HUT77100A

HUT77100A - Granular detergent composition and method for its preparation

Info

Publication number: HUT77100A
Application number: HU9701689A
Authority: HU
Inventors: Peter William Appel; Ian McKinlay Clark; Huig Euser; Colin Sydney Fairclough; Franciscus Hermannus Gortemaker; Terry Instone; Christophe Michel Bruno Joyeux; Stephen Thomas Keningley; Peter Cory Knight; Paul Edward Mcdonald
Original assignee: Unilever N.V.
Priority date: 1994-08-24
Filing date: 1995-07-08
Publication date: 1998-03-02
Also published as: GB9417140D0; PL318787A1; TR199500943A2; ZA955934B; CA2187311A1; AU2983095A; EP0777715A1; BR9508807A; CZ53097A3; SK24097A3; WO1996006151A1

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

EXTRACT

The detergent according to the invention comprises an organic surface-active system comprising anionic and / or nonionic non-soap type surfactants, a detergent builder and additional detergent additives in an amount of 100% by weight. Based on the total weight of the detergent

i) at least 5% by weight of primary alcohol sulfate and / or at least 8% by weight of ethoxylated alcohol nonionic surfactant and / or a total of at least 15% by weight of non-soap type surfactant, ii) by alkali metal aluminosilicate in detergent and iii) 0 Contains from 1 to 5% by weight of antioxidant.

Another object of the present invention is to provide a particulate detergent for the preparation of a high bulk density base powder, mixed with a high-speed mixer / granulator, and granulated, and subsequently dosed into components unsuitable for processing in a high-speed mixer / granulator. Prior to the addition of the solid ingredients, the solution or suspension of the antioxidant in the nonionic surfactant is mixed with the base powder or the antioxidant is added in particulate form.

84581-2227C / VO / LZS

PCT / EP95 / 02 709

Representative:

Danubia Patent and Trademark Office Ltd. Budapest

70 970 1 689

Detergent ^ djclris ejoo-ll ·

UNILEVER NV, Rotterdam NL

inventors:

APPEL Peter William

CLARK lan McKinlay

EUSER Hop

FAIRCLOUGH Colin Sydney GORTEMAKER Francis Hermannus INSTONE Terry

JOYEUX Christophe Michael Bruno KENINGLEY Stephen Thomas KNIGHT Peter Cory McDONALD Paul Edward

Rotterdam, NL Clwyd, GB Vlaardingen, NL Bromborough, GB Mijnsheerenland, NL Great Sution, GB Montluel, FR Bebington, GB Neston, GB Birkenhead, GB

Date of filing: 1995 07

Priority: 1994. 08

International Application Number:

Number of international releases:

08th

24. (9417140.2, GB) PCT / EP95 / 02709

WO 96/06151

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PCT / EP95 / 02 709

FIELD OF THE INVENTION The present invention relates to detergents containing particulate detergents, in particular alcohol sulphate and / or ethoxylated alcohol surfactants, containing high concentrations of effective organic surfactants. Detergents according to the invention show increased stability due to the presence of small amounts of antioxidants.

EP 283 252B and EP 320 219B describe granular detergents in which the bleach activator granulate contains an antioxidant to enhance the stability of the bleach activator.

Various particulate detergents containing antioxidants are also discussed in other documents (JP 50 066 502A, JP 77 003 730B, JP 50 151 905A, JP 78 028 163B, JP 57 128 798A, JP 84 012 720B and JP 73 008 324B). They have the advantage of reducing the odor of the preparations and the discoloration that occurs during storage.

It has been found that effective organic surfactants in high concentration granular detergents, in particular detergents containing primary alcohol sulfate and / or ethoxylated alcohol nonionic surfactants, can improve the stability of the surfactant system by introducing antioxidants, in particular spherically hindered phenols. The increased safety range of the parameters thus positively influences the handling and storage of these highly effective products in bulk, thus increasing the flexibility of the production.

Based on the above, the present invention is a particulate detergent which is anionic and / or nonionic non-soap type surfactant.

84581-2227C / VO / LZS

PCT / EP95 / 02709 contains an organic surfactant system containing detergent builder and an additional amount of detergent to 100% by weight based on the total weight of the detergent

i) at least 5% by weight of C8-C20 primary alcohol sulphate and / or at least 8% C8-C20 ethoxylated alcohol nonionic surfactant and / or a total of at least 15% non-soap-type surfactant, ii) alkali metal in the detergent builder aluminum silicate and iii) 0.01 to 5% by weight of antioxidant.

The surfactant system

The detergents according to the invention contain high concentration, preferably at least 15% by weight, more preferably 15-25% by weight of non-soap organic surfactants. However, as discussed below, certain compositions containing less than 15% by weight of surfactant are within the scope of the invention.

The surfactants may be selected from anionic, cationic, nonionic, amphoteric and internal salt type detergent active compounds, and mixtures thereof. Many suitable detergent-active compounds are commercially available and are described in detail in the literature (Schwartz, Perry and Berch, Surface-Active Agents and Detergents, I and II). Volume].

Anionic surfactants are well known to those skilled in the art. These may be alkylbenzenesulfonates, in particular 884581-2227C / VOZLZS

PCT / EP95 / 02 709

Linear alkylbenzenesulfonates containing C15 alkyl; primary and secondary alkyl sulfates, in particular C8-C15 primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulphonates; dialkyl sulfosuccinates and fatty acid ester sulfonates. Generally, sodium salts of the compounds are preferred.

The nonionic surfactants which may be used include primary and secondary alcohol ethoxylates, preferably 8 to 20 molar aliphatic alcohols ethoxylated with 1 to 20 moles of ethylene oxide per mole of alcohol, more preferably 1-10 moles of ethylene oxide per mole of ethylene oxide. primary and secondary aliphatic alcohols. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, lactobionamides, and polyhydroxy amides (glucamides).

The invention is particularly applicable to detergents in which the surfactant comprises C8-20 primary alcohol sulfate and / or C8-20 exotylated alcohol non-surfactant. Particularly preferred detergents according to the invention comprise at least 5% by weight of C8-C20 primary alcohol sulfate and / or at least 8% by weight, more preferably at least 10% by weight of C8-C20 ethoxylated alcohol nonionic surfactant. If one of these two conditions is met, the total amount of non-soap organic surfactant in the detergents of the present invention need not exceed 15% by weight, but preferably at least 10%, more preferably at least 12% by weight.

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One class of preferred detergents of the present invention includes compositions wherein the amount of C8-C20 primary alcohol sulfate is greater than 5% by weight based on the total weight of the product and optionally combined with 8-20% ethoxylated alcohol nonionic. surfactant.

Preferred detergents according to the invention comprise at least 8% by weight, more preferably at least 10% by weight of the ethoxylated nonionic surfactant, wherein the ratio of the primary alcohol sulfate to the ethoxylated nonionic sulfate is preferably less than 1: 1. Detergents containing a lower proportion of nonionic surfactants, such as detergents containing additional anionic surfactants, are included within the scope of the present invention.

A further class of preferred detergents comprising at least 8 wt%, more preferably 10 wt% ethoxylated non-surfactant surfactant according to the invention are detergents in which the non-soap type surfactant system comprises wholly or substantially nonionic surfactants.

The detergents according to the invention may also contain fatty acid soaps. However, where at least 15% by weight of the surfactant is used, the present fatty acid soap is not included.

The Detergent Creation System

The detergents of the present invention contain as the detergent builder alone or together with one or more additional ingredients, an alkali metal aluminosilicate.

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The total amount of detergent ingredients in detergents is suitably 5-80% by weight, preferably 10-60% by weight.

The basic component of the detergents of the present invention is an alkali metal, preferably sodium aluminosilicate detergent builder. Sodium aluminum silicates (calculated as anhydrous material) may be present in an amount of from 10 to 70% by weight, preferably from 25 to 50% by weight.

The alkali metal aluminosilicate may be crystalline or amorphous or a mixture thereof, having the formula:

0.8-1.5 Na ₂ O Al ₂ O ₃ 0.8-6 SiO ₂ (I).

These materials contain a certain amount of bound water, with an expected value of at least 50 mg CaO / g for calcium ion exchange. Preferred sodium aluminosilicates contain from 1.5 to 3.5 SiO _{2 in} formula (I). By reaction between sodium silicate and sodium aluminate, both amorphous and crystalline materials can be prepared as described in detail in the literature.

Suitable crystalline sodium aluminum silicate ion-exchange detergent builders are disclosed, inter alia, in GB 1 429 143. Preferred sodium aluminosilicates of this type are commercially available as zeolites A and X and mixtures thereof.

The zeolite used may be a product widely used in laundry detergents, commercially available as 4A zeolite. However, in accordance with a preferred embodiment of the invention, the compositions of the invention are described in EP 384

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PCT / EP95 / 02 709

The zeolite P (MAP type zeolite) containing maximum aluminum as described in document 070Α is used. By definition, zeolite MAP is an alkali metal aluminosilicate of type P having a silicon to aluminum ratio of up to 1.33, preferably 0.90-1.33, more preferably 0.90-1.20.

Particularly preferred is the zeolite MAP in which the silicon nitrile aluminum ratio is less than 1.07, more preferably 1.00. The calcium-binding capacity of the MAP zeolite is generally at least 150 mg CaO / g anhydrous.

The zeolite is preferably used in conjunction with an additional detergent builder. Additional organic detergent builders may include polycarboxylate polymers such as polyacrylates, acrylic / malein copolymers and acrylic phosphinates; multivalent monomeric carboxylic acids such as citrates, gluconates, oxysuccinates, mono-, di- and trisuccinates of glycerol, carboxymethyloxy succinate, carboxymethyloxononates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenyl malonates and succinate; and salts of sulfonated fatty acids. This listing is not exclusive ·

Particularly preferred additional organic detergent builders are citrates suitably in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, and acrylic polymers, in particular acrylic / malein copolymers, suitably in an amount of 0.5 to 15% by weight, preferably 1 to 10% by weight. used.

The detergents of the present invention are a flat, crystalline sodium silicate of formula (II)

NaMS _x O _{2x + 1} YH ₂ O (II)

84581-2227C / VOZLZS

PCT / EP95 / 027O9 δ

in which formula

M is sodium or hydrogen, preferably sodium, x is from 1.9 to 4, and y is from 0 to 20.

These materials are known in the art (US 4,664,839, US 4,728,443 and US 4,820,439). These crystalline materials can be easily characterized by their X-ray diffraction curves. Compared to amorphous silicates, these materials are more suitable for binding calcium and magnesium ions.

Preferred of the above materials are those of formula (II) wherein x = 2, i.e. compounds of formula (III), which are a narrower group of compounds of formula (II)

NaMS ₂ O ₅ -YH ₂ O (III)

wherein y is as defined above.

Of the compounds of formula (III), both natural and synthetic compounds are important. Particularly preferred are synthetic materials known in the art as Na-SKS-6. This material is commercially available (manufactured by Hoechst AG, NSZK) and is prepared on the basis of X-ray diffraction curves in US 4,664,839, supra.

The antioxidant

Antioxidant is a substance with increased temperature84581-2227C / VO / LZs

PCT / EP95 / 02709, thus delaying the oxidation of the surfactant system in the composition at temperatures above 100 ° C.

Preferably, the antioxidant is present in an amount of from 0.01 to 2% by weight, more preferably from 0.05 to 1% by weight, more preferably from 0.1 to 0.5% by weight.

One class of preferred antioxidants is spherically inhibited phenols.

Suitable antioxidants include butylated hydroxytoluene (BHT), also known as 2,6-di-tert-butyl-p-cresol, butylated hydroxyl (1,1-dimethyl ethyl) -4-methoxyphenol. -anisole (BHA) and tert-butyl hydroquinone (TBHQ) also known as 1,4-benzoldiol.

Optionally, a metal ion complexing agent may be used

Preferably, the detergent according to the invention may also comprise a transition metal ion complexing complex.

Preferred complexing agents include amino polycarboxylates such as ethylenediamine tetraacetic acid or its salts, and amino polyphosphonates such as ethylene diamine tetramethylene phosphonic acid (ETDMP) or salts thereof (Dequest 2041 and 2047 (manufactured by : Monsanto) or higher molecular weight phosphonates such as diethylene triamine pentamethylene phosphonic acid (DETPMP) and its salts (Dequest 2060 or 2061).

These phosphonates are traditionally used in detergents containing bleaching peroxy compounds fe84581-2227C / VO / LZS

PCT / EP95 / 027O9 as a stabilizer. However, according to the invention, the complexing agents are advantageous for the presence of a bleaching system, whether or not present.

Optionally, a bleaching system may be used

The detergent according to the invention may optionally contain a bleaching system. However, the invention does not relate to the stability of the bleaching agent and is equally applicable to compositions which do not contain a bleach.

Suitable bleaching peroxy compounds include organic peroxyacids and inorganic persols, such as alkali metal perborates, percarbonates, perphosphates, silicates, and persersates. Preferred inorganic persols are sodium perborate monohydrate and tetrahydrate and sodium percarbonate. Suitably, the bleaching peroxy compound is present in an amount of from 5 to 35% by weight, preferably from 10 to 25% by weight.

To improve the bleaching effect at low wash temperatures, bleaching peroxy compounds can be used together with a bleach activator (bleach precursor). The bleach precursor is suitably present in an amount of 1 to 8% by weight, preferably 2 to 5% by weight. Preferred bleach precursors are peroxycarboxylic acid precursors, in particular peracetic acid and peroxybenzoic acid, as well as peroxy-carbonic acid precursors. A particularly preferred bleach precursor for use in the present invention is Ν, Ν, Ν ', Ν'-tetraacetyl ethylene diamine (TAED).

Bleach stabilizer (heavy metal complexing agent) may also be present. Suitable complexing agents are discussed above.

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PCT / EP95 / 02 709

If desired, the bleaching system may also comprise a transition metal bleach catalyst known in the art (EP 458 397A, EP 458 398A and EP 509 787A).

Optionally, other ingredients may be used

For improved cleaning performance and ease of processing, the compositions of the present invention may contain alkali metal carbonate, preferably sodium carbonate. Suitably, the sodium carbonate may be present in an amount of from 1 to 60% by weight, preferably from 2 to 40% by weight. However, compositions containing or free of small amounts of sodium carbonate are within the scope of the invention.

The flow properties of the powder can be improved by the addition of a small amount of a structuring agent such as fatty acid (or fatty acid soap), sugar, acrylate or acrylate / maleate polymer or sodium silicate.

One of the preferred structuring agents is the fatty acid soap, suitably used in an amount of 1-5% by weight.

Other substances present in the compositions of the present invention include, but are not limited to, sodium silicate, re-release agents such as cellulose polymers, other disintegrating or re-disintegrating polymers, fluorescent agents, inorganic salts such as sodium sulfate, foaming agents or foaming agents, as needed, detergent. enzymes, such as enzymes that disrupt and break down proteins, celluloses and amylases, dyes, coloring agents, fragrances, anti-foaming agents, and fabric softeners. The above list is not exclusive.

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Production and bulk density of the washing powder

The invention is particularly useful in the case of compressed washing powders, in which the ingredients are particularly tight, so that they can be at least 650 g / l, especially at least 750 g / l.

Generally, high density washing powders are prepared either by post-compaction of spray-dried powders or by methods other than spray-drying, such as mixing and granulation. In either case, a high-speed mixer / compactor can be advantageously used. Methods using a high-speed mixer / compaction device are described, inter alia, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A.

According to preferred methods of preparing the washing powders according to the invention, the ingredients are mixed in a high-speed mixer / granulator and granulated to form a high bulk density base powder and, optionally, ingredients that are unsuitable for such operation.

The antioxidant may be in the high bulk density powder or may be post-dosed. It is desirable that the distribution of the antioxidant in the final product is as homogeneous as possible.

In a preferred embodiment of the method according to the invention, the solution or suspension of the antioxidant in a nonionic surfactant or a mixture of nonionic surfactant and fatty acid soap is mixed with the base powder prior to the addition of other solid ingredients.

Alternatively, the antioxidant may be dosed either in granular form or in a carrier such as zeolite or sodium carbonate and optionally a binder such as sodium 84581-2227C / VO / LZS.

PCT / EP95 / 02 709

granules containing silicate or acrylate or acrylate / maleate.

The invention is illustrated by the following non-limiting examples. In the absence of any other reference, the data given in parts or in% are by weight.

. 1-6. examples

High bulk density bleaching detergents are prepared according to the following general formulation:

coconut alcohol sulfate 5.52 nonionic 7EO 7.50 nonionic 3EO 5.00 MAP type zeolite 34.76 Sodium soap 1.95 Sodium carbonate 3.13 sodium carboxymethyl cellulose 0.85 BHT see below percarbonate, TAED 30.07 EDTMP (Dequest 2047) 0.42 enzymes 1.42 fragrance additive 0.45 antifoam / fluorescent granules 3.50 water and salts 100% by weight

The composition is prepared as follows. Surfactants, zeolite, sodium carbonate and sodium carboxymethylcellulose in a continuous high-speed mixer / granulator (Recycler)

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PCT / EP95 / 02 709

Lödige) is blended and granulated to produce a high base density base powder. Subsequently, the bleach additive and sodium carbonate, enzyme granulate and antifoam / fluorescent granules are dosed. In some compositions, EDTMP is present in the base powder, while in the case of other compositions, it is added afterwards.

The BHT component is introduced by two different methods:

(a) is introduced into the base powder as a mixture of nonionic surfactant / soap / BHT (in a high-speed mixer / granulator);

b) dosing in powder form.

The following washing powders are produced:

example antioxidant EDTMP First 0.22% BHT (post-dose) postdosed Second 0.4% BHT (post-dose) postdosed Third 0.1% BHT (post-dose) base powder 4th 0.2% BHT (post-dose) base powder 5th 0.3% BHT (post-dose) base powder 6th 0.4% BHT (post-dose) base powder

Example 7

A formulation similar to the above is prepared except that it contains sodium perborate instead of sodium percarbonate. The composition contains post-dose EDTMP and 0.2% BHT after administration.

8-10. examples

High Volume Density Bleaching Detergents Powder 84581-2227C / VO / LZS

PCT / EP95 / 02709 according to the following general formulation:

coconut alcohol sulfate 6.35 nonionic 7EO 8.63 nonionic 3EO 5.75 Sodium soap 2.24 MAP type zeolite 39.99 Sodium carbonate 1.26 sodium carboxymethyl cellulose 0.98 BHT see below Sodium citrate (2H ₂ O) 22.18 EDTMP (Dequest 2047) 1.43 enzymes 1.24 fragrance additive 0.45 antifoam / fluorescent granules 3.20 water and salts 100% by weight

The above-described washing powders are prepared as follows: 1-6. Examples 1 and 2 are used to prepare a high bulk density base powder, then sodium citrate, enzyme granulate, and antifoam / fluorescent granules are subsequently dosed. The EDTMP component is also dosed afterwards. The following powder formulations are prepared:

example antioxidant EDTMP 8th 0.30% BHT (post-dose) postdosed 9th 0.1% BHT + 0.1% BHA (dosed) postdosed 10th 0.05% BHT + 0.05 BHA (dosed) base powder

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Claims

Patent claims

A granular detergent comprising an organic surfactant system containing anionic and / or nonionic non-soap surfactants, a detergent builder and 100% by weight of other detergent additives, characterized in that, based on the total weight of the detergent,

i) at least 5% by weight of a C8-C20 primary alcohol sulfate and / or at least 8% by weight of a C8-C20 ethoxylated alcohol nonionic surfactant and / or a total of at least 15% by weight of a non-soap surfactant; and (iii) 0.01 to 5% by weight of an antioxidant.

Detergent according to Claim 1, characterized in that the organic surfactant system comprises a C 8-20 primary alcohol sulfate and a C 8-20 ethoxylated alcohol nonionic surfactant.

Detergent according to Claim 2, characterized in that it contains at least 5% by weight of primary alcohol sulfate.

Detergent according to Claim 2, characterized in that it comprises at least 15% by weight of a surfactant system containing a C8-20 primary alcohol sulfate and a C8-20 ethoxylated alcohol nonionic surfactant.

Detergent according to claim 2, characterized in that the primary alcohol sulfate contains 8-20 carbon atoms and 8-20 carbon at 84581-2227C / VO / LZS.

PCT / EP95 / 02709 Ethoxylated alcohol contains a surfactant system containing up to 1: 1 nonionic surfactant.

Detergent according to claim 1, characterized in that it contains at least 10% by weight of ethoxylated nonionic surfactant.

Detergent according to Claim 1, characterized in that it contains a spherically inhibited phenol as an antioxidant.

8. A detergent composition according to claim 7, characterized in that it contains an antioxidant selected from butylated hydroxytoluene, butylated hydroxyanisole and tert-butyl hydroquinone.

Detergent according to Claim 1, characterized in that it contains from 0.05% to 2% by weight of an antioxidant.

10. A detergent composition according to claim 1, further comprising a complexing agent for the transition metal ion.

11. A detergent composition according to claim 10 wherein the complexing agent comprises an aminopolycarboxylate or an aminopiphosphonate.

12. A detergent composition according to claim 10, characterized in that it contains a complexing agent comprising ethylenediaminetetramethylene phosphonic acid or a salt thereof.

Detergent according to claim 1, characterized in that it has a bulk density of at least 650 g / l.

14. A detergent according to claim 1, characterized in that it is produced by a process other than spray drying.

15. A process for the preparation of a particulate detergent according to claim 1, wherein said high volume bulk powder is comprised of high-speed detergent ingredients. 84581-2227C / VO / L2S

PCT / EP95 / 02709 is blended and granulated in a powder / granulator and optionally refined in a high speed mixer / granulator, characterized in that a solution or suspension of an antioxidant in nonionic surfactant is mixed before the solid ingredients are added.

16. A process for preparing a particulate detergent according to claim 1, comprising mixing and granulating detergent ingredients in a high volume mixer / granulator and optionally dispensing ingredients not suitable for processing in a high speed mixer / granulator, that the antioxidant is administered in particulate form.

Instead of UNILEVER NV, the agent shall:

DANUBIA

Patent and Trademark Office Ltd.