~ W 0 93/21294 2 1 1 7 ~ ~ 7 P(~r/US93/0324~
U8~ OF MODIFIED ~LYEfiTER8 FO~ T~E wA8~INa OF COTTON-c~D~rrA~ING FAB~CS
:~: : Technical Field T~e present im ntion relates to the u~e of modified polymers known for th~ir soil-release properties, as cleaning agents for cot,ton-containing f~brics; the invention further relates to ~;
certain d~tergent co~positions containing said modified ,polyillers.
Backaround of the invention .
Products used in laundering operation contain a number _:
- ,ingredients which provide certain basic ~enefits. For example, laundry cleaning products are formulated with detergent surfactant systems; to remove a ~ariety of soils from clot~es ~, during washing~ T~ese laundry products can also include - ingredients which provide through--the-wash fabric conditionlna bene;fits such as soft-ning and anti-static performance.
,In ~addition to standard cleanin~, softening and anti-stat~:
benefits, laundry detergent can also impart other desirab!o prop-rties. One is tbe abilitv tO confer soil reiease properties tO fabrics ~oven frcm polyester fibers. .~.e hydrophobic character of polyester fabrics makes thel-W093/21294 ~ 11 7~ 9 7 PCT/US93/03245 ~
laundering difficult, par~icularly as regards oily soil and oilystains. The oily soil or stain preferentially ~'wets~ the fabric. As a result, the oily 50il or stain is difficult to remove in an aqueous laundering process.
Certain po~yesters 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 t~en 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 washinq of the fabric with a detergent composition containing t~e soil release polyesters.
-Such polyesters are disclosed in e.g. US Patent 4 1~6 885 and 4 711 730.
Continuous effort has been put against improving soil release polyesters; in e.g. EPA 272 0~3 have been described such ; improved polyesters. More recently, EPA 311 372 has described further improved soil release agents consisting of sulfoaroyl end-c~pped polyesters.
It has now been surprisingly 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 fa~rics and to disperse such soils, during the main laundering cycle of a laundry process.
It has furt~er been found that the use of the modified polyesters herein in combination with cellulase enzymes as wel as certain soil anti redeposition agents or co-dispersing agents or in combination with a selected class of nonionic surfactants -~ provides unexpectedly improved cleaning benefits on cottor-containing fabrics.
W O 93/21294 ~ 1 1 7 ~ ~ 7 P ~ /US93/03245 Deta~ed_DescriDtion of the Inventlon The present invention is based on the discovery that the selected modified polyesters herein can act in a "surfactant"
mode versus cotton-containing fabrics, thus being able to provide a cleaning effect on such fabrics after only one laundering cycle, as compared to several cycles when functioning in the soil-release agent mode.
T~ il~ eyl~çsters The modified polyesters herein are random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, t~e 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 poly~Qr c~pped at both end by sulphobenzoate groups, prLmarilyn, in the present context most of said copolymers s~i h~rein will be end~capped by sulphobenzoate groups. However, so~e copolymers will be lèss 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 diol, about 10% by weight ethylene glycol about '3% by weight o~
dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weiqht of about 3.000. The polyesters and their method of preparation are described in detail in EPA 311 3~2.
Furthermore, it has been found that the combined use of tne present modified polyesters ~ith a cellulase enzyme and,o-certain co-dispersing agents and/or certain nonionic surfactants provides superior cleaninq benefits.
WOg3/21294 PCT/US93/03245 -21 :~7997 The Cellulase The cellulase usable in the combination with the modified polyesters herein may be any bacterial or fungal cellulase, havin~ a pH optimum of between 5 and 9.5. --Suitable cellulases are disclosed in G~-A-2 075 028; GB-A-2 095 275 and DE-OS-24 47 832.
Ex~ples of such cellulases are cellulase produced by a strain o~`Hu icola insolens (Humicola grisea var. thermoidea~, particular~y by the Hu~icola strain DSM 1800, and cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from t~e ~ep~topancreas 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 gr~nulate, e.g. "marumes" or prill-~, or in tbe form o~ a liquid in whlch the cellulase is provided as a cellulase concentrate suspended in~e.g. a nonionic surf~ctant or dissolved in an aqueous medium.
Preferred cellulases for use herein are characterized in that said cellulase t~ey provide at least lQ% removal of immobilized radioactive lab~lled carboxy~ethyl-cellulose according to the C14CMC-method described in EPA 350 098 at 25xlO-~ by weight of cellulase protein in the laundry test solution.
Most preferred cellulases are those as described in International ~atent App~icatlon W0 ~1~17243. For example, a cellulase preparation useful in ~he compositions of the invention can consist essentially of a homogeneous endoglucanase component, which is immunoreactive ~ith an antibody raised against~a~highly purified 43~D :eliulase derived from Humicola glgn~ QSM ~1800, or whic.~ :s homologous to said ~3kD
wo g3/2.294 2 i 1 7 .~ ~ 7 PCT/US93/03245 The modified polyesters herein typically achieve their cleaning benefits on cotton-containing fabrics by being incorporated into a detergent composition including other detersive inqredients, 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 additi~e: said additive posssibly containing other selected deter~gent active materials, such as soil anti-redeposition agents and co-dispersing agents, and/or cellulase enzyme: in p~rticular, t~e modified polyesters herein can be used to pre-treat cotton-containing fabrics, before the main wash cycle of laundering processs.
~ he detergent compositions herein can be in a liquid or gr~nular form and are pref~rably delivered directly to t~e drum and not indirectly and via the outer casinq ~of the machine This can most easily be achieved by incorporation of the composition in a bag or container from which it can be relea~ed at the start o~ the wash cycle in response to agitation, a rise in temperature or immersion in t~e wash water in the drum. Such a container will be placed i~ the drum, together with the fabrics to be washed. Alternatively the washing machine itself may be adapted to permit direct addition of the compositicn to the drum e.g. by a dispensing arranqement in the access door.
When the compositions are in liquid form, a rigid container such as disclosed in EPA 151 ~4~ 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 ~ith a water impermeable protective material so as to retain t~e contents, such as is disclosed in EPA no. 0 018 6,8. .~lternatively it may ~e formed of a water insoluble synt~etic poivmer~c material provided with an edge sèal or closure designed tO rupture in aqueous media as WO g3/212g4 2 1 I ~ 9 ~ 7 PCT/US93/03245 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 dispos~d along and sealing one edqe of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
In a variant of the bag or container product form, laminated s~eet products can be employed in which a central flexible layer is i~pregnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric-like aesthetic effect. T~e layers may be sealed together so as to remain attached during use or m~y separate on cont~ct with water to facilitate the release of t~e 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 cf substrata is a matter of choice but ~ill 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 invent~on include, amonq others, sponges, paper and woven and non-woven fabrics.
However the preferred means of carryinq out the was~lna process accordinq to the present invention includes the use of a reusable dispensinq device having ~alls that are permeable -^
liquid but impermeable to the solid composition.
,-~ WO93/21294 21 ~ 7~7 PCT/US93/03245 Devices of this kind are disclosed in EPAs Nos. 0 343 069 and 0 344 070. T~e latter Application discloses a device comprising a flexible sheet in the form of a bag extendinq 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 t~e orifice into the washing mediu~. T~e support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, t~is arrang~ent typically comprising radially extending walls extending from a central boss in a spooked wheel configuration, or a similar struc~ure in which the walls have a helical form.
T~e detergent compositions herein contain a surfactant.
A wide r~nge of surfactants can be used in the detergent co~positions. A ~ypical listing of anionic, nonionic, acphol~tic and zwitterionic classes, and species of these ~urfact~nts, is given in US Patont 3 664 961 issued to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suit~ble herein, especially mixtures of sulphonate and sulfate surfactants in a weight ratio of from 5:l to l:2, preferably ~rom 3:1 to 2:3, more preferably from 3:1 to l:l. Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially ll to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a cl2-Cl8 fatty source preferably from a Cl6-Cl8 fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants are alkyl sulfates havin~ from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture ~ith ethoxy sulfates having from lO to 20, preferably lO to 16 carbon atoms in the alkyl radical and an avera~e de~ree of ethoxylation of to ~.
Examples of preferred alkyl sulfates herein are tallo~ al~yl sulfate, coconut alkvl sulfate. and cl4_l5 alkvl sulfates. ~he WO93/21294 - PCT/US93/03245 ;
7~97 cation in each instance is again an alkali ~etal 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 avera~e 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 alip~atic 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.
Especially preferred nonionic surfactants of this type are t~e Cg-Cl5 primary alcohol ethoxylates containing 3-3 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, the C12-C15 pri~ary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, and mixtures thereof.
Anot~er suitable class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (CnH2nO)t2x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbcn atoms; t is from O to 10 and n is 2 or 3; x is from 1.3 to "
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-3 0 070 077, 0 075 996 and 0 094 113.
Also suitable as nonionic surfactants are poly hydroxy ~at~;-acid amide surfac~ants of the formula R2 - C - N - Z, wherein Rl is H, I I
o p~ l ;~
WO93/21294 Z ~ 7 ~ 7 PCT/US93/03245 or Rl is Cl_4 hydrocarbyl, 2-hyàroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is c5_~1 hydrocarbyl, and 7 is a polyhydroxyhydrocar~yl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a strai~ht Cll_l5 alkyl or alkenyl chain such as coconut alkyl or mixtures th~reof, and 2 is derived from a reducing sugar such as gluco~e, fructose, maltose, lactose, in a reductive amination reaction.
A further class of surfactants are the semi-polar surfactants such as amine oxido~. Suitable amine oxides are selected from mono C8-C20~ pr~fer~bly C10-C14 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining N
positions are substituted by methyl, hydroxyethyl or ; hydroxypropyl qroups.
Another clas~ of surfactants are amphoteric surfactants, such a~ poly~cine-based species.
Cationic surfactants can also be used in the detergent compositions hcrein and suitable quaternary ammonium surfactants are selected from mono C8-C16, preferably C10-Cl4 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are su~stituted by methyl, hydroxyet~yl or hydroxypropyl groups.
Mixturos of surfactant types ~re preferred, more especially anionic-nonionic and also anlon~c-nonionic-cationic mixtures.
Particularly preferred mixtures ~re described in British Patent No. 2 040 987 and European Publlsned Application No. 0 087 914.
The detergent compositions can ;--prise from 1%-70% by weight of surfactant, but usually the sur~actant is present in the compositions herein an amount o~ ~-o~ 1~ to 30%, more preferably from 10-25% by weight.
The detergent compositions hereln also contain a builder Builder materials will ~yp~call~ De present at from .~ to 80~
of the detergent compositions herein. The compositions herein wo 93/212g4 2 1 ~ 7 ~ ~ 7 PCT/US93/03245 lo are free or su~stantially free of phosphate-containinq 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.
W~ter insoluble builders can be an inorganic ion exchange material,commonly an inorganic hydrated aluminosilicate materi~l, more particularly a hydrated synthetic zeolite such as ~ydrated Zeolite A, X, B or HS.
, Pref~rred aluminosilicate ion-exchange materials have the unlt cel~ formula Mz ~(AlO2)Z (sio2)yl xH2O
wherein M is a calcium-exchange cation, z and y are ~t least 6;
the ~olar ratio of z to y is from 1.0 ~o 0.5 and x is at least 5, pre~ferably from 7.5 to 2~6, more preferably from lO to 26~.
The aluminosilicate materials are in hydrated form and ar~
preferably crystalline containing from 10% to 28S, morc ;~ prefer~bly from 1~% to 22S water.
T~e above aluminosilicate ion exchange materials are further characterized ~y a particle size diameter of from 0.1 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 co m entional 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 CaC03 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 mq eq.l~
The aluminosilicate ion exchange ~aterials herein are still further characterized by their calcium ion exchange rate which is described in detail in GB-l ~29 1~3.
~ ~ . wO 93/2l2g4 2 1 ~ r~ ~ y 7 PCT/US93/03245 Aluminosilicate ion exchange materials use~ul in the practlce of this invention are commercially available and can be naturally occurrin~ materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchan~e materials is discussed in US Patent No. ~ 985 669. Preferred synt~etic crystalline aluminosilicate ion exchange materials useful herein are available under the desiqnation Zeolite A, Zeolite ~, Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred embodiment, t~e crystalline aluminosilicate ion exchange material is Zeolite A and has t~e formula , Nal2t(Alo2)12 (Si2)123 xH2O
~` wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 ~(Alo2)86(sio2)106~ - 10 .276H20 is also suitable, as well as Zeolite HS of formula Na6 A102)6~Si~2)6] 7-5 H20)-Another suitable water-insoluble, inorganic ~uilder material is layered silicate, e.g. SXS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of scdium silicate (Na2Si20s). 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 oligomerlc carboxylate chelating agent.
Suitable carboxylates containing one carboxy group include lactic acid, glycollic acid and et~er derivatives thereof ~s disclosed in ~elgian Patent Nos. 831 368, 821 369 and 821 370~
Polycarboxylates containing two carboxy qroups include t~e water-soluble salts of succinic acid, malonic acld.
(ethylenedioxy) diacetic acid, maleic acid, diglycollic ac~.
tartaric acid, tartronic acid and fumaric acid, as well as tne ether carboxylates described .n German Offenleqenschrift ~ 446 686,~ and 2 446 687 and U.S. Patent No. 3 93S 257 and ~.e sulf~inyl carboxylates described in Belgian Patent ~o. 840623.
Polycarboxylates containing -~ree carboxv ~rouDs include, particular, water-soluble citrates, aconitrates and citraconates W O 93/21294 ' P ~ /~S93/03245 .`
21179~7 as well as succinate derivatives such as the carbo-xymethyloxysuccinates described in British Patent 1 379 24l, lactoxysuccinates descri~ed in Netherlands Application 7205~73, and the oxypolycarboxylate materials such as 2-oxa-l,1,3-propane tricarboxylates described in ~ritish Patent No. 1 38~ 447.
Polycar~oxylates containing four carboxy groups include oxydisuccinates disclosed in 8ritish Patent No. 1 261 829, l,l,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in ~ritish Patent Nos.
398 421 and l 398 422 and in U.S. Patent No. 3 936 448, and the sulfonated pyrolysed citrates described in British Patent No. l 082 179, while polycarboxylates containing phosphone substituents are d~sclosed in ~ritish Patent No. 1 43~ 000.
~: Alicyclic and heterocyclic polycarboxylates include cyclo-pentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentac~rboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetrac~rboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, l,2,3,4,5,6-hexane hexacar~oxylates and and carboxymethyl derivatives of polyhy~ric 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 car~oxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the preferred granular detergent compositions herein include a mixture of a water-insoluble aluminosilicate builder such` as zeolite A, and water-soluhle carboxylate chelating agent such as citric acid.
Other builder materials that can form part of the builder system for the purposes of the invention inc~ude inorqanic -~W093/21294 2 1 1 7 3 n 7 PCT/US93/03245 materials such as alkali metal car~onates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
In a preferred e~bodiment of the present invention, the detergent coapositions herein will contain a cellulase enzyme such as described above, at levels of from 0.025% to 10% of the conposition.
In ~nother preferred enbodiment of the pres-nt invention, the deterg nt compositions or detergent additives herein will cont~in a soil anti redeposition or soil suspension agent, in combin~tion with the modified polyesters herein.
~-Antiredeposition and soil suspension ~gents suitable herein include cellulo~e derivatives such as metbylcellulose, c~rboxycet~ylcellulo~e and hydroxyethylcellulose, homo- or co-polyoeric polyc~rboxylic ~cids or their salts and polyaminoacid cou~pounds. Polya~rs of this type include t~e poly~crylates and leic anhydride-~crylic acid copoly~ers disclosed in detail in ~EPA~137 669, as wcll as copolymers of maleic anydride wit~
;~ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. Polyaminoacid compounds such as t~ose derivad from aspartic acid are for instance disclosed in ~ritish patent application No. 9226942.2.
These materials are normally used at levels of from 0.025~ ~_ 5~ by weight, of the compositions herein.
The present detergent compositions are preferably in granular form and more preferably in a "compact" form, i.e. havinq a density, which is higher than the density of conventional detergent compositions. The preferred density of ~.~e ;~compositions herein ranges from 550 to 950g/liter, prefera~
650 to 850g/liter of composition, ~easured at 20~C.
WO93/21294 ~ ~1 7 9 9 7 PCT/US93/03245 The present "compact" form of the ~OSt 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 exceedin~ 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5 , by weight of the composition.
~ ~ r 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 sulfate.
The present compositions will typically include optional ingredients that nor~ally form part of detergent compositions.
Enzymes, optical briqhteners, bleaches, bleach activators, suds suppressors, anticacking agents, dyes and pigments are exam~les of such optional inqredients and can be added in varying amounts as desired. ~
Enzymes such as proteases. Ilpases, or amylases are particularly desirable ingredier.ts ~f t~e compositions herein.
Preferred optical briqhteners are anionic in character, examples of which are disodiu~ 4,41-bis-(2-diethanolamino-~-anilino -s- triazin-6-yla~ino~stilbene-2:21 disulphonate disodium 4, - 4l-bis-(2-~orp~olino-4-anilino-s-triazin ylaminostilbene-2:21 - disulphonate, ~lsodium 4,41 - bis-(2~4-dianilino-s-triazin-i-yla~ino)stilbene-2:21 -disulphonate, monosodium~ 11 -DlS-t 2,~-dianilino-s-triazin-i ylamino)stilbene-2-sulphonate, dlsodiu~ ~,41 -bis-(2-anilino-~-(N-methyl-N-2-hydroxyethylamino)-s-~rlazln-6-ylamino)stilbene-2,21 - disulphonate, disodium ~,~; -bis-(4-phenyl-2,1,3-triazol-2~ 17~3~7 WOg3/212g4 PCT/US93/03245 ` ' 15 2-yl)-stilbene-~,21 disulphonate, ~isodium ~ bis(2-anllin (l-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)s~lbene-2,21disulphonate and sodium ~(stilby~ (naphtho-ll~2 1,2,3 - triazole-2il-sulphonate.
Any particulate i~organic perhydrate bleach can be used, in an amount of from 3~ to 40% by weight, more preferably from a~ t~ -25% by weight an~ most preferably from 12% to 20% by weight ^f the compositions. Preferred examples of such bleaches are sodium perborate monohydrate and tetrahydrate, percarbonate, and mixtures thereof.
~ , ~
Another preferred separately mixed ingredient is a peroxv carboxylic acid bleach percursor, commonly referred to as a bl-ach activator, which'is preferably added in a prilled or agglomerated form in granular detergents. Examples of suitable compounds of t~is 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 Paten~
Applic~tion No. 0 062 523. Preferred examples of such compounds are tetracetyl ethylene diamine and sodium 3, 5, ~ trimeehy~
Bleach activators are normally e~ployed at levels o~ from 0.5%
to 10% by weight, more frequently from 1~ to 8% anà preferably from 2% to 6% by weight of t~e composition.
Another optional inqredient 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 exemplifi~d by silica aero~els and xerogels and hydrophobic silicas of various types. These materials can be incorporated as part culates in ~hich the suds suppressor lS advantaqeously releasably incorporated in ~ water-soluble or water-dispersible substantiaIly non-surface-active detergent impermeabie carrier Alternatively the suds suppressor can ke dissolved c- dispersed a liquid carr~er ~nd applied _. sDraylna on ~o one or more o~
the other components.
WO g3/21294 2 1 1 7 .9 ~) 7 PCr/USg3/03245 ~.~
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 ~ixtures are prepared by affixinq the silicone to the surface of the solid silica. ~ preferred silicone suds controlling agent is represented by a hydrophobic silanated tmost 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 dimet~yl silicone `~
fluid having a molecular weight in t~e 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 artollo~a 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, ~hich is a siloxane~glycol copolymer.
The suds suppressors described above are normally e~ployed at levels of from 0.001% to ~% by wei~ht of the composition preferably from 0.01% to 1% by weight. The incorporation of the suds mofidiers is prefera~ly made as separate particulates, and this permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MW copolymers of ethylene oxide and propylene oxlàe whi~h would otherwise adversely affect the dispersibility of t~e matrix~ Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al ~'.S.
Patent No. 3 933 672~
Fabric softening agents c~n also be incorporated `nto detergent compositions in accordance ~ith the present inventicn.
~hese agents may be inorqanic cr organic in type. '~norgan~c softening agents are exempiif ed ~ he s~ectite clavs iisclcs2 in G~-A-l ~oo 898.
WO93/212g4 ~ti 1 7 3 .~3 7 PCT/US93/03245 Organic fabric softening aaents include the water-soluble tertiary amines as disclosed in G8-A-1 400 898. Organic fabric softeninq agents include the water-insoluble tertiary amines as disclosed in G~-A-lsl4276 and EP-B-O 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-~-O 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 softening 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, lev~ls 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. Orqanic fabric softening agents such as the water-in-oluble tertiary amines or di-long-chain amide materials are incorporated at le~els of from 0.5% to 5% by weight, normally fron 1% to 3% by w~ight whilst the high molecular weight polyethylene oxide m~terials and the w~ter-soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. T~ese materials are normally added to the spray dried portion of the composition, although in some instances 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 ~aving molecular weight from 5 000 to 2 200, typically present in the preferred granular detergent ~ompositions herein, at level sucn as to deliver from S to 500 mg/l of said polyvinyl pyrrolidones in the wash solution.
The following examples illustrate the invention and faci'itate its un~erstanding.
W093/2~2g4 2 1 1 7 ~ ~ 1 PCT/US93/03245 The ab~reviations for the individual ingredients have ~.~e 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 ~A45E7: fatty alcohol (C14-C15) ethoxylated with about , ;-~ moles of ethylene oxide 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 - IO micrometer SXS-6: crystalline layered silicate (Hoechst) Copolymer AA/MA: copolymer of acrylic acid and mal~ic acid PAA:~ ~ Polyacrylate polymer CMC:~ carboxymethylcellulose Phosphonate: sodium salt of ethylenediamine tetramethylene phosphonic acid EDTA: æodium ~ialt of et~ylenediamine tetra acetat'e PBl:~ N~B02.H202 TAED: tetra acetyl e~hylene 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 (si7icafsilicone mixture) T~.e modified polyester used throughout the following exampies correspond to the specLes described in C7 aim 2 herein.
he method of preparati~on was as follow:
The~process ~of preparation of the selected polyester here~-~includes ~m~ixlng ~all the monomers in a round bottomed flas~.
stirr~ng at ,80-C, until a clear solutlon results, and cont~ e stirring ror 2~ hours. ~hen transferrinq the contents of ~ne :: ~
21179~7 ,. . WO g3~2~2g4 Pcr/uss3/0324s ~3 round bottomed ~las~ ~o a ~^~rther slngle ~.ecked -ound bottomed flask (typically 1 litre), heating under vacuum for ;5 ~inutes at 200-C, removing from flask and cooling. ~ clear glass solid is o~tained, which is then crushed ~ently ~o be used.
~ x~ple ~:
The following detergent composition was prepared.
... _ .. .
L~S .% by we~g~t FA45E~ 2.5 SODIUM SU WHATE S
PAA 3.5 PROTEASE 1.6 ~CELLU~SE 0.5 MODI~IED OL ESTER O.5 ...
A bundle of soiled ~abrics contalning fabrics which were stained with a range of stains such as partlculate soils, greasy soils, enzymatic soils and bleachable soi1s on cotton and polycotton fabrics were washed in a compac: ~eter~ent with the formulation as shown. One half of each bunale ~as washed with deterqent composition as shown and the oth~ as washed with the same composition without the cellulas~. T~e testing was carried out at ~0'C in water of 25'H (Ger~an ~a~ness). ~11 .esting ~as -~ repeated 4 times.
Stain rèmoval was~ evaluated re!a~lfe to a reference stain -r each type~ previously washed ~nder Identical conditions. ~he formulation used for the wasn;.-~ of ~he ~ererence ~-aDr:-s con~a1ned no ~odified polyester ^r _ei.~iase.
WO 93/212g4 2 1 ~ 7 3 9 7 PCT/US93/0324~ .
Stain re~oval was evaluated using the well known schefe scale of panel score units determined by two judges as follows:
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 , st~ins.
The average data compared to the reference fabric was c~lculated. T~e results on the greasy stains on polycotton m~terial were as follows.
8t-i~ Pr~f-r-no- for x~n~le 1 ,co~on~tlon ver~u~ reference .' Dirty motor oil t1. 1*
Make up +0.5*
, .~, Statistically significant Exam~le 2:
A detergent of formulati~n similar to that described in ~ple ~;~ 1 was used to wash a ~undle of soiled fabrics which were stained with a range of soils of particulate, greasy, enzymatic and b}eachable types. One nalf of eac~ ~undle was was~ed _n the .,, ~ .
formulation described i~ example ;, the other half of the bundle was washed in the identical 20rmula without modified polyester.
The conditions used -_r wasAinq these Dundles were ~O~c and 25 ~ WO g3/212g4 2 1 1 7 9 ~ 7 PCT/US93/03245 water. 4 replicates of each test ~ere carried OUt and the samples were graded accordingly tO the ~ stain removal. This was calculated using the Mc~eth (colour spectrometer) using the conventional 1 a b system. ~he tests were repeated using different levels of modified polyesters between 0.025% and 10%
by weight of the deterqent composition.
The results are detailed below:
L ~l O.025% O.1% -0.5%-~- 10-%-~n r ~oval gr a-y o~ 52% 64~ 69S 73%
polycot~o~ _ .
T~pical greasy stains considered include dirty motor oil, shoe polish and make up.
Figures quoted are average %stain removal enhancement above the reference product.
Enhanced greasy stain removal by the combination of modified polyester and carboxy methyl cellulose.
Polycotton swatches were pretrea~ed a num~er of times with a detersive formulation containing the carboxy methyl cellulose (CMC). The purpose of this was to give the fabric a histor~ Ot CNC deposition onto the cotton of the polycotton. The polycotton was then dryed and stained ~ith dirty motor oll (DMO~. One half of the stains was ~ashed in a deterslve formulation similar to that described in example one to acl as a ,: ~
reference whilst the other half was washed in ~he same for~ulation only containinq the modified poiyester hereln.
WO93/212g4 ~It 7 9 g 7 PCT/US93/03245 The swatches were graded by calculatlng the % stain removal from each tracer using the hunter colour lab system. All data was also compared to swatches which had been treated in 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 Modified CMC/modified ~CMC onlv~ Dolvester Polvester Aver~ge %
stain removal 21% 43% 79%
- '~' Test conditions 40-C/25-H water - ~ replicates Exam~l- 4:
Pretre~tment solution compositions containing the modified polye~ter ~erein ~ere 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 FA45E7 13 17 17 - ~ 30 22 Maleic/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 ranqe of greasy type stains such as dirty motor oil, sun tan lotion ma~e up and lipstick.
All fabrics whic~ had previously been treated with any of tne compositions described showed ~arked improvement in t~e staln removal from the polycotton when c~mpared to an unpretreated stain.
The following compact detergent c^mpositions were also prepare~
-- ~ WO g3/212g4 ~ 3 ~ 7 PCT/US93/03245 COMPACT DETERGENT COMPOSITIONS
lall levels in % bv weiaht~
~X~les: v vI VII VIII TX X XI
L~S il.00 -- 6.50 -- 6.s0 -- __ TAS -- -- 3.25 3.90 2.25 -- --AS 5.00 12.00 -- -- -- 6.00 6.s0 FM SE7 4.00 1.00 2.20 6.00 2.20 3.00 --FA25E3 -- -- -- -- -- 6.00 7.00 CAT -- -- -- 2.45 -- -- --T~llow glucosé am~de -- 10.00 -- -- -- -- --N~ citrate/citric 18.00 5.00 12.0~ 15.00 12.00 4.00 4.00 Z-olite 4A 32.00 15.00 16.00 20.00 15.00 13.00 13.00 SXS-6~ -- 12.00 -- -- __ 12.00 12.00 Copolymer AA/ ~ 4.10 5.00 3.50 3.50 -- 5.00 3.00 ;Pol ~ ptide 3.00 -- 2.00 Pbosphon~te 0.19 1.00 -- -- 1.00 -- --EDTA -- -- 0.32 0.32 -- -- --Na c~rbon~te/ 3.00 2.50 10.00 10.00 10.00 9.00 10.00 bicarbonate Silicate (R2) 3.00 2.002.50 2.50 2.50 3.50 3.50 CNC -- 0-50 -- -- -~ 0-30 ~~
Clay -~ .60 8.60 -- --: --P~ 50 -- 12.00 -- 12.00 Percar~onate -- .-- -- 12.00 -- 23.00 --TAED -- -- 3.20 -- ~.oo 6.00 A.OO
Protease 1.20 1.60 1.40 1.40 1.40 1.40 1.40 ~Cellulase o.so -- 0.30 0.10 0.10 0.10 0.10 Lipase 0.40 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.S0 ~.00 3.50 ~.00 PVP -- 0.50 1.00 -- -- -- --S55 ~ 0.4~0~ o.~o 0.50 0.50 0.50 0.~0 0.50 Modif~ied~polyester 0.30 0.40 0.30 0.50 0.50 0.50 0.50 Minor~s + water Balance to 100%