CZ250593A3 - Liquid detergent composition - Google Patents

Abstract

Liquid detergent compositions containing amine oxides, solid builders and otpionally bleaches and specified water levels are highly stable. Compositions containing an amine oxide, a builder and a polyalkylene glycol confer easy-iron properties on fabrics.

Description

The invention relates to a liquid detergent composition.

Current_technologies

Detergent compositions are known which consist of a carrier suspension in an organic liquid containing a wetting agent. Non-aqueous compositions of this type having good stability are described in European Pat. Nos. 30096 and 120,659.

It is difficult to remove perfectly water from detergents and it is desirable that their hygroscopicity be as low as possible.

It is believed that reducing the hygroscopicity can promote dispersibility of these materials, i.e., facilitate their dispersion in the wash liquid.

The detergent compositions can be introduced into the washing machine by placing them in a reservoir through which water flows and which carries the detergent to the wash zone. Compositions with poor dispersibility can form solid deposits that remain in the container. In some cases, detergents are dispensed into containers that are located in the wash zone. If there is poor access to the tank, there are solid residues, especially when it is not dry when filled with detergent. Dispersibility is expected to improve, especially in the latter case, when the hygroscopicity of the composition is reduced.

Surprisingly, it has been found that small amounts of water can be tolerated in such amine oxide-containing compositions. In general, the amount of water should be at most 5 moles, preferably less than 3, and even more preferably less than 2 mol, based on 1 mol of amine oxide, for example 0.5 to 1.9 mol and preferably 1.0 to 1.7 mol of water, based on 1 mol of amine oxide. By water is meant water which is not contained as crystalline water in solids, which is irrelevant in this context.

Although anhydrous amine oxides are known, they are generally commercially available in the form of aqueous solutions which may contain, for example, 65% by weight. water. It will be appreciated that such solutions are not suitable for the aforementioned purposes and, in accordance with one embodiment of the present invention, means are provided by which solutions can be converted into compositions useful as part of a liquid laundry detergent composition.

The invention relates to a liquid detergent composition which consists of i) a liquid organic phase containing an amine oxide, ii) a solid carrier, iii) at most 5 and preferably less than 2, for example 0.5 to at most 2 and preferably 1.0 to 1.7 mol of water (other than crystal water of any solid present) relative to 1 mole of amine oxide.

The carrier may be water-soluble and, if desired, a bleaching agent may be present.

The invention also relates to a composition which is useful as an additive to liquid detergents and which also comprises an amine oxide, a polyalkylene glycol, which preferably contains ethylene glycol residues and optionally propylene glycol residues and even more preferably polyethylene glycol; and iii at most 5 and preferably less than 2 mol, for example 0.5 to at most 2 mol and preferably 1.0 to 1.7 mol of water, based on 1 mol of amine oxide.

This composition allows the preparation of liquid detergents with good stability that facilitate ironing when a suitable carrier is added. An effective weight ratio of polyalkylene glycol to amine oxide is from 0.5 to 1 to 2 to 1.

This composition can be produced by distilling an aqueous amine oxide solution in the presence of a polyalkylene glycol, preferably polyethylene glycol, preferably under reduced pressure, at a temperature of from 40 to 80 ° C and preferably from 65 to 75 ° C.

Surprisingly, it has been found that the presence of polyalkylene glycol reduces the difficulty of forming the gel which results from the distillation of an aqueous amine oxide solution, if distilled as such, and makes it more difficult.

It has been found that amine oxides, when used in conjunction with a carrier, polyethylene glycol, and preferably another nonionic surfactant, appear to facilitate ironing of the fabrics washed therein.

The present invention also relates to a detergent composition, for example a laundry detergent composition, which comprises an amine oxide, a carrier, and a polyalkylene glycol having a molecular weight of from 10 to 1500, preferably polyethylene glycol, and preferably a nonionic surfactant other than amine oxide.

In many parts of the world, it is desirable to reduce phosphate concentrations in waste water for environmental reasons. The use of phosphates, and in particular condensed phosphates, such as sodium tripolyphosphate, in detergents has been common for many years, but in some cases is now restricted by law for environmental reasons. Accordingly, it is desirable to formulate detergent compositions with good efficacy that do not contain phosphates.

The present invention therefore relates to phosphate-free detergent compositions useful as laundry detergent compositions and comprising

1 / amine oxide,

2) a hydroxy carboxylic acid having 2 to 6 hydroxyl groups and 1 to 5 hydroxyl groups, and

3) a polycarboxylic acid having at least 10 and preferably at least 100, for example 150 to 2000 and preferably 200 to 1000 carboxylic acid groups and containing at most 5 and preferably less than 2 moles of water, relative to 1 mol of amine oxide / excluding water which is optionally present as crystalline water.

The polycarboxylic acid may be a polyacrylic acid, for example a maleicized polyacrylic acid or, more preferably, a carboxymethylcellulose having suitably 100 to 1000, for example 100 to 500 linked glucose units per molecule and expediently having a degree of substitution / number of hydroxyl groups which have been converted to carboxymethyl groups. 35 to 85% and preferably from 45 to 80% fa.

The hydroxy carboxylic acid may be, for example, tartaric acid or preferably citric acid.

Suitably, the composition comprises from 2 to 10% by weight. of the aforementioned component (3), and preferably contains 3 to 9% by weight of said component (3). % and most preferably 5 to 8 wt. Suitably it contains 20 to 50 wt. % and preferably 25 to 40 wt. the above components (2).

Preferably, the composition has a substantially neutral or alkaline reaction and it is preferred that the acidic substances are neutralized by ammonium, substituted ammonium ions or preferably alkali metal ions. It is preferred that at least 1 wt. part of component (3) is present per 8 parts by weight of the composition. components / 2 /.

It is preferred that the liquid compositions contain 25 to 70 wt% and more preferably 30 to 60 wt%, for example 40 to 60 wt%. all solids. The solids preferably form a carrier which may be present in an amount of 25 to 60% by weight of the total composition. A bleaching agent, for example an alkali metal perborate or percarbonate, for example sodium, may be present in an amount of 0 to 25% by weight, for example 1 to 20% by weight. and preferably 5 to 20% by weight, based on the total composition. Optionally, a polycarboxylic acid with at least 10 and preferably at least 100 or 150 to 2000 and preferably 200 to 1000 carboxyl groups, preferably carboxymethylcellulose, may also be present.

Suitably the liquid phase comprises polyalkylene glycol, preferably polyethylene glycol, for example in an amount of 5 to 55% by weight based on the total composition, preferably 10 to 40% by weight based on the total composition, and a nonionic surfactant, suitably in an amount of 5 to 55%. 25 wt. and preferably 7 to 20% by weight, based on the total composition.

The amine oxide is present in an amount of 5 to 100 phy. and more preferably in an amount of 5 to 50 phy weight, based on the weight of the organic substances in the liquid phase.

The carrier can be, for example, a fused phosphate, silicate or zeolite or a hydroxycarboxylic acid containing 2 to 6 carboxylic acids and 1 to 5 hydroxyl groups which may be citric acid or tartaric acid. However, it is more preferred that the carrier is a condensed phosphate, which may be an alkali metal salt, preferably sodium, for example sodium tripolyphosphate.

The molecular weight of the polyethylene glycol may be from 100 to 1500 and preferably from 150 to 500.

It is preferred that the compositions of the invention be formulated as pourable liquids. For this reason, it is preferred that the liquid detergent composition comprises a dispersion of solids in the liquid medium. The solids should have an average particle size of not more than 10 microns. Suitably, the composition has a pour point below 10 ° C. The pour point should be measured by the ASTM test method, designated D 97-66, approved in 1971. It is desirable that at least 90 phy of the composition be used. the particles had a diameter of less than 10 microns. The average particle size may be determined by the average number or average weight method. Preferred ranges are from 1.2 to 8 microns.

The surfactant component in the composition may contain, for example, a nonionic surfactant. Preferably it is an alkylene oxide derivative, wherein the alkylene oxide is preferably ethylene oxide and / or propylene oxide. Most preferably, it is the product of the reaction of an amine, an alkylphenol or an alkanol with ethylene oxide and / or propylene oxide. The alkyl group in the alkylphenol may be straight or branched chain and may contain from 6 to 20 carbon atoms, for example from 6 to 12 carbon atoms. The alkanol may contain from 6 to 20 carbon atoms and preferably from 10 to 16 carbon atoms. The alkanol is preferably a primary or secondary alkanol having a straight or simply branched alkyl chain. Suitably the nonionic surfactant comprises a chain of 1 to 10, preferably 5 to 8 alkylene glycol residues, which means that this is an average value.

The surfactant may consist essentially of an amine oxide which may have an alkyl group having 10 to 18 carbon atoms and preferably up to 16 carbon atoms and two other groups individually selected from alkyl or hydroxyalkyl groups having 1 to 3 carbon atoms. If desired, the composition may contain two or more nonionic surfactants. The pour point can be adjusted by varying the liquid phase in the composition, for example by adding wetting agents and / or low flow point polyethylene glycol. The presence of 10 to 50 wt. and preferably 15 to 30 wt. wetting agents. The wetting agent may be either anionic or cationic.

Such anionic or cationic surfactants are known, anionic surfactants being, for example, soaps, sulfonates of alkylbenzenes or olefins, sulfates of alcohol or alkoxyalcohols; cationic surfactants may suitably be an ammonium salt or hydroxide di-C _L Q ² _-2 - ^ic y ¹ · ·· ^'and preferably di-G ^ g ^ g-alkyl, lower-dialkylammonium salts or hydroxides for example chlorides or sulphates or for example, fabric softeners of the ^C 10-11 -alkyl-, lower dialkyl- (e.g. dimethyl-) type substituted ethylammonium salts. The substituent on the ethyl group may be a -OOCR group in which R is an alkyl group which may have up to 22 carbon atoms; and the anion in the salt may be a R 50 O - group in which R is a lower alkyl group, for example a methyl group. The lower alkyl groups mentioned are expediently methyl groups.

It is preferred that the composition comprises a polyalkylene glycol, for example polyethylene / polypropylene glycol or preferably polyethylene glycol. This contributes to the effectiveness of the compositions in the washing of fabrics and is welcome in terms of biodegradability. Polyalkylene glycols having an average molecular weight of from 100 to 400, and preferably from 150 to 300, are more preferred because they tend to lower the pour point of the liquid compositions, thereby facilitating their use at low temperatures. They suitably comprise 10 to 50 wt.%, Preferably 25 to 45 wt. polyalkylene glycol.

It is highly preferred that the composition comprises a bleaching agent, which is preferably an alkali metal perorate or percarbonate. If desired, bleach activators may be added

- 7 funds. A content of 1 to 20% by weight is preferred. and preferably 2 to 15 wt. bleaching agent.

The composition may also contain additives customary in detergent compositions, for example, optical brighteners, ethylenediaminetetraacetic acid, colorants, perfumes, and / or enzymes.

In the compositions of the present invention, the solid dispersions in nonionic surfactants are remarkably stable, especially when the solid particles have a size of at most 10 microns. Although the solids are sometimes separated, the resulting phase is usually flocculated and is easily dispersible again, since if the relative amounts of solids, polyethylene glycol and wetting agent in the composition are precisely selected, there is only a slight phase separation as the liquid fills the pros. between solid particles released.

The compositions of the invention are preferably produced by a process comprising co-grinding the ingredients.

The parts by weight herein are based on the total weight of the composition, unless the context indicates otherwise.

Examples of the invention

Example 1 Dehydration of alkyldimethylamine oxide

The following procedure yields a 50% (w / w) amine oxide solution having alkyl groups having chains of $ 70, $ ₁₂ , $ 27, and $ 3 of _C16 and 2 methyl groups substituted by its nitrogen atom (DMAO), and this in polyethylene glycol (molecular weight 200) (PEG 200).

PEG 200 equivalent is added to 4 equivalents of DMAO in aqueous solution / about 33% by weight. DMAO /.

The water is removed by distillation under reduced pressure from a 201 liter Quickfit vessel equipped with a nitrogen inlet to the bottom and an about 70 cm long foam breaker or foam disposal head, then through a water cooler to the trap and a vacuum meter.

The cooker is filled to a maximum of 1/3 to 1/2 of its volume (to leave space for foam). The contents are mixed with a paddle stirrer.

- at a speed of 100 rpm and a nitrogen flow is reported. The pressure is reduced and the nitrogen supply is adjusted to the smallest amount. Once the vacuum has stabilized, the temperature is slowly raised to 60-75 ° C. The foaming can be controlled by fine-tuning the vacuum, and optionally a 0.05 to 0.1 equivalent silicone antifoam can be added to the reaction mixture.

Distillation conditions:

201 L vessel, 12 hours, 6.7 kPA at 60 ° C

500 mL flask, 3 hours, 6.0 kPa at 75 ° C.

2a of these conditions when a mixture containing 60 wt.

DMA0 (with minor addition of PEG 200), the product is solid at room temperature, at 50 wt. amine oxide is a liquid.

60 wt. 50 wt. Amine oxide 61.0 Amine oxide 50.0 Free amine 0.7 Free amine 0.6 Water 5.5 water 5.0 PEG 200 35.0 PEG 200 ^ 44.5

Example 2

Composition A was produced as follows:

The liquid components and 7 wt. parts of this mixture were mixed with the enzyme and bentonite, and the residue was mixed with the other solids in the homogenizer and the product was ground to an average particle size of 3 microns (weight average). The two mixtures were then mixed together using a homogenizer.

Composition B was produced as follows:

The components except the enzyme were mixed in a homogenizer and ground to an average particle size of 3 microns (weight average). The enzyme was then added and mixed using a homogenizer.

Table 1

AND /% / (B) / $ / Sodium citrate - 27 Mar: Sodium tripolyphosphate 37 - Sodium carbonate 5 5 Carboxymethylcellulose ^x 1 5 Sodium di-silicate 2 1 Leukophor BUK optical brightener 0.3 0.3 Enzyme (protease and amylase) 0.3 0.3 * Synperonic A 3 2.5 1.3 '' Synperonic '' 87K 7 3.8 Polyethylene glycol, molecular Weight 200 / PEG 200 / 32 36 DMAO / as 100 ^ 10 7.5 Sodium perborate, monohydrate - 10 Tetraacetyl-ethylenediamine - 3 Bentonite 3 - Water 1 0.75

^x Commercial product named Cour lose A 610, degree of substitution 0,5 to 0,7, estimated molecular weight 60 000 to 100 000 · * 'Synperonic' * A 3 and Synperonic 87 K are condensation products of 3 mol ethylene oxide with 7 mol mixture containing 92 ethylene oxide and 8% propylene oxide with a mixture of 2 parts of the N-primary alkanol with 1 part of the primary alkanol, both having several methyl groups in the 2-position.

All the above amounts are by weight.

. The compositions were tested as laundry detergents as follows.

The performance of compositions A and B was compared to that of commercial detergents as follows: washing tests were carried out using a Zanussi PL 1030 washing machine and were carried out at a temperature of 40 and 60 ° C in 1.8 mval.l ^-1 hardness water. Standard materials from ΈΜΡΑ or Krefeld were used to determine the efficacy of each product. The washing machine was filled with four test pieces (10 x 10 cm) of each type of test substance at the same time as 2 kg of pure substance as a load for each wash handle.

The cutoff was measured at ten different locations to determine the increase in light reflectance. The detergent dose was 60 g for compositions A and B and for the commercial product 180 g per batch.

The results were as follows:

Mixture Commercial

A B product

Coupon Deň: 32 ° C 60 ° C 40 ° C 60 ° C Deň: 32 ° C 60 ° C EMPA 101 37.8 50.4 40.0 51.0 29.5 45.9 KREPE1L 10C 46.7 52.2 28.6 43.9 33.7 49.7 EMPA 104 38.6 53.1 33.3 52.4 27.9 46.8 KREEELD 20C 55.3 59.6 37.4 54.2 31.0 49.1 EMPA 111 (blood) 77.1 78.9 31.5 49.8 77.7 80.9 EMPA 112 (cocoa) 25.1 47.8 34.9 47.6 28.3 51.4 EMPA 114 / red wine / 31.7 35.6 49.1 67.2 41.0 43.9 KREPELD 10K / coffee / 56.2 59.9 66.9 72.3 56.6 61.4

The figures given indicate the percentage of increase in light reflectance after washing.

The above results show good performance when compared to a commercial product used in triple weight.

Features facilitating ironing

After using Composition A for 14 days, 27 out of 29 responded positively to the question: 'ironing fabrics better? **

A composition that is substantially equivalent to composition A but modified to the greater consumer interest can be prepared as follows:

Synperonic A 3 Mass kg / te 23,828 % 2.4 Synperonic 87K 71,567 7.2 PSC- 200 320,452 32.1 EMAO / as 100? «/ 97,447 9.7 Sodium carbonate 47,958 4.8 Courlose * 610 9,967 1.0 Sodium di-silicate 18,954 1.9 Sodium tripolyphosphate 366,261 36.6 Ethylenediaminetetraacetic acid 2,002 0.2 Optical brightener 2,998 0.3 Blue 0,029 0.0 Silicone antifoam 0.588 0.1 Bentonite 28,956 2.9 Titan dioxide 2,492 0.2 Perfume 3,000 0.3 Enzyme (protease and amylase) 3,000 0.3 999,500 100.0

Example 3

Liquid suspensions were prepared with the ingredients listed in the following table containing about 50 wt. solids. Composition C was milled to an average particle size of 3 microns. Other compositions were prepared by mixing the solid pre-ground particles with the liquid components, without detecting the particle size.

AND % (B) C * * De <iuest '' 2016 D a phosphonate carrier - - 5 Sodium citrate 52 52 52 Sodium carbonate 10 - 10 Carb oxymethyl cellulose with ^x 6 6 2 Sodium di-silicate 1 1 1 '' Tinopal '' CBS-X. optical brightener 0.2 0.2 0.2 Enzyme (protease and amylase) 0.3 0.3 0.3 '' Synperonie A 5 5.75 5.75 5.75 ' ^from Synperonia''87K 11.25 11.25 11.25 Polyethylene glycol, molecular weight 200 25.5 25.5 54.5 Tetraacetyl-ethylenediamine - 5 - '' Synprolam 55 DMQ 10 10 - Sodium perborate, monohydrate - 7 -

^x Commercial product sold under the name Courlose A 161, degree of substitution 0.5 to 0.7, estimated molecular weight 60,000 to 100,000.

Synperonies A5 and Synperonies 87K are the products of the condensation of 5 moles of ethylene oxide with 7 moles of a mixture containing 92 ethylene oxide and 8% propylene oxide with a mixture of 2 parts of C1-primary alkanol with 1 part of C1-primary alkanol, both having several methyl groups at the 2-position; Synprolam 55 DMQ is an amine oxide having an alkyl group corresponding to said mixtures of ^C 15 ' ^{and C} 1-4 alkanols ^{and 2} methyl groups by which its nitrogen atom is substituted.

The amounts are expressed in percent by weight.

The compositions were tested as laundry detergents as follows: The efficacy of compositions A, B and C was compared with that of commercial datergents. Washing tests were carried out using Miele W 451 washing machines, at 40 and 60 ° C in hard water (7.2 mval.l ¹ ).

Standard products from EMPA or Krefeld were used to determine the efficacy of each product. Three washing machines were each filled with four test specimens (10 x 10 cm) of each type of test substance together with 2 kg of pure substance as a load for each wash batch. Each test sample was measured at twelve different locations to determine the increase in light reflectance for each substance. The detergent dose per batch was 60 g for compositions A, B and C and 180 g for the commercial product.

The results were as follows:

Composition

ABC Commercial product

Substance Deň: 32 ° C 60 ° C Deň: 32 ° C 60 ° C Deň: 32 ° C 60 ° C Deň: 32 ° C 60 ° C EMPA 101 34.7 30.5 32.8 32.7 24.5 22.1 19.8 18.9 KREFELD 10C 41.1 53.2 35.9 56.4 29.2 46 42.4 55.3 EMPA 104 46.5 42.4 46.9 42.8 18.8 19.5 17.1 17.5 KREFELD 20C 39.8 50.2 52.4 49.7 19.3 20.7 29.5 46.3 EMPA 111 67.2 67.8 23.9 54.9 78.3 76.3 74.2 73.7 EMPA 112 40.8 45.6 40.3 35.6 39.8 43.7 38.6 37.2 EMPA 114 21.7 31.2 31.3 65.0 26.4 29.3 33.2 40.3 KREFELD 101C 49.3 53.3 52.8 65.8 51.8 53 53.2 57.1 KREFELD ASI 2 36.9 36.6 43.7 44.8 49 43.8 KREFELD PC12 46.4 43.2 50.8 51.4 44.9 42.1

The numerical values indicate the increase in light reflectance as a percentage after washing.

These results show good performance when compared to a commercial product that was used in triple excess weight.

- 14 777 /

The commercial product contained about one-third of its weight of water, and by comparison, the total content of chemical compounds is about 1: 2.

Example 4

Two liquid detergent compositions containing solids suspended in liquids of the following composition were tested:

A B

% wt. 90 wt Sodium tripolyphosphate 36.7 40.15 Bentonite 2.9 - Sodium carbonate 4.8 5.00 Sodium silicate 1.9 2.00 Carboxymethylcellulose 1.0 1.00 Sodium ethyl diamine tetraacetate 0.2 0.2 Optical brightener 0.5 0.3 Enzymes 0.3 0.3 Titan dioxide 0.25 0.25 Synperonic A 3 2.4 2.4 Synperonic 87K 7.2 7.5 Polyethylene glycol, molecular weight 200 32.0 40.0 Coconut dimethylamine oxide 9.8 - Perfume 0.25 0.8

Then water was added to both compositions at a weight of 1> 1.5%, 2%, 2.5% and 3

Viscosity after 45 min and after 1 day (where indicated) at 20 ° C is evident from the following data:

AND (B) Addition of water viscosity / viscosity % wt. 45 min day 45 min day 0.0 48.0 46.0 1.0 50.8 70.8 2,0 60.2 139.0 3.5 90.4 70.9 304.0 340 3.0 800,000,0 706,000,0

These data show that amine oxide-containing compositions better resist degradation by water.

Compositions A and B were also tested for dispersibility in a commercial Zanussi pump dispenser. In the dispenser, 2.5 times more residue was left at the start of the wash for composition B than for composition A.

Industrial Applicability

The detergent compositions of the present invention represent a new type of detergent, stable over a wide range of temperatures, with good light reflectance for washed fabrics and improved ironing properties.

730b- 7

Claims (10)

PAT3NT0VÁ CLAIMS ^z A liquid detergent composition consisting of a liquid organic phase comprising an amine oxide and a solid phase comprising a carrier, wherein water is present in an amount of at most 5, for example 0.5 to at most 2, and preferably 1.0 to 1.7 moles, %, based on 1 mol of amine oxide, excluding water, which is optionally present as crystalline water or any solids present. 2. A composition useful as an additive to a liquid detergent comprising an amine oxide and a polyalkylene glycol which contains at most 5 and preferably less than 2, for example 0.5 to 5 and preferably 1.0 to 1.7 moles of water, based on 1 mol of amine oxide, A detergent composition comprising an amine oxide, a carrier and a polyalkylene glycol having a molecular weight of from 100 to 1500; A substantially phosphate-free liquid detergent composition comprising an amine oxide, a 2 to 6 carboxylic acid hydroxycarboxylic acid and 1 to 5 hydroxyl groups, and a polycarboxylic acid having at least 10 carboxylic groups, the composition comprising at most 5 and preferably less than 2 moles of water, %, based on 1 mol of amine oxide, excluding water, optionally present as crystalline water, or any solid present. The composition according to any one of the preceding claims, wherein the amine oxide has an alkyl group of 10 to 18 carbon atoms and two other groups individually selected from alkyl groups or hydroxyl groups of 1 to 3 carbon atoms. The composition according to any one of the preceding claims, wherein the carrier is a condensed phosphate, zeolite, silicate or hydroxycarboxylic acid having 2 to 6 carboxyl groups and 1 to 5 hydroxyl groups. The composition of claim 6, wherein the carrier is condensed alkali metal phosphate. Composition according to any one of the preceding claims, wherein the carrier is citric or tartaric acid. * Composition according to any one of the preceding claims, comprising polyethylene glycol having a molecular weight of from 150 to 500. The composition according to any one of the preceding claims, wherein the weight ratio of polyalkylene glycol to amine oxide is preferably from 0.5 to 1 or from 2 to 1. Composition according to any one of the preceding claims, comprising a bleaching agent.