CA2141416A1 - Use of modified polyesters for the removal of grease of fabrics - Google Patents

Abstract

The present invention relates to the use of selected modified polyesters known for their soil-release properties, as cleaning agents for grease stain removal of fabrics, in combination with selected surfactants of low ethoxylation degree.

Description

W094/03~70 ' PCT/US93/06836 2141~

U8E OF MODIFIED ~OLYE8TER8 FOR T~E RBMOVAL

Technical Field The present invention relates to the use of modified polymers known for their soil-release prope-rties, as cleaning agents for grease stain removal of fabrics in combination with a non-ionic surfactant.

Background of the invention Products used in laundering operation contain a number of ingredients which provide certain basic benefits. For example, laundry cleaning products are formulated with detergent surfactant systems to remove a variety of soils from clothes during washing. These laundry products can also include ingredients which provide through-the-wash fabric conditioning benefits such as softening and anti-static performance.
.

In addition to standard cleaning, softening and anti-static benefits, laundry detergent can also impart other desirable W094/03~70 ~ PCT/US93/06836 properties. One is the ability to confer soil release properties to fabrics woven from polyester fibers. The hydrophobic character of polyester fabrics makes their laundering difficult, particularly as regards oily soil and oily stains. The oily soil or stain preferentially "wets"
the fabric. As a result, th.,e oily soil or stain is difficult to remove in an aqueous"iaundering process.

Certain polyesters have been found to be particularly useful as soil release compounds in laundry detergent composition. During the laundering operation, these soil release polyesters adsorb onto the surface of fabrics immersed in the wash solution. The adsorbed polyesters then form a hydrophilic film which remains on the fabric after it is removed from the wash solution and dried. This film can be renewed by subsequent w~ch;ng of the fabric with a detergent composition containing the soil release polyesters.

Such polyesters are disclosed in e.g. US Patent 4 116 885 and 4 711 730.

Continuous effort has been put against improving soil release polyesters; in e.g. EPA 272 033 have been described such improved polyesters. More recently, EPA 311 372 has described further improved soil release agents consisting of sulfoaroyl end-capped polyesters.

It has been found that certain modified polyesters described in EPA 311 342 not only act as a soil release agents on polyester fabrics, but are also able to remove soils from cotton-containing fabrics and to disperse such soils, during the main laundering cycle of a laundry process as described in our co-pending application EP92.202.383.3.

W094/03570 2 ~ PCT/US93/06836 A long-standing problem is the grease stain removal. With present detergent compositions it is difficult to remove efficiently said grease from fabrics especially from polyester fabrics.

It has now been surprisingly found that the modified polyesters as described in EPA 311.342 in combination with selected nonionic surfactants with a low ethoxylation degree, shows an unexpected greasy stain removal of the fabrics.

The detergent composition according to the invention comprises a modified polyester being a random copolymer of dimethyl terephtalate, dimethyl sulfoisophtalate ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulfobenzate and secondarily of mono esters of ethylene glycol and/or propane-diol and a non-ionic surfactant C8_18 primary alcohol ethoxylate containing from 2 to 5 moles of ethylene oxide per mole of alcohol. Most preferred is a detergent composition wherein the non-ionic surfactant is C12_15 primary alcohol ethoxylate cont~i n ing 3 moles of ethylene oxide per mole of alcohol. Present in the detergent composition in a ratio 1 : 0.3 to 1 : 2.0 provides a surprising thickening effect. This provides the formulator with a potentially effective method by which said selected non-ionic surfactant can be processed into granular dertergents.

It has further been found that the claimed modified polyester can have a thickening effect on said selected non-ionic surfactant.

W094/0~7~1 4 1 6 - PCT/US93/068 DETAILS DESCRIPTION OF THE INVENTION

The modified Polyesters The modified polyesters herein are random copolymers of dimethyl terephtalate, dîmethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target being to obtain is a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 342.

Furthermore, it has been found that the combined use of the present modified polyesters with a cellulase enzyme and/or certain co-dispersing agents and/or certain nonionic surfactants provides superior cleaning benefits.

The non-ionic surfactants The non-ionic surfactants according to the present invention are C8_18 primary alcohol ethoxylates containing from 2 to 5 mole of ethylene oxide per mole of alcohol.

W094/03~70 2 1 ~ PCT/US93/06836 Preferred are : a C12_15 primary alcohol ethoxylates containing about 3 moles of ethylene oxide per mole of alcohol The modified polyesters herein are present in the detergent composition at a ratio to the non-ionic surfactants of, from 1 : 0.3 to 1 : 20, preferred is 1 : 6 to 1 : 20.

DETERGENT COMPOSITION

The detergent compositions herein can be in a liquid or granular form and are preferably delivered directly to the drum and not indirectly and via the outer casing of the machine. This can most easily be achieved by incorporation of the composition in a bag or container from which it can be released at the start of the wash cycle in response to agitation, a rise in temperature or immersion in the wash water in the drum. Such a container will be p~aced in the drum, together with the fabrics to be washed. Alternatively the washing machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispensing arrangement in the access door.

When the compositions are in liquid form, a rigid container such as disclosed in EPA 151 549 can be used the detergent composition herein are preferably in granular form, and the container will be flexible, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in EPA no. 0 018 678.
Alternatively it may be formed of a water insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in EPAs nos. 0 011 500, 0 011 501, 0 011 502, and 0 011 968. A
convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a W094/03570 ~ PCT/US93/06836 2 ~ 4~ ~'L6 6 pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

In a variant of the bag or container product form, laminated sheet products can ~e employed in which a central flexible layer is impr,,egnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric-like aesthetic effect. The layers may be sealed together so as to remain attached during use or may separate on contact with water to facilitate the release of the coated or impregnated material.

An alternative laminate form comprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the detergent components are deposited in measured amounts, with a second layer overlying the first layer and sealted thereto in those areas between the pouch-like containers where the two layers are in contact. The components may be deposited in particulate, paste or molten form and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water. The layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution. The number of pouch-like containers per unit area of substrata is a matter of choice but will normally vary between 500 and 25,000 per square meter.

Suitable materials which can be used for the flexible laminate layers in this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.

However the preferred means of carrying out the washing process according to the present invention includes the use of a reusable dispensing device having walls that are W094/03570 7 2~ 6 PCT/US93/06836 permeable to liquid but impermeable to the solid compositlon.

Devices of this kind are disclosed in EPAs Nos. 0 343 069 and 0 344 070. The latter Application discloses a device comprising a flexible sheet in t~e form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing cycle. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent regress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spooked wheel configuration, or a similar structure in which the walls have a helical form.

The detergent compositions herein contain a surfactant.

A wide range of surfactants can be used in the detergent compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3 664 961 issued to Norris on May 23, 1972.

Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source preferably from a C16-Clg fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulphate surfactants are alkyl sulphates having from 12 to W O 94/03570 PC~r/US93/06836 2~ 8 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6. Examples of preferred alkyl sulphates he,rë~i~ are tallow alkyl sulphate, coconut alkyl sulphate, an,~d- C14_15 alkyl sulphates. An exemple of a preferred'~ethoxy sulphate is the so-called AE3S(C12_1s alkyl 3 times ethoxylated sulphate). The cation in each instance is again an alkali metal cation, preferably sodium.

One class of nonionic surfactants particularly useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 5 to 17, preferably from 6 to 14, more preferably from 7 to 12. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

In addition to the selected non-ionic surfactants herein the present compositions can also contain additional non-ionic surfactants such as the C9-C15 primary alcohol ethoxylates containing 6-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.

Another suitable class of additional nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (cnH2no)tzx wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon W094/03~70 21 ~ PCT/US93/06836 ,~ , atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10~ unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Also suitable as additional nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 - C - N - Z, wherein Rl is H, Il I .
O Rl or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11_15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

A further class of surfactants are the semi-polar surfactants such as amine oxides. Suitable amine oxides are selected from mono Cg-C20, preferably C10-Cl4 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Another class of surfactants are amphoteric surfactants, such as polyamine-based species.

Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C8-C16, preferably C10-C14 N-alkyl or alkenyl ammonium surfactants wherein W O 94/03570 ~` ; PC~r/US93/06836 6 ~o ~, remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Mixtures of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic-cationic mixtures. Partic~larly preferred mixtures are described in British Pate~ No. 2 040 987 and European Published Application No. o 087 914. The detergent compositions can comprise from 1%-70% by weight of surfactant, but usually the surfactant is present in the compositions herein an amount of from 1% to 30%, more preferably from 10-25% by weight.

The detergent compositions herein also contain a builder Builder materials will typically be present at from 5% to 80% of the detergent compositions herein. The compositions herein should preferably be free or substantially free of phosphate-containing builders (substantially free being herein defined to constitute less than 1% of the total detergent builder system), and the builder system herein consists of water-soluble builders, water-insoluble builders, or mixtures thereof.

Water insoluble builders can be an inorganic ion eYchAnge material,commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B or HS.

Preferred aluminosilicate ion-exchange materials have the unit cell formula Mz [(A102)Z (sio2)y] xH20 wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form W094/03S70 2 1 4 1 ~ ~ 5 PCT/US93/06836 11 ' ' and are preferably crystalline containing from 10% to 28%, more preferably from 18% to 22% water.

The above aluminosilicate ion exchange materials are further characterized by a particle size diameter of from e ~1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The aluminosilicate ion exchange materials are further characterized by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g. The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is described in detail in GB-1 429 143.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US
Patent No. 3 985 669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula l2[(A12)12 (sio2)12] xH20 wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 [(Alo2)86(sio2)lo6] - 10 W094/03570 i ~` PCT/US93/06836 ~ 12 .276H20 is also suitable, as well as Zeolite HS of formula Na6 t(Alo2)6(sio2)6] 7-5 H2O)-Another suitable water-insoluble, inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered ~siiicate consisting of sodium silicate (Na2Si2O5). The high Ca++/Mg++ binding capacity is mainly a cation exchange mechanism. In hot water, the material becomes more soluble.

The water-soluble builder can be a monomeric or oligomeric carboxylate chelating agent.

Suitable carboxylates containing one carboxy group include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 368, 821 369 and 821 370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2 446 686, and 2 446 687 and U.S. Patent No. 3 935 257 and the sulfinyl carboxylates described in Belgian Patent No. 840623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carbo-xymethyloxysuccinates described in British Patent 1 379 241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1 387 447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the W094/03~70 2~ 6 PCT/US93/06836 sulfosuccinate derivatives disclosed in British Patent Nos.
1 398 421 and 1 398 422 and in U.S. Patent No. 3 936 448, and the sulfonated pyrolysed citrates described in British Patent No. 1 082 179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclo-pentane-cis, ciC, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1 425 343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, or of a layered silicate (SKS/6) and a water-solubie carboxylate chelating agent such as citric acid.

other builder materials that can form part of the builder system for the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates.

Other suitable water-soluble organic salts are the homo-or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two.carbon atoms.

W094/03~70 ~ PCT/US93/06836 ~ 14 O

Polymers of this type are disclosed in GB-A-l,5s6,756.
Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of ; from 20,000 to 70,000, especially about 40,000.

In a preferred embodiment of the present invention, the detergent compositions herein will contain a cellulase enzyme such as described above, at levels of from 0.025% to 10% of the composition.

In another preferred enbodiment of the present invention, the detergent compositions or detergent additives herein will contain a soil anti redeposition or soil suspension agent, in combination with the modified polyesters herein.

Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, homo- or co-polymeric polycarboxylic acids or their salts and polyaminoacid compounds. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.
Polyaminoaccid compounds such as those derived from aspartic acid are for instance disclosed in British patent application n 9226942.2.

These materials are normally used at levels of from 0.5%
to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.

The present detergent compositions are preferably in granular form and more preferably in a "compact" form, i.e.

W094/03570 21 ~ PCT/US93/06836 1~
having a density, which is higher than the density of conventional detergent compositions. The preferred density of the compositions herein ranges from 550 to 950g/liter, preferably 650 to 850g/liter of composition, measured at 20C.

The present "compact" form of the most preferred compositions herein is best reflected, in terms of composition, by the amount of inorganic filler salt;
inorganic filler salts are conventional ingredients of detergent compositions in powder for, in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition.

In the most preferred compositions herein, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.

Inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides.

A preferred filler salt is sodium sulphate.

The present compositions will typically include optional ingredients that normally form part of detergent compositions. Enzymes, optical brighteners, bleaches, bleach activators, suds suppressors, anticacking agents, dyes and pigments are examples of such optional ingredients and can be added in varying amounts as desired.

Enzymes such as proteases, cellulase, lipases, or amylases are particularly desirable ingredients of the compositions herein, in particular cellulase.

-2i~4 16 PCT/US93/06836 The cellulase usable in the combination with the modifiedpolyesters herein may be any bacterial or fungal cellulase, having a pH optimum of between 5 and 9.5.

Suitable cellulases are disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-24 47 83~.

Examples of such cellulases are cellulase produced by a strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly by the Humicola strain DSM 1800, and cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).

The cellulase added to the composition of the invention may be in the form of a non-dusting granulate, e.g.
"marumes" or "prills", or in the form of a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an aqueous medium.

Preferred cellulases for use herein are characterized in that said cellulase they provide at least 10% removal of immobilized radioactive labelled carboxymethyl-cellulose according to the C14CMC-method described in EPA 350 098 at 25x10-6% by weight of cellulase protein in the laundry test solution.

Most preferred cellulases are those as described in International Patent Application WO 91/17243. For example, a cellulase preparation useful in the compositions of the invention can consist essentially of a homogeneous endoglucanase component, which is immunoreactive with an antibody raised against a highly purified 43kD cellulase derived from Humicola insolens, DSM 1800, or which is homologous to said 43kD endoglucanase.

W O 94/03~70 ~ P(~r/US93/06836 ~7 The modified polyesters herein typically achieve their cleaning benefits on cotton-containing fabrics by being incorporated into a detergent composition including other detersive ingredients, at a level of from 0.025% to 10% by weight of the composition.

Alternatively, the modified polyester herein can be added separately, to the laundry cycle, in the form of a detergent additive; said additive posssibly containing other selected detergent active materials, such as soil anti-redeposition agents and co-dispersing agents, and/or cellulase enzyme; in particular, the modified polyesters herein can be used to pre-treat cotton-containing fabrics, before the main wash cycle of a laundering process.

Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:21 di~ulphonate, disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:21 -disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-~2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate, disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-(naphtho-11,21:4,5)-1,2,3 - triazole-211-sulphonate.
-Any particulate inorganic perhydrate bleach can be used,in an amount of from 3% to 40% by weight, more preferably from 8% to 25% by weight and most preferably from 12% to 20%
by weight of the compositions. Preferred examples of such W O 94/03~70 PC~r/US93/06836 2 ~ 6 18 bleaches are sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.

Another preferred separately mixed ingredient is a peroxy carboxylic acid bleach precursor, commonly referred to as a bleach activator, which is preferably added in a prilled or agglomerated form in granular detergents. Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e. during the washing process of the peroxy acid corresponding to the bleach activator). Examples of suitable compounds of this type are disclosed in British Patent Nos.
1586769 and 2143231 and a method for their formation into a prilled form is described in European Published Patent Application No. 0 062 523. Preferred examples of such compounds are tetracetyl ethylene diamine and sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent application 91.870207.7.

Bleach activators are for instance normally employed at levels of from 0.5% to 10% by weight, more frequently from 1% to 8% and preferably from 2% to 6% by weight of the composition.

Optionally metallo-catalysts/MnPC can be used at a preferred about 0.2 part to the total detergent composition according to the invention.

Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica~aerogels and W094/03570 2 1 ~ . i PCT/US93/06836 ~ 19 ' xerogels and hydrophobic silicas of various types. These materials can be incorporated as particuiates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-~ .
surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.

As mentioned above, useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 millimicrons to 20 millimicrons and a specific surface area above 50 m2/g intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200 000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.

A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
An example of such a compound is DC-544, commercially availably from Dow Corning, which is a siloxane/glycol copolymer.

The suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight. The incorporation of the suds mofidiers is preferably made as separate particulates, and this permits the inclusion therein of 2 ~ 6 '`' 20 other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix.
Techniques for forming such suds modifying particulates are disclosed in the previously,~mentioned Bartolotta et al U.S.
Patent No. 3 933 672.

Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in ,type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898.
Organic fabric softening agents include the water-soluble tertiary amines as disclosed in GB-A-l 400 898. Organic fabric softening agents include the water-insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-O 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-O 026 528 and di-long-chain amides as disclosed in EP-B-O 242 919. Other useful organic ingredients of fabric soft~nin~ systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-O 299 575 and 0 313 146.

In the preferred granular detergent compositions herein, levels of smectite clay are normally in the range from 5% to 20%, more preferably from 8% to 15% by weight with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or di-long-chain amide materials are incorporated at levels of from 0.5% to 5~ by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water-soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances W094/03570 2 1 ~ PCT/US93/06836 it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.

The compositions herein may also contain dye-transfer inhibiting agents such as polyvinylpyrrolidones having a molecular weight from 5 000 to 2 200, typically present in the preferred granular detergent compositions herein, at level such as to deliver from 5 to 500 mg/l of said polyvinyl pyrrolidones in the wash solution. Also PVPVI
could be used as dye-transfer inhibiting agent in detergent compositions.

The compositions of the invention may fully contain from 0.05% to 5% by weight of the composition, prefereably from 0.05% to 1% by weight, most preferably from 0.1% tot 0.5% by weight of a chelant (heavy metal sequestrant).

A suitable chelant for inclusion in th~ detergent compositions in accordance with the invention is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

Other chelants include the organic phosphonates, including amino alkylene poly (alkylene phosphonate), alkali metal ethane l-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ~h~ ~ 4~ 22 ion, molar ratio of said metal ion to said phosphonate compound being at least 1:1. Such complexes are described in US-A-4,259,200. Preferably, the organic phosphonate compounds where present are in the form of their magnesium salt. The level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred. Other chelants suitable for inclusion herein include amino polycarboxylate chelants such as EDTA and HEDTA.

Makinq Process Compositions according to the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation and combinations of any of these techniques. The compositions according to the present invention can be prepared with different bulk densities, from conventional granular products to so-called "concentrated" products (i.e. with a bulk density above 600g/1).

EXAMPLES

The following examples illustrate the invention and facilitate its understanding.

The abbreviations for the individual ingredients have the following meaning:

LAS: sodium salt of linear dodecyl benzene sulfonate AS: sodium salt or C14-15 alkyl sulfate TAS: sodium salt of tallow alcohol sulfate FA45E7: fatty alcohol (C14-C15) ethoxylated with about 7 moles of ethylene oxide -W094/03~70 2 I ~ B PCT/US93/06836 FA25E3: fatty alcohol (C12-15) ethoxylated with about 3 moles of ethylene oxide CAT: C12 alkyl trimethyl ammonium chloride Clay: smectite clay Zeolite A4:sodium salt of zeolite 4A with average particle size between 1 - 10 micrometer SRS-6: crystalline layered silicate (Hoechst) Copolymer AA/MA: copolymer of acrylic acid and maleic acid PAA: Polyacrylate polymer CMC: carboxymethylcellulose Phosphonate:sodium salt of ethylenediamine tetramethylene phosphonic acid EDTA: sodium salt of ethylenediamine tetra acetate PB1: NaB02.H202 TAED: tetra acetyl ethylene diamine PVP: Polyvinylpyrrolidone Silicate (R=n): SiO2/Na20=n Cellulase:43kD species according to the description herein above Amylase: Termamyl 60T (Novo-Nordisk) Lipase: Lipolase lOOT (Novo-Nordisk) Protease: Savinase 4T (Novo-Nordisk) SSS: Suds Suppressing System (silica/silicone mixture) The modified polyester used throughout the following examples correspond to the species described in claim 2 herein.
The method of preparation was as follow:
The process of preparation of the selected polyester herein includes mixing all the monomers in a round bottomed flask, stirring at 180C, until a clear solution results, and continue stirring for 24 hours. Then transferring the contents of the round bottomed flask to a further single necked round bottomed flask (typically 1 litre), heating under vacuum for 45 minutes at 200C, removing from flask and cooling. A clear glass solid is obtained, which is then crushed gently to be used.

W094/03570 r PCT/US93/06836 2 ~ ,6 24 Example 1:
The following detergent composition was prepared.

.% by weight FA45E7 2.5 PAA 3.5 PROTEASE 1.6 CELLULASE o.5 MODIFIED POLYESTER 0.5 Testinq ~rocedure:

A bundle of soiled fabrics containing fabrics which were stained with a range of stains such as particulate soils, greasy soils, enzymatic soils and bleachable soils on cotton and polycotton fabrics were washed in a compact detergent with the formulation as shown. One half of each bundle was washed with detergent composition as shown and the other half was washed with the same composition without the cellulase. The testing was carried out at 40C in water of 25H (German hardness). All testing was repeated 4 times.

Stain removal was evaluated relative to a reference stain of each type previously washed under identical conditions. The formulation used for the washing of the reference fabrics contained no modified polyester or cellulase.

Stain removal was evaluated using the well known schefe scale of panel score units determined by two judges as follows:

W O 94/03570 ~ P(~r/US93/06836 1 = I think there is a difference between the two stains.

2 = There is certainly a difference between the two stains.

3 = There is a big difference between the two stains.

4 = There is a black and white difference between the two stains.

The average data compared to the reference fabric was calculated. The results on the greasy stains on polycotton material were as follows.

8tain Preference for exam~le 1 compositio~
versus refere~oe Dirty motor oil +1.1*
Make up +0.5*

* Statistically significant BX~nP1e 2:
A detergent of formulation similar to that described in example 1 was used to wash a bundle of soiled fabrics which were stained with a range of soils of particulate, greasy, enzymatic and bleachable types. One half of each bundle was washed in the formulation described in example 1, the other half of the bundle was washed in the identical formula without modified polyester. The conditions used for washing these bundles were 40C and 25H water. 4 replicates of each test were carried out and the samples were graded accordingly to the % stain removal. This was calculated using the McBeth (colour spectrometer) using the conventional 1 a b system. The tests were repeated using W094/03~70 '~ PCT/US93/06836 ~ 26 different levels of modified polyesters between 0.025% and 10% by weight of the detergent composition.
The results are detailed below:

~QVel o. 025%~` 0.1% 0.5% 10%

8tain reDIov aver~g~
greasy o~ 52~ 64% 69% 73%
polycotton Typical greasy stains considered include dirty motor oil, shoe polish and make up.

Figures quoted are average %stain removal enhancement above the reference product.

Ex~mDle 3:
Enhanced greasy stain removal by the combination of modified polyester and carboxy methyl cellulose.

Polycotton swatches were pretreated a number of times with a detersive formulation containing the carboxy methyl cellulose (CMC). The purpose of this was to give the fabric a history of CMC deposition onto the cotton of the polycotton. The polycotton was then dryed and stained with dirty motor oil (DMO). One half of the stains was washed in a detersive formulation similar to that described in example one to act as a reference whilst the other half was washed in the same formulation only containing the modified polyester herein.
The swatches were graded ~y calculating the % stain removal from each tracer using the hunter colour lab system. All data was also compared to swatches which had been treated in W094/03570 ~ f~ PCT/US93/06836 exactly the same way as described above only with a detersive formulation containing soil release polymer and no CMC. The results are described below.

Reference ModifiedCMC/modified (CMC onlY) polyester~olvester only Average %
stain removal 21% 43% 79%

Test conditions 40~C/25H water - 4 replicates ExamPle 4:
Pretreatment solution compositions containing the modified polyester herein were prepared as shown below Formulation: 1 2 3 4 5 6 Modified polyester 0.5 1.0 3.0 5.0 6.0 6.0 ~aleic/acrylic 46.5 32 5.0 20 64 72 copolymer All the solutions were used to pretreat polycotton fabrics prior to washing which had previously been stained with a range of greasy type stains such as dirty motor oil, sun tan lotion make up and lipstick.
All fabrics which had previously been treated with any of the compositions described showed marked improvement in the stain removal from the polycotton when compared to an unpretreated stain.
The following compact detergent compositions were also prepared:

W094/03~70 PCT/US93/06836 COMPACT DETERGENT COMPOSITIONS
(all levels in % by wei~ht) Examples: V VI VII VIII IX X XI XII
LAS 11.00 -- 6.50 -- 6.50 -- -- --TAS -- -- 3.25 3.90 2.25 -- -- --AS 5.00 ~12.00 -- -- -- 6.00 6.50 6.50 FA45E7 4.00 1.00 2.20 6.00 2.20 3.00 -- --FA25E3 -- -- -- -- -- 6.00 7.00 7.00 CAT -- -- -- 2.45 -- -- -- --Tallow glucose amide -- 10.00 -- -- -- -- -- --Na citrate/citric 18.00 5.00 12.00 15.00 12.00 4.00 4.00 4.00 Zeolite 4A 32.00 15.00 16.00 20.00 14.00 13.00 13.00 12.50 SKS-6 -- 12.00 -- -- -- 12.00 12.00 12.00 Copolymer AA/MA 4.10 5.00 3.50 3.50 -- 5.00 3.00 3.00 Polypeptide 4.00 -- 2.00 2.00 Phosphonate 0.19 1.00 -- -- 1.00 -- -- --EDTA -- -- 0.32 0.32 -- -- -- --Na carbonate/ 3.00 2.50 10.00 10.00 10.00 9.00 10.00 10.00 bicarbonate Silicate (R2) 3.00 2.00 2.50 2.50 2.50 3.50 3.50 3.50 CMC ~~ 0-50 ~~ ~ 0-50 0-30 Clay -- -- 8.60 8.60 -- --- -- --PB1 -- -- 11.50 -- 12.00 -- 12.00 12.00 Percarbonate -- -- -- 12.00 -- 23.00 -- --TAED -- -- 3.20 -- 4.00 6.00 4.00 4.00 Protease 1.20 1.60 1.40 1.40 1.40 1.40 1.40 1.40 Cellulase 0.50 -- 0.30 0.10 0.10 0.10 0.10 0.10 Lipase 0.40 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Amylase 0.20 0.30 -- -- -- -- -- --Na Sulfate 2.00 2.50 3.50 3.50 4.00 3.50 4.00 4.00 PVP -- 0.50 1.00 -- -- -- -- --SSS 0.40 0.40 0.50 0.50 0.50 0.50 0.50 0.50 Modified polyester 0.30 0.40 0.30 0.50 0.50 0.50 0.50 0.50 Minors + water Balance to 100%

29 ~ 6 j Example 5 Enhanced grease stain removal by the combination of r modified SRP and C25E3 (=AE3 in this example).

The combination of SRP and C25E3 has been tested vs products available such as Skip Micro System (SMS) and Skip Regular.

The following remarkable results are obtained concerning greasy stains removal :

a) SMS
Gre~sy St~ln- Remo~l CottonPolyco~ton Polyes~er Referenc- S~S - equ~l do--ge 140g ArleL Ultr--D t 0.325RP - 40 C -0.40 -0.34 -1.02s Arl-l Ultr--D + 0.32SRP + 4.72AE3-40 C -0.16 0.21 0.06 Arlel Ultr--D + 52 AE7 - 60 C -1.13s -1.66s n/e Arl-l Ultr--D + 0.32 SRP - 60 C -1.15s -1. 708 -1.60s Arlel Ultr--D + 82 A~3 nll A~7 - 60 C -0.41 0.01 n/-Arlel Ultrn-D + 0.325RP + 4.72AE3-60 C -0.10 -0.49s -0.44s b) Skip Regular Gre~y St ln- Remo~l CottonPolycotton PoLyester Reference Sklp Regulnr - 215g ~s 140g Arlel Ultr~-D + 4.72 AE3 - 40 C -0.57 -0.71s -1.86s Arlel Ultre-D + 0.32 SRP + 4.72 AE3-40 C-0.26 0.23 0.83s W094/03~70 , ~ , PCT/US93/06836 4~G 30 The comparison with Skip Regular clearly shows that SRP +
AE3 gives better performance than AE3 alone. This is not the case with SMS.

The addition of AE3 a,ls,,o, improves the performance on grease. AE3 and SRP added ~ogether to Ariel Ultra-D either :
I) boost AE3 performance (vs Skip Regular) or, II) show no benefi~ vs AE3 alone (vs SMS).

Exam~le 6 SRP Synergy with nonionic C25E3 (=AE3).

Backqround The polypropylene material of the granulette is a very hydrophobic surface to which oily soils such as DMO are attracted and stuck fast.

Conclusions 1) The effect of SRP on the cleaning of the granulette is dependent on the ratio of SRP to Surfactant. A low ratio of SRP to surfactant results in an improved cleaning. High SRP:surfactant gives worse cleaning.

0.025g SRP/Sg Ariel Ult. 0.05g SRP/3g Ariel Ult.
SRP:NI surfactant ratio (1:6 0:6) (1:2 0:2) Grade of polyprop Clean Dirty Very Dirty Dirty 2) The critical factor in this phenomenon is the presence and type of Nonionic. Surfactant and water alone gives a dirty granulette, as does SRP and water alone.
SRP level ppm 0 50 100 0 0 Product level ppm 0 0 0 6000 10000 Fabric grade Very Dirty Dirty Very Dirty Dirty Dirty W094/03~70 21 ~i ~1 B PCT/US93/06836 3) Significantly, SRP and a nil nonionic Ariel also give a dirty fabric.
SRP level ppm 0 50 0 50 Nonionic level ppm . O 0 500 500 Product level ppm 10000 10000 10000 10000 Fabric grade Dirty Dirty Dirty Clean 4) Use of C25AE3 nonionic results in better cleaning and a further boost to the SRP effect.
SRP level ppm 0 50 Nonionic level ppm 500 AE3 500 AE3 Product level ppm 10000 10000 Fabric grade Clean Very Clean 5) The synergy with nonionic extends to an improved cleaning of Shoe Polish when both SRP and C25E3 are used in the pretreatment and washing of polyester fabric.
Ariel Ultra Ariel 45E7 Ariel Ariel + 0.5%
3.26% 45E7 +0.5% SRP +3.26% C25E3 SRP + 3.26% C25E3 % Removal of Shoe Polish 29 28 35 44 (si~nificant) In result there is a synergistic cleaning benefit when SRP
and nonionic (AE3) are used together wherein the benefit is dependant upon the ratio SRP over nonionic (AE3) as outlined below.

SRP:nonionic ratioBenefit 1:2 No 1:6 Yes 1:10 Yes 1:20Yes (but slightly reduced) W094/03~70 PCT/US93/06836 2~ 32 Example 7 Numerous attemps have been made to thicken C25E3 with various different detergent ingredients with limited success. The use of modified soil release polymers according to this invention provides~a method of thickening C25E3.

By mixing C25E3 with soil release polymer solution in the ratio of one part C25E3 to 0.3 parts soil release polymer at room temperature with mild stirring one forms a thick white viscous paste which does not separate upon standing.

- Different soil release polymers may provide the same thickening effect.
- Higher levels of soil release polymers produce a thicker paste.

Ratio C25E3Soil release Thickening effect polymer 3 0.3 None 2 0.3 Slightly thicker but separates on se~n~ing 1 0.3 Thick stable white paste 1 2.0 Thick stable white paste Conditions Room tempature, mild stirring This above shows the thickening of nonionic surfactant C25E3 by the addition of a soil release polymer solution as described in this application. This provides the formulator with a potentially effective method by which C25E3 can be processed into granular detergents.

Claims (11)

What is claimed is:

1. A detergent composition comprising a modified polyester being a random copolymer of dimethyl terephtalate, dimethyl sulfoisophtalate ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulfobenzate and secondarily of mono esters of ethylene glycol and/or propane-diol and a non-ionic surfactant selected from C8-18 primary alcohol ethoxylate containing from 2 to 5 moles of ethylene oxide per mole of alcohol.

2. A detergent composition according to claim 1 wherein said non-ionic surfactant is a C12-15 primary alcohol ethoxylate containing about 3 moles of ethylene oxide per mole of alcohol.

3. A detergent composition according to claim 2 wherein the ratio of said non-ionic surfactant to : modified polyester is, 1 : 0.3 to 1 : 2Ø

4. The use of a modified polyester being a random copolymer of dimethyl terephtalate, dimethyl sulfoisophtalate ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulfobenzate and secondarily of mono esters of ethylene glycol and/or propane-diol in combination with non-ionic surfactant selected from C8-18 primary alcohol ethoxylates containing from 2 to 5 moles of ethylene oxide per mole of alcohol, as cleaning agent for grease stain removal of fabrics, said fabrics being contacted with an aqueous laundry liquor containing said compounds.

5. The use of claim 4 wherein said compound contains about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol, about 13% by weight of sulfo benzoid acid and about 15% by weight of sulfoisophtalic acid, and has a molecular weight between 2 500 and 3 500.

6. The use of claim 4 or 5 wherein the non-ionic surfactant is a C12-15 primary alcohol ethoxylate containing about 3 moles of ethylene oxide per mole of alcohol.

7. The use of claim 4, 5 or 6 wherein the ratio modified polyester to non-ionic surfactant is 1:6 to 1:20.

8. The use of claims 4-7 wherein said compound is combined with a cellulase enzyme.

9. The use of claims 4-8 wherein said compound is incorporated into a detergent composition including other detersive ingredients, at a level of compound of from 0.025% to 10% by weight of the composition.

10. The use of claims 4-8 wherein said compound is incorporated in a detergent additive composition for the pre-laundering of fabrics.

11. The use of claims 9 or 10 wherein said detergent composition or additive composition is put in a container able to release the composition at the start of the laundering cycle or of the pre-laundering cycle, and said container is placed in the drum of a washing machine, together with the fabrics to be laundered and/or pre-laundered.