WO2005087907A1

WO2005087907A1 - Improvements in or relating to liquid detergent compositions

Info

Publication number: WO2005087907A1
Application number: PCT/GB2005/000909
Authority: WO
Inventors: Alessandro Latini
Original assignee: Reckitt Benckiser N.V.; Reckitt Benckiser (Uk) Limited
Priority date: 2004-03-11
Filing date: 2005-03-10
Publication date: 2005-09-22
Also published as: EP1725641A1; GB0405414D0

Abstract

The present invention relates to liquid detergent compositions, especially compositions which contain a silicone, a cationic polymer and an anionic surfactant.

Description

IMPROVEMENTS IN OR RELATING TO LIQUID DETERGENT COMPOSITIONS The present invention relates to liquid detergent compositions , especially compositions which contain a silicone , a cationic polymer and an anionic surfactant . Liquid detergent compositions comprising surfactants are known . Such compositions can be used, for example, for cleaning laundry, for example for cleaning fine- fabrics or for heavy-duty laundry cleaning .

Liquid laundry detergent compositions that contain silicones are known. Silicories are used as they provide the fibres of the fabric with lubricity leading to improved performance in terms of softness, elasticity, drape, wrinkle resistance etc. However, typically silicones are not effectively deposited onto the textile fibre during the washing process, much of the silicone is washed away. A number of solutions to this problem have been suggested. O0218528 discloses liquid detergent compositions of the type marketed as Ariel Style and describe silicones derivatised to be positively charged (cationic) during the wash and, therefore, more substantive to natural fibres. Typically low or zero amounts of anionic surfactant are used due to low product stability caused by the incompatibilities of the cationic silicone with the anionic surfactant, leading to a reduction in cleaning performance. US 2003/0216278 discusses the inclusion of fabric softening silicones with anionic surfactants. Although a discussion is included on deriv-atised silicones all the preferred silicones and examples illustrate non-derivatised silicone, i.e. polydimethyl siloxane (PDMS) . It is expected that a large amount of the silicone will be washed away and the silicone has to be included in a relatively large amount to provide an effect .

Generally the formulator will avoid ttie inclusion of anionic surfactants to avoid any incompatibilities with cationic silicone needed in the composition. A reduction or elimination of anionic surfactants may lead to a fall in cleaning performance of the composition against greasy stains and a rise in cost, due to the need to include large amounts of expensive nonionic surfactants, or other adjuncts to aid cleaning performance. The inclusion of larger amounts of non-cationic silicones is possible but is wasteful and expensive .

We have found a composition that allocs the inclusion of a significant amount of anionic surfactant and effective amount of a silicone, preferably a silicone that is not cationic .

Accordingly the present invention provides a liquid detergent composition comprising: a) at least one anionic surfacta-nt; b) a silicone; c) a cationic polymer; and d) water.

Alternatively, we provide a method of cleaning laundry comprising adding to a laundry washing machine a composition as described herein.

Alternatively, we provide the use of a cationic polymer, as described herein, to aid the deposition of a silicone, as described herein, in a laundry cleaning process.

Silicone

The composition comprises (by weight of the composition) at least 0.5%, preferably more than 0.8%, or from 1% to 5%, or even from 1% to 3% of a fabric- softening silicone. The fabric-softening silicone typically has the general formula:

wherein, each Rl and R2 in each repeating unit are independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkenyl or phenyl; x is a number from 50 to 300,000, preferably from 100 to 100,000, more preferably from 200 to 50,000; wherein, the alkyl, alkenyl or phenyl are optionally substituted with halogen, amino, hydroxyl groups, quaternary ammonium groups, polyalkoxy groups, carboxyl groups, or nitro groups; and wherein the polymer is terminated by a hydroxyl group, hydrogen or - SiR3, wherein, R3 is hydroxyl, hydrogen, methyl or a functional group.

Preferably Rl and R2 are methyl groups. Preferably some of the Rl and R2 groups are cross- linked to each other or to themselves or both. The degree of cross linked groups is <30% <20%, <15%, <10% ideally less than 5%. Preferably, the silicone is a derivative of polydimethyl siloxane. The silicone typically has an average molecular weight, as measured by viscosity, of from 500 cst to 100,000 cst, or from 700 cst to 70,000 cst or even from 800 cst to 1,000 cst.

The silicone may preferably be a mixture of two or more different types of silicone. The silicone may be a mixture of a high-viscosity silicone and a low viscosity silicone. The silicone may even be a mixture of a functionalised silicone and a non-functionalised silicone.

The silicone, when present in the composition, is preferably in the form of an emulsion (either a micro emulsion or a macro emulsion) , typically having a volume average primary particle size of from 0.01 micrometer to 50 micrometers, preferably from 0.05 micrometer to 5 micrometers . The volume average primary particle size can be measured using a Coulter Multisizer^®. Therefore, the silicon composition preferably contains an emulsifier. Preferably the emulsifier is present in an amount of from 1 to 15 %wt and is anionic or cationic, preferably cationic. The emulsifier may also be nonionic with or without a second anionic or cationic emulsifier.

The structures are completed by terminal moieties which can be noncharged, for example H, OH or Cι_₄alkyl .

Preferred silicones are those available from Dow

Corning under the name DC2-1597, DC2-1607, DC HV 600, DC FM 5750, DC 1665, DC Q2-1652 and DC 2-1391.

Cationic Polymer The cationic polymer is an essential feature of the invention. Preferably the Mw of the cationic poZLymer is between 100 , 000 and 2 , 000 , 000 .

We have found that only a small amount of cationic polymer is required to improve the deposition of the silicone. Due to the small amounts of the cationic polymer the problems of stability with the anionic surfactant are reduced. In addition preferably t-he cationic polymer is more hydrophilic than the silicone. Preferred amounts of cationic polymer are at least 0.001, 0.006, 0.008, 0.01 and 0.02%wt. Maxiimum amounts of cationic polymer are up to 2, 1.5, 1, 0.5 and 0.2%wt.

Preferred cationic polymers are cyclopolymers of: alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers ( (la) or (lb) with acrylamide) containing, as main constituent of the chain, units of formula (la) or (lb) : (CH₂)k _y(CH₂)_k (CH₂)_t—CR₁₂ CR—CH₂ (CH₂)_t CRι CRi CH₅

in which; k and t are equal to 0 or 1, the sum of k+t being equal to 1;

Ri2 denotes a hydrogen atom or a methyl radical; Rxo and Rn, independently of each other, denote a Cl-6 alkyl group, a C 1-5 hydroxyalkyl group, a amido Cl-4 alkyl group, or Rio and Ru can denote, together with the nitrogen atom to which they are attached a heterocyclic groups such as piperidyl or morpholinyl;

Y^" is an suitable counter anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, sulphate or phosphate.

These polymers are described in particular in French patent 2 080 759 and in its Certificate of Addition 2 190 406.

Among the polymers defined above is dimethyldiallylammonium chloride homopolymer sold under the name Merquat^® 100 by the company Nalco (and its homologues of low weight average molecular mass) and copolymers of diallyldimethylammonium chloride and of acrylamide, sold under the name Merquat^® 550.

Other cationic polymers which can be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and cationic chitin derivatives.

Among all the cationic polymers that may be used in the compositions of the present invention, it is preferred to use cationic cyclopolymers, in particular the dimethyldiallylammonium chloride homopolymers or copolymers such as those sold under the names Merquat^® 100, Merquat^® 550 and Merquat^® S by the company Nalco.

A preferred cationic polymer is Polyquaternium-7 which is known also by the following names:

CAS Number: 26590-05-6

Empirical Formula: (C8VH16N-C3VH5NO-Cl)x

Definition: Polyquaternium-7 is the polymerip quaternary ammonium salt consisting of acrylamide and dimethyl diallyl ammonium chloride monomers.

Other Names:

Agequat-500 (CPS)

Agequat-5008 (CPS)

Agequat C-505 (CPS) Conditioner P7 (3V-SIGMA)

N,N-Dimethyl-N-2-Propenyl-2-Propen-1-aminium Chloride,

Polymer with 2-Propenamide

Mackemium 007 (Mclntyre)

Merquat 550 (Nalco) Merquat S (Nalco) 2-Propen-1-aminium, N,N-Dimethyl-N-2-Propenyl- ,

Chloride, Polymer with 2-Propenamide Quatemium-41 Salcare SC10 (Allied Colloids)

Surfactant

The surfactant present in the composition is at least one surfactant chosen from anionic, nonionic, amphoteric, cationic and zwitterionic surfactants and mixtures thereof. Preferably selected from anionic, nonionic or a mixture thereof .

Anionic surfactants may include anionic organic surfactants, usually employed in soluble salt forms, preferably as alkali metal salts, especially as sodium salts. Although other types of anionic surfactants may be utilized, such as higher fatty acyl sarcosides, soaps of fatty acids (including metal soaps and amine soaps) , preferred anionic surfactants are those which are described as of a sulfonate or sulfate type, which may be designated as sulf (on) ates. Especially preferred is the inclusion of a non-ethoxylated anionic surfactant. These include linear higher alkylaryl sulfonates (for example alkylbenzene sulfonates) , higher fatty alcohol sulfates, olefin sulfonates, α-methyl ester sulfonates and paraffin sulfonates. An extensive listing of anionic detergents, including such sulf (on) ate surfactants, is given on pages 25 to 138 of the text Surface Active Agents and Detergents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc. Usually the higher alkyl group of such anionic surfactants has 8 to 24 carbon atoms, especially 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms. An ethoxylated anionic surfactant may be included and the alkoxylate content (preferably ethoxylated or ethoxylated/propoxylated) is in the range of 1 to 4 moles of alkoxy groups per mole of surfactant.

One class of anionic surfactants comprises alkali metal (preferably sodium) alkylaryl sulfonates (especially alkylbenzene sulfonates) , preferably having linear C₉-ι₄ alkyl groups.

Another preferred class of anionic surfactants comprises alkali metal (preferably sodium) alkyl sulfates, preferably having linear alkyl groups of 12 to 18 carbon atoms.

An alternative class of anionic surfactants comprises alkali metal (preferably sodium) alkoxylated sulfates, preferably having linear alkyl groups of 12 to 18 carbon atoms, and preferably having 1 to 4 moles of alkoxy groups per mole of surfactant .

It is known that alkyl benzene sulfonic acids can be produced by a variety of processes in which an alkyl chain is attached to a benzene ring by a catalysed reaction. Various catalysts are known. It is preferred to use an alkyl benzene sulfonic acid produced using an A1C1₃ catalyst. Such alkyl benzene sulfonic acids typically contain at least 25% of the 2-phenyl isomer, that is the isomer in which the alkyl chain is attached to the benzene ring at the 2- position of the alkyl chain. The alkyl benzene sulfonic acid produced by a process using a hydrogen fluoride (HF) catalyst may also be used, but are less preferred. Such alkyl benzene sulfonic acids are commercially available, for example as Solfodac AC 3-1 from Condea or Petresul 550 from Petresa.

Non-ionic surfactants may be selected from, for example, alcohol alkoxylates such as alcohol ethoxylates, also known as alkylpoly(ethylene oxides) and alkylpolyoxyethylene ethers, alkylphenol ethoxylates, ethylene oxide/propylene oxide block copolymers, alkyl polyglucosides, alkanolamides and amine oxides. Alcohol ethoxylates, alkylphenol ethoxylates and ethylene oxide/propylene oxide block copolymers are condensation products of higher alcohols with lower alkylene oxides.

In such non-ionic surfactants the higher fatty moiety will normally be of 11 to 15 carbon atoms and there will usually be present from 3 to 20, preferably from 3 to 15, more preferably from 3 to 10, and most preferably from 3 to 7, moles of alkylene oxide per mole of higher fatty alcohol .

Non-ionic surfactants of interest include alkyl polyglucosides, the hydrophobic carbon chain length varying from 8 to 16 carbon atoms depending on the feedstock (oleochemical or petrochemical) and the hydrophilic polyglucose chain length varying between one and more than eight units of glucose.

Amphoteric surfactants may be selected from, for example, alkyl betaines, alkyl/aryl betaines, amidoalkyl betaines, imidazolinium-type betaines, sulfobetaines and sultaines.

The anionic surfactants are suitably present in a total amount of at least 5 wt%, and more preferably at least 8 wt%, based on the total weight of the composition. The anionic surfactants are also suitably present in an amount of up to 30 wt%, preferably up to 20 wt%, more preferably up to 15 wt%, based on the total weight of the composition.

One or more non-ionic surfactant (s) , when present, is/are suitably present in an amount of at least 0.1 wt%, preferably at least 0.5 wt%, more preferably at least 5 wt%. Good compositions can also be prepared with higher amounts of non-ionic surfactant (s) , for example in an amount of at least 2 wt%, preferably at least 4 wt%, and most preferably at least 8 wt%, on total weight of the composition. One or more nonionic surfactant (s) , when present, is/are suitably present in an amount of up to 30 wt%, preferably up to 25 wt%, more preferably up to 20 wt%, most preferably up to 15 wt%, and especially up to 13 wt%, based on the total weight of the composition. In a preferred feature there is essentially no nonionic surfactant present (<0.1% wt) . In this preferred feature transparent compositions have surprisingly been made.

One or more amphoteric surfactant (s) , when present, is/are suitably present in an amount of at least 0.1 wt%, preferably at least 0.2 wt%, more preferably at least 0.4 wt%, based on the total weight of the composition. Good compositions can also be prepared with higher amounts of amphoteric surfactant (s) , for example from 1 wt%, preferably from 2 wt%, more preferably from 5 wt%, based on the total weight of the composition. One or more amphoteric surfactant (s) , when present, is/are suitably present in an amount up to 30 wt%, preferably up to 20%, more preferably up to 15 wt%, based on the total weight of the composition.

A preferred detergent composition, particularly a laundry detergent composition, includes as surfactant (s) one or more anionic surfactants and one or more non-ionic surfactants. Preferably such surfactant (s) is/are the only surfactant (s) or the major surfactant (s) present in the composition. By this we mean such surfactants in a larger amount by weight than all other surfactant types in total, and preferably constitute at least 60 wt%, preferably at least 80 wt%, and more preferably at least 95 wt%, and most preferably 100 wt% of the total weight of surfactants in the composition, excluding the fatty acid salt.

Especially preferred compositions employ alkyl benzene sulfonic acid neutralised with an alkanolamine as the surfactant, the fatty acid salt and no further surfactants. Alternative preferred compositions also employ one or more non-ionic surfactants, the weight ratio of the alkyl benzene sulfonic acid salt to the latter being at least 2:1, preferably at least 4:1.

In an alternative preferred embodiment the weight ratio so the alkyl benzene sulfonic acid salt to the non-ionic surfactant is at least 1:1, more preferably at least 0.75:1.

The surfactant, or surfactants in total, suitably provides at least 10 wt%, more preferably at least 20 wt%, most preferably at least 30 wt%, and especially at least 50 wt% of the total weight of a detergent composition such as a laundry detergent composition. Suitably the surfactant, or the surfactants in total, provide (s) up to 99 wt%, especially up to 95 wt%, for example up to 70 wt%, of the total weight of the composition.

Fatty Acid

The composition comprises a fatty acid or a fatty acid salt or mixture of both. The composition typically comprises (by weight of the composition) from 1% to 25%wt, or from 4% to 8%wt. Preferred fatty acids are C 12-C18 saturated and/or unsaturated fatty acids, highly preferred is a mixture of such fatty acids. It may be preferred that a mixture of saturated and unsaturated fatty acids is used. For example, preferred coconut derived fatty acids .

Preferred fatty acids are selected from the group consisting of lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, phytanic acid, behenic acid and combinations thereof. The fatty acid may be selected from the group consisting of palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, cis-eleostearic acid, trans- eleostearic acid, linolenic acid, arachidonic acid, and combinations thereof .

Preferred fatty acids are C12-C22 fatty acids comprising a saturated alkyl group. Other preferred fatty acids are C12-C22 fatty acids comprising an unsaturated alkyl group, typically having an iodine value of from 15 to 25, preferably from 18 to 22.

Preferred fatty acids have a cis:trans isomer ratio of from 1:1 to 200:1, preferably from 10:1 to 200:1.

Preferred sources of fatty acid are selected from the group consisting of coconut, soybean, tallow, palm, palm kernel, rapeseed, lard, sunflower, corn, safflower, canola, olive, peanut, and combinations thereof .

The fatty acid salt contains a fatty chain having at least one carbon-carbon double bond. The fatty chain is generally a hydrocarbon chain. Desirably the fatty chain contains from 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms, more preferably 10 to 22 carbon atoms, even more preferably 10 to 18 carbon atoms, and most preferably 12 to 16 carbon atoms. The fatty acid chain may contain only one carbon-carbon double bond, or may contain at least 2, for example, 2, 3 or more carbon-carbon double bonds. The fatty acid chain may be linear or branched although linear is preferred. Examples of suitable fatty acids are coconut fatty acids and palm kernel fatty acids. The fatty acids which are used are generally mixtures of different fatty acids, some of which may contain only saturated fatty chains. The fatty acid salt may be any salt. Desirably, it is in the form of alkali metal, alkaline earth metal, ammonium or a ine salt. Examples of alkali earth metals are sodium, potassium and lithium. Examples of alkali earth metals are calcium and magnesium.

Examples of amine salts are alkanol amine salts.

Preferably present is an alkanolamine that may contain one, two or three alkanol groups, which may be same or different. For example it can contain one, two or three methanol, ethanol, propanol or isopropanol groups. Desirably it is a monoethanolamine, diethanolamine or triethanolamine or a mixture thereof. Particularly desirable is a mixture of monoethanolamine and triethanolamine, for example in a weight ratio of from 2:1 to 1:2, such as 1.25:1 to 1:1.25.

The fatty acid or salt or mixture may be present in the composition in an amount of up to, for example, 20 wt%, for example to 15 wt%, preferably 1 to 10 wt%, especially 6 to 10 wt%.

The detergent composition may also contain at least one solvent .

The organic solvent may be any organic solvent, although it is desirable that it is miscible with water. Examples of organic solvents are glycols, glycerine or an alcohol . Preferred organic solvents are Cι_₄ alcohols such as ethanol and propanol, and C₂-₄ glycols such as monoethylene glycol and monopropylene glycol .

The organic solvent may be present in the composition in any amount, for example in an amount of up to 20 wt%. Preferably it is present in an amount of from 2 to 10 wt%, especially from 3 to 8 wt%.

A detergent composition of the present invention may include any one or more further optional minor components such as desiccants, sequestrants, enzymes, silicones, emulsifying agents, viscosifiers, bleaches, bleach activators, hydrotropes, opacifiers, builders, foam controllers, preservatives, disinfectants, pearlising agents, limescale preventatives (such as citric acid) , optical brighteners, dye transfer inhibitors, colour fading inhibitors, thickeners, gelling agents and aesthetic ingredients, for example fragrances and colorants.

Further optional minor components are present in a total amount of up to 20% wt, 15% wt, 10% wt, 5% wt or at least 0.5% wt, 1% wt, 3% wt,^' 8% or 10% wt .

The liquid detergent composition of the present invention may have a wide variety of uses. Thus it may be used, for example, as a laundry detergent composition, for example, for fine fabrics such as wool or for heavy-duty laundry use such as for a normal wash.

A preferred additional additive is an enzyme, especially a protease, or a mixture of enzymes (such as a protease combined with a lipase and/or a cellulase and/or an amylase, and/or a cutinase, and/or a peroxidase enzyme) . Such enzymes are well known and are adequately described in the literature (see WO 00/23548 page 65 to 68, which is incorporated herein by reference) .

The enzyme will be present in an amount of, by weight, 0 . 1 to 5 . 0% , ideally 0 . 3% to 4 . 0% and preferably 1% to

3 % .

A preferred protease is an enzyme Genencor Properase, supplied by Genencor, address is Genencor International , Inc . 200 Meridian Centre Blvd . Rochester, NY 14618-3916 USA.

Examples

The following compositions were prepared, the figures are %wt of each ingredient present in the composition

LDL2/04 LDL4/04 LDL3/04 LDL5/04

Water 63.9989 64.2869 66.5918 70.9617

Ca salt 0.0050 0.0050 0.0050 citric acid 2.6600 2.6600 5.6000

Na sulfite 0.1000 0.1000 0.1000 0.1000

Na borate 1.5000 1.5000 1.5000

Monopropylene glycol 5.0000 5.0000

Soaps 7.0000 7.0000 8.4212 9.9589

LAS Na 9.2285 9.2285 15.6000 8.9414

C13-C15 NI 7EO (linear) 8.3000 8.3000 8.2560

Crosslinked PDMS 0.3240 0.0360 0.3240 0.3240

Polyquatemium 7 0.0800 0.0800 0.0800 0.0800

DTPMP 0.6406 0.6406 0.6150 0.6150

Enzyme Mixture 0.4000 0.4000 0.4000

PVNO 0.0420 0.0420 0.0420 0.0420

Preservative 0.1200 0.1200 0.1200 0.1200

Dye 0.0010 0.0010 0.0010 0.0010

Fragrance 0.6000 0.6000 0.6000 0.6000

TOTAL 100.0000 100.0000 100.0000 100.0000

pH(5%) 8.7 8.7 8.78 8.7

In addition control compositions were prepared Cl = LDL3/04 without silicone C2 = LDL2/04 without silicone and without polyquatemium 7 C3 = LD 2/04 without polyquatemium 7

In all instances the compositions were rebalanced by the inclusion of additional water.

Softness

Shape

shape recovery, elasticity and fading in Linitest at 40° (10 washes)

Elongation Force (N) at Deformation Fading (DE*) (mm) at 25N 80% elong. (%)

DASH forma e colore liq. 51.5 103.5 44.6 1.4

ARIEL Style liquid 58.4 70.8 42.6 1.2

C3 44.2 134.8 54.0 1.8

LDL2/04 55.6 83.5 43.4 1.2

LDL3/04 61.3 62.7 40.0 1.3

shape recovery and elasticity in washing machine at 40°C (10 washes) (knitted cotton, polo shirt)

Claims

1. A liquid detergent composition comprising: a) at least one anionic surfactant; b) a silicone; c) a cationic polymer; and d) water.

2. A composition as claimed in claim 1 wherein the cationic polymer is a cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers (with acrylamide) containing, as main constituent of the chain, units of formula (la) or (lb) :

in which; k and t are equal to 0 or 1, the sum of k+t being equal to 1;

R₁₂ denotes a hydrogen atom or a methyl radical; Rio and R_u, independently of each other, denote a Cl-6 alkyl group, a C 1-5 hydroxyalkyl group, a amido Cl-4 alkyl group, or Rio and R_u can denote, together with the nitrogen atom to which they are attached a heterocyclic groups such as piperidyl or morpholinyl; Y^" is an suitable counter anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulphate, bisulphite, sulphate or phosphate.

3. A composition according to claim 1 or 2 wherein the surfactant is a non-alkoxylated anionic surfactant .

4. A composition according to claim 2 or 3 which additionally comprises a fatty acid salt.

5. A composition according to claim 3 wherein the fatty acid is a salt of an alkali metal, alkaline earth metal, ammonium or amine salt.

6. A composition according to claim 5 wherein the fatty acid is a salt of an amine .

7. A composition according to any one of the preceding claims wherein the fatty acid salt contains a linear fatty chain.

8. A composition according to any one of the preceding claims which comprises the surfactant in an amount of from 10 to 80 wt% relative to the total amount of the composition.

9. A composition according to any one of the preceding claims which comprises the fatty acid salt in an amount of from 1 to 20 wt%.

10. A composition according to any one of the preceding claims which is a laundry detergent composition.