JPH06100899A - Detergent composition - Google Patents

Abstract

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

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a granular detergent composition having exceptionally good cleaning performance together with high bulk density and excellent powder properties. The composition contains high levels of high performance organic surfactants-the selected ethoxylated alcohol plus an optional small amount of alkyl sulphate-and a zeolite detergent builder, preferably using a high speed mixer / granulator. It is manufactured by an agglomeration process.

[0002]

2. Description of the Prior Art Recently, the tendency of powder detergents is toward an increase in bulk density, for example, above 600 g / l. These high density, or "concentrated" powders have been manufactured by a variety of methods, some of which are post-densif spray dried powders.
ication), and some are based on dry mixing, agglomeration, or other complete non-tower methods.

The move to higher densities, and thus to particles of inherently low porosity, has made compounding high levels of mobile organic components without loss of powder flow properties more difficult. . However, it becomes highly desirable to improve cleaning performance by incorporating higher levels of surfactants and by using surfactants that are believed to have maximum efficacy against oily and greasy soils. Came. Certain such surfactants are
Relatively low degree of ethoxylation (degree of et
ethoxylated alcohols having a hexylation), which are generally mobile liquids at ambient temperature.

With increasing environmental awareness, it has also become desirable to use alkyl sulphates rather than the linear alkyl benzene sulphonates traditionally used in laundry detergents. Alkyl sulphates are readily biodegradable and are obtained from renewable sources such as coconut oil and palm oil. However, they are generally more difficult to process into high quality powder detergents than alkylbenzene sulfonates.

Nonionic surfactants, alkyl sulphates, and mixtures of the two have been found to provide very effective detersive properties, but due to their mobility,
Even at moderate levels, it is difficult to formulate into a free flowing powder that disperses in the wash liquor. When higher proportions of these surfactants are needed to push cleaning performance to higher levels, these difficulties are exacerbated and even exacerbated by the highly concentrated high density powders that have been favored by the consumer and detergent industry in recent years. Is expected to do.

However, the present invention, despite containing relatively high levels of high performance mobile surfactants,
We have successfully formulated high bulk density free-flowing powder detergents that combine good performance with good powder properties and dispersibility. The powders of the present invention contain relatively high levels of zeolite builders and can be produced by the granulation process in a high speed mixer / granulator. Particularly good powder properties are obtained by using the novel zeolite P as a builder, and particularly good detergency is obtained by using the selected nonionic surfactant.

European Patent Application Publication No. 265,203 (U
Nilever) contains 20-80% by weight of alkylbenzenesulfonate or alkylsulfate, 80-20% by weight of ethoxylated nonionic surfactant, and 0-10% by weight of water at 20-80 ° C. Disclosed are surfactant blends that are mobile at temperatures within the range. This surfactant blend is about 25% by weight sprayed onto an absorbent particulate solid material such as spray dried polymer modified Burkeite.
To give a free-flowing powder detergent containing up to a surfactant.

European Patent Application Publication No. 436,240 (U
Nilever) discloses a similar mobile surfactant blend further containing fatty acid soaps. When sprayed onto an absorbent solid material, this blend gives a powder with improved flow and dispersion properties.

British Patent No. 1,462,134 (Pro
Cter & Gamble / Collins) discloses linear or predominantly linear ethoxylated primary alcohols with precisely defined chain length, chain length distribution, ethylene oxide content, ethoxylated distribution, and free alcohol content. .

European Patent Application Publication No. 133,715 (U
nion Carbide) is an alkoxylation having a particularly high peak distribution of the alkoxylated species in which a single major alkoxylated species constitutes 20-40% by weight and the amount of species substantially different from that major species is severely limited. Disclosed are substance mixtures.

European Patent Application Publication No. 384,070 (U
Nilever is a zeolite P with a silicon to aluminum ratio not exceeding 1.33 (zeolite MAP).
Disclosed is the use as a detergent builder. This zeolite has been found to be a more effective and faster calcium ion binder than conventional zeolite 4A.

Filed June 18, 1992, 199
Claim the priority date of June 25, 1 December 12, 1992
Applicant's co-pending European Patent Application Publication No. 92 305,590.9, which will be published in May, is based on zeolite MAP and has high levels of liquid, viscous liquid, oily or waxy components (eg, A free-flowing granular detergent composition is disclosed which contains nonionic surfactants) while exhibiting excellent flow properties.

Example K of that application contains 50% by weight zeolite 4A, 23.4% by weight sodium carbonate, and 2%.
6.6 wt% nonionic surfactant Synperoni
Disclosed is a high bulk density powder consisting of cA3 (a synthetic C _12-15 alcohol with an average degree of ethoxylation of 3). Example 7 also includes 56.6 wt% zeolite MAP, 13.3 wt% sodium carbonate, and 30.1 wt% Synp.
A high bulk density powder consisting of eronic A3 is disclosed. These compositions are not specifically claimed in this application.

Applicant's co-pending UK patent application No. 9125,035.7, filed Nov. 26, 1991, from which the present application claims priority, is alkyl sulphate (20- 80% by weight), an ethoxylated nonionic surfactant (80-20% by weight), and water (0-20% by weight) in the presence of a liquid surfactant composition in a high speed mixer / concentrator in a granular form. Claimed is a method of making a granular detergent composition having a bulk density of at least 650 g / l, comprising treating the starting material.

[0015]

SUMMARY OF THE INVENTION The explicit The present invention has a bulk density of at least 650 g / l, preferably at least 700 g / l, preferably at least 800g / l, (a) ( i) 6. the first C ₈ -C ₁₈ alcohol is a ethoxylated nonionic surfactant having a 5 average degree of ethoxylation not exceeding (60 to 100 wt% of the surfactant system), and (ii) a first C ₈ -C 15-5 consisting essentially of ₁₈ alkyl sulphates (0-40% by weight of surfactant system)
0% by weight surfactant system; (b) 20-60% by weight zeolite; (c) optionally providing a granular detergent composition containing 100% by weight of the total amount of other detergent components. To do.

[0016] DETAILED DESCRIPTION granular detergent composition of the present invention is particularly characterized by high performance organic surfactant system of high-level. At least 15% by weight of the composition is composed of surfactant and may be present in an amount of 50% by weight. The composition preferably contains at least 20% by weight, more preferably at least 25% by weight of a surfactant system.

The surfactant system inherently has a relatively low degree of ethoxylation, and optionally has a small proportion (40% of the surfactant system).
Ethoxylated alcohol with primary alkyl sulphate (not to exceed wt%).

The proportion of primary alkyl sulphate preferably does not exceed 35% by weight (of the surfactant system), more preferably 30% by weight of the surfactant system. The preferred ratio of alkyl sulfate in the surfactant system is 0.1-35.
% By weight, more preferably 5 to 35% by weight, advantageously 1
It is 0 to 30% by weight.

Furthermore, the proportion of alkylsulfates in the surfactant system preferably does not exceed 15% by weight, for example 0.1 to 15% by weight, preferably 0.1 to 10% by weight.

Ethoxylated Alcohol Nonionic Surfactants The ethoxylated alcohol nonionic surfactants used in the detergent compositions of the present invention have a relatively low degree of ethoxylation of no more than 6.5.

If the primary alkyl sulfate is not present,
The average degree of ethoxylation of the nonionic surfactant is preferably at least 4, but lower if the primary alkyl sulphate is present, eg 3-4. Thus, when primary alkyl sulphate is present, the ethoxylated alcohol preferably has an average degree of ethoxylation within the range of 3-6.5.

The preferred range for the average degree of ethoxylation of the nonionic surfactant, whether alkyl sulphate is present or not, is 4-6.5, more preferably 4-.
6, most preferably in the range of 4-5.5.

If the overall degree of ethoxylation meets the above requirements, a mixture of otherwise ethoxylated materials may be used.

The HLB value of the nonionic surfactant preferably does not exceed 11.0, more preferably 10.5. Desirably, the HLB value is in the range of 9.5 to 10.5.

The chain length of ethoxylated alcohols is generally in the range C _{8 to} C ₁₈ , preferably C _{12 to} C ₁₆ ; C
An average chain length of _12-15 is preferred. Particularly preferred are ethoxylated alcohols which consist wholly or mainly of C _12-14 substances.

The ethoxylated alcohol is preferably a primary alcohol, but secondary alcohol ethoxylates are mostly used. The alcohol is preferably wholly or predominantly linear. Suitable alcohols are of plant origin, for example coconut is the most preferred substance. Of the synthetic alcohols, Ziegler alcohols are preferred over oxo-based alcohols.

According to a preferred embodiment of the invention, which provides exceptionally good oily soil detergency, the ethoxylated alcohols (of course always a mixture of species with different numbers of ethylene oxide units) are conventional. Higher single p values than for commercial nonionic surfactants
A "narrow range" with an ethoxylated species distribution that exhibits a relevant value peak.
e) "substances. The content of non-ethoxylated substances is generally low and can be further reduced by so-called" stripping ".

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

These are particularly high-peak mixtures having an average alkoxylation number of at least 4, in which case
At least one alkoxylated species ("major species") comprises about 20-40% by weight of the mixture; above average 3
Or the proportion of species having more alkoxylation units is less than 12% by weight; and species having alkoxylation units greater than 1 and less than 1 respectively, are:
It is present in a weight ratio to the main species of 0.6: 1 to 1: 1. The preferred product mixture contains 80-95% by weight of alkoxylated species having an average number of alkoxylation within ± 2.

However, as used herein,
The term "narrow range" refers to the Union Carbi as described above.
It also covers substances exhibiting peaks that are not high enough to meet the requirements of the claims of the de company application, but practically, for example, the commercially available ICI "Synperoni".
It shows a higher peak than the c "™ ethoxylated alcohol.

Accordingly, this term refers herein to any ethoxylated alcohol product in which the single ethoxylated species comprises 13% or more by weight of the product, preferably 15% or more. Defined as covering. Conventional ethoxylates contain up to about 10% by weight of any ethoxylated species. The main species are
It preferably contains 4 or 5 ethoxylated units.

Preferred for Use in the Compositions of the Invention "
Narrow range "ethoxylated alcohols are either
Having one or more characteristics: at least 20% by weight
Of the ethoxylated alcohols may be composed of a single ethoxylated species; at least one ethoxylated species (hereinafter referred to as the "prevalent species") may comprise 20-40% by weight of the ethoxylated alcohol, and on average The proportion of species having 3 or more ethoxylated units of less than 12% by weight and each having one more or less than average ethoxylated units is 0.6: 1 to 1 relative to the main species. Present in a weight ratio of 1; 80-95% by weight of the ethoxylated alcohol is composed of ethoxylated species having an ethoxylation number on average within ± 2.

An otherwise defined "narrow range" ethoxylate is described in British Patent No. 1,462,132 (Procte).
r & Gamble / Collins). These are substances having an average degree of ethoxylation of 3.5 to 6.5, the amount of substances having an degree of ethoxylation within 2 to 7 EO being at least 63% by weight, the free alcohol being above 5% by weight. Absent. These materials are also suitable for use in the compositions of the present invention.

The table below shows the ethoxylation distributions of some commercially available coco-based ethoxylates: narrow range (NRE7, NRE5 etc.) and broad range (broad-r.
(E7, E3) and the numbers indicate the nominal average degree of ethoxylation in each case.

Using commercially available materials, such as (nominal) 3EO ethoxylates and (nominal) 7EO ethoxylates, in the proper proportions, it is possible to achieve the preferred values of 4-6.5 for the average degree of ethoxylation of the invention. It is within the range.

However, it is particularly preferred to use a single commercial substance, NRE5, NRE4.6 and NRE4.
The substance called 2 is particularly preferred, NRE 4.2 is especially preferred.

According to the invention, it is particularly preferred to use wholly or predominantly linear ethoxylated alcohols which are also "narrow range".

It is also desirable to use "narrow range" ethoxylates with a narrower distribution of chain length than is the case with conventional commercial nonionic surfactants. For example, the aforementioned British Patent No. 1,
No. 462,134 (Procter & Gamble
/ Collins) such that at least 65% by weight of the substance has a chain length within ± 1 carbon atom of the average value.

"Narrow range" ethoxylates are, for example, Vi
sta, Union Carbide, and Hoech
ST is currently marketed in Europe and North America.

[0040]

[Table 1] The primary alcohol sulphate (PAS), which constitutes up to 40% by weight of the primary alkyl sulphate surfactant system and is optionally present, is C ₈ -C ₁₈ ,
Preferably having a chain length ranging from C ₁₂ -C _16, average value is preferably in the range of C _12-15. Especially preferred are PAS consisting wholly or predominantly C ₁₂ -C ₁₄ materials.

If desired, European Patent Application Publication No. 342,
Mixtures of different chain lengths may be used, as described and claimed in No. 917 (Unilever).

As with the ethoxylated alcohols,
Predominantly or completely linear substances are preferred. PA of plant origin
Particularly preferred is S, especially PAS obtained from coconut oil (coco PAS). However, European Patent Application Publication No. 43
It is also within the scope of this invention to use a branched PAS as described and claimed in 9,316 (Unilever).

PAS is present in the form of its sodium or potassium salt, with the sodium salt generally being preferred.

Zeolite Detergent Builder The amount of zeolite builder in the composition of the present invention is from 20 to 20.
60% by weight, usually 25 to 55% by weight, preferably in the range of 25 to 48% by weight in heavy duty detergent compositions.

Depending on the amount and composition of the surfactant system, the zeolite may be the commercially available zeolite 4A currently widely used in laundry powder detergents. For example, the use of Zeolite 4A may result in 30% PAS and 70%
In the presence of 17% by weight of a surfactant, which consists of the nonionic surfactants mentioned above, powders with satisfactory flow properties can be produced.

However, the total amount of surfactant added and / or
Or, as the proportion of nonionic surfactants increases, it becomes increasingly difficult to obtain acceptable powder flow properties. According to a preferred embodiment of the present invention, the zeolite builders incorporated into the composition of the present invention are European Patent Application Publication No. 38
No. 4,070 (Universe Case T304
Zeolite M as described and claimed in 7)
AP. The zeolite MAP has a silicon to aluminum ratio not exceeding 1.33, preferably 0.90 to 1.
33, more preferably 0.90 to 1.20
Is defined as zeolite P-type alkali metal aluminosilicate.

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 / g anhydrous material.

In the present invention, the use of zeolite MAP has nothing to do with its greater binding efficiency,
Has another advantage. It allows the use of higher total surfactant levels and the use of more nonionic surfactant systems without losing powder flow properties.

The preferred zeolite MAPs for use in the present invention are especially finely ground to 0.1-5.0μ, more preferably 0.4-2.0μ, most preferably 0.4-.
Having a d ₅₀ (defined below) in the range of 1.0 μ. The amount "d ₅₀ " indicates that 50% by weight of the particles have a diameter smaller than that number, correspondingly there are "d ₈₀ ", "d ₉₀ ", etc. Particularly preferred substances are d
₉₀ is less than 3μ and d ₅₀ is less than 1μ.

Sodium Carbonate The compositions of the present invention may contain sodium carbonate to increase detergency and to facilitate processing. Sodium carbonate may generally be present in an amount in the range 1 to 60% by weight, preferably 2 to 40% by weight and most preferably 2 to 13% by weight.

Any powder structuring agent (powder st)
powder ) is a small amount of powder structuring agents such as fatty acids (or fatty acid soaps), sugars, acrylates or acrylates /
It is improved by the addition of maleate polymer or sodium silicate.

A preferred powder structuring agent is a fatty acid soap which is suitably present in an amount of 1-5% by weight. It is preferably formulated as the free acid and neutralized in situ, as discussed below in the Processing section.

Powder Flow Properties The compositions of the present invention are characterized by excellent flow properties despite a high content of mobile high performance organic surfactants.

For purposes of this invention, powder flowability is defined by the dynamic flow rate (ml / s) measured by the following procedure. The device used is an inner diameter of 35 mm and a length of 600.
mm cylindrical glass tube. The tube is clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by a smooth cone of polyvinyl chloride having a 15 ° interior angle and a 225 mm diameter low exit orifice. The primary beam sensor is located 150mm above the exit and the secondary beam sensor is 250m above the primary sensor.
Located on m.

In order to measure the dynamic flow rate of the powder sample, the outlet orifice is covered, for example with a piece of card, temporarily closed and the powder is funneled into the top of the cylinder until the powder level is about 10 cm above the upper sensor. The spacer between the funnel and the tube ensures that the filling is uniform. The outlet is then opened and the time t (sec) required for the powder level to drop from the upper sensor to the lower sensor is measured electronically. The measurement is usually repeated 2 or 3 times and averaged. V is the volume of the tube between the upper and lower sensors (ml)
Then, the dynamic flow rate DFR (ml / s) is given by the following equation:

[0056]

[Equation 1] The average value is calculated and calculated by electronic control, and the DFR value is directly read.

The compositions and ingredients of the present invention are generally at least 90 ml / s, preferably at least 100 ml / s.
with a dynamic flow rate of s.

Other Optional Ingredients The fully formulated laundry detergent composition of the present invention further comprises any suitable ingredient normally included, eg, an inorganic salt such as sodium silicate or sodium sulfate; sodium citrate. Organic salts such as; cellulose derivatives, and anti-redeposition agents such as acrylates or acrylate / maleate polymers; fluorescent agents; bleaches, bleach precursors and bleach stabilizers; proteolytic and lipolytic enzymes; dyes; coloring. Spots;
Fragrances; suds suppressors; fiber softening compounds may be included.

Preparation of Detergent Compositions The compositions of the present invention are advantageously prepared by granulating the zeolite and surfactant in a high speed mixer / granulator. If the surfactant system contains PAS, it can be in salt form (generally as an aqueous paste) or free acid (i.
for neutralization in situ).

A particularly preferred method involves the following steps: (i) producing the surfactant system in the form of a homogeneous mobile liquid blend, and (ii) rapidly mobilizing the surfactant blend. Coagulating with zeolites and other solids present in the mixer / granulator.

In the absence of PAS, the surfactant system is simply an ethoxylated alcohol (mixture) already in the form of a homogeneous mobile liquid blend.

If PAS is to be present, the homogeneous mobile liquid blend is prepared by mixing the PAS paste with a nonionic surfactant. Alternatively, the nonionic surfactant is
For example, filed on March 31, 1992,
European Patent Application Publication No. 507,40 published on 7th October
As described and claimed in U.S. Pat. No. 2 (Unilever), PA in alkali, for example, in a loop reactor.
Mixing may be done while neutralizing the S acid.

High Speed Mixer / Densifier
high speed mixer / granulator known as
Batch machines such as ae ™ FS, or Lodi
It is a continuous machine such as the ge ™ Recycler CB30.

The present method was filed on November 26, 1991, from which Applicant claims priority, the applicant's co-pending UK patent application No. 91 25035.7 (Un).
further) and claimed.

The present process provides for the incorporation of high levels of surfactants without loss of powder flow properties, especially when the zeolite component of the composition is zeolite MAP and / or when soap is present as a structurant. to enable.

If a soap is included as a structuring agent, it is preferably a mobile interface (along with a suitable amount of alkali) as such or as a corresponding fatty acid, for neutralization in situ. It is incorporated into the activator blend.

Any of the other optional ingredients listed above may be incorporated at any suitable stage of the process. Bleaching ingredients (bleaching agents, bleaching agent precursors, and bleaching stabilizers), proteolytic and lipolytic enzymes, colored spots, fragrances, and suds suppressor granules are high density granular products according to general powder detergent manufacturing standards. Are most preferably mixed (or post-added) with the high density granular product after being charged into a high speed mixer / granulator.

Of course, the compositions of the present invention may be prepared by other methods including spray drying or the non-tower process, or a combination of the two.

[0069]

The present invention is further illustrated by the following examples, which do not limit the present invention. Parts and percentages are by weight unless otherwise noted.

The abbreviations used in the examples refer to the following substances: Coco PAS--A straight chain C _12-14 primary alcohol sulfate (sodium salt) derived from coconut oil (Philippi).
ne Refining Co. Manufactured); E7 (s)-C _13-15 oxo alcohol 7EO,
Not "narrow range": Synperonic (TM) A7
(Manufactured by ICI); E3 (s)-C _13-15 oxo alcohol 3EO,
Not "narrow range": Synperonic (TM) A7
(ICI Ltd.); E7-- coconut alcohol 7EO, not "narrow range"; E3-- coconut alcohol 3EO, not "narrow range"; NRE7 (s) - C 12-14 Ziegler linear "narrow range" alcohol 7EO : Alfonic (trademark) 7
(Manufactured by Vista); NRE3 (s) - C 12-14 Ziegler linear "narrow range" alcohol 3EO: Alfonic (R) 3
(Manufactured by Vista); NRE7-coconut alcohol 7EO, "narrow range"; NRE5--coconut alcohol 5EO, "narrow range"; NRE4.6-coconut alcohol 4.6EO,
"Narrow range"; NRE4.2-coconut alcohol 4.2EO,
"Narrow range"; NRE3--Cocoalcohol 3EO, "Narrow range"; Zeolite 4A--Wessalith (TM) P powder (from Degussa); Zeolite MAP--European Patent Application Publication No. 384,07.
Zeolite MA prepared by a method similar to that described in Examples 1-3 of Univer.
P; Si: Al ratio 1.07; Polymer--acrylic acid / maleic acid copolymer: So
kalan (trademark) CP5 (manufactured by BASF); LAS --- linear alkylbenzene sulfonate, sodium salt; perborate mono-sodium perborate monohydrate; TAED--tetraacetylethylenediamine, 83% by weight granules As; EDTMP-ethylenediaminetetramethylenephosphonic acid, calcium salt: Dequest (trademark) 2041 or 2047 (Mon)
Santo) (34% by weight active substance); Antifoam-European Patent No. 266 863B (Unil.
Ever) antifoam granules.

Examples 1-10 Detergency Examples 1-4 Detergent compositions were prepared for the following general formulations:

[0072]

[Table 2] The surfactant system was prepared as follows (wt%):

[0073]

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

The major ethoxylated species in the NRE mixture (4
The percentage of EO) was estimated to be 14% by weight.

Detergency (removal of radiolabeled triolein stain from polyester), 5 g / l product concentration, 24 °
(France) Hard water and water temperature 23 ° C, terg
It was compared with an otometer. The results are shown below:

[0076]

Table 4 Example Triolein Removal (%) 1 42.2 2 47.4 3 59.8 4 61.6 Comparison of results for Comparative Example A, Example 1 and Example 3 lost PAS. We show how increasing the proportion of nonionic surfactants increases detergency. Examples 1 and 2
A comparison of the results for, and for Examples 3 and 4 shows the detergency effect obtained by changing to a "narrow range" ethoxylated alcohol. The significantly better results for Example 4 show the advantage of combining these two measurements.

Examples 5-7 In addition, detergency comparisons were carried out with test cloths having a number of different stains. In this experiment, 5g / l product concentration, 2
Performed in a Miele ™ computer controlled washing machine using 6 ° (France) hard water and a 30 minute wash at a water temperature of 20 ° C.

The composition had the following general formulation:

[0079]

[Table 5] The surfactant system was prepared as follows (wt%):

[0080]

[Table 6] The results (expressed as reflectance change at 460 nm) are shown below: Test Cloth 1 : Kaolin and wool fat on polyester / cotton (WFK 10C).

[0081]

Table 7 Reflectance Change (δR ₄₆₀ ) Example 5 10.9 Example 6 11.8 Example 7 12.4 Test Cloth 2 : Kaolin and Wool Fat on Polyester (WFK 30C)

[0082]

[Table 8] Change in reflectance (δR ₄₆₀ ) Example 5 21.4 Example 6 24.5 Example 7 27.5 Test cloth 3 : Kaolin and sebum on cotton (WFK 10)
D)

[0083]

Table 9: Change in reflectance (δR ₄₆₀ ) Example 5 16.5 Example 6 17.4 Example 7 18.8 Test cloth 4 : Kaolin and sebum on polyester (WFK)
30D)

[0084]

Table 10: Change in reflectance (δR ₄₆₀ ) Example 5 18.7 Example 6 21.5 Example 7 25.1 Example 8 Same as in Examples 1 to 4, the same tergotom.
The eter method was used to compare the detergency of various surfactant mixtures containing different ethoxylated coconut alcohols.

In each case, the composition was the same as that shown in Example 1 and the surfactant system was 30% by weight Coco P.
It consisted of AS, and 70% by weight ethoxylated alcohol. The following: (i) by mixing E7 and E3 (wide range) in various ratios, or (ii) by mixing NRE7 and NRE3 (narrow range) in various ratios, or (iii)
By a method using a single narrow range ethoxylate,
An ethoxylated alcohol component was prepared.

The true degree of ethoxylation can be ascertained from the tables hereinabove.

The detergency (removal of radiolabeled triolein from polyester (%)) is shown in the table below as a function of degree of ethoxylation and starting ethoxylated alcohol.

[0088]

[Table 11] These results show the advantage of an average degree of ethoxylation of 6 or less; the improvement obtained by migrating to narrow range ethoxylates; and the special advantage of using a single narrow range material, especially NRE 4.2. Show.

[0089] The surfactant system rich in nonionic from Example 9 (10 wt% coco P
The procedure of Example 8 was repeated with a series of compositions having AS and 90 wt% ethoxylated alcohol). The results are shown in the table below.

[0090]

[Table 12] Again, the advantages of narrow range ethoxylates, especially single substances, are clear.

Example 10 The procedure of Examples 8 and 9 was repeated with a series of compositions in which the surfactant system consisted entirely of ethoxylated nonionic surfactant.

The results are shown in the table below.

[0093]

[Table 13] These results show a pattern similar to that shown by the results of Examples 8 and 9, clearly showing a substantial reduction in detergency at an average degree of ethoxylation of 4 or less in the absence of PAS. .

Examples 11-32-Powder Properties Examples 11 and 12, Comparative Example A Surfactant System, Zeolites, and (in some cases)
Fukae FS100 batch high speed mixer / high bulk density detergent base powder consisting of sodium carbonate
Produced by the agglomeration method in a granulator. These powders are not intended as fully formulated detergent compositions, but by admixing (or post-adding) other ingredients such as bleaching ingredients, enzymes, foam control granules, and perfumes,
It is easily converted into such a composition.

The surfactant system was as follows:

[0096]

Table 14 30 wt% Coco PAS 30 wt% E7 (s) 40 wt% E3 (s) The compositions (parts by weight and percentage) are shown below.

[0097]

[Table 15] A homogeneous liquid blend of surfactants was prepared by neutralizing PAS acid with sodium hydroxide solution in a loop reactor in the presence of nonionic surfactant. Zeolite, and sodium carbonate (if present) were added into the Fukae mixer and the liquid surfactant blend was added to granulate the mixture. The granular product was then dried using a fluid bed.

In the case of Comparative Example A, it was demonstrated that no granular product was obtained. The mixture formed a solid mass.
With the addition of 10 parts of sodium carbonate (Example 11),
A granular material is prepared. Zeolite MAP (Example 1
2) was used at a slightly lower level to formulate the same amount (in parts-adding one virtually a slightly higher percentage) of the surfactant system, without the need to use sodium carbonate, to provide free flowing A granular material was obtained.

Comparative Examples B-E Another attempt to prepare a base powder containing Zeolite 4A using different amounts of surfactant (same system as Examples A, 11 and 12) and carbonate was successful. I didn't.

[0100]

[Table 16] Composition B produced a solid mass, while Compositions C, D, and E initially produced a free flowing powder, however their flowability was lost upon drying.

Examples 12 to 15 Experiments similar to Comparative Examples B to E, but with zeolite MAP, produced powders with good flow properties, even at substantially high surfactant contents. The composition and powder properties are shown below.

[0102]

[Table 17] Examples 16 and 17 Compositions similar to Comparative Examples BE were prepared, but with fatty acid soaps present.

The method of making these powders was slightly different from the previous examples. The sodium salt form of PAS (7
0% by weight), fatty acids, sodium hydroxide solution sufficient to neutralize the fatty acids, and a nonionic surfactant were mixed to produce a homogeneous mobile blend. The components were placed in a Fukae mixer in the order zeolite, carbonate, surfactant blend, granulated / densified as in the previous examples, and finally the product was dried using a fluid bed.

A powder with excellent flow properties was obtained.

[0105]

[Table 18] In these examples, when compared to Comparative Examples C-F, the inclusion of fatty acid soaps produced good high density powders from formulations that could not be processed without it.

Examples 18 and 19 A composition similar to Examples 16 and 17 was prepared by the same method, but with zeolite MAP instead of zeolite 4A.
Was manufactured using.

[0107]

[Table 19] When these examples were compared with Examples 12-15, the soap inclusion improved the flowability, but the zeolite MAP
It has been shown that it is not essential to obtain an acceptable powder with.

Detergent-based powders as described in Examples 20 and 21, Comparative Examples F and G in general Examples 11, 12 and A were prepared using different surfactant systems:

[0109]

Table 20 10 wt% Coco PAS 40 wt% E7 (s) 50 wt% E3 (s) A surfactant system was prepared as a homogeneous mobility blend by the method described in Examples 11, 12 and A. , And other steps were performed in the same manner as in those examples.

[0110]

[Table 21] In the case of Comparative Examples F and G, it was proved that the production of particulate matter was not possible. That is, both mixtures produced a solid mass. Addition of 25 parts of sodium carbonate to the zeolite 4A base composition (Example 20) was necessary to obtain a particulate material. With zeolite MAP (Example 21), only 15 parts of sodium carbonate were required.

Compositions similar to Examples 22 and 23, Comparative Example H Examples 18 and 19 were made, but containing high levels of zeolite.

[0112]

[Table 22] Composition H gave no particulate matter. At this time, 10 parts of sodium carbonate were required to produce a processable formulation. However, when zeolite MAP was used at this level, no carbonate was required despite the high% level of surfactant in the composition (Example 23).

Example 24, Comparative Examples J and K Zeolite-based formulations were prepared with and without soap using the surfactant system of Examples 20-23. The fatty acid soap was blended into the surfactant blend (prepared as in Example 11) by mixing the fatty acid and an equal amount of sodium hydroxide solution prior to placing the surfactant blend in the Fukae mixer.

[0114]

[Table 23] Composition J gave a non-flowing product before and after drying, whereas composition K initially gave a good flowable product, but lost its flowability on drying. A large amount of soap (Example 24) has a bulk density of 920 g / l and 109 ml / s.
It gave an excellent powder with a dynamic flow rate of.

Examples 25 and 26 Compositions similar to Examples 24 and J, but containing zeolite MAP and high levels of surfactant were prepared.

[0116]

[Table 24] Example 27, Comparative Example L Similar compositions to Examples J and K were prepared using different surfactant systems:

[0117]

[Table 25] 40 wt% E7 (s) 60 wt% E3 (s)

[0118]

[Table 26] Composition L initially gave a good product, but lost its flowability when dried. With soap (Example 27), a bulk density of 801 g / l and 139 ml / s
An excellent powder was produced with a dynamic flow rate of.

Examples 28 and 29 Substituting Zeolite MAP for Zeolite 4A,
Examples L and 27 were repeated.

[0120]

[Table 27] No soap formulation was required to obtain good powder properties when using this composition, but vice versa, no benefit was observed.

Example 30 A composition similar to Example 24 but containing a different nonionic surfactant (NRE5) was prepared. All solid components had a particle size of less than 200μ.

The manufacturing method was almost the same as in Example 11. The average residence time of the granular detergent composition in the batch high speed mixer / granulator was about 3 minutes.

[0123]

[Table 28] The resulting granular detergent composition had a bulk density of about 770 g / l and a dynamic flow rate of 101 ml / s.

Examples 31 and 32 A granular detergent composition similar to Example 30 was applied to a continuous high speed mixer / granulator Lodige ™ Recycler.
It was manufactured using CB30.

The liquid surfactant mixture contained fatty acids with a stoichiometric amount of sodium hydroxide, which formed soap during the mixing and thickening process.

The rotation speed is 1600 rpm, and
The average residence time of the granular mixture in the Recycler is about 1
It was 0 seconds.

The composition of the particulate material contained in the Recycler is shown below.

[0128]

[Table 29] Bulk density is about 700 g / l, particle size is 500-60
It was 0 μ, and the powder characteristics were good.

Examples 33-35, Comparative Example M Detergent powders of complete formulation were prepared for the following formulations.

[0130]

[Table 30] Comparative Composition M is a high performance concentrated powder based on a different surfactant system similar to that used for the higher grade powders currently sold in Europe.

[0131]

[Table 31] The total amount of (non-soap) surfactant in each formulation was 17% by weight.

All the base powders are the above-mentioned Fukae
Made in a FS100 batch high speed mixer / granulator.

Composition M was prepared as follows. Zeolites and carbonates (including additional amount for neutralizing LAS acid)
Was placed in a Fukae mixer, followed by LAS acid, followed by homogeneous surfactant blend (nonionic surfactant), fatty acid, and equal amount of sodium hydroxide solution. After granulation, the powder was dried using a fluid bed and the remaining ingredients post-added.

Compositions 33 and 34 were prepared as follows. PAS paste (70%), nonionic surfactant,
Mix the fatty acid and an equal amount of sodium hydroxide solution,
A homogeneous surfactant blend was prepared. The zeolite and carbonate were placed in a Fukae mixer followed by the surfactant blend. After granulation, the powder was dried using a fluid bed and the remaining ingredients post-added.

Composition 35 was prepared similarly except that no carbonate was present during granulation.

[0136]

[Table 32] Detergency Results Miele the soiled laundry using a product concentration of 5 g / l, 26 ° (France) hard water, and a washing temperature of 30 ° C.
It was put in a washing machine and the detergency was evaluated. The measure of detergency is
It was a change in reflectance (460 nm) of the polyester test cloth stained with kaolin and sebum (WFK 30D).

[0137]

[Table 33] δR ₄₆₀ 16.2 15.01
5.7 17.2 Examples 36-38 Another detergent powder formulation containing zeolite MAP and coco nonionic surfactant is shown below.

[0138]

[Table 34] Similar compositions were prepared with the same proportions of a wide range of materials, E7 and E3.
Instead of or as a single substance NRE5, NRE4.6
Alternatively, instead of using one of NRE4.2, it may be formulated containing narrow range coco nonionic surfactants NRE7 and NRE3.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Andrew Paul Chatzpur United Kingdom, El El 11.5 El P, Cruid, Wrexham, Frith, Barry Road, Corina (no address) (72 ) Inventor William Derek Emery United Kingdom, El 62.6 B.P., Merseyside, Willal, Broumbala, Primyard Avenyu, 64, West Garth (72) Inventor Huaygue Eosel The Netherlands, 3135 Hähway Fuller Ruderingen, Sportlane 76 (72) Inventor Michael Hull United Kingdom, Davry A 6.9 Pies, Cheshire, Bahia Wolinton, Helsby, Albanli -Road, Windcliff (no street number) (72) Inventor Christoph Zioye Youu The Netherlands, 3063 Dese Rottter Dam, Oastmarslan 286 (72) Inventor Peter Collie Knight, El, England 64.6 Kyuess, Chessier, South Wilal, Neston, Moorside Avenyu, 71 (72) Inventor Petrus Leonardos Ye Swinkels, The Netherlands, 6367 S. Behlendar, Har・ Juan Huel Dekestraat ・ 8

Claims (12)

[Claims] 1. A granular detergent composition having a bulk density of at least 650 g / l, is the first C ₈ -C ₁₈ alcohol having an average degree of ethoxylation not exceeding 6.5 (a) (i) ethoxylated nonionic surfactant (60-100 wt% of the surfactant system), and (ii) essentially from the first C ₈ -C ₁₈ alkyl sulfate (0-40% by weight of the surfactant system) 15 to 5
0% by weight of a surfactant system; (b) 20 to 60% by weight of zeolite; (c) optionally a total of 100% by weight of other detergent components. 2. A granular detergent composition according to claim 1, wherein the surfactant system (a) contains 0.1 to 35% by weight of alkylsulfate (ii). 3. The granular detergent composition according to claim 1, wherein the surfactant system comprises an alkylsulfate (ii) and the ethoxylated alcohol (i) has an average degree of ethoxylation of 3 to 6.5. 4. The surfactant system does not contain alkylsulfate (ii) and the ethoxylated alcohol (i) is 4 to 6.5.
A granular detergent composition according to claim 1 having an average degree of ethoxylation of. 5. The granular detergent composition according to claim 1, wherein at least 13% by weight of the ethoxylated alcohol is composed of a single ethoxylated species. 6. A granular detergent composition according to claim 5, wherein the single ethoxylated species contains 4 or 5 ethoxylated units per mole of alcohol. 7. The ethoxylated nonionic surfactant is 4 to 4.
A granular detergent composition according to claim 1 consisting of a single material having an average degree of ethoxylation within the range of 5. 8. The zeolite P is zeolite P having a silicon to aluminum ratio not exceeding 1.33.
The granular detergent composition described. 9. The granular detergent composition according to claim 1, which contains 1 to 5% by weight of a fatty acid soap as a powder structuring agent. 10. A high speed mixer / mixing of zeolite, ethoxylated alcohol, primary alkyl sulphate in acid or salt form (if present), and optionally other miscible components.
A method comprising mixing and granulating in a granulator.
A method for producing the granular detergent composition described. 11. A process for producing a surfactant system in the form of (i) a homogeneous liquid blend, and (ii) the homogeneous liquid surfactant blend with zeolite and other solids present in a high speed mixer / granulator. The method of claim 10 including the step of aggregating together. 12. The method of claim 11, wherein the homogeneous liquid surfactant blend further comprises fatty acids and alkalis, or fatty acid soaps.