CZ53097A3 - Loose washing agent and process for preparing thereof - Google Patents

Abstract

A particulate detergent composition containing more than 5 wt.% of C8-20 primary alcohol sulphate and/or at least 8 wt.% of an ethoxylated C8-20 alcohol nonionic surfactant and/or more than 15 wt.% of total non-soap organic surfactant, and a builder system containing alkali metal aluminosilicate, also comprises from 0.01 to 5 wt.% of an antioxidant, preferably a sterically hindered phenol, more preferably butylated hydroxytoluene or butylated hydroxyanisole. The composition exhibits improved stability of the surfactant system on bulk storage and handling.

Description

(57)

A free-flowing detergent composition containing more than 5 wt.% Ce-20 primary alcohol sulfate and / or at least 8 wt. % nonionic surfactant of ethoxylated C 6-20 alcohol, and / or more than 15 wt. and a detergency builder system comprising an alkali metal aluminosilicate, as well as from 0.01 to 5% by weight of an antioxidant, preferably sterile hindered phenol, and more preferably butylated hydroxy toluene or butylated hydroxyanisole.

Technical field

The present invention relates to particulate (bulk) detergent compositions containing high levels of high activity organic surfactants. In particular, it relates to compositions comprising a primary alcohol sulfate (PAS) or nonionic ethoxylated alcohol surfactant, or both. The compositions exhibit improved stability, which is attributable to the presence of low levels of antioxidants.

BACKGROUND OF THE INVENTION

EP 283 252B and EP 320 219B (Procter and Gamble) disclose free flowing detergent compositions having an antioxidant incorporated into bleach activator granules to improve its stability.

Various free-flowing detergents containing antioxidants are also disclosed in JP 50 066 502A / JP 77 003 730B, JP 50 151 905A / JP 78 028 163B, JP 57 128 798A / JP 84012720B (Lion) and JP 73 008 324B ( Daiichi Kogyo Seijaku KK). The benefit is reduced abrasion and discoloration during storage.

It has now been found that for free-flowing detergents containing high levels of surfactant and highly active surfactant, especially those containing primary alcohol sulfate and / or ethoxylated nonionic surfactant, improved stability of the surfactant system can be achieved by incorporating antioxidants especially sterically blocked phenols. The safety margin thus achieved facilitates factory handling and bulk storage of these highly active products, thus providing increased manufacturing flexibility.

SUMMARY OF THE INVENTION

The present invention provides a free-flowing detergent composition comprising (i) an organic surfactant system comprising anionic and / or nonionic non-soap surfactants, wherein the composition comprises more than about 5% C _{8 by} weight. ₂₀ primary alcohol sulphate and / or at least 8 wt. % of non - ionic C ₈ ethoxylated surfactant. ₂₀ alcohol and / or more than 15 wt. (ii) an alkali metal aluminosilicate builder system (iii) 0.01-5% by weight antioxidant, (iv) optionally other detergent ingredients to 100 wt. %, all percentages being based on the total composition.

Surfactant system

The composition according to the invention comprises a high amount of a non-soap organic surfactant, preferably 15 wt. % or more, preferably 15 to 25 wt. %. However, as shown below, some formulations whose total surfactant level does not reach 15 wt. % are also within the scope of the invention.

The surfactants may be selected from anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtures thereof. Many suitable detergent-active compounds are available and are also fully described in the literature, e.g., in the book Surface-Active Agents and Detergents, Parts I and II, by Schwartz, Perry and Berch.

Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates an alkyl chain length of C ₃ -C _1S; primary and secondary alkyl sulfates, especially C ₈ -C ₁₈ primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkylxylene sulfonates; dialkylsulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred.

Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially _C, -C ₂₀ aliphatic alcohols ethoxylated with an average of 1-20 moles of ethylene oxide per mole of alcohol, and in particular a C _1O -C _1S primary and secondary aliphatic alcohols ethoxylated on average 1 to 10 moles of ethyl oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, lactobionamides and polyhydroxyamides (glucamide).

The invention is particularly applicable to compositions comprising a surfactant system comprising a C ₈ -C ₂₀ primary alcohol sulfate, a nonionic surfactant of an ethoxylated C ₁ -C ₂₀ alcohol, or both. Preferred compositions of the invention contain more than 5% by weight C ₈ -C ₂₀ primary alcohol and / or at least 8 wt. % and preferably at least 10 wt. % nonionic surfactant of ethoxylated C ₈ -C ₂₀ alcohol. If one or both of these conditions are met, the total level of the soapless organic need not be

4 surfactants in the compositions of the invention greater than 15 wt. %, but is preferably at least 10 wt. % and more preferably at least 12 wt. %.

One class of preferred compositions of the invention comprises compositions comprising more than 5 wt. %, based on the total product, of the C ₃ -C ₂₀ primary alcohol sulfate, optionally in combination with the nonionic surfactant of the ethoxylated C _and -C ₂₀ alcohol.

Preferred compositions may comprise at least 8 wt. %, and preferably at least 10 wt. % of the ethoxylated nonionic surfactant and the ratio of primary alcohol sulfate to ethoxylated nonionic sulfate may preferably be less than 1: 1. However, it is within the scope of the invention to include compositions containing minor proportions of nonionic surfactant, for example those containing additional anionic surfactants.

Another class of preferred compositions according to the invention also comprises at least 8 wt. % and more preferably at least 10 wt. % of the ethoxylated nonionic surfactant are those whose non-soap surfactant system consists wholly or essentially of nonionic surfactants.

The compositions of the invention may also contain a fatty acid soap. However, when a limit of at least 15% by weight of the total surfactant is applied, it does not include any fatty acid soap.

Detector builder system

The compositions of the invention comprise as detergency builder an alkali metal aluminosilicate, either alone or in conjunction with one or more additional builders.

The total amount of detergency builder in the compositions may suitably range from 5 to 80 wt. %, preferably from 10 to 60 wt. %.

An essential component of the composition of the invention is an aluminosilicate builder of an alkali metal, preferably sodium. Sodium aluminosilicates may generally be incorporated in an amount of from 10 to 70% by weight (on an anhydrous basis) and more preferably from 25 to 50% by weight. %.

The alkali metal aluminosilicate may be crystalline or amorphous or a mixture of both forms, and its general formula is

0.8-1.5 Na ₂ O. AI ₂ O ₃ . 0.8-6 SiO ₂

These substances contain a small proportion of bound water and require a calcium ion exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO ₂ units (in the above formula). Both amorphous and crystalline materials can be readily prepared by the reaction of sodium silicate and sodium aluminate, richly described in the literature.

Suitable crystalline aluminosilicate ion exchange detergency builders are described, for example, in GB 1 429 143 (Procter and 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, which is now widely used in laundry detergents. However, according to a preferred embodiment of the invention, the zeolite builder is incorporated into the compositions

6 according to the invention, the largest measure of 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 having a silicon to aluminum ratio of at most 1.33, preferably in the range of 0.90 to 1.33, and even more preferably in the range of 0.90 to 1.20.

Particularly preferred is zeolite MAP whose silicon to aluminum ratio does not exceed 1.07 and more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per gram of anhydrous material.

The zeolite is preferably used in conjunction with an additional builder. Additional organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic-maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, glycerol tri- and glycerol trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and salts of sulfonated fatty acids. This list is not intended to be exhaustive.

Particularly preferred additional organic buffers are citrates, preferably used in an amount of from 5 to 30 wt. % and preferably from 10 to 25 wt. %, and acrylic polymers, more particularly acrylic-maleic copolymers, preferably used in an amount of 0.5 to 15 wt. % and preferably from 1 to 10 wt. %.

The compositions of the invention may also comprise a layered (lamellar) crystalline sodium silicate composition

NaMSi _x O _{2x + 1} . y H ₂ O

Wherein M denotes sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.

These materials are described in US 4,664,839, US 4,728,443 and US 4,820,439 (Hoechst AG). They are crystalline materials and can be easily characterized by their X-ray diffraction profiles. Compared to amorphous silicates, they are capable of significantly better calcium and magnesium ion bonds.

Preferred materials are those wherein x = 2, i.e., compounds of the formula

NaMSi ₂ 0 ₅ . y H ₂ O.

There is interest in both natural and synthetic compounds of this formula, with a synthetic material known as Na-SKS-6 being particularly preferred. This material is commercially available from Hoechst AG; its manufacture has already been described and the material is defined by its diffractive X-ray profile in the aforementioned US patent 4,664,839.

Antioxidant

An antioxidant is a material capable of prolonging the oxidation of the surfactant system in the composition at elevated temperatures, for example above 100 ° C.

The antioxidant is preferably present in an amount of from 0.01 to 2 wt. %, preferably from 0.05 to 1 wt. % and more particularly from 0.1 to 0.5 wt. %.

One class of preferred antioxidants consists of sterile hindered phenols.

Suitable antioxidants include the following compounds:

(i) Butylated hydroxytoluene (BHT), also known as

2,6-di-tert-butyl-p-cresol;

(ii) butylated hydroxyanisole (BHA), also known as (1,1-dimethylethyl) -4-methoxyphenol;

(iii) tert-butyl hydroquinone (TBHQ), also known as

1,4-benzenediol

Optional metal ion sequestering (masking) agent

Advantageously, the composition of the invention may also contain a sequestering agent for transition metal ions.

Preferred sequestering agents include aminopolycarboxylates such as ethylenediaminetetraacetic acid or salts thereof; or aminopolyphosphonates, for example, ethylenediaminetetramethylenephosphonic acid (ETDMP) or its salts (Dequest ™ ^zaps · - · ^Signs 2041 and 2047 of Monsanto) or higher phosphonates such as diethylene triamine pentamethylenephosphonic acid (DETPMP) and its salts (Dequest ™ 2060 or 2061).

Such phosphonates are usually incorporated into laundry compositions containing peroxide bleaching compounds as bleach stabilizers; but in the context of the present invention sequestering agents are preferably present regardless of the simultaneous presence or absence of a bleach system.

- 9 Optional bleach system

The compositions of the invention may, if desired, contain a bleaching system. However, the invention does not concern the stability of bleaching agents and is equally applicable to bleach-free compositions.

Suitable peroxygen bleach compounds include organic peroxyacids and inorganic persalts such as perborates, percarbonates, perfosphates,. alkali metal persilicates and persulphates. Preferred inorganic persoids are sodium perborate monohydrate and tetrahydrate and sodium percarbonate. The peroxy bleach compound is preferably present in an amount of from 5 to 35 wt. % and preferably from 10 to 25 wt. %.

The flowability of the powder can be improved by incorporating small amounts of a powder structuring agent, for example a fatty acid (or fatty acid soap), sugar, acrylate or acrylic-maleic polymer, or sodium silicate.

A preferred powder structuring agent is a fatty acid soap, preferably present in an amount of from 1 to 5 wt. %.

Other substances which may be present in the detergent compositions of the invention include sodium silicate; soil release agents such as cellulose polymers; other polymers to aid in the release of impurities and to prevent their re-establishment; fluorescent substances; inorganic salts such as sodium sulfate; suds control agents or, if necessary, enhancers; purifying enzymes such as proteases, lipases, cellulases, and amylases; dyes; colored particles; perfumes and fabric softeners (fabric softener). This list is not intended to be exhaustive.

- 10 Production and bulk density

The invention is particularly important for compact washing powders in which the ingredients are particularly close to one another, for example compositions with a bulk density of 650 g / l or more and in particular 750 g / l or more.

High bulk density laundry detergents are generally produced either by post-tower thickening of the spray-dried powder or by totally tower-free routes such as blending and granulation. In both cases, a high speed mixer / granulator may be advantageously used. Methods using high speed mixers / granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).

Preferred methods of making the compositions of the invention will include the step of mixing and granulating the ingredients in a high speed mixer / thickener to form a high bulk density base powder and optionally providing additional ingredients that are unsuitable for such processing.

The antioxidant may either be incorporated into the high bulk density base powder or added subsequently. It is desirable that the antioxidant be distributed as homogeneously as possible in the final product.

According to a preferred method, the solution or suspension of the antioxidant in the nonionic surfactant or in the mixture of the nonionic surfactant and the fatty acid soap is mixed into the base powder prior to the addition of any solid additives.

Another possibility is the additional addition of the antioxidant in the form of particles, either alone or in the form of granules, also containing

A carrier material, for example zeolite or sodium carbonate, and optionally a binder, for example sodium silicate or an acrylate or acrylate-melein polymer.

Examples

The invention is further illustrated by the following non-limiting examples. Parts and percentages are by weight unless otherwise stated.

Examples 1 to 6

High bulk density bleaching compositions were prepared

in the following general composition: coconut alcohol sulfate 5,52 non-ionic 7EO 7.50 non-ionic 3EO 5.00 zeolite MAP 34.76 sodium soap 1.95 sodium carbonate 3.13 sodium carboxymethylcellulose 0.85 BHT see below percarbonate, TAED and the like. 30.07 EDTMP Dequest 2047 0.42 enzymes 1.42 perfume 0.45 granules to control foaming / fluorescence 3.50 water and salts do 100,00

The compositions were prepared as follows. A high bulk density base powder was made by mixing and granulating the surfactants, zeolite, sodium carbonate and sodium carboxymethylcellulose in

- 12 continuous high speed mixer / thickener (Lódige ™ Recycler). Bleaching agents, additional sodium carbonate, enzyme granules, and suds and fluorescence control agent granules were added additionally. EDTMP was incorporated in the base powder for some formulations, and at a later time for others.

BHT (butylated hydroxytoluene) was introduced in two different ways:

(a) into a base powder (in a high speed mixer / granulator) as a mixture of a nonionic surfactant, soap and BHT; or

(b) adding, by adding to the powder form by initial addition. The funds were prepared as follows: example antioxidant EDTMP 1 0.22% BHT, delivered later delivered later 2 0.4% BHT, delivered later delivered later 3 0.1% BHT, delivered later v zákl. powder 4 0.2% BHT, delivered later v zákl. powder 5 0.3% BHT, delivered later v zákl. powder 6 0.4% BHT, delivered later v zákl. powder

Example 7

A similar formulation was prepared containing sodium perborate instead of sodium percarbonate. It contained additionally added EDTMP and additionally added 0.2% BHT.

Examples 8 to 10

- 13 High bulk density non-bleaching detergents were

prepared as follows: coconut alcohol sulfate 6.35 non-ionic 7EO 8.63 non-ionic 3EO 5.75 zeolite MAP 39.99 sodium soap 2.24 sodium carbonate 1.26 sodium carboxymethylcellulose 0.98 BHT see below sodium citrate (2H ₂ O) 22.18 EDTMP Dequest 2047 1.43 enzymes 1.24 perfume 0.45 granules to control foaming / fluorescence 3.20 water and salts do 100,00

The preparation process was as follows: a high bulk density base powder was produced as in Examples 1 to 6; sodium citrate, enzyme granules, and foam control and fluorescence reagent granules were added additionally. EDTMP was delivered later. The funds were prepared as follows:

an example of an antioxidant EDTMP

0.30% BHT, shipped later shipped later

0.1% BHT + 0.1% BHA, shipped later shipped later

0.05% BHT + 0.05% BHA, shipped later shipped later

PATENT CLAIMS

Claims (16)

A free-flowing detergent composition comprising an organic surfactant system comprising anionic and / or nonionic non-soap surfactants, a detergency builder system and other detergent ingredients up to 100% by weight, characterized in that: (i) the composition contains more than 5% C _{8 by} weight. ₂₀ primary alcohol sulphate and / or at least 8 wt. % of non - ionic C ₈ ethoxylated surfactant. ₂₀ alcohol and / or more than 15 wt. (ii) the detergency builder system comprises an alkali metal aluminosilicate, (iii) the composition further comprises 0.01 to 5% by weight of an antioxidant, and all percentages are based on the total composition. 2. The detergent composition of claim 1, wherein the organic surfactant system comprises _C8 . _{20 is a} primary alcohol sulfate and a non-ionic C ₈ ethoxylated surfactant. ₂₀ alcohol. A free-flowing detergent composition according to claim 2 wherein the composition comprises more than 5% by weight of the primary alcohol sulfate. A detergent composition according to claim 2, wherein the composition comprises more than 15% by weight of the surfactant system (i), the system comprising C ₈ . ₂₀ primary - 15 alcohol sulfate and nonionic surfactant ethoxylated C _{3rd 20} alcohol. A detergent composition according to claim 2, characterized in that the surfactant system (i) comprises C ₈ . _{20 is a} primary alcohol sulfate and a non-ionic C ₃ ethoxylated surfactant. ₂₀ alcohol in a ratio of less than 1: 1. 6. The detergent composition of claim 1, wherein the composition comprises at least 10% by weight of an ethoxylated nonionic surfactant. The detergent composition according to claim 1, wherein the antioxidant (iii) is sterically hindered phenol. The detergent composition according to claim 7, wherein the antioxidant (iii) is selected from butylated hydroxytoluene, butylated hydroxyanisole and tert-butyl hydroquinone. A detergent composition according to claim 1 comprising from 0.05 to 2% by weight of an antioxidant (iii). 10. The detergent composition of claim 1, further comprising a sequestering agent for transition metal ions. A detergent composition according to claim 10, wherein the sequestering agent comprises an aminopolycarboxylate or aminopolyphosphonate. - 16 12. A detergent composition according to claim 10, wherein the sequestering agent comprises ethylenediaminetetramethylenephosphonic acid, or a salt thereof. A detergent composition according to claim 1, characterized in that it has a bulk density of at least 650 g / l. 14. A detergent composition according to claim 1, characterized in that it is not the product of a spray drying process. A process for the manufacture of a free-flowing detergent composition according to claim 1, comprising the step of mixing and granulating ingredients in a high speed mixer / thickener to form a high bulk density base powder and optionally adding additional ingredients unsuitable for processing in the high speed mixer / thickener. wherein the solution or suspension of the antioxidant in the nonionic surfactant is mixed with the base powder prior to the addition of any solid additives. A process for producing a free-flowing detergent composition according to claim 1, comprising the step of mixing and granulating ingredients in a high speed mixer / thickener to form a high bulk density base powder and optionally adding additional ingredients unsuitable for processing in the high speed mixer / thickener,