 6.

Table 6

Quantity of dissolved powder (%)

Time (min- 0.5s) 1.0 2.0 3.0 F 53.8 79.2 91.7 94.9 G 42.5 74.4 91.7 96.7 21 59.9 82.9 94.6 97.3 22 59.1 83.9 94.9 97.8

Examples 23 and 24, Comparative Example H

A similar experiment was performed with the fully assembled detergent powder, in which the base powders similar to those used in experiments 21, 22 and F were mixed.

blended with the other ingredients and provided powders with a bulk density of about 800 g / liter with the following general composition: getting married: % by weight zeolite 31.8 Sodium citrate 5.3 Water 9.2 Neónová PAL 15.8 62.1 carbonate 9.7 Perborate mono 15.0 TAED 7.8 EDTMP 0.4 Anti-foaming granules 2.5 silicate 2.5

100.0

The following nonionic surfactants were used:

Exp. Neónová PAL The length of the string (Medium) EO H Synperonic A7 13.65 7.0 23 Dobanol 91-4 10.14 4.0 24 Dobanol 91-4 (70 ep.) cocoPAS (30 ep.) 10.14 4.0 25 Lialet 111-4 11.0 4.0

Dissolution of powders was assessed by the methodology of Examples 21, 22 and F, except that the sample powder size was 25 g. The results are shown in Table 7.

Example 26 and Comparative Example J

This example demonstrates the advantage of a short-chain nonionic surfactant to improve powder dosing from the front of the automatic washing machine container.

The high bulk density particulate detergent composition (about 800 g / L) was prepared with the general composition used in Examples 23-25. The following surfactants were used:

Exp. Neónová PAL Chain length (middle EO) J Synperonic A7 13.65 7.0 26 Dobanol 91-6 (Shell) 10.14 6.0

A similar experimental measurement to that described in Examples 21 and 22 was performed using the same automatic scrubber, program, and powder samples of 25 g to determine residues in the container. 8 minutes after the end of the water wash cycle, the washing machine was stopped and the remainder of the powder was removed from the drawer, dried and weighed directly.

This procedure was repeated three times for each powder. The mean residue remaining in the reservoir was calculated as a percentage of the original powder weight. The results are shown in Table 8.

Taauľka8

Example Medium residue (% by weight) J 13.6 26 2.8

Example 27, Comparative Example K

This example demonstrates, using three different test methods, the advantage of a short-chain nonionic surfactant to improve powder solubility and reduce particulate residue deposited on the laundry items.

The powders had the general composition indicated. In all cases, the base powder was prepared by in-situ neutralization granulation in a high speed mixer / granulator as described in EP 420 417A and EP 506 184A (Unilever), and then the other ingredients were mixed. The finished powders had a material density in the range of 800 to 900 g / l. All had a fine content (particles less than 180 Tm) below 5% by weight.

% by weight

cocoPAS 5.81 neónová PAL 13.16 soap 2.04 zeolite MAP 36.03 carbonate 0.96 SCMC 0.89 Water 4.98

63.88

silicate 2.90 percarbonate 20.50 Mn catalyst 2.40 TAED 4.75 EDTMP 0.37 enzyme granules 1.75 anti-foaming granules 3.00 perfume 0.45

100.00

The following nonionic surfactants were used:

Example K coco 7EO (44 parts) coco 3EO (56 parts)

Example 27 Certain 1012-62

12.75 7EO

12,75 3ΕΟ

10.2 6.2 EO

(i) Solubility test

Each powder sample was dissolved in water at 20 ° C and stirred for 2 minutes. The liquid was then passed through a 100 Tm fiber filter and the solid residue that did not pass through the filter was dried for 24 hours at 100 ° C and weighed.

The residue (% by weight of ^the vzor____________________________________ yl) ________________ Reference Example A 3.4 Example 27 3.2 ii) Test cage

The dosing characteristics of the powders were compared using a model system that simulated powder dosing in an automatic washing machine under more unfavorable conditions than would normally be included in a real washing situation.

For this test, a cylindrical vessel with a diameter of 4 cm and a height of 7 cm was used, made of a steel screen with a pore size of 600 Tm, with a top cap made of Teflon and a bottom cap made of the described screen.

The top cap had a 30 cm metal wire attached as a hinge, and this hinge was attached to a stirrer arm placed above 1 liter of water at 20 ° C in an open container. Using this agitator, the cylindrical vessel suspended at a 45 ° angle could be rotated in a circle of 10 cm diameter for a period of 2 seconds and left for 2 seconds before the start of the next rotation / rest cycle.

g a sample of powder was placed in a cylindrical container which was then closed. The vessel was attached to a stirrer arm that moved down to a position where the top of the cylinder vessel was just below the surface of the water. After a 10-second pause, the instrument performed 15 rotation / idle cycles.

The cylindrical vessel and hinge were removed from the water and the vessel was detached from the hinge. The surface water was carefully discarded and the powder residue transferred to a preweighed container and dried at 100 ° C for 24 hours. Then the percentage of the starting weight (50 g) was calculated from the weight of the dry residue.

Residue (% by weight of the sample)

Comparative Example K 51.6

Example 27 26.6

It should be emphasized that since the powder is enclosed in a cylindrical vessel during the test, the residue values will be much higher than in the real situation when an open dosing device is used. Nevertheless, the test is suitable for detecting differences in wetting and dosing behavior between different preparations and for controlling this behavior under the worst possible conditions.

iii) Black String Test

This test used the Siemens Siwamat Plus 3700 (brand name) front loading automatic washing machine and the following methodology.

A 100 g dose of powder was placed in a flexible dispensing device of the type supplied with commercially available high bulk density powders such as Lever Persil (Trade Mark) Micro Powder System in the United Kingdom: a spherical container of resilient plastic material approximately 4 cm in diameter and approximately 3 cm.

The metering device was placed inside a black cotton pillowcase with dimensions of 30 cm x 60 cm, taking care to hold it vertically, and the liner was then closed with a zipper. The liner containing the (vertical) dispensing device was placed on top of 3.5 kg of dry laundry in the drum of the washing machine.

The machine operated in a heavily soiled mode at a wash temperature of 60 ° C using 15 French water and an inlet temperature of 20 ° C. At the end of the wash cycle, the liner was removed, opened and inverted, and the level of powder residue on its inner surface was determined by visual evaluation using a score system of 1 to 3: score 3 corresponds to a residue of approximately 75% by weight of powder; A panel of five evaluators assessed each string and assigned a score. With each powder, the wash process was performed ten times and scores were averaged from ten replicates. The scores were as follows:

Example K 1.0 Example 27 0.3

Example 28, Comparative Example L

In this example, the dispersibility of high bulk density powders containing various nonionic surfactants was compared by a test adapted to detect the formation of gel surfactant phases upon wetting the powder.

The powders prepared by the high-speed granulation process as described in Example 27 had the following composition (in% by weight) and a material density above 800 g / liter:

L 28 cocoPAS 9.5 9.5 neónová PAL Lordac 7 21.5 - Dobanol 91-6T - 22.7 soap 3.3 - zeolite MAP (anhydrous) 55.2 57.2 SCMC 1.5 1.2 fluorescent substance - 0.4 Water 9.0 9.0 100.0 100.0

The nonionic surfactants in these powders were as follows:

Chain length (middle-

on the) Example L Lordac 7 12.75 7EO Example 28 Dobanol 10.14 6EO 91-6

SK 280568 Br

The dispersion test was performed as follows: 0.3 g of powder sample was placed in a small spoon and moistened holding the spoon horizontally in 10 ° C water for 1 minute. Then the spoon was removed and the excess water was discarded. The wet powder spoon was then placed horizontally in a 500 ml glass of water at 10 ° C and the stirrer was switched on (magnetic and adjusted to obtain a 25 mm vortex). Turbidity (as an indicator of zeolite dispersion) was measured as a function of time.

The dispersion times for 90% were as follows:

Comparative Example L 6.5 minutes Example 28 1.33 minutes

Example 29, Comparative Example M

The procedure of Examples 28 and L was repeated using two additional base powders with a bulk density above 800 g / l, also prepared by high speed granulation as in the previous example. The compositions (in parts by weight) were as follows:

M 29 cocoPAS 6.51 6.51 neónová PAL Lordac 7 6.48 - Lordac 3 8.19 Lialet 111-7 - 6.48 Lialet 111-3 - 8.19 soap 2.26 2.26 zeolite MAP (hydrated) 41.74 41.74 carbonate 1.11 1.11 SCMC 1.02 1.02

The nonionic surfactants were as follows:

Chain Length (Medium)

Example M Lordac 7 12.75 7EO Lordac 3 12.75 3EO Example 29 Lialet 111-7 11.0 7EO Lialet 111-3 11.0 3EO

The dispersion times for 90% were as follows:

Comparative Example M 4.5 minutes Example 29 1.66 minutes

Examples 30 and 31, Comparative Example N

In this experiment, a comparison was made between the pre-dissolved powder detergent and the same powder when added to the tergotometer as a wet powder. The difference shows a delay or loss of detergent attributable to incomplete dissolution of the powder.

Base powders were prepared by high-speed granulation as in the previous examples and the remaining ingredients were post-dosed. The density of the powder material was above 800 g / l and the compositions (in parts by weight) were as follows:

N 30 31 Base powder cocoPAS 6.51 6.51 - neónová PAL N 30 31 Lordac 7 6.48 - - Lordac 3 8.19 - - Lialet 111-7 - 6.48 Lialet 111-3 - 8.19 - VistaNovel II 1012-52 - - 14.67 m '-' dlo 2.26 2.26 2.26 ze> lú MAP (hydrated) 41.7 41.74 41.74 carbonate 1.11 1.11 1.11 SCMC 1.02 1.02 1.02 Pcst-dosed coated percarbonate 16.85 16.85 16.85 compact silicate (80%) 3.67 3.67 3.67

The nonionic surfactants were as follows:

Chain Length (Medium)

Example N Lordac 7 12.75 7EO Lordac 3 12.75 3EO Example 30 Lialet 111-7 11.0 7EO Lialet 111-3 11.0 3EO Example 31 Vista No commanding II 10.2 4.5E

1012-52 (narrow range)

The tests were performed with a radiolabeled triolole new model of soiling on a polyester fabric at 20 ° C in 500 ml of 24 hard water (calcium hardness only) at a product concentration of 5 g / liter.

For the wet powder test, a powder sample (2.5 g) was placed in a pile of cotton cloth (10 cm x 10 cm), moistened with a little demineralized water and allowed to stand for 2 minutes before adding to the wash water. Washing started immediately. For the pre-dissolved powder test, the powders were completely dissolved in the wash water before the wash.

Detergences were expressed as percent removal of triolein contamination, measured after a wash time of 6, 10 and 20 minutes. The percentage of detergent dosing is defined as follows:

Detergence pre-dissolution

Comparative Example N

C is washing% deter (minutes) detergency of the gene pre-dissolution as a powder of friction

6 16.56 6.82 41.2 10 27.31 12.88 47.2 20 40.96 25.14 61.4 Example 30 Washing time (minutes) pre-dissolution detergent. ... ^,, And as a powder theme ^r % detergent dosing 6 11.07 6.95 62.8 10 18.41 12.99 70.6 20 27.69 24.76 89.4

Example 31

Washing time (minutes) detergency % detergent dosing pre-dissolved as a powder 6 60.50 36.07 59.6 10 70.91 52.30 73.8 20 79,36 68.20 85.9

These results show that nonionic short chain surfactants deliver a higher percentage of maximum detergency. The results also show better detergency due to a narrow range material of short chain Vista material compared to a mixture of two wide range materials.

Claims (17)

A particulate detergent composition having a bulk density of at least 600 g / L and comprising a surfactant system comprising a nonionic surfactant, at least one detergent builder and optionally other detergent ingredients, the composition comprising a nonionic surfactant comprising a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C, characterized in that the nonionic surfactant having a mean chain length of less than C ₁₂ has a medium degree of ethoxylation not exceeding 8 and the surfactant system is free of an ethoxylated medium length alkyl chain nonionic surfactant C or more and with an average degree of ethoxylation of less than 7. Detergent composition according to claim 1, characterized in that the nonionic condensation product has an average alkyl chain length in the range from C to C ₅ and a mean degree of ethoxylation of from 2.5 to 8. The detergent composition of claim 1, wherein the surfactant system is substantially free of an ethoxylated nonionic surfactant having an alkyl chain length of C or more. Detergent composition according to claim 1, characterized in that at least 50% by weight of the alcohol from which the nonionic condensation product is derived has an alkyl chain length below C. The detergent composition of claim 4, wherein at least 75% by weight of the alcohol from which the nonionic condensation product is derived has an alkyl chain length below C. 6. A detergent composition according to claim 1, wherein the nonionic condensation product has an average length of an alkyl chain in the range of C to C. '9 II 7. A detergent composition according to claim 1 wherein the alcohol of the nonionic condensation product has an average alkyl chain length in the range of C to C 10 11,5 8. A detergent composition according to claim 1 wherein the intermediate degree of ethoxylation of the nonionic condensation product is in the range of 2.5 to 6.5. The detergent composition of claim 1, wherein the surfactant system comprises an additional anionic surfactant. The detergent composition of claim 9, wherein the anionic surfactant comprises a primary alcohol sulfate. 11. A detergent composition according to claim 1, wherein the surfactant system consists essentially of: (i) from 60 to 100% by weight of ethoxylated nonionic surfactant; and (ii) from 0 to 40% by weight of primary alcohol sulfate C to C. 8 18 12. A detergent composition as claimed in claim 1 comprising from 15 to 50% by weight of a surfactant system. 13. A detergent composition according to claim 1 comprising from 5 to 80% by weight of the detergent component. A detergent composition according to claim 13, characterized in that it contains from 20 to 60%, based on the anhydrous base, of an alkali metal aluminosilicate as a detergent component. 15. A detergent composition as claimed in claim 13 comprising as an detergent component from 20 to 60%, based on the anhydrous base, an alkali metal aluminosilicate comprising zeolite P having a silicon to aluminum ratio not exceeding 1.33. 16. A detergent composition according to claim 1 having a density of at least 700 g / l. Use of a nonionic surfactant which is a condensation product of ethylene oxide with an aliphatic alcohol with an average alkyl chain length of less than C and an intermediate degree of ethoxylation of not more than 8 to improve detergent dosing of the particulate detergent composition at least 600 g / L.