DE69314038T2 - DETERGENT COMPOSITION - Google Patents

Description

The invention relates to deflocculating polymers and liquid detergent compositions containing these polymers, in particular to liquid detergent compositions comprising a dispersion of lamellar droplets in an aqueous continuous phase.

Background and state of the art

Various types of deflocculating polymers are described in the prior art. EP 346 995 describes deflocculating polymers having a hydrophilic backbone and one or more hydrophobic side chains. WO 91/06622 describes deflocculating polymers which are block copolymers consisting of alternating hydrophobic and hydrophilic groups, WO 91/06623 describes deflocculating polymers consisting of non-ionic monomers and ionic monomers, and GB 2 237 813 describes deflocculating polymers consisting of a hydrophobic backbone and one or more hydrophilic side chains.

Deflocculant polymers have been used in liquid detergents, in particular in liquid detergent compositions comprising a dispersion of lamellar droplets in an aqueous continuous phase, as described for example in EP 346 995, WO/91/06622, WO/91/06623 and GB 2 237 813. Other applications are disclosed for deflocculant polymers for all-purpose cleaners, liquid scouring agents, liquid bleach compositions in WO/91/09108, for fabric softener compositions in EP 415698 and use in granular detergent compositions in WO/91/09932.

WO/91/09109 discloses liquid detergent compositions containing deflocculating polymers that are biodegradable.

As a result of the interest of consumers and manufacturers in environmental issues, there is a trend towards the development and adoption of "green" products, i.e. products with ingredients that biodegrade faster and more easily, i.e. a search for ingredients that lead to improved biodegradability of the products.

Surprisingly, the applicants have found a way to improve the biodegradability of deflocculating polymers.

These improved polymers do not suffer from a loss of the beneficial deflocculating effects in liquid or granular detergent compositions. The improvement can be achieved by incorporating a special group into the hydrophilic backbone of the polymer, resulting in polymers that are more biodegradable.

Definition of the invention

The subject-matter for which protection is sought is defined in claims 1 to 8.

Deflocculant polymer with a hydrophilic backbone and one or more hydrophobic side chains

In general, the hydrophilic backbone of the polymer is mainly linear; the main chain or backbone forms at least 50%, preferably more than 75%, most preferably more than 90% by weight of the polymer. Monomer units suitable for incorporation into the hydrophilic backbone are, for example, unsaturated C₁₋₆ acids, ethers, alcohols, aldehydes or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol. Examples of suitable monomer units are acrylic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid, methacrylic acid, maleic acid, vinylacetic acid, itaconic acid, polyethoxy groups, preferably comprising 4 to 50 ethylene oxide groups, polyglycerol, Condensation polymers of polyglycerol and citric anhydride and condensation polymers of α-hydroxy acids or polyacetals.

Any of the above monomers may be present in the hydrophilic backbone in a random arrangement, in a block arrangement or in mixtures thereof.

The hydrophilic framework made of the framework components without hydrophobic side groups is relatively water-soluble at ambient temperature and at a pH of 6.5 to 14.0. Preferably, the solubility is greater than 1 g/L, more preferably greater than 5 g/L, and most preferably greater than 10 g/L.

Preferably, the hydrophobic side chains are part of a monomer unit which is incorporated into the polymer by copolymerizing hydrophobic monomers and hydrophilic monomers which form the backbone of the polymer. The hydrophobic side chains for this use preferably include those which, when isolated from their bond, are relatively water insoluble, i.e. preferably less than 1 g/l, more preferably less than 0.5 g/l, most preferably less than 0.1 g/l of the hydrophobic monomers dissolve in water at ambient temperature and a pH of 3.0 to 12.5.

Examples of relatively hydrophobic groups are butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains. The hydrophobic groups can be linked to the hydrophilic framework directly or via relatively hydrophilic bonds, e.g. polyethoxy bonds.

Deflocculant polymer as a block copolymer with alternating hydrophobic and hydrophilic groups

These polymers have one of the following general structural formulas:

wherein A represents a hydrophobic group, B represents a hydrophilic group and z is an integer which is preferably 0.

The hydrophilic groups of the polymer are preferably composed of hydrophilic monomer units, which can be selected from a variety of units available for the production of polymers. Suitable hydrophilic monomer units are described, for example, in the section on the deflocculating polymer with a hydrophilic backbone and one or more hydrophobic side chains. Particularly preferred hydrophilic groups are polyethoxy groups, preferably those with 4 to 50 ethylene oxide groups, polyglycerol, condensation polymers of polyglycerol and citric anhydride, and condensation polymers of α-hydroxy acids or polyacetals.

The hydrophobic groups of the polymer are preferably selected from saturated and unsaturated alkyl chains, e.g. having 5 to 24 carbon atoms, preferably 6 to 18 carbon atoms, most preferably 8 to 16 carbon atoms and are optionally linked to adjacent hydrophilic groups via an alkoxylene or polyoxyalkylene bond, e.g. a polypropoxy or butyloxy bond with 1 to 50 alkoxylene groups. Other suitable hydrophobic groups are polyoxyalkylene groups comprising 4 to 50 propylene oxide and/or butylene oxide groups.

The hydrophilic groups may be linked to the hydrophobic groups via any possible chemical bond, although the following types of bonds are preferred: -C-O-, -CO-O- or -O-.

Deflocculant polymer with ionic and non-ionic groups

The ionic-nonionic deflocculating polymer comprises a monomer A independently selected from the group of monomer units that are nonionic under the conditions in the liquid detergent product and a monomer B that is ionic under the conditions of the product.

The units falling within the definition of non-ionic monomer A for use in compositions according to the invention are monomers which are non-ionic under most conditions and monomer units which are anionic or cationic but which are neutralized under conditions such as the pH of the product so as to have an acceptably non-ionic character. Preferably, the pH of the product differs by at least one unit, more preferably at least two units, from the pKa value corresponding to the neutralization of the monomer unit in the polymer.

Suitable monomer units that are non-ionic per se are, for example, ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaride and their N-substituted derivatives such as N-(dimethylaminoethyl)acrylamide, vinyl alcohol, vinyl acetate, heterocyclic vinylamides such as vinylpyrrolidone, acrolein, allyl alcohol, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, sugar units such as saccharides and glucosides, glycerin or other polyalcohols.

Suitable monomer units which are anionic under certain conditions but have an acceptable non-ionic character at relatively low pH values of the product, are e.g.: ethylenically unsaturated carboxylic acids, dicarboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citraconic acid.

Suitable monomer units which are cationic under certain conditions but which have an acceptably non-ionic character at relatively high pH values are, for example: aminoalkyl esters of unsaturated carboxylic acids, such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, vinyl or alkylamines, such as vinylpyridine, vinylmorpholine or allylamine.

Mixtures of non-ionic monomers can also be used.

The ionic monomer B can be ionic under most conditions, but it is also possible to use monomer units that are only ionized under the pH conditions of the product. If such ionizable monomer units are used, the pH of the product should preferably differ by at least one unit, more preferably at least two units, from the pKa corresponding to the ionization of the monomer in the polymer.

Examples of generally ionized monomer units are N-(trimethylammoniumethyl)acrylamide chloride or sulfate, N-(trimethylammoniumpropyl)acrylamide chloride or sulfate, 2-sulfatoethyl(meth)acrylate and the ammonium, alkali or alkaline earth salts, or these can be obtained by conversion reactions of monomers A, such as the cationization of sugar units with 2,3-epoxypropyltrimethylammonium chloride, other ethylenically unsaturated quaternary ammonium compounds, such as vinylbenzyltrimethylammonium chloride, quaternary ammonium salts of di-methyl/ethylaminomethyl/ethyl(meth)acrylate, vinylarylsulfonates such as vinylbenzylsulfonate, sodium vinylsulfonate, sodium alkylsulfonate, β-styrenephosphonic acid, sodium p-styrenesulfonate and vinylphosphonic acid. Examples of monomer units which have an acceptably ionized character at relatively high pH values are ethylenically unsaturated carboxylic acids, dicarboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citric acid.

Suitable monomer units which have an acceptably ionized character at relatively low pH values are, for example: aminoalkyl esters of unsaturated carboxylic acids, such as 2-aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, vinyl or alkylamines, such as vinylpyridine, vinylmorpholine or allylamine.

Mixtures of monomer units can also be used.

Preferably, the monomers for use in ionic-nonionic polymers are sufficiently hydrophilic to form at least a 1% by weight solution when dissolved in water at ambient temperature and the pH of the final product.

Preferred ionic-nonionic polymers contain at least two different monomers. The first of these monomers is preferably nonionic, as defined above, the second monomer is preferably ionic under most circumstances, as defined above. Most preferably the ionic monomer is a cationic monomer. Preferably the amount of ionic monomer in the polymer is from 0.1 to 50% by weight based on the polymer, more preferably 1 to 25%, most preferably 4 to 15%.

Summary of the invention

A first group of preferred deflocculating polymers of the invention having a hydrophilic backbone and one or more hydrophobic side chains has the formula (I):

wherein the monomer units may be arranged randomly ;

z is 1;

k is at least 1;

y preferably has a value from 0 to x;

n is at least 1 (and can be determined by the molecular weight);

the ratio of (k + x + y) : z is 4:1 to 1,000:1, preferably 6:1 to 250:1;

the ratio of k : (x + y + z) is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90;

R¹ represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is absent;

R² represents 1 to 50 independently selected alkyleneoxy groups (preferably ethylene oxide or propylene oxide groups) or is absent, with the proviso that when R³ is absent and R⁴ represents hydrogen or contains not more than 4 carbon atoms, then R² contains at least one alkyleneoxy group, preferably more than 3, more preferably more than 5 alkyleneoxy groups, the alkyleneoxy groups preferably having at least 3 carbon atoms;

R³ is a phenylene linking group or is absent ;

R⁴ represents hydrogen or a C₁₋₂₄ alkyl or C₁₋₂₄ alkenyl group, with the proviso that when R² is not present, then R⁴ is not hydrogen and when R³ is also not present, then R⁴ contains at least 2, preferably at least 3, more preferably at least 4, most preferably at least 5 carbon atoms. More preferably R⁴ represents hydrogen or a C₁₋₂₄ alkyl or C₁₋₂₄ alkenyl group, with the provisos that:

a) when R¹ is -O-CO-, R² and R³ must not be present and R⁴ must contain at least 5 carbon atoms ;

b) if R² is not present, R⁴ is not hydrogen and if R³ is not present, then R⁴ must contain at least 5 carbon atoms.

R⁵ represents hydrogen or a group of the formula -COOA⁴;

R6 is hydrogen or C1-4 alkyl and A1, A2, A3 and A4 are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C1-4 radicals or (C2H4O)tH, where t is 1 to 50, where the monomer units may be in a random arrangement.

Each B¹ is independently selected from -CH₂OH, -OH or -H.

For each monomer unit, R¹-R⁶, A¹-A⁴ and B¹ can be independently selected from the above-mentioned groups.

A second group of preferred deflocculating polymers of the present invention having a hydrophilic backbone and one or more hydrophobic side chains are those of formula (II):

where Q² is a molecular unit of the formula (IIa):

in which the monomer units may be arranged randomly ;

z and v are 1;

n is at least 1 (and can be determined from the molecular weight );

k is at least 1;

is present in at least one of the monomer units p, q or r; the ratio of (k + x + y + p + q + r) : z is 4:1 to 1,000:1, preferably 6:1 to 250:1;

the ratio of k : (x + y + p + q + r + z) is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90 ;

R¹-R⁶, A¹-A⁴ and B¹ are as defined for formula I;

R⁷ and R⁸ represent -CH₃ or -H;

R³ and R¹⁰ represent substituent groups such as amino, amine, amide, sulfonate, sulfate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups and are preferably selected from -SO₃Na, -CO-O-C₂H₄-OSO₃Na, -CO-O-NH-C(CH₃)₂-SO₃Na, -CO-NH₂, -O-CO-CH₃, -OH.

For each monomer unit, R¹-R¹², A¹-A⁴ and B¹ can be independently selected from the above-mentioned groups.

Q¹ is a multifunctional monomer that allows branching of the polymer, whereby the monomers of the polymer can be connected to Q¹ in any direction, in any arrangement, possibly forming a branched polymer. Preferably Q¹ is trimethylpropane triacrylate (TMPTA), methylenebisacrylamide or divinyl glycol.

A third group of preferred deflocculating polymers of the present invention having a hydrophilic backbone and one or more hydrophobic side chains, which is particularly suitable for fabric softener compositions containing an aqueous base and one or more fabric softening materials, has the formula (III):

wherein Q³ is derived from a monomeric unit IIIa comprising:

Q4 is derived from the molecular unit IIIb:

and Q⁵ is derived from a monomer unit IIIc:

wherein

n is at least 1;

k is at least 1;

w is 0 to 4;

the ratio of (a + b + c + k) : d is 5:1 to 500:1, wherein the monomer units can be arranged randomly, a, b, c, d, e, f, g, h can be integers or 0;

the ratio of k : (a + b + c + d) is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90;

R¹-R⁶ are as defined in formula I;

R¹¹ and R11* are independently selected from hydrogen or C₁-C₄alkyl radicals;

R¹² is independently selected from C₅-C₂₄ alkyl or alkenyl, aryl, cycloalkyl, hydroxyalkyl or alkoxyalkyl radicals and B¹, B², B³, B⁴ are organic or inorganic anions; Examples of the anions represented by B¹, B², B³, B⁴ are halide ions, sulfate, sulfonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, sulfide, cyanate, acetate and other common inorganic and organic ions. Preferred anions are chloride and methosulfate.

A fourth group of preferred deflocculating polymers of the present invention having a hydrophilic backbone and one or more hydrophobic side chains, which are particularly suitable for fabric softener compositions comprising an aqueous base and one or more fabric softening materials, are those of formula (IV):

wherein

z is 1;

n is at least 1;

k is at least 1;

the ratio of (j + k) : z is 5:1 to 500:1;

the ratio of k:(j+z) is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90; wherein the monomer units may be arranged randomly;

R¹-R⁶ is as defined for formula I;

R¹³ represents -CH₂-, -C₂H₄-, -C₃H₆ or is absent;

R¹⁴ represents 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide groups, or is absent;

R¹⁵ represents -H or -OH.

A fifth group of preferred deflocculating polymers of the present invention having nonionic monomers and ionic monomers has the formula (V):

in which the monomer units may be arranged randomly ;

z is 1;

k is at least 1;

n is at least 1 (and can be determined from the molecular weight);

the ratio of (k + x) : z is 1:1 to 2,000:1, preferably 4:1 to 1,000:1, more preferably 6:1 to 250:1; the ratio of k : (x + z) is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90;

R1 -C3 H6 -N+ -(CH3 )3 (Cl- ), -C2 H4 -OSO3 -(Na+ ), -SO3 -(Na+ ), -C2 H4 ;N+ (CH3 )3 Cl- , -C2 H4 N+ (C2 H6 )2 Cl- , -CH2 N+(CH3 )3 Cl- , -CH2 N+( C&sub2;H&sub6;)&sub2;Cl&supmin; or benzyl-SO₃⊃min;(Na⁺);

R² represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is absent;

R³ and R⁴ are hydrogen or C₁₋₄-alkyl radicals;

Ra is CH₂, C₂H₄, C₃H₆ or is absent;

Rb represents 1 to 50 independently selected alkylene oxide units, preferably ethylene oxide groups or is absent;

Rc is -OH or -H;

and wherein, when R², Ra and Rb are absent, Rc is not -H.

A sixth group of preferred deflocculating polymers of the present invention, which is a block polymer having alternating hydrophobic and hydrophilic groups, is represented by the formula (VI):

wherein the monomer units may be arranged randomly ;

x is 4 to 1,000, preferably 6 to 250;

k is at least 1;

the ratio k:x is 1:99 to 30:70, preferably 2:98 to 20:80, more preferably 5:95 to 10:90;

R¹ represents a C₂₋₂₄-alk(en)yl group, preferably a C₃₋₂₄-alk(en)yl group, more preferably C₅₋₂₄-alk(en)yl group, most preferably C₆₋₂₄-alk(en)yl group and/or 4 to 50 propylene oxide or butylene oxide units;

R² is -CO-;

R³ is -CO-O- or -O-.

The general formulas I to VI are intended to include mixed copolymer forms within a particular polymer molecule when n is 2 or greater, where R¹-R¹⁵ may be different for the individual monomer units.

Molecular weight

Polymers for use in compositions may have a molecular weight between 500 and 1,000,000. Molecular weight is measured by GPC using polyethylene glycol standards. For the purposes of the definition, the molecular weight of the standards is measured using the method for measuring absolute intrinsic viscosity described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710 to 719. Polymers according to the invention preferably have molecular weights of from 750 to 100,000, more preferably from 10,000 to 30,000, most preferably from 2,000 to 10,000.

Incorporation of ketone groups into the polymer

The polymers for use in detergent compositions of the invention can be prepared using conventional polymerization techniques such as radical polymerization, cationic-anionic polymerization or a combination thereof.

The ketone group can be incorporated into the deflocculating polymer as described in the co-pending application GB 9207795.7 filed on 9 April 1992. The ketone groups can be derived, for example, from a compound of formula (X):

wherein each of R⁴ and R⁵, which may be the same or different, represents a group capable of stabilizing a radical.

Preferably, one of R4 and R5 is an aryl or cyano group and the other is an aryl, alkyl or cyano group. Preferably, at least one of R4 and R5 is a phenyl group and the compound in which R4 and R5 are both phenyl groups is particularly preferred. This compound is 2,2-diphenyl-4-methylene-1,3-dioxolane.

Upon heating and in the presence of a radical initiator, the ring of the monomer of formula (X) opens. This product can be used to introduce a ketone function into the polymer by reaction with comonomers.

Biodegradability test

Suitable tests to determine biodegradability are given in the OECD guidelines. Other suitable tests involve the detection of CO₂ released after decomposition of the polymer material, for these tests 14C-labelled polymers can sometimes be used.

Preferred polymers for use in compositions of the invention satisfy one or more of the following tests:

(a) Modified SCAS test as described in OECD Guideline 302a. This test measures the removal of test material by analysis of dissolved organic carbon. It is assumed that 80% removal is a reasonable indication of biodegradability or adsorption.

(b) Modified Sturm test as described in OECD Guideline 301b. This test measures the CO₂ production from the test material under standard conditions, with the polymer enclosed in a closed vessel which is inoculated with bacteria adapted to the test polymer in an enrichment study. Values of a Conversion of 25 to 35% to CO2 in the modified Sturm test and similar tests have been frequently reported for polymers, but can be attributed to the presence of low molecular weight monomers and oligomers. Values of 50% and more in this type of test are indicative of superior biodegradability. A 60% conversion to CO2 in the Sturm test is indicative of rapid biodegradability.

Although it is preferred that polymers for use in the composition of the present invention satisfy both tests, applicants have found that polymers that satisfy either test for biodegradability are suitable for use in the present invention.

Product forms

Deflocculant polymers of the present invention can be used, for example, in liquid detergent compositions, all-purpose cleaners, liquid scouring agents, liquid bleaching compositions as disclosed in WO/91/09108 and also in granular detergent compositions as disclosed in WO/91/09932.

Deflocculant polymers can be used in particular in liquid detergent compositions comprising a dispersion of lamellar droplets in an aqueous continuous phase.

Lamellar droplets are a special class of surfactant structures that are already known from a large number of literature sources, e.g. H.A. Barnes, "Detergents" Chapter 2 in K. Walters (Ed), "Rheometry: Industrial Applications", J. Wiley & Sons, Letchworth 1980.

Such lamellar dispersions are used to impart properties such as consumer-preferred flow and/or hazy appearance. Many can also suspend particulate solids such as detergent builders or scouring particles. Examples of such structured liquids without suspended solids are given in US Patent 4,244,840, while examples of solid particles being suspended are given in EP-A-160,342; EP-A-38,101; EP-A-140,452 and also in the previously mentioned US 4,244,840. Others are disclosed in EP-A-151,884, where the lamellar droplets are referred to as "spherulites".

The presence of lamellar droplets in a liquid detergent product can be detected by means known to those skilled in the art, e.g. optical techniques, various rheometric measurements, X-ray or neutron diffraction and electron microscopy.

The droplets consist of an onion-like configuration of concentric biphases of surfactant molecules between which water or an electrolyte solution (aqueous phase) is trapped. Systems in which such droplets are closely packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.

The viscosity and stability of the liquid product depends on the volume fraction of the liquid occupied by the droplets. In general, when the volume fraction is about 0.6, the droplets almost touch each other (fill gaps). This allows reasonable stability at an acceptable viscosity and provides useful solid suspending properties.

Problems in formulating liquid detergent compositions with a high proportion of lamellar phase are a possible instability and/or high viscosity of the product, as described in patent application EP 346 995. Compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 s-1, more preferably less than 1,500 mPas, most preferably less than 1,000 mPas, particularly preferably 100 to 750 mPas at 21 s-1.

Liquid compositions of the invention are physically stable and have a relatively low viscosity, i.e. a corresponding composition without the deflocculating polymer is less stable and/or has a higher viscosity. In the context of the present invention, physical stability for these systems can be defined as the maximum separation compatible with most manufacturing and storage requirements. This means that "stable" compositions give no more than 10%, preferably no more than 5%, most preferably no more than 2% by volume of phase separation, as evidenced by the appearance of two or more separate phases when stored at 25°C for 21 days from manufacture.

Preferably, liquid compositions of the invention containing polymers of formulae I, II, 2V and VI have a pH of 6 to 14, more preferably 6.5 to 13, particularly preferably 7 to 12. Preferably, liquid compositions of the invention containing polymers of formulae III and IV have a pH of less than 6.0, more preferably less than 5.0, especially 1.5 to 4.5, most preferably 2.0 to 4.0. Liquid compositions of the invention containing polymers of formulae I and II may also have a low pH, i.e. more preferably less than 5.0, especially 1.5 to 4.5, most preferably 2.0 to 4.0.

The amount of deflocculant polymer to be used depends on the product form in which it is used, as well as its function in the product. Generally, the deflocculant polymer is used in an amount of from 0.01 to 5% by weight of the composition, more preferably from 0.1 to 3.0%, most preferably from 0.25 to 2.0%.

Other ingredients

Compositions according to the invention also contain detergent-active materials, preferably in a proportion of 1 to 70% by weight, based on the composition, more preferably in a proportion of 5 to 40% by weight, most preferably 10 to 35% by weight.

In the case of a mixture of surfactants, the exact proportions of each component leading to lamellar structures depend on the type and amount of electrolytes, as in the case of conventional structured fluids.

In the broadest definition, the detergent material may generally comprise one or more surfactants and may be selected from anionic, cationic, non-ionic, zwitterionic and amphoteric types and (provided they are mutually compatible) mixtures thereof. For example, they may be selected from any of the classes, subclasses and specific materials described in "Surface Active Agents", Volume I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents", Volume II, by Schwartz, Perry & Berch (Interscience 1958), in the currently valid edition of "McCutcheon's Emulsifiers & Detergents", published by the McCutcheon Division of the Manufacturing Confectioners Company or in "Tensid-Taschenbuch", H. Stache, 2nd Edition, Carl Hanser Verlag, Munich & Vienna, 1981.

Suitable nonionic surfactants include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, e.g. aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, in particular ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent compounds are primary or secondary, linear or branched alkyl (C6-C18) alcohols with ethylene oxide and products prepared by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.

Preferably, the proportion of nonionic surfactant material is 1 to 40% by weight of the composition, more preferably 2 to 20%.

Compositions of the present invention may contain synthetic anionic surfactant ingredients, preferably present in combination with the nonionic materials mentioned above. Suitable anionic surfactants are usually water-soluble alkali salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl radical being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, particularly those obtained by sulfation of higher (C8-C18) alcohols prepared, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulfonates, particularly linear secondary sodium alkyl (C10-C15) benzene sulfonates; Sodium alkyl glycerol ether sulfates, in particular those ethers of higher alcohols derived from tallow or coconut oil; and synthetic alcohols derived from petroleum; sodium coconut oil fat monoglyceride sulfates and sulfonates, sodium and potassium salts of sulfuric acid esters higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, sodium and potassium salts of fatty acid amides of methyltaurine; alkane monosulfonates such as those resulting from the reaction of α-olefins (C8-C20) with sodium bisulfite and those resulting from the reaction of paraffins with SO2 and Cl2 and hydrolysis with a base to produce a random sulfonate and olefin sulfonates, this term being used to describe the material produced by reacting olefins, particularly C10-C20 α-olefins with SO3. and then neutralized and hydrolyzed to the reaction product. The preferred anionic detergent compounds are sodium (C₁₁-C₁₅) alkylbenzenesulfonates and sodium (C₁₆-C₁₈) alkylsulfates.

In general, the proportion of the above-mentioned soap-like anionic surfactant materials is 1 to 40% by weight of the composition, more preferably 2 to 25%. It is also possible and sometimes preferred to incorporate an alkali soap of a mono- or dicarboxylic acid, in particular a soap of an acid having 12 to 18 carbon atoms, e.g. oleic acid, ricinoleic acid, alk(en)yl succinate, e.g. dodecyl succinate and fatty acids derived from castor oil, rapeseed oil, peanut oil, coconut oil, palm kernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used. Preferably, the proportion of soap in compositions according to the invention is 1 to 35% by weight of the composition, more preferably 5 to 25%. The use of salting-out resistant active materials, as described e.g. in EP 328 177, in particular the use of alkyl polyglycoside surfactants, as disclosed e.g. in EP 70 074, is also possible. Also alkyl monoglucosides can be used.

The compositions may optionally contain electrolyte in an amount sufficient to effect lamellar structuring of the detergent material. Preferably, the compositions contain from 1 to 60%, in particular from 10 to 45%, of a salting-out electrolyte. "Salting-out electrolyte" has the meaning given in the description of EP-A-79 646. Optionally, some salting-out electrolytes (as defined in the description below) may be included.

In any event, it is preferred that compositions according to the invention contain detergent builder material, part or all of which is an electrolyte. In this connection, it should be noted that some detergent materials, e.g. soaps, may also have builder properties.

Examples of phosphorus-containing inorganic detergent builders include water-soluble salts, particularly alkali pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate chelating agents may also be used. However, it is sometimes preferable to minimize the amount of phosphate builders.

Examples of non-phosphorus inorganic detergent builders, if present, include water-soluble alkali carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite nucleus), potassium carbonate, sodium and potassium carbonates, silicates and zeolites.

In the context of inorganic builders, it is preferred to include electrolytes that promote the solubility of other electrolytes, e.g. the use of potassium salts to promote the solubility of sodium salts. This can the amount of dissolved electrolyte can be increased considerably (crystal dissolution), as described in GB patent specification GB 1 302 543.

Examples of organic detergent builders, when present, include alkali, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetylcarboxylates and polyhydroxysulfonates. Specific examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, CMOS, tartrate monosuccinate, tartrate disuccinate and citric acid. Citric acid or salts thereof are preferred builder materials for use in compositions of the invention.

In connection with organic builders, it is also desirable to incorporate polymers into the aqueous continuous phase which are only partially dissolved, as described in EP 301 882. This allows a reduction in viscosity (due to the dissolved polymer) while incorporating a sufficiently high amount to provide a secondary benefit, in particular framework formation, since the part which is not dissolved does not contribute instability which would occur if virtually all were dissolved. Typical amounts are 0.5 to 4.5 wt%.

It is also possible to add to the compositions according to the invention, alternatively or in addition to the partially dissolved polymer, a further polymer which is essentially completely soluble in the aqueous phase and has an electrolyte resistance of more than 5 g of sodium nitrilotriacetate in 100 ml of a 5% by weight aqueous solution of the polymer, the second polymer also having a vapor pressure in 20% aqueous solution which is equal to or less than the vapor pressure of an aqueous comparison solution with 2% or more by weight of polyethylene glycol having an average molecular weight of 6,000, wherein the second polymer has a molecular weight of at least 1,000. The use of such polymers is generally described in EP 301,863. Typical contents are 0.5 to 4.5% by weight.

Preferably, the proportion of non-soap-like builder material is 5 to 40% by weight, based on the composition, more preferably 5 to 25% by weight, based on the composition.

Optional ingredients

In addition to the ingredients already mentioned, a number of optional ingredients may also be present, e.g. foam enhancers such as alkanolamides, in particular monoethanolamides derived from palm kernel oil fatty acids and coconut fatty acids, foam suppressors, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate and, usually present in very small amounts, brightening agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (trademark) from Novo), enzyme stabilisers, soil carriers, germicides and colourants (

Obviously, when selecting materials other than the polymer for use in compositions according to the invention, biodegradable materials are also preferred for environmental reasons.

Production of liquid detergent compositions

Liquid compositions of the invention may be prepared by any conventional method for preparing liquid detergent compositions. A preferred method is to add the electrolyte ingredient (if present) together with the ingredients which are present in lesser quantity, except for the temperature-sensitive ingredients - if present - in water at elevated temperature and then add the framework material - if present - the detergent material (possibly as a premix) with stirring and then cool the mixture and add all temperature-sensitive ingredients in smaller quantities, such as enzymes, perfumes, etc. The deflocculant polymer can be added after the electrolyte ingredient or as the last ingredient. Preferably, the deflocculant polymers are added before the formation of the lamellar structure.

In use, the detergent compositions of the invention are diluted with wash water to form a wash liquor, e.g. for use in a washing machine. The concentration of the liquid detergent composition in the wash liquor is preferably 0.1 to 10%, more preferably 0.1 to 3% by weight.

The invention will now be illustrated by the following non-limiting examples.

Example I Synthesis of a deflocculating polymer:

1) 2,2-Diphenyl-4-methylene-1,3-dioxolane

Procedure:

Water and isopropanol (IPA) were placed in a reaction vessel mounted in a heating bath thermostatted at 100ºC and degassed with oxygen-free nitrogen. DMD was dissolved in acrylic acid-lauryl methacrylate by heating. The mixed monomer solution was then added dropwise to the stirred water/IPA solution over 3 hours. At the same time, the persulfate initiator solution was fed from another dropping funnel over 4 hours. After the addition was complete, heating and stirring was continued for an additional 18 hours. This gave a sticky solid and an emulsion. 92% of the theoretical amount of sodium hydroxide (in 30 mL of water) was added to achieve neutrality (pH 7). The IPA was removed by distillation using a rotary evaporator and the concentrate poured into acetone to precipitate the polymer and remove benzophenone. The polymer was separated, dissolved in water and again precipitated in acetone and the process repeated. Finally, the polymer was redissolved in water, filtered through glass fiber to remove the last traces of benzophenone and then freeze dried. Polymer yield: 29.4 g (94.5%). The polymer was characterized by 1H and 13C NMR, FT-IR and GPC. Molecular weights according to aqueous GPC: Mn = 9800, Mw = 32200, D = 3.3.

Example 2

The following compositions were prepared by adding the citrate together with sufficient NaOH to neutralize the active materials and bring the pH of the final composition to 7 to water at a temperature of 30ºC with stirring and then adding the deflocculating polymer and a premix of Synperonic and Dobs (in acidic form).

Basic composition 1:

Polymer A has the basic structure of formula I, where x = 24, k = 1, y = 0, R¹ -CO-O-, R² and R³ are absent, R⁴ is -C₁₂H₂₅, R⁵ -H, R⁶ -CH₃, A¹ is Na and B¹ is -H. The molecular weight is 32,200.

The following results were obtained:

*) Unreliable results due to rapid phase separation

The polymer is believed to have acceptable biodegradability.

Claims (8)

1. Deflocculant polymer with a backbone in which the polymer has a hydrophilic backbone and one or more hydrophobic side chains or is a block copolymer with alternating hydrophobic and hydrophilic groups or has nonionic monomers and ionic monomers, characterized in that the deflocculant polymer contains 1 to 30 mol% of monomer units of the formula - CH₂ - - CH₂ - in the framework. 2. Deflocculant polymer according to claim 1, characterized in that the polymer has the formula I: in which the monomer units can be arranged randomly; z is 1; k is at least 1; n is at least 1 (and can be determined by the molecular weight); the ratio of (k + x + y) : z is 4:1 to 1,000:1; the ratio of k : (x + y + z) is 1:99 to 30:70; R¹ represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is absent; R² represents 1 to 50 independently selected alkyleneoxy groups or is absent, with the proviso that when R³ is absent and R⁴ represents hydrogen or contains no more than 4 carbon atoms, then R² contains at least one alkyleneoxy group; R³ represents a phenylene bonding group or is absent; R⁴ is hydrogen or a C₁₋₂₄ alkyl or C₁₋₂₄ alkenyl group, with the proviso that when R² is not present, R⁴ is not hydrogen and when R³ is also not present, R contains at least 2 carbon atoms; R⁵ represents hydrogen or a group of the formula -COOA⁴ ; R⁶ is hydrogen or a C₁₋₄-alkyl radical and A¹, A², A³ and A⁴ are independently selected from hydrogen, alkali metals, alkaline earth metals, ammonium and amine bases and C₁₋₄ radicals or (C₂H₄O)tH, where t is 1 to 50, where the monomer units may be in random arrangement; each B¹ is independently selected from -CH₂OH, -OH or -H; for each monomer unit R¹-R⁶, A¹-A⁴ and B¹ can be independently selected from the above-mentioned groups; the formula (II): where Q² is a molecular unit of the formula (IIa): in which the monomer units can be arranged randomly; z and v are 1; n is at least 1 (and can be determined from the molecular weight); k is at least 1; is present in at least one of the monomer units p, q or r; the ratio of (k + x + y + p + q + r) : z is 4:1 to 1,000:1; the ratio of k : (x + y + p + q + r + z) is 1:99 to 30:70; R¹-R⁶, A¹-A⁴ and B¹ are as defined for formula I; R⁷ and R⁸ represent -CH₃ or -H; R⁹⁰ and R¹⁰ represent substituent groups such as amino, amine, amide, sulfonate, sulfate, phosphonate, phosphate, hydroxyl, carboxyl and oxide groups, and are preferably selected from -SO₃Na, -CO-O-C₂H₄-OSO₃Na, -CO-O-NH-C(CH₃)₂-SO₃Na, -CO-NH₂, -O-CO-CH₃, -OH; for each monomer unit R¹-R¹², A¹-A⁴ and B¹ can be independently selected from the above mentioned groups; Q¹ is a multifunctional monomer that allows branching of the polymer, wherein the monomers of the polymer can be connected to Q¹ in any direction, in any arrangement, possibly forming a branched polymer; the formula (III): wherein Q³ is derived from a monomeric unit IIIa which: includes, Q4 from molecular unit IIIb: is derived and Q5 from a monomer unit IIIc: is derived, wherein n is at least 1; k is at least 1; w is 0 to 4; the ratio of (a + b + c + k) : d is 5:1 to 500:1 wherein the monomer units can be arranged randomly, a, b, c, d, e, f, g, h can be integers or 0 ; the ratio of k : (a b + c + d) is 1:99 to 30:70 ; R¹-R⁶ are as defined in formula I; R¹¹ and R11* are independently selected from hydrogen or C₁-C₄ alkyl radicals; R¹² is independently selected from C₅-C₂₄ alkyl or alkenyl, aryl, cycloalkyl, hydroxyalkyl or alkoxyalkyl radicals and B¹, B², B³, B⁴ are organic or inorganic anions; wherein examples of the anions represented by B¹, B², B³, B⁴ are halide ions, sulfate, sulfonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, sulfide, cyanate, acetate and other common inorganic and organic ions; the formula (IV): has, in which z is 1; n is at least 1; k is at least 1; the ratio of (j + k) : z is 5:1 to 500:1; the ratio of k : (j + z) is 1:99 to 30:70; where the monomer units can be arranged randomly; R¹-R⁶ is as defined for formula I; R¹³ represents -CH₂-, -C₂H₄-, -C₃H₆- or is absent ; R¹⁴ represents 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide groups, or is absent; R¹⁵ represents -H or -OH; the formula (V) in which the monomer units can be arranged randomly; z is 1; k is at least 1; n is at least 1 (and can be determined from the molecular weight); the ratio of (k + x) : z is 1:1 to 2,000:1; the ratio of k : (x + z) is 1:99 to 30:70; R1 -C3 H6 -N+ -(CH3 )3 (Cl- ) , -C2 H4 -OSO3 -(Na+ ), -SO3 -(Na+ ) -C2 H4 N+ (CH3 )3 Cl- , -C2 H4 N+ (C2 H6 )2 Cl- , -CH2 N+ (CH3 )3 Cl- , -CH2 N+ (C2 ;H6)2 Cl- or benzyl-SO₃⊃min;(Na⁺); R² represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is absent; R³ and R⁴ are hydrogen or C₁₋₄-alkyl radicals; Ra is CH₂, C₂H₄, C₃H₃ or is absent; Rb represents 1 to 50 independently selected alkylene oxide groups, preferably ethylene oxide groups, or is absent; Rc is -OH or -H; and wherein, when R², R³ and Rb are absent, Rc is not -H or the formula (VI): in which the monomer units can be arranged randomly; x is 4 to 10000; k is at least 1; the ratio k:x is 1:99 to 30:70; R¹ represents a C₂₋₂₄-alk(en)yl group and/or 4 to 50 propylene oxide or butylene oxide units; R² is -CO-; R³ is -CO-O- or -O-. 3. Liquid detergent composition containing a dispersion of lamellar droplets of detergent material in an aqueous continuous phase and further containing a deflocculating polymer according to claim 1. 4. Liquid detergent composition according to claim 3, characterized in that the amount of deflocculant polymer is 0.01 to 5% by weight, based on the composition. 5. Liquid detergent composition according to claim 3, characterized in that the deflocculating polymer satisfies at least one biodegradability test selected from the modified SCAS test and the modified Sturm test. 6. Liquid detergent composition according to claim 3, characterized in that the viscosity of the liquid is less than 2,500 mPas at 21 s⊃min;¹. 7. Liquid detergent composition according to claim 3, characterized in that the liquid contains 1 to 70% by weight of detergent material. 8. Liquid detergent composition according to claim 3, characterized in that the liquid provides less than 10% by volume of phase separation when stored at 25°C for 21 days from the day of manufacture.